铁改性乌拉草生物炭活化过氧乙酸降解水中的罗丹明B

郭琦; 赵保卫; 杨珂; 潘江龙

PDF(2264 KB)

中国环境科学 ›› 2025, Vol. 45 ›› Issue (8) : 4354-4364.

水污染与控制

铁改性乌拉草生物炭活化过氧乙酸降解水中的罗丹明B

郭琦, 赵保卫, 杨珂, 潘江龙

作者信息 +

Iron-modified Carex meyeriana Kunth biochar activating peracetic acid to degrade rhodamine B dye in water

GUO Qi, ZHAO Bao-wei, YANG Ke, PAN Jiang-long

Author information +

文章历史 +

摘要

本研究在300,500和700℃下制备了铁改性/未改性乌拉草生物炭,比较考察了其活化过氧乙酸(PAA)降解水中罗丹明B(RhB)的效能.以700℃铁改性生物炭(Fe-KBC700)为代表材料,研究了反应条件(PAA浓度、Fe-KBC700投加量、RhB浓度、pH值、H₂O₂浓度以及水中常见阴离子和富里酸)的影响,分析了反应过程中的优势活性物种、活化机理和RhB的降解路径.高热解温度和Fe的引入有利于生物炭活化性能的提高,Fe-KBC700/PAA体系可在30min内降解99.8%的RhB,较高的PAA浓度、Fe-KBC700投加量和较低的RhB浓度有利于RhB的降解,而碱性条件和较高的共存H₂O₂浓度会抑制降解,Cl^-、SO₄^2-和NO₃^-几乎不影响RhB的降解,而HCO₃^-和FA会对反应造成一定的抑制效果.RhB的降解主要历经非自由基途径,单线态氧、电子转移过程和高价铁均在反应中检测到,Fe-KBC700的含氧官能团和缺陷是关键的反应位点,并提出两条RhB的降解路径.此外,Fe-KBC700在循环5次后仍可降解75.4%的RhB.本研究可为生物炭催化性能的优化以及铁改性生物炭活化PAA的机理研究提供参考.

Abstract

Fe-modified/unmodified Carex meyeriana Kunth biochars were prepared at 300, 500, and 700℃. The degradation efficiencies of rhodamine B (RhB) in water by peracetic acid (PAA) were compared. The effects of reaction conditions (PAA concentration, Fe-KBC700 dosage, RhB concentration, pH, H₂O₂ concentration, co-existing anion and fulvic acid) on 700℃ iron-modified biochar (Fe-KBC700) were studied. The dominant active species, activation mechanism and degradation pathways of RhB were analyzed. High pyrolysis temperature and the introduction of Fe were beneficial to the improvement of biochars activation properties. Fe-KBC700/PAA system degraded 99.8% of RhB within 30min. Higher PAA concentration, Fe-KBC700dosage and lower RhB concentration were conducive to RhB degradation, while alkaline conditions and higher co-existing H₂O₂ concentration inhibit the reaction. Cl^-, SO₄^2-, and NO₃^- hardly affect the degradation of RhB, while HCO₃^- and fulvic acid could inhibit the reaction. The degradation of RhB was mainly due to the non-radical pathway. Singlet oxygen, electron transfer process and high-valent iron were detected in the reaction. The oxygen-containing functional groups and defects of Fe-KBC700 were the key reaction sites, and two degradation pathways of RhB were inferred. In addition, Fe-KBC700 could degrade 75.4% of RhB after 5 cycles. This study could provide a reference for the optimization of catalytic performance of biochars and the mechanism of activation of PAA by iron-modified biochar.

