Zinc Tantalum Oxynitride (ZnTaO₂N) Photoanode Modified with Cobalt Phosphate Layers for the Photoelectrochemical Oxidation of Alkali Water.

Photoanodes fabricated by the electrophoretic deposition of a thermally prepared zinc tantalum oxynitride (ZnTaO₂N) catalyst onto indium tin oxide (ITO) substrates show photoactivation for the oxygen evolution reaction (OER) in alkaline solutions. The photoactivity of the OER is further boosted by the photodeposition of cobalt phosphate (CoPi) layers onto the surface of the ZnTaO₂N photoanodes. Structural, morphological, and photoelectrochemical (PEC) properties of the modified ZnTaO₂N photoanodes are studied using X-ray diffraction (XRD), scanning electron microscopy (SEM), ultraviolet visible (UV-Vis) diffuse reflectance spectroscopy, and electrochemical techniques. The presence of the CoPi layer significantly improved the PEC performance of water oxidation in an alkaline sulphate solution. The photocurrent-voltage behavior of the CoPi-modified ZnTaO₂N anodes was improved, with the influence being more prominent at lower oxidation potentials. A stable photocurrent density of about 2.3 mA·cm at 1.23 V vs. RHE was attained upon visible light illumination. Relative to the ZnTaO₂N photoanodes, an almost three-fold photocurrent increase was achieved at the CoPi/ZnTaO₂N photoelectrode. Perovskite-based oxynitrides are modified using an oxygen-evolution co-catalyst of CoPi, and provide a new dimension for enhancing the photoactivity of oxygen evolution in solar-assisted water-splitting reactions.