氧化石墨烯及其复合材料去除水体抗生素的研究进展

doi:10.16258/j.cnki.1674-5906.2024.01.015

生态环境学报 ›› 2024, Vol. 33 ›› Issue (1): 144-155.DOI: 10.16258/j.cnki.1674-5906.2024.01.015

氧化石墨烯及其复合材料去除水体抗生素的研究进展

李丹怡¹^,²(), 黄显婷¹^,³, 李继超⁴, 李颖洁¹^,³, 闫家普¹, 林慰¹^,^*()

1.北京师范大学自然科学高等研究院，广东珠海 519087
2.中国水产科学研究院南海水产研究所/农业农村部水产品加工重点实验室，广东广州 510300
3.北京师范大学珠海分校不动产学院，广东珠海 519087
4.聊城市政务服务综合受理中心，山东聊城 252000

收稿日期:2023-09-26 出版日期:2024-01-18 发布日期:2024-03-19
通讯作者: *林慰。E-mail: linwei@bnu.edu.cn
作者简介:李丹怡（1994年生），女，硕士，主要从事水污染控制技术、渔业环境与水产品风险评估等研究。E-mial: lidy27@mail2.sysu.edu.cn
基金资助:
山东省重点研发计划(2020CXGC011404);广东省基础与应用基础研究基金项目(2021A1515110806);科技计划项目(2020B1212030005);海南省自然科学基金项目(321QN0944)

Advances in the Removal of Antibiotics from Water by Graphene Oxide and Its Composites

LI Danyi¹^,²(), HUANG Xianting¹^,³, LI Jichao⁴, LI Yingjie¹^,³, YAN Jiapu¹, LIN Wei¹^,^*()

1. Advanced Institute of Natural Sciences, Beijing Normal University at Zhuhai, Zhuhai 519087, P. R. China
2. Key Laboratory of Aquatic Product Processing, Ministry of Agriculture and Rural Affairs/South China Sea Fisheries Research Institute, Chinese Academy of Fishery Sciences, Guangzhou 510300, P. R. China
3. College of Real Estate, Beijing Normal University, Zhuhai, Zhuhai 519087, P. R. China
4. Liaocheng Government Affairs Service Center, Liaocheng 252000, P. R. China

Received:2023-09-26 Online:2024-01-18 Published:2024-03-19

摘要/Abstract

摘要：

由于具有优异的抗菌性，抗生素被广泛应用于医学领域和养殖行业。然而，近年来对抗生素大规模的使用和排放，在自然界造成了大量的累积，引发了一系列水环境污染问题，严重威胁生态系统安全和人类健康。因此，研发可去除水中过量抗生素的材料已成为当前环境领域的重要研究方向之一。氧化石墨烯（graphene oxide，GO）以其高比表面积、良好亲水性、耐酸碱性、制备简便、成本低廉等优势，成为了一种新兴的抗生素去除材料。该文首先概述了现有的GO及其复合材料分类制备方法，包括空间改造、共价键修饰和金属氧化物改性等。其次，综述了近年来GO及其复合材料在抗生素去除领域的应用、影响因素及作用机制。结果表明，基于吸附原理的GO复合材料吸附去除抗生素效果主要受溶液pH、共存离子、吸附剂投加量、抗生素类别及浓度等多种因素的影响，吸附机制主要包括静电相互作用、π-π相互作用、阳离子-π键作用和氢键作用等，通过引入元素、金属和有机化合物等手段可有效提高GO材料的吸附容量；基于光催化降解原理的抗生素去除过程中，光照条件是最重要影响因素，而其中关键活性物质包括光生空穴、羟基自由基和超氧自由基等，掺杂金属纳米粒子与半导体纳米材料等能够优化其光催化性能。最后，通过对GO及其复合材料制备过程、去除机理和应用场景的综合分析，指出其普适性不高、实际应用不足和环境毒性不明等现存问题，并提出未来应加强材料研发、产业应用和毒性效应评估等方面的研究展望。

关键词: 氧化石墨烯, 复合材料, 抗生素, 吸附, 光催化降解, 去除机理

Abstract:

Antibiotics have been extensively utilized in the medical field and aquaculture industry for their exceptional antibacterial properties. However, the extensive use of antibiotics has led to a series of water pollution issues, posing serious threats to ecosystem safety and human health. Hence, developing new functional materials for removal of excessive antibiotics from water becomes one of the hot environmental topics. Graphene oxide (GO) has become a new material for antibiotic removal due to its diverse merits including high specific surface area, great hydrophilicity, appreciable acid and alkali resistance, simple preparation, and economic properties. This review first summarizes the classification and preparation methods of GO and its composites, including spatial modification, covalent bond modification, and metal oxide modification, etc. Then, we overview the recent advances in the applications, influencing factors, and functional mechanism of GO and its composites designed for antibiotic removal. Based on the adsorption principle, the results show that the effectiveness of GO composites in removing antibiotics is influenced by various factors such as the pH and ion types in the solution, the dosage of adsorbent, and the type and concentration of antibiotics. The adsorption mechanism mainly includes electrostatic interaction, π-π interaction, cation-π bond interaction, and hydrogen bond interaction. The adsorption capacity of GO materials can be significantly enhanced by introducing specific elements, metals, and organic compounds. Notably, light condition plays a crucial role in the photocatalytic degradation of antibiotics by GO composites, and the key active substances include photogenerated holes, hydroxyl radicals, and superoxide radicals. In addition, the addition of doped metal nanoparticles and semiconductor nanomaterials can improve photocatalytic performance. Finally, based on the comprehensive assessment of the preparation processes, removal mechanism, and application scenarios of GO and its composites, several existential issues such as the low application universality, inadequate practical application, and unclear environmental toxicity are highlighted. Therefore, future research should focus on novel material development, industrial application, and toxicity assessment in terms of GO materials-based antibiotics removal in the environment.

