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

Pt-WOx based composites have been known as critical catalysts in the energy industry, yet the electronic reconfiguration at Pt-WOx interfaces for tunable C-O bond activation and Br & oslash;nsted acidity remains poorly understood. This study uncovers an unusual Pt-loading effect on electronic reconfiguration of WOx 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 Br & oslash;nsted acid sites formation via H-spillover, involving H delta+(WO3)n delta 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.