3-dimensional linker-based metal–organic frameworks for sub-angstrom control and enhanced thermal stability
Source abstract
Abstract
Metal–organic frameworks (MOFs) are some of the best materials for energy-efficient separations, like membranes and adsorption processes, due to their nanoporosity and tunability. To tune a MOF for optimum separation of molecules with sub-angstrom differences in size, which is a common challenge in industrial separations, precise control of the local pore environment is required. Here, we explore the concept of “3-dimensional” linkers, i.e., linkers that contain sterically bulky non-planar cores, as a means to attain sub-angstrom control over MOF pore size and to control structural flexibility. In particular, the introduction of 3-dimensional linkers (3DLs) is shown to hinder global breathing transitions in MOFs. Because these linkers occupy a consistent volume regardless of their orientation, they also allow for precise size-based separation of very similar molecules, such as hexane isomers. Furthermore, we discuss the thermal stability of a subset of these materials, characterized through variable temperature X-ray diffraction and porosity measurements.
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Research context
OpenAlex topics: Metal-Organic Frameworks: Synthesis and Applications · Membrane Separation and Gas Transport · Covalent Organic Framework Applications
SciVX discovery tags are terminology-based. OpenAlex topics are source-provided classifications.
References (42)
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1. D.S. Sholl, R.P. Lively, Seven chemical separations to change the world. Nature 532(7600), 435 (2016)10.1038/532435a ↗
2. E. National Academies of Sciences, and Medicine: A Research Agenda for Transforming Separation Science (The National Academies Press, City, 2019).
3. J.R. Li, R.J. Kuppler, H.C. Zhou, Selective gas adsorption and separation in metal-organic frameworks. Chem. Soc. Rev. 38(5), 1477 (2009)10.1039/b802426j ↗
4. J.R. Li, J. Sculley, H.C. Zhou, Metal-organic frameworks for separations. Chem. Rev. 112(2), 869 (2012)10.1021/cr200190s ↗
5. E. Adatoz, A.K. Avci, S. Keskin, Opportunities and challenges of MOF-based membranes in gas separations. Sep. Purif. Technol. 152, 207 (2015)10.1016/j.seppur.2015.08.020 ↗
6. M.S. Denny, J.C. Moreton, L. Benz, S.M. Cohen, Metal-organic frameworks for membrane-based separations. Nat. Rev. Mater. (2016). https://doi.org/10.1038/natrevmats.2016.7810.1038/natrevmats.2016.78 ↗
7. E. National Academies of Sciences, and Medicine: Sustainability in the Chemical Industry: Grand Challenges and Research Needs (The National Academies Press, City, 2006).
8. H. Bux, F.Y. Liang, Y.S. Li, J. Cravillon, M. Wiebcke, J. Caro, Zeolitic imidazolate framework membrane with molecular sieving properties by microwave-assisted solvothermal synthesis. J. Am. Chem. Soc. 131(44), 16000 (2009)10.1021/ja907359t ↗
9. X.C. Huang, Y.Y. Lin, J.P. Zhang, X.M. Chen, Ligand-directed strategy for zeolite-type metal-organic frameworks: Zinc(II) imidazolates with unusual zeolitic topologies. Angew. Chem. Int. Edit. 45(10), 1557 (2006)10.1002/anie.200503778 ↗
10. W. Zhou, H. Wu, M.R. Hartman, T. Yildirim, Hydrogen and methane adsorption in metal-organic frameworks: a high-pressure volumetric study. J. Phys. Chem. C 111(44), 16131 (2007)10.1021/jp074889i ↗
11. K. Zhang, R.P. Lively, C. Zhang, R.R. Chance, W.J. Koros, D.S. Sholl, S. Nair, Exploring the framework hydrophobicity and flexibility of ZIF-8: from biofuel recovery to hydrocarbon separations. J. Phys. Chem. Lett. 4(21), 3618 (2013)10.1021/jz402019d ↗