Key words: graphene oxide, composite, antibiotic, adsorption, photocatalytic degradation, removal mechanism

中图分类号:

李丹怡, 黄显婷, 李继超, 李颖洁, 闫家普, 林慰. 氧化石墨烯及其复合材料去除水体抗生素的研究进展[J]. 生态环境学报, 2024, 33(1): 144-155.

LI Danyi, HUANG Xianting, LI Jichao, LI Yingjie, YAN Jiapu, LIN Wei. Advances in the Removal of Antibiotics from Water by Graphene Oxide and Its Composites[J]. Ecology and Environment, 2024, 33(1): 144-155.

图/表 8

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原料	反应时间	缺点	参考文献
石墨、浓HNO₃、KClO₃/ KClO₄/NaClO₄	3−4 d	生成有害气体、易爆炸	Brodie, 1859
石墨、浓HNO₃、KClO₃、浓H₂SO₄	96 h	生成有害气体、氧化程度过低、易破坏碳结构	Staudenmaier, 1898
石墨、NaNO₃、KMnO₄、浓H₂SO₄、H₂O₂	<2 h	结构影响因素多	Hummers et al., 1958
石墨、H₂SO₄、 H₃PO₄、KMnO₄	12 h	成本高	Marcano et al., 2010
石墨、KMnO₄、H₂O₂	1 h	稳定性低	Chao et al., 2016

原料	反应时间	缺点	参考文献
石墨、浓HNO₃、KClO₃/ KClO₄/NaClO₄	3−4 d	生成有害气体、易爆炸	Brodie, 1859
石墨、浓HNO₃、KClO₃、浓H₂SO₄	96 h	生成有害气体、氧化程度过低、易破坏碳结构	Staudenmaier, 1898
石墨、NaNO₃、KMnO₄、浓H₂SO₄、H₂O₂	<2 h	结构影响因素多	Hummers et al., 1958
石墨、H₂SO₄、 H₃PO₄、KMnO₄	12 h	成本高	Marcano et al., 2010
石墨、KMnO₄、H₂O₂	1 h	稳定性低	Chao et al., 2016

分类	思路	原理	制备方法
石墨烯量子点	自上而下	通过物理或化学方法将大尺寸的石墨烯薄片切割成小尺寸的石墨烯量子点	水热法、电化学法、化学剥离碳纤维法
	自下而上	以小分子作前体通过一系列化学反应制备石墨烯量子点	溶液化学法、超声波法和微波法、可控热解多环芳烃法
	特殊方法	将富勒烯在活泼过渡金属钌催化作用下分解获得系列原子级别的石墨烯量子点	电子束刻蚀法、钌催化C₆₀转化法
共价键修饰氧化石墨烯材料	共价键修饰	有机小分子和聚合物负载到石墨烯或氧化石墨烯表面	原位聚合法、溶液共混法、熔融共混法、乳液共混法、Pickering乳液聚合法
无机纳米氧化石墨烯材料	物理掺杂	金属/金属氧化物与氧化石墨烯复合	水热法、高功率超声法、热剥离法
无机纳米氧化石墨烯材料	化学复合	以氯化亚锡和氧化石墨为原料制备得到二氧化锡/石墨烯复合材料	气热法、原位合成法

分类	思路	原理	制备方法
石墨烯量子点	自上而下	通过物理或化学方法将大尺寸的石墨烯薄片切割成小尺寸的石墨烯量子点	水热法、电化学法、化学剥离碳纤维法
	自下而上	以小分子作前体通过一系列化学反应制备石墨烯量子点	溶液化学法、超声波法和微波法、可控热解多环芳烃法
	特殊方法	将富勒烯在活泼过渡金属钌催化作用下分解获得系列原子级别的石墨烯量子点	电子束刻蚀法、钌催化C₆₀转化法
共价键修饰氧化石墨烯材料	共价键修饰	有机小分子和聚合物负载到石墨烯或氧化石墨烯表面	原位聚合法、溶液共混法、熔融共混法、乳液共混法、Pickering乳液聚合法
无机纳米氧化石墨烯材料	物理掺杂	金属/金属氧化物与氧化石墨烯复合	水热法、高功率超声法、热剥离法
无机纳米氧化石墨烯材料	化学复合	以氯化亚锡和氧化石墨为原料制备得到二氧化锡/石墨烯复合材料	气热法、原位合成法

