Boosting Reactive Oxygen Species Generation Using Inter-Facet Edge Rich WO 3 Arrays for Photoelectrochemical Conversion.

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 O and OH⋅, formations by water oxidation with total Faraday efficiencies of more than 90 % by using inter-facet edge (IFE) rich WO arrays in an electrolyte containing CO . Our results demonstrate that the IFE favors the adsorption of CO 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 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.