杯芳烃衍生物萃取剂分离An(Ⅲ)/Ln(Ⅲ)

Calixarene Derivatives for An(Ⅲ)/Ln(Ⅲ) Separation in Nuclear Fuel Reprocessing

硝酸体系中三价镧系元素与锕系分离的选择性萃取剂的合成与选择是分离-嬗变的重要研究方向之一。配位基的预组织性对萃取剂的萃取能力和选择性具有重要作用,杯芳烃的结构特征为配位基的预组织提供了理想的平台。20世纪90年代以来,研究者们合成了大量新型杯芳烃衍生物萃取剂,萃取分离硝酸溶液中An(Ⅲ)/Ln(Ⅲ),在杯芳烃衍生物萃取剂的结构与性能关系方面做了大量研究,获得一些共性规律性认识。本文在简要说明配位基预组织性对提高萃取能力和分离能力的作用基础上,详细综述了近20年在二苯基氨基甲酰甲基氧化膦(CMPO)、烷基氧化膦、吡啶酰胺等配位基修饰杯芳烃分离An(Ⅲ)/Ln(Ⅲ)的研究进展,阐明了杯芳烃衍生物的结构与配位基的预组织性、萃取能力和An(Ⅲ)/Ln(Ⅲ)分离能力的关系,展望了杯芳烃衍生物结构修饰研究方向及其在乏燃料后处理中的应用前景。

In the process of partitioning HLW,an urgent subject is focus on the development of extraction ligands for actinides（An（Ⅲ）） over lanthanides（Ln（Ⅲ）） with excellent selectivity.It is well known that the preorganization of ligands considerably improves their extraction capacity and selectivity to certain cations.Calixarenes offer ideal platforms to such preorganization.From the 1990s on,large amounts of calixarene derivatives bearing various complexation functionalites to An（Ⅲ） have been synthesized.Many of them showed improved extraction properties and higher extraction selectivity to An（Ⅲ）.In this review,the An（Ⅲ）/Ln（Ⅲ） extraction properties of various calixarene derivatives bearing ligands,such as carbamoylmentylphosphine oxide,dialkylphosphine oxide,picolinamide,and other function moities,were summarized at large.Emphasis was placed on the relationship of the structures of the calixarene derivatives to the preorganization of ligands,the extraction properties and the separation factor of An（Ⅲ）/Ln（Ⅲ）.The developing directions and the potential application of such derivatives for An（Ⅲ）/Ln（Ⅲ） separation were described.