Boosting Reactive Oxygen Species Generation Using Inter‐Facet Edge Rich WO3 Arrays for Photoelectrochemical Conversion

Abstract Water oxidation reaction leaves room to be improved in the development of various solar fuel productions, because of the kinetically sluggish 4‐electron transfer process of oxygen evolution reaction. In this work, we realize reactive oxygen species (ROS), H 2 O 2 and OH⋅, formations by water oxidation with total Faraday efficiencies of more than 90 % by using inter‐facet edge (IFE) rich WO 3 arrays in an electrolyte containing CO 3 2− . Our results demonstrate that the IFE favors the adsorption of CO 3 2− while reducing the adsorption energy of OH⋅, as well as suppresses surface hole accumulation by direct 1‐electron and indirect 2‐electron transfer pathways. Finally, we present selective oxidation of benzyl alcohol by in situ using the formed OH⋅, which delivers a benzaldehyde production rate of ≈768 μmol h −1 with near 100 % selectivity. This work offers a promising approach to tune or control the oxidation reaction in an aqueous solar fuel system towards high efficiency and value‐added product.