Fluorine-Functionalized Pore-Space-Partitioned Metal–Organic Frameworks for One-Step Methane Purification
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Fluorine-Functionalized Pore-Space-Partitioned Metal–Organic Frameworks for One-Step Methane Purification
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  • Jia-Yao Liu
    Jia-Yao Liu
    Key Laboratory of Applied Surface and Colloid Chemistry (MOE), Key Laboratory of Macromolecular Science of Shaanxi Province, School of Chemistry & Chemical Engineering, Shaanxi Normal University, Xi’an 710062, China
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  • Li-Qiu Yang
    Li-Qiu Yang
    Key Laboratory of Applied Surface and Colloid Chemistry (MOE), Key Laboratory of Macromolecular Science of Shaanxi Province, School of Chemistry & Chemical Engineering, Shaanxi Normal University, Xi’an 710062, China
    More by Li-Qiu Yang
  • Yan-Fei Li
    Yan-Fei Li
    Key Laboratory of Applied Surface and Colloid Chemistry (MOE), Key Laboratory of Macromolecular Science of Shaanxi Province, School of Chemistry & Chemical Engineering, Shaanxi Normal University, Xi’an 710062, China
    More by Yan-Fei Li
  • Ying Wang
    Ying Wang
    Key Laboratory of Applied Surface and Colloid Chemistry (MOE), Key Laboratory of Macromolecular Science of Shaanxi Province, School of Chemistry & Chemical Engineering, Shaanxi Normal University, Xi’an 710062, China
    More by Ying Wang
    Orcidhttps://orcid.org/0000-0002-6199-6783
  • Wen-Yu Yuan
    Wen-Yu Yuan
    Key Laboratory of Applied Surface and Colloid Chemistry (MOE), Key Laboratory of Macromolecular Science of Shaanxi Province, School of Chemistry & Chemical Engineering, Shaanxi Normal University, Xi’an 710062, China
    More by Wen-Yu Yuan
    Orcidhttps://orcid.org/0000-0001-8443-1518
  • Quan-Guo Zhai*
    Quan-Guo Zhai
    Key Laboratory of Applied Surface and Colloid Chemistry (MOE), Key Laboratory of Macromolecular Science of Shaanxi Province, School of Chemistry & Chemical Engineering, Shaanxi Normal University, Xi’an 710062, China
    *Email: [email protected]
    More by Quan-Guo Zhai
    Orcidhttps://orcid.org/0000-0003-1117-4017
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Inorganic Chemistry

Cite this: Inorg. Chem. 2026, 65, 10, 5827–5838
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https://doi.org/10.1021/acs.inorgchem.6c00337
Published March 4, 2026

Copyright © 2026 American Chemical Society. This publication is licensed under these Terms of Use.

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Abstract

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The efficient removal of ethane (C2H6) and propane (C3H8) from natural gas is vital for purification. A synergistic pore engineering integrating pore space partition and fluorine functionalization in metal–organic frameworks (MOFs), which may effectively promote the C–H···π and C–H···F interactions for effective methane separation. This strategy was validated using two fluorine-functionalized pore-space-partitioned MOFs (SNNU-707/-708) constructed by introducing varying numbers of −CF3 groups on the pore surface. Single-component adsorption isotherms show high adsorption of SNNU-707/-708 for C2H6 and C3H8 were 94.9/63.6 cm3 g–1 and 96.4/68.9 cm3 g–1, significantly exceeding that of CH4 (18.9/13.4 cm3 g–1). Ideal adsorbed solution theory (IAST) indicated high selectivity values of 85.2/116.6 for C3H8/CH4 (50/50) and 16.7/17.0 for C2H6/CH4 (50/50). Notably, the actual breakthrough interval times of SNNU-707 for C3H8/CH4 (5/95) and C2H6/CH4 (10/90) can reach 502 and 78 min·g–1 and yield high-purity CH4 (>99.5%) at 5.89 mmol g–1 from ternary mixtures. Grand Canonical Monte Carlo (GCMC) simulations attribute this performance to synergistic weak interactions (C–H···π, C–H···F, C–H···O/N) between MOF and alkane. Specially, thanks to the fluorine-functionalized pore environments, both MOFs maintain structural integrity and separation performance under harsh conditions up to 98% relative humidity, which is crucial for practical wet natural gas separation.

