Deciphering promotion of MoP over MoC in Pt catalysts for methanol-assisted water splitting reaction.

Molybdenum-based compounds show promising promotion effects on Pt catalysts for energy-relevant catalysis reactions. Herein, a more effective promotion effect of MoP than MoC was found in assisting Pt nanoparticles for methanol-assisted hydrogen generation in light of the strong metal-support interaction and synergistic effect between Pt and MoP/C nanospheres. Electrochemical analyses and theoretical calculations demonstrated that Pt-MoP/C facilitated the oxidation and removal of CO intermediates more effectively than Pt-MoC/C. This enhanced performance was attributed to the distinct 6-coordination environment of hexagonal MoP and the elevated electron density of Mo induced by phosphorus. These structural and electronic features significantly enhanced electron transfer to Pt, thereby creating strong metal-support interaction and synergistic effect to improve the overall catalytic efficiency. Especially, the unique activities of Moδ+ and Moδ- in the MoP modified the surface structure of Pt, lowered the Pt d-band center, and optimized the local chemical state of Pt atoms, which resulted in more optimized adsorption energy and charge transfer capabilities of intermediates. The Pt-MoP/C electrolyzer thus showed both lower cell voltage than that of Pt-MoC/C and Pt/C electrolyzers in water splitting and methanol-assisted water splitting for hydrogen generation. This study offers insightful information about the promotion effect of molybdenum-based compounds in Pt catalyst systems in energy-relevant catalysis reactions.