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In this work, we developed a strategy to in situ synthesize sub-nanometer metal particle/hierarchically mesoporous metal-organic framework (MOF) composites in emulsion. In this route, water droplets in the emulsion acted as both a solvent of the metal precursors and a template for the hierarchical mesopores of MOFs, and the surfactant was an emulsifier and a reductant for generating metal particles. Au/Zn-MOFs (MOFs formed by Zn 2+ and methylimidazole), Ru/Zn-MOFs, Pd/Zn-MOFs, and Au/Cu-MOFs (MOFs formed by Cu 2+ and methylimidazole) were prepared using this method, in which ultrafine metal particles ( e.g. 0.8 nm) were immobilized uniformly on hierarchically mesoporous MOFs. Au/Zn-MOFs and Au/Cu-MOFs showed outstanding catalytic performances for the selective aerobic oxidation of cyclohexene to 2-cyclohexen-1-one in the absence of an initiator, and Ru/Zn-MOFs were very active and selective for the hydrogenation of diphenyl sulfoxide to diphenyl sulfide. In addition, the catalysts were also very stable in the reactions.

chemical science

<i>In situ</i>synthesis of sub-nanometer metal particles on hierarchically porous metal–organic frameworks<i>via</i>interfacial control for highly efficient catalysis

In situsynthesis of sub-nanometer metal particles on hierarchically porous metal–organic frameworksviainterfacial control for highly efficient catalysis