锆基金属-有机骨架呼吸道防护材料研究进展  

Research Progress on Zirconium-based Metal-organic Frameworks Respiratory Protection Materials

作　　者：王馨博[1] 苏茹月 栗丽[1,2] 梁国杰 赵越[1] 栾志强 李凯[1] 习海玲[1,2] WANG Xinbo;SU Ruyue;LI Li;LIANG Guojie;ZHAO Yue;LUAN Zhiqiang;LI Kai;XI Hailing(Research Institute of Chemical Defense,Beijing 100191,China;State Key Laboratory of NBC Protection for Civilian,Beijing 102205,China)

机构地区：[1]防化研究院,北京100191 [2]国民核生化灾害防护国家重点实验室,北京102205

出　　处：《材料导报》2020年第23期23121-23130,共10页Materials Reports

基　　金：国家重点研发计划项目(2016YFC0204205);国家自然科学基金(21876204);国民核生化灾害防护国家重点实验室基金(SKLNBC2018-04)。

摘　　要：在执行作战、应急救援及事故处理等任务的过程中,经典化学战剂(Chemical warfare agents,CWAs)和有毒工业化学品(Toxic industrial chemicals,TICs)扩散均会对人员呼吸安全造成严重威胁,从而要求防毒面具必须能够同时对CWAs和TICs提供广谱有效的防护。目前,国内外过滤式防毒面具主要使用ASZM-TEDA型浸渍活性炭作为防护材料,该材料对TICs防护性能较差,且表面物理吸附的有毒物质分子室温下易发生解吸。因此,需要设计开发新型呼吸道防护材料,在对CWAs和TICs进行广谱防护的同时,实现有毒物质的原位降解。金属-有机骨架(Metal-organic frameworks,MOFs)材料比表面积高、结构多样,其模块化的构筑方式使人们可以灵活地对MOFs性质进行按需设计,因而被认为是最有潜力实现有毒物质广谱防护和原位消毒的新型呼吸道防护材料。其中,锆基金属-有机骨架(Zr-MOFs)材料具有丰富的表面活性中心与良好的稳定性,并表现出优异的CWAs和TICs吸附与催化降解性能,近年来受到各国研究者的关注。就用于CWAs和TICs吸附消除的Zr-MOFs材料而言,目前的研究工作主要集中于UiO-66-NH 2体系。研究人员分别对其粉体和成型颗粒的吸附性能进行了系统研究,发现UiO-66-NH 2粉体对NH 3、Cl 2和NO 2等多种TICs具有优异的本征吸附能力,并进一步探索通过构筑等级孔隙结构改善有毒物质分子在UiO-66-NH 2成型颗粒孔道内的扩散性质。针对用于CWAs和TICs催化降解的Zr-MOFs材料,目前的研究工作主要围绕具有不同节点连接数的一系列Zr-MOFs展开。研究人员通过优化孔径尺寸、节点连接数以及有机配体种类,实现了对Zr-MOFs有毒物质催化降解性能的有效调控,并拓展研究了Zr-MOFs在多相缓冲介质及纯液体环境中对有毒物质的催化降解能力,以推进其作为防护材料的实际应用。本文围绕Zr-MOFs呼吸道防护材料,在分析其结构与表面酸碱性�During the process of combat,emergency rescue and accident handling,both chemical warfare agents(CWAs)and toxic industrial chemicals(TICs)diffusion will pose a serious threat to the breathing safety of personnel.Therefore,the respirators are required to provide broad-spectrum protection against CWAs and TICs at the same time.The activated carbon impregnated with copper,silver,zinc,molybdenum,and triethy-lenediamine,known as the ASZM-TEDA carbon,is the main protection material used in current gas masks for military and emergency response personnel.Although a variety of chemicals are added,the ASZM-TEDA carbon still has some limitations such as poor protection performance against TICs and a high risk of physically adsorbed toxic molecules releasing at room temperature.It is thus urgent to develop novel respiratory protection materials with broad-spectrum protection and in-situ degradation capabilities against both CWAs and TICs.Metal-organic frameworks(MOFs),characterized by their huge specific surface areas,diverse structures and on-demand modular design,are considered as the novel respiratory protection materials with the greatest potential to achieve broad-spectrum protection and in-situ degradation against toxic chemicals.In recent years,the zirconium-based metal-organic frameworks(Zr-MOFs)have been extensively studied due to their high specific surface areas,various surface active sites,remarkable stabilities,as well as excellent CWAs/TICs adsorption and catalytic degradation performance.In terms of Zr-MOFs used for the adsorption removal of CWAs and TICs,current research work mainly focuses on UiO-66-NH 2.Researchers have systematically studied the adsorption properties of UiO-66-NH 2 powders and granules.They found that UiO-66-NH 2 powders shows excellent intrinsic adsorption capacities for many TICs,such as NH 3,Cl 2,and NO 2.The hierarchical structure was further developed in UiO-66-NH 2 to increase the diffusion rates of toxic molecules through the pores of UiO-66-NH 2 granules.In terms of Zr-MOFs used fo

关 键 词：锆 金属-有机骨架 化学战剂 有毒工业化学品 呼吸道防护 吸附 催化降解 

分 类 号：TB34[一般工业技术—材料科学与工程] TJ92[兵器科学与技术—武器系统与运用工程]