Selectivity Control of Oxygen Reduction Reaction over Mesoporous Transition Metal Oxide Catalysts for Electrified...

Direct electrification of oxygen-associated reactions contributes to large-scale electrical storage and the launch of the green hydrogen economy. The design of the involved catalysts can mitigate the electrical energy losses and improve the control of the reaction products. We evaluate the effect of the interface composition of electrocatalysts on the efficiency and productivity of the oxygen reduction reaction (ORR) and oxygen evolution reaction (OER), both mechanistically and at device levels. The ORR and OER were benchmarked on mesoporous nickel(II) oxide and nickel cobaltite (NiO and NiCo₂O₄, respectively) obtained by a facile template-free hydrothermal synthesis. Physicochemical characterization showed that both NiO and NiCo₂O₄ are mesoporous and have a cubic crystal structure with abundant surface hydroxyl species. NiCo₂O₄ showed higher electrocatalytic activity in OER and selectivity to water as the terminal product of ORR. On the contrary, ORR over NiO yielded hydroxyl radicals as products of a Fenton-like reaction of H₂O₂. The product selectivity in ORR was used to construct two electrolyzers for electrified purification of oxygen and generation of hydroxyl radicals.