Two-Dimensional Metal Phosphorus Trichalcogenide Nanostructure for Sustainable Energy Conversion

Fengmei Wang *
Fengmei Wang
State Key Laboratory of Chemical Resource Engineering, Beijing Advanced Innovation Center for Soft Matter Science and Engineering, Beijing University of Chemical Technology, Beijing 100029, China
CAS Key Laboratory of Nanosystem and Hierarchical Fabrication, National Center for Nanoscience and Technology, Beijing 100190, P. R. China
*Email: [email protected]
More by Fengmei Wang
and
Marshet Getaye Sendeku
Marshet Getaye Sendeku
CAS Key Laboratory of Nanosystem and Hierarchical Fabrication, National Center for Nanoscience and Technology, Beijing 100190, P. R. China
Research Institute of Tsinghua University in Shenzhen, Tsinghua University, Shenzhen 518057, P. R. China
More by Marshet Getaye Sendeku

DOI: 10.1021/bk-2022-1421.ch001

Publication Date (Web):November 21, 2022

Request reuse permissions

Nanostructured Materials for Sustainable Energy: Design, Evaluation, and Applications

Chapter 1pp 1-25

ACS Symposium SeriesVol. 1421

ISBN13: 9780841297531eISBN: 9780841297524

Chapter Views

2761

Citations

LEARN ABOUT THESE METRICS

Chapter Views are the COUNTER-compliant sum of full text article downloads since November 2008 (both PDF and HTML) across all institutions and individuals. These metrics are regularly updated to reflect usage leading up to the last few days.

Citations are the number of other articles citing this article, calculated by Crossref and updated daily. Find more information about Crossref citation counts.

PDF (5 MB)

SUBJECTS:

Go to Nanostructured Materials for Sustainable Energy: Design, Evaluation, and Applications

Get e-Alerts

Abstract

The rational design of novel two-dimensional (2D) materials has long been sought, with a particular objective in catalysis, energy storage, and conversion. The discovery of 2D metal phosphorus trichalcogenides (MPX₃) opens lots of success and breakthroughs in diverse fields such as photocatalysis, electrocatalysis, battery storage, and membrane technologies. In this chapter, a comprehensive overview of the synthesis strategies and applications involving 2D MPX₃-based nanomaterials is presented. The recent development in bottom-up and top-down approaches for obtaining low-dimensional nanostructures and their limitations are briefly discussed. Their common [P₂X₆]^4- unit, which exhibits the advantage of monitoring the adsorption-desorption chemistry in several reactions along with the rich toolbox to entertain various metal elements in their structure, makes them act as a suitable candidate in catalysis and energy storage device. Thus, the present chapter highlights the advances of 2D MPX₃ nanomaterials and promising potential applications in sustainable energy conversion.

This publication is licensed for personal use by The American Chemical Society.

1 Introduction

CHAPTER SECTIONS

Jump To

Modern society is seeking an affordable, environmentally benign, and efficient energy conversion system. On one hand, the dependence of many manufacturing and chemical industries on fossil fuel caused serious energy shortages. On the other hand, the urgent need to obtain energy storage devices that could be able to be used for storing renewable energy sources, such as solar and wind, is vital. To this end, various novel materials with unique nanostructures, especially the two-dimensional (2D) featured nanomaterials, are explored and designed. In the context of these quests, metal phosphorus trichalcogenides (MPX₃, X= S, Se), as the newly emerged van der Waals layered materials, have aroused widespread interest. Generally, the M in MPX₃ represents kinds of metal elements with different valence states (M^II or M^IM^III), including transition metals, one of group II alkaline metals, part of group III, and group IV metals ((Figure a1)). In a representative monolayer, the structure can be seen as a honeycomb configuration of the metal ions disseminated around the [P₂X₆]^4- bipyramids ((Figure b1)) ( 1). When considering the structure of typical M₂²⁺[P₂X₆]^4- compounds, two-thirds of octahedral centers are occupied by M²⁺ cations, and the remaining one-third of the position is filled with P-P dimers, which are covalently bonded to the X atoms. The metal cations stabilize [P₂X₆]^4- frameworks through ionic bonds. The different layers are weakly stacked together via van der Waals interactions. Hence, these compounds are sometimes described as M₂P₂X₆. In addition to the M₂²⁺[P₂X₆]^4- type, there are possibly five other sub-lattices ( 2, 3), which can be denoted as M¹⁺M³⁺[P₂X₆]^4- with two different cation orderings, M_4/3³⁺◻_2/3[P₂X₆]^4- (the “◻” stands for the vacant site), M₂¹⁺M²⁺[P₂X₆]^4- and M₄₊[P₂X₆]^4-. Note that both anion and cation components can be tuned by altering the M and X atoms in MPX₃ to obtain the alloyed analogues. The cation valence state would slightly vary depending on the element chosen. In terms of the crystal system, the widest symmetry of M^IIPS₃ is C2/m with a monoclinic crystal structure. Most M^IIPSe₃ are identified as either monoclinic or rhombohedral crystallographic structures ( 4).

Figure 1. (a) The metal atoms and their valence states constituted in MPX₃ crystals across the periodic table of elements. Filled blocks represent elements for which the layered MPX₃ structure has been reported. (b) Schematic structure of MPX₃ with [P₂X₆]^4- bipyramids enclosing the metal atoms. The X layers are distinguished through X_top and X_bottom.

Although Friedel and Ferrand firstly discovered them in the late 1800s ( 5, 6), significant research development about their interesting structure and physical properties was reported in the early 2000s. In particular, unlike the van der Waals layered transition metal dichalcogenides, several MPX₃ materials demonstrate intrinsic physical properties ( 7, 8), including fundamental magnetism ( 9, 10, 11, 12, 13) and ferroelectricity ( 14, 15). For instance, M^IIPS₃ (M^II= Mn, Fe, Co, and Ni) crystals show the different types of antiferromagnetic moments-distributions with different Neel temperature. It is noted that each of the distinct properties of MPX₃ materials is closely interlinked. The electronic structure determines the magnetic properties and the transition temperature point, as well as the modality of ferroelectricity.

In the context of energy conversion, MPX₃ materials showed great development. Both experimental and theoretical efforts have witnessed the great potential that layered MPX₃ materials hold for deriving many photocatalytic reactions. Particularly, the theoretical results revealed that MPX₃ compounds possess a wide bandgap of 1.2-3.5 eV ( 4), indicating their potential light absorption property which endows them to be an excellent candidate in photo(electro)catalysis for water splitting, carbon dioxide reduction, organic molecular transformation, and so on. In addition, the unusual intercalation-substitution behavior and the incipient ionic conductivity of MPX₃ materials promote their utilization in metal-ion batteries ( 16, 17), such as Li-ion and sodium-ion batteries, and ion-exchange membrane ( 18).

In this chapter, the synthesis methods and application of 2D MPX₃ nanostructures in photocatalysis, electrocatalysis, battery, and ion-exchange membrane is described.

2 Strategies for MPX₃ Synthesis

CHAPTER SECTIONS

Jump To

To date, various synthesis techniques have been adopted for obtaining high-quality bulk and low-dimensional MPX₃ crystals. In this section, the strategies employed for synthesizing both bulk and low-dimensional MPX₃ nanocrystals are presented.

2.1 Bottom-up Method

2.1.1 Chemical Vapor Transport

Chemical vapor transport (CVT) is the most common method for the synthesis of bulk MPX₃ crystals. In a typical procedure, a stoichiometric amount of metal, phosphorus, and chalcogens (S or Se) are mixed and placed in a fused silica ampoule. Subsequently, the mixture is heated at a temperature (denote as T2 region) lower than the decomposition temperature of the target product ((Figure a2)) for several days. A temperature gradient system is used to facilitate the formation of vapour and target products in the other region (denote as T1 region). The heating temperature (400 - 800 °C) in the T2 region is mainly aimed at forming vapor that could be transported to the T1 region, which is at a relatively lower temperature, to form the MPX₃ product ((Figure b-h2)) ( 19, 20). Meanwhile, some additional strategies are applied to achieve efficient growth of the MPX₃ single crystals: i) for efficient transport, the synthesis temperature can be manipulated by adding elemental halogens (such as Cl₂, Br₂, and I₂) as a vapor transport agent ( 21). But, the possible intercalation of halogens into the layers of the as-obtained MPX₃ crystal may occur, and hence the inherent properties of the material may change; ii) the further heating process at ~500 °C is conducted at the T1 region after getting the product to remove the excess sulfur, red phosphorus or transport agent. On account of the low melting point and high vapor pressure of P, S, and Se, they could also serve as vapor transport agents during synthesizing MPX₃ bulk crystals ( 3, 19).

Figure 2. (a) Schematic illustration of the CVT approach. (b-h) the digital images for the resulting MPX₃ crystal.

Despite the extensive use of the CVT method, there are still several drawbacks associated with it, which are described as follows; i) a typical CVT process employed to synthesize MPX₃ materials involves more than three precursors. Hence, there are possibilities for some parasitic reactions to occur, which often lead to the formation of an unwanted phase. The occurrence of such kinds of parasitic reactions is highly pronounced, especially when an attempt is made to grow M^IM^IIIP₂S₆ type layered crystals. For example, the formation of (Cu/Ag)₃PS₄ was noted as an impurity during the growth of the Ag^ICu^IIIP₂S₆ crystal ( 22). ii) CVT process also suffers from the long reaction time, high reaction temperature, and possibility of explosion, which limit the possibility of scaling up the production process. iii) The CVT approach usually synthesizes the bulk crystal. The corresponding nanostructures can be obtained through the additional top-down approaches, including mechanical exfoliation, solution intercalation, electrochemical exfoliation, etc., which will be discussed in the Top-down Method section.

2.1.2 Chemical Vapor Conversion (Deposition)

Chemical vapor conversion ( 11, 23, 24) or chemical vapor deposition ( 25) is the other widely used approach in bottom-up methodology to directly prepare the MPX₃ nanomaterials on certain substrates.

In the chemical vapor conversion process, pre-grown metal precursors (metal oxide, metal hydroxide, or metal sulfide) are directly used to react with a mixture of P and S. The synthesis can be accomplished via a two-step process. In the first step, the metal precursors are directly grown via the hydro/solvothermal method on different substrates such as carbon cloth, fluorine-doped tin oxide (FTO), indium tin oxide (ITO), etc. In the next step, the as-obtained precursor and a mixture of P and S can be kept in a two-zone furnace and subjected to heat treatment. And the P & S vapor can react with the metal precursors to get the two-dimensional MPX₃ nanosheets on the substrates. To achieve the complete conversion process, a custom-designed silica socket tube is used to create a “space confined” condition ((Figure a3)). The term “space confined” here refers to the special configuration of the precursors, including metal precursor and (P + S) powder mixture, in the silica socket tube, where a controlled flow of carrier gas is allowed to transport the P and S in the vapour phase. Compared to CVT, this method is relatively fast and safe.

Figure 3. (a) Schematic illustration for space confined chemical vapor conversion process. (b) AFM images of MPX₃ nanosheets grown via this method ( 11, 24, 26, 27).

The 2D MPX₃ nanosheets with an ultrathin thickness could be achieved by carefully optimizing the reaction temperature, gas flow rate, and P: S ratio. The temperature in the two zones at which the metal sulfide or oxide precursor is found to be very crucial for the optimum growth. Until now, this method has been successfully employed to synthesize several 2D MPX₃ crystals. As shown from the atomic force microscopy (AFM) images ( 11, 24, 26, 27) in (Figure b3), the MPX₃ (M= Ni, Mn, Sn, as well as Ni and Co alloys) nanosheet of varying thickness (10-20 nm) could be obtained via this approach. The growth temperature usually varies from 350 to 600, and the reaction time reported in the aforementioned studies is less than 2 h. As for the growth of MPSe₃ nanosheets, Shifa et al. ( 27) reported that manipulating the temperature for heating the mixture of P and Se powder is required to avoid the parasitic growth of MnSe. The formation of this unwanted impurity was excluded via a pre-heating treatment of the P and Se mixture, which facilitated the mixing of P and Se before their separate diffusion to the target metal precursor. Later, the method has also been employed to design a solid alloy of Ni_1−xCo_xPS₃ nanosheet ( 11). In recent work ( 25), several MPX₃ nanosheets and some alloys were synthesized through the chemical vapor deposition method by using the large-sized MCl₂ as the precursor to controllably get the nanosheets on the substrate. This approach is usually employed to obtain high-quality nanosheets for the field in the electronic device study.

2.2 Top-down Method

The top-down strategy is mainly employed to fabricate low-dimensional MPX₃ nanocrystals from their bulk counterparts. Earlier theoretical works have witnessed the ease of preparing MPX₃ nanosheets from their corresponding bulk crystals. For instance, Kloc and collaborators ( 19) estimated the cleavage energies (E_cl) of several MPX₃ compounds by considering the total energy as a function of the separation between two fractured layers. The authors compared the estimated E_cl value of MPX₃ with graphite (E_cl = 0.36 J/m²) to judge the feasibility of employing the exfoliation technique to experimentally design low-dimensional materials. With the exception of FePSe₃, which has an almost comparable E_cl value with graphite, all calculated values for other MPX₃, including NiPS₃, FePS₃, ZnPS₃, CdPS₃, MnPS_3, and MnPSe₃, are smaller than that of graphite ( 19), indicating the possibility of obtaining 2D MPX₃ crystals via exfoliation from their bulk counterparts. The following subsections highlight different preparation methods to obtain high-quality 2D MPX₃ nanosheets via the exfoliation technique.

2.2.1 Mechanical Exfoliation

Mechanical processes such as ball-milling could be used for the exfoliation of bulk crystals with compact layers into uniform few-layered nanosheets. Through employing a ball mill system, the layered crystals of FePS₃ were exfoliated into a few layers. Throughout this process, zirconium dioxide balls were ball milled at a speed of 580 RPM for 12 h under nitrogen (99.99%) environment. The as-obtained sheets with defect-rich surfaces exhibited an enhanced property such as surface area (6.18 and 49.7 m² g^-1 for the pristine and exfoliated FePS₃, respectively) ( 28). Moreover, this method was also adopted for the preparation of novel 2D/2D heterojunction containing ultrathin MnPS₃ sheets and reduced graphene oxide (rGO). By utilizing high-energy ball milling, it was possible to synthesize a composite structure of rGO with MnPS₃. It is interesting to note that such a structure displayed various intriguing properties, including improved conductivity, high charge transfer capacity, and stability ( 29). While such prominent examples are available in the literature, the method is still less practiced for designing several ultrathin MPX₃ crystals.

In addition, the mechanical cleavage from a single bulk crystal by using Scotch tape is also applied to get an MPX₃ nanosheet for studying its physical properties. This approach can be regarded as a nondestructive exfoliation technique. Thus, the obtained MPX₃ nanosheet demonstrates a clean surface with the perfect crystal quality and few defect sites ( 30). Unfortunately, the production yield is quite low with inferior precision and there is restricted controllability for practical application in the energy conversion field.

2.2.2 Solution and Intercalation Methods

Liquid phase exfoliation is one of the most commonly used methods for relatively large-scale production of ultrathin 2D MPX₃ sheets from the corresponding bulk crystals ( 31, 32, 33). In a typical procedure, the bulk MPX₃ crystal is firstly dispersed in a suitable solvent. And then these crystals are subjected to ultrasonication to yield the corresponding nanosheets. After the ultrasonication process, separation of the bulk crystal is usually required. Ni_1-xFe_xPS₃ with ultrathin thickness was prepared by this method utilizing N,N-dimethyl formamide (DMF) as a solvent ( 34). Moreover, FePS₃ quantum sheets with intriguing properties were prepared through this route ( 35). It has also been reported that mechanical exfoliation could be linked with the liquid phase exfoliation for achieving high-quality MPX₃ nanosheets. For example, exfoliation of MnPS₃ was carried out mechanically on polymethyl methacrylate (PMMA) and polyvinyl alcohol (PVA)- coated SiO₂/Si substrates ( 36). With the subsequent removal of PMMA layer by acetone, the MnPS₃ flakes were easily collected.

2.2.3 Electrochemical Exfoliation Method

The electrochemical exfoliation method is found vital for efficiently unzipping bulk MPX₃ crystals. For instance, huge amounts of large-sized high-quality NiPS₃ monolayers were obtained utilizing this strategy ( 37, 38, 39). Compared to other approaches, the electrochemical exfoliation process affords numerous advantages: 1) easy to achieve scalable fabrication; 2) producing the MPX₃ nanosheet with a large lateral size; 3) cost-effective; 4) having reproducibility and solution processibility. In a typical setup, the targeted MPX₃ crystals, Pt wire, and tetra-n-butylammonium tetrafluoroborate in DMF solution act as the working electrode, counter electrode, and electrolyte solution, respectively. The electrochemical exfoliation is achieved via carefully applying a static bias on the working electrode. This approach is found to be a sonication-free and fast (within few minutes) method to prepare large-sized few-layered flakes with high crystallinity and purity. Meanwhile, much more defective sites, which may serve as the active site for the catalytic reactions, could be introduced into the MPX₃ nanosheets through this electrochemical exfoliation process.

In summary, low dimensional MPX₃ nanocrystals can be obtained via bottom-up and top-down strategies. The chemical vapor conversion method is a directly well-acknowledged synthesis method for 2D MPX₃ crystals on various substrates including flexible carbon cloth, rigid FTO glass etc.. And this method has been employed for designing various transition and post-transition metal-based MPX₃ nanocrystal film as catalyst for photo/electro-catalytic applications or battery storage. Note that some vacancies (like sulfur vacancy) usually exist in these nanocrystals when applying this approach. The chemical vapor deposition approach is a promising technique to directly grow the two-dimensional MPX₃ nanosheets on some certain substrates, which can be further transferred to fabricate the physical devices, including photodetector and field effect transistor. The exfoliation technique has also been widely utilized to obtain 2D MPX₃ crystals with relatively larger lateral size. Among various types of exfoliation approaches, mechanical exfoliation is reported to achieve horizontally micro-sized MPX₃ crystals with high quality. Hence, this approach is anticipated to facilitate the development of 2D MPX₃ nanosheets in basic research of the intrinsic physical property by using one specific nanosheet. Despite this potential advantage, the method still suffers from the issue of scalability. In contrast, liquid phase exfoliation can be employed for large-scale synthesis of MPX₃ sheets, which are then used in energy conversion field.

3 Nanostructured MPX₃-Based Materials for Sustainable Energy Conversion

CHAPTER SECTIONS

Jump To

3.1 Photocatalysis

Photocatalysis is a photochemical catalytic process, which is a greener alternative capable of producing several kinds of fuels and chemicals under solar light illumination. In general, the photocatalysis process can be based on molecular materials (those participating in natural photosynthesis of the green plant) or on crystalline solids, which are usually semiconductor-based heterogeneous photocatalysts. The solid semiconductor system often offers better stability and a simpler separation of products. Typically, the fundamental mechanism and process for the synthesis of fuels and chemicals over a solid semiconductor under light can be briefly described as follows: i) upon light illumination with suitable radiation energy (greater than or equal to the bandgap of the semiconductor), a semiconductor photocatalyst can absorb the photons, resulting in the generation and accumulation of electrons and holes at the conduction band (CB) and valance band (VB), respectively; ii) the photogenerated charge carriers are then separated and transported to the photocatalyst surface; iii) these photoexcited electrons and holes are finally utilized to drive reduction and oxidation reactions ( 40, 41, 42). From the point of thermodynamics, the position of CB and VB is very helpful in judging the suitability of a semiconductor photocatalyst to derive a particular reaction.

It has been experimentally and theoretically realized that layered MPX₃ monolayers possess wide bandgaps ranging from 1.2 to 3.5 eV ((Figure 4)). This offers an immense opportunity for remarkably broader light absorption. Moreover, earlier theoretical works demonstrated that the carrier mobility in monolayer MPX₃ is reasonably high (625.9 cm²V^-1S^-2 for MnPSe₃ monolayer) ( 43), which offers the easier transfer of carriers to reactive sites for the photocatalytic process. Moreover, density functional theory (DFT) studies demonstrated that the 2D monolayer MPX₃ nanosheets possess excellent light absorption and electronic properties, which become a motivation for the photosynthesis investigation of this family. As shown in (Figure 4), the CB minimum and VB maximum of most MPX₃ monolayers straddling with the water splitting and CO₂ reduction redox potentials suggests that they can be studied as suitable candidates for photocatalytic water-splitting or CO₂ reduction reaction.

Figure 4. The VB maximum and CB minimum positions of various MPX₃ monolayers calculated using HSE06 functional in DFT calculations, as well as the redox potentials (V vs Normal Hydrogen Electrode (NHE)) for water splitting and CO₂ reduction at pH = 7 ( 2, 4, 43, 44).

3.1.1 Water Photocatalysis for Hydrogen Gas

Hydrogen (H₂) is regarded as a clean and sustainable source of energy that yields an energy equivalent to 285.8 kJ/mol upon combustion. At present, the large-scale production of H₂ gas relies on methane reforming and water-gas shift reactions, which take place at high temperature (700 – 900 °C) and pressure through using a suitable catalyst. As such, these technologies are energy-intensive and are a potential threat to the environment as they simultaneously produce greenhouse gas (such as CO₂) as a bi-product ( 42). As a viable alternative to this process, photocatalytic H₂ production from naturally available sources such as water and biomass is considered a cleaner route ( 45, 46). Owing to its low-cost and environmentally benign nature, the photocatalytic water-splitting reaction over a semiconductor material has become an elegant alternative to storing solar energy as a clean and carbon-neutral fuel. Since the pioneering work by Honda and Fujishima in 1972 ( 40), numerous kinds of photocatalysts have been developed and studied. By and large, the overall photocatalytic water splitting reaction involves the hydrogen evolution reaction (HER) and oxygen evolution reaction (OER) initiated by electrons from the CB and holes from the VB, respectively. During this process, the thermodynamics and kinetic issues should be taken into account.

The last few decades have seen promising progress in extensively using rationally designed 2D materials for photocatalyzing water splitting, because the 2D feature somehow provides a short distance for the photogenerated electrons and holes to migrate, and thereby reduce the possibility of electron-hole recombination. Meanwhile, a higher specific area with abundant active sites can be easily designed and obtained compared with the corresponding bulk counterparts. In this regard, the MPX₃ family provides a versatile platform to design efficient photocatalysts for water splitting. Several exemplary works that unveil the promising potential of 2D MPX₃ materials have been communicated ((Table 1)). For instance, Wang et. al ( 23) demonstrated that ultrathin hexagonal NiPS₃ nanosheets could produce H₂ gas from water without any sacrificial agents at the rate of ∼26.42 μmol g^-1 h^-1 and 6.46 μmol g^-1 h^-1 under Xe light (λ > 300 nm) and AM1.5 simulated solar light illumination, respectively. Later, other MPX₃-based materials were developed and studied. Few layered FePS₃ quantum sheets ( 35), In_2/3PS₃ ( 24), SnPS₃ ( 26), and CdPS₃ nanosheets ( 47) exhibited reasonable photocatalytic H₂ evolution performance, with the rates reaching 402.4, 875, 665.5, and 10880 μmol g^-1 h^-1 with help of sacrificial agents, respectively. Although several theoretical reports demonstrated the unique potential of this family, experimental efforts to realize overall water splitting to simultaneously get H₂ and O₂ gas from MPX₃ photocatalyst are still lacking.

3.1.2 CO₂ Photocatalysis for Fuels

The growing trend of fossil fuel consumption along with massive anthropogenic CO₂ emission have brought a global energy crisis and climate change, and this attracts global attention. Photocatalytic CO₂ reduction is expected to be an environmentally friendly and sustainable strategy for converting it into high-value chemicals by utilizing solar energy. This strategy combines the reductive half-reaction of CO₂ conversion with an oxidative half-reaction, e.g. H₂O oxidation, to create a carbon-neutral cycle, presenting a viable solution to relieving the energy crisis and greenhouse gas effect.

In a photocatalytic reaction process, the free electrons and holes are generated and migrate independently to the surface of photocatalysts to react with adsorbed species (H₂O, CO₂ etc.) in an aqueous solution. In the case of CO₂ reduction, the photogenerated electrons reduce CO₂ into fuels, while the photogenerated holes oxidize H₂O into O₂. As such, the primary difference between photocatalytic water splitting and CO₂ reduction is the surface reaction of the photogenerated electrons and the proton or H₂O reduction often occurs in competition with CO₂ reduction in an aqueous solution ( 49). In the past few decades, significant achievements have been made on photocatalytic CO₂ reduction over novel visible-light responsive semiconductors, including metal chalcogenide and the MPX₃ group. As shown in (Figure 4), the position of the CB minimum and VB maximum of several MPX₃ monolayers aligned with the reduction potentials of CO₂ to different chemicals, which indicates that they are potential candidates for photocatalytic CO₂ reduction. Thermodynamically, the CB minimum of the MPX₃ semiconductor should be much more positive than the reduction potential of CO₂ to the target product. For instance, the CB minimum of AgInP₂S₆ is more positive than the redox potential of CO₂ to HCOOH, CO, CH₂O, CH₃OH, C₂H_4, and CH₄ chemicals, which means that AgInP₂S₆ could be potentially used as the photocatalyst for those reactions, whereas FePSe₃ is not suitable for photocatalytic CO₂ reduction due to its lower CB minimum position compared to the redox potential values for those reactions.

Table 1. Comparison of the Performance of MPX₃-based Photocatalysts

Photocatalyst	Morphology	Reaction conditions and light source	H₂ production rate (μmol g^-1 h^-1)	Stability (h)	Ref.
MnPS₃	Nanosheets	0.35 M Na₂S & 0.25 M Na₂SO₃ aqueous solution, AM 1.5 solar light illumination	21.2	-	( 27)
MnPS₃	Nanosheets	Pure water, AM 1.5 solar light illumination	3.1	18
MnPSe₃	Nanosheets	0.35 M Na₂S & 0.25 M Na₂SO₃ aqueous solution, AM 1.5 solar light illumination	43.5	-
MnPSe₃	Nanosheets	Pure water, AM 1.5 solar light illumination	6.5	18
NiPS₃	Nanosheets	Pure water, AM 1.5 solar light illumination	6.46	-	( 23)
		0.35 M Na₂S & 0.25 M Na₂SO₃ aqueous solution, 300 W Xe lamp illumination	74.67	-
		Pure water, 300 W Xe lamp illumination	26.42	15
FePS₃	Bulk	10 vol % TEOA aqueous solution, 300 W Xe lamp illumination	94	-	( 35)
	Bulk	Pure water, 300 W Xe lamp illumination	36.1	-
	Quantum sheets	10 vol % TEOA aqueous solution, 300 W Xe lamp illumination	290	40
	Quantum sheets	Pure water, 300 W Xe lamp illumination	89.7	-
CuInP₂S₆	Nanosheets	0.1 M Na₂S & Na₂SO₃ aqueous solution, 300 W Xe lamp illumination with 400 mW/cm²	804	30	( 44)
FePS₃	Flakes	0.1 M Na₂S & Na₂SO₃ aqueous solution Pure water, 300 W Xe lamp illumination	402.4	6	( 48)
Sn₂P₂S₆	Nanosheets	Pure water, AM 1.5 solar light illumination with 100 mW/cm²	202.06	40	( 26)
Sn₂P₂S₆	Nanosheets	0.35 M Na₂S & 0.25 M Na₂SO₃ aqueous solution, AM 1.5 solar light illumination with 100 mW/cm²	665.5	-	( 26)

Recently, Gao. W et al. ( 50) reported atomically thin AgInP₂S₆ nanosheets with sulfur vacancies as the photocatalyst to reduce CO₂ into olefiant gas, in which the ethene is the dominant product. The AgInP₂S₆ nanosheet photocatalyst exhibited the yield-based selectivity of ~73%. In order to suppress the competing HER reaction, the water vapor was used as the source to complete the CO₂ reduction reaction. In another study, Fan Y. et al. ( 51) utilized ferroelectric CuInP₂S₆ with bi- and five-layer to photocatalytically reduce CO₂ to CH₄. The staggered type-II band structure induced by the vertical intrinsic electric fields within the bilayers and the photovoltage built on the surface could drive effective CO₂ reduction, resulting in a long lifetime and redox ability of the photogenerated carriers, and effective light harvesting. High solar-to-fuel efficiency of 8.40 % ~ 32.57 % can be obtained depending on the number of CuInP₂S₆ layers ((Figure 5)).

Figure 5. Photocatalytic CO₂ reduction on bilayer CuInP₂S₆ with schematic type-II band diagram.

Apart from CO₂ reduction photocatalysis, it could be possible to realize other redox processes for organic molecule transformation over the MPX₃ materials under light illumination. In this regard, reaction mechanisms may involve a direct electron or hole transfer between the organic substrate and the photocatalyst, or an indirect carrier transfer, encompassing activation of small molecules (like H₂O, O₂, etc.) as initial steps of the overall reaction. As to the latter one, the generated hydroxyl radical, superoxide radical or hydrogen peroxide will be responsible for consecutive oxidation of organic substrates.

3.2 Electrocatalysis

Electrocatalysis involves the redox reaction in an electrochemical cell with the electrocatalyst facilitating and lowering the overpotential of the specific reactions. The active anode-loaded electrocatalyst is used for oxidation reaction, OER, pollutant oxidation, etc., while the cathode-loaded electrocatalyst is utilized for reduction reaction, HER, organic molecule reduction, etc. Considering the distributed production of different chemicals, the electrochemical strategy is a much greener alternative for replacing the conventional approach to manufacturing chemical proceeds. Notably, the electrocatalytic synthesis is conducted under mild conditions (room temperature, atmospheric pressure), which is different from the demand harsh conditions in thermochemical routes, such as high pressure, high temperature, centralized reaction tank, etc.. When performing the electrochemical reaction, the selection of catalyst depends on the reaction itself and reaction condition, including electrolyte contents, pH, and so on. In an aqueous electrolyte, the water oxidation and reduction reactions have to be noted. For oxygen or hydrogen evolution reactions, the active RuO₂ anode and Pt cathode usually are utilized. But, some non-active anodes (boron-doped diamond, semiconductors with wide bandgap) with poor OER performance will be used for electrochemical oxidation of pollutants ( 52) or chemical synthesis at high redox potential ( 53). The MPX₃-based nanoarchitectures also exhibit electrocatalytic activity toward catalyzing various electrochemical reactions, including HER, OER, CO₂RR, and nitrogen reduction reaction (NRR) ( 54). The following sections will focus on the recent progress in the electrocatalytic activities on several MPX₃-based electrodes.

3.2.1 Electrocatalytic Water Reduction and Oxidation

Electrocatalytic HER is considered an essential route for energy conversion, which could be realized through the water-splitting process. Ideally, the water-splitting process (Equation ((1))) involves two basic sets of reactions, namely HER at the cathode (Equation ((2))) and OER at the anode (Equation ((3))) under certain potentials, which are given as follows:

The past few years have witnessed the potential application of MPX₃ materials for HER electrocatalysis. Owing to their appreciable conductivity and abundant active sites at room temperature, they are acknowledged to be suitable candidates for electrochemical water-splitting. When it comes to 2D morphology, their atomic-level thickness not only enlarges the specific area to expose more active sites but also increases the intrinsic catalytic activity. In 2017, Pumera et al. ( 55) reported a comprehensive study on the HER activity of various few-layered MPSe₃ (M = Cr, Mn, Fe, Zn, Cd, Sn) and MPS₃ (M = Mn, Fe, Co, Ni, Zn, Cd, Sn) materials. It was noted that FePSe₃ showed better performance for hydrogen evolution catalysis under both acidic and alkaline media with robust stability. As for the sulfides, NiPS₃ and CoPS₃ displayed the highest activity. Along with these studies, some theoretical efforts have indicated that HER would be still challenging on the pristine MPS₃ crystals due to the extremely high adsorption free energy for hydrogen ( 34). This calls for the quest to seek various design protocols and modification techniques to precisely tune the intrinsic properties of MPX₃-based electrocatalysts. Recently, the electrical conductivity of FePS₃ nanosheets obtained from amine-assisted exfoliation of the bulk crystal was easily modulated by manipulating the reaction temperature ( 56). As a result, the FePS₃ demonstrated an enhanced HER activity. Likewise, the heterostructured NiPS₃/Ni₂P electrocatalyst ( 57) also showed an appreciable decrease in overpotential and Tafel slope in (Figure a-b6). the epitaxial interface created between Ni₂P and NiPS₃ is found to play a pivotal role in decreasing the energy barrier for the H adsorption, and thereby, enhancing its HER performance ((Figure c6)). The fact that Ni₂P and NiPS₃ possess very similar lattice parameters (a = b = 5.85 and 5.81 Å for NiPS₃ and Ni₂P, respectively) affords the possibility to grow Ni₂P epitaxially at NiPS₃ with only a small interfacial strain (-0.68 %). Interestingly, the built-in electric field generated at this epitaxial interface promotes the acceleration of electron transfer, resulting in improved HER activity ((Figure d6)).

Figure 6. Electrocatalytic HER activity on NiPS₃/Ni₂P electrode. a-b) Comparison of the linear sweep voltammetry profiles (a) and the corresponding Tafel plots (b) for the as-grown NiPS₃, Ni₂P, NiPS₃/Ni₂P electrodes. c) the Gibbs energy profile for H adsorption (ΔG_H*) obtained at the equilibrium potential (U = 0 V) for the as-grown NiPS₃/Ni₂P, Ni₂P (001), Ni₂P (110), and NiPS₃ (110). d) Charge density difference at the heterointerfaces between NiPS₃ and Ni₂P. The electron accumulation and depletion are marked with red and green, respectively. The grey, yellow, purple, and blue colors represent Ni, S, P, and H atoms, which are marked in, respectively.

