分散于金属有机框架的单一铜位点促进神经毒剂模拟物降解  

Single copper sites dispersed on metal-organic frameworks boost the degradation of nerve agent simulants

作　　者：蔡春祺 陈庆庆 苏红艳 黄鹏程 毛俊杰 吴芳英 Chunqi Cai;Qingqing Chen;Hongyan Su;Pengcheng Huang;Junjie Mao;Fang-Ying Wu(School of Chemistry and Chemical Engineering,Nanchang University,Nanchang 330031,China;Key Laboratory of Functional Molecular Solids,Ministry of Education,College of Chemistry and Materials Science,Anhui Normal University,Wuhu 241002,China)

机构地区：[1]School of Chemistry and Chemical Engineering,Nanchang University,Nanchang 330031,China [2]Key Laboratory of Functional Molecular Solids,Ministry of Education,College of Chemistry and Materials Science,Anhui Normal University,Wuhu 241002,China

出　　处：《Science China Materials》2023年第6期2475-2482,共8页中国科学（材料科学（英文版）

基　　金：financially supported by the National Natural Science Foundation of China(21864018,21971002 and 22164013);the Natural Science Foundation of Jiangxi Province(20212BAB203033);the Special Fund for Graduate Innovation in Jiangxi Province(YC2022s010)。

摘　　要：神经毒剂是一类毒性极高的化学战剂,因其对人类的巨大危害,亟需实现对它们的脱毒.目前,锆基金属有机框架(Zr-MOFs)是该领域研究最广的催化剂,但仍需开发新的高效的Zr-MOFs催化剂以实现更快速的水解.本文中,我们报道了一种以UiO-66-NH_(2)为载体的铜单原子催化剂,Cu@UiO-66-NH_(2),它能极大促进神经毒剂模拟物的降解.相比于载体UiO-66-NH_(2)本身,这一单原子催化剂展现出显著的催化活性(半衰期约为2分钟)和良好的循环可用性.实验和理论研究均表明分散的单原子铜锚定于氨基而非UiO-66-NH_(2)的Zr6簇,这一螯合方式有利于与底物和产物的结合.因此,和传统的基于Zr-MOFs的催化机理不同,这一新机理能阐明催化效率增强的实质.The detoxification of nerve agents,a class of extremely toxic chemical warfare agents,is urgently needed because they have remained a threat to humanity.To date,zirconium-based metal-organic frameworks(Zr-MOFs)are the most popular catalysts in this realm.However,it is still essential to develop new and efficient catalysts based on ZrMOFs to achieve more rapid hydrolysis.Herein,we report that the single-atom catalyst(SAC)with Cu single atoms on a UiO-66-NH_(2)support(Cu@UiO-66-NH_(2))could significantly boost the degradation of the nerve agent simulant.Compared with the pristine UiO-66-NH_(2),this SAC exhibited remarkable catalytic activity with a half-life for hydrolysis of~2 min and better reusability in cyclic experiments.Both experimental and theoretical studies suggest that the atomically dispersed Cu species anchored to the amino groups rather than to the Zr6 node of UiO-66-NH_(2)acted as the catalytic active sites,leading to favorable binding geometries with the substrate and the product.A catalytic mechanism on the SAC different from that generally considered on the pristine Zr-MOFs was thus presented to elucidate the enhanced catalytic efficiency.

关 键 词：金属有机框架 单原子催化剂 神经毒剂 催化机理 催化活性 模拟物 化学战剂 催化效率 

分 类 号：TJ92[兵器科学与技术—武器系统与运用工程] TQ426[化学工程]