Boosting Reactive Oxygen Species Formation Over Pd and VOδ Co‐Modified TiO2 for Methane Oxidation into Valuable Oxygenates

Direct photocatalytic methane oxidation into value‐added products provides a promising strategy for methane utilization. However, the inefficient generation of reactive oxygen species (ROS) partly limits the activation of CH4. Herein, it is reported that Pd and VOδ co‐modified TiO2 enables direct and selective methane oxidation into liquid oxygenates in the presence of O2 and H2. Due to the extra ROS production from the in situ formed H2O2, a highly improved yield rate of 5014 µmol g−1 h−1 for liquid oxygenates with a selectivity of 89.3% is achieved over the optimized Pd0.5V0.2‐TiO2 catalyst at ambient temperature, which is much better than those (2682 µmol g−1 h−1, 77.8%) without H2. Detailed investigations also demonstrate the synergistic effect between Pd and VOδ species for enhancing the charge carrier separation and transfer, as well as improving the catalytic activity for O2 reduction and H2O2 production. Pd and VOδ co‐modified TiO2 is developed as an efficient photocatalyst for selective methane oxidation into liquid oxygenates in the presence of O2 and H2. The enhanced performance can be attributed to the synergistic effect between Pd and VOδ species, which enhances the charge carrier separation and promotes reactive oxygen species production from O2 reduction and H2O2 production.