Enzyme-mimicking peripheral substituents beyond the second coordination sphere tune single-atom catalysts for periodate activation.
7 affiliations
- 1Zhejiang Key Laboratory of Environment and Health of New Pollutants, School of Environment, Hangzhou Institute for Advanced Study, University of Chinese Academy of Sciences, Hangzhou, 310024, P.R. China.
- 2Zhejiang Key Laboratory of Low-carbon Control Technology for Industrial Pollution, College of Environment, Zhejiang University of Technology, Hangzhou, Zhejiang, 310032, PR China.
- 3State Key Laboratory of Environmental Chemistry and Ecotoxicology, Research Center for Eco-Environmental Sciences, Chinese Academy of Sciences, Beijing, 100085, PR China.
- 4Zhejiang Key Laboratory of Environment and Health of New Pollutants, School of Environment, Hangzhou Institute for Advanced Study, University of Chinese Academy of Sciences, Hangzhou, 310024, P.R. China. [email protected].
- 5State Key Laboratory of Hydraulics and Mountain River Engineering, College of Architecture and Environment, Sichuan University, Chengdu, 610065, PR China. [email protected].
- 6Zhejiang Key Laboratory of Environment and Health of New Pollutants, School of Environment, Hangzhou Institute for Advanced Study, University of Chinese Academy of Sciences, Hangzhou, 310024, P.R. China. [email protected].
- 7Zhejiang Key Laboratory of Low-carbon Control Technology for Industrial Pollution, College of Environment, Zhejiang University of Technology, Hangzhou, Zhejiang, 310032, PR China. [email protected].
Abstract
Single-atom catalysts (SACs) are promising enzyme-mimetic active centers, yet mimicking long-range regulation by distal binding pockets in natural metalloenzymes remains challenging. Here, we synthesize conjugated organic SACs bearing tunable peripheral substituents beyond the second coordination sphere (denoted as R-FeSAC; R = F, H, or NH₂) to regulate periodate (PI) activation. F-FeSAC outperforms its H- and NH₂-substituted counterparts because long-range electronic regulation reconfigures the Fe-site microenvironment and strengthens PI adsorption and activation. In situ Raman spectroscopy, galvanic oxidation assays, and electrochemical analyses show that R-FeSAC activates PI to form high-potential metastable intermediates, enabling a direct electron-transfer pathway (ETP) for selective pollutant removal through polymerization, rather than radical or singlet-oxygen pathways. Fluorine substitution reinforces Fe-O interaction with PI and accelerates electron-transfer kinetics through an electron-withdrawing effect. Consistent relationships among pollutant half-wave potentials (φ1/2), LUMO(catalyst/PI)-HOMO(pollutant) energy gaps, and degradation reactivity further support the ETP and indicate that pollutant electron-donating ability governs selectivity. Moreover, an F-functionalized membrane exhibits enhanced durability during continuous-flow operation, while a pilot-scale ETP reactor achieves efficient pollutant degradation in real wastewater without iodate leakage. These findings establish beyond-second-sphere peripheral functionalization as an enzyme-inspired strategy for PI activation and polymerization-mediated water purification.
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BibTeX
@article{jin2026enzymemimicking,
title = {{Enzyme-mimicking peripheral substituents beyond the second coordination sphere tune single-atom catalysts for periodate activation.}},
author = {Sijia Jin and Xiaofeng Tang and Zhiqiao He and Shuang Song and Yaqi Cai and Haiyan Zhang and Bo Lai and Tao Zeng},
journal = {Nature communications},
year = {2026},
month = sep,
doi = {10.1038/s41467-026-77805-5},
url = {https://europepmc.org/article/MED/42897163},
note = {CC BY},
}
RIS
TY - JOUR
TI - Enzyme-mimicking peripheral substituents beyond the second coordination sphere tune single-atom catalysts for periodate activation.
AU - Sijia Jin
AU - Xiaofeng Tang
AU - Zhiqiao He
AU - Shuang Song
AU - Yaqi Cai
AU - Haiyan Zhang
AU - Bo Lai
AU - Tao Zeng
PY - 2026
DA - 2026/09/17
JO - Nature communications
DO - 10.1038/s41467-026-77805-5
UR - https://europepmc.org/article/MED/42897163
AB - Single-atom catalysts (SACs) are promising enzyme-mimetic active centers, yet mimicking long-range regulation by distal binding pockets in natural metalloenzymes remains challenging. Here, we synthesize conjugated organic SACs bearing tunable peripheral substituents beyond the second coordination sphere (denoted as R-FeSAC; R = F, H, or NH₂) to regulate periodate (PI) activation. F-FeSAC outperforms its H- and NH₂-substituted counterparts because long-range electronic regulation reconfigures the Fe-site microenvironment and strengthens PI adsorption and activation. In situ Raman spectroscopy, galvanic oxidation assays, and electrochemical analyses show that R-FeSAC activates PI to form high-potential metastable intermediates, enabling a direct electron-transfer pathway (ETP) for selective pollutant removal through polymerization, rather than radical or singlet-oxygen pathways. Fluorine substitution reinforces Fe-O interaction with PI and accelerates electron-transfer kinetics through an electron-withdrawing effect. Consistent relationships among pollutant half-wave potentials (φ1/2), LUMO(catalyst/PI)-HOMO(pollutant) energy gaps, and degradation reactivity further support the ETP and indicate that pollutant electron-donating ability governs selectivity. Moreover, an F-functionalized membrane exhibits enhanced durability during continuous-flow operation, while a pilot-scale ETP reactor achieves efficient pollutant degradation in real wastewater without iodate leakage. These findings establish beyond-second-sphere peripheral functionalization as an enzyme-inspired strategy for PI activation and polymerization-mediated water purification.
SN - 2041-1723
ER -