Copper-based metal–organic framework with two methane traps for efficient CH4/N2 separation

doi:10.1016/j.cjche.2024.12.002

Abstract

Abstract: Unconventional natural gas has become an important supplement to conventional energy sources, and the process of enrichment and purification of methane from low concentration coalbed methane is crucial. To this end, we report a copper-based metal–organic framework (MOF), ZJNU-119Cu, featuring two methane traps constructed with uncoordinated carboxylic acid oxygens and open metal sites. ZJNU-119Cu exhibits a high methane adsorption capacity (58.2 cm³·g^-1) at 298 K and 0.1 MPa and excellent CH₄/N₂ separation performance under dynamic conditions. Density-functional theory calculations combined with grand canonical Monte Carlo simulation theory reveal the interaction mechanism for the uncoordinated carboxylic acid oxygen atoms and open metal sites in ZJNU-119Cu with CH₄. The gas adsorption isotherms, heat of adsorption calculations, and breakthrough separation experiments indicate that this MOF is a very promising adsorbent for CH₄/N₂ separation.

Key words: Natural gas, Adsorption, Separation, Uncoordinated carboxylic acid oxygens, Open metal sites, Methane trap

摘要： Unconventional natural gas has become an important supplement to conventional energy sources, and the process of enrichment and purification of methane from low concentration coalbed methane is crucial. To this end, we report a copper-based metal–organic framework (MOF), ZJNU-119Cu, featuring two methane traps constructed with uncoordinated carboxylic acid oxygens and open metal sites. ZJNU-119Cu exhibits a high methane adsorption capacity (58.2 cm³·g^-1) at 298 K and 0.1 MPa and excellent CH₄/N₂ separation performance under dynamic conditions. Density-functional theory calculations combined with grand canonical Monte Carlo simulation theory reveal the interaction mechanism for the uncoordinated carboxylic acid oxygen atoms and open metal sites in ZJNU-119Cu with CH₄. The gas adsorption isotherms, heat of adsorption calculations, and breakthrough separation experiments indicate that this MOF is a very promising adsorbent for CH₄/N₂ separation.

关键词: Natural gas, Adsorption, Separation, Uncoordinated carboxylic acid oxygens, Open metal sites, Methane trap

Zhiwei Zhao, Yating Wang, Yuhao Tang, Xiaoqing Wang, Feifei Zhang, Jiangfeng Yang. Copper-based metal–organic framework with two methane traps for efficient CH₄/N₂ separation[J]. Chinese Journal of Chemical Engineering, 2025, 79(3): 234-240.