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Introduction

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With the accelerated global industrialization process, the excessive combustion of conventional fossil fuels (coal and petroleum) has not only triggered an energy supply crisis but also posed severe challenges to the global ecological environment and sustainable human development. Due to its relatively clean nature (significantly lower carbon emissions and pollutants generated from combustion compared to coal), high utilization efficiency, and excellent complementarity with renewable energy sources, natural gas is regarded as a crucial transitional energy source for replacing traditional fossil fuels and supporting the stable evolution of the energy structure. (1−4)
Methane (CH4) is the primary component of natural gas, accounting for 70–96% of its total composition. A certain proportion of light hydrocarbon impurities coexist with CH4, including ethane (C2H6, 0–20%) and propane (C3H8, 0.01–5%). Ineffective removal of these impurities will directly reduce combustion efficiency and pose potential risks to the safe operation of transportation equipment. (5,6) Meanwhile, C2H6 and C3H8 are important raw materials in the petrochemical industry, which are used for synthesizing various fine chemicals. Efficient separation of these three components is therefore of great significance, as it can enhance the comprehensive utilization value of natural gas resources, ensure energy security and promote the diversification of chemical feedstocks. (7−10)
Currently, cryogenic distillation is the dominant technology for industrial separation of small-molecule light hydrocarbon mixtures. This technology has inherent limitations, such as high energy consumption, large equipment investment and stringent operating conditions. These deficiencies drive researchers to develop alternative separation technologies with higher energy efficiency, better performance and milder operating conditions. (11−13) Among these alternative technologies, adsorption separation exhibits distinct advantages due to its low energy consumption and simple operation. (14−17) Commonly used adsorbents include carbon-based materials, molecular sieves and zeolites. However, these materials suffer from insufficient adsorption capacity and low selectivity, which limit their separation efficiency. To overcome the challenges of complex separation systems, the design and development of novel adsorbent materials with tunable pore structures and functionalized surfaces are crucial for realizing green and efficient separation processes.
Porous coordination polymers (PCPs), also known as metal–organic frameworks (MOFs), have advanced considerably in light hydrocarbon separation research in recent years. Their tunable pore environments and facile functionalization lay the foundation for this progress. (18−21) Research on separating ternary and more complex gas mixtures is still in its early stages. The main reason lies in the coupling of multicomponent adsorption equilibria and kinetic behaviors. This coupling creates substantial difficulties for the structural design of adsorbents. However, industrial practice has an urgent demand for efficient separation of multicomponent alkane/alkene/alkyne mixtures, especially under humid gas conditions. This demand enhances the practical value of relevant research. (22,23) Water vapor is a common impurity and often exerts a significant negative impact on gas separation performance. For one thing, the coordination between water molecules and unsaturated metal sites in MOFs may destabilize the framework structure. For another, preferential adsorption of water molecules occupies pore space, which noticeably reduces the adsorption capacity for target gases. (24−26) Thus, designing and synthesizing new porous materials with both high water stability and excellent alkane separation performance is crucial to advancing the industrial application of multicomponent gas separation technologies.
Drawing on the basic principles of material surface chemical modification, introducing fluorine atoms can effectively adjust the wetting properties of materials. Studies have confirmed that fluorination modification can significantly improve the hydrophobicity of porous materials. The strong electronegativity of fluorine atoms is the key factor here, as it reduces the material’s surface energy. This hydrophobic treatment effectively blocks the adsorption and diffusion of water molecules in pore channels. It also eases the negative effects of water vapor on the separation selectivity and structural integrity of MOFs at the molecular level. (27−30) In addition, aromatic-rich pore-partitioners in MOFs are capable of partitioning pore space. This partitioning may allow efficient recognition and sieving of alkane molecules with different carbon chain lengths via differentiated C–H···π interactions. (31,32) Synergizing these two approaches is expected to develop a new category of MOF materials. These materials combine high water stability with excellent alkane separation performance, properly addressing the research challenges mentioned earlier. Recently, merged-net strategies and multicomponent assembly have been employed to construct high-connectivity MOFs with enhanced robustness and porosity, demonstrating the power of reticular chemistry in designing stable frameworks for gas storage and separation. (33) In a similar spirit, our work integrates pore-space partition and fluorine functionalization to create a multicomponent MOF platform that combines confined adsorption environments with hydrophobic pore surfaces, addressing the challenge of humid natural gas purification. Therefore, the pore space partition and fluorine functionalization strategies were combined herein to construct two new MOFs (namely SNNU-707 and SNNU-708), in which the hydrophobic −CF3 groups from the ligands 2-(trifluoromethyl)-terephthalic acid (BDC–CF3) and 2,5-bis(trifluoromethyl)-terephthalic acid (BDC-(CF3)2) are positioned on the pore surfaces. These materials are designed for the efficient separation of C2H6 and C3H8 from natural gas under humid conditions.
The introduction of trifluoromethyl groups into the MOF framework may not only provide multiple H···F interactions, but also enhance the framework stability under humid conditions. As a result, SNNU-707 and SNNU-708 show much higher C2H6 and C3H8 uptake capacity than CH4, preliminarily revealing their preferential adsorption characteristics toward C3H8 and C2H6 molecules and further validated by their higher isosteric heats of adsorption and the ideal adsorbed solution theory (IAST) selectivity values. The excellent dynamic separation performance and regenerability were further confirmed through breakthrough experiments for the C3H8/C2H6/CH4 (v/v/v = 5:10:85) ternary mixture with a one-step outlet CH4 purity higher than 99.5% and corresponding yields of 5.89 and 5.50 mmol g–1, respectively. Grand canonical Monte Carlo (GCMC) simulations demonstrate that the primary adsorption sites for C2H6 and C3H8 mainly arise from the synergistic enhancement effect of the polar microenvironment within the MOF framework and multiple weak interactions, such as C–H···π, C–H···O, C–H···N, and C–H···F. Furthermore, the fluorination strategy also effectively suppresses the negative impact of water vapor on adsorption performance, significantly enhancing the applicability and stability of these materials under real operating conditions.

Experimental Section

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Synthesis of [Co2V(OH)(BDC–CF3)3TPP] (SNNU-707)

A mixture of Co(NO3)2·6H2O (60 mg, 0.2 mmol), VCl3 (16 mg, 0.1 mmol), BDC–CF3 (60 mg, 0.26 mmol), 2,4,6-tris(4-pyridyl)-pyridine (TPP) (31 mg, 0.1 mmol), 3 mL N,N’-dimethylformamide (DMF) and one drop of concentrated HCl solution (12 M, 36%–38%) was sealed in a 20 mL glass vial and heated at 120 °C for 3 days. After cooling to room-temperature, dark-red spindle-shaped crystals were obtained by filtering and washing with DMF. The yield was about 54% based on metal salt.

Synthesis of [Co2V(OH)(BDC-(CF3)2)3TPP] (SNNU-708)

A mixture of Co(NO3)2·6H2O (60 mg, 0.2 mmol), VCl3 (16 mg, 0.1 mmol), BDC-(CF3)2 (60 mg, 0.2 mmol), 2,4,6-tris(4-pyridyl)-pyridine (TPP) (21 mg, 0.07 mmol), 4 mL N,N′-dimethylacetamide (DMA) and 0.2 mL tetrafluoroboric acid (HBF4, ≥40%) solution was sealed in a 20 mL glass vial and heated at 120 °C for 3 days. After cooling to room-temperature, dark-red spindle-shaped crystals were obtained by filtering and washing with DMA. The yield was about 78% based on metal salt.

