Enhancing the Activity of Platinum‐Based Nanocrystal Catalysts for Organic Synthesis through Electronic Structure Modification

Abstract

AbstractWe report a systematic study on the correlation of the modified electronic structure of nanocrystal catalysts with the adsorption properties of the substrate and the resultant catalytic activity by using Baeyer–Villiger oxidation catalyzed by composition‐controlled Pt‐based nanocubes (NCs) as a model heterogeneous catalysis reaction. The incorporation of 3d transition metals into Pt to form PtM (M=Zn, Co, and Ni) alloy NCs allowed fine‐tuning of the electronic structure of Pt. PtM NCs with a higher‐lying d band center exhibited higher catalytic performance owing to the enhanced initial activation of the carbonyl group of the substrate. This work emphasizes the importance of fine‐tuning the electronic structure of heterogeneous catalysts to advance their catalytic function.