Reversed ethane/ethylene adsorption in a metal-organic framework via introduction of oxygen

doi:10.1016/j.cjche.2019.09.005

中国化学工程学报 ›› 2020, Vol. 28 ›› Issue (2): 593-597.DOI: 10.1016/j.cjche.2019.09.005

• Materials and Product Engineering • 上一篇下一篇

Reversed ethane/ethylene adsorption in a metal-organic framework via introduction of oxygen

Ling Yang¹, Wei Zhou², Hao Li³, Ali Alsalme⁴, Litao Jia⁵, Jiangfeng Yang¹, Jinping Li¹, Libo Li^1,5,6,7, Banglin Chen³

1 College of Chemistry and Chemical Engineering, Shanxi Key Laboratory of Gas Energy Efficient and Clean Utilization, Taiyuan University of Technology, Taiyuan 030024, China;
2 NIST Center for Neutron Research, National Institute of Standards and Technology, Gaithersburg, MD 20899-6102, United States;
3 Department of Chemistry, University of Texas at San Antonio, One UTSA Circle, San Antonio, TX 78249-0698, United States;
4 Chemistry Department, College of Science, King Saud University, P O Box 2455, Riyadh 11451, Saudi Arabia;
5 State Key Laboratory of Coal Conversion, Institute of Coal Chemistry, Chinese Academy of Sciences, Taiyuan 030024, China;
6 Key Laboratory of Coal Science and Technology, Taiyuan University of Technology, Taiyuan 030024, China;
7 Shanxi Key Laboratory of Gas Energy Efficient and Clean Utilization, Taiyuan 030024, China

收稿日期:2019-08-01 修回日期:2019-09-03 出版日期:2020-02-28 发布日期:2020-05-21
通讯作者: Libo Li, Banglin Chen
基金资助:
We gratefully acknowledge the financial support from the National Natural Science Foundation of China (Nos. 21606163 and 21878205), Coal Bed Methane Joint Foundation of Shanxi (2016012006), Foundation of State Key Laboratory of Coal Conversion (J18-19-610), Welch Foundation (grant AX-1730), and the Distinguished Scientist Fellowship Program (DSFP) at KSU.

Reversed ethane/ethylene adsorption in a metal-organic framework via introduction of oxygen

Ling Yang¹, Wei Zhou², Hao Li³, Ali Alsalme⁴, Litao Jia⁵, Jiangfeng Yang¹, Jinping Li¹, Libo Li^1,5,6,7, Banglin Chen³

1 College of Chemistry and Chemical Engineering, Shanxi Key Laboratory of Gas Energy Efficient and Clean Utilization, Taiyuan University of Technology, Taiyuan 030024, China;
2 NIST Center for Neutron Research, National Institute of Standards and Technology, Gaithersburg, MD 20899-6102, United States;
3 Department of Chemistry, University of Texas at San Antonio, One UTSA Circle, San Antonio, TX 78249-0698, United States;
4 Chemistry Department, College of Science, King Saud University, P O Box 2455, Riyadh 11451, Saudi Arabia;
5 State Key Laboratory of Coal Conversion, Institute of Coal Chemistry, Chinese Academy of Sciences, Taiyuan 030024, China;
6 Key Laboratory of Coal Science and Technology, Taiyuan University of Technology, Taiyuan 030024, China;
7 Shanxi Key Laboratory of Gas Energy Efficient and Clean Utilization, Taiyuan 030024, China

Received:2019-08-01 Revised:2019-09-03 Online:2020-02-28 Published:2020-05-21
Contact: Libo Li, Banglin Chen
Supported by:
We gratefully acknowledge the financial support from the National Natural Science Foundation of China (Nos. 21606163 and 21878205), Coal Bed Methane Joint Foundation of Shanxi (2016012006), Foundation of State Key Laboratory of Coal Conversion (J18-19-610), Welch Foundation (grant AX-1730), and the Distinguished Scientist Fellowship Program (DSFP) at KSU.

