Tailoring Fe(VI) coordination microenvironment for high-efficiency oxidation: ligand-driven electron transfer and polymerization steering

Abstract Utilizing ligand-mediated homogeneous catalysis to enhance oxidant-driven pollutant removal efficiency presents significant research value while posing substantial challenges. This study utilized ethylenediaminetetraacetic acid (EDTA) to alter the coordination environment of ferrate(VI), th...

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Main Authors: Zhi Gao, Yu-Lei Liu, Zhuang-Song Huang, Xiao-Na Zhao, Xian-Shi Wang, Zi-Yi Han, Chong-Wei Cui, Jun Ma, Lu Wang
Format: Article
Language:English
Published: Nature Portfolio 2025-07-01
Series:npj Clean Water
Online Access:https://doi.org/10.1038/s41545-025-00488-w
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author Zhi Gao
Yu-Lei Liu
Zhuang-Song Huang
Xiao-Na Zhao
Xian-Shi Wang
Zi-Yi Han
Chong-Wei Cui
Jun Ma
Lu Wang
author_facet Zhi Gao
Yu-Lei Liu
Zhuang-Song Huang
Xiao-Na Zhao
Xian-Shi Wang
Zi-Yi Han
Chong-Wei Cui
Jun Ma
Lu Wang
author_sort Zhi Gao
collection DOAJ
description Abstract Utilizing ligand-mediated homogeneous catalysis to enhance oxidant-driven pollutant removal efficiency presents significant research value while posing substantial challenges. This study utilized ethylenediaminetetraacetic acid (EDTA) to alter the coordination environment of ferrate(VI), thereby steering electron transfer and the phenoxylation pathways to enhance the pollutant removal, which is realized by the complexation-mediated regulation for kinetics and thermodynamics. For example, the introduction of EDTA increased the rate constant of ferrate(VI) oxidizing phenol by four times (from 50.79 M−1 s−1 to 208 M−1 s−1) and the stoichiometric ratio (∆[phenol]/∆[K2FeO4]) from 0.17:1 to 0.22:1. Theoretical calculation and experimental characterization proved that the in-situ formed metastable Fe(VI)-EDTA complex facilitates the electron transfer from Fe(VI) to benzene ring and the phenoxylation pathways. Consequently, the related polymerization products were produced in greater quantities (about 5 times) and with broader diversity than Fe(VI) alone. In the application to real water, the introduction of EDTA reduced more than half of ferrate(VI)’s dosage previously required for completely removing phenol. This study presents a novel strategy for optimizing ferrate(VI) oxidizing pollutants in water treatment, which presents notable environmental benefits by minimizing ferrate(VI) consumption and enhancing pollutant removal efficiency.
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spelling doaj-art-72897ab32e674e5fb8bb88ec9d5f0c2a2025-08-20T03:03:20ZengNature Portfolionpj Clean Water2059-70372025-07-01811910.1038/s41545-025-00488-wTailoring Fe(VI) coordination microenvironment for high-efficiency oxidation: ligand-driven electron transfer and polymerization steeringZhi Gao0Yu-Lei Liu1Zhuang-Song Huang2Xiao-Na Zhao3Xian-Shi Wang4Zi-Yi Han5Chong-Wei Cui6Jun Ma7Lu Wang8State Key Laboratory of Urban Water Resource and Environment, School of Environment, Harbin Institute of TechnologyState Key Laboratory of Urban Water Resource and Environment, School of Environment, Harbin Institute of TechnologyState Key Laboratory of Urban Water Resource and Environment, School of Environment, Harbin Institute of TechnologyState Key Laboratory of Urban Water Resource and Environment, School of Environment, Harbin Institute of TechnologyState Key Laboratory of Urban Water Resource and Environment, School of Environment, Harbin Institute of TechnologyState Key Laboratory of Urban Water Resource and Environment, School of Environment, Harbin Institute of TechnologyState Key Laboratory of Urban Water Resource and Environment, School of Environment, Harbin Institute of TechnologyState Key Laboratory of Urban Water Resource and Environment, School of Environment, Harbin Institute of TechnologyState Key Laboratory of Urban Water Resource and Environment, School of Environment, Harbin Institute of TechnologyAbstract Utilizing ligand-mediated homogeneous catalysis to enhance oxidant-driven pollutant removal efficiency presents significant research value while posing substantial challenges. This study utilized ethylenediaminetetraacetic acid (EDTA) to alter the coordination environment of ferrate(VI), thereby steering electron transfer and the phenoxylation pathways to enhance the pollutant removal, which is realized by the complexation-mediated regulation for kinetics and thermodynamics. For example, the introduction of EDTA increased the rate constant of ferrate(VI) oxidizing phenol by four times (from 50.79 M−1 s−1 to 208 M−1 s−1) and the stoichiometric ratio (∆[phenol]/∆[K2FeO4]) from 0.17:1 to 0.22:1. Theoretical calculation and experimental characterization proved that the in-situ formed metastable Fe(VI)-EDTA complex facilitates the electron transfer from Fe(VI) to benzene ring and the phenoxylation pathways. Consequently, the related polymerization products were produced in greater quantities (about 5 times) and with broader diversity than Fe(VI) alone. In the application to real water, the introduction of EDTA reduced more than half of ferrate(VI)’s dosage previously required for completely removing phenol. This study presents a novel strategy for optimizing ferrate(VI) oxidizing pollutants in water treatment, which presents notable environmental benefits by minimizing ferrate(VI) consumption and enhancing pollutant removal efficiency.https://doi.org/10.1038/s41545-025-00488-w
spellingShingle Zhi Gao
Yu-Lei Liu
Zhuang-Song Huang
Xiao-Na Zhao
Xian-Shi Wang
Zi-Yi Han
Chong-Wei Cui
Jun Ma
Lu Wang
Tailoring Fe(VI) coordination microenvironment for high-efficiency oxidation: ligand-driven electron transfer and polymerization steering
npj Clean Water
title Tailoring Fe(VI) coordination microenvironment for high-efficiency oxidation: ligand-driven electron transfer and polymerization steering
title_full Tailoring Fe(VI) coordination microenvironment for high-efficiency oxidation: ligand-driven electron transfer and polymerization steering
title_fullStr Tailoring Fe(VI) coordination microenvironment for high-efficiency oxidation: ligand-driven electron transfer and polymerization steering
title_full_unstemmed Tailoring Fe(VI) coordination microenvironment for high-efficiency oxidation: ligand-driven electron transfer and polymerization steering
title_short Tailoring Fe(VI) coordination microenvironment for high-efficiency oxidation: ligand-driven electron transfer and polymerization steering
title_sort tailoring fe vi coordination microenvironment for high efficiency oxidation ligand driven electron transfer and polymerization steering
url https://doi.org/10.1038/s41545-025-00488-w
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