It has been reported that the [P₂X₆]^4- units exposed at the edges of 2D MPX₃ could favor H adsorption and facilitate HER catalysis ( 55, 58, 59). Importantly, the P and S on the edge are postulated to be preferable sites for hydrogen adsorption and desorption ( 31, 32). Taking FePS₃ as an example, Mukherjee et al. ( 32) unveiled the excellent HER catalytic activity and stability under a wide pH range (acidic, alkaline, phosphate buffer, and 3.5 wt% aqueous NaCl solution) due to the P and S acting as the H adsorption sites. Also, both P and Se in FePSe₃ are found to promote an enhanced catalytic activity when compared with Fe-based sulfides, phosphides, and other layered selenides ( 31). In contrast to the edge, the basal plane is reported to be inert. To promote the HER activity of this plane, numerous strategies such as heteroatom doping, strain engineering, and creating vacancies could be applied. For instance, Wang et al. ( 37) attempted to engineer the basal surface of NiPS₃ by introducing nonmetal atoms (C, N, B). The study revealed that doping B and C in NiPS₃ could alter the behavior of NiPS₃ from semiconducting to a metal, which results in an enhanced HER performance. Moreover, the C, N co-doped NiPS₃ display Pt-like activity in alkaline solution.

Although a plethora of works are reported on the application of MPX₃-based materials for HER catalysis, realizing superb OER performance and stability from such electrodes is still challenging. Until now, some attempts have been made to examine the water oxidation at the MPX₃ surface. This is usually accomplished by dynamic structural change accompanied by the surface transformation of the catalyst surface, forming metal oxide or hydroxide phase as an active site. For example, Konkena et al. ( 60) investigated the OER activity of NiPS₃ nanosheets obtained via ionic surfactant-assisted exfoliation of its bulk counterpart. The nanosheet electrocatalyst displayed as low as 250 mV onset potential and robust stability for over 160 h. Combined theoretical and in situ structural studies enabled the identification of the NiPS₃@NiOOH core-shell structure. In another study, Zhu and coworkers ( 28) investigated the OER activity of FePS₃ and found that the overpotential and Tafel slope of this electrode could reach 390 mV and 58 mV dec⁻¹, respectively. By employing theoretical calculations and post-structural characterizations, the authors revealed the introduction of in-plane defects in FePS₃ layers after exfoliation and the formation of a FePS₃-FeOOH heterostructure during the OER catalysis play a significant role on enhancing its catalytic activity.

In electrocatalysis, the reconstruction of an electrode material could change its inherent electrical and catalytic properties. Therefore, identifying the active site in heterogeneous catalysis is very crucial, yet still remains an ongoing challenge. In an attempt to investigate the structural chemistry in relation to the concept of the active site, quite limited success has already been achieved in discovering the surface reconstruction phenomena utilizing MPX₃ based materials. Hence, the real catalytic active site in this family is still debating, which requires further experimental and theoretical efforts. Besides, there are still some challenges that urgently require an in-depth systematic study: i) what is the origin of the observed surface transformation of the catalyst? ii) what is the relationship between the observed activity and structural change? iii) what are the real active species under the real reaction condition? As such, a case-by-case investigation of the aforementioned issues would offer a complete understanding of the overall process.

3.2.2 Electrocatalytic CO₂ Reduction Reaction

Electrochemical transformation of CO₂ to various hydrocarbons, alcohols, and carboxylics via the CO₂ reduction reaction (CO₂RR) is one of the most effective approaches. Compared with photocatalytic CO₂ reduction, electrocatalytic process could be much more attractive in practical applications since the process can be powered by renewable electricity ( 61, 62), which becomes abundant and affordable recently. Thus, CO₂ conversion to value-added chemicals with high selectivity and faradaic efficiency through the electrochemical process attracts much more attention in this field. Electrocatalytic CO₂RR could proceed through 2-, 4-, 6-, or even 18- electron transfer to produce various chemicals. The typical half-reaction involved in CO₂ electrolysis is summarized in (Figure 4) and (Table 2) ( 63). The products could be classified into C₁, C_2, and C₃₊ according to the number of carbon atoms in the chemicals. In an aqueous electrolyte, HER via water reduction usually competes with the CO₂RR, resulting in a decrease in the current efficiency of the overall reaction.

With respect to thermodynamics, CO₂ is a very stable molecule with a strong C=O bond (750 kJ mol^-1); thus, it must overcome a large energy barrier to induce CO₂ conversion at a more negative potential than the values shown in (Table 2). In addition, CO₂ reduction is generally initiated through single-electron transfer to a CO₂ molecule to obtain *CO₂·^- radical, which occurs at a potential of -1.9 V (vs standard hydrogen electrode (SHE)), thereby leading to a larger thermodynamic barrier for CO₂ reduction into certain products ( 64). Catalytic strategies have thus been developed to bypass the formation of CO₂·^- through proton-assisted multiple-electron transfer to reduce the energy barrier during the CO₂ conversion process.

Table 2. Half Reactions of CO₂RR for Various Products Along with the Corresponding Standard Redox Potential (25 °C, 1 Atmosphere of Gases and 1 M Solutes in Aqueous Solution)

Half-reaction	E⁰/V (vs. SHE)
CO₂ + e^- → *CO₂^-	-1.90
CO₂ + 2H⁺ + 2e^- → HCOOH (aq)	-0.61
CO₂ + 2H⁺ + 2e^- → CO (g) + H₂O	-0.53
CO₂ + 6H⁺ + 6e^- → CH₃OH (aq) + H2O	-0.38
CO₂ + 8H⁺ + 8e^- → CH₄ (g) + 2H₂O	-0.24
2CO₂ + 8H⁺ + 8e^- → CH₃COOH (aq) + 2H₂O	-0.30
2CO₂ + 10H⁺ + 10e^- → CH₃CHO (aq) + 3H₂O	-0.35
2CO₂ + 12H⁺ + 12e^- → C₂H₅OH (aq) +3H₂O	-0.33
2CO₂ + 12H⁺ + 12e^- → C₂H₄ (g) + 4H₂O	-0.34
2CO₂ + 14H⁺ + 14e^- → C₂H₆ (g) + 4H₂O	-0.27
3CO₂ + 18H⁺ + 18e^- → C₃H₇OH (aq) + 5H₂O	-0.32

As a three-phase chemical reaction, the electrochemical CO₂RR mainly includes the steps of diffusion, adsorption, activation, cleavage, dimerization, and product desorption. (Figure 7) demonstrates the possible pathways from gaseous CO₂ to various products. Briefly, the CO₂ molecule in the electrolyte can be captured by the active sites of catalysts and activated into two possible intermediates HCOO* or *COOH via proton-electron (H⁺/e^-) transfer steps. With another electron transfer, HCOO* tends to be reduced to formate (HCOO^-) or formic acid (HCOOH), while *COOH acts as the dominating intermediate for CO formation or C²⁺ products. The catalyst surfaces with weakly bound *CO intermediate lead to desorption of *CO and formation of CO, while the optimized surface with the sufficiently strong binding *CO intermediate makes further reactions possible to get C₂ or C₂₊ products through the dimerization carbon-carbon coupling step.

Figure 7. (a) Overview of the primary pathways for CO₂RR towards different products. b-c) Electrocatalytic CO₂RR for different products at different potentials over Fe₂P₂S₆ nanosheets (b), and optimized adsorption of CO₂ molecular over Fe₂P₂S₆ surface (c), in which red and blue regions represent positive and negative charges, respectively.

Apart from commonly used metal catalysts, such as Cu, Ag and Pd etc., MPX₃ materials also exhibit application in electrocatalytic CO₂RR due to their relatively poor hydrogen evolution in the aqueous electrolyte. In recent work, Fe₂P₂S₆ nanosheet was used as the electrocatalyst for alcohols through the CO₂RR process ( 65). It exhibited highly selective hydrogenation of CO₂ to methanol and ethanol ((Figure b7)) with a total faradaic efficiency of 88.3% at -0.20 V (vs reversible hydrogen electrode (RHE)). The strong adsorption of CO₂ molecule at the bridge site above two Fe atoms with an end-on pattern, along with the nearby S bonded to the C atom, indicate strong binding interactions between CO₂ and Fe₂P₂S₆ nanosheet ((Figure c7)). And the catalytic activity of other MPX₃ materials in CO₂RR still deserve further exploration and study.

3.3 Battery

The layered MPX₃ crystals possess the intercalation behavior to entertain the foreign species, including molecules and ions, within their van der Waals gaps. This feature creates a suitable platform for the realization of various ion-related batteries based on M^IIPX₃ materials. Li⁺ and Na⁺ ions are shown to electrochemically intercalate into the M^IIPX₃ crystals ( 66, 67). In the intercalation process, the stabilization of the cations, such as Fe²⁺, Co^2+, and Ni²⁺, in the octahedral chalcogen site is crucial to keep promising storage properties ( 67). And some factors will influence the performance of the Li⁺ or Na⁺ secondary battery system. For instance, the difference between the Li⁺/Li potential and the accepting d level, namely |△G| free energy, in the M^IIPX₃ would affect the potential and capacity of the Li-ion battery. Generally, high formation energy for the intercalates, like Li_xNiPS₃, is related to the high potential of the host compound. Thus the nickel, whose accepting d band is e_g, based M^IIPX₃ phase was proved to be a good candidate used in Li-ion batteries ( 68).

In addition, the ideal size of the van der Waals gap presents the suitable space to accommodate the Li⁺ or Na⁺ ions without crystal expansion of the MPX₃. The unchanged cell volume is a notable advantage of the MPX₃ compounds used as a cathode due to their broader van der Waals gap viz. 3.20 Å for NiPS₃ ( 69), 3.22 Å for MnPSe₃ ( 70), and 3.5 Å for MnPS₃ ( 71) than the metal dichalcogenides (TiS₂, ZrS₂ etc.) ((Figure 8)). This family of MPX₃ materials could possess attractive Li or Na storage properties for rechargeable batteries with the ideal capacities of over 1300 mA h g^-1 through the electrochemical reaction of MPX₃+ 9Li⁺/Na⁺ + 9e^- → 3Li/Na₂X+ Li/Na₃P + M, where nine Li⁺ or Na⁺ ions per molecule of MPX₃ intercalation ( 72, 73). The formation of the lithium or sodium phosphides and chalcogenides endow these materials with improved conductivity, and thus the increased rate and cycling performance with high specific capacity could be obtained for the MPX₃-based batteries.

Figure 8. Expansion Δc/n in Li host intercalates as a function of the initial width of the van der Waals gap ( 69, 70, 71).

Q. Liang et al. ( 74) reported the Li/Na ions storage properties of typical FePS₃, NiPS₃, and CoPS₃ nanosheets synthesized through the solid-state method. Compared with specific capacity (< 800 mA h g^-1 at 0.05 A g^-1) of the bulk counterparts ( 73, 75), these nanosheets demonstrated better performance with a discharge capacity of 1100 mA h g^-1 at the current density of 0.05 A g^-1 and initial coulombic efficiency of 61.2% ((Figure a-b9)). The high crystallinity, large surface area, abundant ion diffusion pathway, and improved contact with the electrolyte or collector of the nanosheet materials account for the promoted storage properties. Later, the same group also synthesized Sn⁴⁺P₂S₆ nanosheets on graphene to fabricate a hybrid structure as the active material in an anode for a sodium ion full cell ( 76). Furthermore, the strategies, including polymer intercalation ( 74), constructing hybrid structure ( 29), or heteroatom doping ( 59) were employed to increase the Li/Na ion storage capacity and stability.

Figure 9. Electrochemical performance of NiPS₃ nanosheet electrode used for Li-ion battery. (a) Cyclic voltammetric curves for the first four cycles at 0.1 mV/s. (b) The representative galvanostatic charge-discharge profiles for the four cycles at 0.05 A/g.

3.4 Ion Exchange Membrane

The MPX₃ compounds have a specifically ionic feature along with the metal ion movement or poling, which is mutually connected by [P₂S₆]^4- bridging ligands ( 77). Thus, the MPX₃ materials could also be treated as ionic salts. The high mobility of the metal cations in the crystal structures endows them with the ion-exchange property during the intercalation process. The fairly ionic M-S bonding still exhibits enough lability to allow M cation to “jump” or “transfer” under very mild conditions ( 78). In this case, the pristine M cation sites as the vacancies could be occupied or intercalated by other suitable cations (like Li⁺, Na⁺, H^+, etc.) in the aqueous solution to maintain neutrality. There is a heterogeneous equilibrium between M ions and the solvated P₂S₆^4-. Taking CdPS₃ as an example, the fairly ionic Cd-S bond makes the Cd vacancies easily form by using KCl/K₂CO₃ solution with help of ethylene diamine tetraacetic acid (EDTA) molecules at 50 °C ( 18, 79). The K⁺ intercalation occurs simultaneously and then the ion exchange process between K⁺ and Li⁺ or H⁺ could be achieved in the LiCl or HCl solution ((Figure 10)). After those ions transfer and exchange processes, Cd_0.85PS₃Li_0.3 or Cd_0.85PS₃Li_0.15H_0.15 with different structural features were obtained to act as the proton membrane. The ordered water molecular network between the layers in this membrane could form to provide a proton transport channel and achieve high proton conductivity in the end.

Figure 10. Ion-exchange property in layered CdPS₃ material as proton exchange membrane.

4 Conclusion

CHAPTER SECTIONS

Jump To

In this chapter, a family of MPX₃ nanostructures used in the energy conversion field is discussed. As van der Waals layered materials, MPX₃ crystals possess the structural backbone of hexagonal [P₂X₆]^4- complex arrays. The metal cation stabilizing this structure can be readily varied, resulting in correlated physical behaviors. The big difference between MPX₃ and common layered transition metal dichalcogenide is the bonding form of M-X. The strong ionic bonding in MPX₃ endows them with rich functionalities, including intercalation effect, comparatively large bandgaps, magnetism, ferroelectricity, etc.. After reviewing the methods for MPX₃ nanostructure synthesis, and applications in catalysis, batteries, and ion exchange membrane, it is fair to say that the potential of the MPX₃ class has yet to be thoroughly explored. The 2D MPX₃ crystals with an ultrathin feature, defect interface, large surface area, tunable interlayer spacings, better conductivity, a robust interface are promising alternatives for energy conversion or storage. Although the photocatalytic and electrocatalytic water splitting, carbon dioxide reduction, as well as ion battery storage properties of the MPX₃ group have been reported, their industrial application in those fields has not been achieved. In the future, thus, the most scalable synthesis protocols and the stable rational design of MPX₃ nanomaterials are desirable for practical application.

Acknowledgments

CHAPTER SECTIONS

Jump To

This work was supported by the National Natural Science Foundation of China (Nos. 22179029 and 21805057). The authors also gratefully acknowledge the support of Youth Innovation Promotion Association CAS, and contribution of Mr. Ning Gao on this book chapter writing.

References

CHAPTER SECTIONS

Jump To

This chapter references 79 other publications.

