Enhanced reactivity and electron efficiency of nanoscale zero-valent iron for nitroaromatic compounds reduction through modification with anthraquinone-2-carboxylic acid

Humic substances (HS) modification favors the reactivity of nanoscale zero-valent iron (nZVI) for water decontamination from nitro-compounds like nitrobenzene (NB), whereas the structural complexity of HS hinders the elucidation of its mechanism. Herein, anthraquinone-2-carboxylic acid (AQC) was emp...

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Main Authors: Yuxin Li, Shiqi Yang, Zihan Liu, Yiyang Pan, Pengfei Zhang, Zhiqiu Qu, Chao Shan
Format: Article
Language:English
Published: Elsevier 2025-08-01
Series:Chemical Engineering Journal Advances
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Online Access:http://www.sciencedirect.com/science/article/pii/S2666821125001322
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author Yuxin Li
Shiqi Yang
Zihan Liu
Yiyang Pan
Pengfei Zhang
Zhiqiu Qu
Chao Shan
author_facet Yuxin Li
Shiqi Yang
Zihan Liu
Yiyang Pan
Pengfei Zhang
Zhiqiu Qu
Chao Shan
author_sort Yuxin Li
collection DOAJ
description Humic substances (HS) modification favors the reactivity of nanoscale zero-valent iron (nZVI) for water decontamination from nitro-compounds like nitrobenzene (NB), whereas the structural complexity of HS hinders the elucidation of its mechanism. Herein, anthraquinone-2-carboxylic acid (AQC) was employed as a typical model molecule for HS. Through AQC modification, the water contact angle of nZVI evidently increased from 6° to 19°-46°, and the rate constant and electron efficiency for NB reduction under aerobic condition was substantially elevated by 6–10.3 times and 2.5–2.8 times, respectively. Among the AQC-modified nZVI materials with varied molar ratios of AQC/Fe (0.1–3 %), 1 % AQC-nZVI not only exhibited the optimal reactivity and electron efficiency, but also demonstrated enhanced reactivity for various nitroaromatic compounds. Moreover, AQC modification could advance the complete reduction of NB by nZVI to aniline and minimize the accumulation of intermediates. In addition, AQC-nZVI materials could maintain an excellent reduction efficiency over a wide pH range (4–9). Mechanistically, the increase of surface hydrophobicity of nZVI owing to AQC modification promoted the adsorption affinity for NB and redirected more electron transfer to NB. Leveraging both anthraquinone and carboxylic groups, AQC served as electron shuttle to mediate the electron transfer from nZVI to NB whilst accelerating the Fe(II)/Fe(III) circulation. Electrochemical impedance spectroscopy revealed a pronounced decrease in the charge transfer resistance of nZVI from 381.4 Ω to 252.8–337.4 Ω due to AQC modification, thereby facilitating the interfacial electron transfer. This study offers insights into the HS-enhanced reactivity and selectivity of nZVI for water decontamination from nitroaromatic compounds.
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spelling doaj-art-b7f71a3fec2449f7acac6cd296cb12702025-08-26T04:14:35ZengElsevierChemical Engineering Journal Advances2666-82112025-08-012310083510.1016/j.ceja.2025.100835Enhanced reactivity and electron efficiency of nanoscale zero-valent iron for nitroaromatic compounds reduction through modification with anthraquinone-2-carboxylic acidYuxin Li0Shiqi Yang1Zihan Liu2Yiyang Pan3Pengfei Zhang4Zhiqiu Qu5Chao Shan6State Key Laboratory of Water Pollution Control and Green Resource Recycling, School of Environment, Nanjing University, Nanjing 210023, ChinaState Key Laboratory of Water Pollution Control and Green Resource Recycling, School of Environment, Nanjing University, Nanjing 210023, ChinaState Key Laboratory of Water Pollution Control and Green Resource Recycling, School of Environment, Nanjing University, Nanjing 210023, ChinaState Key Laboratory of Water Pollution Control and Green Resource Recycling, School of Environment, Nanjing University, Nanjing 210023, ChinaState Key Laboratory of Water Pollution Control and Green Resource Recycling, School of Environment, Nanjing University, Nanjing 210023, ChinaState Key Laboratory of Water Pollution Control and Green Resource Recycling, School of Environment, Nanjing University, Nanjing 210023, ChinaState Key Laboratory of Water Pollution Control