生物质炭材料活化过硫酸盐降解有机污染物的研究进展

doi:10.3969/j.issn.1673-5854.2024.02.007

摘要/Abstract

摘要：

作为经济、易得的含碳材料，生物质炭已应用于高级氧化领域。以硫酸根自由基为基础的高级氧化工艺是降解有机污染物的有效方法之一。本文综述了过硫酸盐的特点及其氧化降解有机污染物的反应原理，重点分析了生物质炭材料的非金属改性（氮掺杂、硼掺杂和硫掺杂）、金属改性、表面修饰等改性方式对其活化过硫酸盐降解有机污染物的影响，讨论了生物质炭基催化剂对典型有机污染物的降解效果与机理，并展望了生物质炭基材料在活化过硫酸盐降解有机污染物领域的技术挑战和发展前景。

关键词: 生物质炭基材料, 活化, 过硫酸盐, 降解, 有机污染物

Abstract:

As an economical and readily available carbon-containing material, carbon derived from biomass had been used in advanced oxidation fields. The advanced oxidation process based on sulfate radical was one of the effective approachs to degrade organic pollutants. In this review, the characteristics of persulfate and the reaction principle of oxidative degradation of organic pollutants were reviewed. The effects of non-metallic modification(nitrogen doping, boron doping and sulfur doping), metal modification and surface modification on the degradation of organic pollutants by persulfate activated by biochar materials were analyzed. The activation properties and mechanism of different kinds of biochar-based materials on persulfate, as well as the degradation effect and mechanism of the carbon-based materials on typical organic pollutants were discussed. Finally, the technical challenges and development prospects of carbon-based materials in the field of activated persulfate degradation of organic pollutants were proposed, in order to provide the reference for the research on persulfate degradation of organic pollutants.

Key words: biomass derived carbon-based materials, activation, persulfate, degradation, organic pollutants

中图分类号:

TQ35

刘艳艳, 蒋剑春, 李保军. 生物质炭材料活化过硫酸盐降解有机污染物的研究进展[J]. 生物质化学工程, 2024, 58(2): 55-63.

Yanyan LIU, Jianchun JIANG, Baojun LI. Research Progress of Biomass Carbon-based Materials Activating Persulfate to Degrade Organic Pollutants[J]. Biomass Chemical Engineering, 2024, 58(2): 55-63.

