Enhanced photocatalytic hydrogen evolution of Ru/TiO2-x via oxygen vacancy-assisted hydrogen spillover process

Hydrogen spillover effects will significantly improve the activity of photocatalytic hydrogen evolution reactions (HER), while their introduction and optimization require the construction of an excellent metal/support structure. In this study, we have synthesized Ru/TiO2-x catalysts with controlled oxygen vacancy (OVs) concentrations using a simple one-pot solvothermal method. The results show that Ru/TiO2-x3 with the optimal OVs concentration exhibits an unprecedentedly high H2 evolution rate of 13604 μmol·g-1·h-1, which was 45.7 and 2.2 times higher than that of TiO2-x (298 μmol·g-1·h-1) and Ru/TiO2 (6081 μmol·g-1·h-1). Controlled experiments, detailed characterizations, and theoretical calculations have revealed that the introduction of OVs on the carrier contributes to the hydrogen spillover effect in the metal/support system photocatalyst and that the process of hydrogen spillover in this system can be optimized by modulating the OVs concentration. This study proposes a strategy to decrease the energy barrier of hydrogen spillover and enhance photocatalytic HER activity. Moreover, it investigates the effect of OVs concentration on the hydrogen spillover effect in the photocatalytic metal/supports system.