Striking Stabilization Effect of Spinel Cobalt Oxide Oxygen Evolution Electrocatalysts in Neutral pH by Dual‐Sites Iron Incorporation

Abstract

Developing stable and efficient nonprecious‐metal‐based oxygen evolution catalysts in the neutral electrolyte is a challenging but essential goal for various electrochemical systems. Particularly, cobalt‐based spinels have drawn a considerable amount of attention but most of them operate in alkali solutions. However, the frequently studied Co–Fe spinel system never exhibits appreciable stability in nonbasic conditions, not to mention attract further investigation on its key structural motif and transition states for activity loss. Herein, we report exceptional stable Co–Fe spinel oxygen evolution catalysts (~30% Fe is optimal) in a neutral electrolyte, owing to its unique metal ion arrangements in the crystal lattice. The introduced iron content enters both the octahedral and tetrahedral sites of the spinel as Fe2+ and Fe3+ (with Co ions having mixed distribution as well). Combining density functional theory calculations, we find that the introduction of Fe to Co3O4 lowers the covalency of metal‐oxygen bonds and can help suppress the oxidation of Co2+/3+ and O2−. It implies that the Co–Fe spinel will have minor surface reconstruction and less lattice oxygen loss during the oxygen evolution reaction process in comparison with Co3O4 and hence show much better stability. These findings suggest that there is still much chance for the spinel structures, especially using reasonable sublattices engineering via multimetal doping to develop advanced oxygen evolution catalysts.

l-Lysine-induced green synthesis of CoS/Co3O4 nanoframes for efficient electrocatalytic oxygen evolution

“…To date, Co-based catalysts, especially oxides and sulfides, have attracted great attention in OER catalysis due to their special crystal structure, variable valence states and tunable composition. [16][17][18][19][20][21][22] However, the insufficient intrinsic activity, limited electronic conductivity and limited active sites of single Co-based catalysts would not meet the practical demands of the OER process in ZAB technology. [23][24][25] To overcome these obstacles, constructing CoS/Co 3 O 4 heterojunctions is a powerful strategy through the partial sulfurization of Co 3 O 4 .…”