摘要/Abstract

摘要： Separation of ethane from ethylene is a very important but challenging process in the petrochemical industry. Finding an alternative method would reduce the energy needed to make 170 million tons of ethylene manufactured worldwide each year. Adsorptive separation using C₂H₆-selective porous materials to directly produce high-purity C₂H₄ is more energy-efficient. We herein report the “reversed C₂H₆/C₂H₄ adsorption” in a metal-organic framework Cr-BTC via the introduction of oxygen on its open metal sites. The oxidized Cr-BTC(O₂) can bind C₂H₆ over C₂H₄ through the active Cr-superoxo sites, which was elucidated by the gas sorption isotherms and density functional theory calculations. This material thus exhibits a good performance for the separation of 50/50 C₂H₆/C₂H₄ mixtures to produce 99.99% pure C₂H₄ in a single separation operation.

关键词: Metal-organic frameworks, Adsorptive separation, Open metal sites, Reversed ethane/ethylene adsorption, Density-functional theory calculation, Breakthrough curves

Abstract: Separation of ethane from ethylene is a very important but challenging process in the petrochemical industry. Finding an alternative method would reduce the energy needed to make 170 million tons of ethylene manufactured worldwide each year. Adsorptive separation using C₂H₆-selective porous materials to directly produce high-purity C₂H₄ is more energy-efficient. We herein report the “reversed C₂H₆/C₂H₄ adsorption” in a metal-organic framework Cr-BTC via the introduction of oxygen on its open metal sites. The oxidized Cr-BTC(O₂) can bind C₂H₆ over C₂H₄ through the active Cr-superoxo sites, which was elucidated by the gas sorption isotherms and density functional theory calculations. This material thus exhibits a good performance for the separation of 50/50 C₂H₆/C₂H₄ mixtures to produce 99.99% pure C₂H₄ in a single separation operation.

Key words: Metal-organic frameworks, Adsorptive separation, Open metal sites, Reversed ethane/ethylene adsorption, Density-functional theory calculation, Breakthrough curves

Ling Yang, Wei Zhou, Hao Li, Ali Alsalme, Litao Jia, Jiangfeng Yang, Jinping Li, Libo Li, Banglin Chen. Reversed ethane/ethylene adsorption in a metal-organic framework via introduction of oxygen[J]. 中国化学工程学报, 2020, 28(2): 593-597.

