Mechanistic Study of the Direct Hydrodeoxygenation of <i>m</i>‑Cresol over WO_<i>x</i>‑Decorated Pt/C Catalysts

Hydrodeoxygenation (HDO) of <i>m</i>-cresol to produce toluene over carbon-supported Pt and Pt-WO_<i>x</i> catalysts was studied. In stark contrast to Pt/C that exhibits only modest selectivity and low stability for this reaction, Pt-WO_<i>x</i>/C was found to be unusually active and selective to toluene with greater than 94% selectivity to this product while exhibiting little to no deactivation under a wide range of reaction conditions. Reactivity studies in combination with density functional theory (DFT) calculations for the adsorption and reaction of <i>m</i>-cresol on structurally optimized WO_<i>x</i>-decorated Pt(111) structures indicate that the HDO reaction on Pt-WO_<i>x</i>/C proceeds via a direct hydrogenolysis of the C–O bond in <i>m</i>-cresol adsorbed on oxygen vacancy (or redox) sites on WO_<i>x</i> species. The DFT results also indicate that Pt helps stabilize the WO_<i>x</i> film while facilitating oxygen vacancy formation