12. D. Fairen-Jimenez, S.A. Moggach, M.T. Wharmby, P.A. Wright, S. Parsons, T. Düren, Opening the gate: framework flexibility in ZIF-8 explored by experiments and simulations. J. Am. Chem. Soc. 133(23), 8900 (2011)10.1021/ja202154j ↗
13. L.K. Macreadie, E.J. Mensforth, R. Babarao, K. Konstas, S.G. Telfer, C.M. Doherty, J. Tsanaktsidis, S.R. Batten, M.R. Hill, CUB-5: a contoured aliphatic pore environment in a cubic framework with potential for benzene separation applications. J. Am. Chem. Soc. 141(9), 3828 (2019)10.1021/jacs.8b13639 ↗
14. J. Bedard, S.S. Chitnis, Three-dimensional synthons for cage-dense inorganic polymers and materials. Chem. Mater. 35(20), 8338 (2023)10.1021/acs.chemmater.3c02133 ↗
15. K.B. Idrees, K.O. Kirlikovali, C. Setter, H. Xie, H. Brand, B. Lal, F. Sha, C.S. Smoljan, X. Wang, T. Islamoglu, L.K. Macreadie, O.K. Farha, Robust carborane-based metal-organic frameworks for hexane separation. J. Am. Chem. Soc. 145(43), 23433 (2023)10.1021/jacs.3c04641 ↗
16. K.B. Idrees, Z. Li, H.M. Xie, K.O. Kirlikovali, M. Kazem-Rostami, X.J. Wang, X.J. Wang, T.Y. Tai, T. Islamoglu, J.F. Stoddart, R.Q. Snurr, O.K. Farha, Separation of aromatic hydrocarbons in porous materials. J. Am. Chem. Soc. 144(27), 12212 (2022)10.1021/jacs.2c03114 ↗
17. L.K. Macreadie, K.B. Idrees, C.S. Smoljan, O.K. Farha, Expanding linker dimensionality in metal-organic frameworks for sub-angstrom pore control for separation applications. Angew. Chem. Int. Ed. Engl. (2023). https://doi.org/10.1002/anie.20230409410.1002/anie.202304094 ↗
18. C.S. Smoljan, Z. Li, H. Xie, C.J. Setter, K.B. Idrees, F.A. Son, F. Formalik, S. Shafaie, T. Islamoglu, L.K. Macreadie, R.Q. Snurr, O.K. Farha, Engineering metal-organic frameworks for selective separation of hexane isomers using 3-dimensional linkers. J. Am. Chem. Soc. 145(11), 6434 (2023)10.1021/jacs.2c13715 ↗
19. K.B. Idrees, Z.J. Chen, X. Zhang, M.R. Mian, R.J. Drout, T. Islamoglu, O.K. Farha, Tailoring pore aperture and structural defects in zirconium-based metal-organic frameworks for krypton/xenon separation. Chem. Mater. 32(9), 3776 (2020)10.1021/acs.chemmater.9b05048 ↗
20. B. Lal, K.B. Idrees, H. Xie, C.S. Smoljan, S. Shafaie, T. Islamoglu, O.K. Farha, Pore aperture control toward size-exclusion-based hydrocarbon separations. Angew. Chem. Int. Ed. Engl. (2023). https://doi.org/10.1002/anie.20221905310.1002/anie.202219053 ↗
21. J. Zhou, T. Ke, Y. Song, H. Cai, Z. Wang, L. Chen, Q. Xu, Z. Zhang, Z. Bao, Q. Ren, Q. Yang, Highly efficient separation of C8 aromatic isomers by rationally designed nonaromatic metal-organic frameworks. J. Am. Chem. Soc. 144(46), 21417 (2022)10.1021/jacs.2c10595 ↗
22. J. Zhou, T. Ke, F. Steinke, N. Stock, Z. Zhang, Z. Bao, X. He, Q. Ren, Q. Yang, Tunable confined aliphatic pore environment in robust metal-organic frameworks for efficient separation of gases with a similar structure. J. Am. Chem. Soc. 144(31), 14322 (2022)10.1021/jacs.2c05448 ↗
23. J. Zhou, T. Ke, X. Zhu, B. Jin, Z. Bao, Z. Zhang, Y. Yang, Q. Ren, Q. Yang, Combination of low-polar and polar binding sites in aliphatic MOFs for the efficient C(2)H(6)/C(2)H(4) separation. ACS Appl. Mater. Interfaces 15(2), 3387 (2023)10.1021/acsami.2c21261 ↗
24. A. Schneemann, V. Bon, I. Schwedler, I. Senkovska, S. Kaskel, R.A. Fischer, Flexible metal-organic frameworks. Chem. Soc. Rev. 43(16), 6062 (2014)10.1039/C4CS00101J ↗
25. N. Behera, J.G. Duan, W.Q. Jin, S. Kitagawa, The chemistry and applications of flexible porous coordination polymers. Energychem 3(6), 100067 (2021)10.1016/j.enchem.2021.100067 ↗
26. S. Li, W.Y. Han, Q.F. An, K.T. Yong, M.J. Yin, Defect engineering of MOF-based membrane for gas separation. Adv. Funct. Mater. (2023). https://doi.org/10.1002/adfm.20230344710.1002/adfm.202303447 ↗
