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Chemical, thermal and mechanical stabilities of metal–organic frameworks

Abstract

The construction of thousands of well-defined, porous, metal–organic framework (MOF) structures, spanning a broad range of topologies and an even broader range of pore sizes and chemical functionalities, has fuelled the exploration of many applications. Accompanying this applied focus has been a recognition of the need to engender MOFs with mechanical, thermal and/or chemical stability. Chemical stability in acidic, basic and neutral aqueous solutions is important. Advances over recent years have made it possible to design MOFs that possess different combinations of mechanical, thermal and chemical stability. Here, we review these advances and the associated design principles and synthesis strategies. We focus on how these advances may render MOFs effective as heterogeneous catalysts, both in chemically harsh condensed phases and in thermally challenging conditions relevant to gas-phase reactions. Finally, we briefly discuss future directions of study for the production of highly stable MOFs.

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Figure 1: The chemical (acid–base) stability of some representative metal–organic frameworks based on literature data.
Figure 2: Selected sections of representative metal–organic framework materials.
Figure 3: Connectivity of Zr6 nodes in zirconium-based metal–organic frameworks and the associated carboxylate molecules required to link nodes together.
Figure 4: Catalytic oxidation of water using Ir-containing derivatives of UiO-67.
Figure 5: Catalytic hydrolysis of the nerve agent soman (known as GD) by NU-1000.
Figure 6: Oxidative dehydrogenation of cyclohexene to benzene using V-UiO-66 as a catalyst.

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Acknowledgements

The authors acknowledge the US Defense Threat Reduction Agency (grant HDTRA10-1-0023; nerve agents), the Institute of Catalysis for Energy Processes at Northwestern University (V-AIM catalytic chemistry), the DOE Separations and Analysis program (MOF synthesis methods), and the Inorganometallic Catalyst Design Center, an Energy Frontier Research Center, funded by the US Department of Energy, Office of Science, Basic Energy Sciences (awards DE FG02-03ER15457, DE-FG02-08ER15967 and DE-SC0012702, respectively) for support.

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Howarth, A., Liu, Y., Li, P. et al. Chemical, thermal and mechanical stabilities of metal–organic frameworks. Nat Rev Mater 1, 15018 (2016). https://doi.org/10.1038/natrevmats.2015.18

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