Results and Discussion

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Structure Description

SNNU-707 and SNNU-708 were successfully produced under similar solvothermal conditions by reacting cobalt(II) nitrate hexahydrate and vanadium(III) chloride with the pore-partitioning agent TPP, along with different dicarboxylic acid ligands BDC–CF3 and BDC-(CF3)2, respectively (Figure 1a). The heterometallic composition was confirmed through energy-dispersive X-ray spectroscopy (Figure S1). Single-crystal X-ray diffraction analysis revealed that SNNU-707 and SNNU-708 are well-known pacs-MOFs (pacs = partitioned acs net) (Figure S2), (34−37) differing mainly in the number of −CF3 groups decorating their pore environments (Figures 1b–e and S3–S4). In terms of space groups, SNNU-707 crystallizes in the hexagonal space group P63/mmc, while SNNU-708 adopts the trigonal space group P-3, with detailed crystallographic data provided in Table S1. The difference in space groups stems from the symmetry of the dicarboxylic acid ligands used. SNNU-707 employs the monosubstituted ligand BDC–CF3, which has higher molecular symmetry and favors a hexagonal packing arrangement. In contrast, SNNU-708 is built from the disubstituted ligand BDC-(CF3)2. The presence of two −CF3 groups reduces the ligand symmetry through steric and electronic effects, leading to crystallization in a trigonal system with lower symmetry. Taking SNNU-707 as an example, its secondary building unit (SBU) is a 9-connected trinuclear cluster formed by three metal centers (Co/V) bridged through μ3-O atoms and interconnected via the dicarboxylic acid ligand BDC–CF3. Each metal center adopts an octahedral geometry, coordinating to one N atom from a TPP ligand, one μ3–O atom, and four carboxylate O atoms derived from four distinct BDC–CF3 ligands. The structure of pacs-MOFs typically contains two types of cages: octahedral cages (o-cages) and trigonal-bipyramidal cages (t-cages). (38) In SNNU-707, the o-cage is constructed from six Co2V-clusters, six BDC–CF3 linkers, and two TPP ligands, with an estimated dimension of approximately 4.5 Å. The t-cage is composed of five metal clusters, six BDC–CF3 linkers, and three TPP ligands, with a cage dimension of about 4.5 Å. SNNU-708 shares a similar cage architecture with SNNU-707. The key difference is that BDC–CF3 is substituted by BDC-(CF3)2. The o-cage and t-cage of SNNU-708 have dimensions of roughly 4.5 Å and 4.5 Å, respectively (Figures 1f,g and S5). Both compounds possess well-defined pore-partitioned structures. The TPP ligand divides the 1D channels along the c-axis into approximately cylindrical cage-like subunits (Figure 1b,c). However, their pore surfaces are functionalized with different numbers of −CF3 groups. This variation in −CF3 modification may affect their gas adsorption and separation performance differently. Notably, the presence of −CF3 groups also helps enhance the stability of these MOFs under humid conditions, which aligns with the earlier requirement for water-stable porous materials.

Figure 1

Figure 1. Structural features of SNNU-707/-708: (a) metal clusters and organic linkers. (b, c) porous frameworks viewed along the c-axis direction. (d, e) porous frameworks viewed along the a-axis direction. (f, g) side views of octahedral cages (o-cages) and trigonal-bipyramidal cages (t-cages).

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Purity and Stability

Powder X-ray diffraction (PXRD) patterns of SNNU-707 and SNNU-708 are consistent with the simulated patterns derived from single-crystal data. This confirms their high crystallinity and phase purity. Furthermore, their structural integrity remains unimpaired without framework collapse after adsorption and breakthrough experiments (Figures S6–S7). To evaluate the stability of the two compounds in acids, bases and water, they were immersed in solutions with different pH values. After soaking in solutions of pH = 1, 3, 5, 7, 9, and 11 for 3 days, the MOF samples retained their original PXRD patterns. This highlights their excellent stability under acidic, alkaline and aqueous conditions (Figures 2a and S8–S9). Gas adsorption measurements on the soaked SNNU-708 sample further verified its structural stability. The C3H8 adsorption capacity at 298 K was nearly identical to that of the pristine sample (Figure 2b). In addition, immersion in various solvents did not alter the PXRD patterns of SNNU-707 and SNNU-708. These patterns still matched well with the simulated ones, confirming their robust chemical stability (Figures S10–S11).

Figure 2

Figure 2. Gas adsorption performance of SNNU-707/-708: (a) PXRD patterns of SNNU-708 immersed in pH-1–11 solution for 3 days. (b) adsorption isotherms of C3H8 on SNNU-708 at 298 K after immersing in pH-1–11 solution for 3 days. (c) N2 at 77 K with pore size distributions. (d–f) C3H8, C2H6 and CH4 at 273, 283, and 298 K. (g) summary and comparison of C3H8 and C2H6 adsorption capacities for selected reported MOFs adsorbents are presented. (h) the Qst values for C3H8, C2H6 and CH4 at 298 K. (i) the IAST selectivity for 50/50 C3H8/CH4 and C2H6/CH4.

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Thermal stability of the two MOFs was further evaluated via thermogravimetric analysis (TGA). Results show that SNNU-707 and SNNU-708 exhibit similar thermal decomposition behaviors (Figure S12). A continuous weight loss is observed from room temperature to approximately 200 °C. This weight loss is attributed to the gradual removal of solvent molecules confined in the pores. Subsequently, a distinct plateau emerges in the temperature range of 200 °C to nearly 400 °C. This indicates that the MOFs maintain structural stability within this interval. With further increase in temperature, continuous weight loss occurs again, primarily resulting from the decomposition of the ligands. TGA results confirm that both MOFs possess high thermal stability. This property endows them with potential for practical applications in industrial separation fields.

