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Theoretical Study on the Reduction Mechanism of Np(VI) by Hydrazine Derivatives
Xiao-Bo Li1,2, Qun-Yan Wu2, Cong-Zhi Wang2
1Guangxi Key Laboratory of Processing for Non-ferrous Metals and Featured Materials, School of Resources, Environment and Materials, Guangxi University, Nanning 530004, China.
Abstract:
The key to effective separation of neptunium from the spent fuel reprocessing process is to adjust and control its valence state. Hydrazine and its derivatives have been experimentally confirmed to be effective salt-free reductants for reducing Np(VI) to Np(V). We theoretically studied the reduction reactions of Np(VI) with three hydrazine derivatives (2-hydroxyethyl hydrazine (HOC2H4N2H3), methyl hydrazine (CH3N2H3), and formyl hydrazide (CHON2H3)) and obtained the free radical ion mechanism and the free radical mechanism. Their potential energy profiles (PEPs) suggest that the free radical mechanism is the most probable reaction. Based on the energy barrier of the free radical ion mechanism, the trend of the reduction ability of the three hydrazine derivatives is HOC2H4N2H3 > CH3N2H3 > CHON2H3, which is in excellent agreement with the experimental results. Lastly, the analyses of natural bond orbitals (NBOs), quantum theory of atoms-in-molecules (QTAIM), and electron localization function (ELF) have been carried out to explore the bonding evolution of the structures along the reaction pathways. This work provides an insight into the reduction mechanism of Np(VI) with hydrazine derivatives from the theoretical perspective and helps to design more effective reductants for the separation of U/Np and Np/Pu in spent fuel reprocessing.
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