Ligand-Modulated Electronic Structure of Pt Clusters for Enhanced Methanol Oxidation

Precise electronic regulation of platinum (Pt) catalysts is essential for optimizing key intermediate energy barriers in the methanol oxidation reaction (MOR). However, conventional coordination engineering strategies for electronic modulation are often hindered by size mismatch between ligands and metal active sites, leading to stochastic reaction mechanisms and suboptimal modulation. In this work, we designed a series of structurally well-defined Pt clusters coordinated with nitrogen-, phosphorus-, and sulfur-containing organic molecules, enabling single-variable manipulation and maximized coordination interactions. Our results reveal a pronounced coordination-dependent performance order of Pt–N > Pt–P > Pt–S. Notably, the N-coordinated catalyst achieves a 5-fold mass activity enhancement and enhanced stability. Mechanistic insights from in situ Fourier transform infrared and density functional theory calculations confirm that N-coordination optimizes Pt electron structure and lowers energy barriers for intermediate adsorption/desorption. This work elucidates the intrinsic modulation mechanism and offers valuable insights into the rational design of high-efficiency Pt-based MOR catalysts.