图/表 2

参考文献 54

1	LIU H P, MA S L, SHAO L, et al. Defective engineering in graphitic carbon nitride nanosheet for efficient photocatalytic pathogenic bacteria disinfection[J/OL]. Applied Catalysis B: Environmental, 2020, 261: 118201[2023-07-10]. https://doi.org/10.1016/j.apcatb.2019.118201.
2	WANG A F, ZHOU P, TIAN D Q, et al. Enhanced oxidation of fluoroquinolones by visible light-induced peroxydisulfate: The significance of excited triplet state species[J/OL]. Applied Catalysis B: Environmental, 2022, 316: 121631[2023-07-10]. https://doi.org/10.1016/j.apcatb.2022.121631.
3	WANG M M, WANG Y F, LI Y F, et al. Persulfate oxidation of tetracycline, antibiotic resistant bacteria, and resistance genes activated by Fe doped biochar catalysts: Synergy of radical and non-radical processes[J/OL]. Chemical Engineering Journal, 2023, 464: 142558[2023-07-10]. https://doi.org/10.1016/j.cej.2023.142558.
4	黄明杰. 氧化铜活化过硫酸盐或氧气降解典型酚类污染物的机理研究[D]. 武汉: 华中科技大学, 2020.
5	耿国敏. 基于过硫酸盐高级氧化法降解氯酚有机污染物的研究[D]. 济南: 齐鲁工业大学, 2021.
6	闫岩. 制药废水中的重要污染物对尾草履虫(Paramecium caudatum)的毒性实验研究[D]. 哈尔滨: 哈尔滨师范大学, 2014.
7	LI K, XU S J, LIU X B, et al. The organic contaminants degradation in Mn-NrGO and peroxymonosulfate system: The significant synergistic effect between Mn nanoparticles and doped nitrogen[J/OL]. Chemical Engineering Journal, 2022, 438: 135630[2023-07-10]. https://doi.org/10.1016/j.cej.2022.135630.
8	SONG G, QIN F Z, YU J F, et al. Tailoring biochar for persulfate-based environmental catalysis: Impact of biomass feedstocks[J/OL]. Journal of Hazardous Materials, 2022, 424: 127663[2023-07-10]. https://doi.org/10.1016/j.jhazmat.2021.127663.
9	金旭明. 过渡金属单原子催化剂活化过硫酸盐降解水中有机污染物的研究[D]. 杭州: 浙江大学, 2021.
10	佚名. 聚苯醚文献综合介绍[J]. 北化科技, 1973, (5): 26- 51.
11	王芳, 杨哲, 陈莹, 等. 多级孔氮掺杂葡萄糖衍生碳的催化氧化应用[J]. 精细化工, 2023, 40 (7): 1553- 1561.
12	袁扬帆. 生物炭表面调控对活化过硫酸盐去除有机污染物的机制研究[D]. 扬州: 扬州大学, 2023.
13	李家琦. 铁氮共掺杂生物炭对过硫酸钠的活化效能及机理研究[D]. 广州: 广东工业大学, 2023.
14	YANG S J, XU S S, TONG J Y, et al. Overlooked role of nitrogen dopant in carbon catalysts for peroxymonosulfate activation: Intrinsic defects or extrinsic defects?[J/OL]. Applied Catalysis B: Environmental, 2021, 295: 120291[2023-07-10]. https://doi.org/10.1016/j.apcatb.2021.120291.
15	DUAN R, MA S L, XU S J, et al. Soybean straw biochar activating peroxydisulfate to simultaneously eliminate tetracycline and tetracycline resistance bacteria: Insights on the mechanism[J/OL]. Water Research, 2022, 218: 118489[2023-07-10]. https://doi.org/10.1016/j.watres.2022.118489.
16	HE M F, ZHAO P, DUAN R, et al. Insights on the electron transfer pathway of phenolic pollutant degradation by endogenous N-doped carbonaceous materials and peroxymonosulfate system[J/OL]. Journal of Hazardous Materials, 2022, 424: 127568[2023-07-10]. https://doi.org/10.1016/j.jhazmat.2021.127568.
17	WANG H Z , GUO W Q , LIU B H , et al. Edge-nitrogenated biochar for efficient peroxydisulfate activation: An electron transfer mechanism[J]. Water Research, 2019, 160, 405- 414. doi: 10.1016/j.watres.2019.05.059
18	ANNAMALAI S, SHIN W S. Efficient degradation of trimethoprim with ball-milled nitrogen-doped biochar catalyst via persulfate activation[J/OL]. Chemical Engineering Journal, 2022, 440: 135815[2023-07-10]. https://doi.org/10.1016/j.cej.2022.135815.
19	王清, 张凤宝, 范晓彬, 等. 氮掺杂中空多孔碳材料活化过一硫酸盐催化降解双酚A[J]. 化学工业与工程, 2022, 39 (6): 1- 13.
20	TIAN W J, LIN J K, ZHANG H Y, et al. Kinetics and mechanism of synergistic adsorption and persulfate activation by N-doped porous carbon for antibiotics removals in single and binary solutions[J/OL]. Journal of Hazardous Materials, 2022, 423: 127083[2023-07-10]. https://doi.org/10.1016/j.jhazmat.2021.127083.
21	LIAO J, XIONG T, DING L, et al. Design of a renewable hydroxyapatite-biocarbon composite for the removal of uranium(VI) with high-efficiency adsorption performance[J/OL]. Biochar, 2022, 4(1): 29[2023-07-10]. https://doi.org/10.1007/s42773-022-00154-1.
