Abstract
Metal porphyrin structure is believed to be the active site for microbiological reductive dechlorination. In this work, a biomimetic Hemin catalyst was used for the electrochemical dechlorination of trichloroethylene (TCE). Cyclic voltammetric analysis demonstrates the high electrochemical reactivity of Hemin toward reductive dechlorination of TCE, which is further confirmed by controlled potential electrolysis. TCE can be fully dechlorinated to acetylene, ethylene, and ethane. Density functional theory calculations show the appearance of unpaired electron spins on coordinatively unsaturated Fe sites. The breakage of the Fe–Cl bond in Hemin with the formation of coordinatively unsaturated sites shows reactivity toward TCE-to-dichloroethylene (DCE) conversion, but sites with the coordination to Cl atoms have no reactivity. Lowering the applied potential to generates coordinatively unsaturated sites, showing much higher reactivity toward TCE reduction compared with sites. The energy barrier involving complete dechlorination of TCE was decreased from 1.83 eV by sites to 0.86 eV by sites. sites can continue to contribute to TCE dechlorination in electrochemical systems. Our study provides a novel biomimetic electrochemical approach for the dechlorination of TCE in groundwater.
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Data Availability Statement
No data, models, or code were generated or used during the study.
Acknowledgments
This work was financially supported by the National Natural Science Foundation of China (Grant Nos. 41807188 and 51978537), the Fundamental Research Funds for the Central Universities (2042021kf0201), and the Start-up Fund for Distinguished Scholars, Wuhan University (1403-413100041, 1403-600460022). The numerical calculations in this paper have been done on the supercomputing system in the Supercomputing Center of the University of Science and Technology of China.
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Published In
Journal of Environmental Engineering
Volume 148 • Issue 8 • August 2022
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© 2022 American Society of Civil Engineers.
History
Received: Dec 3, 2021
Accepted: Mar 26, 2022
Published online: May 27, 2022
Published in print: Aug 1, 2022
Discussion open until: Oct 27, 2022
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