1
Chittari B. L. Park Y. Lee D. Han M. MacDonald A. H. Hwang E. Jung J. Electronic and Magnetic Properties of Single-Layer MPX₃ Metal Phosphorous Trichalcogenides Phys. Rev. B 2016 94 18 184428
Google Scholar
1
Electronic and magnetic properties of single-layer MPX3 metal phosphorous trichalcogenides
Chittari, Bheema Lingam; Park, Youngju; Lee, Dongkyu; Han, Moonsup; MacDonald, Allan H.; Hwang, Euyheon; Jung, Jeil
Physical Review B (2016), 94 (18), 184428/1-184428/16CODEN: PRBHB7; ISSN:2469-9950. (American Physical Society)
We survey the electronic structure and magnetic properties of two-dimensional (2D) MPX3 (M=V,Cr,Mn,Fe,Co,Ni,Cu,Zn, and X=S,Se,Te) transition-metal chalcogenophosphates to shed light on their potential role as single-layer van der Waals materials that possess magnetic order. Our ab initio calcns. predict that most of these single-layer materials are antiferromagnetic semiconductors. The band gaps of the antiferromagnetic states decrease as the at. no. of the chalcogen atom increases (from S to Se to Te), leading in some cases to half-metallic ferromagnetic states or to nonmagnetic metallic states. We find that the competition between antiferromagnetic and ferromagnetic states can be substantially influenced by gating and by strain engineering. The sensitive interdependence we find between magnetic, structural, and electronic properties establishes the potential of this 2D materials class for applications in spintronics.
2
Susner M. A. Chyasnavichyus M. McGuire M. A. Ganesh P. Maksymovych P. Metal Thio- and Selenophosphates as Multifunctional van der Waals Layered Materials Adv. Mater. 2017 29 38 1602852
Google Scholar
There is no corresponding record for this reference.
3
Samal R. Sanyal G. Chakraborty B. Rout C. S. Two-Dimensional Transition Metal Phosphorous Trichalcogenides (MPX₃): A Review on Emerging Trends, Current State and Future Perspectives J. Mater. Chem. A 2021 9 5 2560 2591
Google Scholar
3
Two-dimensional transition metal phosphorous trichalcogenides (MPX3): a review on emerging trends, current state and future perspectives
Samal, Rutuparna; Sanyal, Gopal; Chakraborty, Brahmananda; Rout, Chandra Sekhar
Journal of Materials Chemistry A: Materials for Energy and Sustainability (2021), 9 (5), 2560-2591CODEN: JMCAET; ISSN:2050-7496. (Royal Society of Chemistry)
A review. Profound scientific attention has been devoted to the expansive family of functional 2D materials soon after the isolation of graphene and the discovery of Dirac physics. Of particular note, the re-emergence of layer architecture metal thio(seleno) phosphate materials (MPX3, X = S, Se) materials with appreciable tunability in dimension and proximity on correlated ground states opened novel potential avenues for the ultimate theor. (structural, magnetic) and realistic research. The wide spanned bandgap of 1.2-3.5 eV harnessed multifarious fundamental magnetic, electronic, ferroelec., optical, intercalation properties and their prominent implementation in a plethora of applications, such as Li-ion batteries, field-effect transistors, visible and UV photodetectors, photo-electrochem. reactions and hydrogen (H2) storage. This review examines many of the scarcely touched aspects, such as multiple Dirac cones, vibrational properties, and responses in the presence of strain of MPX3 materials. In addn., the latest advancement in the emergent applications, physiochem. properties and assorted growth methodologies considering the palpable vol. of research has been explored in detail in order to bring across a more complete discussion and outlook. We strongly believe that this review will be very handy for researchers working in various branches of science and engineering, such as physics, chem., materials science, and chem. engineering.
4
Wang F. Shifa T. A. Yu P. He P. Liu Y. Wang F. Wang Z. Zhan X. Lou X. Xia F. He J. New Frontiers on van der Waals Layered Metal Phosphorous Trichalcogenides Adv. Funct. Mater. 2018 28 37 1802151
Google Scholar
There is no corresponding record for this reference.
5
Friedel M. C. Soufre et ses composés—sur une nouvelle série de sulfophosphures, les thiohypophosphates CR l’Academie. Sci. Ser 1894 3 119 260
Google Scholar
There is no corresponding record for this reference.
6
Ouvrard G. Brec R. Rouxel J. Structural determination of some MPS₃ layered phases (M = Mn, Fe, Co, Ni and Cd) Mater. Res. Bull. 1985 20 1181 1189
Google Scholar
6
Structural determination of some MPS3 layered phases (M = Mn, Fe, Co, Ni and Cd)
Ouvrard, G.; Brec, R.; Rouxel, J.
Materials Research Bulletin (1985), 20 (10), 1181-9CODEN: MRBUAC; ISSN:0025-5408.
The structures of most of the MPS3 phases (M = Mn, Fe, Co, Ni, Cd) were detd. from single-crystal anal. They show the expected CdCl2 structural type, some weak disorder on the cationic sites being detected on NiPS3 and CoPS3. Fair stoichiometry is inferred for the phases since no interslab cation could be seen in the Van der Waals' gap of the structures. Polytypism may occur in NiPS3. At. parameters are given.
7
Hwangbo K. Zhang Q. Jiang Q. Wang Y. Fonseca J. Wang C. Diederich G. M. Gamelin D. R. Xiao D. Chu J. H. Yao W. Xu X. Highly Anisotropic Excitons and Multiple Phonon Bound States in a van der Waals Antiferromagnetic Insulator Nat. Nanotechnol. 2021 16 6 655 660
Google Scholar
7
Highly anisotropic excitons and multiple phonon bound states in a van der Waals antiferromagnetic insulator
Hwangbo, Kyle; Zhang, Qi; Jiang, Qianni; Wang, Yong; Fonseca, Jordan; Wang, Chong; Diederich, Geoffrey M.; Gamelin, Daniel R.; Xiao, Di; Chu, Jiun-Haw; Yao, Wang; Xu, Xiaodong
Nature Nanotechnology (2021), 16 (6), 655-660CODEN: NNAABX; ISSN:1748-3387. (Nature Portfolio)
Two-dimensional (2D) semiconductors enable the investigation of light-matter interactions in low dimensions1,2. Yet, the study of elementary photoexcitations in 2D semiconductors with intrinsic magnetic order remains a challenge due to the lack of suitable materials3,4. Here, we report the observation of excitons coupled to zigzag antiferromagnetic order in the layered antiferromagnetic insulator NiPS3. The exciton exhibits a narrow photoluminescence linewidth of roughly 350μeV with near-unity linear polarization. When we reduce the sample thickness from five to two layers, the photoluminescence is suppressed and eventually vanishes for the monolayer. This suppression is consistent with the calcd. bandgap of NiPS3, which is highly indirect for both the bilayer and the monolayer5. Furthermore, we observe strong linear dichroism (LD) over a broad spectral range. The optical anisotropy axes of LD and of photoluminescence are locked to the zigzag direction. Furthermore, their temp. dependence is reminiscent of the in-plane magnetic susceptibility anisotropy. Hence, our results indicate that LD and photoluminescence could probe the symmetry breaking magnetic order parameter of 2D magnetic materials. In addn., we observe over ten exciton-A1g-phonon bound states on the high-energy side of the exciton resonance, which we interpret as signs of a strong modulation of the ligand-to-metal charge-transfer energy by electron-lattice interactions. Our work establishes NiPS3 as a 2D platform for exploring magneto-exciton physics with strong correlations.
8
Kang S. Kim K. Kim B. H. Kim J. Sim K. I. Lee J. U. Lee S. Park K. Yun S. Kim T. Nag A. Walters A. Garcia-Fernandez M. Li J. Chapon L. Zhou K. J. Son Y. W. Kim J. H. Cheong H. Park J. G. Coherent Many-Body Exciton in van der Waals Antiferromagnet NiPS₃ Nature 2020 583 7818 785 789
Google Scholar
8
Coherent many-body exciton in van der Waals antiferromagnet NiPS3
Kang, Soonmin; Kim, Kangwon; Kim, Beom Hyun; Kim, Jonghyeon; Sim, Kyung Ik; Lee, Jae-Ung; Lee, Sungmin; Park, Kisoo; Yun, Seokhwan; Kim, Taehun; Nag, Abhishek; Walters, Andrew; Garcia-Fernandez, Mirian; Li, Jiemin; Chapon, Laurent; Zhou, Ke-Jin; Son, Young-Woo; Kim, Jae Hoon; Cheong, Hyeonsik; Park, Je-Geun
Nature (London, United Kingdom) (2020), 583 (7818), 785-789CODEN: NATUAS; ISSN:0028-0836. (Nature Research)
Abstr.: An exciton is the bosonic quasiparticle of electron-hole pairs bound by the Coulomb interaction. Bose-Einstein condensation of this exciton state has long been the subject of speculation in various model systems2,3, and examples have been found more recently in optical lattices and two-dimensional materials4-9. Unlike these conventional excitons formed from extended Bloch states4-9, excitonic bound states from intrinsically many-body localized states are rare. Here we show that a spin-orbit-entangled exciton state appears below the Neel temp. of 150 K in NiPS3, an antiferromagnetic van der Waals material. It arises intrinsically from the archetypal many-body states of the Zhang-Rice singlet10,11, and reaches a coherent state assisted by the antiferromagnetic order. Using configuration-interaction theory, we det. the origin of the coherent excitonic excitation to be a transition from a Zhang-Rice triplet to a Zhang-Rice singlet. We combine three spectroscopic tools-resonant inelastic X-ray scattering, photoluminescence and optical absorption-to characterize the exciton and to demonstrate an extremely narrow excitonic linewidth below 50 K. The discovery of the spin-orbit-entangled exciton in antiferromagnetic NiPS3 introduces van der Waals magnets as a platform to study coherent many-body excitons.
9
Joy P. A. Vasudevan S. Magnetism in the Layered Transition-Metal Thiophosphates MPS₃ (M=Mn, Fe, and Ni) Phys. Rev. B 1992 46 9 5425 5433
Google Scholar
9
Magnetism in the layered transition-metal thiophosphates MPS3 (M = manganese, iron, and nickel)
Joy, P. A.; Vasudevan, S.
Physical Review B: Condensed Matter and Materials Physics (1992), 46 (9), 5425-33CODEN: PRBMDO; ISSN:0163-1829.
Anisotropic magnetic susceptibilities of single crystals of the layered transition-metal thiophosphates MnPS3, FePS3, and NiPS3 have been measured as a function of temp. The materials order antiferromagnetically at low temps., the Neel temps. being 78, 123, and 155 K, resp. In the ordered state, the magnetization axis lies perpendicular to the layers of MnPS3 and FePS3, while for NiPS3 it lies in the layer. In the paramagnetic regime, the anisotropies of these compds. are different; while the susceptibility for MnPS3 is isotropic and that for NiPS3 shows only a weak anisotropy, FePS3 exhibits highly anisotropic susceptibility. The anisotropic susceptibilities have been analyzed to obtain information on the state of the magnetic ions and the nature of magnetic interactions between them. The results show that MnPS3, FePS3, and NiPS3 form a unique class of compds. Although all three compds. are isostructural with the magnetic lattice being the two-dimensional honeycomb, the spin dimensionalities for the three are different. While MnPS3 is best described by the isotropic Heisenberg Hamiltonian, FePS3 is most effectively treated by the Ising model and NiPS3 by the anisotropic Heisenberg Hamiltonian. The origin of the anisotropy in these compds. has been discussed, and it is shown how it arises from a combination of spin-orbit coupling and the trigonal distortion of the MS6 octahedra. The magnetic exchange const., J and the zero-field splitting energies of the ground state of the transition-metal ion have been evaluated from the anisotropic paramagnetic susceptibilities.
10
Wildes A. R. Simonet V. Ressouche E. McIntyre G. J. Avdeev M. Suard E. Kimber S. A. J. Lançon D. Pepe G. Moubaraki B. Hicks T. J. Magnetic Structure of the Quasi-Two-Dimensional Antiferromagnet NiPS₃ Phys. Rev. B 2015 92 22 224408
Google Scholar
10
Magnetic structure of the quasi-two-dimensional antiferromagnet NiPS3
Wildes, A. R.; Simonet, V.; Ressouche, E.; McIntyre, G. J.; Avdeev, M.; Suard, E.; Kimber, S. A. J.; Lancon, D.; Pepe, G.; Moubaraki, B.; Hicks, T. J.
Physical Review B: Condensed Matter and Materials Physics (2015), 92 (22), 224408/1-224408/11CODEN: PRBMDO; ISSN:1098-0121. (American Physical Society)
The magnetic structure of the quasi-two-dimensional antiferromagnet NiPS3 has been detd. by magnetometry and a variety of neutron diffraction techniques. The expts. show that the samples must be carefully handled, as gluing influences the magnetometry measurements while preferred orientation complicates the interpretation of powder diffraction measurements. Our global set of consistent measurements show numerous departures from previously published results. We show that the compd. adopts a k = [010] antiferromagnetic structure with the moment directions mostly along the a axis, and that the paramagnetic susceptibility is isotropic. The crit. behavior was also investigated through the temp. dependence of the magnetic Bragg peaks below the N´eel temp.
11
Wang F. Mathur N. Janes A. N. Sheng H. He P. Zheng X. Yu P. DeRuiter A. J. Schmidt J. R. He J. Jin S. Defect-Mediated Ferromagnetism in Correlated Two-Dimensional Transition Metal Phosphorus Trisulfides Sci. Adv. 2021 7 43 eabj4086
Google Scholar
There is no corresponding record for this reference.
12
Wang X. Cao J. Lu Z. Cohen A. Kitadai H. Li T. Tan Q. Wilson M. Lui C. H. Smirnov D. Sharifzadeh S. Ling X. Spin-Induced Linear Polarization of Photoluminescence in Antiferromagnetic van der Waals Crystals Nat. Mater. 2021 20 7 964 970
Google Scholar
12
Spin-induced linear polarization of photoluminescence in antiferromagnetic van der Waals crystals
Wang, Xingzhi; Cao, Jun; Lu, Zhengguang; Cohen, Arielle; Kitadai, Hikari; Li, Tianshu; Tan, Qishuo; Wilson, Matthew; Lui, Chun Hung; Smirnov, Dmitry; Sharifzadeh, Sahar; Ling, Xi
Nature Materials (2021), 20 (7), 964-970CODEN: NMAACR; ISSN:1476-1122. (Nature Portfolio)
Antiferromagnets are promising components for spintronics due to their terahertz resonance, multilevel states and absence of stray fields. However, the zero net magnetic moment of antiferromagnets makes the detection of the antiferromagnetic order and the investigation of fundamental spin properties notoriously difficult. Here, we report an optical detection of Neel vector orientation through an ultra-sharp photoluminescence in the van der Waals antiferromagnet NiPS3 from bulk to atomically thin flakes. The strong correlation between spin flipping and elec. dipole oscillator results in a linear polarization of the sharp emission, which aligns perpendicular to the spin orientation in the crystal. By applying an in-plane magnetic field, we achieve manipulation of the photoluminescence polarization. This correlation between emitted photons and spins in layered magnets provides routes for investigating magneto-optics in two-dimensional materials, and hence opens a path for developing opto-spintronic devices and antiferromagnet-based quantum information technologies.
13
Kim K. Lim S. Y. Lee J. U. Lee S. Kim T. Y. Park K. Jeon G. S. Park C. H. Park J. G. Cheong H. Suppression of Magnetic Ordering in XXZ-Type Antiferromagnetic Monolayer NiPS₃ Nat. Commun. 2019 10 1 345
Google Scholar
13
Suppression of magnetic ordering in XXZ-type antiferromagnetic monolayer NiPS3
Kim Kangwon; Lim Soo Yeon; Lee Jae-Ung; Cheong Hyeonsik; Lee Sungmin; Park Kisoo; Park Je-Geun; Lee Sungmin; Kim Tae Yun; Park Kisoo; Park Cheol-Hwan; Park Je-Geun; Kim Tae Yun; Park Cheol-Hwan; Jeon Gun Sang
Nature communications (2019), 10 (1), 345 ISSN:.
How a certain ground state of complex physical systems emerges, especially in two-dimensional materials, is a fundamental question in condensed-matter physics. A particularly interesting case is systems belonging to the class of XY Hamiltonian where the magnetic order parameter of conventional nature is unstable in two-dimensional materials leading to a Berezinskii-Kosterlitz-Thouless transition. Here, we report how the XXZ-type antiferromagnetic order of a magnetic van der Waals material, NiPS3, behaves upon reducing the thickness and ultimately becomes unstable in the monolayer limit. Our experimental data are consistent with the findings based on renormalization-group theory that at low temperatures a two-dimensional XXZ system behaves like a two-dimensional XY one, which cannot have a long-range order at finite temperatures. This work provides the experimental examination of the XY magnetism in the atomically thin limit and opens opportunities of exploiting these fundamental theorems of magnetism using magnetic van der Waals materials.
14
Belianinov A. He Q. Dziaugys A. Maksymovych P. Eliseev E. Borisevich A. Morozovska A. Banys J. Vysochanskii Y. Kalinin S. V. CuInP₂S₆ Room Temperature Layered Ferroelectric Nano Lett. 2015 15 6 3808 3814
Google Scholar
14
CuInP2S6 Room Temperature Layered Ferroelectric
Belianinov, A.; He, Q.; Dziaugys, A.; Maksymovych, P.; Eliseev, E.; Borisevich, A.; Morozovska, A.; Banys, J.; Vysochanskii, Y.; Kalinin, S. V.
Nano Letters (2015), 15 (6), 3808-3814CODEN: NALEFD; ISSN:1530-6984. (American Chemical Society)
The authors explore ferroelec. properties of cleaved 2-dimensional flakes of copper indium thiophosphate, CuInP2S6 (CITP), and probe size effects along with limits of ferroelec. phase stability, by ambient and ultra high vacuum scanning probe microscopy. CITP belongs to the only material family known to display ferroelec. polarization in a van der Waals, layered crystal at room temp. and above. The authors' measurements directly reveal stable, ferroelec. polarization as evidenced by domain structures, switchable polarization, and hysteresis loops. At room temp. the domain structure of flakes thicker than 100 nm is similar to the cleaved bulk surfaces, whereas <50 nm polarization disappears. The authors ascribe this behavior to a known instability of polarization due to depolarization field. Also, polarization switching at high bias is also assocd. with ionic mobility, as evidenced both by macroscopic measurements and by formation of surface damage under the tip at a bias of 4 V-likely due to copper redn. Mobile Cu ions may therefore also contribute to internal screening mechanisms. The existence of stable polarization in a van-der-Waals crystal naturally points toward new strategies for ultimate scaling of polar materials, quasi-2D, and single-layer materials with advanced and nonlinear dielec. properties that are presently not found in any members of the growing graphene family.
15
Dziaugys A. Banys J. Macutkevic J. Sobiestianskas R. Vysochanskii Y. Dipolar Glass Phase in Ferrielectrics: CuInP₂S₆ and Ag_0.1Cu_0.9InP₂S₆ Crystals Phys. Status Solidi A 2010 207 8 1960 1967
Google Scholar
15
Dipolar glass phase in ferrielectrics: CuInP2S6 and Ag0.1Cu0.9InP2S6 crystals
Dziaugys, Andrius; Banys, Juras; Macutkevic, Jan; Sobiestianskas, Ricardas; Vysochanskii, Yulian
Physica Status Solidi A: Applications and Materials Science (2010), 207 (8), 1960-1967CODEN: PSSABA; ISSN:1862-6300. (Wiley-VCH Verlag GmbH & Co. KGaA)
The dielec. properties of CuInP2S6 and Ag0.1Cu0.9InP2S6 crystals were investigated in wide frequency (20 Hz-3 GHz) and temp. ranges (25-360 K). The low frequencies dielec. spectra at high temps. are highly influenced by the high ionic cond. The temp. dependences of the static dielec. permittivity and the mean relaxation time reveal the first order order-disorder ferrielec. phase transition at Tc = 288 K in Ag0.1Cu0.9InP2S6. The cond. and its activation energy exhibit only a weak change close to the ferrielec. phase transition temp. in both investigated crystals. The freezing phenomena in CuInP2S6 and Ag0.1Cu0.9InP2S6 revealed the complex dielec. permittivity behavior characteristic for transition into dipolar glass state.
16
Silipigni L. Schiro L. Scolaro L. M. De Luca G. Salvato G. Lithium Ions Conduction in Li_2xMn_1-xPS₃ Films Philos. Mag. 2014 94 35 4026 4036
Google Scholar
16
Lithium ions conduction in Li2xMn1-xPS3 films
Silipigni, L.; Schiro, L.; Monsu Scolaro, L.; De Luca, G.; Salvato, G.
Philosophical Magazine (2014), 94 (35), 4026-4036CODEN: PMHABF; ISSN:1478-6435. (Taylor & Francis Ltd.)
Li2xMn1-xPS3 films have been synthesized by exfoliating MnPS3 through the successive intercalations of K+ and Li+ ions. Their dielec. response has been measured from 80 to 350 K in the frequency range of (102-106) Hz. The obtained data have been analyzed in terms of both complex permittivity ε* and the ac cond. σac. The frequency dependence of σac has been interpreted in terms of the Jonscher's law, whose exponent n decreases by increasing temp. The n values lie between 0.479 and 0.501 and are typical of materials in which the ac cond. is due to multiple hops of carriers. By analyzing the σdc temp. dependence, the obsd. dielec. response has been attributed to the intercalated lithium ions, and the Li2xMn1-xPS3 films have been classified as hopping charge carrier systems.
17
Kuzminskii Y. V. Voronin B. M. Redin N. N. Iron and Nickel Phosphorus Trisulfides as Electroactive Materials for Primary Lithium Batteries J. Power Sources 1995 55 2 133 141
Google Scholar
17
Iron and nickel phosphorus trisulfides as electroactive materials for primary lithium batteries
Kuzminskii, Y. V.; Voronin, B. M.; Redin, N. N.
Journal of Power Sources (1995), 55 (2), 133-41CODEN: JPSODZ; ISSN:0378-7753. (Elsevier)
The theor. specific capacities of a family of layered compds. MPX3 (M = Fe, Co, Ni; X = S, Se) for current-producing reactions involving 1.5, 2, 6 and 9 lithium atoms per MPX3 mol. have been estd. These data show that FePS3 and NiPS3 are good electroactive materials for primary lithium cells. Conditions which allow one to shorten substantially the synthesis time of iron and nickel phosphorus trisulfides in ampules are presented. According to cond. measurements in the 293-673 K temp. range, NiPS3 is an intrinsic and FePS3 an extrinsic semiconductor. The discharge characteristics of Li/MPS3 (M = Fe, Ni) cells with an org. electrolyte have been studied; they confirmed that the participation of nine electrons in the redox process is possible. For a primary button cell of the std. size 2325, with a FePS3 cathode, the specific capacity and specific energy values obtained in a discharge 1.8-1.2 V range at load resistances of 3.0 to 30 kΩ were 500-1160 Ah/kg and 700-1770 Wh/kg (on a pure FePS3 basis), resp.
18
Qian X. Chen L. Yin L. Liu Z. Pei S. Li F. Hou G. Chen S. Song L. Thebo K. H. Cheng H. M. Ren W. CdPS₃ Nanosheets-Based Membrane with High Proton Conductivity Enabled by Cd Vacancies Science 2020 370 6516 596 600
Google Scholar
18
CdPS3 nanosheets-based membrane with high proton conductivity enabled by Cd vacancies
Qian, Xitang; Chen, Long; Yin, Lichang; Liu, Zhibo; Pei, Songfeng; Li, Fan; Hou, Guangjin; Chen, Shuangming; Song, Li; Thebo, Khalid Hussain; Cheng, Hui-Ming; Ren, Wencai
Science (Washington, DC, United States) (2020), 370 (6516), 596-600CODEN: SCIEAS; ISSN:1095-9203. (American Association for the Advancement of Science)
P transport in nanochannels under humid conditions is crucial for the application in energy storage and conversion. However, existing materials, including Nafion, suffer from limited cond. of up to 0.2 S per cm. The authors report a class of membranes assembled with 2-dimensional transition-metal P trichalcogenide nanosheets, in which the transition-metal vacancies enable exceptionally high ion cond. A Cd0.85PS3Li0.15H0.15 membrane exhibits a p conduction dominant cond. of ∼0.95 S per cm at 90°elsius and 98% relative humidity. This performance mainly originates from the abundant p donor centers, easy p desorption, and excellent hydration of the membranes induced by Cd vacancies. The authors also obsd. superhigh Li ion cond. in Cd0.85PS3Li0.3 and Mn0.77PS3Li0.46 membranes.
19
Du K. Z. Wang X. Z. Liu Y. Hu P. Utama M. I. Gan C. K. Xiong Q. Kloc C. Weak Van der Waals Stacking, Wide-Range Band Gap, and Raman Study on Ultrathin Layers of Metal Phosphorus Trichalcogenides ACS Nano 2016 10 2 1738 1743
Google Scholar
19
Weak Van der Waals Stacking, Wide-Range Band Gap, and Raman Study on Ultrathin Layers of Metal Phosphorus Trichalcogenides
Du, Ke-zhao; Wang, Xing-zhi; Liu, Yang; Hu, Peng; Utama, M. Iqbal Bakti; Gan, Chee Kwan; Xiong, Qihua; Kloc, Christian
ACS Nano (2016), 10 (2), 1738-1743CODEN: ANCAC3; ISSN:1936-0851. (American Chemical Society)
2D semiconducting metal phosphorus trichalcogenides, particularly the bulk crystals of MPS3 (M = Fe, Mn, Ni, Cd and Zn) sulfides and MPSe3 (M = Fe and Mn) selenides, have been synthesized, crystd. and exfoliated into monolayers. The Raman spectra of monolayer FePS3 and 3-layer FePSe3 show the strong intralayer vibrations and structural stability of the atomically thin layers under ambient condition. The band gaps can be adjusted by element choices in the range of 1.3-3.5 eV. The wide-range band gaps suggest their optoelectronic applications in a broad wavelength range. The calcd. cleavage energies of MPS3 are smaller than that of graphite. Therefore, the monolayers used for building of heterostructures by van der Waals stacking could be considered as the candidates for artificial 2D materials with unusual ferroelec. and magnetic properties.
20
Nitsche R. Wild P. Crystal Growth of Metal-Phosphorus-Sulfur Compounds by Vapor Transport Mater. Res. Bull. 1970 5 6 419 423
Google Scholar
20
Crystal growth of metal-phosphorus-sulfur compounds by vapor transport
Nitsche, Rudolf; Wild, Petr
Materials Research Bulletin (1970), 5 (6), 419-23CODEN: MRBUAC; ISSN:0025-5408.
Single crystals of the thiophosphates: Cu3PS4, InPS4, GaPS4, BiPS4 and the thiohypophosphates Sn2P2S6, Cd2P2S6, Fe2P2S6, and Mn2P2S6 were grown in sizes up to 10 mm by vapor transport with I. Lattice parameters and space groups are given.
21
Gusmao R. Sofer Z. Pumera M. Metal Phosphorous Trichalcogenides (MPCh₃ ): From Synthesis to Contemporary Energy Challenges Angew. Chem. Int. Ed. Engl. 2019 58 28 9326 9337
Google Scholar
21
Metal Phosphorous Trichalcogenides (MPCh3 ): From Synthesis to Contemporary Energy Challenges
Gusmao Rui; Sofer Zdenek; Pumera Martin
Angewandte Chemie (International ed. in English) (2019), 58 (28), 9326-9337 ISSN:.
Owing to their unique physical and chemical properties, layered two-dimensional (2D) materials have been established as the most significant topic in materials science for the current decade. This includes layers comprising mono-element (graphene, phosphorene), di-element (metal dichalcogenides), and even multi-element. A distinctive class of 2D layered materials is the metal phosphorous trichalcogenides (MPCh3 , Ch=S, Se), first synthesized in the late 1800s. Having an unusual intercalation behavior, MPCh3 were intensively studied in the 1970s for their magnetic properties and as secondary electrodes in lithium batteries, but fell from scrutiny until very recently, being 2D nanomaterials. Based on their synthesis and most significant properties, the present surge of reports related to water-splitting catalysis and energy storage are discussed in detail. This Minireview is intended as a baseline for the anticipated new wave of researchers who aim to explore these 2D layered materials for their electrochemical energy applications.
22
Gave M. A. Bilc D. Mahanti S. D. Breshears J. D. Kanatzidis M. G. On the Lamellar Compounds CuBiP₂Se₆, AgBiP₂Se₆ and AgBiP₂S₆. Antiferroelectric Phase Transitions due to Cooperative Cu⁺ and Bi³⁺ Ion Motion Inorg. Chem. 2005 44 15 5293 5303
Google Scholar
22
On the Lamellar Compounds CuBiP2Se6, AgBiP2Se6 and AgBiP2S6. Antiferroelectric Phase Transitions Due to Cooperative Cu+ and Bi3+ Ion Motion
Gave, Matthew A.; Bilc, Daniel; Mahanti, S. D.; Breshears, Jean D.; Kanatzidis, Mercouri G.
Inorganic Chemistry (2005), 44 (15), 5293-5303CODEN: INOCAJ; ISSN:0020-1669. (American Chemical Society)
CuBiP2Se6, AgBiP2Se6, and AgBiP2S6 were prepd. from the corresponding elements. CuBiP2Se6 and AgBiP2Se6 crystallize in the space group R‾3 with a 6.5532(16) and c 39.762(13) Å for CuBiP2Se6 and a 6.6524(13) and c 39.615(15) Å for AgBiP2Se6. AgBiP2S6 crystallizes in the triclinic space group P‾1 with a 6.3833(13), b 7.1439(14), c 9.5366(19) Å, α 91.89(3), β 91.45(3), γ 94.05(3)°. CuBiP2Se6 was found to exhibit a temp.-dependent antiferroelec. ordering of the Cu+ and Bi3+ ions in the lattice. An intermediate and a fully ordered structure were refined at 173 and 97 K, resp. Electronic band and total energy calcns. at the DFT level clearly suggest that the antiferroelec. model is energetically favored over the paraelec. and hypothetical ferrielec. models. This phase transition can be classified as a 2nd-order Jahn-Teller distortion. The antiferroelec. state of CuBiP2Se6 is an indirect gap semiconductor. The compds. were characterized with DTA and solid-state UV/visible diffuse reflectance spectroscopy. Generalized implications regarding the expected ferroelec. behavior of compds. in the CuMP2Se6 system (M = trivalent metal) are discussed.
23
Wang F. Shifa T. A. He P. Cheng Z. Chu J. Liu Y. Wang Z. Wang F. Wen Y. Liang L. He J. Two-Dimensional Metal Phosphorus Trisulfide Nanosheet with Solar Hydrogen-Evolving Activity Nano Energy 2017 40 673 680
Google Scholar
23
Two-dimensional metal phosphorus trisulfide nanosheet with solar hydrogen-evolving activity
Wang, Fengmei; Shifa, Tofik Ahmed; He, Peng; Cheng, Zhongzhou; Chu, Junwei; Liu, Yang; Wang, Zhenxing; Wang, Feng; Wen, Yao; Liang, Lirong; He, Jun
Nano Energy (2017), 40 (), 673-680CODEN: NEANCA; ISSN:2211-2855. (Elsevier Ltd.)
The development and utilization of photocatalysts to realize water-splitting without any external bias or sacrificial agents has received the limelight. As a novel two-dimensional layered material, metal phosphorus trichalcogenides (MPTs) cause wide research interest, presently. However, the growth of ultrathin two-dimensional MPT crystals is a great challenge to hinder their application. Here, we initially grow few-at. layered nickel phosphorus trisulfide (NiPS3) as promising photocatalyst for hydrogen evolution. The as-prepd. NiPS3 hexagonal nanosheet, as thin as few at. layers (≤ 3.5 nm), has lateral size of larger than 15 μm. These ultrathin NiPS3 crystals can directly generate hydrogen gas from pure water without any sacrificial agents under sunlight. With UV photoelectron spectrometer and electrochem. impedance spectroscopy, we show that the attractive photocatalytic activity of the ultrathin NiPS3 crystals arise from their appropriate positions of the band edges. This discovery is expected to make a contribution to develop next generation solar-fuel conversion catalysts for H2 prodn.
24
Yu P. Meng J. Wang F. Sendeku M. G. Wu B. Sui X. Gao N. Zhan X. Lou X. Wang Z. He J. Carbonate-Ion-Mediated Photogenerated Hole Transfer to Boost Hydrogen Production J. Phys. Chem. C 2022 126 25 10367 10377
Google Scholar
24
Carbonate-Ion-Mediated Photogenerated Hole Transfer to Boost Hydrogen Production
Yu, Peng; Meng, Jun; Wang, Fengmei; Sendeku, Marshet Getaye; Wu, Binglan; Sui, Xinyu; Gao, Ning; Zhan, Xueying; Lou, Xiaoding; Wang, Zhenxing; He, Jun
Journal of Physical Chemistry C (2022), 126 (25), 10367-10377CODEN: JPCCCK; ISSN:1932-7447. (American Chemical Society)
Sustainable and scalable H2 evolution through water photocatalysis is an attractive path for carbon-neutral energy supply; however, it is severely limited by sluggish charge sepn. and photocorrosion of semiconductor photocatalysts. Here, we demonstrate that earth-abundant carbonate ions, widely existing in daily-life water, serve as a hole mediator to redirect the photogenerated hole transfer pathway and then promote the hole-transfer kinetics. The accelerated hole transfer could efficiently reduce the recombination of electron-hole pairs for continuous H2 prodn. with improved photostability of catalysts, including layered indium phosphorus sulfide (In4/3P2S6) and cadmium sulfide. A sustainable H2 evolution rate of 5.1 mmol g-1 h-1 within 60 h or more operation is achieved in the presence of CO32- anions. In situ ESR (ESR) spectroscopy studies and transient absorption (TA) measurements reveal that the CO32-/CO3- redox couple could rapidly shuttle the photogenerated holes from OH radicals anchored on the catalyst surface, effectively eliminating the recombination of electron-hole pairs and catalyst oxidn. for boosted H2 generation. The carbonate-ion-mediated hole-transfer strategy provides a new paradigm for designing a cost-effective and advanced photosynthetic system in practical applications.
25
Zhou J. Zhu C. Zhou Y. Dong J. Li P. Zhang Z. Wang Z. Lin Y. C. Shi J. Zhang R. Zheng Y. Yu H. Tang B. Liu F. Wang L. Liu L. Liu G. B. Hu W. Gao Y. Yang H. Gao W. Lu L. Wang Y. Suenaga K. Liu G. Ding F. Yao Y. Liu Z. Composition and Phase Engineering of Metal Chalcogenides and Phosphorous Chalcogenides Nat. Mater. 2022
Google Scholar
There is no corresponding record for this reference.
https://doi.org/10.1038/s41563-022-01291-5.
Google Scholar
There is no corresponding record for this reference.
26
Sendeku M. G. Wang F. Cheng Z. Yu P. Gao N. Zhan X. Wang Z. He J. Nonlayered Tin Thiohypodiphosphate Nanosheets: Controllable Growth and Solar-Light-Driven Water Splitting ACS Appl. Mater. Interfaces 2021 13 11 13392 13399
Google Scholar
26
Nonlayered Tin Thiohypodiphosphate Nanosheets: Controllable Growth and Solar-Light-Driven Water Splitting
Sendeku, Marshet G.; Wang, Fengmei; Cheng, Zhongzhou; Yu, Peng; Gao, Ning; Zhan, Xueying; Wang, Zhenxing; He, Jun
ACS Applied Materials & Interfaces (2021), 13 (11), 13392-13399CODEN: AAMICK; ISSN:1944-8244. (American Chemical Society)
As a promising candidate in various fields, including energy conversion and electronics, layered van der Waals metal phosphorus trichalcogenides (MPX3) have been widely explored. In addn. to the layered structures, MPX3 comprising post-transition metals (i.e., Sn and Pb) are known to form a unique 3D framework with nonlayered structure. However, the nonlayered two-dimensional (2D) crystals of this family have remained unexplored until now. Herein, we successfully synthesized 2D nonlayered tin thiohypodiphosphate (Sn2P2S6) nanosheets, having an indirect bandgap of 2.25 eV and a thickness down to ~ 10 nm. The as-obtained nanosheets demonstrate promising photocatalytic water splitting activity to generate H2 in pure water under simulated solar light (AM 1.5G). Moreover, the ultrathin Sn2P2S6 catalyst shows auspicious performance and stability with a continuous operation of 40 h. This work is not only an expansion of the MPX3 family, but it is also a major milestone in the search for new materials for future energy conversion.
27
Shifa T. A. Wang F. Cheng Z. He P. Liu Y. Jiang C. Wang Z. He J. High Crystal Quality 2D Manganese Phosphorus Trichalcogenide Nanosheets and Their Photocatalytic Activity Adv. Funct. Mater. 2018 28 18 1800548
Google Scholar
There is no corresponding record for this reference.
28
Zhu W. Gan W. Muhammad Z. Wang C. Wu C. Liu H. Liu D. Zhang K. He Q. Jiang H. Zheng X. Sun Z. Chen S. Song L. Exfoliation of Ultrathin FePS₃ Layers as a Promising Electrocatalyst for the Oxygen Evolution Reaction Chem. Commun. 2018 54 35 4481 4484
Google Scholar
28
Exfoliation of ultrathin FePS3 layers as a promising electrocatalyst for the oxygen evolution reaction
Zhu, Wen; Gan, Wei; Muhammad, Zahir; Wang, Changda; Wu, Chuanqiang; Liu, Hengjie; Liu, Daobin; Zhang, Ke; He, Qun; Jiang, Hongliang; Zheng, Xusheng; Sun, Zhe; Chen, Shuangming; Song, Li
Chemical Communications (Cambridge, United Kingdom) (2018), 54 (35), 4481-4484CODEN: CHCOFS; ISSN:1359-7345. (Royal Society of Chemistry)
Few-layer ternary FePS3 nanosheets, prepd. via chem. vapor transport synthesis and ball-milling exfoliation, exhibit excellent electrocatalytic performance for the oxygen evolution reaction in an alk. medium. Combined with first principles calcns., our X-ray spectroscopy and HRTEM results clearly reveal that the introduction of in-plane defects in FePS3 layers after exfoliation and formation of a FePS3-FeOOH heterostructure during the OER process largely contribute to the catalytic activity enhancement.
29
Sang Y. Wang L. Cao X. Ding G. Ding Y. Hao Y. Xu N. Yu H. Li L. Peng S. Emerging 2D-Layered MnPS₃/rGO Composite as a Superior Anode for Sodium-Ion Batteries J. Alloys Compd. 2020 831 154775
Google Scholar
29
Emerging 2D-Layered MnPS3/rGO composite as a superior anode for sodium-ion batteries
Sang, Yan; Wang, Lvxuan; Cao, Xi; Ding, Gaofei; Ding, Yonghao; Hao, Yanan; Xu, Na; Yu, Hanzhi; Li, Linlin; Peng, Shengjie
Journal of Alloys and Compounds (2020), 831 (), 154775CODEN: JALCEU; ISSN:0925-8388. (Elsevier B.V.)
Two-dimensional (2D) layered materials were widely studied due to their unique Na storage properties and rapid ion transport rates. Herein, the authors synthesized a 2-dimensional layered transition metal P sulfide MnPS3 by one step high-temp. solid-phase synthesis. After combining with graphene by high-energy ball milling followed by high-temp. Ar calcination, the novel 2D/2D heterojunction of extra-thin MnPS3/rGO was successfully prepd. The resultant MnPS3/rGO hybrid can strengthen the cond. of the material and ameliorate the vol. change during the insertion/extn. process of the Na-ion storage, compared to the pristine MnPS3. As a result, the 2D/2D heterojunction of ultra-thin MnPS3/rGO composite exhibits high cycling performance (290 mA-h g-1 after 150 cycles at 0.2 A g-1), capacity retention rates up to 92%. The superior performance is ascribed to the combination of extra-thin MnPS3 nanosheets with graphene, which effectively enhances the interface contact area and the electronic transmission rate, greatly improving the adaptability of vol. change and interfacial charge transfer abilities. This work provides a novel and promising MnPS3/rGO anode for Na-ion batteries.
30
Liu J. Li X. B. Wang D. Lau W.-M. Peng P. Liu L.-M. Diverse and Tunable Electronic Structures of Single-layer Metal Phosphorus Trichalcogenides for Photocatalytic Water Splitting J. Chem. Phys. 2014 140 5 054707
Google Scholar
30
Diverse and tunable electronic structures of single-layer metal phosphorus trichalcogenides for photocatalytic water splitting
Liu, Jian; Li, Xi-Bo; Wang, Da; Lau, Woon-Ming; Peng, Ping; Liu, Li-Min
Journal of Chemical Physics (2014), 140 (5), 054707/1-054707/7CODEN: JCPSA6; ISSN:0021-9606. (American Institute of Physics)
The family of bulk metal phosphorus trichalcogenides (APX3, A = MII, MI0.5MIII0.5; X = S, Se; MI, MII, and MIII represent Group-I, Group-II, and Group-III metals, resp.) has attracted great attentions because such materials not only own magnetic and ferroelec. properties, but also exhibit excellent properties in hydrogen storage and lithium battery because of the layered structures. Many layered materials have been exfoliated into two-dimensional (2D) materials, and they show distinct electronic properties compared with their bulks. Here the authors present a systematical study of single-layer metal phosphorus trichalcogenides by d. functional theory calcns. The results show that the single layer metal phosphorus trichalcogenides have very low formation energies, which indicates that the exfoliation of single layer APX3 should not be difficult. The family of single layer metal phosphorus trichalcogenides exhibits a large range of band gaps from 1.77 to 3.94 eV, and the electronic structures are greatly affected by the metal or the chalcogenide atoms. The calcd. band edges of metal phosphorus trichalcogenides further reveal that single-layer ZnPSe3, CdPSe3, Ag0.5Sc0.5PSe3, and Ag0.5In0.5PX3 (X = S and Se) have both suitable band gaps for visible-light driving and sufficient over-potentials for water splitting. More fascinatingly, single-layer Ag0.5Sc0.5PSe3 is a direct band gap semiconductor, and the calcd. optical absorption further convinces that such materials own outstanding properties for light absorption. Such results demonstrate that the single layer metal phosphorus trichalcogenides own high stability, versatile electronic properties, and high optical absorption, thus such materials have great chances to be high efficient photocatalysts for water-splitting. (c) 2014 American Institute of Physics.
31
Mukherjee D. Austeria M. P. Sampath S. Few-Layer Iron Selenophosphate, FePSe₃: Efficient Electrocatalyst toward Water Splitting and Oxygen Reduction Reactions ACS Appl. Energy Mater. 2018 1 1 220 231
Google Scholar
31
Few-Layer Iron Selenophosphate, FePSe3: Efficient Electrocatalyst toward Water Splitting and Oxygen Reduction Reactions
Mukherjee, Debdyuti; Muthu, Austeria P.; Sampath, S.
ACS Applied Energy Materials (2018), 1 (1), 220-231CODEN: AAEMCQ; ISSN:2574-0962. (American Chemical Society)
There has been a spurt of activity in using layered MPX3 (M = transition metal, X = chalcogen, S/Se/Te) compds. in various studies including catalysis and devices. In the present study, low band gap, ternary iron selenophosphate (FePSe3) is introduced as an excellent and highly stable trifunctional electrocatalyst for hydrogen evolution, oxygen evolution, and oxygen redn. reactions. It is obsd. that the present catalyst is useful in evolving hydrogen over a wide pH range including seawater environment. D. functional theory calcns. reveal various parameters that help improve the electrocatalytic activity of the layered material. Covalency of the Fe-Se bond, distortion in the crystal structure, and adsorption properties are shown to be responsible for the obsd. high catalytic activity.
32
Mukherjee D. Austeria P. M. Sampath S. Two-Dimensional, Few-Layer Phosphochalcogenide, FePS₃: A New Catalyst for Electrochemical Hydrogen Evolution over Wide pH Range ACS Energy Lett. 2016 1 2 367 372
Google Scholar
32
Two-Dimensional, Few-Layer Phosphochalcogenide, FePS3: A New Catalyst for Electrochemical Hydrogen Evolution over Wide pH Range
Mukherjee, Debdyuti; Austeria, P. Muthu; Sampath, S.
ACS Energy Letters (2016), 1 (2), 367-372CODEN: AELCCP; ISSN:2380-8195. (American Chemical Society)
A layered MPS3-type compd., FePS3, is introduced as an electrocatalyst for hydrogen evolution reaction (HER). The non-noble metal-based FePS3 is a semiconductor that could be solvent exfoliated into few-layer, two-dimensional (2D) nanosheets. The 2-dimensional thin sheets exhibit very good catalytic activity and stability toward HER over a wide pH range of acidic, alk., phosphate buffer, and 3.5% aq. NaCl solns. The Tafel slope and exchange c.d. in acidic medium are ∼(45-50) mV/dec and 1±0.2 × 10-3 A/cm2, resp. The stability of the catalyst is very good. D. functional theory calcns. reveal P and S as favorable hydrogen adsorption sites. This material opens up a new class of ternary, layered semiconductors for various electrocatalytic studies and might also become important from a device physics point of view.
33
Jenjeti R. N. Kumar R. Sampath S. Two-Dimensional, Few-layer NiPS₃ for Flexible Humidity Sensor with High Selectivity J. Mater. Chem. A 2019 7 24 14545 14551
Google Scholar
33
Two-dimensional, few-layer NiPS3 for flexible humidity sensor with high selectivity
Jenjeti, Ramesh Naidu; Kumar, Rajat; Sampath, S.
Journal of Materials Chemistry A: Materials for Energy and Sustainability (2019), 7 (24), 14545-14551CODEN: JMCAET; ISSN:2050-7496. (Royal Society of Chemistry)
Chem. and elec. sensitive two-dimensional (2D) nanomaterials are of immense interest as probing electrodes for wearable electronic devices. A new family of two dimensional (2D) layered materials, namely metal phosphochalcogenides (MPX3), are potential candidates towards the development of sensors for various analytes. Herein, we demonstrate the ability of few-layer NiPS3 nanosheets for humidity sensing by fabricating a cost-effective, flexible sensor device. The results indicate that the NiPS3 nanosheet-based humidity sensors possess high sensitivity with a response of ∼106, superior selectivity, and most importantly, rapid response, recovery times and good reproducibility. Response times of ∼1-2 s at low humidity levels and ∼3 s at high humidity levels with recovery times of ∼2-3 s are obsd. The device was tested in both flat and bent states, causing no prominent changes in the response; hence, the sensor is an excellent candidate for use in flexible devices. The characteristics of the NiPS3-based sensor were further investigated using complex impedance studies and in situ Raman spectroscopy to understand the sensing mechanism. The fast response and recovery assocd. with the NiPS3-based humidity sensors allow real time monitoring of human respiration and water evapn. on skin. These humidity sensors can also be utilized for non-contact anal. and hence will be an attractive candidate for health and environmental monitoring.
34
Song B. Li K. Yin Y. Wu T. Dang L. Caban-Acevedo M. Han J. Gao T. Wang X. Zhang Z. Schmidt J. R. Xu P. Jin S. Tuning Mixed Nickel Iron Phosphosulfide Nanosheet Electrocatalysts for Enhanced Hydrogen and Oxygen Evolution ACS Catal. 2017 7 12 8549 8557
Google Scholar
34
Tuning Mixed Nickel Iron Phosphosulfide Nanosheet Electrocatalysts for Enhanced Hydrogen and Oxygen Evolution
Song, Bo; Li, Kai; Yin, Ying; Wu, Tao; Dang, Lianna; Caban-Acevedo, Miguel; Han, Jiecai; Gao, Tangling; Wang, Xianjie; Zhang, Zhihua; Schmidt, J. R.; Xu, Ping; Jin, Song
ACS Catalysis (2017), 7 (12), 8549-8557CODEN: ACCACS; ISSN:2155-5435. (American Chemical Society)
Highly efficient earth-abundant electrocatalysts for the hydrogen evolution reaction (HER) and oxygen evolution reaction (OER) are of great importance for renewable energy conversion systems. Herein, guided by theor. calcns., we demonstrate highly efficient water splitting in alk. soln. using quaternary mixed nickel iron phosphosulfide (Ni1-xFexPS3) nanosheets (NSs), even though neither NiPS3 nor FePS3 is a good HER (or OER) electrocatalyst. With tuned electronic structure and improved elec. cond. induced by mixing appropriate amt. of Fe into NiPS3, Ni0.9Fe0.1PS3 NSs display excellent HER activity (an overpotential of 72 mV vs reversible hydrogen electrode (RHE) at a geometric catalytic c.d. of -10 mA cm-2 and a Tafel slope of 73 mV dec-1), which is among the best HER catalysts under alk. conditions. Ni0.9Fe0.1PS3 NSs also show a good apparent OER activity (an overpotential of 329 mV vs RHE at a catalytic c.d. of 20 mA cm-2 and a Tafel slope of 69 mV dec-1), although structural investigation indicates the formation of Ni(Fe)OOH and Ni(Fe)(OH)2 layers on the catalyst surface after OER reactions as likely the real active species. These mixed nickel iron phosphosulfide non-precious-metal electrocatalysts with enhanced intrinsic activity and long-term stability and durability should have great potential in overall water-splitting applications.
35
Cheng Z. Shifa T. A. Wang F. Gao Y. He P. Zhang K. Jiang C. Liu Q. He J. High-Yield Production of Monolayer FePS₃ Quantum Sheets via Chemical Exfoliation for Efficient Photocatalytic Hydrogen Evolution Adv. Mater. 2018 30 26 1707433
Google Scholar
There is no corresponding record for this reference.
36
Dinh Hoa L. Thanh Luan P. Ghimire G. Dinh Loc D. Lee Y. H. Revealing Antiferromagnetic Transition of van der Waals MnPS₃ via Vertical Tunneling Electrical Resistance Measurement APL Mater. 2019 7 8 081102
Google Scholar
There is no corresponding record for this reference.
37
Wang J. Li X. Wei B. Sun R. Yu W. Hoh H. Y. Xu H. Li J. Ge X. Chen Z. Su C. Wang Z. Activating Basal Planes of NiPS₃ for Hydrogen Evolution by Nonmetal Heteroatom Doping Adv. Funct. Mater. 2020 30 12 1908708
Google Scholar
37
Activating Basal Planes of NiPS3 for Hydrogen Evolution by Nonmetal Heteroatom Doping
Wang, Jun; Li, Xinzhe; Wei, Bin; Sun, Rong; Yu, Wei; Hoh, Hui Ying; Xu, Haomin; Li, Jing; Ge, Xingbo; Chen, Zuxin; Su, Chenliang; Wang, Zhongchang
Advanced Functional Materials (2020), 30 (12), 1908708CODEN: AFMDC6; ISSN:1616-301X. (Wiley-VCH Verlag GmbH & Co. KGaA)
NiPS3, one of the most promising catalysts among transition metal trichalcogenidophosphates (MTPs) in hydrogen evolution reaction (HER) electrocatalysis, is still inhibited by its unsatisfactory activity originating from its semiconducting nature and inert basal plane. Here, it is proposed, for the first time, to engineer the basal surface activity of NiPS3 by nonmetal heteroatom doping, and predict that the degree to which the valance band of NiPS3 is filled dominates not only the elec. cond. of the catalyst, but also the strength of hydrogen adsorption at its surface. Direct exptl. evidence is offered that in all the single nonmetal doping samples, C-doped NiPS3 exhibits the optimum activity owing to its moderate filled state of valance band and that C, N codoping even shows Pt-like activity with an ultralow overpotential of 53.2 mV to afford 10 mA cm-2 c.d. and a high exchange c.d. of 0.7 mA cm-2 in 1 M KOH. The findings that less valance electrons of dopants than substitutional atoms are of pivotal importance for improving HER activity of NiPS3 catalyst pave the way for readily designing novel MTPs of ever high performance to replace the incumbent Pt-based catalysts.
38
Li X. Fang Y. Wang J. Wei B. Qi K. Hoh H. Y. Hao Q. Sun T. Wang Z. Yin Z. Zhang Y. Lu J. Bao Q. Su C. High-Yield Electrochemical Production of Large-Sized and Thinly Layered NiPS₃ Flakes for Overall Water Splitting Small 2019 15 30 1902427
Google Scholar
There is no corresponding record for this reference.
39
Sekine T. Jouanne M. Julien C. Balkanski M. Raman Scattering in the Antiferromagnet FePS₃ Intercalated with Lithium Mater. Sci. Eng. B Solid State Mater. Adv. Technol. 1989 3 1−2 91 95
Google Scholar
There is no corresponding record for this reference.
40
Fujishima A. Honda K. Electrochemical Photolysis of Water at a Semiconductor Electrode Nature 1972 238 5358 37 38
Google Scholar
40
Electrochemical photolysis of water at a semiconductor electrode
Fujishima, Akira; Honda, Kenichi
Nature (London, United Kingdom) (1972), 238 (5358), 37-8CODEN: NATUAS; ISSN:0028-0836.
For electrochem. decompn. of H2O, a p.d. of >1.23 V is necessary between the anode and the cathode. This p.d. is equal to the energy of radiation with wavelength of ∼1000 nm. This energy, in the form of visible light, can be used effectively in an electrochem. system to decomp. H2O. A novel type of electrochem. cell was developed, in which a TiO2 electrode was connected with a Pt-black electrode through an external load. The direction of current revealed that oxidn. occurred at the TiO2 electrode and redn. at the Pt-black electrode. To increase the efficiency of the process, more reducible species, such as dissolved O2 or Fe3+, must be added in the Pt electrode compartment. The use of a p-type semiconductor electrode instead of Pt leads to more effective electrochem. photolysis of H2O.
41
Nakata K. Fujishima A. TiO₂ Photocatalysis: Design and Applications J. Photochem. Photobiol. C 2012 13 3 169 189
Google Scholar
41
TiO2 photocatalysis: Design and applications
Nakata, Kazuya; Fujishima, Akira
Journal of Photochemistry and Photobiology, C: Photochemistry Reviews (2012), 13 (3), 169-189CODEN: JPPCAF; ISSN:1389-5567. (Elsevier B.V.)
