Effective adjustment and control of the oxidation state of plutonium(Pu)and neptunium(Np)is an indispensable component of Np/Pu separation in spent nuclear fuel reprocessing.Some hydrazine derivatives including methyl...Effective adjustment and control of the oxidation state of plutonium(Pu)and neptunium(Np)is an indispensable component of Np/Pu separation in spent nuclear fuel reprocessing.Some hydrazine derivatives including methylhydrazine(CH_(3)N_(2)H_(3))effectively achieves the reduction of Np(Ⅵ)to Np(V)without reducing Pu(Ⅳ).Herein,we explored the reduction mechanisms of Pu(Ⅳ)and Np(Ⅵ)by CH_(3)N_(2)H_(3)in HNO_(3)solution using scalar-relativistic density functional theory.We elucidated the difference in the reduction mechanism between Np(Ⅵ)and Pu(Ⅳ)ions by CH_(3)N_(2)H_(3).The energy barrier for the reduction of[NpⅥO_(2)(H_(2)O)_(5)]^(2+)and[NpⅥO_(2)(NO_(3))(H_(2)O)_(3)]^(+)by CH_(3)N_(2)H_(3)is largely different due to the coordination of nitrate ion.Moreover,the energy barrier of the reduction of[NpⅥO_(2)(H_(2)O)_(5)]^(2+)is apparently lower than that of[PuⅣ(NO_(3))_(2)(H_(2)O)_(7)]^(2+),which is in line with the experimental observations.The results of Mayer bond order and localized molecular orbitals clarify the structural evolution of the reaction pathways.Analysis of the spin density demonstrates that the first Np(Ⅵ)and Pu(Ⅳ)reduction belongs to the outer-sphere electron transfer and the second Np(Ⅵ)and Pu(Ⅳ)reduction is the hydrogen transfer.This study explains theoretically why CH_(3)N_(2)H_(3)reduces Np(Ⅵ)but not Pu(Ⅳ),and helps to design promising reductants for the Np/Pu separation in spent nuclear fuel reprocessing.展开更多
为评估处置库的安全性,核素化学形态信息是准确预测核素的运移行为研究的前提。鉴于我国核能工业的迅速发展以及建立环境中核素的确认需求,在我国开展处置库周围核素的化学形态研究具有十分重要的意义。针对地下水中元素种态分布的研究...为评估处置库的安全性,核素化学形态信息是准确预测核素的运移行为研究的前提。鉴于我国核能工业的迅速发展以及建立环境中核素的确认需求,在我国开展处置库周围核素的化学形态研究具有十分重要的意义。针对地下水中元素种态分布的研究需求,以JAVA为开发工具、MySQL作为数据库、Tomcat为容器,开发了一套B/S架构的元素种态分布模拟软件。针对模拟计算中遇到的化学反应平衡非线性方程组求解收敛困难的问题,引入了根据化学反应势能求解的方法和反应因子控制迭代步长,实现了对化学反应非线性方程快速地求解,并可拓展多相平衡计算。以塔木素地下水中镎为考察对象,利用所开发化学形态模拟软件(simulation software on chemical species,SSCS)计算环境中镎的形态和量,并对比PHREEQC的计算结果,相对偏差在10%以内,针对环境中痕量元素的分布,提供了理论计算的解决方案。展开更多
基金supported by the National Natural Science Foundation of China(Nos.U2067212,22376197,U1867205)the National Science Fund for Distinguished Young Scholars(No.21925603)。
文摘Effective adjustment and control of the oxidation state of plutonium(Pu)and neptunium(Np)is an indispensable component of Np/Pu separation in spent nuclear fuel reprocessing.Some hydrazine derivatives including methylhydrazine(CH_(3)N_(2)H_(3))effectively achieves the reduction of Np(Ⅵ)to Np(V)without reducing Pu(Ⅳ).Herein,we explored the reduction mechanisms of Pu(Ⅳ)and Np(Ⅵ)by CH_(3)N_(2)H_(3)in HNO_(3)solution using scalar-relativistic density functional theory.We elucidated the difference in the reduction mechanism between Np(Ⅵ)and Pu(Ⅳ)ions by CH_(3)N_(2)H_(3).The energy barrier for the reduction of[NpⅥO_(2)(H_(2)O)_(5)]^(2+)and[NpⅥO_(2)(NO_(3))(H_(2)O)_(3)]^(+)by CH_(3)N_(2)H_(3)is largely different due to the coordination of nitrate ion.Moreover,the energy barrier of the reduction of[NpⅥO_(2)(H_(2)O)_(5)]^(2+)is apparently lower than that of[PuⅣ(NO_(3))_(2)(H_(2)O)_(7)]^(2+),which is in line with the experimental observations.The results of Mayer bond order and localized molecular orbitals clarify the structural evolution of the reaction pathways.Analysis of the spin density demonstrates that the first Np(Ⅵ)and Pu(Ⅳ)reduction belongs to the outer-sphere electron transfer and the second Np(Ⅵ)and Pu(Ⅳ)reduction is the hydrogen transfer.This study explains theoretically why CH_(3)N_(2)H_(3)reduces Np(Ⅵ)but not Pu(Ⅳ),and helps to design promising reductants for the Np/Pu separation in spent nuclear fuel reprocessing.
文摘为评估处置库的安全性,核素化学形态信息是准确预测核素的运移行为研究的前提。鉴于我国核能工业的迅速发展以及建立环境中核素的确认需求,在我国开展处置库周围核素的化学形态研究具有十分重要的意义。针对地下水中元素种态分布的研究需求,以JAVA为开发工具、MySQL作为数据库、Tomcat为容器,开发了一套B/S架构的元素种态分布模拟软件。针对模拟计算中遇到的化学反应平衡非线性方程组求解收敛困难的问题,引入了根据化学反应势能求解的方法和反应因子控制迭代步长,实现了对化学反应非线性方程快速地求解,并可拓展多相平衡计算。以塔木素地下水中镎为考察对象,利用所开发化学形态模拟软件(simulation software on chemical species,SSCS)计算环境中镎的形态和量,并对比PHREEQC的计算结果,相对偏差在10%以内,针对环境中痕量元素的分布,提供了理论计算的解决方案。
