Two-Dimensional Restructuring of Cu₂O Can Improve the Performance of Nanosized n-TiO₂/p-Cu₂O Photoelectrodes under...

p-Cu₂O/n-TiO₂ photoanodes were produced by electrodeposition of octahedral p-type Cu₂O nanoparticles over n-type TiO₂ nanotubes. The photoresponse of the composite p-n photoanodes was evaluated in photoelectrochemical cells operating at "zero-bias" conditions under either visible or UV-vis irradiation. In both operating conditions, the produced electrodes invariably followed the p-n-based photoanode operations but exhibited lower photoelectrochemical performance as compared to the bare n-TiO₂ photoanode under UV-vis light. The reported experimental analysis evidenced that such decreased photoactivity is mainly induced by the scarce efficiency of the nanosized p-n interfaces upon irradiation. To overcome such limitation, a restructuring of the originally electrodeposited p-Cu₂O was promoted, following a photoelectrochemical post-treatment strategy. p-Cu₂O, restructured in a 2D leaf-like morphology, allowed reaching an improved photoelectrochemical performance for the p-n-based photoanode under UV-vis light. As compared to the bare n-TiO₂ behavior, such improvement consisted of photoanodic currents up to three times larger. An analysis of the mechanisms driving the transition from compact (∼100 nm) octahedral p-Cu₂O to wider (∼1 μm) 2D leaf-like structures was performed, which highlighted the pivotal role played by the irradiated n-TiO₂ NTs.