In this review, recent developments in the area of TiO2 photocatalysis research, in terms of new materials from a structural design perspective, have been summarized. The dimensionality assocd. with the structure of a TiO2 material can affect its properties and functions, including its photocatalytic performance, and also more specifically its surface area, adsorption, reflectance, adhesion, and carrier transportation properties. The authors provide a brief introduction to the current situation in TiO2 photocatalysis, and describe structurally controlled TiO2 photocatalysts which can be classified into zero-, one-, two-, and three-dimensional structures. Furthermore, novel applications of TiO2 surfaces for the fabrication of wettability patterns and for printing are discussed.
42
Chiesa P. Consonni S. Kreutz T. Williams R. Co-Production of Hydrogen, Electricity and CO₂ from Coal with Commercially Ready Technology. PartA: Performance and Emissions Int. J. Hydrogen Energy 2005 30 7 747 767
Google Scholar
42
Co-production of hydrogen, electricity and CO2 from coal with commercially ready technology. Part A: Performance and emissions
Chiesa, Paolo; Consonni, Stefano; Kreutz, Thomas; Williams, Robert
International Journal of Hydrogen Energy (2005), 30 (7), 747-767CODEN: IJHEDX; ISSN:0360-3199. (Elsevier Ltd.)
This two-part paper investigates performances, costs and prospects of using com. ready technol. to convert coal to H2 and electricity, with CO2 capture and storage. Part A focuses on plant configuration and the evaluation of performances and CO2 emissions. Part B focuses on economics, establishing benchmarks for the assessment of novel technologies and guidelines for technol. development. In the co-prodn. plants considered in the paper, coal is gasified to synthesis gas in an entrained flow gasifier. The syngas is cooled, cleaned of particulate matter, and shifted (to primarily H2 and CO2) in sour water-gas shift reactors. After further cooling, H2S is removed from the syngas using a phys. solvent (Selexol); CO2 is then removed from the syngas, again using Selexol; after being stripped from the solvent, the CO2 is dried and compressed to 150 bar for pipeline transport and underground storage. High purity H2 (99.999%) is extd. from the H2-rich syngas via a pressure swing adsorption (PSA) unit and delivered at 60 bar. The PSA purge gas is compressed and burned in a conventional gas turbine combined cycle, generating co-product electricity. The H2/electricity ratio can be varied by lowering the steam-to-carbon ratio in the syngas or by letting part of the de-carbonized syngas bypass the PSA unit. Performances and emissions of H2/electricity co-prodn. with CO2 capture are compared with those of a system that vents the CO2. We examine different methods of syngas heat recovery (quench vs. radiant cooling) and explore the effects of changing the electricity/H2 ratio, gasifier pressure and hydrogen purity. Results show that state-of-the-art com. technol. allows transferring to de-carbonized hydrogen 57-58% of coal LHV, while exporting to the grid decarbonized electricity amounting to 2-6% of coal LHV. In contrast to decarbonizing coal IGCC electricity, which entails a loss of 6-8 percentage points of electricity conversion when capturing CO2 as an alternative to venting it, CO2 capture for H2 prodn. gives a minor energy penalty (∼ 2 percentage points of export electricity). For H2 prodn., the efficiency gain achievable by hot syngas cooling vs. quench is a modest 2 percentage point increase in electricity for export, compared to 2-4 percentage points in the electricity case. Reducing H2 purity or increasing gasification pressure has minor effects on performance.
43
Zhang X. Zhao X. Wu D. Jing Y. Zhou Z. MnPSe₃ Monolayer: A Promising 2D Visible-Light Photohydrolytic Catalyst with High Carrier Mobility Adv. Sci. 2016 3 10 1600062
Google Scholar
43
MnPSe3 Monolayer: A Promising 2D Visible-Light Photohydrolytic Catalyst with High Carrier Mobility
Zhang Xu; Zhao Xudong; Wu Dihua; Jing Yu; Zhou Zhen
Advanced science (Weinheim, Baden-Wurttemberg, Germany) (2016), 3 (10), 1600062 ISSN:2198-3844.
The 2D material single-layer MnPSe3 would be a promising photocatalyst for water splitting, as indicated by the proper positions of band edges, strong absorption in visible-light spectrum, broad applicability (pH = 0 - 7), and high carrier mobility.
44
Yu P. Wang F. Meng J. Shifa T. A. Sendeku M. G. Fang J. Li S. Cheng Z. Lou X. He J. Few-Layered CuInP₂S₆ Nanosheet with Sulfur Vacancy Boosting Photocatalytic Hydrogen Evolution CrystEngComm 2021 591 598
Google Scholar
44
Few-layered CuInP2S6 nanosheet with sulfur vacancy boosting photocatalytic hydrogen evolution
Yu, Peng; Wang, Fengmei; Meng, Jun; Shifa, Tofik Ahmed; Sendeku, Marshet Getaye; Fang, Ju; Li, Shuxian; Cheng, Zhongzhou; Lou, Xiaoding; He, Jun
CrystEngComm (2021), 23 (3), 591-598CODEN: CRECF4; ISSN:1466-8033. (Royal Society of Chemistry)
Photochem. water splitting offers an economic and sustainable approach for solar energy conversion into hydrogen fuel to mitigate the problem of greenhouse gas emissions. To this end, exploring novel semiconductor photocatalysts, which have efficient light absorption and thermodynamically favorable band alignment for water splitting, is crucial. Here, we rationally develop a new photocatalyst of CuInP2S6 nanosheets to generate hydrogen gas under light illumination. The CuInP2S6 nanosheet (with a thickness of around 4-7 nm) photocatalyst exhibits a high hydrogen prodn. rate of 804μmol g-1 h-1, eight times higher than that of the microsheet counterpart, due to the introduced abundant sulfur vacancies. Exptl. characterization and theor. calcns. verify that the prolonged carrier lifetime and optimized band alignment in ultrathin CuInP2S6 nanosheets boost photocatalytic hydrogen evolution. This work opens a new avenue for photocatalysis via using novel layered binary metal phosphorous trichalcogenides.
45
Navarro R. M. Sánchez-Sánchez M. C. Alvarez-Galvan M. C. Valle F. d. Fierro J. L. G. Hydrogen Production from Renewable Sources: Biomass and Photocatalytic Opportunities Energy Environ. Sci. 2009 2 1 35 54
Google Scholar
45
Hydrogen production from renewable sources: biomass and photocatalytic opportunities
Navarro, R. M.; Sanchez-Sanchez, M. C.; Alvarez-Galvan, M. C.; del Valle, F.; Fierro, J. L. G.
Energy & Environmental Science (2009), 2 (1), 35-54CODEN: EESNBY; ISSN:1754-5706. (Royal Society of Chemistry)
A review. The demand for hydrogen over the coming decade is expected to grow for both traditional uses (ammonia, methanol, refinery) and running fuel cells. At least in the near future, this thirst for hydrogen will be quenched primarily through the reforming of fossil fuels. However, reforming fossil fuels emits huge amts. of carbon dioxide. One approach to reduce carbon dioxide emissions, which is considered first in this review, is to apply reforming methods to alternative renewable materials. Such materials might be derived from plant crops, agricultural residues, woody biomass, etc. Clean biomass is a proven source of renewable energy that is already used for generating heat, electricity, and liq. transportation fuels. Clean biomass and biomass-derived precursors such as ethanol and sugars are appropriate precursors for producing hydrogen through different conversion strategies. Virtually no net greenhouse gas emissions result because a natural cycle is maintained, in which carbon is extd. from the atm. during plant growth and released during hydrogen prodn. The second option explored here is hydrogen prodn. from water splitting by means of the photons in the visible spectrum. The sun provides silent and precious energy that is distributed fairly evenly all over the earth. However, its tremendous potential as a clean, safe and economical energy source cannot be exploited unless it is accumulated or converted into more useful forms of energy. Finally, this review discusses the use of semiconductors, more specifically CdS and CdS-based semiconductors, which are able to absorb photons in the visible region of the spectrum. The energy stored within a semiconductor as electronic energy (electrons and holes) can be used to split water mols. by simultaneous reactions into H2 and O2. This conversion of solar energy into a clean fuel (H2) is perhaps the greatest challenge for scientists in the 21st century.
46
Shimura K. Yoshida H. Heterogeneous Photocatalytic Hydrogen Production from Water and Biomass Derivatives Energy Environ. Sci. 2011 4 7 2467 2481
Google Scholar
46
Heterogeneous photocatalytic hydrogen production from water and biomass derivatives
Shimura, Katsuya; Yoshida, Hisao
Energy & Environmental Science (2011), 4 (7), 2467-2481CODEN: EESNBY; ISSN:1754-5706. (Royal Society of Chemistry)
A review. Hydrogen, a clean energy carrier, should be produced from not the irreproducible fossil fuels but renewable resources. Currently hydrogen is mainly produced by the reforming of petroleum and natural gas at high temp., which consumes huge energy. Thus, development of an alternative hydrogen prodn. method is absolutely imperative to mitigate the environmental and energy issues. Photocatalytic hydrogen prodn. from water and renewable resources is one of the attractive systems, since it can utilize the solar energy. In this short review, we remind you that the systems of the photocatalytic hydrogen prodn. from water and biomass derivs., such as ethanol, glycerol, sugars and methane, should be considered as available candidates for the hydrogen prodn. method from renewable resources and solar energy, and these systems have been improved by developments of new photocatalysts with some cocatalysts, modifications of photocatalysts, optimization of reaction conditions, and so on.
47
Zhang Y. Zhao Y. Bao C. Xiao Y. Xiang Y. Song M. Huang W. Ma L. Hou H. Chen X. Facile synthesis of cadmium phosphorus trisulfide nanosheets for highly efficient photocatalytic performance J. Alloys Compd. 2022 909 164731
Google Scholar
47
Facile synthesis of cadmium phosphorus trisulfide nanosheets for highly efficient photocatalytic performance
Zhang, Yue; Zhao, Yadi; Bao, Cunyou; Xiao, Yue; Xiang, Yuesong; Song, Mengting; Huang, Wenjuan; Ma, Liang; Hou, Huayi; Chen, Xiangbai
Journal of Alloys and Compounds (2022), 909 (), 164731CODEN: JALCEU; ISSN:0925-8388. (Elsevier B.V.)
With the rise of two-dimensional (2D) materials, layered metal thiophosphates (MPS3), as an important branch, have attracted much attention because of their excellent phys. and chem. properties. Cadmium phosphorus trisulfide (CdPS3), as a promising photocatalyst, can be used for hydrogen evolution and org. degrdn. Herein, high-quality 2D CdPS3 few layers are obtained by exfoliating bulk CdPS3 crystal. The optical properties of the as-obtained CdPS3 few layers show good light-harvesting ability, endowing it with excellent photocatalytic hydrogen evolution performance (10.88 mmol g-1 h-1) and high org. degrdn. performance (more than 92% within 30 min) under Xe lamp irradn. This research provides opportunities for the prepn. and application of other 2D MPS3 type materials in the field of photocatalysis.
48
Cheng Z. Sendeku M. G. Liu Q. Layered Metal Phosphorous Trichalcogenides Nanosheets: Facile Synthesis and Photocatalytic Hydrogen Evolution Nanotechnology 2020 31 13 135405
Google Scholar
48
Layered metal phosphorous trichalcogenides nanosheets: Facile synthesis and photocatalytic hydrogen evolution
Cheng, Zhongzhou; Sendeku, Marshet Getaye; Liu, Quanlin
Nanotechnology (2020), 31 (13), 135405CODEN: NNOTER; ISSN:1361-6528. (IOP Publishing Ltd.)
Layered transition metal phosphorous trichalcogenide (MPX3) materials have attracted immense attention due to their excellent optical and elec. properties. However, the controllable synthesis of ultrathin MPX3 nanosheets is still challenging. Here, we present a facile phosphosulfurization scheme to prep. high-quality layered FePS3 nanosheets, with ~ 20 nm in thickness. The optical properties of the as-obtained FePS3 show good light-harvesting ability, which endows it with excellent photocatalytic hydrogen evolution performance (402.4μmol g-1 h-1) under the simulated solar illumination. We further show that other MPX3 family members such as In2/3PS3 and CdPS3 can be also synthesized by the same approach. Our finding can offer a feasible approach for rationally designing other MPX3 materials for various applications.
49
Chang X. Wang T. Gong J. CO₂ Photo-reduction: Insights into CO₂ Activation and Reaction on Surfaces of Photocatalysts Energy Environ. Sci. 2016 9 7 2177 2196
Google Scholar
49
CO2 photo-reduction: insights into CO2 activation and reaction on surfaces of photocatalysts
Chang, Xiaoxia; Wang, Tuo; Gong, Jinlong
Energy & Environmental Science (2016), 9 (7), 2177-2196CODEN: EESNBY; ISSN:1754-5706. (Royal Society of Chemistry)
Large amts. of anthropogenic CO2 emissions assocd. with increased fossil fuel consumption have led to global warming and an energy crisis. The photocatalytic redn. of CO2 into solar fuels such as methane or methanol is believed to be one of the best methods to address these two problems. In addn. to light harvesting and charge sepn., the adsorption/activation and redn. of CO2 on the surface of heterogeneous catalysts remain a scientifically crit. challenge, which greatly limits the overall photoconversion efficiency and selectivity of CO2 redn. This review describes recent advances in the fundamental understanding of CO2 photoredn. on the surface of heterogeneous catalysts and particularly provides an overview of enhancing the adsorption/activation of CO2 mols. The reaction mechanism and pathways of CO2 redn. as well as their dependent factors are also analyzed and discussed, which is expected to enable an increase in the overall efficiency of CO2 redn. through minimizing the reaction barriers and controlling the selectivity towards the desired products. The challenges and perspectives of CO2 photoredn. over heterogeneous catalysts are presented as well.
50
Gao W. Li S. He H. Li X. Cheng Z. Yang Y. Wang J. Shen Q. Wang X. Xiong Y. Zhou Y. Zou Z. Vacancy-Defect Modulated Pathway of Photoreduction of CO₂ on Single Atomically Thin AgInP₂S₆ Sheets into Olefiant Gas Nat. Commun. 2021 12 1 4747
Google Scholar
50
Vacancy-defect modulated pathway of photoreduction of CO2 on single atomically thin AgInP2S6 sheets into olefiant gas
Gao, Wa; Li, Shi; He, Huichao; Li, Xiaoning; Cheng, Zhenxiang; Yang, Yong; Wang, Jinlan; Shen, Qing; Wang, Xiaoyong; Xiong, Yujie; Zhou, Yong; Zou, Zhigang
Nature Communications (2021), 12 (1), 4747CODEN: NCAOBW; ISSN:2041-1723. (Nature Research)
Abstr.: Artificial photosynthesis, light-driving CO2 conversion into hydrocarbon fuels, is a promising strategy to synchronously overcome global warming and energy-supply issues. The quaternary AgInP2S6 at. layer with the thickness of ∼ 0.70 nm were successfully synthesized through facile ultrasonic exfoliation of the corresponding bulk crystal. The sulfur defect engineering on this at. layer through a H2O2 etching treatment can excitingly change the CO2 photoredn. reaction pathway to steer dominant generation of ethene with the yield-based selectivity reaching ∼73% and the electron-based selectivity as high as ∼89%. Both DFT calcn. and in-situ FTIR spectra demonstrate that as the introduction of S vacancies in AgInP2S6 causes the charge accumulation on the Ag atoms near the S vacancies, the exposed Ag sites can thus effectively capture the forming *CO mols. It makes the catalyst surface enrich with key reaction intermediates to lower the C-C binding coupling barrier, which facilitates the prodn. of ethene.
51
Fan Y. Song X. Ai H. Li W. Zhao M. Highly Efficient Photocatalytic CO₂ Reduction in Two-Dimensional Ferroelectric CuInP₂S₆ Bilayers ACS Appl. Mater. Interfaces 2021 13 29 34486 34494
Google Scholar
51
Highly efficient photocatalytic CO2 reduction in two-dimensional ferroelectric CuInP2S6 bilayers
Fan, Yingcai; Song, Xiaohan; Ai, Haoqiang; Li, Weifeng; Zhao, Mingwen
ACS Applied Materials & Interfaces (2021), 13 (29), 34486-34494CODEN: AAMICK; ISSN:1944-8244. (American Chemical Society)
Photocatalytic CO2 conversion into reproducible chem. fuels (e.g., CO, CH3OH, or CH4) provides a promising scheme to solve the increasing environmental problems and energy demands simultaneously. However, the efficiency is severely restricted by the high overpotential of the CO2 redn. reaction (CO2RR) and rapid recombination of photoexcited carriers. Here, we propose that a novel type-II photocatalytic mechanism based on two-dimensional (2D) ferroelec. multilayers would be ideal for addressing these issues. Using d.-functional theory and nonadiabatic mol. dynamics calcns., we find that the ferroelec. CuInP2S6 bilayers exhibit a staggered band structure induced by the vertical intrinsic elec. fields. Different from the traditional type-II band alignment, the unique structure of the CuInP2S6 bilayer not only effectively suppresses the recombination of photogenerated electron-hole (e-h) pairs but also produces a sufficient photovoltage to drive the CO2RR. The predicted recombination time of photogenerated e-h pairs, 1.03 ns, is much longer than the transferring times of photoinduced electrons and holes, 5.45 and 0.27 ps, resp. Moreover, the overpotential of the CO2RR will decrease by substituting an S atom with a Cu atom, making the redox reaction proceed spontaneously under solar radiation. The solar-to-fuel efficiency with an upper limit of 8.40% is achieved in the CuInP2S6 bilayer and can be further improved to 32.57% for the CuInP2S6 five-layer. Our results indicate that this novel type-II photocatalytic mechanism would be a promising way to achieve highly efficient photocatalytic CO2 conversion based on the 2D ferroelec. multilayers.
52
De Battisti, A.; Martínez-Huitle, C. A. , Electrocatalysis in Wastewater Treatment. In Electrochemical Water and Wastewater Treatment; Martínez-Huitle, C. A., Rodrigo, M. A., Scialdone, O. , Eds.; Butterworth-Heinemann: 2018; pp 119− 131.
Google Scholar
There is no corresponding record for this reference.
53
de Freitas Araujo K. C. da Silva D. R. dos Santos E. V. Varela H. Martinez-Huitle C. A. Investigation of Persulfate Production on BDD Anode by Understanding the Impact of Water Concentration J. Electroanal. Chem. 2020 860 113927
Google Scholar
There is no corresponding record for this reference.
54
Huang H. Li F. Xue Q. Zhang Y. Yin S. Chen Y. Salt-Templated Construction of Ultrathin Cobalt Doped Iron Thiophosphite Nanosheets toward Electrochemical Ammonia Synthesis Small 2019 15 51 1903500
Google Scholar
54
Salt-Templated Construction of Ultrathin Cobalt Doped Iron Thiophosphite Nanosheets toward Electrochemical Ammonia Synthesis
Huang, Hao; Li, Fumin; Xue, Qi; Zhang, Ying; Yin, Shiwei; Chen, Yu
Small (2019), 15 (51), 1903500CODEN: SMALBC; ISSN:1613-6810. (Wiley-VCH Verlag GmbH & Co. KGaA)
Exploiting efficient electrocatalysts for electrochem. N redn. (NRR) is highly desired and deeply meaningful for realizing sustainable NH3 (NH3) prodn. under ambient conditions. The Fe protein contains one [Fe4S4] cluster and P cluster, which play an important role for transfer electron during the N fixing of nitrogenases. Based on the understanding of nitrogenase, the rising-star 2-dimensional Fe thiophosphite (FePS3) nanomaterials may be highly active electrocatalysts toward NRR due to the ideal elemental compn. 2D FePS3 nanosheets are successfully synthesized by a facile salt-templated method. The FePS3 nanosheets show better electrocatalytic NH3 yield and faradaic efficiency (FE) than Fe2S3, which demonstrates that the P element indeed improves the NRR activity of Fe-S. Theor., Co incorporation not only effectively prompts the cond. of FePS3, but also enhances the catalytic activities of Fe-edge sites. Exptl., Co-doped FePS3 (Co-FePS3) nanosheets exhibit a remarkable electrocatalytic performance toward NRR, such as high NH3 yield rate of 90.6μg h-1 mgcat-1, high FE of 3.38%, and an excellent long-term stability. Being the 1st theor. and exptl. report regarding FePS3-based electrocatalyst toward NRR, this work represents an important beginning to the family of metal thiophosphite as advanced electrocatalysts toward NRR.
55
Mayorga-Martinez C. C. Sofer Z. Sedmidubsky D. Huber S. Eng A. Y. Pumera M. Layered Metal Thiophosphite Materials: Magnetic, Electrochemical, and Electronic Properties ACS Appl. Mater. Interfaces 2017 9 14 12563 12573
Google Scholar
55
Layered Metal Thiophosphite Materials: Magnetic, Electrochemical, and Electronic Properties
Mayorga-Martinez, Carmen C.; Sofer, Zdenek; Sedmidubsky, David; Huber, Stepan; Eng, Alex Yong Sheng; Pumera, Martin
ACS Applied Materials & Interfaces (2017), 9 (14), 12563-12573CODEN: AAMICK; ISSN:1944-8244. (American Chemical Society)
Beyond graphene, transitional metal dichalcogenides, and black phosphorus, there are other layered materials called metal thiophosphites (MPSx), which are recently attracting the attention of scientists. Here we present the synthesis, structural and morphol. characterization, magnetic properties, electrochem. performance, and the calcd. d. of states of different layered metal thiophosphite materials with a general formula MPSx, and as a result of varying the metal component, we obtain CrPS4, MnPS3, FePS3, CoPS3, NiPS3, ZnPS3, CdPS3, GaPS4, SnPS3, and BiPS4. SnPS3, ZnPS3, CdPS3, GaPS4, and BiPS4 exhibit only diamagnetic behavior due to core electrons. By contrast, trisulfides with M = Mn, Fe, Co, and Ni, as well as CrPS4, are paramagnetic at high temps. and undergo a transition to antiferromagnetic state on cooling. Within the trisulfides series the Neel temp. characterizing the transition from paramagnetic to antiferromagnetic phase increases with the increasing at. no. and the orbital component enhancing the total effective magnetic moment. Interestingly, in terms of catalysis NiPS3, CoPS3, and BiPS4 show the highest efficiency for hydrogen evolution reaction (HER), while for the oxygen evolution reaction (OER) the highest performance is obsd. for CoPS3. Finally, MnPS3 presents the highest oxygen redn. reaction (ORR) activity compared to the other MPSx studied here. This great catalytic performance reported for these MPSx demonstrates their promising capabilities in energy applications.
56
Yu Z. Peng J. Liu Y. Liu W. Liu H. Guo Y. Amine-Assisted Exfoliation and Electrical Conductivity Modulation Toward Few-layer FePS₃ Nanosheets for Efficient Hydrogen Evolution J. Mater. Chem. A 2019 7 23 13928 13934
Google Scholar
56
Amine-assisted exfoliation and electrical conductivity modulation toward few-layer FePS3 nanosheets for efficient hydrogen evolution
Yu, Zhi; Peng, Jing; Liu, Yuhua; Liu, Wenxiu; Liu, Haifeng; Guo, Yuqiao
Journal of Materials Chemistry A: Materials for Energy and Sustainability (2019), 7 (23), 13928-13934CODEN: JMCAET; ISSN:2050-7496. (Royal Society of Chemistry)
Layered metal phosphorus trichalcogenides (MPX3, M = transition metal, X = S or Se) have been established as new efficient catalysts for water splitting, with FePS3 as one representative example. Here, a novel amine-assisted exfoliation strategy is presented to obtain few-layer FePS3 nanosheets, whose intrinsic elec. cond. can be easily regulated by adjusting the reaction temp. The improved elec. cond. originates from the increase of the Fe3+/Fe2+ ratio, while matrix crystallinity also plays a vital role in this aspect. The combined effect of mixed valence and crystallinity results in superior HER performance with a decrease of the overpotential of 147 mV and a drop of the Tafel slope from 139-94 mV dec-1.
57
Lian Q. Zhong L. Du C. Luo Y. Zhao J. Zheng Y. Xu J. Ma J. Liu C. Li S. Yan Q. Interfacing Epitaxial Dinickel Phosphide to 2D Nickel Thiophosphate Nanosheets for Boosting Electrocatalytic Water Splitting ACS Nano 2019 13 7 7975 7984
Google Scholar
There is no corresponding record for this reference.
58
Gusmão R. Sofer Z. Sedmidubský D. Huber Š. Pumera M. The Role of the Metal Element in Layered Metal Phosphorus Triselenides upon Their Electrochemical Sensing and Energy Applications ACS Catal. 2017 7 12 8159 8170
Google Scholar
58
The Role of the Metal Element in Layered Metal Phosphorus Triselenides upon Their Electrochemical Sensing and Energy Applications
Gusmao, Rui; Sofer, Zdenek; Sedmidubsky, David; Huber, Stepan; Pumera, Martin
ACS Catalysis (2017), 7 (12), 8159-8170CODEN: ACCACS; ISSN:2155-5435. (American Chemical Society)
The no. of layered materials seems to be ever-growing, from mono- to multielement, with affiliates and applications being tested continuously. Chalcogenophosphites, also designated as metal phosphorus chalcogenides (MPXn), have attracted great interest because of not only their magnetic properties but also promising capabilities in energy applications. Herein, bulk crystals of different layered metal triselenophosphites, with a general formula MPSe3 (M = Cd, Cr, Fe, Mn, Sn, Zn), were synthesized. Structural and morphol. characterization was performed prior to testing their electrochem. performance. From the set of ternary layered materials, FePSe3, followed by MnPSe3, yielded the highest efficiency for the hydrogen evolution reaction (HER) both in acidic and alk. media with good stability after 100 cycles. MnPSe3 also holds the lowest oxidn. potential for cysteine, although this is due to the presence of MnO2 in the structure as detected by XPS. For the oxygen evolution reaction, the best performance was obsd. for FePSe3, although the stability of the material was not as good as in the case of HER. These findings have profound implications in the application of these layered ternary compds. in energy-related fields.
59
Hao Y. Huang A. Han S. Huang H. Song J. Sun X. Wang Z. Li L. Hu F. Xue J. Peng S. Plasma-Treated Ultrathin Ternary FePSe₃ Nanosheets as a Bifunctional Electrocatalyst for Efficient Zinc–Air Batteries ACS Appl. Mater. Interfaces 2020 12 26 29393 29403
Google Scholar
59
Plasma-Treated Ultrathin Ternary FePSe3 Nanosheets as a Bifunctional Electrocatalyst for Efficient Zinc-Air Batteries
Hao, Yanan; Huang, Aijian; Han, Silin; Huang, Hongjiao; Song, Junnan; Sun, Xiaoli; Wang, Zhiguo; Li, Linlin; Hu, Feng; Xue, Jianjun; Peng, Shengjie
ACS Applied Materials & Interfaces (2020), 12 (26), 29393-29403CODEN: AAMICK; ISSN:1944-8244. (American Chemical Society)
Developing novel bifunctional electrocatalysts with advanced oxygen electrocatalytic activity is pivotal for next-generation energy-storage devices. Herein, we present ultrathin oxygen-doped FePSe3 (FePSe3-O) nanosheets by Ar/O2 plasma treatment, with remarkable surface atom reorganization. Such surface atom reorganization generates multiple cryst.-amorphous interfaces that benefit the kinetics of oxygen evolution reaction, achieving a low overpotential of only 261 mV at 10 mA cm-2 with a small Tafel slope of 41.13 mV dec-1. D. functional theory calcn. indicates that oxygen doping can also modulate the elec. states at the Fermi level with a decreased band gap responsible for the enhanced electrocatalytic performance. Such unique FePSe3-O nanosheets can be further fabricated as the air cathode in rechargeable liq. zinc-air batteries (ZABs), which deliver a high open circuit potential of 1.47 V, a small charge-discharge voltage gap of 0.80 V, and good cycling stability for more than 800 circles. As a proof of concept, the flexible solid-state ZABs assembled with FePSe3-O nanosheets as cathode also display a favorable charge-discharge performance, durable stability, and good bendability. This work sheds new insights into the rational design of defect-rich ternary thiophosphate nanosheets by plasma treatment toward enhanced oxygen electrocatalysts in metal-air batteries.
60
Konkena B. Masa J. Botz A. J. R. Sinev I. Xia W. Koßmann J. Drautz R. Muhler M. Schuhmann W. Metallic NiPS₃@NiOOH Core–Shell Heterostructures as Highly Efficient and Stable Electrocatalyst for the Oxygen Evolution Reaction ACS Catal. 2017 7 1 229 237
Google Scholar
60
Metallic NiPS3@NiOOH Core-Shell Heterostructures as Highly Efficient and Stable Electrocatalyst for the Oxygen Evolution Reaction
Konkena, Bharathi; Masa, Justus; Botz, Alexander J. R.; Sinev, Ilya; Xia, Wei; Kossmann, Joerg; Drautz, Ralf; Muhler, Martin; Schuhmann, Wolfgang
ACS Catalysis (2017), 7 (1), 229-237CODEN: ACCACS; ISSN:2155-5435. (American Chemical Society)
We report metallic NiPS3@NiOOH core-shell heterostructures as an efficient and durable electrocatalyst for the oxygen evolution reaction, exhibiting a low onset potential of 1.48 V (vs. RHE) and stable performance for over 160 h. The atomically thin NiPS3 nanosheets are obtained by exfoliation of bulk NiPS3 in the presence of an ionic surfactant. The OER mechanism was studied by a combination of SECM, in situ Raman spectroscopy, SEM, and XPS measurements, which enabled direct observation of the formation of a NiPS3@NiOOH core-shell heterostructure at the electrode interface. Hence, the active form of the catalyst is represented as NiPS3@NiOOH core-shell structure. Moreover, DFT calcns. indicate an intrinsic metallic character of the NiPS3 nanosheets with densities of states (DOS) similar to the bulk material. The high OER activity of the NiPS3 nanosheets is attributed to a high d. of accessible active metallic-edge and defect sites due to structural disorder, a unique NiPS3@NiOOH core-shell heterostructure, where the presence of P and S modulates the surface electronic structure of Ni in NiPS3, thus providing excellent conductive pathway for efficient electron-transport to the NiOOH shell. These findings suggest that good size control during liq. exfoliation may be advantageously used for the formation of elec. conductive NiPS3@NiOOH core-shell electrode materials for the electrochem. water oxidn.
61
Bushuyev O. S. De Luna P. Dinh C. T. Tao L. Saur G. van de Lagemaat J. Kelley S. O. Sargent E. H. What Should We Make with CO₂ and How Can We Make It ? Joule 2018 2 5 825 832
Google Scholar
61
What Should We Make with CO2 and How Can We Make It?
Bushuyev, Oleksandr S.; De Luna, Phil; Dinh, Cao Thang; Tao, Ling; Saur, Genevieve; van de Lagemaat, Jao; Kelley, Shana O.; Sargent, Edward H.
Joule (2018), 2 (5), 825-832CODEN: JOULBR; ISSN:2542-4351. (Cell Press)
In this forward-looking Perspective, we discuss the current state of technol. and the economics of electrocatalytic transformation of CO2 into various chem. fuels. Our anal. finds that short-chain simple building-block mols. currently present the most economically compelling targets. Making an optimistic prediction of technol. advancement in the future, we propose the gradual rise of photocatalytic, CO2 polymn., biohybrid, and mol. machine technologies to augment and enhance already practical electrocatalytic CO2 conversion methods.
62
Nitopi S. Bertheussen E. Scott S. B. Liu X. Y. Engstfeld A. K. Horch S. Seger B. Stephens I. E. L. Chan K. Hahn C. Norskov J. K. Jaramillo T. F. Chorkendorff I. Progress and Perspectives of Electrochemical CO₂ Reduction on Copper in Aqueous Electrolyte Chem. Rev. 2019 119 12 7610 7672
Google Scholar
62
Progress and Perspectives of Electrochemical CO2 Reduction on Copper in Aqueous Electrolyte
Nitopi, Stephanie; Bertheussen, Erlend; Scott, Soren B.; Liu, Xinyan; Engstfeld, Albert K.; Horch, Sebastian; Seger, Brian; Stephens, Ifan E. L.; Chan, Karen; Hahn, Christopher; Noerskov, Jens K.; Jaramillo, Thomas F.; Chorkendorff, Ib
Chemical Reviews (Washington, DC, United States) (2019), 119 (12), 7610-7672CODEN: CHREAY; ISSN:0009-2665. (American Chemical Society)
A review. To date, copper is the only heterogeneous catalyst that has shown a propensity to produce valuable hydrocarbons and alcs., such as ethylene and ethanol, from electrochem. CO2 redn. (CO2R). There are variety of factors that impact CO2R activity and selectivity, including the catalyst surface structure, morphol., compn., the choice of electrolyte ions and pH, the electrochem. cell design, etc. Many of these factors are often intertwined, which can complicate catalyst discovery and design efforts. Here we take a broad and historical view of these different aspects and their complex interplay in CO2R catalysis on Cu, with the purpose of providing new insights, crit. evaluations, and guidance to the field with regards to research directions and best practices. First, we describe the various exptl. probes and complementary theor. methods that have been used to discern the mechanisms by which products are formed, and next we present our current understanding of the complex reaction networks for CO2R on Cu. Then we analyze two key methods that have been used in attempts to alter the activity and selectivity of Cu: nanostructuring and the formation of bimetallic electrodes. Finally, we offer some perspectives on the future outlook for electrochem. CO2R.
63
Zhao K. Quan X. Carbon-Based Materials for Electrochemical Reduction of CO₂ to C₂₊ Oxygenates: Recent Progress and Remaining Challenges ACS Catal. 2021 11 4 2076 2097
Google Scholar
63
Carbon-Based Materials for Electrochemical Reduction of CO2 to C2+ Oxygenates: Recent Progress and Remaining Challenges
Zhao, Kun; Quan, Xie
ACS Catalysis (2021), 11 (4), 2076-2097CODEN: ACCACS; ISSN:2155-5435. (American Chemical Society)
A review. Electrochem. redn. of CO2 to multicarbon (C2+) products is desirable because of the higher energy d. and economic value of C2+ products and the significant scientific issue for coupling of multicarbons. However, efficient conversion of CO2 into C2+ products remains challenging because of the difficulty in C-C coupling. Recently, numerous papers have reported carbon-based materials for C2+ products prodn. from CO2 electrochem. redn. Because of the unique properties of carbon-based materials in C2+ prodn., carbon-based materials can be used as a potential alternative for the electrocatalytic conversion of CO2. This Review summarized recent progresses in the formation of C2+ oxygenates from CO2 redn. on carbon-based materials. In this Review, we highlighted the strategies available for achieving C-C coupling on carbon-based electrocatalysts and revealed the relationships between intermediate adsorption energy and the selectivity of oxygenate prodn. from CO2 redn. Moreover, we provided the understandings for fabricating active sites of CO2 redn. on carbon-based materials and related mechanisms of C2+ oxygenate generation. The remaining challenges and opportunities for the electrochem. conversion of CO2 into C2+ oxygenates were discussed.
64
Birdja Y. Y. Pérez-Gallent E. Figueiredo M. C. Göttle A. J. Calle-Vallejo F. Koper M. T. M. Advances and Challenges in Understanding the Electrocatalytic Conversion of Carbon Dioxide to Fuels Nat. Energy 2019 4 9 732 745
Google Scholar
64
Advances and challenges in understanding the electrocatalytic conversion of carbon dioxide to fuels
Birdja, Yuvraj Y.; Perez-Gallent, Elena; Figueiredo, Marta C.; Gottle, Adrien J.; Calle-Vallejo, Federico; Koper, Marc T. M.
Nature Energy (2019), 4 (9), 732-745CODEN: NEANFD; ISSN:2058-7546. (Nature Research)
A review. The electrocatalytic redn. of carbon dioxide is a promising approach for storing (excess) renewable electricity as chem. energy in fuels. Here, we review recent advances and challenges in the understanding of electrochem. CO2 redn. We discuss existing models for the initial activation of CO2 on the electrocatalyst and their importance for understanding selectivity. Carbon-carbon bond formation is also a key mechanistic step in CO2 electroredn. to high-d. and high-value fuels. We show that both the initial CO2 activation and C-C bond formation are influenced by an intricate interplay between surface structure (both on the nano- and on the mesoscale), electrolyte effects (pH, buffer strength, ion effects) and mass transport conditions. This complex interplay is currently still far from being completely understood. In addn., we discuss recent progress in in situ spectroscopic techniques and computational techniques for mechanistic work. Finally, we identify some challenges in furthering our understanding of these themes.
65
Ji L. Chang L. Zhang Y. Mou S. Wang T. Luo Y. Wang Z. Sun X. Electrocatalytic CO₂ Reduction to Alcohols with High Selectivity over a Two-Dimensional Fe₂P₂S₆ Nanosheet ACS Catal. 2019 9 11 9721 9725
Google Scholar
65
Electrocatalytic CO2 Reduction to Alcohols with High Selectivity over a Two-Dimensional Fe2P2S6 Nanosheet
Ji, Lei; Chang, Le; Zhang, Ya; Mou, Shiyong; Wang, Ting; Luo, Yonglan; Wang, Zhiming; Sun, Xuping
ACS Catalysis (2019), 9 (11), 9721-9725CODEN: ACCACS; ISSN:2155-5435. (American Chemical Society)
Electrochem. conversion of CO2 into alcs. provides an attractive path toward achieving a carbon-neutral cycle, while its efficiency is challenged by identifying active electrocatalysts for the CO2 redn. reaction (CO2RR). In this work, we report the Fe2P2S6 nanosheet acts as an efficient CO2RR electrocatalyst toward highly selective hydrogenation of CO2 to alcs. This catalyst is capable of achieving a high total Faradaic efficiency (FEmethanol+ethanol) of 88.3%, with a FEmethanol up to 65.2% at -0.20 V vs the reversible hydrogen electrode in 0.5 M KHCO3 soln., much higher than most reported CO2RR electrocatalysts. D. functional theory calcns. indicate that Fe atom on the Fe2P2S6 surface can be regared as the active site for alc. formation.
66
Thompson A. H. Whittingham M. S. Transition Metal Phosphorus Trisulfides as Battery Cathodes Mater. Res. Bull. 1977 12 7 741 744
Google Scholar
66
Transition metal phosphorus trisulfides as battery cathodes
Thompson, A. H.; Whittingham, M. S.
Materials Research Bulletin (1977), 12 (7), 741-4CODEN: MRBUAC; ISSN:0025-5408.
The layered, transition-metal P trisulfides exhibit electrochem. activity. NiPS3 reacts with >4 Li resulting in a cell with a theor. energy double that of TiS2.
67
Brec R. Review on structural and chemical properties of transition metal phosphorous trisulfides MPS₃ Solid State Ion. 1986 22 1 3 30
Google Scholar
There is no corresponding record for this reference.
68
Foot P. J. S. Katz T. Patel S. N. Nevett B. A. Pieecy A. R. Balchin A. A. The Structures and Conduction Mechanisms of Lithium-intercalated and Lithium-Substituted Nickel Phosphorus Trisulphide (NiPS₃), and the Use of the Material as a Secondary Battery Electrode Phys. Status Solidi A 1987 100 1 11 29
Google Scholar
68
The structures and conduction mechanisms of lithium-intercalated and lithium-substituted nickel phosphorus trisulfide (NiPS3), and the use of the material as a secondary battery electrode
Foot, P. J. S.; Katz, T.; Patel, S. N.; Nevett, B. A.; Piercy, A. R.; Balchin, A. A.
Physica Status Solidi A: Applied Research (1987), 100 (1), 11-29CODEN: PSSABA; ISSN:0031-8965.
A review with 35 refs. The crystal structure and conduction of the title compds. are discussed and the possible use of these NiPS3 compds. as battery electrodes is suggested. An app. is given for the electrochem. lithiation of NiPS3 to form LixNiPS3.
69
Rouxel J. Brec R. Low-Dimensional Chalcogenides as Secondary Cathodic Materials: Some Geometric and Electronic Aspects Annu. Rev. Mater. Sci. 1986 16 1 137 162
Google Scholar
69
Low-dimensional chalcogenides as secondary cathodic materials: some geometric and electronic aspects
Rouxel, J.; Brec, R.
Annual Review of Materials Science (1986), 16 (), 137-62CODEN: ARMSCX; ISSN:0084-6600.
A review with 45 refs. on electronic and ionic cond. and reversibility of the title cathodic materials for batteries. The geometric aspects assocd. with intercalation (parameter expansion, long distance, and local structures), electronic transfer, and phase transitions are analyzed.
70
Li X. Wu X. Yang J. Half-Metallicity in MnPSe₃ Exfoliated Nanosheet with Carrier Doping J. Am. Chem. Soc. 2014 136 31 11065 11069
Google Scholar
70
Half-Metallicity in MnPSe3 Exfoliated Nanosheet with Carrier Doping
Li, Xingxing; Wu, Xiaojun; Yang, Jinlong
Journal of the American Chemical Society (2014), 136 (31), 11065-11069CODEN: JACSAT; ISSN:0002-7863. (American Chemical Society)
Searching two-dimensional (2D) half-metallic crystals that are feasible in expt. is essential to develop next-generation nanospintronic devices. Here, a 2-dimensional exfoliated MnPSe3 nanosheet with novel magnetism is 1st proposed based on 1st-principles calcns. In particular, the evaluated low cleavage energy and high in-plane stiffness indicate that the free-standing MnPSe3 nanosheet can be exfoliated from its bulk structure in expt. The MnPSe3 nanosheet is an antiferromagnetic semiconductor at its ground state, whereas both electron and hole doping induce its transition from antiferromagnetic semiconductor to ferromagnetic half-metal. Also, the spin-polarization directions of 2-dimensional half-metallic MnPSe3 are opposite for electron and hole doping, which can be controlled by applying an external voltage gate. The Monte Carlo simulation based on the Ising model suggests the Curie temp. of the doped 2-dimensional MnPSe3 crystal is up to 206 K. These advantages render the 2-dimensional MnPSe3 crystal with great potentials for application in elec.-field controlled spintronic devices.
71
Cabria I. El-Meligi A. A. DFT Simulation of Hydrogen Storage on Manganese Phosphorous Trisulphide (MnPS₃) Int. J. Hydrogen Energy 2018 43 11 5903 5912
Google Scholar
71
DFT simulation of hydrogen storage on manganese phosphorous trisulfide (MnPS3)
Cabria, I.; El-Meligi, A. A.
International Journal of Hydrogen Energy (2018), 43 (11), 5903-5912CODEN: IJHEDX; ISSN:0360-3199. (Elsevier Ltd.)
Manganese phosphorous trisulfide, MnPS3, is a solid layered material. The H2 gravimetric storage capacity of powd. MnPS3 at 80.15, 173.15, and 298.15° K and at moderate pressures was recently exptl. measured. The origin of storage capacity of this material is not well understood. The main hypothesis is that H2 is stored in powd. MnPS3 pores. Pores were modeled as two parallel MnPS3 layers sepd. by a certain distance. D. functional theory (DFT) simulations of the H2 interaction with the MnPS3 layer surface were performed to test this hypothesis. Simulations indicated H2 adsorption on the MnPS3 layer surface was energetically favorable, but only by a physisorption mechanism. Gravimetric capacity calcns. of powd. MnPS3 pores were also performed and were in reasonable agreement with exptl. results. A comparison of calcd. and exptl. gravimetric capacity showed that H2 storage on powd. MnPS3 was mainly due to in-pore compression; the contribution of the physisorption process to storage was very small.
72
Kuzminskii Y. V. Voronin B. M. Redin N. N. Iron and Nickel Phosphorus Trisulfides as Electroactive Materials for Primary Lithium Batteries J. Power Sources 1995 55 2 133 141
Google Scholar
72
Iron and nickel phosphorus trisulfides as electroactive materials for primary lithium batteries
Kuzminskii, Y. V.; Voronin, B. M.; Redin, N. N.
Journal of Power Sources (1995), 55 (2), 133-41CODEN: JPSODZ; ISSN:0378-7753. (Elsevier)
The theor. specific capacities of a family of layered compds. MPX3 (M = Fe, Co, Ni; X = S, Se) for current-producing reactions involving 1.5, 2, 6 and 9 lithium atoms per MPX3 mol. have been estd. These data show that FePS3 and NiPS3 are good electroactive materials for primary lithium cells. Conditions which allow one to shorten substantially the synthesis time of iron and nickel phosphorus trisulfides in ampules are presented. According to cond. measurements in the 293-673 K temp. range, NiPS3 is an intrinsic and FePS3 an extrinsic semiconductor. The discharge characteristics of Li/MPS3 (M = Fe, Ni) cells with an org. electrolyte have been studied; they confirmed that the participation of nine electrons in the redox process is possible. For a primary button cell of the std. size 2325, with a FePS3 cathode, the specific capacity and specific energy values obtained in a discharge 1.8-1.2 V range at load resistances of 3.0 to 30 kΩ were 500-1160 Ah/kg and 700-1770 Wh/kg (on a pure FePS3 basis), resp.
73
Kuzminskii Y. V. Voronin B. M. Petrushina I. M. Redin N. N. Prikhodko G. P. Nickel Phosphorus Trisulfide: An Electroactive Material for Medium-Temperature Lithium Batteries J. Power Sources 1995 55 1 1 6
Google Scholar
There is no corresponding record for this reference.
74
Liang Q. Zheng Y. Du C. Luo Y. Zhang J. Li B. Zong Y. Yan Q. General and Scalable Solid-State Synthesis of 2D MPS₃ (M = Fe, Co, Ni) Nanosheets and Tuning Their Li/Na Storage Properties Small Methods 2017 1 12 1700304
Google Scholar
There is no corresponding record for this reference.
75
Fujii Y. Miura A. Rosero-Navarro N. C. Higuchi M. Tadanaga K. FePS₃ Electrodes in All-Solid-State Lithium Secondary Batteries Using Sulfide-Based Solid Electrolytes Electrochim. Acta 2017 241 370 374
Google Scholar
75
FePS3 electrodes in all-solid-state lithium secondary batteries using sulfide-based solid electrolytes
Fujii, Yuta; Miura, Akira; Rosero-Navarro, Nataly Carolina; Higuchi, Mikio; Tadanaga, Kiyoharu
Electrochimica Acta (2017), 241 (), 370-374CODEN: ELCAAV; ISSN:0013-4686. (Elsevier Ltd.)
In bulk-type all-solid-state Li batteries with sulfide-based solid electrolytes, composite electrodes, in which an active material, a solid electrolyte, and a conductive additive are mixed, were used to enhance Li-ion diffusion and electronic cond. However, the addn. of electrolytes and electron-conductive additives to the composite electrodes decreases the amt. of active materials in the batteries. FePS3 was employed as the electrode in an all-solid-state Li secondary battery, without mixing the solid electrolytes and conductive additives. The all-solid-state cell using the FePS3 electrode exhibited reversible charge-discharge behavior for >30 cycles under a const. c.d. of 0.13 mA cm-2 at room temp. The discharge capacity of the cell was 107 mAh g-1 at the 30th cycle. This behavior was comparable to that of a cell with an electrode including a solid electrolyte and/or a conductive additive, indicating that the FePS3 electrode had sufficient paths of Li ions and of electron conduction. Probably FePS3 is an attractive Fe-based electrode for an all-solid-state battery using a sulfide-based solid electrolyte.
76
Liang Q. Zheng Y. Du C. Luo Y. Zhao J. Ren H. Xu J. Yan Q. Asymmetric-Layered Tin Thiophosphate: An Emerging 2D Ternary Anode for High-Performance Sodium Ion Full Cell ACS Nano 2018 12 12 12902 12911
Google Scholar
76
Asymmetric-Layered Tin Thiophosphate: An Emerging 2D Ternary Anode for High-Performance Sodium Ion Full Cell
Liang, Qinghua; Zheng, Yun; Du, Chengfeng; Luo, Yubo; Zhao, Jin; Ren, Hao; Xu, Jianwei; Yan, Qingyu
ACS Nano (2018), 12 (12), 12902-12911CODEN: ANCAC3; ISSN:1936-0851. (American Chemical Society)
The emerging Na ion batteries (SIBs) are believed to be prospective substitutes for Li ion batteries (LIBs) because of the wide distribution of Na resources. However, to compensate for the sluggish reaction kinetics and higher intrinsic potential of Na+ compared to Li+, cost-effective, reliable, and sustainable electrode materials must be explored for practical applications. Here, 2D ternary tin thiophosphate (SnP2S6) nanosheets (∼10 nm thickness) grown on graphene (denoted as SPS/G hybrid) are demonstrated as intriguing anodes for SIBs. The asym.-layered structure and ternary compn. enable the SPS/G hybrid with a high reversible capacity (1230 mAh/g at 50 mA/g), superior rate capability (200 mAh/g at 15 A/g), and an exceptional capacity retention of 76% after 1000 cycles at 2.0 A/g. A prototype Na-ion full cell constructed by pairing with the Na3V2O2(PO4)3F cathode affords a high capacity of 470 mAh/g at 30 mA/g (on the basis of anode wt.) and good cyclic capacity of 360 mAh/g at 150 mA/g. Such 2D ternary chalcogenides with low-cost elements are promising materials for superior SIBs.
77
Brec, R. , Review on Structural and Chemical Properties of Transition Metal Phosphorus Trisulfides MPS₃. In Intercalation in Layered Materials; Dresselhaus, M. S. , Ed.; Springer US: Boston, MA, 1986; pp 93− 124.
Google Scholar
There is no corresponding record for this reference.
78
Clement R. P. Garnier O. Jegoudez J. Coordination Chemistry of the Lamellar MPS₃ Materials: Metal-Ligand Cleavage as the Source of an Unusual Cation-Transfer Intercalation Process Inorg. Chem. 1986 25 1404 1409
Google Scholar
78
Coordination chemistry of the lamellar MPS3 materials: metal-ligand cleavage as the source of an unusual "cation-transfer" intercalation process
Clement, Rene; Garnier, Odile; Jegoudez, Jocelyne
Inorganic Chemistry (1986), 25 (9), 1404-9CODEN: INOCAJ; ISSN:0020-1669.
Several MPS3 lamellar materials exhibit a very unusual intercalation chem. based on a cation-transfer process between the solid and a solvent. This contrasts with the electron-transfer processes that governs the intercalation chem. of the layered dichalcogenides MX2. Although the MPS3 layers are made up of infinite arrays of P2S64- units coordinated to the M2+ cations, the metal-ligand (M-S) bonding still exhibits enough lability to allow the M2+ cations to jump, under very mild conditions, from intra- toward interlamellar sites (or the opposite) and even to be removed from the material, provided a suitable cation is available to intercalate the lattice and maintain elec. neutrality. Depending on the metal, the solvent, and the guest species, the reaction may take place spontaneously or require an assist, usually by complexing the leaving M2+ cations (EDTA). Small inserted ions (Na+, K+, etc.) are strongly solvated and mobile, and they can in turn be exchanged. To rationalize this behavior, it is suggested that the intercalation chem. of the MPS3 involves a chem. transformation of the whole of the material, rather than a diffusional process of the guest species within the host lattice. The MPS3 layered materials are considered as polynuclear complexes that can undergo heterogeneous equil. with their constitutive species M2+ and P2S64- and other species present in soln. In support of this mechanism, MPS3 materials were successfully prepd. by mixing aq. solns. of Na4P2S6 and transition-metal salts. Some implications of this mechanism are discussed.
79
Wang F. He J. Speeding Protons with Metal Vacancies Science 2020 370 6516 525 526
Google Scholar
79
Speeding protons with metal vacancies
Wang, Fengmei; He, Jun
Science (Washington, DC, United States) (2020), 370 (6516), 525-526CODEN: SCIEAS; ISSN:1095-9203. (American Association for the Advancement of Science)
Proton exchange membranes (PEMs) find applications not only in fuel cells and sensors but as chem. filters and in biol. systems. In particular, the Nafion (Chemours Company) PEM, which consists of sulfonated tetrafluoroethylene-based fluoropolymer-copolymer, is widely used in practical electrochem. processes. It has a high proton cond. up to 0.2 S/cm below 80°C and high relative humidity (RH) (>93%), but its cond. drops severely at higher temps. or at low RH (below 50%). On page 596 of this issue, Qian et al. report a new class of proton membranes assembled from two-dimensional (2D) layered transition-metal phosphorus trichalcogenide (TMPTC) nanosheets in which metal vacancies boost ion cond. These membranes exhibit a proton cond. of ∼0.95 S/cm at 90°C and 98% RH but still have a cond. of 0.26 S/cm even at 60% RH.

