Temperature-controlled flexible metal-organic frameworks for propylene/propane separation

doi:10.1016/j.cjche.2025.06.018

Abstract

Abstract: The efficient separation of C₃H₆ and C₃H₈ is a key challenge in the petrochemical industry. A zinc-based flexible metal-organic framework (Zn-anthracenedicarboxylic acid (ADC)-triazole (TRZ)) was designed through dual ligand construction. The material forms a two-dimensional layered structure via TRZ ligands, with ADC ligands serving as interlayer pillars to construct a three-dimensional pillar-layered structure, combining the stability of rigid aromatic rings with the dynamic responsiveness of flexible structures. The flexible pores of Zn-ADC-TRZ can be reversibly opened and closed under the thermal effect, and the adsorption capacity and the opening pressure of the gas can be adjusted with the increase of temperature, thereby enabling achieve the best separation effect under different partial pressures of the gas. Specifically, temperature modulation leads to increase the opening pressure of Zn-ADC-TRZ, enabling significant adsorption difference between C₃H₆ and C₃H₈. At 313 K and 50 kPa, Zn-ADC-TRZ achieves the highest adsorption ratio (24) of C₃H₆ and C₃H₈ while maintaining substantial C₃H₆ adsorption capacity, thereby facilitating efficient separation of equimolar gases. This work demonstrates the potential of temperature-responsive flexible metal-organic frameworks for energy-efficient olefin purification, offering novel insights into low-energy consumption separation technology.

Key words: Metal–organic frameworks, Dynamic recognition, Temperature-controlled, C₃H₆/C₃H₈ separation

摘要： The efficient separation of C₃H₆ and C₃H₈ is a key challenge in the petrochemical industry. A zinc-based flexible metal-organic framework (Zn-anthracenedicarboxylic acid (ADC)-triazole (TRZ)) was designed through dual ligand construction. The material forms a two-dimensional layered structure via TRZ ligands, with ADC ligands serving as interlayer pillars to construct a three-dimensional pillar-layered structure, combining the stability of rigid aromatic rings with the dynamic responsiveness of flexible structures. The flexible pores of Zn-ADC-TRZ can be reversibly opened and closed under the thermal effect, and the adsorption capacity and the opening pressure of the gas can be adjusted with the increase of temperature, thereby enabling achieve the best separation effect under different partial pressures of the gas. Specifically, temperature modulation leads to increase the opening pressure of Zn-ADC-TRZ, enabling significant adsorption difference between C₃H₆ and C₃H₈. At 313 K and 50 kPa, Zn-ADC-TRZ achieves the highest adsorption ratio (24) of C₃H₆ and C₃H₈ while maintaining substantial C₃H₆ adsorption capacity, thereby facilitating efficient separation of equimolar gases. This work demonstrates the potential of temperature-responsive flexible metal-organic frameworks for energy-efficient olefin purification, offering novel insights into low-energy consumption separation technology.

关键词: Metal–organic frameworks, Dynamic recognition, Temperature-controlled, C₃H₆/C₃H₈ separation

Jiamin Zhang, Yanhui Dai, Yang Chen, Jinping Li, Libo Li. Temperature-controlled flexible metal-organic frameworks for propylene/propane separation[J]. Chinese Journal of Chemical Engineering, 2025, 86(10): 72-78.

Jiamin Zhang, Yanhui Dai, Yang Chen, Jinping Li, Libo Li. Temperature-controlled flexible metal-organic frameworks for propylene/propane separation[J]. 中国化学工程学报, 2025, 86(10): 72-78.

