Active sites for the selective hydrodeoxygenation of m-cresol on WOx-modified Pt

•Pt stabilizes the submonolayer WOx in a partially reduced form.•m-Cresol adsorbs on undercoordinated W cations in surface WOx deposits with the aromatic ring tilted away from the surface via the hydroxyl oxygen.•Weak interaction between the aromatic ring and the oxide surface enhances selective CO bond scission. Adsorption and reaction of m-cresol on Pt(111) and WOx-modified Pt(111) surfaces was characterized using temperature programmed desorption (TPD), high resolution electron energy loss spectroscopy (HREELS), and X-ray photoelectron spectroscopy (XPS). The results of this study show that on Pt(111) a strong interaction between the aromatic ring and the Pt surface facilitates CC bond cleavage resulting in decomposition at relatively low temperatures. In contrast, on WOx-modified Pt(111), m-cresol bonds to oxygen vacancy sites on the WOx deposits via the hydroxyl oxygen with the aromatic ring tilted away from the surface, resulting in a bonding configuration that promotes selective CO bond cleavage and limits ring hydrogenation. XPS results also show that interactions at the Pt-WOx interface help stabilize submonolayer WOx deposits in a partially reduced state, thereby maintaining a high concentration of the oxygen vacancy adsorption sites. [Display omitted]