References

[1] S. Chu, A. Majumdar, Opportunities and challenges for a sustainable energy future, Nature 488 (7411) (2012) 294-303.
[2] D.S. Sholl, R.P. Lively, Seven chemical separations to change the world, Nature 532 (7600) (2016) 435-437.
[3] Y.B. He, W. Zhou, G.D. Qian, B.L. Chen, Methane storage in metal-organic frameworks, Chem. Soc. Rev. 43 (16) (2014) 5657-5678.
[4] Z.Y. Han, X.F. Bai, Y.L. Zhao, W.L. Li, Q.Y. Sun, Z.H. Xie, L.F. Ding, R. Li, J.R. Li, Green and scalable synthesis of a dual-ligand Zn-MOF with unprecedented space-time yield in aqueous media and efficient CH₄/N₂ separation, Green Chem. 26 (21) (2024) 10867-10875.
[5] X. Zhang, J.R. Li, Recovery of greenhouse gas as cleaner fossil fuel contributes to carbon neutrality, Green Energy Environ. 8 (2) (2023) 351-353.
[6] S.J. Du, Y. Wu, X.J. Wang, Q.B. Xia, J. Xiao, X. Zhou, Z. Li, Facile synthesis of ultramicroporous carbon adsorbents with ultra-high CH₄ uptake by in situ ionic activation, AIChE J. 66 (7) (2020) e16231.
[7] J.F. Yang, H.H. Bai, H. Shang, J. Wang, J.P. Li, S.G. Deng, Experimental and simulation study on efficient CH₄/N₂ separation by pressure swing adsorption on silicalite-1 pellets, Chem. Eng. J. 388 (2020) 124222.
[8] I.A.A.C. Esteves, M.S.S. Lopes, P.M.C. Nunes, J.P.B. Mota, Adsorption of natural gas and biogas components on activated carbon, Sep. Purif. Technol. 62 (2) (2008) 281-296.
[9] S.M. Kuznicki, V.A. Bell, S. Nair, H.W. Hillhouse, R.M. Jacubinas, C.M. Braunbarth, B.H. Toby, M. Tsapatsis, A titanosilicate molecular sieve with adjustable pores for size-selective adsorption of molecules, Nature 412 (6848) (2001) 720-724.
[10] J.Q. Liu, X. Tang, X.W. Liang, L.G. Wu, F.F. Zhang, Q. Shi, J.F. Yang, J.X. Dong, J.P. Li, Superhydrophobic zeolitic imidazolate framework with suitable SOD cage for effective CH₄/N₂ adsorptive separation in humid environments, AIChE J. 68 (5) (2022) e17589.
[11] S.S. Li, J. Chen, Y. Wang, K.B. Li, K.J. Li, W.J. Guo, X.R. Zhang, J.Q. Liu, X. Tang, J.F. Yang, J.P. Li, Adsorption and separation of CH₄/N₂ by electrically neutral skeleton AlPO molecular sieves, Sep. Purif. Technol. 286 (2022) 120497.
[12] K.V. Kumar, F. Rodriguez-Reinoso, Co-adsorption of N₂ in the presence of CH₄ within carbon nanospaces: evidence from molecular simulations, Nanotechnology 24 (3) (2013) 035401.
[13] B. Majumdar, S.J. Bhadra, R.P. Marathe, S. Farooq, Adsorption and diffusion of methane and nitrogen in Barium exchanged ETS-4, Ind. Eng. Chem. Res. 50 (5) (2011) 3021-3034.
[14] M. Chang, J.H. Ren, Q.Y. Yang, D.H. Liu, A robust calcium-based microporous metal-organic framework for efficient CH₄/N₂ separation, Chem. Eng. J. 408 (2021) 127294.
[15] D. Saha, H.A. Grappe, A. Chakraborty, G. Orkoulas, Postextraction separation, on-board storage, and catalytic conversion of methane in natural gas: a review, Chem. Rev. 116 (19) (2016) 11436-11499.
[16] J.F. Yang, B.J. Du, J.Q. Liu, R. Krishna, F.F. Zhang, W. Zhou, Y. Wang, J.P. Li, B.L. Chen, MIL-100Cr with open Cr sites for a record N₂O capture, Chem. Commun. 54 (100) (2018) 14061-14064.
[17] K.X. Yao, Y.L. Chen, Y. Lu, Y.F. Zhao, Y. Ding, Ultramicroporous carbon with extremely narrow pore distribution and very high nitrogen doping for efficient methane mixture gases upgrading, Carbon 122 (2017) 258-265.
