Parallelized Reaction Pathway and Stronger Internal Band Bending by Partial Oxidation of Metal Sulfide–Graphene Composites: Important Factors of Synergistic Oxygen Evolution Reaction Enhancement

The electrocatalytic performance of transition metal sulfide (TMS)–graphene composites has been simply regarded as the results of high conductivity and the large surface/volume ratio. However, unavoidable factors such as degree of oxidation of TMSs have been hardly considered for the origin of this catalytic activity of TMS–graphene composites. To accomplish the reliable application of TMS-based electrocatalytic materials, a clear understanding of the thermodynamic stability of TMS and effects of oxidation on catalytic activity is necessary. In addition, the mechanism of charge transfer at the TMS–graphene interface must be studied in depth to properly design composite materials. Herein, we report a comprehensive study of the physical chemistry at the junction of a Co1–xNixS2–graphene composite, which is a prototype designed to unravel the mechanisms of charge transfer between TMS and graphene. Specifically, the thermodynamic stability and the effects of oxidation of TMSs during the oxygen evolution react...