Disordered-Layer-Mediated Reverse Metal–Oxide Interactions for Enhanced Photocatalytic Water Splitting

In heterogeneous catalysts, metal–oxide interactions occur spontaneously but often in an undesired way leading to the oxidation of metal nanoparticles. Manipulating such interactions to produce highly active surface of metal nanoparticles can warrant the optimal catalytic activity but has not been established to date. Here we report that a prior reduced TiO2 support can reverse the interaction with Pt nanoparticles and augment the metallic state of Pt, exhibiting a 3-fold increase in hydrogen production rate compared to that of conventional Pt/TiO2. Spatially resolved electron energy loss spectroscopy of the Ti valence state and the electron density distribution within Pt nanoparticles provide direct evidence supporting that the Pt/TiO2/H2O triple junctions are the most active catalytic sites for water reduction. Our reverse metal–oxide interaction scheme provides a breakthrough in the stagnated hydrogen production efficiency and can be applied to other heterogeneous catalyst systems composed of metal nanoparticles with reducible oxide supports.