摘要
为了安全地,可持续地发展和利用核能,必须建立新一代的,包括先进的锕系元素分离流程及安全可靠的核废物处理/处置流程在内的核燃料循环体系。由于锕系元素络合化学的基础研究在核燃料循环体系的开发中起着十分重要的作用,近年来锕系元素与各种配体的络合成为相当热门的研究课题。有的配体作为萃取剂或反萃剂用于后处理过程中锕系元素的分离,另一些配体存在于环境中通过络合或氧化还原反应来决定锕系元素的物种形式及迁移行为。因此,只有在基础科学的层面上来研究锕系元素的络合化学,才能有助于解释和预测锕系元素在分离过程和环境迁移中的行为。许多热力学和光谱学方法可以用来研究锕系元素在溶液中的络合反应,提供关于锕系元素络合物的本性(如:离子价/共价,外界/内界络合),能量(如:自由能,热焓,热熵,热容)和结构的基础科学信息。本文有选择地介绍几种近年来常用于锕系元素络合化学研究的热力学和光谱学方法,包括微量热学,吸收光谱和荧光光谱学,以及X射线吸收光谱学。本文重点不在阐述方法原理,而在举例说明使用这些方法能得到的科学信息。
Complexation of actinide elements with various ligands has become a subject of significant interest in recent years,due to the rapid development of nuclear energy and the demand for advanced actinide separation processes.Some ligands play very important roles in actinide separations,while other ligands determine the speciation of actinides and their transport in the environment.Therefore,fundamental understanding of actinide complexation is critical to the development of advanced fuel cycles,including the used fuel reprocessing and the safe management of nuclear wastes.A number of thermodynamic and spectroscopic techniques can be applied to the studies of actinide complexation in solution,providing fundamental information on the nature（e.g.,ionic bonding vs covalency,outer sphere vs inner sphere）,energetics（e.g.,free energy,enthalpy,entropy and heat capacity） and structures of actinide complexes.This paper briefly reviews the application of selected thermodynamic and spectroscopic techniques that have been frequently used in recent years for studying actinide complexation,including microcalorimetry,optical absorption and fluorescence spectroscopy,and X-ray absorption spectroscopy.Emphasis is placed on demonstrating,with examples,the scientific information that can be extracted from the measurements with the techniques.
出处
《化学进展》
SCIE
CAS
CSCD
北大核心
2011年第7期1295-1307,共13页
Progress in Chemistry
关键词
锕系元素
络合
热力学
光谱学
actinide elements
complexation
thermodynamics
spectroscopy
