碳基材料水相光化学老化:结构解析、机制与理论研究进展

Photochemical Aging of Carbon-Based Materials in Water: A Review of Structural Analysis, Mechanisms, and Theoretical Advances

  • 摘要: 碳基材料,包括人为源的碳量子点(Carbon Quantum Dots, CQDs)、碳纳米管(Carbon Nanotubes, CNTs)、石墨烯(Graphene, GR)及其衍生物(Graphene Oxide, GO),以及自然源的烟炱(soot)和生物炭(Biochar)等,因其独特的多尺度结构特征和广泛的应用前景而备受关注。文章系统综述这些碳基材料在水相环境中的光化学老化行为,重点揭示其作用机制与理论进展。首先,系统总结了各类碳基材料在微观形貌、晶体结构、表面官能团及异质性成分上的差异。在此基础上探讨了材料本征属性(如碳原子杂化、表面缺陷、官能团类型及金属杂质含量)如何协同调控其光化学老化的速率和路径。。进一步地,文章深入剖析了不同碳基材料在水相中“光激发-载流子分离-界面反应”的共通老化机制及其主导路径切换的调控因素。此外,还总结了当前先进表征技术(如原位光谱、高分辨质谱)及理论计算(DFT/AIMD)在解析碳基材料原始结构及老化中间产物方面的应用进展,为全面理解该类材料在水环境中的长期归趋与生态风险提供了关键理论基础。

     

    Abstract: Carbon-based materials, including anthropogenic carbon quantum dots (CQDs), carbon nanotubes (CNTs), graphene (GR) and its derivatives (GO), as well as natural soot and biochar, have garnered significant attention due to their unique multi-scale structural characteristics and broad application prospects. This review systematically summarizes the differences in micro-morphology, crystal structure, surface functional groups, and heterogeneous composition of various carbon-based materials. On this basis, it explores how intrinsic material properties (such as carbon atom hybridization, surface defects, functional group types, and metal impurity content) synergistically regulate the rate and pathway of their photochemical aging. Furthermore, the article delves into the unified aging mechanism of “photoexcitation - charge carrier separation - interfacial reaction” for different carbon-based materials in the aqueous phase, along with the regulatory factors governing the switching of dominant pathways. Additionally, the current advances in advanced characterization techniques (e.g., in-situ spectroscopy, high-resolution mass spectrometry) and theoretical calculations (DFT/AIMD) for resolving the pristine structures and aging intermediates of carbon-based materials are summarized, providing a key theoretical foundation for a comprehensive understanding of the long-term fate and ecological risks of such materials in aquatic environments.

     

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