WO3/BiVO4 Type-II Heterojunction Arrays Decorated with Oxygen-Deficient ZnO Passivation Layer: A Highly Efficient and Stable Photoanode.

In the present work, we report a ternary WO3/BiVO4/ZnO photoanode with boosted PEC efficiency and stability toward highly efficient water splitting. The type-II WO3/BiVO4 heterojunction arrays are firstly prepared by hydrothermal growth of WO3 nanoplate arrays onto the substrates of fluorine-doped tin oxide (FTO)-coated glass, followed by spin-coating of BiVO4 layers onto the WO3 nanoplate surfaces. After that, thin ZnO layers are further introduced onto the WO3/BiVO4 heterojunction arrays via atomic layer deposition (ALD), leading to the construction of ternary WO3/BiVO4/ZnO photoanodes. It is verified that the ZnO thin layer in the WO3/BiVO4/ZnO photoanode contains abundant oxygen vacancies, which could act as an effective passivation layer to enhance the charge separation and surface water oxidation kinetics of photogenerated carriers. The as-prepared WO3/BiVO4/ZnO photoanode produces a photocurrent of 2.96 mA cm-2 under simulated sunlight with an incident photon-to-current conversion efficiency (IPCE) of ∼72.8% at 380 nm at a potential of 1.23 V versus RHE without cocatalysts, both of which are comparable to the state-of-the-art WO3/BiVO4 counterparts. Moreover, the photocurrent of the WO3/BiVO4/ZnO photoanode shows only 9% decay after 6 h, suggesting its high photoelectrochemical (PEC) stability.