22	XIA W, SONG B, YI H, et al. From aquatic biota to autogenous N-doping biochar: Using a highly efficient nonradical dominant process for sulfamethoxazole degradation[J/OL]. Journal of Cleaner Production, 2022, 373: 133750[2023-07-10]. https://doi.org/10.1016/j.jclepro.2022.133750.
23	DOU J B, CHENG J, LU Z J, et al. Biochar co-doped with nitrogen and boron switching the free radical based peroxydisulfate activation into the electron-transfer dominated nonradical process[J/OL]. Applied Catalysis B: Environmental, 2022, 301: 120832[2023-07-10]. https://doi.org/10.1016/j.apcatb.2021.120832.
24	LIU B H, GUO W Q, WANG H Z, et al. B-doped graphitic porous biochar with enhanced surface affinity and electron transfer for efficient peroxydisulfate activation[J/OL]. Chemical Engineering Journal, 2020, 396: 125119[2023-07-10]. https://doi.org/10.1016/j.cej.2020.125119.
25	ZUO J X, SHEN J M, KANG J, et al. B-doped NiFe₂O_x based on the activation of peroxymonosulfate for degrading 2, 4-dichlorophenoxyacetic acid in water[J/OL]. Chemical Engineering Journal, 2023, 459: 141565[2023-07-10]. https://doi.org/10.1016/j.cej.2023.141565.
26	CHEN L, WANG Y X, CHENG S, et al. Nitrogen defects/boron dopants engineered tubular carbon nitride for efficient tetracycline hydrochloride photodegradation and hydrogen evolution[J/OL]. Applied Catalysis B: Environmental, 2022, 303: 120932[2023-07-10]. https://doi.org/10.1016/j.apcatb.2021.120932.
27	XIE J M , ZHUANG R , DU Y X , et al. Advances in sulfur-doped carbon materials for use as anodes in sodium-ion batteries[J]. New Carbon Materials, 2023, 38 (2): 305- 316. doi: 10.1016/S1872-5805(22)60630-9
28	WANG H Z, GUO W Q, LIU B H, et al. Sludge-derived biochar as efficient persulfate activators: Sulfurization-induced electronic structure modulation and disparate nonradical mechanisms[J/OL]. Applied Catalysis B: Environmental, 2020, 279: 119361[2023-07-10]. https://doi.org/10.1016/j.apcatb.2020.119361.
29	CHEN H Y, CHEN R Z, YANG S J, et al. Sustainable heterolytic cleavage of peroxymonosulfate by promoting Fe(Ⅲ)/Fe(Ⅱ) cycle: The role of in-situ sulfur[J/OL]. Chemical Engineering Journal, 2022, 446: 137257[2023-07-10]. https://doi.org/10.1016/j.cej.2022.137257.
30	DING D H, YANG S J, QIAN X Y, et al. Nitrogen-doping positively whilst sulfur-doping negatively affect the catalytic activity of biochar for the degradation of organic contaminant[J/OL]. Applied Catalysis B: Environmental, 2020, 263: 118348[2023-07-10]. https://doi.org/10.1016/j.apcatb.2019.118348.
31	SUN C, CHEN T, HUANG Q X, et al. Activation of persulfate by CO₂-activated biochar for improved phenolic pollutant degradation: Performance and mechanism[J/OL]. Chemical Engineering Journal, 2020, 380: 122519[2023-07-10]. https://doi.org/10.1016/j.cej.2019.122519.
32	HUA L, CHENG T Z, LIANG Z Y, et al. Investigation of the mechanism of phytate-modified biochar-catalyzed persulfate degradation of Ponceau 2R[J/OL]. Biochar, 2022, 4(1): 6[2023-07-10]. https://doi.org/10.1007/s42773-022-00136-3.
33	ZHU M S, KONG L S, XIE M, et al. Carbon aerogel from forestry biomass as a peroxymonosulfate activator for organic contaminants degradation[J/OL]. Journal of Hazardous Materials, 2021, 413: 125438[2023-07-10]. https://doi.org/10.1016/j.jhazmat.2021.125438.
34	TANG R D, GONG D X, DENG Y C, et al. π-π stacking derived from graphene-like biochar/g-C₃N₄ with tunable band structure for photocatalytic antibiotics degradation via peroxymonosulfate activation[J/OL]. Journal of Hazardous Materials, 2022, 423: 126944[2023-07-10]. https://doi.org/10.1016/j.jhazmat.2021.126944.
35	孙晨. 改性生物炭对于水中重金属与有机污染物去除的性能与机理[D]. 杭州: 浙江大学, 2021.
36	董康妮, 谢更新, 晏铭, 等. 磺化生物炭活化过硫酸盐去除水中盐酸四环素[J]. 中国环境科学, 2022, 42 (8): 3650- 3657.
37	刘雅妮. 碳基材料活化过硫酸盐降解有机污染物的性能机理及活性位点分析[D]. 长沙: 湖南大学, 2020.
38	WANG X H, ZHANG P, WANG C P, et al. Metal-rich hyperaccumulator-derived biochar as an efficient persulfate activator: Role of intrinsic metals(Fe, Mn and Zn) in regulating characteristics, performance and reaction mechanisms[J/OL]. Journal of Hazardous Materials, 2022, 424: 127225[2023-07-10]. https://doi.org/10.1016/j.jhazmat.2021.127225.
