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Theoretical perspectives on the reduction of Pu(Ⅳ)and Np(Ⅵ)by methylhydrazine in HNO_(3)solution:Implications for Np/Pu separation
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作者 Xiaobo Li Qunyan Wu +3 位作者 Congzhi Wang Jianhui Lan Meng Zhang Weiqun Shi 《Chinese Chemical Letters》 SCIE CAS CSCD 2024年第7期306-312,共7页
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
关键词 NEPTUNIUM PLUTONIUM methylhydrazine Reduction mechanism Np/Pu separation
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