Figure 1
Figure 1. (a) The metal atoms and their valence states constituted in MPX₃ crystals across the periodic table of elements. Filled blocks represent elements for which the layered MPX₃ structure has been reported. (b) Schematic structure of MPX₃ with [P₂X₆]^4- bipyramids enclosing the metal atoms. The X layers are distinguished through X_top and X_bottom.
High Resolution Image
Download MS PowerPoint Slide
Figure 2
Figure 2. (a) Schematic illustration of the CVT approach. (b-h) the digital images for the resulting MPX₃ crystal.
High Resolution Image
Download MS PowerPoint Slide
Reproduced with permission from ref ( 19). Copyright 2016, American Chemical Society.
Figure 3
Figure 3. (a) Schematic illustration for space confined chemical vapor conversion process. (b) AFM images of MPX₃ nanosheets grown via this method ( 11, 24, 26, 27).
High Resolution Image
Download MS PowerPoint Slide
Figure 4
Figure 4. The VB maximum and CB minimum positions of various MPX₃ monolayers calculated using HSE06 functional in DFT calculations, as well as the redox potentials (V vs Normal Hydrogen Electrode (NHE)) for water splitting and CO₂ reduction at pH = 7 ( 2, 4, 43, 44).
High Resolution Image
Download MS PowerPoint Slide
Figure 5
Figure 5. Photocatalytic CO₂ reduction on bilayer CuInP₂S₆ with schematic type-II band diagram.
High Resolution Image
Download MS PowerPoint Slide
Reproduced with permission from ref ( 51). Copyright 2021, American Chemical Society.
Figure 6
Figure 6. Electrocatalytic HER activity on NiPS₃/Ni₂P electrode. a-b) Comparison of the linear sweep voltammetry profiles (a) and the corresponding Tafel plots (b) for the as-grown NiPS₃, Ni₂P, NiPS₃/Ni₂P electrodes. c) the Gibbs energy profile for H adsorption (ΔG_H*) obtained at the equilibrium potential (U = 0 V) for the as-grown NiPS₃/Ni₂P, Ni₂P (001), Ni₂P (110), and NiPS₃ (110). d) Charge density difference at the heterointerfaces between NiPS₃ and Ni₂P. The electron accumulation and depletion are marked with red and green, respectively. The grey, yellow, purple, and blue colors represent Ni, S, P, and H atoms, which are marked in, respectively.
High Resolution Image
Download MS PowerPoint Slide
Reproduced with permission from ref ( 57). Copyright 2019, American Chemical Society.
Figure 7
Figure 7. (a) Overview of the primary pathways for CO₂RR towards different products. b-c) Electrocatalytic CO₂RR for different products at different potentials over Fe₂P₂S₆ nanosheets (b), and optimized adsorption of CO₂ molecular over Fe₂P₂S₆ surface (c), in which red and blue regions represent positive and negative charges, respectively.
High Resolution Image
Download MS PowerPoint Slide
Reproduced with permission from ref ( 65). Copyright 2019, American Chemical Society.
Figure 8
Figure 8. Expansion Δc/n in Li host intercalates as a function of the initial width of the van der Waals gap ( 69, 70, 71).
High Resolution Image
Download MS PowerPoint Slide
Figure 9
Figure 9. Electrochemical performance of NiPS₃ nanosheet electrode used for Li-ion battery. (a) Cyclic voltammetric curves for the first four cycles at 0.1 mV/s. (b) The representative galvanostatic charge-discharge profiles for the four cycles at 0.05 A/g.
High Resolution Image
Download MS PowerPoint Slide
Reproduced with permission from ref ( 74). Copyright 2017, Wiley-VCH.
Figure 10
Figure 10. Ion-exchange property in layered CdPS₃ material as proton exchange membrane.
High Resolution Image
Download MS PowerPoint Slide
Reproduced with permission from ref ( 79). Copyright 2020, Science.
References
CHAPTER SECTIONS
Jump To
This chapter references 79 other publications.
1. 1
  Chittari B. L. Park Y. Lee D. Han M. MacDonald A. H. Hwang E. Jung J. Electronic and Magnetic Properties of Single-Layer MPX₃ Metal Phosphorous Trichalcogenides Phys. Rev. B 2016 94 18 184428
  1
  Electronic and magnetic properties of single-layer MPX3 metal phosphorous trichalcogenides
  Chittari, Bheema Lingam; Park, Youngju; Lee, Dongkyu; Han, Moonsup; MacDonald, Allan H.; Hwang, Euyheon; Jung, Jeil
  Physical Review B (2016), 94 (18), 184428/1-184428/16CODEN: PRBHB7; ISSN:2469-9950. (American Physical Society)
  We survey the electronic structure and magnetic properties of two-dimensional (2D) MPX3 (M=V,Cr,Mn,Fe,Co,Ni,Cu,Zn, and X=S,Se,Te) transition-metal chalcogenophosphates to shed light on their potential role as single-layer van der Waals materials that possess magnetic order. Our ab initio calcns. predict that most of these single-layer materials are antiferromagnetic semiconductors. The band gaps of the antiferromagnetic states decrease as the at. no. of the chalcogen atom increases (from S to Se to Te), leading in some cases to half-metallic ferromagnetic states or to nonmagnetic metallic states. We find that the competition between antiferromagnetic and ferromagnetic states can be substantially influenced by gating and by strain engineering. The sensitive interdependence we find between magnetic, structural, and electronic properties establishes the potential of this 2D materials class for applications in spintronics.
2. 2
  Susner M. A. Chyasnavichyus M. McGuire M. A. Ganesh P. Maksymovych P. Metal Thio- and Selenophosphates as Multifunctional van der Waals Layered Materials Adv. Mater. 2017 29 38 1602852
  There is no corresponding record for this reference.
3. 3
  Samal R. Sanyal G. Chakraborty B. Rout C. S. Two-Dimensional Transition Metal Phosphorous Trichalcogenides (MPX₃): A Review on Emerging Trends, Current State and Future Perspectives J. Mater. Chem. A 2021 9 5 2560 2591
  3
  Two-dimensional transition metal phosphorous trichalcogenides (MPX3): a review on emerging trends, current state and future perspectives
  Samal, Rutuparna; Sanyal, Gopal; Chakraborty, Brahmananda; Rout, Chandra Sekhar
  Journal of Materials Chemistry A: Materials for Energy and Sustainability (2021), 9 (5), 2560-2591CODEN: JMCAET; ISSN:2050-7496. (Royal Society of Chemistry)
  A review. Profound scientific attention has been devoted to the expansive family of functional 2D materials soon after the isolation of graphene and the discovery of Dirac physics. Of particular note, the re-emergence of layer architecture metal thio(seleno) phosphate materials (MPX3, X = S, Se) materials with appreciable tunability in dimension and proximity on correlated ground states opened novel potential avenues for the ultimate theor. (structural, magnetic) and realistic research. The wide spanned bandgap of 1.2-3.5 eV harnessed multifarious fundamental magnetic, electronic, ferroelec., optical, intercalation properties and their prominent implementation in a plethora of applications, such as Li-ion batteries, field-effect transistors, visible and UV photodetectors, photo-electrochem. reactions and hydrogen (H2) storage. This review examines many of the scarcely touched aspects, such as multiple Dirac cones, vibrational properties, and responses in the presence of strain of MPX3 materials. In addn., the latest advancement in the emergent applications, physiochem. properties and assorted growth methodologies considering the palpable vol. of research has been explored in detail in order to bring across a more complete discussion and outlook. We strongly believe that this review will be very handy for researchers working in various branches of science and engineering, such as physics, chem., materials science, and chem. engineering.
4. 4
  Wang F. Shifa T. A. Yu P. He P. Liu Y. Wang F. Wang Z. Zhan X. Lou X. Xia F. He J. New Frontiers on van der Waals Layered Metal Phosphorous Trichalcogenides Adv. Funct. Mater. 2018 28 37 1802151
  There is no corresponding record for this reference.
5. 5
  Friedel M. C. Soufre et ses composés—sur une nouvelle série de sulfophosphures, les thiohypophosphates CR l’Academie. Sci. Ser 1894 3 119 260
  There is no corresponding record for this reference.
6. 6
  Ouvrard G. Brec R. Rouxel J. Structural determination of some MPS₃ layered phases (M = Mn, Fe, Co, Ni and Cd) Mater. Res. Bull. 1985 20 1181 1189
  6
  Structural determination of some MPS3 layered phases (M = Mn, Fe, Co, Ni and Cd)
  Ouvrard, G.; Brec, R.; Rouxel, J.
  Materials Research Bulletin (1985), 20 (10), 1181-9CODEN: MRBUAC; ISSN:0025-5408.
  The structures of most of the MPS3 phases (M = Mn, Fe, Co, Ni, Cd) were detd. from single-crystal anal. They show the expected CdCl2 structural type, some weak disorder on the cationic sites being detected on NiPS3 and CoPS3. Fair stoichiometry is inferred for the phases since no interslab cation could be seen in the Van der Waals' gap of the structures. Polytypism may occur in NiPS3. At. parameters are given.
7. 7
  Hwangbo K. Zhang Q. Jiang Q. Wang Y. Fonseca J. Wang C. Diederich G. M. Gamelin D. R. Xiao D. Chu J. H. Yao W. Xu X. Highly Anisotropic Excitons and Multiple Phonon Bound States in a van der Waals Antiferromagnetic Insulator Nat. Nanotechnol. 2021 16 6 655 660
  7
  Highly anisotropic excitons and multiple phonon bound states in a van der Waals antiferromagnetic insulator
  Hwangbo, Kyle; Zhang, Qi; Jiang, Qianni; Wang, Yong; Fonseca, Jordan; Wang, Chong; Diederich, Geoffrey M.; Gamelin, Daniel R.; Xiao, Di; Chu, Jiun-Haw; Yao, Wang; Xu, Xiaodong
  Nature Nanotechnology (2021), 16 (6), 655-660CODEN: NNAABX; ISSN:1748-3387. (Nature Portfolio)
  Two-dimensional (2D) semiconductors enable the investigation of light-matter interactions in low dimensions1,2. Yet, the study of elementary photoexcitations in 2D semiconductors with intrinsic magnetic order remains a challenge due to the lack of suitable materials3,4. Here, we report the observation of excitons coupled to zigzag antiferromagnetic order in the layered antiferromagnetic insulator NiPS3. The exciton exhibits a narrow photoluminescence linewidth of roughly 350μeV with near-unity linear polarization. When we reduce the sample thickness from five to two layers, the photoluminescence is suppressed and eventually vanishes for the monolayer. This suppression is consistent with the calcd. bandgap of NiPS3, which is highly indirect for both the bilayer and the monolayer5. Furthermore, we observe strong linear dichroism (LD) over a broad spectral range. The optical anisotropy axes of LD and of photoluminescence are locked to the zigzag direction. Furthermore, their temp. dependence is reminiscent of the in-plane magnetic susceptibility anisotropy. Hence, our results indicate that LD and photoluminescence could probe the symmetry breaking magnetic order parameter of 2D magnetic materials. In addn., we observe over ten exciton-A1g-phonon bound states on the high-energy side of the exciton resonance, which we interpret as signs of a strong modulation of the ligand-to-metal charge-transfer energy by electron-lattice interactions. Our work establishes NiPS3 as a 2D platform for exploring magneto-exciton physics with strong correlations.
8. 8
  Kang S. Kim K. Kim B. H. Kim J. Sim K. I. Lee J. U. Lee S. Park K. Yun S. Kim T. Nag A. Walters A. Garcia-Fernandez M. Li J. Chapon L. Zhou K. J. Son Y. W. Kim J. H. Cheong H. Park J. G. Coherent Many-Body Exciton in van der Waals Antiferromagnet NiPS₃ Nature 2020 583 7818 785 789
  8
  Coherent many-body exciton in van der Waals antiferromagnet NiPS3
  Kang, Soonmin; Kim, Kangwon; Kim, Beom Hyun; Kim, Jonghyeon; Sim, Kyung Ik; Lee, Jae-Ung; Lee, Sungmin; Park, Kisoo; Yun, Seokhwan; Kim, Taehun; Nag, Abhishek; Walters, Andrew; Garcia-Fernandez, Mirian; Li, Jiemin; Chapon, Laurent; Zhou, Ke-Jin; Son, Young-Woo; Kim, Jae Hoon; Cheong, Hyeonsik; Park, Je-Geun
  Nature (London, United Kingdom) (2020), 583 (7818), 785-789CODEN: NATUAS; ISSN:0028-0836. (Nature Research)
  Abstr.: An exciton is the bosonic quasiparticle of electron-hole pairs bound by the Coulomb interaction. Bose-Einstein condensation of this exciton state has long been the subject of speculation in various model systems2,3, and examples have been found more recently in optical lattices and two-dimensional materials4-9. Unlike these conventional excitons formed from extended Bloch states4-9, excitonic bound states from intrinsically many-body localized states are rare. Here we show that a spin-orbit-entangled exciton state appears below the Neel temp. of 150 K in NiPS3, an antiferromagnetic van der Waals material. It arises intrinsically from the archetypal many-body states of the Zhang-Rice singlet10,11, and reaches a coherent state assisted by the antiferromagnetic order. Using configuration-interaction theory, we det. the origin of the coherent excitonic excitation to be a transition from a Zhang-Rice triplet to a Zhang-Rice singlet. We combine three spectroscopic tools-resonant inelastic X-ray scattering, photoluminescence and optical absorption-to characterize the exciton and to demonstrate an extremely narrow excitonic linewidth below 50 K. The discovery of the spin-orbit-entangled exciton in antiferromagnetic NiPS3 introduces van der Waals magnets as a platform to study coherent many-body excitons.
9. 9
  Joy P. A. Vasudevan S. Magnetism in the Layered Transition-Metal Thiophosphates MPS₃ (M=Mn, Fe, and Ni) Phys. Rev. B 1992 46 9 5425 5433
  9
  Magnetism in the layered transition-metal thiophosphates MPS3 (M = manganese, iron, and nickel)
  Joy, P. A.; Vasudevan, S.
  Physical Review B: Condensed Matter and Materials Physics (1992), 46 (9), 5425-33CODEN: PRBMDO; ISSN:0163-1829.
  Anisotropic magnetic susceptibilities of single crystals of the layered transition-metal thiophosphates MnPS3, FePS3, and NiPS3 have been measured as a function of temp. The materials order antiferromagnetically at low temps., the Neel temps. being 78, 123, and 155 K, resp. In the ordered state, the magnetization axis lies perpendicular to the layers of MnPS3 and FePS3, while for NiPS3 it lies in the layer. In the paramagnetic regime, the anisotropies of these compds. are different; while the susceptibility for MnPS3 is isotropic and that for NiPS3 shows only a weak anisotropy, FePS3 exhibits highly anisotropic susceptibility. The anisotropic susceptibilities have been analyzed to obtain information on the state of the magnetic ions and the nature of magnetic interactions between them. The results show that MnPS3, FePS3, and NiPS3 form a unique class of compds. Although all three compds. are isostructural with the magnetic lattice being the two-dimensional honeycomb, the spin dimensionalities for the three are different. While MnPS3 is best described by the isotropic Heisenberg Hamiltonian, FePS3 is most effectively treated by the Ising model and NiPS3 by the anisotropic Heisenberg Hamiltonian. The origin of the anisotropy in these compds. has been discussed, and it is shown how it arises from a combination of spin-orbit coupling and the trigonal distortion of the MS6 octahedra. The magnetic exchange const., J and the zero-field splitting energies of the ground state of the transition-metal ion have been evaluated from the anisotropic paramagnetic susceptibilities.
10. 10
  Wildes A. R. Simonet V. Ressouche E. McIntyre G. J. Avdeev M. Suard E. Kimber S. A. J. Lançon D. Pepe G. Moubaraki B. Hicks T. J. Magnetic Structure of the Quasi-Two-Dimensional Antiferromagnet NiPS₃ Phys. Rev. B 2015 92 22 224408
  10
  Magnetic structure of the quasi-two-dimensional antiferromagnet NiPS3
  Wildes, A. R.; Simonet, V.; Ressouche, E.; McIntyre, G. J.; Avdeev, M.; Suard, E.; Kimber, S. A. J.; Lancon, D.; Pepe, G.; Moubaraki, B.; Hicks, T. J.
  Physical Review B: Condensed Matter and Materials Physics (2015), 92 (22), 224408/1-224408/11CODEN: PRBMDO; ISSN:1098-0121. (American Physical Society)
  The magnetic structure of the quasi-two-dimensional antiferromagnet NiPS3 has been detd. by magnetometry and a variety of neutron diffraction techniques. The expts. show that the samples must be carefully handled, as gluing influences the magnetometry measurements while preferred orientation complicates the interpretation of powder diffraction measurements. Our global set of consistent measurements show numerous departures from previously published results. We show that the compd. adopts a k = [010] antiferromagnetic structure with the moment directions mostly along the a axis, and that the paramagnetic susceptibility is isotropic. The crit. behavior was also investigated through the temp. dependence of the magnetic Bragg peaks below the N´eel temp.
11. 11
  Wang F. Mathur N. Janes A. N. Sheng H. He P. Zheng X. Yu P. DeRuiter A. J. Schmidt J. R. He J. Jin S. Defect-Mediated Ferromagnetism in Correlated Two-Dimensional Transition Metal Phosphorus Trisulfides Sci. Adv. 2021 7 43 eabj4086
  There is no corresponding record for this reference.
12. 12
  Wang X. Cao J. Lu Z. Cohen A. Kitadai H. Li T. Tan Q. Wilson M. Lui C. H. Smirnov D. Sharifzadeh S. Ling X. Spin-Induced Linear Polarization of Photoluminescence in Antiferromagnetic van der Waals Crystals Nat. Mater. 2021 20 7 964 970
  12
  Spin-induced linear polarization of photoluminescence in antiferromagnetic van der Waals crystals
  Wang, Xingzhi; Cao, Jun; Lu, Zhengguang; Cohen, Arielle; Kitadai, Hikari; Li, Tianshu; Tan, Qishuo; Wilson, Matthew; Lui, Chun Hung; Smirnov, Dmitry; Sharifzadeh, Sahar; Ling, Xi
  Nature Materials (2021), 20 (7), 964-970CODEN: NMAACR; ISSN:1476-1122. (Nature Portfolio)
  Antiferromagnets are promising components for spintronics due to their terahertz resonance, multilevel states and absence of stray fields. However, the zero net magnetic moment of antiferromagnets makes the detection of the antiferromagnetic order and the investigation of fundamental spin properties notoriously difficult. Here, we report an optical detection of Neel vector orientation through an ultra-sharp photoluminescence in the van der Waals antiferromagnet NiPS3 from bulk to atomically thin flakes. The strong correlation between spin flipping and elec. dipole oscillator results in a linear polarization of the sharp emission, which aligns perpendicular to the spin orientation in the crystal. By applying an in-plane magnetic field, we achieve manipulation of the photoluminescence polarization. This correlation between emitted photons and spins in layered magnets provides routes for investigating magneto-optics in two-dimensional materials, and hence opens a path for developing opto-spintronic devices and antiferromagnet-based quantum information technologies.
13. 13
  Kim K. Lim S. Y. Lee J. U. Lee S. Kim T. Y. Park K. Jeon G. S. Park C. H. Park J. G. Cheong H. Suppression of Magnetic Ordering in XXZ-Type Antiferromagnetic Monolayer NiPS₃ Nat. Commun. 2019 10 1 345
  13
  Suppression of magnetic ordering in XXZ-type antiferromagnetic monolayer NiPS3
  Kim Kangwon; Lim Soo Yeon; Lee Jae-Ung; Cheong Hyeonsik; Lee Sungmin; Park Kisoo; Park Je-Geun; Lee Sungmin; Kim Tae Yun; Park Kisoo; Park Cheol-Hwan; Park Je-Geun; Kim Tae Yun; Park Cheol-Hwan; Jeon Gun Sang
  Nature communications (2019), 10 (1), 345 ISSN:.
  How a certain ground state of complex physical systems emerges, especially in two-dimensional materials, is a fundamental question in condensed-matter physics. A particularly interesting case is systems belonging to the class of XY Hamiltonian where the magnetic order parameter of conventional nature is unstable in two-dimensional materials leading to a Berezinskii-Kosterlitz-Thouless transition. Here, we report how the XXZ-type antiferromagnetic order of a magnetic van der Waals material, NiPS3, behaves upon reducing the thickness and ultimately becomes unstable in the monolayer limit. Our experimental data are consistent with the findings based on renormalization-group theory that at low temperatures a two-dimensional XXZ system behaves like a two-dimensional XY one, which cannot have a long-range order at finite temperatures. This work provides the experimental examination of the XY magnetism in the atomically thin limit and opens opportunities of exploiting these fundamental theorems of magnetism using magnetic van der Waals materials.
14. 14
  Belianinov A. He Q. Dziaugys A. Maksymovych P. Eliseev E. Borisevich A. Morozovska A. Banys J. Vysochanskii Y. Kalinin S. V. CuInP₂S₆ Room Temperature Layered Ferroelectric Nano Lett. 2015 15 6 3808 3814
  14
  CuInP2S6 Room Temperature Layered Ferroelectric
  Belianinov, A.; He, Q.; Dziaugys, A.; Maksymovych, P.; Eliseev, E.; Borisevich, A.; Morozovska, A.; Banys, J.; Vysochanskii, Y.; Kalinin, S. V.
  Nano Letters (2015), 15 (6), 3808-3814CODEN: NALEFD; ISSN:1530-6984. (American Chemical Society)
  The authors explore ferroelec. properties of cleaved 2-dimensional flakes of copper indium thiophosphate, CuInP2S6 (CITP), and probe size effects along with limits of ferroelec. phase stability, by ambient and ultra high vacuum scanning probe microscopy. CITP belongs to the only material family known to display ferroelec. polarization in a van der Waals, layered crystal at room temp. and above. The authors' measurements directly reveal stable, ferroelec. polarization as evidenced by domain structures, switchable polarization, and hysteresis loops. At room temp. the domain structure of flakes thicker than 100 nm is similar to the cleaved bulk surfaces, whereas <50 nm polarization disappears. The authors ascribe this behavior to a known instability of polarization due to depolarization field. Also, polarization switching at high bias is also assocd. with ionic mobility, as evidenced both by macroscopic measurements and by formation of surface damage under the tip at a bias of 4 V-likely due to copper redn. Mobile Cu ions may therefore also contribute to internal screening mechanisms. The existence of stable polarization in a van-der-Waals crystal naturally points toward new strategies for ultimate scaling of polar materials, quasi-2D, and single-layer materials with advanced and nonlinear dielec. properties that are presently not found in any members of the growing graphene family.
15. 15
  Dziaugys A. Banys J. Macutkevic J. Sobiestianskas R. Vysochanskii Y. Dipolar Glass Phase in Ferrielectrics: CuInP₂S₆ and Ag_0.1Cu_0.9InP₂S₆ Crystals Phys. Status Solidi A 2010 207 8 1960 1967
  15
  Dipolar glass phase in ferrielectrics: CuInP2S6 and Ag0.1Cu0.9InP2S6 crystals
  Dziaugys, Andrius; Banys, Juras; Macutkevic, Jan; Sobiestianskas, Ricardas; Vysochanskii, Yulian
  Physica Status Solidi A: Applications and Materials Science (2010), 207 (8), 1960-1967CODEN: PSSABA; ISSN:1862-6300. (Wiley-VCH Verlag GmbH & Co. KGaA)
  The dielec. properties of CuInP2S6 and Ag0.1Cu0.9InP2S6 crystals were investigated in wide frequency (20 Hz-3 GHz) and temp. ranges (25-360 K). The low frequencies dielec. spectra at high temps. are highly influenced by the high ionic cond. The temp. dependences of the static dielec. permittivity and the mean relaxation time reveal the first order order-disorder ferrielec. phase transition at Tc = 288 K in Ag0.1Cu0.9InP2S6. The cond. and its activation energy exhibit only a weak change close to the ferrielec. phase transition temp. in both investigated crystals. The freezing phenomena in CuInP2S6 and Ag0.1Cu0.9InP2S6 revealed the complex dielec. permittivity behavior characteristic for transition into dipolar glass state.
16. 16
  Silipigni L. Schiro L. Scolaro L. M. De Luca G. Salvato G. Lithium Ions Conduction in Li_2xMn_1-xPS₃ Films Philos. Mag. 2014 94 35 4026 4036
  16
  Lithium ions conduction in Li2xMn1-xPS3 films
  Silipigni, L.; Schiro, L.; Monsu Scolaro, L.; De Luca, G.; Salvato, G.
  Philosophical Magazine (2014), 94 (35), 4026-4036CODEN: PMHABF; ISSN:1478-6435. (Taylor & Francis Ltd.)
  Li2xMn1-xPS3 films have been synthesized by exfoliating MnPS3 through the successive intercalations of K+ and Li+ ions. Their dielec. response has been measured from 80 to 350 K in the frequency range of (102-106) Hz. The obtained data have been analyzed in terms of both complex permittivity ε* and the ac cond. σac. The frequency dependence of σac has been interpreted in terms of the Jonscher's law, whose exponent n decreases by increasing temp. The n values lie between 0.479 and 0.501 and are typical of materials in which the ac cond. is due to multiple hops of carriers. By analyzing the σdc temp. dependence, the obsd. dielec. response has been attributed to the intercalated lithium ions, and the Li2xMn1-xPS3 films have been classified as hopping charge carrier systems.
17. 17
  Kuzminskii Y. V. Voronin B. M. Redin N. N. Iron and Nickel Phosphorus Trisulfides as Electroactive Materials for Primary Lithium Batteries J. Power Sources 1995 55 2 133 141
  17
  Iron and nickel phosphorus trisulfides as electroactive materials for primary lithium batteries
  Kuzminskii, Y. V.; Voronin, B. M.; Redin, N. N.
  Journal of Power Sources (1995), 55 (2), 133-41CODEN: JPSODZ; ISSN:0378-7753. (Elsevier)
  The theor. specific capacities of a family of layered compds. MPX3 (M = Fe, Co, Ni; X = S, Se) for current-producing reactions involving 1.5, 2, 6 and 9 lithium atoms per MPX3 mol. have been estd. These data show that FePS3 and NiPS3 are good electroactive materials for primary lithium cells. Conditions which allow one to shorten substantially the synthesis time of iron and nickel phosphorus trisulfides in ampules are presented. According to cond. measurements in the 293-673 K temp. range, NiPS3 is an intrinsic and FePS3 an extrinsic semiconductor. The discharge characteristics of Li/MPS3 (M = Fe, Ni) cells with an org. electrolyte have been studied; they confirmed that the participation of nine electrons in the redox process is possible. For a primary button cell of the std. size 2325, with a FePS3 cathode, the specific capacity and specific energy values obtained in a discharge 1.8-1.2 V range at load resistances of 3.0 to 30 kΩ were 500-1160 Ah/kg and 700-1770 Wh/kg (on a pure FePS3 basis), resp.
18. 18
  Qian X. Chen L. Yin L. Liu Z. Pei S. Li F. Hou G. Chen S. Song L. Thebo K. H. Cheng H. M. Ren W. CdPS₃ Nanosheets-Based Membrane with High Proton Conductivity Enabled by Cd Vacancies Science 2020 370 6516 596 600
  18
  CdPS3 nanosheets-based membrane with high proton conductivity enabled by Cd vacancies
  Qian, Xitang; Chen, Long; Yin, Lichang; Liu, Zhibo; Pei, Songfeng; Li, Fan; Hou, Guangjin; Chen, Shuangming; Song, Li; Thebo, Khalid Hussain; Cheng, Hui-Ming; Ren, Wencai
  Science (Washington, DC, United States) (2020), 370 (6516), 596-600CODEN: SCIEAS; ISSN:1095-9203. (American Association for the Advancement of Science)
  P transport in nanochannels under humid conditions is crucial for the application in energy storage and conversion. However, existing materials, including Nafion, suffer from limited cond. of up to 0.2 S per cm. The authors report a class of membranes assembled with 2-dimensional transition-metal P trichalcogenide nanosheets, in which the transition-metal vacancies enable exceptionally high ion cond. A Cd0.85PS3Li0.15H0.15 membrane exhibits a p conduction dominant cond. of ∼0.95 S per cm at 90°elsius and 98% relative humidity. This performance mainly originates from the abundant p donor centers, easy p desorption, and excellent hydration of the membranes induced by Cd vacancies. The authors also obsd. superhigh Li ion cond. in Cd0.85PS3Li0.3 and Mn0.77PS3Li0.46 membranes.
19. 19
  Du K. Z. Wang X. Z. Liu Y. Hu P. Utama M. I. Gan C. K. Xiong Q. Kloc C. Weak Van der Waals Stacking, Wide-Range Band Gap, and Raman Study on Ultrathin Layers of Metal Phosphorus Trichalcogenides ACS Nano 2016 10 2 1738 1743
  19
  Weak Van der Waals Stacking, Wide-Range Band Gap, and Raman Study on Ultrathin Layers of Metal Phosphorus Trichalcogenides
  Du, Ke-zhao; Wang, Xing-zhi; Liu, Yang; Hu, Peng; Utama, M. Iqbal Bakti; Gan, Chee Kwan; Xiong, Qihua; Kloc, Christian
  ACS Nano (2016), 10 (2), 1738-1743CODEN: ANCAC3; ISSN:1936-0851. (American Chemical Society)
  2D semiconducting metal phosphorus trichalcogenides, particularly the bulk crystals of MPS3 (M = Fe, Mn, Ni, Cd and Zn) sulfides and MPSe3 (M = Fe and Mn) selenides, have been synthesized, crystd. and exfoliated into monolayers. The Raman spectra of monolayer FePS3 and 3-layer FePSe3 show the strong intralayer vibrations and structural stability of the atomically thin layers under ambient condition. The band gaps can be adjusted by element choices in the range of 1.3-3.5 eV. The wide-range band gaps suggest their optoelectronic applications in a broad wavelength range. The calcd. cleavage energies of MPS3 are smaller than that of graphite. Therefore, the monolayers used for building of heterostructures by van der Waals stacking could be considered as the candidates for artificial 2D materials with unusual ferroelec. and magnetic properties.
20. 20
  Nitsche R. Wild P. Crystal Growth of Metal-Phosphorus-Sulfur Compounds by Vapor Transport Mater. Res. Bull. 1970 5 6 419 423
  20
  Crystal growth of metal-phosphorus-sulfur compounds by vapor transport
  Nitsche, Rudolf; Wild, Petr
  Materials Research Bulletin (1970), 5 (6), 419-23CODEN: MRBUAC; ISSN:0025-5408.
  Single crystals of the thiophosphates: Cu3PS4, InPS4, GaPS4, BiPS4 and the thiohypophosphates Sn2P2S6, Cd2P2S6, Fe2P2S6, and Mn2P2S6 were grown in sizes up to 10 mm by vapor transport with I. Lattice parameters and space groups are given.
21. 21
  Gusmao R. Sofer Z. Pumera M. Metal Phosphorous Trichalcogenides (MPCh₃ ): From Synthesis to Contemporary Energy Challenges Angew. Chem. Int. Ed. Engl. 2019 58 28 9326 9337
  21
  Metal Phosphorous Trichalcogenides (MPCh3 ): From Synthesis to Contemporary Energy Challenges
  Gusmao Rui; Sofer Zdenek; Pumera Martin
  Angewandte Chemie (International ed. in English) (2019), 58 (28), 9326-9337 ISSN:.
  Owing to their unique physical and chemical properties, layered two-dimensional (2D) materials have been established as the most significant topic in materials science for the current decade. This includes layers comprising mono-element (graphene, phosphorene), di-element (metal dichalcogenides), and even multi-element. A distinctive class of 2D layered materials is the metal phosphorous trichalcogenides (MPCh3 , Ch=S, Se), first synthesized in the late 1800s. Having an unusual intercalation behavior, MPCh3 were intensively studied in the 1970s for their magnetic properties and as secondary electrodes in lithium batteries, but fell from scrutiny until very recently, being 2D nanomaterials. Based on their synthesis and most significant properties, the present surge of reports related to water-splitting catalysis and energy storage are discussed in detail. This Minireview is intended as a baseline for the anticipated new wave of researchers who aim to explore these 2D layered materials for their electrochemical energy applications.
22. 22
  Gave M. A. Bilc D. Mahanti S. D. Breshears J. D. Kanatzidis M. G. On the Lamellar Compounds CuBiP₂Se₆, AgBiP₂Se₆ and AgBiP₂S₆. Antiferroelectric Phase Transitions due to Cooperative Cu⁺ and Bi³⁺ Ion Motion Inorg. Chem. 2005 44 15 5293 5303
  22
  On the Lamellar Compounds CuBiP2Se6, AgBiP2Se6 and AgBiP2S6. Antiferroelectric Phase Transitions Due to Cooperative Cu+ and Bi3+ Ion Motion
  Gave, Matthew A.; Bilc, Daniel; Mahanti, S. D.; Breshears, Jean D.; Kanatzidis, Mercouri G.
  Inorganic Chemistry (2005), 44 (15), 5293-5303CODEN: INOCAJ; ISSN:0020-1669. (American Chemical Society)
  CuBiP2Se6, AgBiP2Se6, and AgBiP2S6 were prepd. from the corresponding elements. CuBiP2Se6 and AgBiP2Se6 crystallize in the space group R‾3 with a 6.5532(16) and c 39.762(13) Å for CuBiP2Se6 and a 6.6524(13) and c 39.615(15) Å for AgBiP2Se6. AgBiP2S6 crystallizes in the triclinic space group P‾1 with a 6.3833(13), b 7.1439(14), c 9.5366(19) Å, α 91.89(3), β 91.45(3), γ 94.05(3)°. CuBiP2Se6 was found to exhibit a temp.-dependent antiferroelec. ordering of the Cu+ and Bi3+ ions in the lattice. An intermediate and a fully ordered structure were refined at 173 and 97 K, resp. Electronic band and total energy calcns. at the DFT level clearly suggest that the antiferroelec. model is energetically favored over the paraelec. and hypothetical ferrielec. models. This phase transition can be classified as a 2nd-order Jahn-Teller distortion. The antiferroelec. state of CuBiP2Se6 is an indirect gap semiconductor. The compds. were characterized with DTA and solid-state UV/visible diffuse reflectance spectroscopy. Generalized implications regarding the expected ferroelec. behavior of compds. in the CuMP2Se6 system (M = trivalent metal) are discussed.
23. 23
  Wang F. Shifa T. A. He P. Cheng Z. Chu J. Liu Y. Wang Z. Wang F. Wen Y. Liang L. He J. Two-Dimensional Metal Phosphorus Trisulfide Nanosheet with Solar Hydrogen-Evolving Activity Nano Energy 2017 40 673 680
  23
  Two-dimensional metal phosphorus trisulfide nanosheet with solar hydrogen-evolving activity
  Wang, Fengmei; Shifa, Tofik Ahmed; He, Peng; Cheng, Zhongzhou; Chu, Junwei; Liu, Yang; Wang, Zhenxing; Wang, Feng; Wen, Yao; Liang, Lirong; He, Jun
  Nano Energy (2017), 40 (), 673-680CODEN: NEANCA; ISSN:2211-2855. (Elsevier Ltd.)
  The development and utilization of photocatalysts to realize water-splitting without any external bias or sacrificial agents has received the limelight. As a novel two-dimensional layered material, metal phosphorus trichalcogenides (MPTs) cause wide research interest, presently. However, the growth of ultrathin two-dimensional MPT crystals is a great challenge to hinder their application. Here, we initially grow few-at. layered nickel phosphorus trisulfide (NiPS3) as promising photocatalyst for hydrogen evolution. The as-prepd. NiPS3 hexagonal nanosheet, as thin as few at. layers (≤ 3.5 nm), has lateral size of larger than 15 μm. These ultrathin NiPS3 crystals can directly generate hydrogen gas from pure water without any sacrificial agents under sunlight. With UV photoelectron spectrometer and electrochem. impedance spectroscopy, we show that the attractive photocatalytic activity of the ultrathin NiPS3 crystals arise from their appropriate positions of the band edges. This discovery is expected to make a contribution to develop next generation solar-fuel conversion catalysts for H2 prodn.
24. 24
  Yu P. Meng J. Wang F. Sendeku M. G. Wu B. Sui X. Gao N. Zhan X. Lou X. Wang Z. He J. Carbonate-Ion-Mediated Photogenerated Hole Transfer to Boost Hydrogen Production J. Phys. Chem. C 2022 126 25 10367 10377
  24
  Carbonate-Ion-Mediated Photogenerated Hole Transfer to Boost Hydrogen Production
  Yu, Peng; Meng, Jun; Wang, Fengmei; Sendeku, Marshet Getaye; Wu, Binglan; Sui, Xinyu; Gao, Ning; Zhan, Xueying; Lou, Xiaoding; Wang, Zhenxing; He, Jun
  Journal of Physical Chemistry C (2022), 126 (25), 10367-10377CODEN: JPCCCK; ISSN:1932-7447. (American Chemical Society)
  Sustainable and scalable H2 evolution through water photocatalysis is an attractive path for carbon-neutral energy supply; however, it is severely limited by sluggish charge sepn. and photocorrosion of semiconductor photocatalysts. Here, we demonstrate that earth-abundant carbonate ions, widely existing in daily-life water, serve as a hole mediator to redirect the photogenerated hole transfer pathway and then promote the hole-transfer kinetics. The accelerated hole transfer could efficiently reduce the recombination of electron-hole pairs for continuous H2 prodn. with improved photostability of catalysts, including layered indium phosphorus sulfide (In4/3P2S6) and cadmium sulfide. A sustainable H2 evolution rate of 5.1 mmol g-1 h-1 within 60 h or more operation is achieved in the presence of CO32- anions. In situ ESR (ESR) spectroscopy studies and transient absorption (TA) measurements reveal that the CO32-/CO3- redox couple could rapidly shuttle the photogenerated holes from OH radicals anchored on the catalyst surface, effectively eliminating the recombination of electron-hole pairs and catalyst oxidn. for boosted H2 generation. The carbonate-ion-mediated hole-transfer strategy provides a new paradigm for designing a cost-effective and advanced photosynthetic system in practical applications.
