Large-scale screening of hypothetical metal–organic frameworks

Abstract

Metal–organic frameworks (MOFs) are porous materials constructed from modular molecular building blocks, typically metal clusters and organic linkers. These can, in principle, be assembled to form an almost unlimited number of MOFs, yet materials reported to date represent only a tiny fraction of the possible combinations. Here, we demonstrate a computational approach to generate all conceivable MOFs from a given chemical library of building blocks (based on the structures of known MOFs) and rapidly screen them to find the best candidates for a specific application. From a library of 102 building blocks we generated 137,953 hypothetical MOFs and for each one calculated the pore-size distribution, surface area and methane-storage capacity. We identified over 300 MOFs with a predicted methane-storage capacity better than that of any known material, and this approach also revealed structure–property relationships. Methyl-functionalized MOFs were frequently top performers, so we selected one such promising MOF and experimentally confirmed its predicted capacity.

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Figure 1: Visual summary of the hypothetical MOF-generation strategy.
Figure 2: Influence of structural variations on predicted methane adsorption.
Figure 3: Partial list of building blocks used in the large-scale screening process.
Figure 4: Adaptive three-stage screening to identify the best MOFs for methane storage.
Figure 5: Structure–property relationships obtained from the database of hypothetical MOFs.
Figure 6: Comparison of experimental and simulated isotherms for NOTT-107 and PCN 14.

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Acknowledgements

The authors thank Y. Aktan and M. Tsao for the supporting calculations, as well as M.A. Wilmer for significant contributions to the website interface to the hypothetical MOF database. R.Q.S. acknowledges support by the Defense Threat Reduction Agency (grant HDTRA1-09-1-0007). Computational work was supported through the resources provided by Information Technology at Northwestern University as part of its shared cluster program, Quest. J.T.H. and O.K.F. acknowledge support from the US Deptartment of Energy, Office of Science, Basic Energy Sciences program (grant DE-FG02-08ER15967) and the Northwestern Nanoscale Science and Engineering Center. C.E.W. acknowledges support from a Fellowship from the Initiative for Sustainability and Energy at Northwestern and a Ryan Fellowship from the Northwestern University International Institute for Nanotechnology.

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C.E.W. designed the research, implemented the algorithms and performed the simulations with assistance from M.L. and guidance from R.Q.S. O.K.F helped in ligand and node selection. The NOTT-107 ligand was synthesized by O.K.F. and C.Y.L. NOTT-107 was synthesized and activated by O.K.F. NOTT-107 physical characterization was done by B.G.H. Experimental data interpretation and MOF-activation methodology was developed by J.T.H. and O.K.F. All authors discussed the results, contributed to writing the manuscript and commented on it.

Corresponding author

Correspondence to Randall Q. Snurr.

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The authors declare no competing financial interests.

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Wilmer, C., Leaf, M., Lee, C. et al. Large-scale screening of hypothetical metal–organic frameworks. Nature Chem 4, 83–89 (2012). https://doi.org/10.1038/nchem.1192

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