In theory, suitable metal ions doping into the surface of BiVO₄ photoanodes could improve its water oxidation performance effectively. But the common homogeneous reaction strategy is not well applicable for the preparation of BiVO₄ film photoanodes with metal ions surface doping. Herein, a photoelectrochemical treating approach was reported to prepare BiVO₄ films with W or Mo surface doping in saturated tungstate and molybdate-containing electrolyte, respectively. The doping of W or Mo into the surface of BiVO₄ film was attributed to the following reactions. Firstly, the photocorrosion of BiVO₄ film photoelectrodes resulted in the dissolution of VO₄³⁺ from BiVO₄ lattice under AM 1.5 G illumination. Then, the WO₄²⁺ or MoO₄²⁺ in the saturated electrolyte entered and occupied the dissolved sites of VO₄³⁺ on BiVO₄ surface through ions exchange reaction. Due to the lower radiative recombination of carrier as well as higher electrocatalytic water oxidation activity, the resultant W or Mo doped BiVO₄ films as photoanodes showed better solar water oxidation activity, kinetics and stability, although their light harvesting property and morphological feature were close to the pristine BiVO₄ film photoanode. The present work provides a new and effective approach for the achievement of metal ions doping into the surface of BiVO₄ photoanodes, which could inspire the preparation of similar photoanode materials.

理论上，适当的金属离子掺杂到BiVO ₄光阳极表面可以有效提高其水氧化性能。但常见的均相反应策略不适用于制备具有金属离子表面掺杂的BiVO _{4薄膜光阳极。}本文报道了一种光电化学处理方法，分别在饱和钨酸盐和钼酸盐电解质中制备具有 W 或 Mo 表面掺杂的BiVO _4薄膜。将W或Mo掺杂到BiVO ₄薄膜表面归因于以下反应。首先，BiVO ₄薄膜光电极的光腐蚀导致 VO ₄ ³⁺从 BiVO中溶解出来。AM 1.5  G 照明下的_4格。然后，饱和电解液中的WO ₄ ²⁺或MoO ₄ ²⁺进入并通过离子交换反应占据BiVO _{4表面VO 4} ^{3+的溶解位点。}由于载流子的较低的辐射复合以及较高的电催化水氧化活性，W或Mo掺杂的BiVO ₄薄膜作为光阳极表现出更好的太阳能水氧化活性、动力学和稳定性，尽管它们的光收集性能和形态特征接近原始的 BiVO ₄薄膜光阳极。目前的工作为实现金属离子掺杂到BiVO ₄光阳极表面提供了一种新的有效方法，这可能会激发类似光阳极材料的制备。