Efficient acetylene/carbon dioxide separation with excellent dynamic capacity and low regeneration energy by anion-pillared hybrid materials

Abstract

Adsorptive separation of acetylene/carbon dioxide mixtures by porous materials is an important and challenging task due to their similar sizes and physical properties. Here, remarkable acetylene/carbon dioxide separation featuring a high dynamic breakthrough capacity for acetylene (4.3 mmol·g^–1) as well as an ultralow acetylene regeneration energy (29.5 kJ·mol^–1) was achieved with the novel TiF₆^2–-pillared material ZU-100 (TIFSIX-bpy-Ni). Construction of a pore structure with abundant TiF₆^2– anion sites and pores with appropriate sizes enabled formation of acetylene clusters through hydrogen bonds and intermolecular interactions, which afforded a high acetylene capacity (8.3 mmol·g^–1) and high acetylene/carbon dioxide uptake ratio (1.9) at 298 K and 1 bar. Moreover, the NbO₅^2– anion-pillared material ZU-61 investigated for separation of acetylene/carbon dioxide. In addition, breakthrough experiments were also conducted to further confirm the excellent dynamic acetylene/carbon dioxide separation performance of ZU-100.

Graphical abstract

Keywords

adsorption / acetylene/carbon dioxide separation / dynamic capacity / anion-pillared hybrid material

References

[1] Luna-Triguero A, Vicent-Luna J M, Madero-Castro R M, Gomez-Alvarez P, Calero S. Acetylene storage and separation using metal-organic frameworks with open metal sites. ACS Applied Materials & Interfaces, 2019, 11( 34): 31499– 31507

[2] Matsuda R, Kitaura R, Kitagawa S, Kubota Y, Belosludov R V, Kobayashi T, Sakamoto H, Chiba T, Takata M, Kawazoe Y, Mita Y. Highly controlled acetylene accommodation in a metal−organic microporous material. Nature, 2005, 436( 7048): 238– 241

[3] Xiang S, Zhou W, Gallegos J M, Liu Y, Chen B L. Exceptionally high acetylene uptake in a microporous metal−organic framework with open metal sites. Journal of the American Chemical Society, 2009, 131( 34): 12415– 12419

[4] Foo M L, Matsuda R, Hijikata Y, Krishna R, Sato H, Horike S, Hori A, Duan J, Sato Y, Kubota Y, Takata M, Kitagawa S. An adsorbate discriminatory gate effect in a flexible porous coordination polymer for selective adsorption of CO₂ over C₂H₂. Journal of the American Chemical Society, 2016, 138( 9): 3022– 3030

[5] Peng Y, Pham T, Li P, Wang T, Chen Y, Chen K J, Forrest K A, Space B, Cheng P, Zaworotko M J, Zhang Z. Robust ultramicroporous metal−organic frameworks with benchmark affinity for acetylene. Angewandte Chemie International Edition, 2018, 57( 34): 10971– 10975

[6] Yao Z, Zhang Z, Liu L, Li Z, Zhou W, Zhao Y, Han Y, Chen B, Krishna R, Xiang S. Extraordinary separation of acetylene-containing mixtures with microporous metal−organic frameworks with open O donor sites and tunable robustness through control of the helical chain secondary building units. Chemistry, 2016, 22( 16): 5676– 5683

[7] Scott H S, Shivanna M, Bajpai A, Madden D G, Chen K J, Pham T, Forrest K A, Hogan A, Space B, Perry J J IV, Zaworotko M J. Highly selective separation of C₂H₂ from CO₂ by a new dichromate-based hybrid ultramicroporous material. ACS Applied Materials & Interfaces, 2017, 9( 39): 33395– 33400

[8] Li P, He Y, Zhao Y, Weng L, Wang H, Krishna R, Wu H, Zhou W, O’Keeffe M, Han Y, Chen B. A rod-packing microporous hydrogen-bonded organic framework for highly selective separation of C₂H₂/CO₂ at room temperature. Angewandte Chemie International Edition, 2015, 54( 2): 574– 577

[9] Zhang L, Jiang K, Zhang J, Pei J, Shao K, Cui Y, Yang Y, Li B, Chen B, Qian G. Low-cost and high-performance microporous metal−organic framework for separation of acetylene from carbon dioxide. ACS Sustainable Chemistry & Engineering, 2019, 7( 1): 1667– 1672

[10] Zhang J, Chen X. Optimized acetylene/carbon dioxide sorption in a dynamic porous crystal. Journal of the American Chemical Society, 2009, 131( 15): 5516– 5521

[11] Qazvini O, Babarao R, Telfer S. Multipurpose metal-organic framework for the adsorption of acetylene: ethylene purification and carbon dioxide removal. Chemistry of Materials, 2019, 31( 13): 4919– 4926

[12] Moreau F, da Silva I, Al Smail N, Easun T, Savage M, Godfrey M, Parker S, Manuel P, Yang S, Schroder M. Unravelling exceptional acetylene and carbon dioxide adsorption within a tetra-amide functionalized metal−organic framework. Nature Communications, 2017, 8( 1): 14085

