Theoretical study of p-block metal–nitrogen–carbon single-atom catalysts for heterogeneous Fenton-like reaction

Abstract

The heterogeneous Fenton-like reaction has been widely used in water purification and environmental remediation due to the highly reactive nature of hydroxyl radicals. Nevertheless, the intrinsic structure–activity relationship for heterogeneous Fenton-like reaction catalysts remains to be clarified. Metal/nitrogen/carbon (M/N/C) single-atom catalysts (SACs) provide an ideal opportunity to reveal the relationship between the structure and activity. In this work, the detailed catalytic mechanism and activity of H₂O₂ decomposition on p-block main-group metal/nitrogen/carbon (PM/N/C) catalysts were investigated systematically. A volcano relationship between the catalytic activity and the adsorption energies of reaction intermediates was found for H₂O₂ decomposition on PM/N/C SACs. PM-N₂C₂ and PM-C₄ exhibit higher H₂O₂ decomposition activity than PM-N₄, indicating that reducing the N/C ratio in the coordination environment can effectively adjust the catalytic activity. By altering the N/C coordination environment, it is possible to modify the p-band position of p-block main-group metal atoms in PM/N/C SACs, thereby enhancing the catalytic activity of H₂O₂ decomposition.