A Site Distance Effect Induced by Reactant Molecule Matchup in Single-Atom Catalysts for Fenton-Like Reactions

Understanding the site interaction nature of single-atom catalysts (SACs), especially densely populated SACs, is vital for their application to various catalytic reactions. Herein, we report a site distance effect, which emphasizes how well the distance of the adjacent copper atoms (denoted as d_Cu1-Cu1 ) matches with the reactant peroxydisulfate (PDS) molecular size to determine the Fenton-like reaction reactivity on the carbon-supported SACs. The optimized d_Cu1-Cu1 in the range of 5-6 Å, which matches the molecular size of PDS, endows the catalyst with a nearly two times higher turnover frequency than that of d_Cu1-Cu1 beyond this range, accordingly achieving record-breaking kinetics for the oxidation of emerging organic contaminants. Further studies suggest that this site distance effect originates from the alteration of PDS adsorption to a dual-site structure on Cu₁ -Cu₁ sites when d_Cu1-Cu1 falls within 5-6 Å, significantly enhancing the interfacial charge transfer and consequently resulting in the most efficient catalyst for PDS activation so far.