Visible-Light Selective Photooxidation of Aromatic Hydrocarbons via Ligand-to-Metal Charge Transfer Transition on Nb2O5

Abstract

This study shows that a vacuum heat treatment of Nb2O5 permits the ligand-to-metal charge transfer (LMCT) transition between its surface and adsorbed aromatic hydrocarbons, which corresponds to visible light (>390 nm) absorption. Selective photooxidation of aromatic hydrocarbons to form the corresponding carbonyl compounds could effectively proceed under visible light irradiation by using this LMCT transition, and the catalytic activity is much superior to that of TiO2. Specifically, the LMCT bands of toluene-adsorbed Nb2O5 correlated well with the action spectrum for toluene photooxidation, suggesting that the reaction proceeded via the LMCT photoexcitation. We successfully detected toluene radical cation and its further oxidation product of benzylperoxy radical as intermediate species on toluene-adsorbed Nb2O5 through the LMCT transition. These findings suggest a novel reaction mechanism for the selective photooxidation of aromatic hydrocarbons via LMCT transition on Nb2O5.