导出引用

郭琦, 赵保卫, 杨珂, 潘江龙. 铁改性乌拉草生物炭活化过氧乙酸降解水中的罗丹明B[J]. 中国环境科学. 2025, 45(8): 4354-4364

GUO Qi, ZHAO Bao-wei, YANG Ke, PAN Jiang-long. Iron-modified Carex meyeriana Kunth biochar activating peracetic acid to degrade rhodamine B dye in water[J]. China Environmental Science. 2025, 45(8): 4354-4364

中图分类号： X703.5

参考文献

[1] Du R, Zhang Y, Bian Y, et al. Rhodamine and related substances in food: Recent updates on pretreatment and analysis methods [J]. Food Chemistry, 2024,459:140384.
[2] Chebbi M, Youcef S, Youcef L, et al. Single and combined treatment processes for rhodamine B removal by coagulation-flocculation and adsorption [J]. RSC Advances, 2024,14(51):37833-37845.
[3] Valli nachiyar C, Rakshi A D, Sandhya S, et al. Developments in treatment technologies of dye-containing effluent: A review [J]. Case Studies in Chemical and Environmental Engineering, 2023,7:100339.
[4] Lin J, Ye W, Xie M, et al. Environmental impacts and remediation of dye-containing wastewater [J]. Nature Reviews Earth & Environment, 2023,4(11):785-803.
[5] 汤崇锹,金丽丽,黄辉,等.基于过氧乙酸的高级氧化技术去除水中新污染物:现状与挑战[J].环境化学, 2025,44(2):395-404. Tang C Q, Jin L L, Huang H, et al. Peracetic acid - based advanced oxidation processes for the removal ofemerging contaminants from water: status and challenges [J]. Environmental Chemistry, 2025,44(2): 395-404.
[6] Lin J, Zou J, CAI H, et al. Hydroxylamine enhanced Fe(II)-activated peracetic acid process for diclofenac degradation: Efficiency, mechanism and effects of various parameters [J]. Water Research, 2021,207:117796.
[7] He L, Zou J, Wu J, et al. Highly Efficient Degradation of Emerging Contaminants with Sodium Bicarbonate-Enhanced Mn(II)/Peracetic Acid Process: Formation and Contribution of Mn(V) [J]. Environmental Science & Technology, 2024,58(45):20313-20326.
[8] 王华哲,乔成桓,战树岩,等.过氧乙酸活化功能材料开发与水环境应用[J].环境化学, 2023,42(11):3613-3627. Wang H Z, Qiao C H, Zhan S Y, et al. Development and application of peracetic acid activation-orientedfunctional materials in water treatment [J]. Environmental Chemistry, 2023,42(11):3613-3627.
[9] An L, Wang J, Wang J, et al. Efficient peroxymonosulfate activation by iron-cobalt bimetallic biochar for rapid removal of antibiotic resistant bacteria, antibiotic resistance genes, and ampicillin: The coexisting of free-radical and non-radical pathways [J]. Separation and Purification Technology, 2024,342:127025.
[10] Ning R, Dong Y, Yang S, et al. Fe-N co-doped biochar derived from biomass waste triggers peracetic acid activation for efficient water decontamination [J]. Journal of Hazardous Materials, 2024,470: 134139.
[11] Shi C, Wang Y, Zhang K, et al. Fe-biochar as a safe and efficient catalyst to activate peracetic acid for the removal of the acid orange dye from water [J]. Chemosphere, 2022,307:135686.
[12] Lu J, Lu Q, Di L, et al. Iron-based biochar as efficient persulfate activation catalyst for emerging pollutants removal: A review [J]. Chinese Chemical Letters, 2023,34(11):108357.
[13] Wang L, Wei J, Li Y, et al. A state-of-the-art review on heterogeneous catalysts-mediated activation of peracetic acid for micropollutants degradation: Classification of reaction pathways, mechanisms, influencing factors and DFT calculation [J]. Chemical Engineering Journal, 2023,477:147051.
[14] Li S, Dai C, Duan Y, et al. Non-radical pathways in peracetic acid-based micropollutant degradation: A comprehensive review of mechanisms, detection methods, and promising applications [J]. Separation and Purification Technology, 2024,330:125240.