References

[1] A. Cadiau, K. Adil, P.M. Bhatt, Y. Belmabkhout, M. Eddaoudi, A metal-organic framework-based splitter for separating propylene from propane, Science 353 (6295) (2016) 137-140.
[2] H. Wang, X.L. Dong, V. Colombo, Q.N. Wang, Y.Y. Liu, W. Liu, X.L. Wang, X.Y. Huang, D.M. Proserpio, A. Sironi, Y. Han, J. Li, Tailor-made microporous metal-organic frameworks for the full separation of propane from propylene through selective size exclusion, Adv. Mater. 30 (49) (2018) e1805088.
[3] D.F. Lv, J.H. Xu, P.J. Zhou, S. Tu, F. Xu, J. Yan, H.X. Xi, Z.W. Liu, W.B. Yuan, Q. Fu, X. Chen, Q.B. Xia, Highly selective separation of propylene/propane mixture on cost-effectively four-carbon linkers based metal-organic frameworks, Chin. J. Chem. Eng. 51 (2022) 126-134.
[4] L. Zhang, R.C. Gao, X. Liu, B. Zhang, L. Hou, Y.Y. Wang, Unique H₂O vortex in one new MOF material strengthening C3H6 adsorption and unprecedented purification from C2H4/C3H8/C3H6 mixtures, Adv. Funct. Mater. 35 (17) (2025) 2420927.
[5] J.J.H.B. Sattler, J. Ruiz-Martinez, E. Santillan-Jimenez, B.M. Weckhuysen, Catalytic dehydrogenation of light alkanes on metals and metal oxides, Chem. Rev. 114 (20) (2014) 10613-10653.
[6] D.S. Sholl, R.P. Lively, Seven chemical separations to change the world, Nature 532 (7600) (2016) 435-437.
[7] D. Liu, J.Y. Pei, X. Zhang, X.W. Gu, H.M. Wen, B.L. Chen, G.D. Qian, B. Li, Scalable green synthesis of robust ultra-microporous Hofmann clathrate material with record C3H6 storage density for efficient C3H6/C3H8 separation, Angew. Chem. Int. Ed. 62 (12) (2023) e202218590.
[8] Y.J. Tian, C.H. Deng, Y.L. Peng, X. Zhang, Z.J. Zhang, M.J. Zaworotko, State of the art, challenges and prospects in metal-organic frameworks for the separation of binary propylene/propane mixtures, Coord. Chem. Rev. 506 (2024) 215697.
[9] Y. Su, J.J. Zheng, K.I. Otake, N. Hosono, S. Kitagawa, C. Gu, Controlling guest diffusion by local dynamic motion in soft porous crystals to separate water isotopologues and similar gases, Acc. Chem. Res. 57 (24) (2024) 3455-3464.
[10] O. Singh, H.S. Khairun, H. Joshi, B. Sarkar, N.K. Gupta, Advancing light olefin production: Exploring pathways, catalyst development, and future prospects, Fuel 379 (2025) 132992.
[11] Y. Su, K.I. Otake, J.J. Zheng, P. Wang, Q. Lin, S. Kitagawa, C. Gu, Diffusion-rate sieving of propylene and propane mixtures in a cooperatively dynamic porous crystal, Nat. Commun. 15 (1) (2024) 2898.
[12] I. Amghizar, L.A. Vandewalle, K.M. Van Geem, G.B. Marin, New trends in olefin production, Engineering 3 (2) (2017) 171-178.
[13] B. Liang, X. Zhang, Y. Xie, R.B. Lin, R. Krishna, H. Cui, Z.Q. Li, Y.S. Shi, H. Wu, W. Zhou, B.L. Chen, An ultramicroporous metal-organic framework for high sieving separation of propylene from propane, J. Am. Chem. Soc. 142 (41) (2020) 17795-17801.
[14] J.J. Peng, H. Wang, D.H. Olson, Z. Li, J. Li, Efficient kinetic separation of propene and propane using two microporous metal organic frameworks, Chem. Commun. 53 (67) (2017) 9332-9335.
[15] P. Hu, J. Han, J. Zhou, H. Wang, C. Xiong, H. Liu, X.T. Zhou, Y.Q. Wang, H.B. Ji, Customized H-bonding acceptor and aperture chemistry within a metal-organic framework for efficient C3H6/C3H8 separation, Chem. Eng. J. 426 (2021) 131302.
[16] S.U. Rege, R.T. Yang, Propane/propylene separation by pressure swing adsorption: Sorbent comparison and multiplicity of cyclic steady states, Chem. Eng. Sci. 57 (7) (2002) 1139-1149.
[17] G.D. Wang, Y.Z. Li, W.J. Shi, L. Hou, Y.Y. Wang, Z.H. Zhu, Active sites decorated nonpolar pore-based MOF for one-step acquisition of C2H4 and recovery of C3H6, Angew. Chem. Int. Ed. 62 (43) (2023) e202311654.
[18] P.J. Bereciartua, A. Cantin, A. Corma, J.L. Jorda, M. Palomino, F. Rey, S. Valencia, E.W. Corcoran Jr, P. Kortunov, P.I. Ravikovitch, A. Burton, C. Yoon, Y. Wang, C. Paur, J. Guzman, A.R. Bishop, G.L. Casty, Control of zeolite framework flexibility and pore topology for separation of ethane and ethylene, Science 358 (6366) (2017) 1068-1071.
