石墨烯在水环境中的转化和降解行为研究进展

doi:10.11896/cldb.201903004

材料导报

2019, Vol. 33

Issue (3): 395-401 https://doi.org/10.11896/cldb.201903004

材料与可持续发展（二）--材料绿色制造与加工^*

石墨烯在水环境中的转化和降解行为研究进展

马李璇¹, 李凯¹, 宁平¹, 梅毅², 王驰², 孙鑫¹

1 昆明理工大学环境科学与工程学院,昆明 650000
2 昆明理工大学化学工程学院,昆明 650000

Transformation and Degradation Behavior of Graphene in WaterEnvironment: a Review

MA Lixuan¹, LI Kai¹, NING Ping¹, MEI Yi², WANG Chi², SUN Xin¹

1 Faculty of Environmental Science and Engineering, Kunming University of Science and Technology, Kunming 650000
2 Faculty of Chemical Engineering, Kunming University of Science and Technology, Kunming 650000

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摘要随着石墨烯的大量生产和广泛应用,向水环境中释放的石墨烯类垃圾和副产物与日俱增,从而带来不良的生态效应,极大地增加了石墨烯在环境和人体中的暴露概率。与此同时,石墨烯的生态毒性和环境效应引起了研究者的重视。石墨烯可以进入藻类、鼠内引起氧化应激反应,可以进入细胞与DNA及蛋白质等生物大分子物质相互作用,对生物体产生一定的毒性。此外,石墨烯具有巨大的比表面积和强烈的π电子活性,对有机污染物具有良好的吸附性能,进而对水环境中的有毒有害物质产生富集作用,改变污染物的迁移、转化和生态风险。
研究发现,石墨烯在水环境中主要以团聚的形态存在,具有生物难降解性和强烈的疏水性。其衍生物氧化石墨烯在水体中能形成稳定的悬浮物,具有长期迁移性和亲水性的特点。这些特点使得不同形态的石墨烯在外界环境的作用下发生相互转化,甚至降解,导致它的理化性质、迁移性、吸附能力发生改变。这种改变会影响石墨烯的其他环境行为如迁移归趋、对环境污染物的吸附性能以及生态毒性等,因此研究水环境中石墨烯的转化和降解对评价其环境风险具有重要意义。外界环境如水体理化性质,化学、光热、生物介质与石墨烯的作用机制是近年来研究的重点。通过研究环境介质对石墨烯的结构性能和活性的改变,可以为分析石墨烯在水体中的生态效应的动态变化及其与有机污染物之间的相互作用提供理论基础。水环境中的pH值、盐溶液类型、离子强度、溶解性有机质等因素对石墨烯的聚合状态有不同程度的影响。尤其是溶解性有机质,它既可以通过空间位阻效应促进石墨烯的分散,又可以通过缠绕、交联促进石墨烯的团聚,进一步增加了研究石墨烯的转化和降解机制的难度。石墨烯在光照作用下产生的活性自由基是其结构性质变化的主要原因,而石墨烯与微生物的作用机制主要是酶促氧化。
本文就石墨烯的光转化、热转化、化学转化及生物降解的过程和原理进行了综述,分析了影响石墨烯在水环境中转化和降解的因素及转化前后的环境效应。

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	马李璇
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关键词: 石墨烯转化生物降解环境影响

Abstract: With the mass production and extensive applications of graphene, the graphene wastes and by-products are inevitably released into water environment, which brings about harmful ecological effect and enormously raises the exposure probability of graphene in the environment and human body. Therefore, the ecological toxicity and environmental effects of graphene have aroused wide attention from researchers. Graphene can get access to algae, mice, and induce the oxidation stress. It can also enter cells and interact with biological macro-molecules like DNA and protein, producing certain toxicity to living organisms. Besides, owing to the large specific surface area and strong π electron activity, graphene exhibits favorable adsorption performance for organic pollutants, which makes toxic or harmful substances in water environment enriched on graphene, and further changes the migration, transformation and ecological risk of pollutants.
It has been found that graphene mainly exists in agglomerated form in water environment, and shows biodegradability and strong hydrophobicity. While, its derivative, graphene oxide, can form a stable suspension in water, and presented long-term mobility and hydrophilicity. These features enable graphene in different forms undergo mutual transformation even degradation under the action of the external environment, resulting in changes of its physicochemical properties, mobility, and adsorption capacity. These changes will further affect other environmental behaviors of graphene such as migration trend, adsorption of environmental pollutants, and ecological toxicity. Therefore, it is of great significance to study the transformation and degradation of graphene for evaluating its environmental risk in water environment.In resent years, the mechanism between graphene and external conditions, such as physical and chemical properties of water, and chemical, optothermal, biological media has become the focus of research. By studying the changes of the structure and activity of graphene in environmental media, a theoretical reference can be provided for the analysis of dynamic changes of the ecological effects of graphene and their interactions with organic pollutants. Factors like pH, salt solution type, ionic strength, dissolved organic matter (DOM) in water environment affect the polymerization state of graphene in different degree. Especially, DOM can not only promote the dispersion of graphene through steric hindrance, but also promote the agglomeration of graphene by winding and cross-linking, which makes it more difficult to study the mechanism of transformation and degradation of graphene. The main reason for the change of structure and properties of graphene is the active free radical produced by graphene under light irradiation, and the mechanism of interaction between graphene and microorganisms is mainly attributed to enzymatic oxidation.
In this article, the process and mechanisms of the photo-transformation, thermal-transformation, chemical-transformation and bio-degradation of graphene are reviewed. The factors affecting the transformation and degradation of graphene in water environment and the environmental effects before and after transformation are analyzed.

Key words: graphene transformation bio-degradation environmental impact

出版日期: 2019-02-10 发布日期: 2019-02-13

ZTFLH:

O613.71

基金资助: 国家自然科学基金(41807373)

作者简介: 马李璇,2016年6月毕业于云南民族大学,获得理学学士学位。现为昆明理工大学环境科学与工程学院硕士研究生,在李凯副教授的指导下进行研究。目前主要研究领域为石墨烯的改性及对有机污染物的吸附。李凯,昆明理工大学环境科学与工程学院副教授、博士生导师。现为昆明理工大学学科方向团队“燃煤烟气净化及资源化”团队负责人。宁平,昆明理工大学环境科学与工程学院院长,党委书记,教授,博士研究生导师。王驰,昆明理工大学化学工程学院讲师,硕士研究生导师。wangchikg@163.com

引用本文:

马李璇, 李凯, 宁平, 梅毅, 王驰, 孙鑫. 石墨烯在水环境中的转化和降解行为研究进展[J]. 材料导报, 2019, 33(3): 395-401.
MA Lixuan, LI Kai, NING Ping, MEI Yi, WANG Chi, SUN Xin. Transformation and Degradation Behavior of Graphene in WaterEnvironment: a Review. Materials Reports, 2019, 33(3): 395-401.

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http://www.mater-rep.com/CN/10.11896/cldb.201903004 或 http://www.mater-rep.com/CN/Y2019/V33/I3/395

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