Gas Adsorption Properties

N2 adsorption–desorption measurements at 77 K were employed to characterize the permanent porosity of the two MOF materials. As presented in Figure 2c, both SNNU-707 and SNNU-708 display typical Type I adsorption isotherms, with pore sizes mainly ranging from 6.0 to 6.1 Å, confirming their microporous structural features. The saturated adsorption capacities are 321.7 cm3 g–1 and 242.5 cm3 g–1 with BET specific surface areas of 1114 m2 g–1 and 849.6 m2 g–1, showing a stepwise decreasing trend and confirming the successful functionalization of different −CF3 groups.
To further investigate the adsorption properties of the two MOF materials toward C3H8, C2H6, and CH4, single-component gas adsorption–desorption measurements were conducted at 273, 283, and 298 K (Figures 2d–f and Table S2). As shown in Figure 2f, at 298 K and 1 bar, the adsorption capacities of SNNU-707/-708 for CH4, C2H6, and C3H8 are 18.9/13.4 cm3 g–1, 94.9/63.6 cm3 g–1, and 96.4/68.9 cm3 g–1, respectively. Notably, both compounds exhibit significantly higher adsorption capacities for C3H8 and C2H6 than for CH4, following the order C3H8 > C2H6 > CH4. Among them, SNNU-707 demonstrates superior adsorption capacity for C3H8 and C2H6 compared to many reported MOFs, such as Zr-DMTDC, (2) Zn(ADC)(TED)0.5, (39) JLU-Liu15, (40) UiO-66, (41) and Ni-MOF (42) (Figure 2g and Table S3). These results strongly support our proposal that C–H···π interactions between the aromatic partitioners in MOFs and alkanes can effectively enhance their alkane separation performance.
Given the relatively low concentrations of C2H6 (0–20%) and C3H8 (0.01–5%) in natural gas, the adsorption behaviors of C2H6 at 10 kPa and C3H8 at 5 kPa are key parameters for evaluating natural gas separation and purification performance. At 298 K and 10 kPa, their adsorption capacities for C2H6 are 30.8 cm3 g–1 and 23.5 cm3 g–1, respectively. At 298 K and 5 kPa, the adsorption capacities for C3H8 reach 63.6 cm3 g–1 and 45.3 cm3 g–1. These values correspond to 32.5%/36.9% and 66%/65.7% of their respective saturated adsorption capacities, reflecting good low-pressure adsorption potential. Notably, the adsorption capacities of SNNU-707 exceed those of many famous MOF adsorbetns, such as Co-MOF (23.8/36.6), (43) BSF-1 (15/26.9), (4) ZJNU-402 (11/49), (44) TIFSIX-Cu-TPA (22.4/44.8), (45) UTSA-35a (29.1/36.7), (46) and Fe-NDC(SO3H)-TPH (21.45/48.8), (47) indicating stronger interactions with C2H6 and C3H8 molecules (Tables S4–S5). Based on the adsorption isotherm profiles (Figures S13–S15), in the low-pressure region approaching the partial pressures of actual natural gas impurities (C2H6: 10 kPa, C3H8: 5 kPa), both SNNU-707 and SNNU-708 exhibit a steep initial rise in adsorption for C2H6 and C3H8, indicating rapid adsorption kinetics and high affinity even at extremely low concentrations. This behavior can be attributed to the synergistic effect between the ordered cage structure formed by the partitioned pore channels in the materials and the surface −CF3 groups: the pore partitioning creates size-matched confinement spaces, facilitating selective capture of target alkane molecules; while the introduction of −CF3 groups further enhances the pore surface’s recognition and binding capacity for C2H6 and C3H8 through weak interactions such as C–H···F. These experimental results confirm that both MOF materials are capable of effectively capturing and enriching C3H8 and C2H6 molecules. This capability creates favorable conditions for the one-step removal of these two light hydrocarbon impurities from natural gas.
In contrast, the two MOFs exhibit lower CH4 adsorption capacity under the same conditions. Their CH4 adsorption isotherms show an essentially linear relationship within the tested pressure range, which reflects weaker interactions between CH4 molecules and the MOF frameworks. Such differences in adsorption performance stem from the enhanced synergistic effects between aromatic partitioners and alkanes. C3H8 possesses higher polarizability and more C–H bonds, enabling it to form stronger, hydrogen-bond-like specific interactions with aromatic rings. By comparison, C2H6 has fewer C–H bonds, leading to fewer and weaker C–H···π interactions. On the other hand, CH4 barely forms such directional interactions with the framework. This adsorption mode evolves from weaker van der Waals forces to stronger C–H···π cooperative effects, ultimately leading to the trend in saturated adsorption capacities: CH4 < C2H6 < C3H8. On the other hand, the −CF3 groups introduced in the dicarboxylate linkers can form C–H···F hydrogen-bond interactions with alkane molecules, further modulating adsorption behavior. However, as the number of −CF3 groups on the pore surface increases from SNNU-707 to SNNU-708, the pores gradually become obstructed, reducing the accessible adsorption space for all alkane molecules and leading to a slight decrease in adsorption capacity.
The adsorption enthalpy (Qst) of porous materials can serve as a direct indicator of the strength of interactions between the adsorbent and various gas molecules. Therefore, the adsorption isotherm data at 273 and 298 K were fitted using the Virial equation, and the Qst values of the two MOFs were further calculated (Figures 2h, S16–S23 and Tables S6–S8). At the limit of zero coverage, the Qst values of SNNU-707/-708 follow the descending order: C3H8 (36.4/41.1 kJ mol–1) > C2H6 (26.0/28.1 kJ mol–1) > CH4 (17.0/16.9 kJ mol–1), which is consistent with the trend in adsorption capacities. This indicates that both MOFs exhibit stronger binding affinity for C3H8 and C2H6 than for CH4, thereby promoting preferential adsorption of C3H8 and C2H6. Such adsorption behavior makes them ideal adsorbents for removing CH4 from C3H8/C2H6/CH4 ternary mixtures. The data further show that an increase in the number of −CF3 groups enhances the adsorption interactions with C2H6 and C3H8. Specifically, compared to SNNU-707 containing a single −CF3 group, SNNU-708 with two −CF3 groups exhibits an increasement in Qst values of approximately 4.7 kJ mol–1 for C3H8 and 2.1 kJ mol–1 for C2H6, while the Qst value for CH4 remains essentially unchanged. This difference clearly demonstrates that introducing additional −CF3 groups selectively strengthens interactions with larger, more polarizable alkane molecules (C2H6/C3H8), thereby thermodynamically enhancing the adsorption selectivity of MOFs for C3H8/C2H6 over CH4.
Based on the strong affinity of SNNU-707/-708 toward C3H8 and C2H6, their separation performance for C3H8/CH4 and C2H6/CH4 mixed gases were further evaluated within the temperature range of 273–298 K using the ideal adsorbed solution theory (IAST) (Figures 2i, S24–S31 and Tables S9–S12). The calculated results show that at 298 K and 1 bar, the IAST selectivity of SNNU-708 for C3H8/CH4 (50:50) reaches as high as 116.6, which is significantly higher than that of SNNU-707 (85.2). Its selectivity for C2H6/CH4 (50:50) also slightly increases to 17.0 (compared to 16.7 for SNNU-707). This trend fully aligns with the selective enhancement effect of −CF3 groups on larger alkane molecules, as reflected in the Qst data. The additional −CF3 groups in SNNU-708 strengthen the van der Waals interactions with C3H8 and C2H6 without significantly affecting CH4 adsorption, thereby further enlarging the differences in adsorption capacity and binding strength for C3H8 and C2H6 relative to CH4. This leads to thermodynamically superior separation selectivity. Although these values are not the highest reported, they are still higher than or comparable to those of many reported MOF adsorbents under similar conditions, such as InOF-1 (90, 17), (48) JUC-106 (82.5, 12.4), (49) Iso-MOF-4 (80, 8.5), (50) FIR-7a-ht (78.8, 14.6), (51) and UPC-32 (28, 5.8). (52) This also demonstrates the excellent capability of SNNU-707/-708 in separating C3H8/CH4 and C2H6/CH4 mixed gases.
To evaluate the practical separation performance, dynamic breakthrough experiments were further conducted on SNNU-707/-708 using C3H8/CH4, C2H6/CH4, and C3H8/C2H6/CH4 gas mixtures. As shown in Figure 3, due to its low adsorption capacity and weak interaction with the MOF framework, CH4 elutes first from the breakthrough column, while C3H8 and C2H6 are retained longer in the column owing to stronger adsorption until saturation is reached. When C3H8/CH4 and C2H6/CH4 equimolar binary mixtures were introduced at a total flow rate of 2 mL·min–1 under 298 K and 1 bar, the separation times for SNNU-707/-708 were of 59.3/50.1 min g–1 and 38.7/33.6 min g–1, respectively (Figure 3a). This indicates that the separation performance slightly decreases as the number of −CF3 groups increases, which partially blocks the pore channels, consistent with the trend observed in adsorption measurements. SNNU-707, modified with single −CF3 group, achieves relatively longer separation times. Further dynamic breakthrough tests were performed on two MOFs using 5/95 C3H8/CH4 and 10/90 C2H6/CH4 gas mixtures. As shown in Figures 3b,c, the separation times for SNNU-707 were 502- and 78 min g–1, respectively, while those for SNNU-708 were 423.5- and 62.4 min g–1.