39	HUANG P, ZHANG P, WANG C P, et al. Enhancement of persulfate activation by Fe-biochar composites: Synergism of Fe and N-doped biochar[J/OL]. Applied Catalysis B: Environmental, 2022, 303: 120926[2023-07-10]. https://doi.org/10.1016/j.apcatb.2021.120926.
40	TONG J, CHEN L, CAO J, et al. Biochar supported magnetic MIL-53-Fe derivatives as an efficient catalyst for peroxydisulfate activation towards antibiotics degradation[J]. Separation and Purification Technology, 2022, 294: 121064[2023-07-10]. https://doi.org/10.1016/j.seppur.2022.121064.
41	MO Z H, TAN Z X, LIANG J L, et al. Iron-rich digestate biochar toward sustainable peroxymonosulfate activation for efficient anaerobic digestate dewaterability[J/OL]. Journal of Hazardous Materials, 2023, 443: 130200[2023-07-10]. https://doi.org/10.1016/j.jhazmat.2022.130200.
42	梁文静. 莲藕生物炭负载硫化纳米零价铁活化过硫酸盐降解污染场地中十溴联苯醚的机制研究[D]. 太原: 太原理工大学, 2021.
43	刘文杰. 含油浮渣衍生碳活化过硫酸盐降解水中有机污染物的性能和机理研究[D]. 广州: 广东工业大学, 2021.
44	LI K, MA S L, XU S J, et al. The mechanism changes during bisphenol A degradation in three iron functionalized biochar/peroxymonosulfate systems: The crucial roles of iron contents and graphitized carbon layers[J/OL]. Journal of Hazardous Materials, 2021, 404: 124145[2023-07-10]. https://doi.org/10.1016/j.jhazmat.2020.124145.
45	LI Y, MA S L, XU S J, et al. Novel magnetic biochar as an activator for peroxymonosulfate to degrade bisphenol A: Emphasizing the synergistic effect between graphitized structure and CoFe₂O₄[J/OL]. Chemical Engineering Journal, 2020, 387: 124094[2023-07-10]. https://doi.org/10.1016/j.cej.2020.124094.
46	WANG S Z, WANG J L. Bimetallic and nitrogen co-doped biochar for peroxymonosulfate(PMS) activation to degrade emerging contaminants[J/OL]. Separation and Purification Technology, 2023, 307: 122807[2023-07-10]. https://doi.org/10.1016/j.seppur.2022.122807.
47	QIAN L A, YAN S, YONG X Y, et al. Effective degradation of chloramphenicol in wastewater by activated peroxymonosulfate with Fe-rich porous biochar derived from petrochemical sludge[J/OL]. Chemosphere, 2023, 310: 136839[2023-07-10]. https://doi.org/10.1016/j.chemosphere.2022.136839.
48	DONG C D, CHEN C W, NGUYEN T B, et al. Degradation of phthalate esters in marine sediments by persulfate over Fe-Ce/biochar composites[J/OL]. Chemical Engineering Journal, 2020, 384: 123301[2023-07-10]. https://doi.org/10.1016/j.cej.2019.123301.
49	LIAO J, XIONG T, DING L, et al. Design of a renewable hydroxyapatite-biocarbon composite for the removal of uranium(VI) with high-efficiency adsorption performance[J/OL]. Biochar, 2022, 4(1): 29[2023-07-10]. https://doi.org/10.1007/s42773-022-00154-1.
50	苏浩杰, 吴俊峰, 王召东, 等. 生物炭及其复合材料活化过硫酸盐研究进展[J]. 材料工程, 2023, 51 (2): 80- 90.
51	LONG L L, SU L L, HU W, et al. Micro-mechanism of multi-pathway activation peroxymonosulfate by copper-doped cobalt silicate: The dual role of copper[J/OL]. Applied Catalysis B: Environmental, 2022, 309: 121276[2023-07-10]. https://doi.org/10.1016/j.apcatb.2022.121276.
52	罗昊昱. 金属基生物炭材料的制备及对过硫酸钠的活化机理研究[D]. 广州: 广东工业大学, 2019.
53	朱建华. ZIFs衍生碳骨架材料活化过硫酸盐降解有机污染物的研究[D]. 南昌: 华东交通大学, 2021.
54	金灿, 刘云龙, 霍淑平, 等. 木质素基多孔炭材料及其在水体净化中的应用研究进展[J]. 林产化学与工业, 2021, 41 (4): 111- 123.

原料raw materials	N掺杂方式N doping method	降解物degradants	降解率degradation rate	参考文献reference
大豆秸秆soybean stalk	内源N endogenous N	四环素tetracycline	46.36%	[15]
壳聚糖chitosan	内源N endogenous N	对羟基苯甲酸酯parabens	100%	[16]
玉米芯corncob	外源N exogenous N	磺胺嘧啶sulfadiazine	95.4%	[17]
桑树mulberry	外源N exogenous N	甲氧苄啶trimethoprim	97%	[18]
氮掺杂多孔炭nitrogen-doped porous carbon	内源N endogenous N	磺胺甲恶唑sulfamethoxazole	79.1%	[20]
木浆纤维素wood pulp cellulose	内源N endogenous N	双氯芬酸diclofenac	834.8 mg/g	[21]
牛粪cattle manure	内源N endogenous N	双酚A bisphenol A	502.6 mg/g	[14]
螺旋藻spiral algae	内源N endogenous N	磺胺甲恶唑sulfamethoxazole	97.59%	[22]
麦秸粉wheat straw powder	内源N endogenous N	四环素tetracycline	59%	[23]

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