Effects of functional groups for CO₂ capture using metal organic frameworks

Abstract

Metal organic frameworks (MOFs) are promising adsorbents for CO₂ capture. Functional groups on organic linkers of MOFs play important roles in improving the CO₂ capture ability by enhancing the CO₂ sorption affinity. In this work, the functionalization effects on CO₂ adsorption were systematically investigated by rationally incorporating various functional groups including –SO₃H, –COOH, –NH₂, –OH, –CN, –CH₃ and –F into a MOF-177 template using computational methods. Asymmetries of electron density on the functionalized linkers were intensified, introducing significant enhancements of the CO₂ adsorption ability of the modified MOF-177. In addition, three kinds of molecular interactions between CO₂ and functional groups were analyzed and summarized in this work. Especially, our results reveal that –SO₃H is the best-performing functional group for CO₂ capture in MOFs, better than the widely used –NH₂ or –F groups. The current study provides a novel route for future MOF modification toward CO₂ capture.

Graphical abstract

Keywords

metal-organic frameworks / functional groups / CO₂ capture / GCMC / DFT

References

[1] Zhao C, Chen X, Anthony E J, Jiang X, Duan L, Wu Y, Dong W, Zhao C. Capturing CO₂ in flue gas from fossil fuel-fired power plants using dry regenerable alkali metal-based sorbent. Progress in Energy and Combustion Science, 2013, 39(6): 515–534

[2] Wang M, Liu J, Shen F, Cheng H, Dai J, Long Y. Theoretical study of stability and reaction mechanism of CuO supported on ZrO₂ during chemical looping combustion. Applied Surface Science, 2016, 367: 485–492

[3] Darensbourg D J, Chung W C, Wang K, Zhou H C. Sequestering CO₂ for short-term storage in MOFs: copolymer synthesis with oxiranes. ACS Catalysis, 2014, 4(5): 1511–1515

[4] Yu J, Wang S, Yu H. Experimental studies and rate-based simulations of CO₂ absorption with aqueous ammonia and piperazine blended solutions. International Journal of Greenhouse Gas Control, 2016, 50: 135–146

[5] Rochelle G T. Amine scrubbing for CO₂ capture. Science, 2009, 325(5948): 1652–1654

[6] Lin Y. Metal organic framework membranes for separation applications. Current Opinion in Chemical Engineering, 2015, 8: 21–28

[7] Lin J Y. Molecular sieves for gas separation. Science, 2016, 353(6295): 121–122

[8] Wu Y, Chen X, Fan M, Jiang G, Kong Y, Bland A E. Development of K and N based composite CO₂ sorbents (KN) dried with a supercritical fluid. Chemical Engineering Journal, 2015, 262: 1192–1198

[9] Yang Q, Zhong C, Chen J F. Computational study of CO₂ storage in metal-organic frameworks. Journal of Physical Chemistry C, 2008, 112(5): 1562–1569

[10] Yang S, Liu Z, Yan X, Liu C, Zhang Z, Liu H, Chai L. Catalytic oxidation of elemental mercury in coal-combustion flue gas over the CuAlO₂ catalyst. Energy & Fuels, 2019, 33(11): 11380–11388

[11] Yang H, Xu Z, Fan M, Gupta R, Slimane R B, Bland A E, Wright I. Progress in carbon dioxide separation and capture: a review. Journal of Environmental Sciences (China), 2008, 20(1): 14–27

[12] Figueroa J D, Fout T, Plasynski S, McIlvried H, Srivastava R D. Advances in CO₂ capture technology—the US department of energy’s carbon sequestration program. International Journal of Greenhouse Gas Control, 2008, 2(1): 9–20

[13] Liu H, Xie X, Chen H, Yang S, Liu C, Liu Z, Yang Z, Li Q, Yan X. SO₂ promoted ultrafine nano-sulfur dispersion for efficient and stable removal of gaseous elemental mercury. Fuel, 2020, 261: 116367

[14] Zhang Z, Yao Z Z, Xiang S, Chen B. Perspective of microporous metal-organic frameworks for CO₂ capture and separation. Energy & Environmental Science, 2014, 7(9): 2868–2899