Figure 3

Figure 3. Dynamic breakthrough performance of SNNU-707/-708: (a) for 50/50 C2H6/CH4 and C3H8/CH4 mixtures. (b, c) for 10/90 C2H6/CH4 mixtures and 5/95 C3H8/CH4 mixtures. (d, e) for 5/10/85 C3H8/C2H6/CH4 mixtures. (f, g) for 5/10/85 C3H8/C2H6/CH4 mixtures in the moist and dry environments. (h, i) cycling test results.

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To assess the potential of the materials in practical natural gas separation, dynamic breakthrough experiments were further conducted using a ternary gas mixture with a representative industrial composition (C3H8/C2H6/CH4 = 5:10:85, v/v/v). As shown in Figures 3d,e, when the ternary gas mixture was introduced into the breakthrough column at a flow rate of 2 mL·min–1, CH4 was rapidly eluted with high purity (99.85%/99.58%) and exhibited the shortest breakthrough interval times (27/22.4 min g–1) for both MOF adsorbents. In contrast, C2H6 and C3H8 were significantly delayed due to stronger adsorption interactions, resulting in distinct differences in breakthrough times for each component. Notably, the separation time intervals between CH4 and C2H6, as well as between CH4 and C3H8, reached 77.6/72.5 min g–1 and 447.2/351.1 min g–1, respectively. These extended separation intervals facilitate the cyclic regeneration of the adsorption column. Furthermore, calculations reveal that the two materials exhibit CH4 productivity values of 5.89 and 5.50 mmol g–1, which surpass those of many reported MOF materials, including ZJNU-402 (0.42 mmol g–1), (44) Zn-BPZ-SA (1.56 mmol g–1), (53) MIL-101-Cr (2.66 mmol g–1), (54) ZUL-C1 (5.42 mmol g–1), (1) Fe-NDC(SO3H)-TPH (3.49 mmol g–1), (47) and γ-CDMOF-1 (2.10 mmol g–1) (3) (Table S13). Notably, the breakthrough behavior at 273 K further validates the outstanding alkane-sieving performance of both MOF materials (Figures S32–S33). At this lower temperature, the adsorption of C2H6 and C3H8 is significantly enhanced, as reflected by the extended separation intervals (C3H8/CH4: 698.2/648.6 min·g–1; C2H6/CH4: 164.3/149.1 min·g–1) compared to those observed at 298 K. Meanwhile, CH4 maintains its rapid breakthrough characteristics. These results demonstrate a further widening of the separation window among the components, highlighting the promising potential of these materials for practical separation applications even under low-temperature conditions. Moreover, when the total flow rate was adjusted to 4 mL min–1, SNNU-707 and SNNU-708 still exhibited relatively excellent separation performance for C3H8/CH4 (232.7/172.8 min g–1) and C2H6/CH4 (45.6/43.6 min g–1) (Figures S34–S35). Clearly, controlled adsorption separation of the three gas components has been successfully achieved.
Subsequently, to investigate whether humidity affects the separation performance of the two MOFs, the separation of C3H8/C2H6/CH4 mixtures under humid conditions were evaluated under relative humidity of 98%. As shown in Figures 3f,g, the breakthrough times of the three gases show no significant changes, indicating that both MOFs maintain good separation performance for C3H8/C2H6/CH4 and exhibit remarkable moisture resistance even under extreme humidity. Moreover, the cycling stability of the adsorbent is another key factor determining its practical separation efficiency. (43) After three consecutive cycles, the breakthrough curves of SNNU-707/-708 closely overlap with those of the initial experiments, demonstrating excellent regeneration and cycling stability. The postcycled samples also retained their original crystallinity (Figures 3h,i and S6–S7), further confirming the outstanding structural stability and regeneration performance of these materials under natural gas purification conditions.