25. 25
  Zhou J. Zhu C. Zhou Y. Dong J. Li P. Zhang Z. Wang Z. Lin Y. C. Shi J. Zhang R. Zheng Y. Yu H. Tang B. Liu F. Wang L. Liu L. Liu G. B. Hu W. Gao Y. Yang H. Gao W. Lu L. Wang Y. Suenaga K. Liu G. Ding F. Yao Y. Liu Z. Composition and Phase Engineering of Metal Chalcogenides and Phosphorous Chalcogenides Nat. Mater. 2022
  There is no corresponding record for this reference.
  https://doi.org/10.1038/s41563-022-01291-5.
  There is no corresponding record for this reference.
26. 26
  Sendeku M. G. Wang F. Cheng Z. Yu P. Gao N. Zhan X. Wang Z. He J. Nonlayered Tin Thiohypodiphosphate Nanosheets: Controllable Growth and Solar-Light-Driven Water Splitting ACS Appl. Mater. Interfaces 2021 13 11 13392 13399
  26
  Nonlayered Tin Thiohypodiphosphate Nanosheets: Controllable Growth and Solar-Light-Driven Water Splitting
  Sendeku, Marshet G.; Wang, Fengmei; Cheng, Zhongzhou; Yu, Peng; Gao, Ning; Zhan, Xueying; Wang, Zhenxing; He, Jun
  ACS Applied Materials & Interfaces (2021), 13 (11), 13392-13399CODEN: AAMICK; ISSN:1944-8244. (American Chemical Society)
  As a promising candidate in various fields, including energy conversion and electronics, layered van der Waals metal phosphorus trichalcogenides (MPX3) have been widely explored. In addn. to the layered structures, MPX3 comprising post-transition metals (i.e., Sn and Pb) are known to form a unique 3D framework with nonlayered structure. However, the nonlayered two-dimensional (2D) crystals of this family have remained unexplored until now. Herein, we successfully synthesized 2D nonlayered tin thiohypodiphosphate (Sn2P2S6) nanosheets, having an indirect bandgap of 2.25 eV and a thickness down to ~ 10 nm. The as-obtained nanosheets demonstrate promising photocatalytic water splitting activity to generate H2 in pure water under simulated solar light (AM 1.5G). Moreover, the ultrathin Sn2P2S6 catalyst shows auspicious performance and stability with a continuous operation of 40 h. This work is not only an expansion of the MPX3 family, but it is also a major milestone in the search for new materials for future energy conversion.
27. 27
  Shifa T. A. Wang F. Cheng Z. He P. Liu Y. Jiang C. Wang Z. He J. High Crystal Quality 2D Manganese Phosphorus Trichalcogenide Nanosheets and Their Photocatalytic Activity Adv. Funct. Mater. 2018 28 18 1800548
  There is no corresponding record for this reference.
28. 28
  Zhu W. Gan W. Muhammad Z. Wang C. Wu C. Liu H. Liu D. Zhang K. He Q. Jiang H. Zheng X. Sun Z. Chen S. Song L. Exfoliation of Ultrathin FePS₃ Layers as a Promising Electrocatalyst for the Oxygen Evolution Reaction Chem. Commun. 2018 54 35 4481 4484
  28
  Exfoliation of ultrathin FePS3 layers as a promising electrocatalyst for the oxygen evolution reaction
  Zhu, Wen; Gan, Wei; Muhammad, Zahir; Wang, Changda; Wu, Chuanqiang; Liu, Hengjie; Liu, Daobin; Zhang, Ke; He, Qun; Jiang, Hongliang; Zheng, Xusheng; Sun, Zhe; Chen, Shuangming; Song, Li
  Chemical Communications (Cambridge, United Kingdom) (2018), 54 (35), 4481-4484CODEN: CHCOFS; ISSN:1359-7345. (Royal Society of Chemistry)
  Few-layer ternary FePS3 nanosheets, prepd. via chem. vapor transport synthesis and ball-milling exfoliation, exhibit excellent electrocatalytic performance for the oxygen evolution reaction in an alk. medium. Combined with first principles calcns., our X-ray spectroscopy and HRTEM results clearly reveal that the introduction of in-plane defects in FePS3 layers after exfoliation and formation of a FePS3-FeOOH heterostructure during the OER process largely contribute to the catalytic activity enhancement.
29. 29
  Sang Y. Wang L. Cao X. Ding G. Ding Y. Hao Y. Xu N. Yu H. Li L. Peng S. Emerging 2D-Layered MnPS₃/rGO Composite as a Superior Anode for Sodium-Ion Batteries J. Alloys Compd. 2020 831 154775
  29
  Emerging 2D-Layered MnPS3/rGO composite as a superior anode for sodium-ion batteries
  Sang, Yan; Wang, Lvxuan; Cao, Xi; Ding, Gaofei; Ding, Yonghao; Hao, Yanan; Xu, Na; Yu, Hanzhi; Li, Linlin; Peng, Shengjie
  Journal of Alloys and Compounds (2020), 831 (), 154775CODEN: JALCEU; ISSN:0925-8388. (Elsevier B.V.)
  Two-dimensional (2D) layered materials were widely studied due to their unique Na storage properties and rapid ion transport rates. Herein, the authors synthesized a 2-dimensional layered transition metal P sulfide MnPS3 by one step high-temp. solid-phase synthesis. After combining with graphene by high-energy ball milling followed by high-temp. Ar calcination, the novel 2D/2D heterojunction of extra-thin MnPS3/rGO was successfully prepd. The resultant MnPS3/rGO hybrid can strengthen the cond. of the material and ameliorate the vol. change during the insertion/extn. process of the Na-ion storage, compared to the pristine MnPS3. As a result, the 2D/2D heterojunction of ultra-thin MnPS3/rGO composite exhibits high cycling performance (290 mA-h g-1 after 150 cycles at 0.2 A g-1), capacity retention rates up to 92%. The superior performance is ascribed to the combination of extra-thin MnPS3 nanosheets with graphene, which effectively enhances the interface contact area and the electronic transmission rate, greatly improving the adaptability of vol. change and interfacial charge transfer abilities. This work provides a novel and promising MnPS3/rGO anode for Na-ion batteries.
30. 30
  Liu J. Li X. B. Wang D. Lau W.-M. Peng P. Liu L.-M. Diverse and Tunable Electronic Structures of Single-layer Metal Phosphorus Trichalcogenides for Photocatalytic Water Splitting J. Chem. Phys. 2014 140 5 054707
  30
  Diverse and tunable electronic structures of single-layer metal phosphorus trichalcogenides for photocatalytic water splitting
  Liu, Jian; Li, Xi-Bo; Wang, Da; Lau, Woon-Ming; Peng, Ping; Liu, Li-Min
  Journal of Chemical Physics (2014), 140 (5), 054707/1-054707/7CODEN: JCPSA6; ISSN:0021-9606. (American Institute of Physics)
  The family of bulk metal phosphorus trichalcogenides (APX3, A = MII, MI0.5MIII0.5; X = S, Se; MI, MII, and MIII represent Group-I, Group-II, and Group-III metals, resp.) has attracted great attentions because such materials not only own magnetic and ferroelec. properties, but also exhibit excellent properties in hydrogen storage and lithium battery because of the layered structures. Many layered materials have been exfoliated into two-dimensional (2D) materials, and they show distinct electronic properties compared with their bulks. Here the authors present a systematical study of single-layer metal phosphorus trichalcogenides by d. functional theory calcns. The results show that the single layer metal phosphorus trichalcogenides have very low formation energies, which indicates that the exfoliation of single layer APX3 should not be difficult. The family of single layer metal phosphorus trichalcogenides exhibits a large range of band gaps from 1.77 to 3.94 eV, and the electronic structures are greatly affected by the metal or the chalcogenide atoms. The calcd. band edges of metal phosphorus trichalcogenides further reveal that single-layer ZnPSe3, CdPSe3, Ag0.5Sc0.5PSe3, and Ag0.5In0.5PX3 (X = S and Se) have both suitable band gaps for visible-light driving and sufficient over-potentials for water splitting. More fascinatingly, single-layer Ag0.5Sc0.5PSe3 is a direct band gap semiconductor, and the calcd. optical absorption further convinces that such materials own outstanding properties for light absorption. Such results demonstrate that the single layer metal phosphorus trichalcogenides own high stability, versatile electronic properties, and high optical absorption, thus such materials have great chances to be high efficient photocatalysts for water-splitting. (c) 2014 American Institute of Physics.
31. 31
  Mukherjee D. Austeria M. P. Sampath S. Few-Layer Iron Selenophosphate, FePSe₃: Efficient Electrocatalyst toward Water Splitting and Oxygen Reduction Reactions ACS Appl. Energy Mater. 2018 1 1 220 231
  31
  Few-Layer Iron Selenophosphate, FePSe3: Efficient Electrocatalyst toward Water Splitting and Oxygen Reduction Reactions
  Mukherjee, Debdyuti; Muthu, Austeria P.; Sampath, S.
  ACS Applied Energy Materials (2018), 1 (1), 220-231CODEN: AAEMCQ; ISSN:2574-0962. (American Chemical Society)
  There has been a spurt of activity in using layered MPX3 (M = transition metal, X = chalcogen, S/Se/Te) compds. in various studies including catalysis and devices. In the present study, low band gap, ternary iron selenophosphate (FePSe3) is introduced as an excellent and highly stable trifunctional electrocatalyst for hydrogen evolution, oxygen evolution, and oxygen redn. reactions. It is obsd. that the present catalyst is useful in evolving hydrogen over a wide pH range including seawater environment. D. functional theory calcns. reveal various parameters that help improve the electrocatalytic activity of the layered material. Covalency of the Fe-Se bond, distortion in the crystal structure, and adsorption properties are shown to be responsible for the obsd. high catalytic activity.
32. 32
  Mukherjee D. Austeria P. M. Sampath S. Two-Dimensional, Few-Layer Phosphochalcogenide, FePS₃: A New Catalyst for Electrochemical Hydrogen Evolution over Wide pH Range ACS Energy Lett. 2016 1 2 367 372
  32
  Two-Dimensional, Few-Layer Phosphochalcogenide, FePS3: A New Catalyst for Electrochemical Hydrogen Evolution over Wide pH Range
  Mukherjee, Debdyuti; Austeria, P. Muthu; Sampath, S.
  ACS Energy Letters (2016), 1 (2), 367-372CODEN: AELCCP; ISSN:2380-8195. (American Chemical Society)
  A layered MPS3-type compd., FePS3, is introduced as an electrocatalyst for hydrogen evolution reaction (HER). The non-noble metal-based FePS3 is a semiconductor that could be solvent exfoliated into few-layer, two-dimensional (2D) nanosheets. The 2-dimensional thin sheets exhibit very good catalytic activity and stability toward HER over a wide pH range of acidic, alk., phosphate buffer, and 3.5% aq. NaCl solns. The Tafel slope and exchange c.d. in acidic medium are ∼(45-50) mV/dec and 1±0.2 × 10-3 A/cm2, resp. The stability of the catalyst is very good. D. functional theory calcns. reveal P and S as favorable hydrogen adsorption sites. This material opens up a new class of ternary, layered semiconductors for various electrocatalytic studies and might also become important from a device physics point of view.
33. 33
  Jenjeti R. N. Kumar R. Sampath S. Two-Dimensional, Few-layer NiPS₃ for Flexible Humidity Sensor with High Selectivity J. Mater. Chem. A 2019 7 24 14545 14551
  33
  Two-dimensional, few-layer NiPS3 for flexible humidity sensor with high selectivity
  Jenjeti, Ramesh Naidu; Kumar, Rajat; Sampath, S.
  Journal of Materials Chemistry A: Materials for Energy and Sustainability (2019), 7 (24), 14545-14551CODEN: JMCAET; ISSN:2050-7496. (Royal Society of Chemistry)
  Chem. and elec. sensitive two-dimensional (2D) nanomaterials are of immense interest as probing electrodes for wearable electronic devices. A new family of two dimensional (2D) layered materials, namely metal phosphochalcogenides (MPX3), are potential candidates towards the development of sensors for various analytes. Herein, we demonstrate the ability of few-layer NiPS3 nanosheets for humidity sensing by fabricating a cost-effective, flexible sensor device. The results indicate that the NiPS3 nanosheet-based humidity sensors possess high sensitivity with a response of ∼106, superior selectivity, and most importantly, rapid response, recovery times and good reproducibility. Response times of ∼1-2 s at low humidity levels and ∼3 s at high humidity levels with recovery times of ∼2-3 s are obsd. The device was tested in both flat and bent states, causing no prominent changes in the response; hence, the sensor is an excellent candidate for use in flexible devices. The characteristics of the NiPS3-based sensor were further investigated using complex impedance studies and in situ Raman spectroscopy to understand the sensing mechanism. The fast response and recovery assocd. with the NiPS3-based humidity sensors allow real time monitoring of human respiration and water evapn. on skin. These humidity sensors can also be utilized for non-contact anal. and hence will be an attractive candidate for health and environmental monitoring.
34. 34
  Song B. Li K. Yin Y. Wu T. Dang L. Caban-Acevedo M. Han J. Gao T. Wang X. Zhang Z. Schmidt J. R. Xu P. Jin S. Tuning Mixed Nickel Iron Phosphosulfide Nanosheet Electrocatalysts for Enhanced Hydrogen and Oxygen Evolution ACS Catal. 2017 7 12 8549 8557
  34
  Tuning Mixed Nickel Iron Phosphosulfide Nanosheet Electrocatalysts for Enhanced Hydrogen and Oxygen Evolution
  Song, Bo; Li, Kai; Yin, Ying; Wu, Tao; Dang, Lianna; Caban-Acevedo, Miguel; Han, Jiecai; Gao, Tangling; Wang, Xianjie; Zhang, Zhihua; Schmidt, J. R.; Xu, Ping; Jin, Song
  ACS Catalysis (2017), 7 (12), 8549-8557CODEN: ACCACS; ISSN:2155-5435. (American Chemical Society)
  Highly efficient earth-abundant electrocatalysts for the hydrogen evolution reaction (HER) and oxygen evolution reaction (OER) are of great importance for renewable energy conversion systems. Herein, guided by theor. calcns., we demonstrate highly efficient water splitting in alk. soln. using quaternary mixed nickel iron phosphosulfide (Ni1-xFexPS3) nanosheets (NSs), even though neither NiPS3 nor FePS3 is a good HER (or OER) electrocatalyst. With tuned electronic structure and improved elec. cond. induced by mixing appropriate amt. of Fe into NiPS3, Ni0.9Fe0.1PS3 NSs display excellent HER activity (an overpotential of 72 mV vs reversible hydrogen electrode (RHE) at a geometric catalytic c.d. of -10 mA cm-2 and a Tafel slope of 73 mV dec-1), which is among the best HER catalysts under alk. conditions. Ni0.9Fe0.1PS3 NSs also show a good apparent OER activity (an overpotential of 329 mV vs RHE at a catalytic c.d. of 20 mA cm-2 and a Tafel slope of 69 mV dec-1), although structural investigation indicates the formation of Ni(Fe)OOH and Ni(Fe)(OH)2 layers on the catalyst surface after OER reactions as likely the real active species. These mixed nickel iron phosphosulfide non-precious-metal electrocatalysts with enhanced intrinsic activity and long-term stability and durability should have great potential in overall water-splitting applications.
35. 35
  Cheng Z. Shifa T. A. Wang F. Gao Y. He P. Zhang K. Jiang C. Liu Q. He J. High-Yield Production of Monolayer FePS₃ Quantum Sheets via Chemical Exfoliation for Efficient Photocatalytic Hydrogen Evolution Adv. Mater. 2018 30 26 1707433
  There is no corresponding record for this reference.
36. 36
  Dinh Hoa L. Thanh Luan P. Ghimire G. Dinh Loc D. Lee Y. H. Revealing Antiferromagnetic Transition of van der Waals MnPS₃ via Vertical Tunneling Electrical Resistance Measurement APL Mater. 2019 7 8 081102
  There is no corresponding record for this reference.
37. 37
  Wang J. Li X. Wei B. Sun R. Yu W. Hoh H. Y. Xu H. Li J. Ge X. Chen Z. Su C. Wang Z. Activating Basal Planes of NiPS₃ for Hydrogen Evolution by Nonmetal Heteroatom Doping Adv. Funct. Mater. 2020 30 12 1908708
  37
  Activating Basal Planes of NiPS3 for Hydrogen Evolution by Nonmetal Heteroatom Doping
  Wang, Jun; Li, Xinzhe; Wei, Bin; Sun, Rong; Yu, Wei; Hoh, Hui Ying; Xu, Haomin; Li, Jing; Ge, Xingbo; Chen, Zuxin; Su, Chenliang; Wang, Zhongchang
  Advanced Functional Materials (2020), 30 (12), 1908708CODEN: AFMDC6; ISSN:1616-301X. (Wiley-VCH Verlag GmbH & Co. KGaA)
  NiPS3, one of the most promising catalysts among transition metal trichalcogenidophosphates (MTPs) in hydrogen evolution reaction (HER) electrocatalysis, is still inhibited by its unsatisfactory activity originating from its semiconducting nature and inert basal plane. Here, it is proposed, for the first time, to engineer the basal surface activity of NiPS3 by nonmetal heteroatom doping, and predict that the degree to which the valance band of NiPS3 is filled dominates not only the elec. cond. of the catalyst, but also the strength of hydrogen adsorption at its surface. Direct exptl. evidence is offered that in all the single nonmetal doping samples, C-doped NiPS3 exhibits the optimum activity owing to its moderate filled state of valance band and that C, N codoping even shows Pt-like activity with an ultralow overpotential of 53.2 mV to afford 10 mA cm-2 c.d. and a high exchange c.d. of 0.7 mA cm-2 in 1 M KOH. The findings that less valance electrons of dopants than substitutional atoms are of pivotal importance for improving HER activity of NiPS3 catalyst pave the way for readily designing novel MTPs of ever high performance to replace the incumbent Pt-based catalysts.
38. 38
  Li X. Fang Y. Wang J. Wei B. Qi K. Hoh H. Y. Hao Q. Sun T. Wang Z. Yin Z. Zhang Y. Lu J. Bao Q. Su C. High-Yield Electrochemical Production of Large-Sized and Thinly Layered NiPS₃ Flakes for Overall Water Splitting Small 2019 15 30 1902427
  There is no corresponding record for this reference.
39. 39
  Sekine T. Jouanne M. Julien C. Balkanski M. Raman Scattering in the Antiferromagnet FePS₃ Intercalated with Lithium Mater. Sci. Eng. B Solid State Mater. Adv. Technol. 1989 3 1−2 91 95
  There is no corresponding record for this reference.
40. 40
  Fujishima A. Honda K. Electrochemical Photolysis of Water at a Semiconductor Electrode Nature 1972 238 5358 37 38
  40
  Electrochemical photolysis of water at a semiconductor electrode
  Fujishima, Akira; Honda, Kenichi
  Nature (London, United Kingdom) (1972), 238 (5358), 37-8CODEN: NATUAS; ISSN:0028-0836.
  For electrochem. decompn. of H2O, a p.d. of >1.23 V is necessary between the anode and the cathode. This p.d. is equal to the energy of radiation with wavelength of ∼1000 nm. This energy, in the form of visible light, can be used effectively in an electrochem. system to decomp. H2O. A novel type of electrochem. cell was developed, in which a TiO2 electrode was connected with a Pt-black electrode through an external load. The direction of current revealed that oxidn. occurred at the TiO2 electrode and redn. at the Pt-black electrode. To increase the efficiency of the process, more reducible species, such as dissolved O2 or Fe3+, must be added in the Pt electrode compartment. The use of a p-type semiconductor electrode instead of Pt leads to more effective electrochem. photolysis of H2O.
41. 41
  Nakata K. Fujishima A. TiO₂ Photocatalysis: Design and Applications J. Photochem. Photobiol. C 2012 13 3 169 189
  41
  TiO2 photocatalysis: Design and applications
  Nakata, Kazuya; Fujishima, Akira
  Journal of Photochemistry and Photobiology, C: Photochemistry Reviews (2012), 13 (3), 169-189CODEN: JPPCAF; ISSN:1389-5567. (Elsevier B.V.)
  In this review, recent developments in the area of TiO2 photocatalysis research, in terms of new materials from a structural design perspective, have been summarized. The dimensionality assocd. with the structure of a TiO2 material can affect its properties and functions, including its photocatalytic performance, and also more specifically its surface area, adsorption, reflectance, adhesion, and carrier transportation properties. The authors provide a brief introduction to the current situation in TiO2 photocatalysis, and describe structurally controlled TiO2 photocatalysts which can be classified into zero-, one-, two-, and three-dimensional structures. Furthermore, novel applications of TiO2 surfaces for the fabrication of wettability patterns and for printing are discussed.
42. 42
  Chiesa P. Consonni S. Kreutz T. Williams R. Co-Production of Hydrogen, Electricity and CO₂ from Coal with Commercially Ready Technology. PartA: Performance and Emissions Int. J. Hydrogen Energy 2005 30 7 747 767
  42
  Co-production of hydrogen, electricity and CO2 from coal with commercially ready technology. Part A: Performance and emissions
  Chiesa, Paolo; Consonni, Stefano; Kreutz, Thomas; Williams, Robert
  International Journal of Hydrogen Energy (2005), 30 (7), 747-767CODEN: IJHEDX; ISSN:0360-3199. (Elsevier Ltd.)
  This two-part paper investigates performances, costs and prospects of using com. ready technol. to convert coal to H2 and electricity, with CO2 capture and storage. Part A focuses on plant configuration and the evaluation of performances and CO2 emissions. Part B focuses on economics, establishing benchmarks for the assessment of novel technologies and guidelines for technol. development. In the co-prodn. plants considered in the paper, coal is gasified to synthesis gas in an entrained flow gasifier. The syngas is cooled, cleaned of particulate matter, and shifted (to primarily H2 and CO2) in sour water-gas shift reactors. After further cooling, H2S is removed from the syngas using a phys. solvent (Selexol); CO2 is then removed from the syngas, again using Selexol; after being stripped from the solvent, the CO2 is dried and compressed to 150 bar for pipeline transport and underground storage. High purity H2 (99.999%) is extd. from the H2-rich syngas via a pressure swing adsorption (PSA) unit and delivered at 60 bar. The PSA purge gas is compressed and burned in a conventional gas turbine combined cycle, generating co-product electricity. The H2/electricity ratio can be varied by lowering the steam-to-carbon ratio in the syngas or by letting part of the de-carbonized syngas bypass the PSA unit. Performances and emissions of H2/electricity co-prodn. with CO2 capture are compared with those of a system that vents the CO2. We examine different methods of syngas heat recovery (quench vs. radiant cooling) and explore the effects of changing the electricity/H2 ratio, gasifier pressure and hydrogen purity. Results show that state-of-the-art com. technol. allows transferring to de-carbonized hydrogen 57-58% of coal LHV, while exporting to the grid decarbonized electricity amounting to 2-6% of coal LHV. In contrast to decarbonizing coal IGCC electricity, which entails a loss of 6-8 percentage points of electricity conversion when capturing CO2 as an alternative to venting it, CO2 capture for H2 prodn. gives a minor energy penalty (∼ 2 percentage points of export electricity). For H2 prodn., the efficiency gain achievable by hot syngas cooling vs. quench is a modest 2 percentage point increase in electricity for export, compared to 2-4 percentage points in the electricity case. Reducing H2 purity or increasing gasification pressure has minor effects on performance.
43. 43
  Zhang X. Zhao X. Wu D. Jing Y. Zhou Z. MnPSe₃ Monolayer: A Promising 2D Visible-Light Photohydrolytic Catalyst with High Carrier Mobility Adv. Sci. 2016 3 10 1600062
  43
  MnPSe3 Monolayer: A Promising 2D Visible-Light Photohydrolytic Catalyst with High Carrier Mobility
  Zhang Xu; Zhao Xudong; Wu Dihua; Jing Yu; Zhou Zhen
  Advanced science (Weinheim, Baden-Wurttemberg, Germany) (2016), 3 (10), 1600062 ISSN:2198-3844.
  The 2D material single-layer MnPSe3 would be a promising photocatalyst for water splitting, as indicated by the proper positions of band edges, strong absorption in visible-light spectrum, broad applicability (pH = 0 - 7), and high carrier mobility.
44. 44
  Yu P. Wang F. Meng J. Shifa T. A. Sendeku M. G. Fang J. Li S. Cheng Z. Lou X. He J. Few-Layered CuInP₂S₆ Nanosheet with Sulfur Vacancy Boosting Photocatalytic Hydrogen Evolution CrystEngComm 2021 591 598
  44
  Few-layered CuInP2S6 nanosheet with sulfur vacancy boosting photocatalytic hydrogen evolution
  Yu, Peng; Wang, Fengmei; Meng, Jun; Shifa, Tofik Ahmed; Sendeku, Marshet Getaye; Fang, Ju; Li, Shuxian; Cheng, Zhongzhou; Lou, Xiaoding; He, Jun
  CrystEngComm (2021), 23 (3), 591-598CODEN: CRECF4; ISSN:1466-8033. (Royal Society of Chemistry)
  Photochem. water splitting offers an economic and sustainable approach for solar energy conversion into hydrogen fuel to mitigate the problem of greenhouse gas emissions. To this end, exploring novel semiconductor photocatalysts, which have efficient light absorption and thermodynamically favorable band alignment for water splitting, is crucial. Here, we rationally develop a new photocatalyst of CuInP2S6 nanosheets to generate hydrogen gas under light illumination. The CuInP2S6 nanosheet (with a thickness of around 4-7 nm) photocatalyst exhibits a high hydrogen prodn. rate of 804μmol g-1 h-1, eight times higher than that of the microsheet counterpart, due to the introduced abundant sulfur vacancies. Exptl. characterization and theor. calcns. verify that the prolonged carrier lifetime and optimized band alignment in ultrathin CuInP2S6 nanosheets boost photocatalytic hydrogen evolution. This work opens a new avenue for photocatalysis via using novel layered binary metal phosphorous trichalcogenides.
45. 45
  Navarro R. M. Sánchez-Sánchez M. C. Alvarez-Galvan M. C. Valle F. d. Fierro J. L. G. Hydrogen Production from Renewable Sources: Biomass and Photocatalytic Opportunities Energy Environ. Sci. 2009 2 1 35 54
  45
  Hydrogen production from renewable sources: biomass and photocatalytic opportunities
  Navarro, R. M.; Sanchez-Sanchez, M. C.; Alvarez-Galvan, M. C.; del Valle, F.; Fierro, J. L. G.
  Energy & Environmental Science (2009), 2 (1), 35-54CODEN: EESNBY; ISSN:1754-5706. (Royal Society of Chemistry)
  A review. The demand for hydrogen over the coming decade is expected to grow for both traditional uses (ammonia, methanol, refinery) and running fuel cells. At least in the near future, this thirst for hydrogen will be quenched primarily through the reforming of fossil fuels. However, reforming fossil fuels emits huge amts. of carbon dioxide. One approach to reduce carbon dioxide emissions, which is considered first in this review, is to apply reforming methods to alternative renewable materials. Such materials might be derived from plant crops, agricultural residues, woody biomass, etc. Clean biomass is a proven source of renewable energy that is already used for generating heat, electricity, and liq. transportation fuels. Clean biomass and biomass-derived precursors such as ethanol and sugars are appropriate precursors for producing hydrogen through different conversion strategies. Virtually no net greenhouse gas emissions result because a natural cycle is maintained, in which carbon is extd. from the atm. during plant growth and released during hydrogen prodn. The second option explored here is hydrogen prodn. from water splitting by means of the photons in the visible spectrum. The sun provides silent and precious energy that is distributed fairly evenly all over the earth. However, its tremendous potential as a clean, safe and economical energy source cannot be exploited unless it is accumulated or converted into more useful forms of energy. Finally, this review discusses the use of semiconductors, more specifically CdS and CdS-based semiconductors, which are able to absorb photons in the visible region of the spectrum. The energy stored within a semiconductor as electronic energy (electrons and holes) can be used to split water mols. by simultaneous reactions into H2 and O2. This conversion of solar energy into a clean fuel (H2) is perhaps the greatest challenge for scientists in the 21st century.
46. 46
  Shimura K. Yoshida H. Heterogeneous Photocatalytic Hydrogen Production from Water and Biomass Derivatives Energy Environ. Sci. 2011 4 7 2467 2481
  46
  Heterogeneous photocatalytic hydrogen production from water and biomass derivatives
  Shimura, Katsuya; Yoshida, Hisao
  Energy & Environmental Science (2011), 4 (7), 2467-2481CODEN: EESNBY; ISSN:1754-5706. (Royal Society of Chemistry)
  A review. Hydrogen, a clean energy carrier, should be produced from not the irreproducible fossil fuels but renewable resources. Currently hydrogen is mainly produced by the reforming of petroleum and natural gas at high temp., which consumes huge energy. Thus, development of an alternative hydrogen prodn. method is absolutely imperative to mitigate the environmental and energy issues. Photocatalytic hydrogen prodn. from water and renewable resources is one of the attractive systems, since it can utilize the solar energy. In this short review, we remind you that the systems of the photocatalytic hydrogen prodn. from water and biomass derivs., such as ethanol, glycerol, sugars and methane, should be considered as available candidates for the hydrogen prodn. method from renewable resources and solar energy, and these systems have been improved by developments of new photocatalysts with some cocatalysts, modifications of photocatalysts, optimization of reaction conditions, and so on.
47. 47
  Zhang Y. Zhao Y. Bao C. Xiao Y. Xiang Y. Song M. Huang W. Ma L. Hou H. Chen X. Facile synthesis of cadmium phosphorus trisulfide nanosheets for highly efficient photocatalytic performance J. Alloys Compd. 2022 909 164731
  47
  Facile synthesis of cadmium phosphorus trisulfide nanosheets for highly efficient photocatalytic performance
  Zhang, Yue; Zhao, Yadi; Bao, Cunyou; Xiao, Yue; Xiang, Yuesong; Song, Mengting; Huang, Wenjuan; Ma, Liang; Hou, Huayi; Chen, Xiangbai
  Journal of Alloys and Compounds (2022), 909 (), 164731CODEN: JALCEU; ISSN:0925-8388. (Elsevier B.V.)
  With the rise of two-dimensional (2D) materials, layered metal thiophosphates (MPS3), as an important branch, have attracted much attention because of their excellent phys. and chem. properties. Cadmium phosphorus trisulfide (CdPS3), as a promising photocatalyst, can be used for hydrogen evolution and org. degrdn. Herein, high-quality 2D CdPS3 few layers are obtained by exfoliating bulk CdPS3 crystal. The optical properties of the as-obtained CdPS3 few layers show good light-harvesting ability, endowing it with excellent photocatalytic hydrogen evolution performance (10.88 mmol g-1 h-1) and high org. degrdn. performance (more than 92% within 30 min) under Xe lamp irradn. This research provides opportunities for the prepn. and application of other 2D MPS3 type materials in the field of photocatalysis.
48. 48
  Cheng Z. Sendeku M. G. Liu Q. Layered Metal Phosphorous Trichalcogenides Nanosheets: Facile Synthesis and Photocatalytic Hydrogen Evolution Nanotechnology 2020 31 13 135405
  48
  Layered metal phosphorous trichalcogenides nanosheets: Facile synthesis and photocatalytic hydrogen evolution
  Cheng, Zhongzhou; Sendeku, Marshet Getaye; Liu, Quanlin
  Nanotechnology (2020), 31 (13), 135405CODEN: NNOTER; ISSN:1361-6528. (IOP Publishing Ltd.)
  Layered transition metal phosphorous trichalcogenide (MPX3) materials have attracted immense attention due to their excellent optical and elec. properties. However, the controllable synthesis of ultrathin MPX3 nanosheets is still challenging. Here, we present a facile phosphosulfurization scheme to prep. high-quality layered FePS3 nanosheets, with ~ 20 nm in thickness. The optical properties of the as-obtained FePS3 show good light-harvesting ability, which endows it with excellent photocatalytic hydrogen evolution performance (402.4μmol g-1 h-1) under the simulated solar illumination. We further show that other MPX3 family members such as In2/3PS3 and CdPS3 can be also synthesized by the same approach. Our finding can offer a feasible approach for rationally designing other MPX3 materials for various applications.
49. 49
  Chang X. Wang T. Gong J. CO₂ Photo-reduction: Insights into CO₂ Activation and Reaction on Surfaces of Photocatalysts Energy Environ. Sci. 2016 9 7 2177 2196
  49
  CO2 photo-reduction: insights into CO2 activation and reaction on surfaces of photocatalysts
  Chang, Xiaoxia; Wang, Tuo; Gong, Jinlong
  Energy & Environmental Science (2016), 9 (7), 2177-2196CODEN: EESNBY; ISSN:1754-5706. (Royal Society of Chemistry)
  Large amts. of anthropogenic CO2 emissions assocd. with increased fossil fuel consumption have led to global warming and an energy crisis. The photocatalytic redn. of CO2 into solar fuels such as methane or methanol is believed to be one of the best methods to address these two problems. In addn. to light harvesting and charge sepn., the adsorption/activation and redn. of CO2 on the surface of heterogeneous catalysts remain a scientifically crit. challenge, which greatly limits the overall photoconversion efficiency and selectivity of CO2 redn. This review describes recent advances in the fundamental understanding of CO2 photoredn. on the surface of heterogeneous catalysts and particularly provides an overview of enhancing the adsorption/activation of CO2 mols. The reaction mechanism and pathways of CO2 redn. as well as their dependent factors are also analyzed and discussed, which is expected to enable an increase in the overall efficiency of CO2 redn. through minimizing the reaction barriers and controlling the selectivity towards the desired products. The challenges and perspectives of CO2 photoredn. over heterogeneous catalysts are presented as well.
50. 50
  Gao W. Li S. He H. Li X. Cheng Z. Yang Y. Wang J. Shen Q. Wang X. Xiong Y. Zhou Y. Zou Z. Vacancy-Defect Modulated Pathway of Photoreduction of CO₂ on Single Atomically Thin AgInP₂S₆ Sheets into Olefiant Gas Nat. Commun. 2021 12 1 4747
  50
  Vacancy-defect modulated pathway of photoreduction of CO2 on single atomically thin AgInP2S6 sheets into olefiant gas
  Gao, Wa; Li, Shi; He, Huichao; Li, Xiaoning; Cheng, Zhenxiang; Yang, Yong; Wang, Jinlan; Shen, Qing; Wang, Xiaoyong; Xiong, Yujie; Zhou, Yong; Zou, Zhigang
  Nature Communications (2021), 12 (1), 4747CODEN: NCAOBW; ISSN:2041-1723. (Nature Research)
  Abstr.: Artificial photosynthesis, light-driving CO2 conversion into hydrocarbon fuels, is a promising strategy to synchronously overcome global warming and energy-supply issues. The quaternary AgInP2S6 at. layer with the thickness of ∼ 0.70 nm were successfully synthesized through facile ultrasonic exfoliation of the corresponding bulk crystal. The sulfur defect engineering on this at. layer through a H2O2 etching treatment can excitingly change the CO2 photoredn. reaction pathway to steer dominant generation of ethene with the yield-based selectivity reaching ∼73% and the electron-based selectivity as high as ∼89%. Both DFT calcn. and in-situ FTIR spectra demonstrate that as the introduction of S vacancies in AgInP2S6 causes the charge accumulation on the Ag atoms near the S vacancies, the exposed Ag sites can thus effectively capture the forming *CO mols. It makes the catalyst surface enrich with key reaction intermediates to lower the C-C binding coupling barrier, which facilitates the prodn. of ethene.
51. 51
  Fan Y. Song X. Ai H. Li W. Zhao M. Highly Efficient Photocatalytic CO₂ Reduction in Two-Dimensional Ferroelectric CuInP₂S₆ Bilayers ACS Appl. Mater. Interfaces 2021 13 29 34486 34494
  51
  Highly efficient photocatalytic CO2 reduction in two-dimensional ferroelectric CuInP2S6 bilayers
  Fan, Yingcai; Song, Xiaohan; Ai, Haoqiang; Li, Weifeng; Zhao, Mingwen
