双金属与多金属复合吸附剂去除水体氟化物的研究进展
Research Progress on Bimetallic and Multimetallic Composite Adsorbents for Fluoride Removal from Aqueous Solutions
DOI: 10.12677/ms.2026.164087, PDF,   
作者: 李云飞, 孙同飞：武汉工程大学化学与环境工程学院，湖北 武汉；曾思恬：武汉工程大学兴发矿业学院资源与安全工程学院，湖北 武汉
关键词: 多金属吸附剂；层状双氢氧化物；金属有机框架；氟；Multimetallic Adsorbents； Layered Double Hydroxides； Metal-Organic Frameworks； Fluoride
摘要: 氟化物作为水体常见污染物，过量排放导致严重环境与健康问题，如氟斑牙和骨氟中毒。本文综述了双金属及多金属复合吸附剂在水体氟去除中的研究进展，聚焦吸附法作为高效、低成本处理技术的优势。常见的双金属体系包括Fe-Al、Fe-Zr、Mg-Al等氧化物/氢氧化物，以及LDH层状结构；多金属组合如Mg-La-Fe、Mg-Ce-Mn等通过协同效应提升吸附容量和选择性；此外，金属–非金属复合(如Al-Zr改性生物炭)和MOF-on-MOF异质结构(如Ce/Zr-MOF)展现出高比表面积和抗干扰能力。吸附机理主要涉及离子交换、静电吸引、内球络合和表面沉淀，多金属位点互补显著提高性能，这些材料均表现出良好的选择性和较好的吸附性能，克服单一金属的pH敏感性，适用于复杂水体。未来研究应注重绿色合成、低成本原料和工业应用，推动氟资源回收与可持续治理。
Abstract: Fluoride, as a common pollutant in water bodies, poses severe environmental and health risks due to excessive discharge, such as dental fluorosis and skeletal fluorosis. This review summarizes the research progress on bimetallic and multimetallic composite adsorbents for fluoride removal from water, focusing on the advantages of adsorption as an efficient and low-cost treatment technology. Common bimetallic systems include Fe-Al, Fe-Zr, and Mg-Al oxides/hydroxides, as well as LDH layered structures; multimetallic combinations, such as Mg-La-Fe and Mg-Ce-Mn, enhance adsorption capacity and selectivity through synergistic effects; additionally, metal-nonmetal composites (e.g., Al-Zr modified biochar) and MOF-on-MOF heterostructures (e.g., Ce/Zr-MOF) exhibit high specific surface areas and strong anti-interference capabilities. The adsorption mechanisms primarily involve ion exchange, electrostatic attraction, inner-sphere complexation, and surface precipitation. The complementarity of multimetallic sites significantly improves performance, demonstrating good selectivity and adsorption efficiency, overcoming the pH sensitivity of single-metal materials, and suitability for complex water matrices. Future research should prioritize green synthesis, low-cost raw materials, and industrial applications to promote fluoride resource recovery and sustainable management.
文章引用：李云飞, 孙同飞, 曾思恬. 双金属与多金属复合吸附剂去除水体氟化物的研究进展[J]. 材料科学, 2026, 16(4): 213-221. https://doi.org/10.12677/ms.2026.164087

