biostudies-literatureMo FNational Natural Science Foundation of China as a Shandong Joint Fund ProjectMinistry of Science and Technology of People's Republic of China as a Key Technology Research and Development Program ProjectTianjin Science and Technology Bureau as a Key Science and Technology Supporting ProjectMinistry of Science and Technology of People's Republic of China as a Key Technology Research and Development Program Projecte2300281120https://www.ebi.ac.uk/biostudies/studies/S-EPMC10104488biostudies-literatureUnknown120(15)The performance optimization of isolated atomically dispersed metal active sites is critical but challenging. Here, TiO₂@Fe species-N-C catalysts with Fe atomic clusters (ACs) and satellite Fe-N₄ active sites were fabricated to initiate peroxymonosulfate (PMS) oxidation reaction. The AC-induced charge redistribution of single atoms (SAs) was verified, thus strengthening the interaction between SAs and PMS. In detail, the incorporation of ACs optimized the HSO₅^- oxidation and SO₅^·-desorption steps, accelerating the reaction progress. As a result, the Vis/TiFeAS/PMS system rapidly eliminated 90.81% of 45 mg/L tetracycline (TC) in 10 min. The reaction process characterization suggested that PMS as an electron donor would transfer electron to Fe species in TiFeAS, generating ¹O₂. Subsequently, the h_VB⁺ can induce the generation of electron-deficient Fe species, promoting the reaction circulation. This work provides a strategy to construct catalysts with multiple atom assembly-enabled composite active sites for high-efficiency PMS-based advanced oxidation processes (AOPs).Proceedings of the National Academy of Sciences of the United States of AmericaThe optimized Fenton-like activity of Fe single-atom sites by Fe atomic clusters-mediated electronic configuration modulation.PMC101044882019YFC1804104S19ZC60133U1906222Ouyang SXue WHou ZZhou QWang QWang SSong CMo FWang JfalseThe optimized Fenton-like activity of Fe single-atom sites by Fe atomic clusters-mediated electronic configuration modulation.The performance optimization of isolated atomically dispersed metal active sites is critical but challenging. Here, TiO₂@Fe species-N-C catalysts with Fe atomic clusters (ACs) and satellite Fe-N₄ active sites were fabricated to initiate peroxymonosulfate (PMS) oxidation reaction. The AC-induced charge redistribution of single atoms (SAs) was verified, thus strengthening the interaction between SAs and PMS. In detail, the incorporation of ACs optimized the HSO₅^- oxidation and SO₅^·-desorption steps, accelerating the reaction progress. As a result, the Vis/TiFeAS/PMS system rapidly eliminated 90.81% of 45 mg/L tetracycline (TC) in 10 min. The reaction process characterization suggested that PMS as an electron donor would transfer electron to Fe species in TiFeAS, generating ¹O₂. Subsequently, the h_VB⁺ can induce the generation of electron-deficient Fe species, promoting the reaction circulation. This work provides a strategy to construct catalysts with multiple atom assembly-enabled composite active sites for high-efficiency PMS-based advanced oxidation processes (AOPs).2023-01-01T00:00:00Z2023 Apr2025-04-22T15:55:57.212Z2025-04-06T01:35:22.602ZS-EPMC101044883701120210.1073/pnas.2300281120