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Reduction of Np( vi ) with hydrazinopropionitrile via water-mediated proton transfer
Effectively adjusting and controlling the valence state of neptunium (Np) is essential in its separation during spent fuel reprocessing. Hydrazine and its derivatives as free-salts can selectively reduce Np( vi ) to Np( v ). Reduction mechanisms of Np( vi ) with hydrazine and four derivatives have b...
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Published in: | Physical chemistry chemical physics : PCCP 2022-07, Vol.24 (29), p.17782-17791 |
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Main Authors: | , , , , , , , |
Format: | Article |
Language: | English |
Subjects: | |
Citations: | Items that this one cites Items that cite this one |
Online Access: | Get full text |
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Summary: | Effectively adjusting and controlling the valence state of neptunium (Np) is essential in its separation during spent fuel reprocessing. Hydrazine and its derivatives as free-salts can selectively reduce Np(
vi
) to Np(
v
). Reduction mechanisms of Np(
vi
) with hydrazine and four derivatives have been explored using multiple theoretical methods in our previous works. Herein, we examine the reduction mechanism of Np(
vi
) with hydrazinopropionitrile (NCCH
2
N
2
H
3
) which exhibits faster kinetics than most other hydrazine derivatives probably due to its σ–π hyperconjugation effect. Free radical ion pathways I, II and III involving the three types of hydrazine H atoms were found that correspond to the experimentally established mechanism of reduction of two Np(
vi
)
via
initial oxidation to [NCCH
2
N
2
H
3
]
+
˙, followed by conversion to NCCH
2
N
2
H (+2H
3
O
+
) and ultimately to CH
3
CN + N
2
. Potential energy profiles suggest that the second redox stage is rate-determining for all three pathways. Pathway I with water-mediated proton transfer is energetically preferred for hydrazinopropionitrile. Analyses using the approaches of localized molecular orbitals (LMOs), quantum theory of atoms in molecules (QTAIM), and intrinsic reaction coordinate (IRC) elucidate the bonding evolution for the structures on the reaction pathways. The results of the spin density reveal that the reduction of the first Np(
vi
) ion is the outer-sphere electron transfer, while that of the second Np(
vi
) ion is the hydrogen transfer. This work offers new insights into the nature of reduction of Np(
vi
) by hydrazinopropionitrile
via
water-mediated proton transfer, and provides a basis for designing free-salt reductants for Np separations. |
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ISSN: | 1463-9076 1463-9084 |
DOI: | 10.1039/d2cp01730j |