参考文献

[1] 李凤嫣, 蒋天宇, 余涛, 等. 环境中氟的来源及健康风险评估研究进展[J]. 岩矿测试, 2021, 40(6): 793-807.
[2] Zhao, X., Zhang, J., Dai, Z., Lei, Y., Liu, X. and Liu, G. (2022) Simple Preparation and Efficient Fluoride Removal of La Anchored Zr-Based Metal-Organic Framework Adsorbent. Journal of Environmental Chemical Engineering, 10, Article 108807. [Google Scholar] [CrossRef] 
[3] 黄忠, 何宾宾, 张险峰, 等. 磷化工体系中氟资源回收工艺的系统协同与集成优化研究综述[J]. 生态产业科学与磷氟工程, 2025, 40(8): 70-74.
[4] Zhou, Z., Lu, Y., Zhan, W., Guo, L., Du, Y., Zhang, T.C., et al. (2022) Four Stage Precipitation for Efficient Recovery of N, P, and F Elements from Leachate of Waste Phosphogypsum. Minerals Engineering, 178, Article 107420. [Google Scholar] [CrossRef] 
[5] Rathi, B.S., Kumar, P.S., Rangasamy, G., Badawi, M. and Aminabhavi, T.M. (2024) Membrane-Based Removal of Fluoride from Groundwater. Chemical Engineering Journal, 488, Article 150880. [Google Scholar] [CrossRef] 
[6] 王怡可, 李金城, 聂耳, 等. 含氟废水处理技术研究进展[J]. 工业用水与废水, 2026, 57(1): 8-12+58.
[7] Hegde, R.M., Rego, R.M., Potla, K.M., Kurkuri, M.D. and Kigga, M. (2020) Bio-Inspired Materials for Defluoridation of Water: A Review. Chemosphere, 253, Article 126657. [Google Scholar] [CrossRef] [PubMed]
[8] 朱雅娴, 陈志辉, 徐浩元, 等. 多元金属氧化物及其复合材料用于污水除氟的研究进展[J]. 现代化工, 2026, 46(1): 23-8+35.
[9] Liu, J., Wang, Y., Li, H., Zhang, X., Zeng, M., Cao, B., et al. (2025) Carbonization-Derived Al@Carbon Composite for Efficient Fluoride Elimination: Structural Modification, Selective Adsorption, and Dual Ligand Exchange Mechanism. Journal of Colloid and Interface Science, 698, Article 138060. [Google Scholar] [CrossRef] [PubMed]
[10] Wei, Y., Wang, L., Li, H., Yan, W. and Feng, J. (2022) Synergistic Fluoride Adsorption by Composite Adsorbents Synthesized from Different Types of Materials—A Review. Frontiers in Chemistry, 10, Article 900660. [Google Scholar] [CrossRef] [PubMed]
[11] Cheng, Y., Yang, X., Duan, G., Zhang, C., Yang, W., Zhao, H., et al. (2025) Advanced Metal-Contained Composites for Fluoride Removal from Wastewater: Mechanism, Preparation, Properties and Applications. Frontiers of Chemical Science and Engineering, 19, Article 39. [Google Scholar] [CrossRef] 
[12] Musa, N., Allam, B.K., Singh, N.B. and Banerjee, S. (2023) Investigation on Water Defluoridation via Batch and Continuous Mode Using Ce-Al Bimetallic Oxide: Adsorption Dynamics, Electrochemical and LCA Analysis. Environmental Pollution, 328, Article 121639. [Google Scholar] [CrossRef] [PubMed]
[13] Yang, L., Tian, X., Liu, Z., Yu, H., Peng, Z., Hai, C., et al. (2024) Performance and Mechanism of Lanthanum-Modified MnO2 for Defluoridation from Water: The Role of MnO2 Crystal Forms. Chemical Engineering Journal, 492, Article 152343. [Google Scholar] [CrossRef] 
[14] Chen, W., Tang, H., Li, H., Zhao, Y., Wang, X., Chen, J., et al. (2023) Efficient Defluoridation of Water by Utilizing Nanosized Ce-Fe Bimetal Oxyhydroxides Encapsulated Inside Porous Polystyrene Anion Exchanger. Chemical Engineering Journal, 461, Article 141820. [Google Scholar] [CrossRef] 
[15] Ren, C., Zhou, M., Liu, Z., Liang, L., Li, X., Lu, X., et al. (2021) Enhanced Fluoride Uptake by Layered Double Hydroxides under Alkaline Conditions: Solid-State NMR Evidence of the Role of Surface >MgOH Sites. Environmental Science & Technology, 55, 15082-15089. [Google Scholar] [CrossRef] [PubMed]
[16] Tolkou, A.K. and Zouboulis, A.I. (2023) Fluoride Removal from Water Sources by Adsorption on MOFs. Separations, 10, Article 467. [Google Scholar] [CrossRef] 
[17] Wei, L., Zietzschmann, F., Rietveld, L.C. and van Halem, D. (2021) Fluoride Removal from Water by Ca-Al-CO3 Layered Double Hydroxides and Simultaneous Acidification. Journal of Water Process Engineering, 40, Article 101957. [Google Scholar] [CrossRef] 
[18] Mondal, P. and Purkait, M.K. (2019) Preparation and Characterization of Novel Green Synthesized Iron-Aluminum Nanocomposite and Studying Its Efficiency in Fluoride Removal. Chemosphere, 235, 391-402. [Google Scholar] [CrossRef] [PubMed]
[19] Águila-Martínez, I., Pérez-Tavares, J.A., González-Aguiñaga, E., Cardoso-Avila, P.E., Pérez Ladrón de Guevara, H. and Patakfalvi, R. (2025) Synthesis and Application of Fe3O4-ZrO2 Magnetic Nanoparticles for Fluoride Adsorption from Water. Inorganics, 13, Article 248. [Google Scholar] [CrossRef] 
[20] 孔德松, 程蓉, 邓敏, 等. 不同二元类水滑石对水中氟离子吸附性能研究[J]. 环境科学与技术, 2024, 47(9): 54-64.
[21] 王星天, 曹亮, 朱俊峰, 等. 镁镧铁三元金属氢氧化物纳米复合材料的合成及对水中氟砷共除的吸附性能[J]. 内蒙古水利, 2024(S2): 16-18.
[22] 刘艳芳, 高玮, 刘蕊, 等. 铝锆改性生物炭对水体低浓度氟的吸附特性[J]. 环境科学, 2023, 44(4): 2147-2157.
[23] Gitari, W.M., Izuagie, A.A. and Gumbo, J.R. (2020) Synthesis, Characterization and Batch Assessment of Groundwater Fluoride Removal Capacity of Trimetal Mg/Ce/Mn Oxide-Modified Diatomaceous Earth. Arabian Journal of Chemistry, 13, 1-16. [Google Scholar] [CrossRef] 
[24] Mei, L., Wei, J., Yang, R., Ke, F., Peng, C., Hou, R., et al. (2023) Zirconium/Lanthanum-Modified Chitosan/Polyvinyl Alcohol Composite Adsorbent for Rapid Removal of Fluoride. International Journal of Biological Macromolecules, 243, Article 125155. [Google Scholar] [CrossRef] [PubMed]
[25] Song, J., Yu, Y., Han, X., Yang, W., Pan, W., Jian, S., et al. (2024) Novel MOF(Zr)-on-MOF(Ce) Adsorbent for Elimination of Excess Fluoride from Aqueous Solution. Journal of Hazardous Materials, 463, Article 132843. [Google Scholar] [CrossRef] [PubMed]
[26] Jian, S., Shi, F., Zhu, Y., Jiang, W., Liu, Y., Yang, W., et al. (2024) Ce-MOFs and Ce/Mn Bimetallic MOFs for Efficient Fluoride Removal and Their Defluoridation Mechanism. Colloids and Surfaces A: Physicochemical and Engineering Aspects, 701, Article 134938. [Google Scholar] [CrossRef] 
[27] Liu, W., Liu, P., Yang, Y., Wu, J., Wang, J., Xu, M., et al. (2025) Engineering Oxygen Vacancies on Anorthite for Efficient Surface Adsorption of Fluoride. Surfaces and Interfaces, 57, Article 105785. [Google Scholar] [CrossRef] 

为你推荐