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

Abstract

We 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 dband 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.