Loading…

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...

Full description

Saved in:
Bibliographic Details
Published in:Physical chemistry chemical physics : PCCP 2022-07, Vol.24 (29), p.17782-17791
Main Authors: Li, Xiao-Bo, Wu, Qun-Yan, Wang, Cong-Zhi, Lan, Jian-Hui, Zhang, Meng, Gibson, John K., Chai, Zhi-Fang, Shi, Wei-Qun
Format: Article
Language:English
Subjects:
Citations: Items that this one cites
Items that cite this one
Online Access:Get full text
Tags: Add Tag
No Tags, Be the first to tag this record!
Description
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.
ISSN:1463-9076
1463-9084
DOI:10.1039/d2cp01730j