and Green Resource Recycling, School of Environment, Nanjing University, Nanjing 210023, China; Research Center for Environmental Nanotechnology (ReCENT), Nanjing University, Nanjing 210023, China; Corresponding author.Humic substances (HS) modification favors the reactivity of nanoscale zero-valent iron (nZVI) for water decontamination from nitro-compounds like nitrobenzene (NB), whereas the structural complexity of HS hinders the elucidation of its mechanism. Herein, anthraquinone-2-carboxylic acid (AQC) was employed as a typical model molecule for HS. Through AQC modification, the water contact angle of nZVI evidently increased from 6° to 19°-46°, and the rate constant and electron efficiency for NB reduction under aerobic condition was substantially elevated by 6–10.3 times and 2.5–2.8 times, respectively. Among the AQC-modified nZVI materials with varied molar ratios of AQC/Fe (0.1–3 %), 1 % AQC-nZVI not only exhibited the optimal reactivity and electron efficiency, but also demonstrated enhanced reactivity for various nitroaromatic compounds. Moreover, AQC modification could advance the complete reduction of NB by nZVI to aniline and minimize the accumulation of intermediates. In addition, AQC-nZVI materials could maintain an excellent reduction efficiency over a wide pH range (4–9). Mechanistically, the increase of surface hydrophobicity of nZVI owing to AQC modification promoted the adsorption affinity for NB and redirected more electron transfer to NB. Leveraging both anthraquinone and carboxylic groups, AQC served as electron shuttle to mediate the electron transfer from nZVI to NB whilst accelerating the Fe(II)/Fe(III) circulation. Electrochemical impedance spectroscopy revealed a pronounced decrease in the charge transfer resistance of nZVI from 381.4 Ω to 252.8–337.4 Ω due to AQC modification, thereby facilitating the interfacial electron transfer. This study offers insights into the HS-enhanced reactivity and selectivity of nZVI for water decontamination from nitroaromatic compounds.http://www.sciencedirect.com/science/article/pii/S2666821125001322Water treatmentNanoscale zero-valent ironHumic substance analogQuinoneConcerted proton electron transfer
spellingShingle Yuxin Li
Shiqi Yang
Zihan Liu
Yiyang Pan
Pengfei Zhang
Zhiqiu Qu
Chao Shan
Enhanced reactivity and electron efficiency of nanoscale zero-valent iron for nitroaromatic compounds reduction through modification with anthraquinone-2-carboxylic acid
Chemical Engineering Journal Advances
Water treatment
Nanoscale zero-valent iron
Humic substance analog
Quinone
Concerted proton electron transfer
title Enhanced reactivity and electron efficiency of nanoscale zero-valent iron for nitroaromatic compounds reduction through modification with anthraquinone-2-carboxylic acid
title_full Enhanced reactivity and electron efficiency of nanoscale zero-valent iron for nitroaromatic compounds reduction through modification with anthraquinone-2-carboxylic acid
title_fullStr Enhanced reactivity and electron efficiency of nanoscale zero-valent iron for nitroaromatic compounds reduction through modification with anthraquinone-2-carboxylic acid
title_full_unstemmed Enhanced reactivity and electron efficiency of nanoscale zero-valent iron for nitroaromatic compounds reduction through modification with anthraquinone-2-carboxylic acid
title_short Enhanced reactivity and electron efficiency of nanoscale zero-valent iron for nitroaromatic compounds reduction through modification with anthraquinone-2-carboxylic acid
title_sort enhanced reactivity and electron efficiency of nanoscale zero valent iron for nitroaromatic compounds reduction through modification with anthraquinone 2 carboxylic acid
topic Water treatment
Nanoscale zero-valent iron
Humic substance analog
Quinone
Concerted proton electron transfer
url http://www.sciencedirect.com/science/article/pii/S2666821125001322
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AT zihanliu enhancedreactivityandelectronefficiencyofnanoscalezerovalentironfornitroaromaticcompoundsreductionthroughmodificationwithanthraquinone2carboxylicacid
AT yiyangpan enhancedreactivityandelectronefficiencyofnanoscalezerovalentironfornitroaromaticcompoundsreductionthroughmodificationwithanthraquinone2carboxylicacid
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