摘要
有机磷酸酯类神经毒剂具有极高毒性,威胁着人类的生命与健康,因此亟需开发针对其的高效降解材料.锆基金属有机框架(Zr-MOFs)材料,如MOF-808、UiO-66-NH2、NU-912-I等,能够模拟磷酸三酯酶活性中心,对神经毒剂水解展现出极高的催化能力.除了Zr-MOFs的组成和孔道尺寸外,晶体的形貌同样影响材料的催化位点可及性、亲/疏水性等,进而影响催化性能.本文通过调控NU-912和NU-912-I的生长条件,合成了绣球花状的NU-912-HYD和NU-912-I-HYD.在6%mol的催化剂用量条件下,NU-912-HYD和NU-912-I-HYD催化水解神经毒剂模拟物二甲基-4-硝基苯基磷酸(DMNP)的半衰期在1 min以内,表现出极高的催化性能.水解性能的提高是由于绣球花状的MOFs材料表面暴露出更多的活性位点以及材料亲水性的提高.进一步,通过相转化法将NU-912-HYD和NU-912-I-HYD与亲水性材料聚丙烯腈(PAN)结合制备成NU-912-HYD/PAN和NU-912-I-HYD/PAN薄膜,并将其用于湿度下对DMNP的固态水解.这些薄膜在99%相对湿度下和室温条件下,能够在3 h内完全水解DMNP,展示了良好的催化水解性能.该结果为其在防护材料方面的应用层面提供了进一步的理论基础.
Phosphorus-based nerve agents exhibit extremely high toxicity and pose a significant threat to human life and health.Therefore,it is urgently needed for the development of highly efficient detoxification materials for these agents.Zirconium-based metal-organic frameworks(Zr-MOFs),such as MOF-808,UiO-66-NH2,and NU-912-I,can mimic the active site of phosphotriesterase and demonstrate exceptional catalytic activity toward the hydrolysis of nerve agents.Besides the composition and pore size,the crystal morphology of Zr-MOFs also influences the accessibility of catalytic sites,hydrophilicity/hydrophobicity,and ultimately the catalytic performance.In this study,we synthesized hydrangea-like NU-912-HYD and NU-912-I-HYD by modulating the growth conditions of NU-912 and NU-912-I.At a catalyst loading of 6%mol,NU-912-HYD and NU-912-I-HYD reduced the half-life of the nerve agent simulant dimethyl 4-nitrophenyl phosphate(DMNP)to less than 1 minute,demonstrating enhanced catalytic performance.Experimental results confirmed that the improved hydrolysis efficiency was attributed to the increased exposure of active sites and enhanced hydrophilicity of the materials.Furthermore,NU-912-HYD and NU-912-I-HYD were combined with the hydrophilic polymer polyacrylonitrile(PAN)via phase inversion to prepare NU-912-HYD/PAN and NU-912-I-HYD/PAN composite films for solid-state DMNP hydrolysis.These films achieved complete hydrolysis of DMNP within 3 hours under 99%relative humidity,exhibiting excellent catalytic performance.These findings provide a theoretical foundation for their potential application in protective materials.
作者
路世博
侯文杰
李淑文
张晶晶
武杰
LU Shibo;HOU Wenjie;LI Shuwen;ZHANG Jingjing;WU Jie(College of Chemistry,Zhengzhou University,Zhengzhou,450001,China;State Key Laboratory of Chemistry for NBC Hazards Protection,Beijing,102205,China)
出处
《环境化学》
北大核心
2025年第7期2718-2726,共9页
Environmental Chemistry
基金
河南省自然科学基金(232300421144)资助.
关键词
神经毒剂及其模拟物
锆基金属有机框架
催化水解
聚合物
nerve agents and their simulants
zirconium-based metal-organic frameworks(Zr-MOFs)
catalytic hydrolysis
polymer