In Situ Infrared Spectroscopy

In situ infrared spectroscopy was employed to characterize MOFs adsorbed with CH4, C2H6, and C3H8, aiming to clarify how material structures modulate gas adsorption behaviors. Figures 4a–f present infrared spectra that reflect interactions between these three gas molecules and SNNU-707/-708 under pressure conditions spanning 0 to 760 mmHg. With increasing system pressure, the intensities of certain originally weak or undetectable characteristic absorption peaks were remarkably enhanced. For SNNU-707, introduction of C3H8 rendered its C–H stretching vibration peak (∼2960 cm–1) clearly distinguishable. This peak was barely detectable at 0 mmHg but exhibited obvious intensification at 760 mmHg. In parallel, C2H6 showed a broad absorption peak near this wavenumber, with its characteristic signal gradually strengthening as pressure rose. This trend directly verifies the stepwise adsorption and enrichment of C3H8 and C2H6 within the pores of SNNU-707. By contrast, the C–H stretching vibration peak of CH4 appeared at ∼3014 cm–1, and its intensity varied only slightly before and after CH4 exposure. This result testifies to weak interactions between CH4 molecules and the MOF framework (Figures 4a–c). SNNU-708 yielded analogous experimental outcomes (Figures 4d–f). These results confirm that C3H8 and C2H6 form stronger C–H···π interactions with aromatic rings in both MOFs compared to CH4, which is consistent with the aforementioned adsorption and breakthrough data. Additionally, the bending vibration characteristic peak of CH4 was clearly identified at approximately 1302 cm–1.

Figure 4

Figure 4. In situ FT-IR spectra of SNNU-707 and SNNU-708: (a–c) loading C3H8, C2H6 and CH4 in SNNU-707 at different pressures. (d–f) loading C3H8, C2H6 and CH4 in SNNU-708 at different pressures. (g, h) comparison of MOF samples before and after loading paraffin with 760 mmHg.

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To elucidate differences in interactions between various gas molecules and the MOF materials, we conducted comparative analysis of infrared spectra for pristine samples and those after gas adsorption at 760 mmHg (Figures 4g,h). Spectral data demonstrate that for both SNNU-707 and SNNU-708, aromatic ring skeleton stretching vibration peaks exhibit the most prominent enhancement after C3H8 adsorption, followed by C2H6, while peak enhancement associated with CH4 is negligible. This phenomenon indicates that C2+ alkanes, benefiting from their high polarizability and strong C–H bond energy, effectively reinforce C–H···π interactions with aromatic rings. This further amplifies the discrepancy in adsorption selectivity of MOFs toward alkane molecules with different carbon chain lengths, which is in line with our design objectives. Notably, during the gradual introduction of C3H8, a characteristic absorption peak with steadily increasing intensity emerged in the range of 1820–1840 cm–1. Under identical conditions, no such signal was detected upon introduction of C2H6 or CH4, implying that this vibrational mode is specifically linked to C3H8 adsorption. This absorption peak can be attributed to strong C–H···F and C–H···π interactions between C3H8 and the −CF3 groups as well as TPP within pore channels. These interactions induce a significant blue shift in carboxylate-related vibrational modes of dicarboxylate linkers, providing direct spectroscopic evidence at the molecular vibrational level for the unique host–guest interactions between the MOF framework and C3H8. This finding further offers critical spectral support for the materials’ capacity to selectively adsorb and separate C3H8/C2H6/CH4 mixtures.