[13] Zhang Y, Hu J, Krishna R, Wang L, Yang L, Cui X, Duttwyler S, Xing H. Rational design of microporous MOFs with anionic boron cluster functionality and cooperative dihydrogen binding sites for highly selective capture of acetylene. Angewandte Chemie International Edition, 2020, 59( 40): 17664– 17669

[14] Liu R, Liu Q, Krishna R, Wang W, He C, Wang Y. Water-stable europium 1,3,6,8-tetrakis(4-carboxylphenyl)pyrene framework for efficient C₂H₂/CO₂ separation. Inorganic Chemistry, 2019, 58( 8): 5089– 5095

[15] Xie Y, Cui H, Wu H, Lin R, Zhou W, Chen B. Electrostatically driven selective adsorption of carbon dioxide over acetylene in an ultramicroporous material. Angewandte Chemie International Edition, 2021, 60( 17): 9604– 9609

[16] Wang J, Zhang Y, Su Y, Liu X, Zhang P, Lin R, Chen S, Deng Q, Zeng Z, Deng S, Chen B. Fine pore engineering in a series of isoreticular metal−organic frameworks for efficient C₂H₂/CO₂ separation. Nature Communications, 2022, 13( 1): 200

[17] Qazvini O, Babarao R, Telfer S. Selective capture of carbon dioxide from hydrocarbons using a metal−organic framework. Nature Communications, 2021, 12( 1): 197

[18] Choi D, Kim D, Kang D, Kang M, Chae Y, Hong C. Highly selective CO₂ separation from a CO₂/C₂H₂ mixture using a diamine-appended metal−organic framework. Angewandte Chemie International Edition, 2021, 9( 37): 21424– 21428

[19] Shi Y, Xie Y, Cui H, Ye Y, Wu H, Zhou W, Arman H, Lin R, Chen B. Highly selective adsorption of carbon dioxide over acetylene in an ultramicroporous metal−organic framework. Advanced Materials, 2021, 33( 45): 2105880

[20] Ye Y, Xian S, Cui H, Tan K, Gong L, Liang B, Pham T, Pandey H, Krishna R, Lan P, Forrest K A, Space B, Thonhauser T, Li J, Ma S. Metal−organic framework based hydrogen-bonding nanotrap for efficient acetylene storage and separation. Journal of the American Chemical Society, 2022, 144( 4): 1681– 1689

[21] Dong Q, Zhang X, Liu S, Lin R, Guo Y, Ma Y, Yonezu A, Krishna R, Liu G, Duan J, Matsuda R, Jin W, Chen B. Tuning gate-opening of a flexible metal−organic framework for ternary gas sieving separation. Angewandte Chemie International Edition, 2020, 59( 50): 22756– 22762

[22] Fan W, Yuan S, Wang W, Feng L, Liu X, Zhang X, Wang X, Kang Z, Dai F, Yuan D, Sun D, Zhou H C. Optimizing multivariate metal−organic frameworks for efficient C₂H₂/CO₂ separation. Journal of the American Chemical Society, 2020, 142( 19): 8728– 8737

[23] Pei J, Shao K, Wang J, Wen H, Yang Y, Cui Y, Krishna R, Li B, Qian G. A chemically stable hofmann-type metal−organic framework with sandwich-like binding sites for benchmark acetylene capture. Advanced Materials, 2020, 32( 24): 1908275

[24] Mukherjee S, He Y, Franz D, Wang S, Xian W, Bezrukov A, Space B, Xu Z, He J, Zaworotko M. Halogen-C₂H₂ binding in ultramicroporous metal−organic frameworks (MOFs) for benchmark C₂H₂/CO₂ separation selectivity. Chemistry, 2020, 26( 22): 4923– 4929

[25] Kumar N, Mukherjee S, Harvey-Reid N, Bezrukov A, Tan K, Martins V, Vandichel M, Pham T, van Wyk L, Oyekan K, Kumar A, Forrest K A, Patil K M, Barbour L J, Space B, Huang Y, Kruger P E, Zaworotko M J. Breaking the trade-off between selectivity and adsorption capacity for gas separation. Chem, 2021, 7( 11): 3085– 3098

[26] Yang L, Yan L, Wang Y, Liu Z, He J, Fu Q, Liu D, Gu X, Dai P, Li L, Zhao X. Adsorption site selective occupation strategy within a metal−organic framework for highly efficient sieving acetylene from carbon dioxide. Angewandte Chemie International Edition, 2021, 60( 9): 4570– 4574

[27] Luo F, Yan C, Dang L, Krishna R, Zhou W, Wu H, Dong X, Han Y, Hu T L, O’Keeffe M, Wang L, Luo M, Lin R B, Chen B. UTSA-74: a MOF-74 isomer with two accessible binding sites per metal center for highly selective gas separation. Journal of the American Chemical Society, 2016, 138( 17): 5678– 5684

[28] Zhang L, Jiang K, Yang L, Li L, Hu E, Yang L, Shao K, Xing H, Cui Y, Yang Y, Li B, Chen B, Qian G. Benchmark C₂H₂/CO₂ separation in an ultra-microporous metal−organic framework via copper(I)-alkynyl chemistry. Angewandte Chemie International Edition, 2021, 60( 29): 15995– 16002