[15] Xue X, Xue N, Ouyang D, et al. Biochar-Based Single-Atom Catalyst with Fe-N₃O-C Configuration for Efficient Degradation of Organic Dyes by Peroxymonosulfate Activation [J]. ACS Applied Materials & Interfaces, 2023,15(49):57003-57014.
[16] Zheng J, Lin Q, Wu Y, et al. Key coordination of oxygen doping in Fe single-atoms enhances nonradical activation of peroxymonosulfate: The formation of high-valent Fe species and electron transfer [J]. Chemical Engineering Journal, 2024,489:151307.
[17] Tian X, Liu S, Zhang B, et al. Carbonized polyaniline-activated peracetic acid advanced oxidation process for organic removal: Efficiency and mechanisms [J]. Environmental Research, 2023,219: 115035.
[18] Guo Q, Zhao B, Zhang Y, et al. Iron-doped Carex meyeriana Kunth biochars activate peracetic acid for efficient degradation of acid orange 7 dye in water: Key role of non-radical pathways [J]. Journal of Water Process Engineering, 2025,74:107835.
[19] Hou J, Xu J, Tang R, et al. Activation of peracetic acid by biochar for sulfamethoxazole degradation: Revealing roles of the active sites [J]. Journal of the Taiwan Institute of Chemical Engineers, 2023,152: 105184.
[20] Wu F, Yue X, Xu Y, et al. Peanut-shell-derived biochar mediated peracetic acid activation for the elimination of acetaminophen via an electron-transfer regime [J]. Separation and Purification Technology, 2025,353:128150.
[21] Wang Y, Lin Y, Yang C, et al. Calcination temperature regulates non-radical pathways of peroxymonosulfate activation via carbon catalysts doped by iron and nitrogen [J]. Chemical Engineering Journal, 2023,451:138468.
[22] Wu L, Li Z, Cheng P, et al. Efficient activation of peracetic acid by mixed sludge derived biochar: Critical role of persistent free radicals [J]. Water Research, 2022,223:119013.
[23] Dong Y, Du W, Guo M. Persulfate activation by N-doped ilmenite/biochar catalyst for tetracycline degradation under visible light: A synergy of active species and electron transfer [J]. Journal of Water Process Engineering, 2024,67:106287.
[24] Jawad A, Lang J, Liao Z, et al. Activation of persulfate by CuOx@Co-LDH: A novel heterogeneous system for contaminant degradation with broad pH window and controlled leaching [J]. Chemical Engineering Journal, 2018,335:548-559.
[25] Wang J, Xiong B, Miao L, et al. Applying a novel advanced oxidation process of activated peracetic acid by CoFe₂O₄ to efficiently degrade sulfamethoxazole [J]. Applied Catalysis B: Environmental, 2021,280: 119422.
[26] Kong D, He L, Shen S, et al. Unveiling the mechanisms of peracetic acid activation by iron-rich sludge biochar for sulfamethoxazole degradation with wide adaptability [J]. Journal of Environmental Management, 2023,347:119119.
[27] Yang K, Zhai Z, Liu H, et al. Peracetic acid activation by natural chalcopyrite for metronidazole degradation: Unveiling the effects of Cu-Fe bimetallic sites and sulfur species [J]. Separation and Purification Technology, 2023,305:122500.
[28] Kim J, Zhang T, Liu W, et al. Advanced Oxidation Process with Peracetic Acid and Fe(II) for Contaminant Degradation [J]. Environmental Science & Technology, 2019,53(22):13312-13322.
[29] Wu J, Zou J, Lin J, et al. Overlooked Role of Coexistent Hydrogen Peroxide in Activated Peracetic Acid by Cu(II) for Enhanced Oxidation of Organic Contaminants [J]. Environmental Science & Technology, 2024,58(35):15741-15754.
