Stabilization of High‐Valent Molecular Cobalt Sites through Oxidized Phosphorus in Reduced Graphene Oxide for Enhanced Oxygen Evolution Catalysis

Abstract Heterogeneous molecular cobalt (Co) sites represent one type of classical catalytic sites for electrochemical oxygen evolution reaction (OER) in alkaline solutions. There are dynamic equilibriums between Co 2+ , Co 3+ and Co 4+ states coupling with OH − /H + interaction before and during the OER event. Since the emergence of Co 2+ sites is detrimental to the OER cycle, the stabilization of high‐valent Co sites to shift away from the equilibrium becomes critical and is proposed as a new strategy to enhance OER. Herein, phosphorus (P) atoms were doped into reduced graphene oxide to link molecular Co 2+ acetylacetonate toward synthesizing a novel heterogeneous molecular catalyst. By increasing the oxidation states of P heteroatoms, the linked Co sites were spontaneously oxidized from 2+ to 3+ states in a KOH solution through OH − ions coupling at an open circuit condition. With excluding the Co 2+ sites, the as‐derived Co sites with 3+ initial states exhibited intrinsically high OER activity, validating the effectiveness of the strategy of stabilizing high valence Co sites.