[29] Chen K J, Scott H, Madden D, Pham T, Kumar A, Bajpai A, Lusi M, Forrest K, Space B, Perry J IV, Zaworotko M J. Benchmark C₂H₂/CO₂ and CO₂/C₂H₂ separation by two closely related hybrid ultramicroporous materials. Chem, 2016, 1( 5): 753– 765

[30] Jiang M D, Cui X L, Yang L F, Yang Q W, Zhang Z Q, Yang Y W, Xing H B. A thermostable anion-pillared metal−organic framework for C₂H₂/C₂H₄ and C₂H₂/CO₂ separations. Chemical Engineering Journal, 2018, 352 : 803– 810

[31] Cui X, Chen K, Xing H, Yang Q, Krishna R, Bao Z, Wu H, Zhou W, Dong X, Han Y, Li B, Ren Q, Zaworotko M J, Chen B. Pore chemistry and size control in hybrid porous materials for acetylene capture from ethylene. Science, 2016, 353( 6295): 141– 144

[32] Nugent P, Belmabkhout Y, Burd S, Cairns A, Luebke R, Forrest K, Pham T, Ma S, Space B, Wojtas L, Eddaoudi M, Zaworotko M J. Porous materials with optimal adsorption thermodynamics and kinetics for CO₂ separation. Nature, 2013, 495( 7439): 80– 84

[33] Cui X, Niu Z, Shan C, Yang L, Hu J, Wang Q, Lan P C, Li Y, Wojtas L, Ma S, Xing H. Efficient separation of xylene isomers by a guest-responsive metal−organic framework with rotational anionic sites. Nature Communications, 2020, 11( 1): 5456

[34] Lin R B, Li L, Wu H, Arman H, Li B, Lin R G, Zhou W, Chen B. Optimized separation of acetylene from carbon dioxide and ethylene in a microporous material. Journal of the American Chemical Society, 2017, 139( 23): 8022– 8028

[35] Lee J, Chuah C Y, Kim J, Kim Y, Ko N, Seo Y, Kim K, Bae T H, Lee E. Separation of acetylene from carbon dioxide and ethylene by a water-stable microporous metal−organic framework with aligned imidazolium groups inside the channels. Angewandte Chemie International Edition, 2018, 57( 26): 7869– 7873

[36] Ye Y, Ma Z, Lin R B, Krishna R, Zhou W, Lin Q, Zhang Z, Xiang S, Chen B. Pore space partition within a metal−organic framework for highly efficient C₂H₂/CO₂ separation. Journal of the American Chemical Society, 2019, 141( 9): 4130– 4136

[37] Li Y, Wang Y, Xue Y, Li H, Zhai Q, Li S, Jiang Y, Hu M, Bu X. Ultramicroporous building units as a path to bi-microporous metal−organic frameworks with high acetylene storage and separation performance. Angewandte Chemie International Edition, 2019, 58( 38): 13590– 13595

[38] Niu Z, Cui X, Pham T, Verma G, Lan P, Shan C, Xing H, Forrest K, Suepaul S, Space B, Nafady A, Al-Enizi A M, Ma S. A MOF-based ultra-strong acetylene nano-trap for highly efficient C₂H₂/CO₂ separation. Angewandte Chemie International Edition, 2021, 60( 10): 5283– 5288

[39] Duan J, Jin W, Krishna R. Natural gas purification using a porous coordination polymer with water and chemical stability. Inorganic Chemistry, 2015, 54( 9): 4279– 4284

[40] Qian Q, Gu X, Pei J, Wen H, Wu H, Zhou W, Li B, Qian G. A novel anion-pillared metal−organic framework for highly efficient separation of acetylene from ethylene and carbon dioxide. Journal of Materials Chemistry A, 2021, 9( 14): 9248– 9255

[41] Li H, Liu C, Chen C, Di Z, Yuan D, Pang J, Wei W, Wu M, Hong M. An unprecedented pillar-cage fluorinated hybrid porous framework with highly efficient acetylene storage and separation. Angewandte Chemie International Edition, 2021, 60( 14): 7547– 7552

[42] Zhang Z, Cui X, Jiang X, Ding Q, Cui J, Zhang Y, Belmabkhout Y, Adil K, Eddaoudi M, Xing H. Efficient splitting of trans-/cis-olefins using an anion-pillared ultramicroporous metal−organic framework with guest-adaptive pore channels. Engineering, 2022, 11 : 80– 86

Acknowledgements

This work was financially supported by the Zhejiang Provincial Natural Science Foundation of China (Grant No. LR20B060001), the National Natural Science Foundation of China (Grant Nos. 22122811, 21938011, and 21890764), and the Research Computing Center in College of Chemical and Biological Engineering at Zhejiang University.

Electronic Supplementary Material

Supplementary material is available in the online version of this article at https://dx.doi.org/10.1007/s11705-022-2183-x and is accessible for authorized users.

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