Toward Robust Photoelectrochemical Operation of Cuprous Oxide Nanowire Photocathodes Using a Strategically Designed Solution-Processed Titanium Oxide Passivation Coating.

To date, TiO films prepared by atomic layer deposition are widely used to prepare CuO nanowire (NW)-based photocathodes with photoelectrochemical (PEC) durability as this approach enables conformal coating and furnishes chemical robustness. However, this common approach requires complicated interlayers and makes the fabrication of photocathodes with reproducible performance and long-term stability difficult. Although sol-gel-based approaches have been well established for coating surfaces with oxide thin films, these techniques have rarely been studied for oxide passivation in PEC applications, because the sol-gel coating methods are strongly influenced by surface chemical bonding and have been mainly demonstrated on flat substrates. As a unique strategy based on solution processing, herein, we suggest a creative solution for two problems encountered in the conformal coating of surfaces with oxide layers: (i) how to effectively prevent corrosion of materials with hydrophilic surfaces by simply using a single TiO surface protection layer instead of a complex multilayer structure and (ii) guaranteeing perfect chemical durability. A Cu(OH) NW can be easily prepared as an intermediate phase by anodization of a Cu metal, where the former inherently possesses a hydrophilic hydroxylated surface and thus, enables thorough coating with TiO precursor solutions. Chemically robust nanowires are then generated as the final product via the phase transformation of Cu(OH) to CuO via sintering at 600 °C. The coated NWs exhibit excellent PEC properties and a stable performance. Consequently, the perfect chemical isolation of the CuO NWs from the electrolyte allows a remarkable PEC operation with the maintenance of the initial photocurrent for more than one day.