Defective Graphene on the Transition-Metal Surface: Formation of Efficient Bifunctional Catalysts for Oxygen Evolution/Reduction Reactions in Alkaline Media

Supported single-atom catalysts (SACs) have attracted enormous attention because of their high selectivity, activity, and efficiency, compared to conventional nanoparticles and metal bulk catalysts. However, all of these unique merits rely on the stability of the SAC, as reported by many investigators. To avoid aggregation of single-metal atoms and maintain the high performance of the SAC, various substrates have been tried to support them, particularly on graphene nanosheets. A spontaneous interface phenomenon between graphene and the Co (and Ni) substrate discovered in this work is that the holes in the graphene layer can stimulate metal atoms to pop up from a metal substrate and fill the double vacancy in graphene (DV-G) and stabilize on the graphene surface. The unique structure of the lifted metal atom is expected to be useful for the bifunctional SAC for electrocatalytic oxygen evolution reactions (OERs) and oxygen reduction reactions (ORRs). Our first-principles calculations indicate that the DV-G on the Co(0001) surface can serve as an excellent bifunctional OER/ORR catalyst in alkaline media with extremely low overpotentials of 0.39 V for OER and only 0.36 V for ORR processes, which are even lower than those for previously reported bifunctional catalysts. We believe that the catalytic activity stems from the interface coupling effect between the DV-G and metal substrate, as well as the charge redistribution in the graphitic sheet