Biomimetic Dual-Iron-Site Single-Atom Nanozymes for N 2 -Selective Electrocatalytic Denitrification

Electrocatalytic denitrification (ECDN) for the reduction of NO to N offers an effective and environmentally benign method for removing nitrogen from wastewater, but challenges remain for poor N selectivity. To address this issue, this study reports a dual-iron-site single-atom nanozyme (SAN, FePc@F...

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Vydáno v:Environmental science & technology Ročník 59; číslo 31; s. 16775
Hlavní autoři: Song, Wanchao, Liu, Guoshuai, Zou, Hua, Yao, Yuan, You, Shijie
Médium: Journal Article
Jazyk:angličtina
Vydáno: United States 12.08.2025
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ISSN:1520-5851
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Abstract Electrocatalytic denitrification (ECDN) for the reduction of NO to N offers an effective and environmentally benign method for removing nitrogen from wastewater, but challenges remain for poor N selectivity. To address this issue, this study reports a dual-iron-site single-atom nanozyme (SAN, FePc@FeNOC) electrocatalyst, resembling the natural cytochrome c-dependent nitric oxide reductase (cNOR). The FePc@FeNOC electrocatalyst exhibits a NO removal efficiency as high as 96.1%, accounting for N selectivity of 93.3% and Faradaic efficiency of 82.8% at a reaction time of 10 h. The theoretical results reveal that the potential-determining step of ECDN to N is more thermodynamically favorable than that to NH by FePc@FeNOC, as indicated by the lower free energy barrier for *NO to *N O (0.82 eV) compared with that for *NO to *NOH (0.87 eV). The *N O intermediate demonstrates enhanced charge separation compared with *NOH. The charge redistribution strengthens the electrostatic coupling between FePc@FeNOC and *N O , which not only stabilizes the intermediate structure but also creates a thermodynamic driving force for N formation. We further demonstrate that the superior N -selectivity (90%) of FePc@FeNOC can offer a promising electrocatalyst for removing nitrogen from realistic photovoltaic wastewater with a low energy consumption of 9.8 kWh kgN . This work provides a proof-in-concept demonstration of mimicking cNOR toward the sustainable treatment of nitrate-contaminated wastewater.
AbstractList Electrocatalytic denitrification (ECDN) for the reduction of NO to N offers an effective and environmentally benign method for removing nitrogen from wastewater, but challenges remain for poor N selectivity. To address this issue, this study reports a dual-iron-site single-atom nanozyme (SAN, FePc@FeNOC) electrocatalyst, resembling the natural cytochrome c-dependent nitric oxide reductase (cNOR). The FePc@FeNOC electrocatalyst exhibits a NO removal efficiency as high as 96.1%, accounting for N selectivity of 93.3% and Faradaic efficiency of 82.8% at a reaction time of 10 h. The theoretical results reveal that the potential-determining step of ECDN to N is more thermodynamically favorable than that to NH by FePc@FeNOC, as indicated by the lower free energy barrier for *NO to *N O (0.82 eV) compared with that for *NO to *NOH (0.87 eV). The *N O intermediate demonstrates enhanced charge separation compared with *NOH. The charge redistribution strengthens the electrostatic coupling between FePc@FeNOC and *N O , which not only stabilizes the intermediate structure but also creates a thermodynamic driving force for N formation. We further demonstrate that the superior N -selectivity (90%) of FePc@FeNOC can offer a promising electrocatalyst for removing nitrogen from realistic photovoltaic wastewater with a low energy consumption of 9.8 kWh kgN . This work provides a proof-in-concept demonstration of mimicking cNOR toward the sustainable treatment of nitrate-contaminated wastewater.
Author Zou, Hua
Song, Wanchao
Liu, Guoshuai
You, Shijie
Yao, Yuan
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  givenname: Guoshuai
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  surname: Yao
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  organization: MIIT Key Laboratory of Critical Materials Technology for New Energy Conversion and Storage, School of Chemistry and Chemical Engineering, Harbin Institute of Technology, Harbin 150001, China
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  givenname: Shijie
  orcidid: 0000-0001-8178-9418
  surname: You
  fullname: You, Shijie
  organization: State Key Laboratory of Urban Water Resource and Environment, School of Environment, Harbin Institute of Technology, Harbin 150090, China
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Issue 31
Keywords electrocatalytic denitrification
single-atom nanozyme
N2 selectivity
N−N coupling
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Snippet Electrocatalytic denitrification (ECDN) for the reduction of NO to N offers an effective and environmentally benign method for removing nitrogen from...
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StartPage 16775
SubjectTerms Biomimetics
Catalysis
Denitrification
Iron - chemistry
Nitrogen
Wastewater
Title Biomimetic Dual-Iron-Site Single-Atom Nanozymes for N 2 -Selective Electrocatalytic Denitrification
URI https://www.ncbi.nlm.nih.gov/pubmed/40737536
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