Manipulating the Fate of Charge Carriers with Tungsten Concentration: Enhancing Photoelectrochemical Water Oxidation of Bi₂WO₆

Abstract Bismuth tungstate (Bi₂WO₆) thin film photoanode has exhibited an excellent photoelectrochemical (PEC) performance when the tungsten (W) concentration is increased during the fabrication. Plate‐like Bi₂WO₆ thin film with distinct particle sizes and surface area of different exposed facets are successfully prepared via hydrothermal reaction. The smaller particle size in conjunction with higher exposure extent of electron‐dominated {010} crystal facet leads to a shorter electron transport pathway to the bulk surface, assuring a lower charge transfer resistance and thus minimal energy loss. In addition, it is proposed based on the results from conductive atomic force microscopy that higher W concentration plays a crucial role in facilitating the charge transport of the thin film. The “self‐doped” of W in Bi₂WO₆ will lead to the higher carrier density and improved conductivity. Thus, the variation in the W concentration during a synthesis can be served as a promising strategy for future W based photoanode design to achieve high photoactivity in water splitting application.