Theoretical insights into the reduction mechanism of neptunyl nitrate by hydrazine derivatives
Theoretical insights into the reduction mechanism of neptunyl nitrate by hydrazine derivatives
复制标题
肼衍生物还原硝酸庚酯机理的理论见解
DOI：
10.1515/ract-2021-1120
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发表时间：
2022-04
影响因子：
1.8
通讯作者：
Wei-Qun Shi
中科院分区：
文献类型：
--
作者：
Zhong-Ping Cheng;Xiao-Bo Li;Qun-Yan Wu;Zhi-Fang Chai;Wei-Qun Shi
抽象。在先进的乏燃料循环中，镎的价态控制和调节对于高效分离镎具有重要意义。肼及其衍生物作为无盐试剂可以选择性地将Np（VI）还原为Np（V），但其还原机理尚不清楚。用相对论密度泛函理论研究了N_2H_4及其衍生物HOC_2H_4N_2H_3和CHON_2H_3对[NpVIO_2（H_2O）_2（NO_3）_2]的还原反应. [NpVIO_2（H_2O）_2（NO_3）_2]与三种还原剂反应的热力学能对取代基敏感，HOC_2H_4N_2H_3增强了反应的热力学能力，而CHON_2H_3则相反。HOC_2H_4N_2H_3和CHON_2H_3与N_2H_4相比具有较低的能垒，这可能与肼衍生物分子内存在氢键有关。这些氧化还原反应的本质是还原剂中的氢原子逐渐转移到镎基的轴氧原子上，伴随着N-H键的解离和Oax-H键的形成。热力学和动力学结果表明，HOC_2H_4N_2H_3还原Np（VI）是最有利的反应。本文的工作为Np（VI）还原为Np（V）提供了理论依据，这对开发更有效的游离盐还原剂用于乏燃料后处理中的镎与铀、钚的分离具有重要意义。
Abstract. In the advanced spent fuel cycle, the control and adjustment of neptunium valence state is greatly important for the highly efficient separation of neptunium. Hydrazine and its derivatives as salt-free reagents can selectively reduce Np(VI) to Np(V), but their reduction mechanisms are still unclear. We explored the reduction of [NpVIO2(H2O)2(NO3)2] by N2H4 and its two derivatives HOC2H4N2H3 and CHON2H3 using scalar relativistic density functional theory. The thermodynamic energy of the reactions [NpVIO2(H2O)2(NO3)2] with three reductants are sensitive to the substitution group, HOC2H4N2H3 enhances thermodynamic ability of the reaction and CHON2H3 shows contrary result. Both HOC2H4N2H3 and CHON2H3 have lower energy barrier compared to N2H4 based on the potential energy profiles (PEPs), which probably attributes to the intramolecular hydrogen bond of hydrazine derivatives. The nature of these redox reactions is that the hydrogen atom of reductants is gradually transferred to the axis oxygen atom of neptunyl, which accompanies the N–H bond dissociation and Oax–H bond formation. The reduction of Np(VI) with HOC2H4N2H3 is the most favorable reaction based on the thermodynamic and kinetic results. This work providestheoretical perspective into the reduction of Np(VI) to Np(V), which is beneficial to the development of more effective free-salt reductants for the separation ofneptunium from uranium and plutonium in spent fuel reprocessing.
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DOI：
10.2172/4341712
发表时间：
1957-04
期刊：
--
影响因子：
--
作者：
E. R. Irish;W. H. Reas
通讯作者：
E. R. Irish;W. H. Reas
影响因子：
1.8
作者：
Y. Ban;T. Asakura;Y. Morita
通讯作者：
Y. Ban;T. Asakura;Y. Morita
影响因子：
1.8
作者：
H. Hui;Ye Guoan;Tang Hongbin;Zheng Weifang;Li Gaoliang;Lin Rushan
通讯作者：
H. Hui;Ye Guoan;Tang Hongbin;Zheng Weifang;Li Gaoliang;Lin Rushan
影响因子：
4.6
作者：
Xia Yang;Yan-Fang Liang;Songdong Ding;Shoujian Li;Z. Chai;Dongqi Wang
通讯作者：
Xia Yang;Yan-Fang Liang;Songdong Ding;Shoujian Li;Z. Chai;Dongqi Wang
DOI：
10.1524/ract.2010.1677
发表时间：
2010
期刊：
--
影响因子：
--
作者：
T. Yan;W. Zheng;C. Zuo;L. Xian;Y. Zhang;X. Bian;R. Li;Y. Di
通讯作者：
T. Yan;W. Zheng;C. Zuo;L. Xian;Y. Zhang;X. Bian;R. Li;Y. Di