Geometric Optimization of Bismuth Vanadate Core-Shell Nanowire Photoanodes using Atomic Layer Deposition

In this study, systematic geometric tuning of core-shell nanowire (NW) architectures is used to decouple the contributions from light absorption, charge separation, and charge transfer kinetics in photoelectrochemical water oxidation. Core-shell-shell NW arrays were fabricated using a combination of hydrothermal synthesis of ZnO and atomic layer deposition (ALD) of SnO₂ and BiVO₄. The length and spacing of the NW scaffold, as well as the BiVO₄ film thickness, were systematically tuned to optimize the photoelectrochemical performance. A photocurrent of 4.4 mA/cm² was measured at 1.23 V vs RHE for sulfite oxidation and 4.0 mA/cm² at 1.80 V vs RHE for water oxidation without a cocatalyst, which are the highest values reported to date for an ALD-deposited photoanode. Electromagnetic simulations demonstrate that spatial heterogeneity in light absorption along the core-shell NW length has a critical role in determining internal quantum efficiency. The mechanistic understandings in this study highlight the benefits of systematically optimizing electrode geometry at the nanoscale when designing photoelectrodes.