Ordered macro-microporous metal-organic framework single crystals

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Science  12 Jan 2018:
Vol. 359, Issue 6372, pp. 206-210
DOI: 10.1126/science.aao3403

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Mesoporous metal-organic frameworks

The diffusion limitations on gas storage and catalytic reaction of microporous materials can often be overcome if they are incorporated into a mesoporous structure with much larger pores. Shen et al. grew ordered arrays of microcrystals of the ZIF-8 metal-organic framework, in which zinc ions are bridged by 2-methylimidazole linkers, inside a porous polystyrene template. These materials showed higher reaction rates for the Knoevenagel reaction between benzaldehydes and malononitriles and better catalyst recyclability.

Science, this issue p. 206


We constructed highly oriented and ordered macropores within metal-organic framework (MOF) single crystals, opening up the area of three-dimensional–ordered macro-microporous materials (that is, materials containing both macro- and micropores) in single-crystalline form. Our methodology relies on the strong shaping effects of a polystyrene nanosphere monolith template and a double-solvent–induced heterogeneous nucleation approach. This process synergistically enabled the in situ growth of MOFs within ordered voids, rendering a single crystal with oriented and ordered macro-microporous structure. The improved mass diffusion properties of such hierarchical frameworks, together with their robust single-crystalline nature, endow them with superior catalytic activity and recyclability for bulky-molecule reactions, as compared with conventional, polycrystalline hollow, and disordered macroporous ZIF-8.

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