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作 者:邓云盼[1] 杨波[1] 余刚[2] 卓琼芳 邓述波[2] 张鸿[1]
机构地区:[1]深圳大学化学与环境工程学院,深圳518060 [2]清华大学环境学院持久性有机物研究中心,北京100084 [3]环保部华南环境科学研究所,广州510665
出 处:《化学进展》2016年第4期564-576,共13页Progress in Chemistry
基 金:国家自然科学基金项目(No.21547011;21177089;11275130;21307036);国家高技术研究发展计划(863)项目(No.2013AA06A305)资助~~
摘 要:卤代有机物是环境领域的主要污染物类型之一。氢解脱卤是实现卤代有机物降解的有效途径,而探索不同催化氢解脱卤方法已成为该领域持续的研究热点。其中,金属配位化合物因其特殊的电子效应及空间效应可有效进行氢解脱卤,从而成为近年来报道的新型催化脱卤方法。基于此,本文总结了各种类型金属配合物进行氟、氯及溴代有机物催化脱卤过程的反应类型及过程机理,指出了配合物与卤代有机物之间电子转移状况、空间结构及配体亲卤性对脱卤反应起决定作用。另外,还探讨了中心离子、配体、卤代有机物类型和还原剂等影响因素对配位催化脱卤反应的作用机制,提出了当前配位催化脱卤研究存在的问题,并对今后该领域的实用性研究进行了展望。Halogenated organic compounds(HOCs) are attributed as one of the major environmental contaminants.Hydrodehalogenation(HDH) has become an effective approach to degrade HOCs.Therefore,exploring various methods of catalytic HDH has persistently attracted many research concerns in this field.Among these methods,due to its special electronic effect and steric effect,metal complexes(MCs) have also presented the efficient catalytic dehalogenation performance.So the catalytic dehalogenation by MCs is reported as the novel HDH method in many recent studies.In this review,the reaction types and mechanisms are summarized for the catalytic dehalogenation processes of fluorinated,chlorinated,and brominated organic compounds using various MCs.It is indicated that the electron transfer conditions,spatial structure,and the affinity of ligand to halogen in HOCs play the major roles to dehalogenation reaction.Additionally,the influential factors including central metal ions,ligands,types of HOCs,reductants,etc.are discussed and analyzed for their effects on catalytic dehalogenation reaction.Finally,it is proposed about existing problems of the catalytic dehalogenation using MCs.Moreover,the future trends for the development of this method to HOCs degradation are prospected.
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