Overall photosynthesis of H₂O₂ by an inorganic semiconductor

Artificial photosynthesis of H₂O₂ using earth-abundant water and oxygen is a promising approach to achieve scalable and cost-effective solar fuel production. Recent studies on this topic have made significant progress, yet are mainly focused on using  organic polymers. This set of photocatalysts is susceptible to potent oxidants (e.g. hydroxyl radical) that are inevitably formed during H₂O₂ generation. Here, we report an inorganic Mo-doped faceted BiVO₄ (Mo:BiVO₄) system that is resistant to radical oxidation and exhibits a high overall H₂O₂ photosynthesis efficiency among inorganic photocatalysts, with an apparent quantum yield of 1.2% and a solar-to-chemical conversion efficiency of 0.29% at full spectrum, as well as an apparent quantum yield of 5.8% at 420 nm. The surface-reaction kinetics and selectivity of Mo:BiVO₄ were tuned by precisely loading CoO_x and Pd on {110} and {010} facets, respectively. Time-resolved spectroscopic investigations of photocarriers suggest that depositing select cocatalysts on distinct facet tailored the interfacial energetics between {110} and {010} facets and enhanced charge separation in Mo:BiVO₄, therefore overcoming a key challenge in developing efficient inorganic photocatalysts. The promising H₂O₂ generation efficiency achieved by delicate design of catalyst spatial and electronic structures sheds light on applying robust inorganic particulate photocatalysts to artificial photosynthesis of H₂O₂.