27. F. Dorosti, L. Ge, H. Wang, Z.H. Zhu, A path forward: understanding and mitigating defects in polycrystalline membranes. Prog. Mater. Sci. 137, 101123 (2023)10.1016/j.pmatsci.2023.101123 ↗
28. W.B. Li, P.C. Su, H.Y. Tang, Y.S. Lin, Y.Q. Yu, Hetero-polycrystalline membranes with narrow and rigid pores for molecular sieving. Small (2023). https://doi.org/10.1002/smll.20220554210.1002/smll.202205542 ↗
29. F. Formalik, K.H. Shi, F. Joodaki, X.J. Wang and R.Q. Snurr: Exploring the structural, dynamic, and functional properties of metal-organic frameworks through molecular modeling. Adv. Funct. Mater. (2023).10.1002/adfm.202308130 ↗
30. Y. Liu, J.H. Her, A. Dailly, A.J. Ramirez-Cuesta, D.A. Neumann, C.M. Brown, Reversible structural transition in MIL-53 with large temperature hysteresis. J. Am. Chem. Soc. 130(35), 11813 (2008)10.1021/ja803669w ↗
31. T. Loiseau, C. Serre, C. Huguenard, G. Fink, F. Taulelle, M. Henry, T. Bataille, G. Ferey, A rationale for the large breathing of the porous aluminum terephthalate (MIL-53) upon hydration. Chemistry 10(6), 1373 (2004)10.1002/chem.200305413 ↗
32. A. Ghoufi, A. Subercaze, Q. Ma, P.G. Yot, Y. Ke, I. Puente-Orench, T. Devic, V. Guillerm, C. Zhong, C. Serre, G. Férey, G. Maurin, Comparative guest, thermal, and mechanical breathing of the porous metal organic framework MIL-53(Cr): a computational exploration supported by experiments. J. Phys. Chem. C 116(24), 13289 (2012)10.1021/jp303686m ↗
33. Y.G. Chung, P. Bai, M. Haranczyk, K.T. Leperi, P. Li, H.D. Zhang, T.C. Wang, T. Duerinck, F.Q. You, J.T. Hupp, O.K. Farha, J.I. Siepmann, R.Q. Snurr, Computational screening of nanoporous materials for hexane and heptane isomer separation. Chem. Mater. 29(15), 6315 (2017)10.1021/acs.chemmater.7b01565 ↗
34. S. Baker-Branstetter: Why High Octane Fuels Matter for Fuel Economy, City, 2015).
35. S.P.G.C. Insights: para-Xylene, in Chemical Economics Handbook, (S&P Global Inc., City, 2022).
36. L.K. Macreadie, O.T. Qazvini, R. Babarao, Reversing benzene/cyclohexane selectivity through varying supramolecular interactions using aliphatic isoreticular MOFs. ACS Appl. Mater. Interfaces 13(26), 30885 (2021)10.1021/acsami.1c08823 ↗
37. S. Mukherjee, D. Sensharma, O.T. Qazvini, S. Dutta, L.K. Macreadie, S.K. Ghosh, R. Babarao, Advances in adsorptive separation of benzene and cyclohexane by metal-organic framework adsorbents. Coordin. Chem. Rev. 437, 213852 (2021)10.1016/j.ccr.2021.213852 ↗
38. C. Healy, K.M. Patil, B.H. Wilson, L. Hermanspahn, N.C. Harvey-Reid, B.I. Howard, C. Kleinjan, J. Kolien, F. Payet, S.G. Telfer, T.D. Bennett, The thermal stability of metal-organic frameworks. Coordin. Chem. Rev. 419, 213388 (2020)10.1016/j.ccr.2020.213388 ↗
39. A.J. Howarth, Y.Y. Liu, P. Li, Z.Y. Li, T.C. Wang, J. Hupp, O.K. Farha, Chemical, thermal and mechanical stabilities of metal-organic frameworks. Nat. Rev. Mater. 1(3), 1–15 (2016)10.1038/natrevmats.2015.18 ↗
40. B. Yeskendir, J.P. Dacquin, Y. Lorgouilloux, C. Courtois, S. Royer, J. Dhainaut, From metal-organic framework powders to shaped solids: recent developments and challenges. Mater. Adv. 2(22), 7139 (2021)10.1039/D1MA00630D ↗
41. F.A. Son, K.M. Fahy, M.A. Gaidimas, C.S. Smoljan, M.C. Wasson, O.K. Farha, Investigating the mechanical stability of flexible metal-organic frameworks. Commun. Chem. 6(1), 185 (2023)10.1038/s42004-023-00981-8 ↗
42. R. Gaillac, P. Pullumbi, F.X. Coudert, ELATE: an open-source online application for analysis and visualization of elastic tensors. J. Phys.-Condens. Mat. 28(27), 275201 (2016)10.1088/0953-8984/28/27/275201 ↗