[30] Li J, Zou J, Zhang S, et al. Sodium tetraborate simultaneously enhances the degradation of acetaminophen and reduces the formation potential of chlorinated by-products with heat-activated peroxymonosulfate oxidation [J]. Water Research, 2022,224:119095.
[31] Wang Z, Wang J, Xiong B, et al. Application of Cobalt/Peracetic Acid to Degrade Sulfamethoxazole at Neutral Condition: Efficiency and Mechanisms [J]. Environmental Science & Technology, 2020,54(1): 464-475.
[32] Pan S, Guo X, Li R, et al. Activation of peroxymonosulfate via a novel UV/hydrated Fe(III) oxide coupling strategy for norfloxacin removal: Performance and mechanism [J]. Separation and Purification Technology, 2022,300:121909.
[33] 王诗生,杨玉,盛广宏,等.改性生物炭活化过硫酸盐降解盐酸四环素[J].中国环境科学, 2024,44(11):6122-31. Wang S S, Yang Y, Sheng G H, et al. Modified biochar activated persulfate for degradation of tetracycline [J]. China Environmental Science, 2024,44(11):6122-31.
[34] Miao F, Ren W, Zhou H, et al. Carbon-based peracetic acid activation towards advanced water purification [J]. Applied Catalysis B: Environment and Energy, 2025,363:124807.
[35] Li Y, Dong H, Xiao J, et al. Insights into a novel CuS/percarbonate/ tetraacetylethylenediamine process for sulfamethazine degradation in alkaline medium [J]. Journal of Hazardous Materials, 2022,435: 128999.
[36] Cheng Y, Wang Z, Wang J, et al. New insights into the degradation of micro-pollutants in the hydroxylamine enhanced Fe(II)/peracetic acid process: Contribution of reactive species and effects of pH [J]. Journal of Hazardous Materials, 2023,441:129885.
[37] Wang Z, Chen Z, Li Q, et al. Non-Radical Activation of Peracetic Acid by Powdered Activated Carbon for the Degradation of Sulfamethoxazole [J]. Environmental Science & Technology, 2023, 57(28):10478-10488.
[38] 郑大洋,邹佳丽,徐皓,等.污泥生物炭活化过一硫酸盐降解环丙沙星[J].环境科学, 2023,44(12):6801-6810. Zheng D Y, Zou J L, Xu H, et al. Degradation of ciprofloxacin by activating peroxymonosulfate with sludge biochar [J]. Environmental Science, 2023,44(12):6801-6810.
[39] Zhou Z, Yang Y, Xue G, et al. Efficient degradation of fluoroquinolone antibiotics in the landfill leachate by sludge biochar activated peracetic acid: Radical vs non-radical process [J]. Chemical Engineering Journal, 2024,480:148048.
[40] He L, Zou J, Wu Z, et al. Waste manganese sand activated peracetic acid for efficient degradation of emerging contaminants: Resource utilization and dual-phase mechanism [J]. Chemical Engineering Journal, 2025,504:159144.
[41] Liu B, Huang B, Ma X, et al. Recent advances in peracetic acid-based advanced oxidation processes for emerging pollutants elimination: A review [J]. Journal of Environmental Chemical Engineering, 2024,12(3):112927.
[42] 胡虹,潘承欢,刘义青.Fe(Ⅲ)联合过氧乙酸降解水中土霉素[J].中国环境科学, 2025,45(3):1272-1279. Hu H, Pan C H, Liu Y Q. Degradation of oxytetracycline by Fe(III) combined with peracetic acid [J]. China Environmental Science, 2025, 45(3):1272-1279.
[43] Li S, Zou J, Wu J, et al. Protocatechuic acid enhanced the selective degradation of sulfonamide antibiotics in Fe(III)/peracetic acid process under actually neutral pH conditions [J]. Water Research, 2024,259: 121891.
[44] Qian Y, Huang J, Chen J, et al. Activation of peracetic acid by RuO₂/MWCNTs to degrade sulfamethoxazole at neutral condition [J]. Chemical Engineering Journal, 2022,431:134217.
[45] Deng J, Dong H, Zhang S, et al. Insights into the pH-dependent mechanism of peracetic acid activation by biochar-supported zero- valent iron/cobalt bimetallic nanoparticles: The shift of reactive sites and the dual role of hydrogen peroxide [J]. Journal of Hazardous Materials, 2024,476:135207.