CrSe2 based single-cluster catalysts with controllable charge states for the oxygen reduction and hydrogen evolution reactions

Development of affordable catalysts for the oxygen reduction reaction (ORR) and hydrogen evolution reaction (HER) represents a central task for advancing electrochemical systems such as fuel cells and metal-air batteries. This study reported the ORR and HER performance of a set of single cluster catalysts (SCCs) with atomically dispersed 3d/4d/5d transition metal cluster (TM3) embedded in a two-dimensional (2D) defective CrSe2 substrate. Distinguishing from the conventional SCCs with positive charge active center, the unique electronegativity discrepancy between the metal clusters and the substrate renders the active center controllable charge states from negative to positive. Our investigations indicate that the TM3 cluster helps tuning the adsorption performance of the intermediates, and therefore enhancing the electrocatalytic activity of the SCCs. Among all the candidates, we demonstrated that the less reported elements of Ir and Ag exhibit the best performance of HER and ORR with low overpotentials of -0.059 and 0.61 V, respectively. Our work provides a prototype to rationally regulate the charge states of catalysts, which could potentially contribute to the development of new kinds of catalysts and serve as a valuable theoretical reference for the experimental rationalization of SCCs.