[15] Gu C, Liu J, Hu J, Wu D. Highly selective separations of C₂H₂/C₂H₄ and C₂H₂/C₂H₆ in metal-organic frameworks via pore environment design. Industrial & Engineering Chemistry Research, 2019, 58(43): 19946–19957

[16] Hu J, Liu Y, Liu J, Gu C. Chelation of transition metals into MOFs as a promising method for enhancing CO₂ capture: a computational study. AIChE Journal. American Institute of Chemical Engineers, 2020, 66(2): e16835

[17] Li S, Chung Y G, Simon C M, Snurr R Q. High-throughput computational screening of multivariate metal–organic frameworks (MTV-MOFs) for CO₂ capture. Journal of Physical Chemistry Letters, 2017, 8(24): 6135–6141

[18] An J, Rosi N L. Tuning MOF CO₂ adsorption properties via cation exchange. Journal of the American Chemical Society, 2010, 132(16): 5578–5579

[19] Pal A, Chand S, Das M C. A water-stable twofold interpenetrating microporous MOF for selective CO₂ adsorption and separation. Inorganic Chemistry, 2017, 56(22): 13991–13997

[20] Zheng S T, Bu J T, Li Y, Wu T, Zuo F, Feng P, Bu X. Pore space partition and charge separation in cage-within-cage indium-organic frameworks with high CO₂ uptake. Journal of the American Chemical Society, 2010, 132(48): 17062–17064

[21] Tanabe K K, Cohen S M. Postsynthetic modification of metal-organic frameworks—a progress report. Chemical Society Reviews, 2011, 40(2): 498–519

[22] Hu J, Liu Y, Liu J, Gu C. Effects of water vapor and trace gas impurities in flue gas on CO₂ capture in zeolitic imidazolate frameworks: the significant role of functional groups. Fuel, 2017, 200: 244–251

[23] Xiang Z, Leng S, Cao D. Functional group modification of metal-organic frameworks for CO₂ capture. Journal of Physical Chemistry C, 2012, 116(19): 10573–10579

[24] Zheng B, Bai J, Duan J, Wojtas L, Zaworotko M J. Enhanced CO₂ binding affinity of a high-uptakerht-type metal-organic framework decorated with acylamide groups. Journal of the American Chemical Society, 2010, 133(4): 748–751

[25] An J, Geib S J, Rosi N L. High and selective CO₂ uptake in a cobalt adeninate metal-organic framework exhibiting pyrimidine-and amino-decorated pores. Journal of the American Chemical Society, 2009, 132(1): 38–39

[26] Ye Y, Zhang H, Chen L, Chen S, Lin Q, Wei F, Zhang Z, Xiang S. Metal-organic framework with rich accessible nitrogen sites for highly efficient CO₂ capture and separation. Inorganic Chemistry, 2019, 58(12): 7754–7759

[27] Hu J, Liu Y, Liu J, Gu C, Wu D. High CO₂ adsorption capacities in UiO type MOFs comprising heterocyclic ligand. Microporous and Mesoporous Materials, 2018, 256: 25–31

[28] Liu Y, Liu J, Chang M, Zheng C. Effect of functionalized linker on CO₂ binding in zeolitic imidazolate frameworks: density functional theory study. Journal of Physical Chemistry C, 2012, 116(32): 16985–16991

[29] Liu Y, Liu J, Chang M, Zheng C. Theoretical studies of CO₂ adsorption mechanism on linkers of metal–organic frameworks. Fuel, 2012, 95: 521–527

[30] Zhang Y B, Furukawa H, Ko N, Nie W, Park H J, Okajima S, Cordova K E, Deng H, Kim J, Yaghi O M. Introduction of functionality, selection of topology, and enhancement of gas adsorption in multivariate metal-organic framework-177. Journal of the American Chemical Society, 2015, 137(7): 2641–2650

[31] Accelrys Software Inc. Materials Studio Release Notes, release 4.4. Accelrys Software Inc.: San Diego, CA, 2008

[32] Yang Q, Vaesen S, Ragon F, Wiersum A D, Wu D, Lago A, Devic T, Martineau C, Taulelle F, Llewellyn P L, A water stable metal-organic framework with optimal features for CO₂ capture. Angewandte Chemie International Edition, 2013, 52(39): 10316–10320

