Selective Photocatalytic Conversion of Methane Induced by Lewis Acid–Base Pair on the Surface of In2O3/TiO2 Heterojunction Photocatalyst

The efficient catalytic conversion of light-driven methane (CH4) is still very challenging. Here, the surface-reconstructed In2O3/TiO2 heterojunction photocatalyst is successfully prepared by a two-step operation of ion exchange and calcination, and the efficient selective photocatalytic conversion of CH4 is achieved. In the absence of O2, the formation rates of ethane (C2H6) and hydrogen (H2) are 68.9 and 78.6 μmol h–1 g–1, respectively, which corresponds to the stoichiometric ratio. However, in the presence of O2 or water (H2O) as the oxidant, CH4 is converted to CO, and the CO formation rates are 113.2 and 94.4 μmol h–1 g–1, respectively. Our results show that the In3–O2– Lewis acid–base pair on the In2O3/TiO2 surface can realize the adsorption and activation of CH4. Moreover, the photogenerated hole-induced reactive oxygen centers (Ti4+O·–Ti4+OH– and Ti4+O2–Ti4+O·–) on the surface of In2O3/TiO2 are identified as the active species for inducing the dissociation of CH4 into ·CH3 radicals, which in turn are coupled into C2H6 by ·CH3. In contrast, in the presence of O2, the surface superoxide anion (O2–), surface ·O– radicals, and O22– anions are identified as the active species for inducing the oxidation of CH4 into CO.