参考文献

[1] P.Q. Liao, W.X. Zhang, J.P. Zhang, X.M. Chen, Efficient purification of ethene by an ethane-trapping metal-organic framework, Nat. Commun. 6(2015) 8697.
[2] J.R. Li, R.J. Kuppler, H.C. Zhou, Selective gas adsorption and separation in metalorganic frameworks, Chem. Soc. Rev. 38(5) (2009) 1477-1504.
[3] D.S. Sholl, R.P. Lively, Seven chemical separations to change the world, Nature 532(7600) (2016) 435-437.
[4] P.J. Bereciartua, Á. Cantín, A. Corma, J.L. Jordá, M. Palomino, F. Rey, S. Valencia, E.W. Corcoran, 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.
[5] 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) 3402-3405.
[6] R.B. Lin, S.C. Xiang, H.B. Xing, W. Zhou, B.L. Chen, Exploration of porous metalorganic frameworks for gas separation and purification, Coord. Chem. Rev. 378(2019) 87-103.
[7] 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.
[8] 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), 1805088.
[9] X. Zhao, Y. Wang, D.-S. Li, X. Bu, P. Feng, Metal-organic frameworks for separation, Adv. Mater. 30(49) (2018), 1705189.
[10] L. Li, H. Wen, C. He, R.B. Lin, R. Krishna, H. Wu, W. Zhou, J. Li, B. Li, B. Chen, A metalorganic framework with suitable pore size and specific functional sites for the removal of trace propyne from propylene, Angew. Chem. Int. Ed. 57(46) (2018) 15183-15188.
[11] P.Q. Liao, N.Y. Huang, W.X. Zhang, J.P. Zhang, X.M. Chen, Controlling guest conformation for efficient purification of butadiene, Science 356(6343) (2017) 1193-1196.
[12] L. Li, R.B. Lin, R. Krishna, X. Wang, B. Li, H. Wu, Flexible-robust metal-organic framework for efficient removal of propyne from propylene, J. Am. Chem. Soc. 139(23) (2017) 7733-7736.
[13] B. Li, X.L. Cui, D. O'Nolan, H.M. Wen, M.D. Jiang, R. Krishna, H. Wu, R.B. Lin, Y.S. Chen, D.Q. Yuan, H.B. Xing, W. Zhou, Q.L. Ren, G.D. Qian, M.J. Zaworotko, B.L. Chen, An ideal molecular sieve for acetylene removal from ethylene with record selectivity and productivity, Adv. Mater. 29(47) (2017), 1704210.
[14] X.L. Cui, K.J. Chen, H.B. Xing, Q.W. Yang, R. Krishna, Z.B. Bao, H. Wu, W. Zhou, X.L. Dong, Y. Han, B. Li, Q.L. Ren, M.J. Zaworotko, B.L. Chen, Pore chemistry and size control in hybrid porous materials for acetylene capture from ethylene, Science 353(6295) (2016) 141-144.
[15] 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.
[16] Z. Bao, G. Chang, H. Xing, R. Krishna, Q. Ren, B. Chen, Potential of microporous metal-organic frameworks for separation of hydrocarbon mixtures, Energy Environ. Sci. 9(12) (2016) 3612-3641.
[17] M.L. Foo, R. Matsuda, Y. Hijikata, R. Krishna, H. Sato, S. Horike, A. Hori, J.G. Duan, Y. Sato, Y. Kubota, M. Takata, S. Kitagawa, An adsorbate discriminatory gate effect in a flexible porous coordination polymer for selective adsorption of CO₂ over C₂H₂, J. Am. Chem. Soc. 138(9) (2016) 3022-3030.
[18] P. Nugent, Y. Belmabkhout, S.D. Burd, A.J. Cairns, R. Luebke, K. Forrest, T. Pham, S. Ma, B. Space, L. Wojtas, M. Eddaoudi, M.J. Zaworotko, Porous materials with optimal adsorption thermodynamics and kinetics for CO₂ separation, Nature 495(7439) (2013) 80-84.
[19] K. Li, D.H. Olson, J. Seidel, T.J. Emge, H. Gong, H. Zeng, J. Li, Zeolitic imidazolate frameworks for kinetic separation of propane and propene, J. Am. Chem. Soc. 131(30) (2009) 10368-10369.
[20] H. Furukawa, K.E. Cordova, M. O'Keeffe, O.M. Yaghi, The chemistry and applications of metal-organic frameworks, Science 341(6149) (2013), 1230444.
[21] S. Kitagawa, R. Kitaura, S. Noro, Functional porous coordination polymers, Angew. Chem. Int. Ed. 43(18) (2004) 2334-2375.
[22] H. Li, L. Li, R.B. Lin, W. Zhou, Z. Zhang, S. Xiang, B. Chen, Porous metal-organic frameworks for gas storage and separation:Status and challenges, Energy Chem. 1(1) (2019)100006.
