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.