[18] L.Y. Li, L.F. Yang, J.W. Wang, Z.G. Zhang, Q.W. Yang, Y.W. Yang, Q.L. Ren, Z.B. Bao, Highly efficient separation of methane from nitrogen on a squarate-based metal-organic framework, AIChE J. 64 (10) (2018) 3681-3689.
[19] Y. Chen, Y. Wang, Y. Wang, Q.Z. Xiong, J.F. Yang, L.B. Li, J.P. Li, B. Mu, Improving CH₄ uptake and CH₄/N₂ separation in pillar-layered metal-organic frameworks using a regulating strategy of interlayer channels, AIChE J. 68 (11) (2022) e17819.
[20] Z. Niu, X.L. Cui, T. Pham, P.C. Lan, H.B. Xing, K.A. Forrest, L. Wojtas, B. Space, S.Q. Ma, A metal-organic framework based methane nano-trap for the capture of coal-mine methane, Angew. Chem. Int. Ed. 58 (30) (2019) 10138-10141.
[21] M. Chang, F. Wang, Y. Wei, Q.Y. Yang, J.X. Wang, D.H. Liu, J.F. Chen, Separation of CH₄/N₂ by an ultra-stable metal-organic framework with the highest breakthrough selectivity, AIChE J. 68 (9) (2022) e17794.
[22] F.F. Zhang, H. Shang, B.L. Zhai, X.M. Li, Y.Y. Zhang, X.Q. Wang, J.P. Li, J.F. Yang, Thermodynamic-kinetic synergistic separation of CH₄/N₂ on a robust aluminum-based metal-organic framework, AIChE J. 69 (6) (2023) e18079.
[23] M.I. Mohideen, B. Xiao, P.S. Wheatley, A.C. McKinlay, Y. Li, A.M. Slawin, D.W. Aldous, N.F. Cessford, T. Duren, X. Zhao, R. Gill, K.M. Thomas, J.M. Griffin, S.E. Ashbrook, R.E. Morris, Protecting group and switchable pore-discriminating adsorption properties of a hydrophilic-hydrophobic metal-organic framework, Nat. Chem. 3 (4) (2011) 304-310.
[24] D.F. Lv, Y. Wu, J.Y. Chen, Y.H. Tu, Y.N. Yuan, H.X. Wu, Y.W. Chen, B.Y. Liu, H.X. Xi, Z. Li, Q.B. Xia, Improving CH₄/N₂ selectivity within isomeric Al-based MOFs for the highly selective capture of coal-mine methane, AIChE J. 66 (9) (2020) e16287.
[25] P. Zhou, X.X. Wang, L.L. Yue, L.H. Fan, Y.B. He, A microporous MOF constructed by cross-linking helical chains for efficient purification of natural gas and ethylene, Inorg. Chem. 60 (19) (2021) 14969-14977.
[26] A.L. Myers, J.M. Prausnitz, Thermodynamics of mixed-gas adsorption, AIChE J. 11 (1) (1965) 121-127.
[27] K.V. Kumar, S. Gadipelli, B. Wood, K.A. Ramisetty, A.A. Stewart, C.A. Howard, D.J.L. Brett, F. Rodriguez-Reinoso, Characterization of the adsorption site energies and heterogeneous surfaces of porous materials, J. Mater. Chem. A 7 (17) (2019) 10104-10137.
[28] X.Y. Ren, T.J. Sun, J.L. Hu, S.D. Wang, Highly enhanced selectivity for the separation of CH₄ over N₂ on two ultra-microporous frameworks with multiple coordination modes, Microporous Mesoporous Mater. 186 (2014) 137-145.
[29] M. Chang, Y.J. Zhao, Q.Y. Yang, D.H. Liu, Microporous metal-organic frameworks with hydrophilic and hydrophobic pores for efficient separation of CH₄/N₂ mixture, ACS Omega 4 (11) (2019) 14511-14516.
[30] C.E. Kivi, B.S. Gelfand, H. Dureckova, H.T.K. Ho, C. Ma, G.K.H. Shimizu, T.K. Woo, D.T. Song, 3D porous metal-organic framework for selective adsorption of methane over dinitrogen under ambient pressure, Chem. Commun. 54 (100) (2018) 14104-14107.
[31] Y.Q. Wu, D.H. Yuan, D.W. He, J.C. Xing, S. Zeng, S.T. Xu, Y.P. Xu, Z.M. Liu, Decorated traditional zeolites with subunits of metal-organic frameworks for CH₄/N₂ separation, Angew. Chem. Int. Ed. 58 (30) (2019) 10241-10244.