  ACS Applied Materials & Interfaces (2021), 13 (29), 34486-34494CODEN: AAMICK; ISSN:1944-8244. (American Chemical Society)
  Photocatalytic CO2 conversion into reproducible chem. fuels (e.g., CO, CH3OH, or CH4) provides a promising scheme to solve the increasing environmental problems and energy demands simultaneously. However, the efficiency is severely restricted by the high overpotential of the CO2 redn. reaction (CO2RR) and rapid recombination of photoexcited carriers. Here, we propose that a novel type-II photocatalytic mechanism based on two-dimensional (2D) ferroelec. multilayers would be ideal for addressing these issues. Using d.-functional theory and nonadiabatic mol. dynamics calcns., we find that the ferroelec. CuInP2S6 bilayers exhibit a staggered band structure induced by the vertical intrinsic elec. fields. Different from the traditional type-II band alignment, the unique structure of the CuInP2S6 bilayer not only effectively suppresses the recombination of photogenerated electron-hole (e-h) pairs but also produces a sufficient photovoltage to drive the CO2RR. The predicted recombination time of photogenerated e-h pairs, 1.03 ns, is much longer than the transferring times of photoinduced electrons and holes, 5.45 and 0.27 ps, resp. Moreover, the overpotential of the CO2RR will decrease by substituting an S atom with a Cu atom, making the redox reaction proceed spontaneously under solar radiation. The solar-to-fuel efficiency with an upper limit of 8.40% is achieved in the CuInP2S6 bilayer and can be further improved to 32.57% for the CuInP2S6 five-layer. Our results indicate that this novel type-II photocatalytic mechanism would be a promising way to achieve highly efficient photocatalytic CO2 conversion based on the 2D ferroelec. multilayers.
52. 52
  De Battisti, A.; Martínez-Huitle, C. A. , Electrocatalysis in Wastewater Treatment. In Electrochemical Water and Wastewater Treatment; Martínez-Huitle, C. A., Rodrigo, M. A., Scialdone, O. , Eds.; Butterworth-Heinemann: 2018; pp 119− 131.
  There is no corresponding record for this reference.
53. 53
  de Freitas Araujo K. C. da Silva D. R. dos Santos E. V. Varela H. Martinez-Huitle C. A. Investigation of Persulfate Production on BDD Anode by Understanding the Impact of Water Concentration J. Electroanal. Chem. 2020 860 113927
  There is no corresponding record for this reference.
54. 54
  Huang H. Li F. Xue Q. Zhang Y. Yin S. Chen Y. Salt-Templated Construction of Ultrathin Cobalt Doped Iron Thiophosphite Nanosheets toward Electrochemical Ammonia Synthesis Small 2019 15 51 1903500
  54
  Salt-Templated Construction of Ultrathin Cobalt Doped Iron Thiophosphite Nanosheets toward Electrochemical Ammonia Synthesis
  Huang, Hao; Li, Fumin; Xue, Qi; Zhang, Ying; Yin, Shiwei; Chen, Yu
  Small (2019), 15 (51), 1903500CODEN: SMALBC; ISSN:1613-6810. (Wiley-VCH Verlag GmbH & Co. KGaA)
  Exploiting efficient electrocatalysts for electrochem. N redn. (NRR) is highly desired and deeply meaningful for realizing sustainable NH3 (NH3) prodn. under ambient conditions. The Fe protein contains one [Fe4S4] cluster and P cluster, which play an important role for transfer electron during the N fixing of nitrogenases. Based on the understanding of nitrogenase, the rising-star 2-dimensional Fe thiophosphite (FePS3) nanomaterials may be highly active electrocatalysts toward NRR due to the ideal elemental compn. 2D FePS3 nanosheets are successfully synthesized by a facile salt-templated method. The FePS3 nanosheets show better electrocatalytic NH3 yield and faradaic efficiency (FE) than Fe2S3, which demonstrates that the P element indeed improves the NRR activity of Fe-S. Theor., Co incorporation not only effectively prompts the cond. of FePS3, but also enhances the catalytic activities of Fe-edge sites. Exptl., Co-doped FePS3 (Co-FePS3) nanosheets exhibit a remarkable electrocatalytic performance toward NRR, such as high NH3 yield rate of 90.6μg h-1 mgcat-1, high FE of 3.38%, and an excellent long-term stability. Being the 1st theor. and exptl. report regarding FePS3-based electrocatalyst toward NRR, this work represents an important beginning to the family of metal thiophosphite as advanced electrocatalysts toward NRR.
55. 55
  Mayorga-Martinez C. C. Sofer Z. Sedmidubsky D. Huber S. Eng A. Y. Pumera M. Layered Metal Thiophosphite Materials: Magnetic, Electrochemical, and Electronic Properties ACS Appl. Mater. Interfaces 2017 9 14 12563 12573
  55
  Layered Metal Thiophosphite Materials: Magnetic, Electrochemical, and Electronic Properties
  Mayorga-Martinez, Carmen C.; Sofer, Zdenek; Sedmidubsky, David; Huber, Stepan; Eng, Alex Yong Sheng; Pumera, Martin
  ACS Applied Materials & Interfaces (2017), 9 (14), 12563-12573CODEN: AAMICK; ISSN:1944-8244. (American Chemical Society)
  Beyond graphene, transitional metal dichalcogenides, and black phosphorus, there are other layered materials called metal thiophosphites (MPSx), which are recently attracting the attention of scientists. Here we present the synthesis, structural and morphol. characterization, magnetic properties, electrochem. performance, and the calcd. d. of states of different layered metal thiophosphite materials with a general formula MPSx, and as a result of varying the metal component, we obtain CrPS4, MnPS3, FePS3, CoPS3, NiPS3, ZnPS3, CdPS3, GaPS4, SnPS3, and BiPS4. SnPS3, ZnPS3, CdPS3, GaPS4, and BiPS4 exhibit only diamagnetic behavior due to core electrons. By contrast, trisulfides with M = Mn, Fe, Co, and Ni, as well as CrPS4, are paramagnetic at high temps. and undergo a transition to antiferromagnetic state on cooling. Within the trisulfides series the Neel temp. characterizing the transition from paramagnetic to antiferromagnetic phase increases with the increasing at. no. and the orbital component enhancing the total effective magnetic moment. Interestingly, in terms of catalysis NiPS3, CoPS3, and BiPS4 show the highest efficiency for hydrogen evolution reaction (HER), while for the oxygen evolution reaction (OER) the highest performance is obsd. for CoPS3. Finally, MnPS3 presents the highest oxygen redn. reaction (ORR) activity compared to the other MPSx studied here. This great catalytic performance reported for these MPSx demonstrates their promising capabilities in energy applications.
56. 56
  Yu Z. Peng J. Liu Y. Liu W. Liu H. Guo Y. Amine-Assisted Exfoliation and Electrical Conductivity Modulation Toward Few-layer FePS₃ Nanosheets for Efficient Hydrogen Evolution J. Mater. Chem. A 2019 7 23 13928 13934
  56
  Amine-assisted exfoliation and electrical conductivity modulation toward few-layer FePS3 nanosheets for efficient hydrogen evolution
  Yu, Zhi; Peng, Jing; Liu, Yuhua; Liu, Wenxiu; Liu, Haifeng; Guo, Yuqiao
  Journal of Materials Chemistry A: Materials for Energy and Sustainability (2019), 7 (23), 13928-13934CODEN: JMCAET; ISSN:2050-7496. (Royal Society of Chemistry)
  Layered metal phosphorus trichalcogenides (MPX3, M = transition metal, X = S or Se) have been established as new efficient catalysts for water splitting, with FePS3 as one representative example. Here, a novel amine-assisted exfoliation strategy is presented to obtain few-layer FePS3 nanosheets, whose intrinsic elec. cond. can be easily regulated by adjusting the reaction temp. The improved elec. cond. originates from the increase of the Fe3+/Fe2+ ratio, while matrix crystallinity also plays a vital role in this aspect. The combined effect of mixed valence and crystallinity results in superior HER performance with a decrease of the overpotential of 147 mV and a drop of the Tafel slope from 139-94 mV dec-1.
57. 57
  Lian Q. Zhong L. Du C. Luo Y. Zhao J. Zheng Y. Xu J. Ma J. Liu C. Li S. Yan Q. Interfacing Epitaxial Dinickel Phosphide to 2D Nickel Thiophosphate Nanosheets for Boosting Electrocatalytic Water Splitting ACS Nano 2019 13 7 7975 7984
  There is no corresponding record for this reference.
58. 58
  Gusmão R. Sofer Z. Sedmidubský D. Huber Š. Pumera M. The Role of the Metal Element in Layered Metal Phosphorus Triselenides upon Their Electrochemical Sensing and Energy Applications ACS Catal. 2017 7 12 8159 8170
  58
  The Role of the Metal Element in Layered Metal Phosphorus Triselenides upon Their Electrochemical Sensing and Energy Applications
  Gusmao, Rui; Sofer, Zdenek; Sedmidubsky, David; Huber, Stepan; Pumera, Martin
  ACS Catalysis (2017), 7 (12), 8159-8170CODEN: ACCACS; ISSN:2155-5435. (American Chemical Society)
  The no. of layered materials seems to be ever-growing, from mono- to multielement, with affiliates and applications being tested continuously. Chalcogenophosphites, also designated as metal phosphorus chalcogenides (MPXn), have attracted great interest because of not only their magnetic properties but also promising capabilities in energy applications. Herein, bulk crystals of different layered metal triselenophosphites, with a general formula MPSe3 (M = Cd, Cr, Fe, Mn, Sn, Zn), were synthesized. Structural and morphol. characterization was performed prior to testing their electrochem. performance. From the set of ternary layered materials, FePSe3, followed by MnPSe3, yielded the highest efficiency for the hydrogen evolution reaction (HER) both in acidic and alk. media with good stability after 100 cycles. MnPSe3 also holds the lowest oxidn. potential for cysteine, although this is due to the presence of MnO2 in the structure as detected by XPS. For the oxygen evolution reaction, the best performance was obsd. for FePSe3, although the stability of the material was not as good as in the case of HER. These findings have profound implications in the application of these layered ternary compds. in energy-related fields.
59. 59
  Hao Y. Huang A. Han S. Huang H. Song J. Sun X. Wang Z. Li L. Hu F. Xue J. Peng S. Plasma-Treated Ultrathin Ternary FePSe₃ Nanosheets as a Bifunctional Electrocatalyst for Efficient Zinc–Air Batteries ACS Appl. Mater. Interfaces 2020 12 26 29393 29403
  59
  Plasma-Treated Ultrathin Ternary FePSe3 Nanosheets as a Bifunctional Electrocatalyst for Efficient Zinc-Air Batteries
  Hao, Yanan; Huang, Aijian; Han, Silin; Huang, Hongjiao; Song, Junnan; Sun, Xiaoli; Wang, Zhiguo; Li, Linlin; Hu, Feng; Xue, Jianjun; Peng, Shengjie
  ACS Applied Materials & Interfaces (2020), 12 (26), 29393-29403CODEN: AAMICK; ISSN:1944-8244. (American Chemical Society)
  Developing novel bifunctional electrocatalysts with advanced oxygen electrocatalytic activity is pivotal for next-generation energy-storage devices. Herein, we present ultrathin oxygen-doped FePSe3 (FePSe3-O) nanosheets by Ar/O2 plasma treatment, with remarkable surface atom reorganization. Such surface atom reorganization generates multiple cryst.-amorphous interfaces that benefit the kinetics of oxygen evolution reaction, achieving a low overpotential of only 261 mV at 10 mA cm-2 with a small Tafel slope of 41.13 mV dec-1. D. functional theory calcn. indicates that oxygen doping can also modulate the elec. states at the Fermi level with a decreased band gap responsible for the enhanced electrocatalytic performance. Such unique FePSe3-O nanosheets can be further fabricated as the air cathode in rechargeable liq. zinc-air batteries (ZABs), which deliver a high open circuit potential of 1.47 V, a small charge-discharge voltage gap of 0.80 V, and good cycling stability for more than 800 circles. As a proof of concept, the flexible solid-state ZABs assembled with FePSe3-O nanosheets as cathode also display a favorable charge-discharge performance, durable stability, and good bendability. This work sheds new insights into the rational design of defect-rich ternary thiophosphate nanosheets by plasma treatment toward enhanced oxygen electrocatalysts in metal-air batteries.
60. 60
  Konkena B. Masa J. Botz A. J. R. Sinev I. Xia W. Koßmann J. Drautz R. Muhler M. Schuhmann W. Metallic NiPS₃@NiOOH Core–Shell Heterostructures as Highly Efficient and Stable Electrocatalyst for the Oxygen Evolution Reaction ACS Catal. 2017 7 1 229 237
  60
  Metallic NiPS3@NiOOH Core-Shell Heterostructures as Highly Efficient and Stable Electrocatalyst for the Oxygen Evolution Reaction
  Konkena, Bharathi; Masa, Justus; Botz, Alexander J. R.; Sinev, Ilya; Xia, Wei; Kossmann, Joerg; Drautz, Ralf; Muhler, Martin; Schuhmann, Wolfgang
  ACS Catalysis (2017), 7 (1), 229-237CODEN: ACCACS; ISSN:2155-5435. (American Chemical Society)
  We report metallic NiPS3@NiOOH core-shell heterostructures as an efficient and durable electrocatalyst for the oxygen evolution reaction, exhibiting a low onset potential of 1.48 V (vs. RHE) and stable performance for over 160 h. The atomically thin NiPS3 nanosheets are obtained by exfoliation of bulk NiPS3 in the presence of an ionic surfactant. The OER mechanism was studied by a combination of SECM, in situ Raman spectroscopy, SEM, and XPS measurements, which enabled direct observation of the formation of a NiPS3@NiOOH core-shell heterostructure at the electrode interface. Hence, the active form of the catalyst is represented as NiPS3@NiOOH core-shell structure. Moreover, DFT calcns. indicate an intrinsic metallic character of the NiPS3 nanosheets with densities of states (DOS) similar to the bulk material. The high OER activity of the NiPS3 nanosheets is attributed to a high d. of accessible active metallic-edge and defect sites due to structural disorder, a unique NiPS3@NiOOH core-shell heterostructure, where the presence of P and S modulates the surface electronic structure of Ni in NiPS3, thus providing excellent conductive pathway for efficient electron-transport to the NiOOH shell. These findings suggest that good size control during liq. exfoliation may be advantageously used for the formation of elec. conductive NiPS3@NiOOH core-shell electrode materials for the electrochem. water oxidn.
61. 61
  Bushuyev O. S. De Luna P. Dinh C. T. Tao L. Saur G. van de Lagemaat J. Kelley S. O. Sargent E. H. What Should We Make with CO₂ and How Can We Make It ? Joule 2018 2 5 825 832
  61
  What Should We Make with CO2 and How Can We Make It?
  Bushuyev, Oleksandr S.; De Luna, Phil; Dinh, Cao Thang; Tao, Ling; Saur, Genevieve; van de Lagemaat, Jao; Kelley, Shana O.; Sargent, Edward H.
  Joule (2018), 2 (5), 825-832CODEN: JOULBR; ISSN:2542-4351. (Cell Press)
  In this forward-looking Perspective, we discuss the current state of technol. and the economics of electrocatalytic transformation of CO2 into various chem. fuels. Our anal. finds that short-chain simple building-block mols. currently present the most economically compelling targets. Making an optimistic prediction of technol. advancement in the future, we propose the gradual rise of photocatalytic, CO2 polymn., biohybrid, and mol. machine technologies to augment and enhance already practical electrocatalytic CO2 conversion methods.
62. 62
  Nitopi S. Bertheussen E. Scott S. B. Liu X. Y. Engstfeld A. K. Horch S. Seger B. Stephens I. E. L. Chan K. Hahn C. Norskov J. K. Jaramillo T. F. Chorkendorff I. Progress and Perspectives of Electrochemical CO₂ Reduction on Copper in Aqueous Electrolyte Chem. Rev. 2019 119 12 7610 7672
  62
  Progress and Perspectives of Electrochemical CO2 Reduction on Copper in Aqueous Electrolyte
  Nitopi, Stephanie; Bertheussen, Erlend; Scott, Soren B.; Liu, Xinyan; Engstfeld, Albert K.; Horch, Sebastian; Seger, Brian; Stephens, Ifan E. L.; Chan, Karen; Hahn, Christopher; Noerskov, Jens K.; Jaramillo, Thomas F.; Chorkendorff, Ib
  Chemical Reviews (Washington, DC, United States) (2019), 119 (12), 7610-7672CODEN: CHREAY; ISSN:0009-2665. (American Chemical Society)
  A review. To date, copper is the only heterogeneous catalyst that has shown a propensity to produce valuable hydrocarbons and alcs., such as ethylene and ethanol, from electrochem. CO2 redn. (CO2R). There are variety of factors that impact CO2R activity and selectivity, including the catalyst surface structure, morphol., compn., the choice of electrolyte ions and pH, the electrochem. cell design, etc. Many of these factors are often intertwined, which can complicate catalyst discovery and design efforts. Here we take a broad and historical view of these different aspects and their complex interplay in CO2R catalysis on Cu, with the purpose of providing new insights, crit. evaluations, and guidance to the field with regards to research directions and best practices. First, we describe the various exptl. probes and complementary theor. methods that have been used to discern the mechanisms by which products are formed, and next we present our current understanding of the complex reaction networks for CO2R on Cu. Then we analyze two key methods that have been used in attempts to alter the activity and selectivity of Cu: nanostructuring and the formation of bimetallic electrodes. Finally, we offer some perspectives on the future outlook for electrochem. CO2R.
63. 63
  Zhao K. Quan X. Carbon-Based Materials for Electrochemical Reduction of CO₂ to C₂₊ Oxygenates: Recent Progress and Remaining Challenges ACS Catal. 2021 11 4 2076 2097
  63
  Carbon-Based Materials for Electrochemical Reduction of CO2 to C2+ Oxygenates: Recent Progress and Remaining Challenges
  Zhao, Kun; Quan, Xie
  ACS Catalysis (2021), 11 (4), 2076-2097CODEN: ACCACS; ISSN:2155-5435. (American Chemical Society)
  A review. Electrochem. redn. of CO2 to multicarbon (C2+) products is desirable because of the higher energy d. and economic value of C2+ products and the significant scientific issue for coupling of multicarbons. However, efficient conversion of CO2 into C2+ products remains challenging because of the difficulty in C-C coupling. Recently, numerous papers have reported carbon-based materials for C2+ products prodn. from CO2 electrochem. redn. Because of the unique properties of carbon-based materials in C2+ prodn., carbon-based materials can be used as a potential alternative for the electrocatalytic conversion of CO2. This Review summarized recent progresses in the formation of C2+ oxygenates from CO2 redn. on carbon-based materials. In this Review, we highlighted the strategies available for achieving C-C coupling on carbon-based electrocatalysts and revealed the relationships between intermediate adsorption energy and the selectivity of oxygenate prodn. from CO2 redn. Moreover, we provided the understandings for fabricating active sites of CO2 redn. on carbon-based materials and related mechanisms of C2+ oxygenate generation. The remaining challenges and opportunities for the electrochem. conversion of CO2 into C2+ oxygenates were discussed.
64. 64
  Birdja Y. Y. Pérez-Gallent E. Figueiredo M. C. Göttle A. J. Calle-Vallejo F. Koper M. T. M. Advances and Challenges in Understanding the Electrocatalytic Conversion of Carbon Dioxide to Fuels Nat. Energy 2019 4 9 732 745
  64
  Advances and challenges in understanding the electrocatalytic conversion of carbon dioxide to fuels
  Birdja, Yuvraj Y.; Perez-Gallent, Elena; Figueiredo, Marta C.; Gottle, Adrien J.; Calle-Vallejo, Federico; Koper, Marc T. M.
  Nature Energy (2019), 4 (9), 732-745CODEN: NEANFD; ISSN:2058-7546. (Nature Research)
  A review. The electrocatalytic redn. of carbon dioxide is a promising approach for storing (excess) renewable electricity as chem. energy in fuels. Here, we review recent advances and challenges in the understanding of electrochem. CO2 redn. We discuss existing models for the initial activation of CO2 on the electrocatalyst and their importance for understanding selectivity. Carbon-carbon bond formation is also a key mechanistic step in CO2 electroredn. to high-d. and high-value fuels. We show that both the initial CO2 activation and C-C bond formation are influenced by an intricate interplay between surface structure (both on the nano- and on the mesoscale), electrolyte effects (pH, buffer strength, ion effects) and mass transport conditions. This complex interplay is currently still far from being completely understood. In addn., we discuss recent progress in in situ spectroscopic techniques and computational techniques for mechanistic work. Finally, we identify some challenges in furthering our understanding of these themes.
65. 65
  Ji L. Chang L. Zhang Y. Mou S. Wang T. Luo Y. Wang Z. Sun X. Electrocatalytic CO₂ Reduction to Alcohols with High Selectivity over a Two-Dimensional Fe₂P₂S₆ Nanosheet ACS Catal. 2019 9 11 9721 9725
  65
  Electrocatalytic CO2 Reduction to Alcohols with High Selectivity over a Two-Dimensional Fe2P2S6 Nanosheet
  Ji, Lei; Chang, Le; Zhang, Ya; Mou, Shiyong; Wang, Ting; Luo, Yonglan; Wang, Zhiming; Sun, Xuping
  ACS Catalysis (2019), 9 (11), 9721-9725CODEN: ACCACS; ISSN:2155-5435. (American Chemical Society)
  Electrochem. conversion of CO2 into alcs. provides an attractive path toward achieving a carbon-neutral cycle, while its efficiency is challenged by identifying active electrocatalysts for the CO2 redn. reaction (CO2RR). In this work, we report the Fe2P2S6 nanosheet acts as an efficient CO2RR electrocatalyst toward highly selective hydrogenation of CO2 to alcs. This catalyst is capable of achieving a high total Faradaic efficiency (FEmethanol+ethanol) of 88.3%, with a FEmethanol up to 65.2% at -0.20 V vs the reversible hydrogen electrode in 0.5 M KHCO3 soln., much higher than most reported CO2RR electrocatalysts. D. functional theory calcns. indicate that Fe atom on the Fe2P2S6 surface can be regared as the active site for alc. formation.
66. 66
  Thompson A. H. Whittingham M. S. Transition Metal Phosphorus Trisulfides as Battery Cathodes Mater. Res. Bull. 1977 12 7 741 744
  66
  Transition metal phosphorus trisulfides as battery cathodes
  Thompson, A. H.; Whittingham, M. S.
  Materials Research Bulletin (1977), 12 (7), 741-4CODEN: MRBUAC; ISSN:0025-5408.
  The layered, transition-metal P trisulfides exhibit electrochem. activity. NiPS3 reacts with >4 Li resulting in a cell with a theor. energy double that of TiS2.
67. 67
  Brec R. Review on structural and chemical properties of transition metal phosphorous trisulfides MPS₃ Solid State Ion. 1986 22 1 3 30
  There is no corresponding record for this reference.
68. 68
  Foot P. J. S. Katz T. Patel S. N. Nevett B. A. Pieecy A. R. Balchin A. A. The Structures and Conduction Mechanisms of Lithium-intercalated and Lithium-Substituted Nickel Phosphorus Trisulphide (NiPS₃), and the Use of the Material as a Secondary Battery Electrode Phys. Status Solidi A 1987 100 1 11 29
  68
  The structures and conduction mechanisms of lithium-intercalated and lithium-substituted nickel phosphorus trisulfide (NiPS3), and the use of the material as a secondary battery electrode
  Foot, P. J. S.; Katz, T.; Patel, S. N.; Nevett, B. A.; Piercy, A. R.; Balchin, A. A.
  Physica Status Solidi A: Applied Research (1987), 100 (1), 11-29CODEN: PSSABA; ISSN:0031-8965.
  A review with 35 refs. The crystal structure and conduction of the title compds. are discussed and the possible use of these NiPS3 compds. as battery electrodes is suggested. An app. is given for the electrochem. lithiation of NiPS3 to form LixNiPS3.
69. 69
  Rouxel J. Brec R. Low-Dimensional Chalcogenides as Secondary Cathodic Materials: Some Geometric and Electronic Aspects Annu. Rev. Mater. Sci. 1986 16 1 137 162
  69
  Low-dimensional chalcogenides as secondary cathodic materials: some geometric and electronic aspects
  Rouxel, J.; Brec, R.
  Annual Review of Materials Science (1986), 16 (), 137-62CODEN: ARMSCX; ISSN:0084-6600.
  A review with 45 refs. on electronic and ionic cond. and reversibility of the title cathodic materials for batteries. The geometric aspects assocd. with intercalation (parameter expansion, long distance, and local structures), electronic transfer, and phase transitions are analyzed.
70. 70
  Li X. Wu X. Yang J. Half-Metallicity in MnPSe₃ Exfoliated Nanosheet with Carrier Doping J. Am. Chem. Soc. 2014 136 31 11065 11069
  70
  Half-Metallicity in MnPSe3 Exfoliated Nanosheet with Carrier Doping
  Li, Xingxing; Wu, Xiaojun; Yang, Jinlong
  Journal of the American Chemical Society (2014), 136 (31), 11065-11069CODEN: JACSAT; ISSN:0002-7863. (American Chemical Society)
  Searching two-dimensional (2D) half-metallic crystals that are feasible in expt. is essential to develop next-generation nanospintronic devices. Here, a 2-dimensional exfoliated MnPSe3 nanosheet with novel magnetism is 1st proposed based on 1st-principles calcns. In particular, the evaluated low cleavage energy and high in-plane stiffness indicate that the free-standing MnPSe3 nanosheet can be exfoliated from its bulk structure in expt. The MnPSe3 nanosheet is an antiferromagnetic semiconductor at its ground state, whereas both electron and hole doping induce its transition from antiferromagnetic semiconductor to ferromagnetic half-metal. Also, the spin-polarization directions of 2-dimensional half-metallic MnPSe3 are opposite for electron and hole doping, which can be controlled by applying an external voltage gate. The Monte Carlo simulation based on the Ising model suggests the Curie temp. of the doped 2-dimensional MnPSe3 crystal is up to 206 K. These advantages render the 2-dimensional MnPSe3 crystal with great potentials for application in elec.-field controlled spintronic devices.
71. 71
  Cabria I. El-Meligi A. A. DFT Simulation of Hydrogen Storage on Manganese Phosphorous Trisulphide (MnPS₃) Int. J. Hydrogen Energy 2018 43 11 5903 5912
  71
  DFT simulation of hydrogen storage on manganese phosphorous trisulfide (MnPS3)
  Cabria, I.; El-Meligi, A. A.
  International Journal of Hydrogen Energy (2018), 43 (11), 5903-5912CODEN: IJHEDX; ISSN:0360-3199. (Elsevier Ltd.)
  Manganese phosphorous trisulfide, MnPS3, is a solid layered material. The H2 gravimetric storage capacity of powd. MnPS3 at 80.15, 173.15, and 298.15° K and at moderate pressures was recently exptl. measured. The origin of storage capacity of this material is not well understood. The main hypothesis is that H2 is stored in powd. MnPS3 pores. Pores were modeled as two parallel MnPS3 layers sepd. by a certain distance. D. functional theory (DFT) simulations of the H2 interaction with the MnPS3 layer surface were performed to test this hypothesis. Simulations indicated H2 adsorption on the MnPS3 layer surface was energetically favorable, but only by a physisorption mechanism. Gravimetric capacity calcns. of powd. MnPS3 pores were also performed and were in reasonable agreement with exptl. results. A comparison of calcd. and exptl. gravimetric capacity showed that H2 storage on powd. MnPS3 was mainly due to in-pore compression; the contribution of the physisorption process to storage was very small.
72. 72
  Kuzminskii Y. V. Voronin B. M. Redin N. N. Iron and Nickel Phosphorus Trisulfides as Electroactive Materials for Primary Lithium Batteries J. Power Sources 1995 55 2 133 141
  72
  Iron and nickel phosphorus trisulfides as electroactive materials for primary lithium batteries
  Kuzminskii, Y. V.; Voronin, B. M.; Redin, N. N.
  Journal of Power Sources (1995), 55 (2), 133-41CODEN: JPSODZ; ISSN:0378-7753. (Elsevier)
  The theor. specific capacities of a family of layered compds. MPX3 (M = Fe, Co, Ni; X = S, Se) for current-producing reactions involving 1.5, 2, 6 and 9 lithium atoms per MPX3 mol. have been estd. These data show that FePS3 and NiPS3 are good electroactive materials for primary lithium cells. Conditions which allow one to shorten substantially the synthesis time of iron and nickel phosphorus trisulfides in ampules are presented. According to cond. measurements in the 293-673 K temp. range, NiPS3 is an intrinsic and FePS3 an extrinsic semiconductor. The discharge characteristics of Li/MPS3 (M = Fe, Ni) cells with an org. electrolyte have been studied; they confirmed that the participation of nine electrons in the redox process is possible. For a primary button cell of the std. size 2325, with a FePS3 cathode, the specific capacity and specific energy values obtained in a discharge 1.8-1.2 V range at load resistances of 3.0 to 30 kΩ were 500-1160 Ah/kg and 700-1770 Wh/kg (on a pure FePS3 basis), resp.
73. 73
  Kuzminskii Y. V. Voronin B. M. Petrushina I. M. Redin N. N. Prikhodko G. P. Nickel Phosphorus Trisulfide: An Electroactive Material for Medium-Temperature Lithium Batteries J. Power Sources 1995 55 1 1 6
  There is no corresponding record for this reference.
74. 74
  Liang Q. Zheng Y. Du C. Luo Y. Zhang J. Li B. Zong Y. Yan Q. General and Scalable Solid-State Synthesis of 2D MPS₃ (M = Fe, Co, Ni) Nanosheets and Tuning Their Li/Na Storage Properties Small Methods 2017 1 12 1700304
  There is no corresponding record for this reference.
75. 75
  Fujii Y. Miura A. Rosero-Navarro N. C. Higuchi M. Tadanaga K. FePS₃ Electrodes in All-Solid-State Lithium Secondary Batteries Using Sulfide-Based Solid Electrolytes Electrochim. Acta 2017 241 370 374
  75
  FePS3 electrodes in all-solid-state lithium secondary batteries using sulfide-based solid electrolytes
  Fujii, Yuta; Miura, Akira; Rosero-Navarro, Nataly Carolina; Higuchi, Mikio; Tadanaga, Kiyoharu
  Electrochimica Acta (2017), 241 (), 370-374CODEN: ELCAAV; ISSN:0013-4686. (Elsevier Ltd.)
  In bulk-type all-solid-state Li batteries with sulfide-based solid electrolytes, composite electrodes, in which an active material, a solid electrolyte, and a conductive additive are mixed, were used to enhance Li-ion diffusion and electronic cond. However, the addn. of electrolytes and electron-conductive additives to the composite electrodes decreases the amt. of active materials in the batteries. FePS3 was employed as the electrode in an all-solid-state Li secondary battery, without mixing the solid electrolytes and conductive additives. The all-solid-state cell using the FePS3 electrode exhibited reversible charge-discharge behavior for >30 cycles under a const. c.d. of 0.13 mA cm-2 at room temp. The discharge capacity of the cell was 107 mAh g-1 at the 30th cycle. This behavior was comparable to that of a cell with an electrode including a solid electrolyte and/or a conductive additive, indicating that the FePS3 electrode had sufficient paths of Li ions and of electron conduction. Probably FePS3 is an attractive Fe-based electrode for an all-solid-state battery using a sulfide-based solid electrolyte.
76. 76
  Liang Q. Zheng Y. Du C. Luo Y. Zhao J. Ren H. Xu J. Yan Q. Asymmetric-Layered Tin Thiophosphate: An Emerging 2D Ternary Anode for High-Performance Sodium Ion Full Cell ACS Nano 2018 12 12 12902 12911
  76
  Asymmetric-Layered Tin Thiophosphate: An Emerging 2D Ternary Anode for High-Performance Sodium Ion Full Cell
  Liang, Qinghua; Zheng, Yun; Du, Chengfeng; Luo, Yubo; Zhao, Jin; Ren, Hao; Xu, Jianwei; Yan, Qingyu
  ACS Nano (2018), 12 (12), 12902-12911CODEN: ANCAC3; ISSN:1936-0851. (American Chemical Society)
  The emerging Na ion batteries (SIBs) are believed to be prospective substitutes for Li ion batteries (LIBs) because of the wide distribution of Na resources. However, to compensate for the sluggish reaction kinetics and higher intrinsic potential of Na+ compared to Li+, cost-effective, reliable, and sustainable electrode materials must be explored for practical applications. Here, 2D ternary tin thiophosphate (SnP2S6) nanosheets (∼10 nm thickness) grown on graphene (denoted as SPS/G hybrid) are demonstrated as intriguing anodes for SIBs. The asym.-layered structure and ternary compn. enable the SPS/G hybrid with a high reversible capacity (1230 mAh/g at 50 mA/g), superior rate capability (200 mAh/g at 15 A/g), and an exceptional capacity retention of 76% after 1000 cycles at 2.0 A/g. A prototype Na-ion full cell constructed by pairing with the Na3V2O2(PO4)3F cathode affords a high capacity of 470 mAh/g at 30 mA/g (on the basis of anode wt.) and good cyclic capacity of 360 mAh/g at 150 mA/g. Such 2D ternary chalcogenides with low-cost elements are promising materials for superior SIBs.
77. 77
  Brec, R. , Review on Structural and Chemical Properties of Transition Metal Phosphorus Trisulfides MPS₃. In Intercalation in Layered Materials; Dresselhaus, M. S. , Ed.; Springer US: Boston, MA, 1986; pp 93− 124.
  There is no corresponding record for this reference.
78. 78
  Clement R. P. Garnier O. Jegoudez J. Coordination Chemistry of the Lamellar MPS₃ Materials: Metal-Ligand Cleavage as the Source of an Unusual Cation-Transfer Intercalation Process Inorg. Chem. 1986 25 1404 1409
  78
  Coordination chemistry of the lamellar MPS3 materials: metal-ligand cleavage as the source of an unusual "cation-transfer" intercalation process
  Clement, Rene; Garnier, Odile; Jegoudez, Jocelyne
  Inorganic Chemistry (1986), 25 (9), 1404-9CODEN: INOCAJ; ISSN:0020-1669.
  Several MPS3 lamellar materials exhibit a very unusual intercalation chem. based on a cation-transfer process between the solid and a solvent. This contrasts with the electron-transfer processes that governs the intercalation chem. of the layered dichalcogenides MX2. Although the MPS3 layers are made up of infinite arrays of P2S64- units coordinated to the M2+ cations, the metal-ligand (M-S) bonding still exhibits enough lability to allow the M2+ cations to jump, under very mild conditions, from intra- toward interlamellar sites (or the opposite) and even to be removed from the material, provided a suitable cation is available to intercalate the lattice and maintain elec. neutrality. Depending on the metal, the solvent, and the guest species, the reaction may take place spontaneously or require an assist, usually by complexing the leaving M2+ cations (EDTA). Small inserted ions (Na+, K+, etc.) are strongly solvated and mobile, and they can in turn be exchanged. To rationalize this behavior, it is suggested that the intercalation chem. of the MPS3 involves a chem. transformation of the whole of the material, rather than a diffusional process of the guest species within the host lattice. The MPS3 layered materials are considered as polynuclear complexes that can undergo heterogeneous equil. with their constitutive species M2+ and P2S64- and other species present in soln. In support of this mechanism, MPS3 materials were successfully prepd. by mixing aq. solns. of Na4P2S6 and transition-metal salts. Some implications of this mechanism are discussed.
79. 79
  Wang F. He J. Speeding Protons with Metal Vacancies Science 2020 370 6516 525 526
  79
  Speeding protons with metal vacancies
  Wang, Fengmei; He, Jun
  Science (Washington, DC, United States) (2020), 370 (6516), 525-526CODEN: SCIEAS; ISSN:1095-9203. (American Association for the Advancement of Science)
  Proton exchange membranes (PEMs) find applications not only in fuel cells and sensors but as chem. filters and in biol. systems. In particular, the Nafion (Chemours Company) PEM, which consists of sulfonated tetrafluoroethylene-based fluoropolymer-copolymer, is widely used in practical electrochem. processes. It has a high proton cond. up to 0.2 S/cm below 80°C and high relative humidity (RH) (>93%), but its cond. drops severely at higher temps. or at low RH (below 50%). On page 596 of this issue, Qian et al. report a new class of proton membranes assembled from two-dimensional (2D) layered transition-metal phosphorus trichalcogenide (TMPTC) nanosheets in which metal vacancies boost ion cond. These membranes exhibit a proton cond. of ∼0.95 S/cm at 90°C and 98% RH but still have a cond. of 0.26 S/cm even at 60% RH.