[19] Y.X. Wang, S.B. Peh, D. Zhao, Alternatives to cryogenic distillation: advanced porous materials in adsorptive light olefin/paraffin separations, Small 15 (25) (2019) e1900058.
[20] E. Perez-Botella, S. Valencia, F. Rey, Zeolites in adsorption processes: State of the art and future prospects, Chem. Rev. 122 (24) (2022) 17647-17695.
[21] R.L. Siegelman, E.J. Kim, J.R. Long, Porous materials for carbon dioxide separations, Nat. Mater. 20 (8) (2021) 1060-1072.
[22] X. Zhao, Y.X. Wang, D.S. Li, X.H. Bu, P.Y. Feng, Metal-organic frameworks for separation, Adv. Mater. 30 (37) (2018) 1705189.
[23] W.G. Cui, T.L. Hu, X.H. Bu, Metal-organic framework materials for the separation and purification of light hydrocarbons, Adv. Mater. 32 (3) (2020) e1806445.
[24] K. Adil, Y. Belmabkhout, R.S. Pillai, A. Cadiau, P.M. Bhatt, A.H. Assen, G. Maurin, M. Eddaoudi, Gas/vapour separation using ultra-microporous metal-organic frameworks: Insights into the structure/separation relationship, Chem. Soc. Rev. 46 (11) (2017) 3402-3430.
[25] L. Jiao, J.Y.R. Seow, W.S. Skinner, Z.U. Wang, H.L. Jiang, Metal-organic frameworks: Structures and functional applications, Mater. Today 27 (2019) 43-68.
[26] W.J. Wang, D. Chen, F.Y. Li, X. Xiao, Q. Xu, Metal-organic-framework-based materials as platforms for energy applications, Chem 10 (1) (2024) 86-133.
[27] Y.W. Chen, Z.W. Qiao, D.F. Lv, C.X. Duan, X.J. Sun, H.X. Wu, R.F. Shi, Q.B. Xia, Z. Li, Efficient adsorptive separation of C3H6 over C3H8 on flexible and thermoresponsive CPL-1, Chem. Eng. J. 328 (2017) 360-367.
[28] L. Yu, X. Han, H. Wang, S. Ullah, Q.B. Xia, W.Y. Li, J.N. Li, I. da Silva, P. Manuel, S. Rudic, Y.Q. Cheng, S.H. Yang, T. Thonhauser, J. Li, Pore distortion in a metal-organic framework for regulated separation of propane and propylene, J. Am. Chem. Soc. 143 (46) (2021) 19300-19305.
[29] P.X. Liu, J.H. Li, F.R. Yan, X. Lian, J. Xu, Y. Chen, Y.T. Liu, Q. Shi, X.L. Cui, L.B. Sun, J.P. Li, L.B. Li, Immobilization of lewis basic sites into a quasi-molecular-sieving metal-organic framework for enhanced C3H6/C3H8 separation, Adv. Funct. Mater. 34 (45) (2024) 2406664.
[30] X.Q. Wang, R. Krishna, L.B. Li, B. Wang, T. He, Y.Z. Zhang, J.R. Li, J.P. Li, Guest-dependent pressure induced gate-opening effect enables effective separation of propene and propane in a flexible MOF, Chem. Eng. J. 346 (2018) 489-496.
[31] Y. Chen, Y.S. Yang, Y. Wang, Q.Z. Xiong, J.F. Yang, S.C. Xiang, L.B. Li, J.P. Li, Z.J. Zhang, B.L. Chen, Ultramicroporous hydrogen-bonded organic framework material with a thermoregulatory gating effect for record propylene separation, J. Am. Chem. Soc. 144 (37) (2022) 17033-17040.
[32] C. Gu, N. Hosono, J.J. Zheng, Y. Sato, S. Kusaka, S. Sakaki, S. Kitagawa, Design and control of gas diffusion process in a nanoporous soft crystal, Science 363 (6425) (2019) 387-391.
[33] Y. Su, K.I. Otake, J.J. Zheng, H. Xu, Q. Wang, H.M. Liu, F. Huang, P. Wang, S. Kitagawa, C. Gu, Switching molecular recognition selectivities by temperature in a diffusion-regulatory porous material, Nat. Commun. 15 (1) (2024) 144.
[34] Y. Lim, B. Kim, J. Kim, Data-driven design of flexible metal-organic frameworks for gas storage, Chem. Mater. 36 (11) (2024) 5465-5473.
[35] Y.H. Huang, J.M. Wan, T. Pan, K. Ge, Y.N. Guo, J.G. Duan, J.F. Bai, W.Q. Jin, S. Kitagawa, Delicate softness in a temperature-responsive porous crystal for accelerated sieving of propylene/propane, J. Am. Chem. Soc. 145 (44) (2023) 24425-24432.
[36] L.Q. Yang, Y. Wang, W.Y. Yuan, Q.G. Zhai, Shifting C2H₂/CO₂ adsorption and separation in pillar-layered metal-organic frameworks finely-regulated by molecular rotation, Small 21 (6) (2025) e2409939.