In Situ Reconstruction of Metal Oxide Cathodes for Ammonium Generation from High-Strength Nitrate Wastewater: Elucidating the Role of the Substrate in the Performance of Co3O4-x

In situ electrochemical reconstruction is important for transition metal oxides explored as electrocatalysts for electrochemical nitrate reduction reactions (ENRRs). Herein, we report substantial performance enhancement of ammonium generation on Co, Fe, Ni, Cu, Ti, and W oxide-based cathodes upon reconstruction. Among them, the performance of a freestanding ER-Co₃O_4-x/CF (Co₃O₄ grown on Co foil subjected to electrochemical reduction) cathode was superior to its unreconstructed counterpart and other cathodes; e.g., an ammonium yield of 0.46 mmol h^-1 cm^-2, an ammonium selectivity of 100%, and a Faradaic efficiency of 99.9% were attained at -1.3 V in a 1400 mg L^-1 NO₃^--N solution. The reconstruction behaviors were found to vary with the underlying substrate. The inert carbon cloth only acted as a supporting matrix for immobilizing Co₃O₄, without appreciable electronic interactions between them. A combination of physicochemical characterizations and theoretical modeling provided compelling evidence that the CF-promoted self-reconstruction of Co₃O₄ induced the evolution of metallic Co and the creation of oxygen vacancies, which promoted and optimized interfacial nitrate adsorption and water dissociation, thus boosting the ENRR performance. The ER-Co₃O_4-x/CF cathode performed well over wide ranges of pH and applied current and at high nitrate loadings, ensuring its high efficacy in treating high-strength real wastewater.