[32] F. Zheng, L.H. Chen, R.D. Chen, Z.G. Zhang, Q.W. Yang, Y.W. Yang, B.G. Su, Q.L. Ren, Z.B. Bao, A robust two-dimensional layered metal-organic framework for efficient separation of methane from nitrogen, Sep. Purif. Technol. 281 (2022) 119911.
[33] M. Chang, Y.J. Zhao, D.H. Liu, J.F. Yang, J.P. Li, C.L. Zhong, Methane-trapping metal-organic frameworks with an aliphatic ligand for efficient CH₄/N₂ separation, Sustain. Energy Fuels 4 (1) (2020) 138-142.
[34] S.M. Wang, M. Shivanna, Q.Y. Yang, Nickel-based metal-organic frameworks for coal-bed methane purification with record CH₄/N₂ selectivity, Angew. Chem. Int. Ed. 61 (15) (2022) e202201017.
[35] H. Sato, W. Kosaka, R. Matsuda, A. Hori, Y. Hijikata, R.V. Belosludov, S. Sakaki, M. Takata, S. Kitagawa, Self-accelerating CO sorption in a soft nanoporous crystal, Science 343 (6167) (2014) 167-170.
[36] S. Bordiga, L. Regli, F. Bonino, E. Groppo, C. Lamberti, B. Xiao, P.S. Wheatley, R.E. Morris, A. Zecchina, Adsorption properties of HKUST-1 toward hydrogen and other small molecules monitored by IR, Phys. Chem. Chem. Phys. 9 (21) (2007) 2676-2685.
[37] W.G. Qiu, Y. Wang, C.Q. Li, Z.C. Zhan, X.H. Zi, G.Z. Zhang, R. Wang, H. He, Effect of activation temperature on catalytic performance of CuBTC for CO oxidation, Chin. J. Catal. 33 (4-6) (2012) 986-992.
[38] V.L. Sushkevich, D. Palagin, M. Ranocchiari, J.A. van Bokhoven, Selective anaerobic oxidation of methane enables direct synthesis of methanol, Science 356 (6337) (2017) 523-527.
[39] Y.J. Liu, N. Cui, P.L. Jia, W. Huang, In-situ FT-IR spectroscopy investigation of CH₄ and CO₂ reaction, Catalysts 10 (1) (2020) 131.
[40] G.A. Ozin, D.F. McIntosh, S.A. Mitchell, J. Garcia Prieto, Methane activation. Photochemical reaction of copper atoms in solid methane, J. Am. Chem. Soc. 103 (6) (1981) 1574-1575.
[41] P.X. Liu, L.L. Fan, J.H. Li, Z.D. Wu, Y. Wang, Y. Chen, J.K. Gao, J.F. Yang, J.P. Li, B.L. Chen, L.B. Li, A microporous titanium metal-organic framework with double nanotraps for record CH₄/N₂ separation, Chem. Mater. 36 (6) (2024) 2925-2932.
[42] W. Gong, Y. Xie, A. Yamano, S. Ito, X.H. Tang, E.W. Reinheimer, C.D. Malliakas, J.Q. Dong, Y. Cui, O.K. Farha, Modulator-dependent dynamics synergistically enabled record SO₂ uptake in Zr(IV) metal-organic frameworks based on pyrene-cored molecular quadripod ligand, J. Am. Chem. Soc. 145 (49) (2023) 26890-26899.
[43] F. Zheng, R.D. Chen, Z.X. Ding, Y. Liu, Z.G. Zhang, Q.W. Yang, Y.W. Yang, Q.L. Ren, Z.B. Bao, Interlayer symmetry control in flexible-robust layered metal-organic frameworks for highly efficient C₂H₂/CO₂ separation, J. Am. Chem. Soc. 145 (36) (2023) 19903-19911.
[44] Y.F. Gu, J.J. Zheng, K.I. Otake, S. Sakaki, H. Ashitani, Y. Kubota, S. Kawaguchi, M.S. Yao, P. Wang, Y. Wang, F.T. Li, S. Kitagawa, Soft corrugated channel with synergistic exclusive discrimination gating for CO₂ recognition in gas mixture, Nat. Commun. 14 (1) (2023) 4245.

Copper-based metal–organic framework with two methane traps for efficient CH₄/N₂ separation

Copper-based metal–organic framework with two methane traps for efficient CH₄/N₂ separation

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