GCMC Simulation

To clarify host–guest interactions at the molecular level and gain in-depth understanding of the differential adsorption behaviors of the two MOFs toward alkane molecules, grand canonical Monte Carlo (GCMC) simulations were implemented (Figure 5). The simulation results indicate that CH4, C2H6, and C3H8 molecules are distributed in both types of cages present in SNNU-707 and SNNU-708. In the o-cages, both CH4 and C2H6 exhibit three main adsorption sites: Site I and Site II primarily rely on C–Hgas···πTPP interactions (CH4: 3.087–4.106 Å/3.411, 3.551 Å; C2H6: 2.723–4.106 Å/2.691–3.568 Å), while Site III is mainly governed by C–Hgas···πBDC interactions (CH4: 3.866–3.974 Å/3.160–3.435 Å; C2H6: 3.579–3.961 Å/3.029–4.146 Å). In addition, gas molecules also interact with the fluorine atoms on the dicarboxylate ligands via C–H···F interactions (CH4: 2.622–4.129 Å/3.002–4.059 Å; C2H6: 3.393–3.829 Å/2.594–4.285 Å) (Figures 5a,b,g,h). Compared to CH4 and C2H6, due to the larger size, C3H8 molecules occupy two main adsorption sites: Site I primarily involves C–Hgas···πTPP interactions (3.343–4.237 Å/2.984–4.269 Å), while Site II mainly involves C–Hgas···πBDC (3.709–4.053 Å/3.101–4.338 Å) and C–H···F interactions (2.967–4.056 Å/2.893–4.165 Å) (Figures 5c,i). Overall, the analysis reveals that in the o-cages, C2H6 and C3H8 exhibit more numerous and stronger interactions with SNNU-707/-708 than CH4 does.

Figure 5

Figure 5. GCMC simulated adsorption binding sites for C3H8, C2H6 and CH4 in cages of SNNU-707/-708: (a–c) adsorption binding sites for C3H8, C2H6 and CH4 in o-cages of SNNU-707. (d–f) adsorption binding sites for C3H8, C2H6 and CH4 in t-cages of SNNU-707. (g–i) adsorption binding sites for C3H8, C2H6 and CH4 in o-cages of SNNU-708. (j–l) adsorption binding sites for C3H8, C2H6 and CH4 in t-cages of SNNU-708.

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In the other primary adsorption region, the t-cages, three gas molecules can interact with the MOF framework through multiple interaction sites provided by the oxygen-enriched Co2V-clusters, the nonpolar aromatic rings and fluorine atoms on the BDC ligands, and the nitrogen atoms in the TPP ligands. These interactions occur at three key adsorption sites: near the metal clusters, at the cage windows, and adjacent to the TPP ligands, via C–H···O, C–H···F, C–H···π, and C–H···N interactions. For SNNU-707, CH4/C2H6/C3H8 interact with the framework through C–H···O (2.880–4.113 Å/2.681–4.079 Å/2.952–4.130 Å), C–H···F (3.692–4.203 Å/2.941–3.751 Å/2.920–4.231 Å), C–H···πBDC (4.008, 4.047 Å/3.172–4.198 Å/3.079–4.105 Å), C–H···πTPP (C2H6: 3.205–4.214 Å; C3H8: 3.424–4.247 Å), and C–H···N (3.994/4.195 Å/2.937–4.024 Å/2.881–4.030 Å). SNNU-708 exhibits similar interaction modes. The three gas molecules (CH4/C2H6/C3H8) interact with the MOF framework through C–H···O (3.461, 4.175 Å/2.716–4.127 Å/3.235–4.056 Å), C–H···F (2.572–4.020 Å/2.622–4.101 Å/2.411–4.146 Å), C–H···πBDC (3.826, 4.167 Å/3.300–4.149 Å/2.984–3.982 Å), C–H···πTPP (3.859 Å/3.014–3.568 Å/3.266–3.908 Å), and C–H···N (3.245–3.892 Å/3.319–3.493 Å/3.701–4.007 Å).
The GCMC simulation results are consistent with the isothermal adsorption experimental data of the two MOFs. Due to the higher number of hydrogen atoms in C3H8 and its better molecular size compatibility with the cage cavity, both MOFs can form more numerous and stronger interactions with C3H8. Furthermore, the stepwise modification with −CF3 groups enables fine-tuning of the chemical environment on the pore surface. First, although alkanes are nonpolar molecules and exhibit good compatibility with −CF3-modified surfaces, excessive −CF3 groups can render the pore surface “overly hydrophobic,” thereby weakening the electrostatic induction effects with the weak polarity of alkanes. Second, −CF3 is a strong electron-withdrawing group; excessive introduction significantly reduces the electron cloud density of the benzene rings, weakening the C–H···π interactions between alkane molecules and the aromatic rings and thus diminishing the van der Waals adsorption driving force. Additionally, the presence of two −CF3 groups slightly increases steric hindrance and creates relatively narrower kinetic channels at the pore windows, partially blocking alkane molecules from accessing originally stronger adsorption sites (such as metal clusters or TPP nitrogen sites), which is unfavorable for the synergistic formation of multiple weak interactions. Consequently, chemical modification of the pore surface plays a crucial regulatory role in both the binding capacity and transport kinetics of guest molecules. Compared to SNNU-708, SNNU-707 forms stronger interactions with alkane molecules. Evidently, due to differences in the number of hydrogen donors and molecular sizes among the three alkanes, multicarbon alkanes can establish more numerous and stronger interactions with pore channels modified with an appropriate number of −CF3 groups. This provides a reasonable explanation for the selective capture performance of SNNU-707/-708 toward C3H8/C2H6/CH4.

Conclusions

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In summary, two Co2V-pacs-MOFs (SNNU-707 and SNNU-708) were by rationally designed and synthesized by applying the pore space partition strategy based on the fluorine-containing ligands 2-(trifluoromethyl)terephthalic acid and 2,5-bis(trifluoromethyl)terephthalic acid. These MOF materials are applied for the efficient separation and recovery of C2H6 and C3H8 from natural gas. By modulating the number of −CF3 groups on the dicarboxylate linkers, SNNU-707 demonstrates superior adsorption performance for C2H6 and C3H8, as well as enhanced separation capabilities for C3H8/CH4 and C2H6/CH4, owing to its more suitable pore size and optimized pore-surface microenvironment. Notably, both SNNU-707 and SNNU-708 enable the effective one-step separation of ternary C3H8/C2H6/CH4 gas mixtures. This study demonstrates that the combination of pore space partition and introduction of −CF3 groups to tailor the pore environment of MOFs can achieve efficient adsorption and purification of natural gas under humid conditions. This approach holds significant importance for advancing the industrial application of multicomponent gas separation technologies.

