金属有机框架材料的绿色合成

doi:10.11962/1006-4990.2020-0148

摘要/Abstract

摘要：

金属有机框架化合物（Metal-organic frameworks,简称MOFs）是由金属离子（或簇）与有机配体配位并经由自组装而形成的一类多孔材料^[1]。MOFs具有极其发达的孔道结构,比表面积和孔容远超其他多孔材料。有机/无机杂化这一特点也赋予了MOFs其他材料（例如沸石、活性炭等）所不具备的无限结构功能可调性^[2]。此外,MOFs具有移除客体分子而主体框架完好保持的持久孔道或孔穴,这使得MOFs具有超乎寻常的化学及物理稳定性。正是基于以上这些特点,MOFs在许多领域有着丰富的应用^[3-4],例如催化^[5]、H₂储存^[6]、CO₂捕集^[7]、药物运输^[8]、污染物吸附^[9]、生物医学成像^[10]等方面。MOFs的商业化探索成为了目前的热点。MOFs的很多应用都与可持续发展及“绿色材料”有关,但MOFs本身的合成过程也需要考虑可持续性和环境影响。金属有机化学所面临的环境挑战是独特的,因为它将金属离子、有机配体的危害联系在一起,且合成过程大多需要大量能耗。主要介绍了金属有机框架材料的绿色可持续合成,主要分为4个方面：1）使用更安全或生物相容性的配体;2）使用更绿色、低成本的金属源;3）绿色溶剂的开发;4）无溶剂合成法。

关键词: 金属有机框架化合物, 多孔材料, 绿色合成

Abstract:

Metal-organic frameworks（MOFs） are a class of porous materials formed by self-assembly of metal ions（or clus-ters） with organic ligands^[1] MOFs have extremely developed pore structure,and their specific surface area and pore volume are far superior to other porous materials.The feature of organic/inorganic hybridization has also given infinite structural and functional tunability to MOFs that other materials（such as zeolite and activated carbon,etc.） do not possess^[2].In addition,MOFs have persistent pores and cavitation that remove the guest molecules while the host framework remains intact,which makes MOFs exceptionally chemically and physically stable.Based on these characteristics,MOFs have many applications in many fields^[3-4],such as catalysis^[5],H₂ storage^[6],CO₂ capture^[7],drug delivery^[8],pollutants adsorption^[9],biomedical imaging^[10] and so on.The commercialization of MOFs has become a hot spot.Many applications of MOFs are related to sustainable development and “green materials”,but the synthesis process of MOFs itself also needs to consider sustainability and environ-mental impacts.The environmental challenges facing metal organic chemistry are unique because they link the hazards of metalions and organic ligands,and most of the synthesis process requires a lot of energy.This review mainly introduces the green and sustainable synthesis of metal-organic framework materials,which are mainly divided into four aspects：1）using safer or biocompatible ligands;2）using greener,low-cost metal sources;3）development of green solvents;4）solvent-free synthesis.

Key words: metal organic frameworks, porous materials, green synthesis

中图分类号:

O611

张彦星,吴一楠,李风亭. 金属有机框架材料的绿色合成[J]. 无机盐工业, 2021, 53(2): 17-23.

Zhang Yanxing,Wu Yinan,Li Fengting. Synthesis of metal organic frameworks material[J]. Inorganic Chemicals Industry, 2021, 53(2): 17-23.

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金属盐种类	优势	缺陷
氯化物	溶解性强	腐蚀性强
硝酸盐、高氯酸盐	溶解性强	强氧化性
碳酸盐	廉价易得,副产物安全	溶解性弱
氧化物、氢氧化物	来源广泛,无有毒副产物	溶解性弱

溶剂种类	优势	缺陷
传统有机溶剂	溶解性强,易形成模板	毒性强,成本高,副产物有毒,处置困难
绿色有机溶剂	绿色安全,毒性较低	成本较高
离子溶剂	难挥发,易回收	毒性强,稳定性较低
水	绿色安全,成本低,无有毒副产物	溶解性较低,适用范围较小
超（近）临界水	反应速率高,无有毒副产物	能耗高,不适用于热稳定性低的配体

方法	优势	缺陷
热化学法	产率高,反应彻底,副产物少	能耗高,不适用于热稳定性低的配体
干球磨法	能耗低,可连续反应	反应速率低,反应不彻底
液体辅助球磨法	反应较彻底,反应速率快,可连续反应	液体添加量难控制,适用范围较小

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