摘要
基于固体Al阴极分离锕系元素(An)与裂变产物(FP)的电解精炼技术是极具前景的干法后处理流程之一。本研究采用暂态电化学法系统研究了Pu^(3+)在固体Al阴极上的电化学行为。循环伏安法(CV)和方波伏安法(SWV)研究结果表明,Pu^(3+)在Al阴极上可一步还原为合金,且该反应为不可逆,Pu^(3+)与Al形成合金的电位与温度的关系式为E^(θ,*)(Pu^(3+)/PuAl n)(vs.Cl-/Cl_(2))=-2.944+9.84×10^(-4)T。开路计时电位法(OCP)结合相图表明,Pu^(3+)在固体Al阴极上可生成Pu_(3)Al、PuAl、PuAl_(2)、PuAl_(3)和PuAl_(4)五种合金化合物,且计算得到了不同温度时PuAl_(4)的Gibbs生成自由能。
The electrolytic separation of actinides(An)from fission products(FPs)on solid Al cathode is one of the most promising pyrochemical reprocessing processes.In this work,the electrochemical behaviour of Pu^(3+)on active Al solid cathode was studied through the transient electrochemical method.Based on the results of cyclic voltammetry(CV)and square wave voltammetry(SWV),Pu^(3+)can be reduced into alloy through a one-step three-electrons transfer process on Al cathode,and the reaction is irreversible.The relationship between the reduction potential of the alloy formed by Pu^(3+)with Al and temperature is E^(θ,*)(Pu^(3+)/PuAl n)(vs.Cl-/Cl_(2))=-2.944+9.84×10^(-4)T.Five Pu alloys(involving Pu_(3)Al,PuAl,PuAl_(2),PuAl_(3),and PuAl_(4))are formed according to the results of open circuit chronopotentiometry(OCP)together with phase diagrams of Pu-Al.Furthermore,the formation Gibbs free energies of PuAl_(4)at different temperature are calculated.
作者
孟照凯
林如山
王有群
陈辉
宋鹏
何辉
叶国安
MENG Zhao-kai;LIN Ru-shan;WANG You-qun;CHEN Hui;SONG Peng;HE Hui;YE Guo-an(China Institute of Atomic Energy,P.O.Box 275(26),Beijing 102413,China;State Key Laboratory of Nuclear Resources and Environment,East China University of Technology,Nanchang 330013,China)
出处
《核化学与放射化学》
CAS
CSCD
北大核心
2023年第2期133-138,I0003,共7页
Journal of Nuclear and Radiochemistry
