Function-oriented design of robust metal cocatalyst for photocatalytic hydrogen evolution on metal/titania composites.

While the precise design of catalysts is one of ultimate goals in catalysis, practical strategies often fall short, especially for complicated photocatalytic processes. Here, taking the hydrogen evolution reaction (HER) as an example, we introduce a theoretical approach for designing robust metal cocatalysts supported on TiO2 using density functional theory calculations adopting on-site Coulomb correction and/or hybrid functionals. The approach starts with clarifying the individual function of each metal layer of metal/TiO2 composites in photocatalytic HER, covering both the electron transfer and surface catalysis aspects, followed by conducting a function-oriented optimization via exploring competent candidates. With this approach, we successfully determine and verify bimetallic Pt/Rh/TiO2 and Pt/Cu/TiO2 catalysts to be robust substitutes for conventional Pt/TiO2. The right metal type as well as the proper stacking sequence are demonstrated to be key to boosting performance. Moreover, we tentatively identify the tunneling barrier height as an effective descriptor for the important electron transfer process in photocatalysis on metal/oxide catalysts. We believe that this study pushes forward the frontier of photocatalyst design towards higher water splitting efficiency. Photocatalytic performances require both active catalytic surfaces and efficient electron transfer steps. Here the authors introduce a function-oriented catalyst design strategy optimizing both aspects and generalize an effective electron transfer descriptor on metal/oxide catalysts.