Supporting Information

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The Supporting Information is available free of charge at https://pubs.acs.org/doi/10.1021/acs.inorgchem.6c00337.

  • Additional experimental details, tables of crystal data, additional crystal structure pictures, PXRD, TGA, virial fitting, and IAST selectivity results for SNNU-707/-708 (PDF)

Accession Codes

Deposition Numbers 2522027–2522028 contain the supplementary crystallographic data for this paper. These data can be obtained free of charge via the joint Cambridge Crystallographic Data Centre (CCDC) and Fachinformationszentrum Karlsruhe Access Structures service.

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Author Information

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  • Corresponding Author
    • Quan-Guo Zhai - Key Laboratory of Applied Surface and Colloid Chemistry (MOE), Key Laboratory of Macromolecular Science of Shaanxi Province, School of Chemistry & Chemical Engineering, Shaanxi Normal University, Xi’an 710062, China;  Orcidhttps://orcid.org/0000-0003-1117-4017;  Email: [email protected]
  • Authors
    • Jia-Yao Liu - Key Laboratory of Applied Surface and Colloid Chemistry (MOE), Key Laboratory of Macromolecular Science of Shaanxi Province, School of Chemistry & Chemical Engineering, Shaanxi Normal University, Xi’an 710062, China
    • Li-Qiu Yang - Key Laboratory of Applied Surface and Colloid Chemistry (MOE), Key Laboratory of Macromolecular Science of Shaanxi Province, School of Chemistry & Chemical Engineering, Shaanxi Normal University, Xi’an 710062, China
    • Yan-Fei Li - Key Laboratory of Applied Surface and Colloid Chemistry (MOE), Key Laboratory of Macromolecular Science of Shaanxi Province, School of Chemistry & Chemical Engineering, Shaanxi Normal University, Xi’an 710062, China
    • Ying Wang - Key Laboratory of Applied Surface and Colloid Chemistry (MOE), Key Laboratory of Macromolecular Science of Shaanxi Province, School of Chemistry & Chemical Engineering, Shaanxi Normal University, Xi’an 710062, China;  Orcidhttps://orcid.org/0000-0002-6199-6783
    • Wen-Yu Yuan - Key Laboratory of Applied Surface and Colloid Chemistry (MOE), Key Laboratory of Macromolecular Science of Shaanxi Province, School of Chemistry & Chemical Engineering, Shaanxi Normal University, Xi’an 710062, China;  Orcidhttps://orcid.org/0000-0001-8443-1518
  • Notes
    The authors declare no competing financial interest.

Acknowledgments

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This work is financially supported by the National Natural Science Foundation of China (224711490), and the Youth Innovation Team of Shaanxi Universities (2023 and 24JP038).

References

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  • Abstract

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    Figure 1

    Figure 1. Structural features of SNNU-707/-708: (a) metal clusters and organic linkers. (b, c) porous frameworks viewed along the c-axis direction. (d, e) porous frameworks viewed along the a-axis direction. (f, g) side views of octahedral cages (o-cages) and trigonal-bipyramidal cages (t-cages).

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    Figure 2

    Figure 2. Gas adsorption performance of SNNU-707/-708: (a) PXRD patterns of SNNU-708 immersed in pH-1–11 solution for 3 days. (b) adsorption isotherms of C3H8 on SNNU-708 at 298 K after immersing in pH-1–11 solution for 3 days. (c) N2 at 77 K with pore size distributions. (d–f) C3H8, C2H6 and CH4 at 273, 283, and 298 K. (g) summary and comparison of C3H8 and C2H6 adsorption capacities for selected reported MOFs adsorbents are presented. (h) the Qst values for C3H8, C2H6 and CH4 at 298 K. (i) the IAST selectivity for 50/50 C3H8/CH4 and C2H6/CH4.

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    Figure 3

    Figure 3. Dynamic breakthrough performance of SNNU-707/-708: (a) for 50/50 C2H6/CH4 and C3H8/CH4 mixtures. (b, c) for 10/90 C2H6/CH4 mixtures and 5/95 C3H8/CH4 mixtures. (d, e) for 5/10/85 C3H8/C2H6/CH4 mixtures. (f, g) for 5/10/85 C3H8/C2H6/CH4 mixtures in the moist and dry environments. (h, i) cycling test results.

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    Figure 4

    Figure 4. In situ FT-IR spectra of SNNU-707 and SNNU-708: (a–c) loading C3H8, C2H6 and CH4 in SNNU-707 at different pressures. (d–f) loading C3H8, C2H6 and CH4 in SNNU-708 at different pressures. (g, h) comparison of MOF samples before and after loading paraffin with 760 mmHg.

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    Figure 5

    Figure 5. GCMC simulated adsorption binding sites for C3H8, C2H6 and CH4 in cages of SNNU-707/-708: (a–c) adsorption binding sites for C3H8, C2H6 and CH4 in o-cages of SNNU-707. (d–f) adsorption binding sites for C3H8, C2H6 and CH4 in t-cages of SNNU-707. (g–i) adsorption binding sites for C3H8, C2H6 and CH4 in o-cages of SNNU-708. (j–l) adsorption binding sites for C3H8, C2H6 and CH4 in t-cages of SNNU-708.

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  • Supporting Information

    Supporting Information

    The Supporting Information is available free of charge at https://pubs.acs.org/doi/10.1021/acs.inorgchem.6c00337.

    • Additional experimental details, tables of crystal data, additional crystal structure pictures, PXRD, TGA, virial fitting, and IAST selectivity results for SNNU-707/-708 (PDF)

    Accession Codes

    Deposition Numbers 2522027–2522028 contain the supplementary crystallographic data for this paper. These data can be obtained free of charge via the joint Cambridge Crystallographic Data Centre (CCDC) and Fachinformationszentrum Karlsruhe Access Structures service.


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