Facilitation of Fenton‐Like Reaction of Copper‐Nitrogen‐Doped Carbon‐Based Nanocatalysts by Enhancing Hydroxyl Adsorption on Single‐Atom Cu‐NxC4‐x Sites

Abstract Copper‐nitrogen‐doped carbon‐based nanocatalysts (Cu‐NCs), containing atomically dispersed Cu‐N x C 4‐ x sites, are efficient in boosting the Fenton‐like reaction. However, the mechanisms of the Fenton‐like reaction, including the pH effect on the products and the effect of the coordination environment on catalytic activity, remain controversial, restricting the development of Cu‐NCs. Cu‐NCs are experimentally synthesized with Cu‐N 4 sites and prove that the Fenton‐like reaction generates mainly hydroxyl radicals (·OH) in the acidic but ·OH and superoxide radicals (·O 2 − ) in the neutral. The density functional theory (DFT) calculations reveal that the catalytic activity of Cu‐NCs in the Fenton‐like reaction is associated with the adsorption strength of ·OH at the Cu site. Further investigation of the effect of the coordination environment of Cu‐NCs indicates that the Cu‐N 2 C 2 site, which can enhance the ·OH adsorption strength, is an ideal catalyst site for the Fenton‐like reaction. These results open the way to facilitating the catalytic activity of Cu‐NCs in the Fenton‐like reaction.