Revealing alternative mechanism for H-spillover and C-O bond cleavage reactions over interfacial Pt-WOx catalysts during glycerol hydrogenolysis

Abstract

Pt-WO_x based composites have been known as critical catalysts in the energy industry, yet the electronic reconfiguration at Pt-WO_x interfaces for tunable C-O bond activation and Brønsted acidity remains poorly understood. This study uncovers an unusual Pt-loading effect on electronic reconfiguration of WO_x crystals, introducing an alternative H-spillover pathway that doubles C-O bond cleavage activity. Catalyst characterization (XPS, UV–Vis DRS, Raman, TEM) reveals that increasing Pt/W ratios generate additional O 2p orbital holes, promoting charge transfer from O to W sites, and forming reconfigured active centers for selective C-O bond activation. Furthermore, experiments on 2-butanol dehydration demonstrate in-situ Brønsted acid sites formation via H-spillover, involving H^δ+(WO₃)_n^δ− centers in tandem C-O bond breaking. The Pt/W/Al catalyst achieves 56.6 % selectivity for 1,3-propanediol at 50 wt% glycerol medium. The fundamental studies on electronic coupling effect at Pt-O-W interfaces are crucial for the rational design of solid acid catalysts for future bio-refineries.