Modulating the Electronic Structures of Pt on Pt/TiO 2 Catalyst for Boosting Toluene Oxidation.

Surface hydroxyl groups commonly exist on the catalyst and present a significant role in the catalytic reaction. Considering the lack of systematical researches on the effect of the surface hydroxyl group on reactant molecule activation, the PtO x /TiO 2 and PtO x - y (OH) y /TiO 2 catalysts were constructed and studied for a comprehensive understanding of the roles of the surface hydroxyl group in the oxidation of volatiles organic compounds. The PtO x /TiO 2 formed by a simple treatment with nitric acid presented greatly enhanced activity for toluene oxidation in which the turnover frequency of toluene oxidation on PtOx/TiO 2 was around 14 times as high as that on PtO x - y (OH) y /TiO 2 . Experimental and theoretical results indicated that adsorption/activation of toluene and reactivity of oxygen atom on the catalyst determined the toluene oxidation on the catalyst. The removal of surface hydroxyl groups on PtO x promoted strong electronic coupling of the Pt 5d orbital in PtO x and C 2p orbital in toluene, facilitating the electron transfers from toluene to PtO x and subsequently the adsorption/activation of toluene. Additionally, the weak Pt-O bond promoted the activation of surface lattice oxygen, accelerating the deep oxidation of activated toluene. This study clarifies the inhibiting effect of surface hydroxyl groups on PtO x in toluene oxidation, providing a further understanding of hydrocarbon oxidation.