[33] Zhou Y X, Chen Y Z, Hu Y, Huang G, Yu S H, Jiang H L. MIL-101-SO₃H: a highly efficient Brønsted acid catalyst for heterogeneous alcoholysis of epoxides under ambient conditions. Chemistry (Weinheim an der Bergstrasse, Germany), 2014, 20(46): 14976–14980

[34] Sarkisov L, Harrison A. Computational structure characterisation tools in application to ordered and disordered porous materials. Molecular Simulation, 2011, 37(15): 1248–1257

[35] Gu C, Liu J, Hu J, Wu D. Metal-organic frameworks chelated by zinc fluorides for ultra-high affinity to acetylene during C₂/C₁ separations. Fuel, 2020, 266: 117037

[36] Yang Y, Liu J, Wang Z. Reaction mechanisms and chemical kinetics of mercury transformation during coal combustion. Progress in Energy and Combustion Science, 2020, 79: 100844

[37] Wang Z, Liu J, Yang Y, Liu F, Ding J. Heterogeneous reaction mechanism of elemental mercury oxidation by oxygen species over MnO₂ catalyst. Proceedings of the Combustion Institute, 2019, 37(3): 2967–2975

[38] Wang Z, Liu J, Yang Y, Yu Y, Yan X, Zhang Z. AMn₂O₄ (A= Cu, Ni and Zn) sorbents coupling high adsorption and regeneration performance for elemental mercury removal from syngas. Journal of Hazardous Materials, 2020, 388: 121738

[39] Ikeda A, Nakao Y, Sato H, Sakaki S. Binding energy of transition-metal complexes with large p-conjugate systems. Density functional theory vs post-Hartree-Fock methods. Journal of Physical Chemistry A, 2007, 111(30): 7124–7132

[40] Ramsahye N, Maurin G, Bourrelly S, Llewellyn P, Serre C, Loiseau T, Devic T, Ferey G. Probing the adsorption sites for CO₂ in metal organic frameworks materials MIL-53 (Al, Cr) and MIL-47(V) by density functional theory. Journal of Physical Chemistry C, 2008, 112(2): 514–520

[41] Delley B. From molecules to solids with the DMol³ approach. Journal of Chemical Physics, 2000, 113(18): 7756–7764

[42] Lee T B, Kim D, Jung D H, Choi S B, Yoon J H, Kim J, Choi K, Choi S H. Understanding the mechanism of hydrogen adsorption into metal organic frameworks. Catalysis Today, 2007, 120(3-4): 330–335

[43] Wang Z, Liu J, Yang Y, Yu Y, Yan X, Zhang Z. Insights into the catalytic behavior of LaMnO₃ perovskite for Hg⁰ oxidation by HCl. Journal of Hazardous Materials, 2020, 383: 121156

[44] Potoff J J, Siepmann J I. Vapor-liquid equilibria of mixtures containing alkanes, carbon dioxide, and nitrogen. AIChE Journal. American Institute of Chemical Engineers, 2001, 47(7): 1676–1682

[45] Rappé A K, Casewit C J, Colwell K, Goddard W III, Skiff W. UFF, a full periodic table force field for molecular mechanics and molecular dynamics simulations. Journal of the American Chemical Society, 1992, 114(25): 10024–10035

[46] Momany F A. Determination of partial atomic charges from ab initio molecular electrostatic potentials. Application to formamide, methanol, and formic acid. Journal of Physical Chemistry, 1978, 82(5): 592–601

[47] Campañá C, Mussard B, Woo T K. Electrostatic potential derived atomic charges for periodic systems using a modified error functional. Journal of Chemical Theory and Computation, 2009, 5(10): 2866–2878

[48] Argueta E, Shaji J, Gopalan A, Liao P, Snurr R Q, Gómez-Gualdrón D A. Molecular building block-based electronic charges for high-throughput screening of metal-organic frameworks for adsorption applications. Journal of Chemical Theory and Computation, 2018, 14(1): 365–376

