多铌钒氧簇在DMMP和CEES降解中的碱催化与氧化催化功能调控

Sarin and sulfur mustard are two kinds of typical chemical warfare agents (CWAs), which have been used in wars and terror attacks widely and cause a huge threat to the safety and health of people. The efficient decontamination of sarin and sulfur mustard under mild conditions has not only scientific significance but also practical application for protecting people's lives. This project intends to take the degradation of dimethyl methylphosphonate (DMMP, sarin analogue) and (2-chloroethyl)ethyl sulfide (CEES, sulfur mustard analogue) as catalytic model reactions, use polyoxovanadoniobate clusters as catalysts, and control the alkaline and oxidizability of catalysts through the design of catalysts. The purpose of this study is to degrade DMMP and CEES under mild condition, establish kinetic model in the homogeneous system, and propose the catalytic mechanism. Furthermore, we will investigate the synthesis methods of heterogeneous catalysts, the interaction between the catalysts and substrates in the catalytic deactivation reaction. Through this project, the efficient decontamination of DMMP and CEES under mild conditions will be realized. In addition, the structure and catalytic property relationship will be built and the active sites of catalysts and the mechanism will be revealed. These studies will lay the foundation for the potential applications as a new kind of protective material in the future.

沙林毒气和芥子气是战争和恐怖袭击中常用的两种典型化学战剂，它们对人民生命安全造成了潜在的威胁。若能在温和条件下实现对这两种分子的高效降解，不仅具有科学意义，而且对于保护人民生命安全也将具有重要的应用价值。本项目拟以酸碱性及氧化还原性可调控的多铌钒氧簇为催化剂，以沙林毒气类似物甲基磷酸二甲酯（DMMP）和芥子气类似物2-氯乙基乙基硫醚（CEES）的降解为模型反应，研究多铌钒氧簇在温和条件下催化降解DMMP和CEES特性，建立均相体系的动力学模型，解析催化作用机理；研究多铌钒氧簇催化剂在MOF孔道中装载、在LDH层间嵌入等非均相化途径以及在非均相体系中催化剂与底物分子的表界面作用性质。通过本项目的实施，创制温和条件下高效降解DMMP和CEES的多金属氧簇绿色催化剂，总结催化剂性能调控规律，揭示催化剂活性中心结构和作用机制，为其在新一代防护材料中的实际应用奠定理论基础。

近年来，随着区域冲突的升级和恐怖活动的加剧，化学战剂对军队和人民生命安全造成了严重威胁，因此化学战剂的高效催化降解成为研究的热点。本项目聚焦多铌钒氧簇的结构设计，调控其碱催化及氧化催化特性并探究其稳定负载的新途径。将其应用于神经毒剂模拟物的水解降解和芥子气模拟物的氧化降解反应中，探究表界面作用和催化机理。主要取得的成果如下：（1）设计合成了结构新颖的双阴离子簇化合物，其可配制成洗消剂在几分钟内实现G类神经毒剂模拟物DECP的水解降解和芥子气模拟物CEES的氧化降解。还制备了钒帽型多铌氧簇化合物，其可在非均相条件下催化CEES的氧化降解；（2）通过实验和理论计算相结合的方式探究了六铌氧簇催化VX模拟物氧化降解的反应机理并提出相应的活性物种为氢过氧Nb(η1-OOH)；（3）将多铌氧簇与长烷基链季铵盐或双金属氢氧化物结合，实现了在微乳体系和非均相体系中对多种化学战剂模拟物的高效催化降解。

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