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天然黏土矿物储量丰富、廉价易得，独特的晶体结构和表面性质赋予其物理吸附和化学反应性能，是环境友好材料研究的热点。埃洛石属于高岭土族黏土矿物，具有中空管状结构、高比表面积、丰富孔结构、较高的机械性能、无毒害等特点，在水处理、土壤污染治理和大气污染控制等领域展现出巨大的潜力。然而天然埃洛石杂质含量多、功能性有限，经提纯加工、表面改性和功能化修饰后可提升其在环境处理方面的性能。本文介绍了埃洛石纳米管的基本物化性质以及有机改性、纳米改性、聚合物改性、复合改性等策略，系统阐述了其作为环境矿物材料的应用进展。
Abstract：Clay minerals as environmentally friendly materials are abundant, cheap, and easy to obtain. Their unique crystal structure and surface properties endow them superior physical adsorption and chemical reaction properties The environmental pollution treatment mainly depends on the structure and properties of the used materials. Halloysite belongs to one of Kaolin clay minerals. It has some characteristics of a hollow tubular structure, high specific surface area, rich pore structure, high mechanical properties, and non-toxicity. The crystal structure and adsorption characteristics of halloysite are used to treat environmental pollutants, such as dyes, heavy metal ions, organic pollutants, etc.. However, natural halloysite contains a lot of impurities and shows limited functionality. The performance of HNTs in environmental application can be improved after purification, surface modification, and functionalization. In recent years, researchers conducted some related research on structural modification and functionalization of halloysite, including heat treatment, chemical modification, and composite modification. High-temperature and acid-base treatments affect the specific surface area, porosity, and adsorption capacity of halloysite, enhancing the adsorption capacity for pollutants. The surface of halloysite is rich in hydroxyl groups(i.e., Si–OH and Al–OH), which can be used as sites for surface modification or functionalization, such as changing the surface wettability or introducing functional groups, metals nanoparticles, and metal oxides, etc.. Compounding halloysite with nanomaterials or polymers can form functional nanocomposites, which expands their applications in soil remediation, air purification, and improvement of wastewater quality. Organic substances can be introduced into the structure of halloysite through various methods such as ion exchange, surface modification, covalent bonding, and intercalation modification, thereby giving them enhanced dispersibility, stability, adsorption capacity, and chemical activity. The application of these modification methods can effectively tailor the surface properties and activities of halloysite. Grafting of silane on halloysite surfaces can directlly regulate its surface hydrophilicity and charge characteristics. Electrostatic interactions and hydrogen bonds interactions occur between halloysite and metal anions and organic dyes, which can be used for treatment of wastewater. Halloysite and modified halloysite can be used as catalyst carriers and enzyme-immobilized carriers for the degradation of pollutants. The mechanical strength and thermal stability of halloysite can be significantly improved through the deposition or coating of nanoparticles on halloysite. Since ultrafine halloysite powder is difficult to recycle and easily cause secondary pollution, the functionalization of halloysite with magnetic materials can solve the problem of separating and collecting them from the matrix after use. In addition, the performance of halloysite can be precisely controlled via changing of the size, shape, and distribution of anchored nanoparticles. The stability of the loaded nanoparticles can be improved through ligands, polymers, surfactants, or ionic liquids during the synthesis process. Halloysite can be mixed with polymer to prepare a composite for synergistic enhancement of the materials performance. In addition, the modification also gives halloysite some functions like magnetic, optical and electrical properties, providing broader possibilities for the application of halloysite in environmental fields. These application researches of halloysite in environmental area increase the economic value of halloysite minerals. However, the regeneration of halloysite after treating pollutants is still a challenge. In addition, the adsorption effect of halloysite could change in complicated polluted environments, and the type and concentration of pollutants need to be considered in specific applications. The existing research on halloysite in environmental pollutant control mainly focuses on water pollution and air pollution. Future work should focus on its application as a soil conditioner to reduce the mobility of various pollutants in the soil environment. Summary and prospects The great interest in application of halloysite as an environmental mineral material is due to its unique physicochemical properties such as tubular structure, hydrophilicity, high specific surface area, high stability, ion exchange capacity and negatively charged external surface. The application performance of halloysite in environmental pollution control fields such as water treatment and air pollution control can be greatly improved through surface modification or nanoparticle loading. However, it is necessary to address the corresponding science and technique problems. For instance, it is difficult to achieve 100% pollutant removal efficacy by halloysite in actual complex and diverse natural environments. The recovery and regeneration of halloysite powder after use should be also considered. The large-scale purification technology and surface modification technology of halloysite need to be further optimized. The future development direction in this area includes understanding the interfacial interaction mechanism, optimizing the production process, expanding the application field, and strengthening the combination with other technologies to improve the treatment efficacy. Halloysite is a promising and cost-effective material in pollutant treatment, and future studies should pay more attentions to the improvement of operability, regeneration and processing capacity in practical applications.
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基本信息:
DOI：10.14062/j.issn.0454-5648.20240187
中图分类号:TD985
引用信息:
[1]陈翔宇,刘明贤.埃洛石环境矿物材料的制备及应用研究进展[J].硅酸盐学报,2024,52(10):3230-3242.DOI:10.14062/j.issn.0454-5648.20240187.
基金信息:
国家自然基金面上项目(52073121)
2024-03-05
2024
2024-09-15
2024
2024-09-20
1
2024-08-13
2024-08-13
2024-08-13