Effects of electrolyte anion adsorption on the activity and stability of single atom electrocatalysts

A single metal site incorporated in N-doped carbon (M/N/C) is a promising electrocatalyst. Here, we perform a computation investigation of the effect of electrolyte anion adsorption on the activity and stability of single-atom catalysts (MN4) with M as transition metal and p-block metal. The MN4 site on two different graphene structures (bulk graphene and graphene edge) is studied under electrochemical conditions for the oxygen reduction reaction (ORR) and the CO2 reduction reaction (CO2RR). Because of the two-dimensional nature of the catalyst, reaction intermediates and electrolyte ions can interact with both sides of the single-atom catalyst. As a result, the electrolyte anions compete with water and adsorbate on the single metal site, in some cases either poisoning or modifying the catalyst activity and thermodynamic stability. We find most electrolyte anions adsorbs on the single metal site under ORR conditions but not at the lower potentials for the CO2RR. Still, the adsorption of water and gas molecules can occur under CO2RR conditions. For example, under ORR conditions, the thermodynamic driving force of the *SO4-FeN4 site in the 0.1 M H2SO4 solution is about 0.47–0.56 eV lower than the *O-FeN4 site in water, depending on the local carbon structure. Additionally, the stabilization by electrolyte anions depends on the nature of the metal atom. Our study demonstrates the important role of electrolytes and the coordination environment for the activity and stability of the M/N/C catalyst.