Two-Dimensional Metal Phosphorus Trichalcogenide Nanostructure for Sustainable Energy Conversion

Chapter Views

Citations

Abstract

1 Introduction

Figure 1

2 Strategies for MPX3 Synthesis

2.1 Bottom-up Method

2.1.1 Chemical Vapor Transport

Figure 2

2.1.2 Chemical Vapor Conversion (Deposition)

Figure 3

2.2 Top-down Method

2.2.1 Mechanical Exfoliation

2.2.2 Solution and Intercalation Methods

2.2.3 Electrochemical Exfoliation Method

3 Nanostructured MPX3-Based Materials for Sustainable Energy Conversion

3.1 Photocatalysis

Figure 4

3.1.1 Water Photocatalysis for Hydrogen Gas

3.1.2 CO2 Photocatalysis for Fuels

Figure 5

3.2 Electrocatalysis

3.2.1 Electrocatalytic Water Reduction and Oxidation

Figure 6

3.2.2 Electrocatalytic CO2 Reduction Reaction

Figure 7

3.3 Battery

Figure 8

Figure 9

3.4 Ion Exchange Membrane

Figure 10

4 Conclusion

Acknowledgments

References

Figure 1

Figure 2

Figure 3

Figure 4

Figure 5

Figure 6

Figure 7

Figure 8

Figure 9

Figure 10

References

2 Strategies for MPX₃ Synthesis

3 Nanostructured MPX₃-Based Materials for Sustainable Energy Conversion

3.1.2 CO₂ Photocatalysis for Fuels

3.2.2 Electrocatalytic CO₂ Reduction Reaction