[23] P. Li, Q. Chen, T.C. Wang, N.A. Vermeulen, B.L. Mehdi, A. Dohnalkoya, N.D. Browning, D. Shen, R. Anderson, D.A. Gomez-Gualdron, F.M. Cetin, J. Jagiello, A.M. Asiri, J.F. Stoddart, O.K. Farha, Hierarchically engineered mesoporous metal-organic frameworks toward cell-free immobilized enzyme systems, Chem 4(5) (2018) 1022-1034.
[24] C. Wang, D. Liu, W. Lin, Metal-organic frameworks as a tunable platform for designing functional molecular materials, J. Am. Chem. Soc. 135(36) (2013) 13222-13234.
[25] B. Chen, S. Xiang, G. Qian, Metal-organic frameworks with functional pores for recognition of small molecules, Acc. Chem. Res. 43(8) (2010) 1115-1124.
[26] B. Li, M. Chrzanowski, Y. Zhang, S. Ma, Applications of metal-organic frameworks featuring multi-functional sites, Coord. Chem. Rev. 307(2016) 106-129.
[27] S. Yang, A.J. Ramirez-Cuesta, R. Newby, V. Garcia-Sakai, P. Manuel, S.K. Callear, S.I. Campbell, C.C. Tang, M. Schröder, Supramolecular binding and separation of hydrocarbons within a functionalized porous metal-organic framework, Nat. Chem. 7(2) (2015) 121-129.
[28] Y. Bai, Y. Dou, L.-H. Xie, W. Rutledge, J.-R. Li, H.-C. Zhou, Zr-based metal-organic frameworks:design, synthesis, structure, and applications, Chem. Soc. Rev. 45(8) (2016) 2327-2367.
[29] Q.L. Zhu, Q. Xu, Metal-organic framework composites, Chem. Soc. Rev. 43(16) (2014) 5468-5512.
[30] Q.G. Zhai, X.H. Bu, C.Y. Mao, X. Zhao, L. Daemen, Y.Q. Cheng, A.J. Ramirez-Cuesta, P.Y. Feng, An ultra-tunable platform for molecular engineering of high-performance crystalline porous materials, Nat. Commun. 7(2016), 13645.
[31] E.D. Bloch, W.L. Queen, R. Krishna, J.M. Zadrozny, C.M. Brown, J.R. Long, Hydrocarbon separations in a metal-organic framework with open iron(II) coordination sites, Science 335(6076) (2012) 1606-1610.
[32] R.B. Lin, L. Li, H.L. Zhou, H. Wu, C.H. He, S. Li, R. Krishna, J. Li, W. Zhou, B. Chen, Molecular sieving of ethylene from ethane using a rigid metal-organic framework, Nat. Mater. 17(12) (2018) 1128-1133.
[33] R.-B. Lin, H. Wu, L. Li, X.-L. Tang, Z. Li, J. Gao, H. Cui, W. Zhou, B. Chen, Boosting ethane/ethylene separation within Isoreticular Ultramicroporous metal-organic frameworks, J. Am. Chem. Soc. 140(40) (2018) 12940-12946.
[34] O.T. Qazvini, R. Babarao, Z.L. Shi, Y.B. Zhang, S.G. Telfer, A robust ethane-trapping metal-organic framework with a high capacity for ethylene purification, J. Am. Chem. Soc. 141(12) (2019) 5014-5020.
[35] C. Gücüyener, J. van den Bergh, J. Gascon, F. Kapteijn, Ethane/ethene separation turned on its head:selective ethane adsorption on the metal-organic framework ZIF-7 through a gate-opening mechanism, J. Am. Chem. Soc. 132(50) (2010) 17704-17706.
[36] J. Pires, M.L. Pinto, V.K. Saini, Ethane selective IRMOF-8 and its significance in ethane-ethylene separation by adsorption, ACS Appl. Mater. Interfaces 6(15) (2014) 12093-12099.
[37] Y. Chen, Z. Qiao, H. Wu, D. Lv, R. Shi, Q. Xia, J. Zhou, Z. Li, An ethane-trapping MOF PCN-250 for highly selective adsorption of ethane over ethylene, Chem. Eng. Sci. 175(2018) 110-117.
[38] L. Li, R.-B. Lin, R. Krishna, H. Li, S. Xiang, H. Wu, J. Li, W. Zhou, B. Chen, Ethane/ethylene separation in a metal-organic framework with iron-peroxo sites, Science 362(6413) (2018) 443-446.
[39] L.J. Murray, M. Dinca, J. Yano, S. Chavan, S. Bordiga, C.M. Brown, J.R. Long, HighlySelective and reversible O₂ binding in Cr₃(1,3,5-benzenetricarboxylate)2, J. Am. Chem. Soc. 132(23) (2010) 7856-7857.

Reversed ethane/ethylene adsorption in a metal-organic framework via introduction of oxygen

Reversed ethane/ethylene adsorption in a metal-organic framework via introduction of oxygen

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