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n-BiVO4 is a favorable photoelectrode candidate for a photoelectrochemical (PEC) water splitting reaction owing to its suitable energy level edge locations for an oxygen evolution reaction. On the other hand, the sluggish water oxidation kinetics of BiVO4 photoanodes when used individually make it necessary to use a hole blocking layer as well as water oxidation catalysts to overcome the high kinetic barrier for the PEC water oxidation reaction. Here, we describe a very simple synthetic strategy to fabricate nanocomposite photoanodes that synergistically address both of these critical limitations. In particular, we examine the effect of a SnO2 buffer layer over BiVO4 films and further modify the photoanode surface with a crystalline nickel tungstate (NiWO4) nanoparticle film to boost PEC water oxidation. When NiWO4 is incorporated over BiVO4/SnO2 films, the PEC performance of the resultant triple-layer NiWO4/BiVO4/SnO2 films for the oxygen evolution reaction (OER) is further improved. The enhanced performance for the PEC OER is credited to the synergetic effect of the individual layers and the introduction of a SnO2 buffer layer over the BiVO4 film. The optimized NiWO4/BiVO4/SnO2 electrode demonstrated both enriched visible light absorption and achieves charge separation and transfer efficiencies of 23% and 30%, respectively. The photoanodic current density for the OER on optimized NiWO4/BiVO4/SnO2 photoanode shows a maximum photocurrent of 0.93 mA/cm2 at 1.23 V vs. RHE in a phosphate buffer solution (pH~7.5) under an AM1.5G solar simulator, which is an incredible five-fold and two-fold enhancement compared to its parent BiVO4 photoanode and BiVO4/SnO2 photoanodes, respectively. Further, the incorporation of the NiWO4 co-catalyst over the BiVO4/SnO2 film increases the interfacial electron transfer rate across the composite/solution interface.

Cooperative Catalytic Behavior of SnO2 and NiWO4 over BiVO4 Photoanodes for Enhanced Photoelectrochemical Water Splitting Performance