The complexation of pentavalent neptunium,Np(Ⅴ),with nitrate ion in an ionic liquid solution has been studied spectroscopically for the first time.The characteristic f-f transition absorption band of Np(Ⅴ)in the NIR...The complexation of pentavalent neptunium,Np(Ⅴ),with nitrate ion in an ionic liquid solution has been studied spectroscopically for the first time.The characteristic f-f transition absorption band of Np(Ⅴ)in the NIR region changes significantly upon the titration of nitrate ion into the solution,revealing strong complexation of Np(Ⅴ)with nitrate ion in the ionic liquid.Most notably,the absorption band of Np(Ⅴ)almost disappears when a sufficiently high concentration of nitrate ion is present in the solution.Such a rare optically“silent”species can be assigned to the 1:2 Np(Ⅴ)/nitrate complex with a centrosymmetric coordination environment where Np sits at the inversion center.展开更多
The recycling of neptunium(Np)from nuclear wastes is crucial for the sustainable development of nuclear energy,yet it is still a challenging task owing to the complexity of Np chemistry.Precise control of oxidation st...The recycling of neptunium(Np)from nuclear wastes is crucial for the sustainable development of nuclear energy,yet it is still a challenging task owing to the complexity of Np chemistry.Precise control of oxidation state is highly desirable for the effective recovery of Np.In this study,we report an innovative strategy for Np recovery through in-situ coordination and reduction of Np(Ⅴ)in a biphasic extraction system.By leveraging the synergistic effects of coordination by a P=O donating ligand(trialkyl phosphine oxide,TRPO)and reduction by hydroquinone(HQ)in the organic phase,efficient Np(Ⅴ)-to-Np(Ⅳ)conversion and high distribution ratio(D)of Np were achieved in a single extraction contact.The reduction mechanism of Np was elucidated through spectroscopic and theoretical analyses.This work enriches the redox chemistry of Np and provides a novel pathway for Np recovery in advanced nuclear fuel cycles.展开更多
The demand for ^(238)Pu (nuclear battery heat source) drives the separation of its precursor,^(237)Np,from spent nuclear fuel (SNF).However,the co-existence of multi-valence states (Ⅳ/Ⅴ/Ⅵ) of Np and similar redox b...The demand for ^(238)Pu (nuclear battery heat source) drives the separation of its precursor,^(237)Np,from spent nuclear fuel (SNF).However,the co-existence of multi-valence states (Ⅳ/Ⅴ/Ⅵ) of Np and similar redox behavior with Pu(Ⅳ) hinder the effective separation of Np.N-Butyraldehyde (n-C_(3)H_(7)CHO) selectively reduces Np(Ⅵ) to Np(Ⅴ) without reducing Pu(Ⅳ).Herein,we examined the reduction mechanisms of Np(Ⅵ) and Pu(Ⅳ) by n-C3H7CHO using relativistic density functional theory.Based on the results of the potential energy profiles,the reductions of both Np(Ⅵ) and Pu(Ⅳ) by n-C_(3)H_(7)CHO are thermodynamically feasible,whereas only the former is kinetically achievable.It uncovers that n-C_(3)H_(7)CHO can only reduce Np(Ⅵ) to Np(Ⅴ) owing to kinetically controlled selective reduction.The analyses of spin density and bond distance indicate that the reduction nature for the first Np(Ⅵ)/Pu(Ⅳ) belongs to hydrogen atom transfer,whereas that for the second one involves outer-sphere electron transfer.Localized molecular orbitals (LMOs) analysis discloses the bonding evolution during the reduction process of Np(Ⅵ)/Pu(Ⅳ).This study elucidates the reason behind the kinetically controlled selective reduction of Np(Ⅵ)/Pu(Ⅳ) by nC3H7CHO at the molecular level and offers in-depth perspectives on the isolation of specific metal ions from the view of kinetic control.展开更多
基金the financial support from the National Natural Science Foundation of China(Nos.21790372 and 21822606)Beijing Natural Science Foundation(No.JQ20041)。
文摘The complexation of pentavalent neptunium,Np(Ⅴ),with nitrate ion in an ionic liquid solution has been studied spectroscopically for the first time.The characteristic f-f transition absorption band of Np(Ⅴ)in the NIR region changes significantly upon the titration of nitrate ion into the solution,revealing strong complexation of Np(Ⅴ)with nitrate ion in the ionic liquid.Most notably,the absorption band of Np(Ⅴ)almost disappears when a sufficiently high concentration of nitrate ion is present in the solution.Such a rare optically“silent”species can be assigned to the 1:2 Np(Ⅴ)/nitrate complex with a centrosymmetric coordination environment where Np sits at the inversion center.
基金the financial support from the National Natural Science Foundation of China(22325603)the financial support from the National Natural Science Foundation of China(22376116)+3 种基金the financial support from the National Natural Science Foundation of China(22076130)the Young Elite Scientists Sponsorship Program by China Association for Science and Technology(CAST)(2023QNRC001)the Fundamental Research Funds for the Central Universities(20826041D4117)the Natural Science Foundation of Sichuan(2025ZNSFSC0109)。
文摘The recycling of neptunium(Np)from nuclear wastes is crucial for the sustainable development of nuclear energy,yet it is still a challenging task owing to the complexity of Np chemistry.Precise control of oxidation state is highly desirable for the effective recovery of Np.In this study,we report an innovative strategy for Np recovery through in-situ coordination and reduction of Np(Ⅴ)in a biphasic extraction system.By leveraging the synergistic effects of coordination by a P=O donating ligand(trialkyl phosphine oxide,TRPO)and reduction by hydroquinone(HQ)in the organic phase,efficient Np(Ⅴ)-to-Np(Ⅳ)conversion and high distribution ratio(D)of Np were achieved in a single extraction contact.The reduction mechanism of Np was elucidated through spectroscopic and theoretical analyses.This work enriches the redox chemistry of Np and provides a novel pathway for Np recovery in advanced nuclear fuel cycles.
基金supported by the National Natural Science Foundation of China(Nos.22376197,U2441225,22076188).
文摘The demand for ^(238)Pu (nuclear battery heat source) drives the separation of its precursor,^(237)Np,from spent nuclear fuel (SNF).However,the co-existence of multi-valence states (Ⅳ/Ⅴ/Ⅵ) of Np and similar redox behavior with Pu(Ⅳ) hinder the effective separation of Np.N-Butyraldehyde (n-C_(3)H_(7)CHO) selectively reduces Np(Ⅵ) to Np(Ⅴ) without reducing Pu(Ⅳ).Herein,we examined the reduction mechanisms of Np(Ⅵ) and Pu(Ⅳ) by n-C3H7CHO using relativistic density functional theory.Based on the results of the potential energy profiles,the reductions of both Np(Ⅵ) and Pu(Ⅳ) by n-C_(3)H_(7)CHO are thermodynamically feasible,whereas only the former is kinetically achievable.It uncovers that n-C_(3)H_(7)CHO can only reduce Np(Ⅵ) to Np(Ⅴ) owing to kinetically controlled selective reduction.The analyses of spin density and bond distance indicate that the reduction nature for the first Np(Ⅵ)/Pu(Ⅳ) belongs to hydrogen atom transfer,whereas that for the second one involves outer-sphere electron transfer.Localized molecular orbitals (LMOs) analysis discloses the bonding evolution during the reduction process of Np(Ⅵ)/Pu(Ⅳ).This study elucidates the reason behind the kinetically controlled selective reduction of Np(Ⅵ)/Pu(Ⅳ) by nC3H7CHO at the molecular level and offers in-depth perspectives on the isolation of specific metal ions from the view of kinetic control.
