Cobalt-Doped Black TiO₂ Nanotube Array as a Stable Anode for Oxygen Evolution and Electrochemical Wastewater...

TiO₂ has long been recognized as a stable and reusable photocatalyst for water splitting and pollution control. However, it is an inefficient anode material in the absence of photoactivation due to its low electron conductivity. To overcome this limitation, a series of conductive TiO₂ nanotube array electrodes have been developed. Even though nanotube arrays are effective for electrochemical oxidation initially, deactivation is often observed within a few hours. To overcome the problem of deactivation, we have synthesized cobalt-doped Black-TiO₂ nanotube array (Co-Black NTA) electrodes that are stable for more than 200 h of continuous operation in a NaClO₄ electrolyte at 10 mA cm^-2. Using X-ray photoelectron spectroscopy, X-ray absorption spectroscopy, electron paramagnetic resonance spectroscopy, and DFT simulations, we are able to show that bulk oxygen vacancies (O_v) are the primary source of the enhanced conductivity of Co-Black. Cobalt doping both creates and stabilizes surficial oxygen vacancies, O_v, and thus prevents surface passivation. The Co-Black electrodes outperform dimensionally stable IrO₂ anodes (DSA) in the electrolytic oxidation of organic-rich wastewater. Increasing the loading of Co leads to the formation of a CoO film on top of Co-Black electrode. The CoO /Co-Black composite electrode was found to have a lower OER overpotential (352 mV) in comparison to a DSA IrO₂ (434 mV) electrode and a stability that is greater than 200 h in a 1.0 M KOH electrolyte at a current density of 10 mA cm^-2.