Ultrathin Cobalt Oxide Overlayer Promotes Catalytic Activity of Cobalt Nitride for the Oxygen Reduction Reaction

The oxygen reduction reaction (ORR) plays a crucial role in various energy devices such as proton-exchange membrane fuel cells (PEMFCs) and metal-air batteries. Owing to the scarcity of the current state-of-the-art Pt-based catalysts, cost-effective Pt-free materials such as transition metal nitrides and their derivatives have gained overwhelming interest as alternatives. In particular, cobalt nitride (CoN) has demonstrated a reasonably high ORR activity. However, the nature of its active phase still remains elusive. Here, we employ density functional theory calculations to study the surface reactivity of rocksalt (RS) and zincblend (ZB) cobalt nitride. The performances of the catalysts terminated by the facets of (100), (110), and (111) are studied for the ORR. We demonstrate that the cobalt nitride surface is highly susceptible to oxidation under ORR conditions. The as-formed oxide overlayer on the facets of CoN_RS(100) and CoN_ZB(110) presents a significant promotional effect in reducing the ORR overpotential, thereby increasing the activity in comparison with those of the pure CoNs. The results of this work rationalize a number of experimental reports in the literature and disclose the nature of the active phase of cobalt nitrides for the ORR. Moreover, they offer guidelines for understanding the activity of other transition metal nitrides and designing efficient catalysts for future generation of PEMFCs.