Electrocatalytic arsenite oxidation in bicarbonate solutions combined with CO₂ reduction to formate

Sunlight-driven water-energy nexus technologies are receiving increasing attention. This study presents a hybrid electrochemical system that catalyzes the oxidation of As(III) to As(V) with a nanoparticulate TiO₂ electrocatalyst (Ti/Ir_1-xTa_xO_y/TiO₂; denoted as an n-TEC) while simultaneously converting CO₂ to formate on a Bi electrode in aqueous bicarbonate solutions at circum-neutral pH. Linear sweep voltammograms of n-TEC exhibit a specific As(III) oxidation peak (E_p,As), at which the Faradaic efficiency (FE) of As(V) production is ∼100 %. However, the application of a potential higher than the peak (E > E_p,As) leads to a significant decrease in the FE due to water oxidation. Upon the addition of chloride, the oxidation of water and chloride occur competitively, producing reactive chlorine species responsible for mediating the oxidation of As(III). The Bi electrodes synthesized via the electrodeposition of Bi³⁺ typically show high FEs of >80 % for formate production in bicarbonate solution purged with CO₂. The addition of chloride significantly enhances the current while maintaining the FE. The n-TEC catalyst and Bi electrodes are paired in a single device equipped with a membrane, and significant effort is made to achieve the same FEs in both the anodic and cathodic reactions as in their half-reactions. Finally, the optimized n-TEC/Bi pair is coupled with a low-cost, commercially available photovoltaic (PV). Various technical factors that drive the overall reactions with the PV are considered, and maximum FEs of ∼95 % are achieved for the production of both As(V) and formate.