Interlayer Charge Transfer Regulates Single-Atom Catalytic Activity on Electride/Graphene 2D Heterojunctions

Single-atom catalysts with structure and activity tunability have attracted significant attention for energy and environmental applications. Herein we present a first-principles study of single-atom catalysis on two-dimensional graphene and electride heterostructures. The anion electron gas in the electride layer enables a colossal electron transfer to the graphene layer, with the degree of transfer being controllable by the selection of electride. The charge transfer tunes the d-orbital electron occupancy of a single metal atom, enhancing the catalytic activity of hydrogen evolution reactions and oxygen reduction reactions. The strong correlation between the adsorption energy E_ads and the charge variation Δq suggests that interfacial charge transfer is a critical catalytic descriptor for the heterostructure-based catalysts. The polynomial regression model proves the importance of charge transfer and accurately predicts the adsorption energy of ions and molecules. This study provides a strategy to obtain high-efficiency single-atom catalysts using two-dimensional heterostructures.