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.
Bibliographical noteFunding Information:
We thank the National Natural Science Foundation of China (grants 21606087, 21436005, 51621001, 21576095, and 21606088), the Fundamental Research Funds for the Central Universities (grants 2017PY004 and 2017MS069), the Guangdong Natural Science Foundation (grants 2014A030310445, 2016A050502004, and 2017A030312005), and the Welch Foundation (grant AX-1730) for financial support. K.S. thanks D. Tong for help with the schematic design and Y. Zhao for GFP preparation. K.S., Y.L., and B.C. conceived the idea and designed the experiments. K.S. synthesized the materials and carried out most of the structural characterization. Y.H., L.L., and D.Z. performed the HRTEM images and analyzed the results. K.S., L.Z., X.C., J.C., and J.L. performed the catalytic tests and some structural characterization. K.S., Y.L., B.C., and R.L. cowrote the paper. All authors discussed and commented on the manuscript. All data are reported in the main text and supplementary materials. K.S. and Y.L. are inventors on a patent/patent application (201710819873.9) held/submitted by South China University of Technology that covers the method for preparing ordered macroporous MOF single crystals.
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