抗生素	吸附材料	吸附率 (吸附容量)	反应条件	去除机理	参考文献
左氧氟沙星	天冬氨酸-功能化氧化石墨烯-氧化锌 (GO-ZnO)	95.12% (73.15 mg·g⁻¹)	pH=7; t=25 ℃; 投加量为0.6 g·L⁻¹; 初始质量浓度为30 mg·L⁻¹	静电相互作用、氢键、π-π相互作用	Ismail et al., 2023
磺胺	锰原子-氮掺杂氧化石墨烯 (Mn-NGO)	98.7%	pH为微酸性或中性; t =25 ℃; 投加量为1 g·L⁻¹; 初始质量浓度为10 mg·L⁻¹	阳离子-π键、静电吸引、光催化降解 (羟基自由基、超氧自由基等)	Lü et al., 2023
土霉素恶喹酸甲氧苄啶	柠檬酸改性氧化石墨烯- 羧甲基纤维素膜 (GO-CMC)	OTC: 33.8% (102.05 mg·g⁻¹) OA: 97.2% (256.68 mg·g⁻¹) TMP: 83.3% (370.93 mg·g⁻¹)	pH=5(OTC)/7(OA)/8(TMP); t=30 ℃; 投加量为1 g·L⁻¹; 初始质量浓度为100 mg·L⁻¹	阳离子-π键、 π-π相互作用	Juengchareo-npoon et al., 2021
四环素	磁性氧化石墨烯海绵 (MGOS)	85% (473 mg·g⁻¹)	pH=10; t =35 ℃; 投加量为0.6 g·L⁻¹; 初始质量浓度为400 mg·L⁻¹	静电相互作用、阳离子-π键	Yu et al., 2017
四环素	磁性氧化石墨烯/氧化钨 (GO/W₁₈O₄₉)	>79% (318.18 mg·g⁻¹)	pH=5; t=40 ℃; 初始质量浓度为100 mg·L⁻¹	π-π相互作用、静电吸引、络合作用、阳离子交换、氢键	Qiao et al., 2023
环丙沙星	氧化石墨烯/海藻酸钙-聚丙烯酰胺 (GO/Ca-Alg₂-PAM)	6.846 mg·g⁻¹	t=25 ℃; 投加量为0.9 g·L⁻¹	‒	Choi et al., 2022
环丙沙星	几丁质/氧化石墨烯纳米材料 (nGO)	(282±11) mg·g⁻¹	pH=6.3; t =25 ℃; 投加量为5 g·L⁻¹	π-π堆积、静电吸引、孔隙作用	González et al., 2018
环丙沙星诺氟沙星	氧化镁/壳聚糖/氧化石墨烯(MgO/Chit/GO)	CIP: 1111 mg·g⁻¹ NOR: 1000 mg·g⁻¹	pH=7; t =25 ℃; 投加量为0.5 g·L⁻¹	π-π相互作用、静电相互作用	Nazraz et al., 2019

氧化石墨烯及其复合材料去除水体抗生素的研究进展

Advances in the Removal of Antibiotics from Water by Graphene Oxide and Its Composites

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抗生素	光催化剂	去除效率	反应条件	关键活性物质	参考文献
诺氟沙星	四氧二铁酸钴-还原氧化石墨烯-溴化氧铋 (CoFe₂O₄-rGO-BiOBr)	88.7%	t=20 ℃; 投加量为0.3 g·L⁻¹; 初始质量浓度为5 mg·L⁻¹	光生空穴、羟基自由基	Zhang et al., 2020b
四环素金霉素土霉素强力霉素	钒酸铋/二氧化钛/还原氧化石墨烯(BiVO₄/TiO₂/rGO)	TC: 96.2% CTC: 97.5% OTC: 98.7% DXC: 99.6%	λ>420 nm; 初始质量浓度为10 mg·L⁻¹	羟基自由基、超氧自由基	Wang et al., 2019b
头孢氨苄	氨基化二氧化锰/氧化石墨烯/臭氧化和质子功能化石墨相氮化碳(MnO₂-NH₂/GO/p-C₃N₄)	100%	初始质量浓度为1 mg·L⁻¹	光生空穴、羟基自由基、超氧自由基	Yang et al., 2022
甲氧苄啶	铜铁层状双氢氧化物涂层/氧化石墨烯 (CuFe-LDH/GO)	90.8%	t=(25±2) ℃; λ=254 nm; pH=8.8; 投加量为0.25 g·L⁻¹; 初始质量浓度为20 mg·L⁻¹	硫酸根自由基、光生电子	Vasseghian et al., 2023
土霉素	溴氧化铋/二硫化钼/氧化石墨烯异质结(BiOBr/MoS₂/GO)	>98%	室温; λ=380 nm; 投加量为1 g·L⁻¹; 初始质量浓度为10 mg·L⁻¹	光生空穴、羟基自由基、超氧自由基	Li et al., 2021
头孢克洛	伊红Y/氧化石墨烯(GO/EY)	97%	pH=7; 投加量为0.1 g·L⁻¹; 初始质量浓度为2 mg·L⁻¹	单态氧、过氧化氢	Luo et al., 2021

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