Identifying the active sites in unequal iron-nitrogen single-atom catalysts

Abstract

Abstract Single-atom catalysts (SACs) have become one of the most attractive frontier research fields in catalysis and energy conversion. However, due to the atomic heterogeneity of SACs and limitations of ensemble-averaged measurements, the essential active sites responsible for governing specific catalytic properties and mechanisms remain largely concealed. In this study, we develop a quantitative method of single-atom catalysis–fluorescence correlation spectroscopy (SAC-FCS), leveraging the atomic structure-dependent catalysis kinetics and single-turnover resolution of single-molecule fluorescence microscopy. This method enables us to investigate the oxidase-like single-molecule catalysis on unidentical iron-nitrogen (Fe-N) coordinated SACs, quantifying the active sites and their kinetic parameters. The findings reveal the significant differences of single sites from the average behaviors and corroborate the oxidase-like catalytic mechanism of the Fe-N active sites. We anticipate that the method will give essential insights into the rational design and application of SACs.