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 Co2+, Co3+ and Co4+ states coupling with OH-/H+ interaction before and during the OER event. Since the emergence of Co2+ 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 Co2+ 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 Co2+ 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.
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