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

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. The plate‐like Bi2WO6 synthesized with higher tungsten (W) concentration exhibits superior photoelectrochemical performance than the stoichiometric ratio (W:Bi = 1:2) due to smaller particle size and higher exposure extent of electron‐dominated {010} crystal facet is generated. Furthermore, the W enrichment increases the charge carrier density and facilitates the charge transport in the Bi2WO6 thin film.