[49] Manz T A, Sholl D S. Chemically meaningful atomic charges that reproduce the electrostatic potential in periodic and nonperiodic materials. Journal of Chemical Theory and Computation, 2010, 6(8): 2455–2468

[50] Cornell W D, Cieplak P, Bayly C I, Gould I R, Merz K M, Ferguson D M, Spellmeyer D C, Fox T, Caldwell J W, Kollman P A. A second generation force field for the simulation of proteins, nucleic acids, and organic molecules. Journal of the American Chemical Society, 1995, 117(19): 5179–5197

[51] Torrisi A, Bell R G, Mellot-Draznieks C. Predicting the impact of functionalized ligands on CO₂ adsorption in MOFs: a combined DFT and Grand Canonical Monte Carlo study. Microporous and Mesoporous Materials, 2013, 168: 225–238

[52] Gu C, Liu J, Hu J, Wu D. Highly efficient separations of C₂H₂ from C₂H₂/CO and C₂H₂/H₂ in metal-organic frameworks with ZnF₂ chelation: a molecular simulation study. Fuel, 2020, 271: 117598

[53] Steiner T, Desiraju G R. Distinction between the weak hydrogen bond and the van der Waals interaction. Chemical Communications, 1998, (8): 891–892

[54] Paulini R, Müller K, Diederich F. Orthogonal multipolar interactions in structural chemistry and biology. Angewandte Chemie International Edition, 2005, 44(12): 1788–1805

[55] Jeziorski B, Moszynski R, Szalewicz K. Perturbation theory approach to intermolecular potential energy surfaces of van der Waals complexes. Chemical Reviews, 1994, 94(7): 1887–1930

[56] Shao Y, Gan Z, Epifanovsky E, Gilbert A T B, Wormit M, Kussmann J, Lange A W, Behn A, Deng J, Feng X, et al. Advances in molecular quantum chemistry contained in the Q-Chem 4 program package. Molecular Physics, 2015, 113(2): 184–215

[57] Fioretos K A, Psofogiannakis G M, Froudakis G E. Ab-initio study of the adsorption and separation of NO_x and SO_x gases in functionalized IRMOF ligands. Journal of Physical Chemistry C, 2011, 115(50): 24906–24914

[58] Gu C, Liu Y, Liu J, Hu J, Wang W. Ab initio study of gas adsorption in metal-organic frameworks modified by lithium: the significant role of Li-containing functional groups. Journal of Physical Chemistry C, 2018, 122(32): 18395–18404

[59] Gu C, Liu J, Hu J, Wang W. Metal-organic frameworks grafted by univariate and multivariate heterocycles for enhancing CO₂ capture: a molecular simulation study. Industrial & Engineering Chemistry Research, 2019, 58(6): 2195–2205

[60] Millward A R, Yaghi O M. Metal-organic frameworks with exceptionally high capacity for storage of carbon dioxide at room temperature. Journal of the American Chemical Society, 2005, 127(51): 17998–17999

[61] Phan A, Doonan C J, Uribe-Romo F J, Knobler C B, O’Keeffe M, Yaghi O M. Synthesis, structure, and carbon dioxide capture properties of zeolitic imidazolate frameworks. Accounts of Chemical Research, 2010, 43(1): 58–67

[62] Chowdhury P, Bikkina C, Meister D, Dreisbach F, Gumma S. Comparison of adsorption isotherms on Cu-BTC metal organic frameworks synthesized from different routes. Microporous and Mesoporous Materials, 2009, 117(1-2): 406–413

[63] Anderson R, Rodgers J, Argueta E, Biong A, Gómez-Gualdrón D A. Role of pore chemistry and topology in the CO₂ capture capabilities of MOFs: from molecular simulation to machine learning. Chemistry of Materials, 2018, 30(18): 6325–6337

Acknowledgements

This work was supported by the National Natural Science Foundation of China (Grant Nos. 51676079 and 21773104), Fundamental Research Funds for the Central Universities (No. 2019kfyR-CPY021) and China Scholarship Council (No. 201906160014).ƒ

Electronic Supplementary Material

Supplementary material is available in the online version of this article at https://doi.org/10.1007/s11705-020-1961-6 and is accessible for authorized users.

RIGHTS & PERMISSIONS

2020 Higher Education Press