Theoretical prediction of a graphene-like 2D uranyl material with p-orbital antiferromagnetism

Zhao, Xiaokun; Cao, Changsu; Liu, Jin‐Cheng; Lu, Jun‐Bo; Li, Jun; Hu, Han‐Shi

doi:10.1039/d2sc02017c

Cited by 3 publications

(3 citation statements)

References 88 publications

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“…The optimization calculations were carried out using the hybrid density functional B3LYP , within the Gaussian 16 program, as previously described in the calculations for actinide complexes. − The 6-31G(d) basis set was used for the C, O, N, and H atoms, while the relativistic effective core potential (RECP) with 60 core electrons and the ECP60MWB-SEG valence basis set , were applied for the Np atom. The aqueous environment was simulated using the solvation model density (SMD).…”

Section: Methodsmentioning

confidence: 99%

Insights into the Reduction Mechanisms of Np(VI) to Np(V) by Carbohydrazide

Wang

et al. 2023

J. Phys. Chem. A

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An efficient approach to Np separation in the Plutonium Uranium Reduction EXtraction (PUREX) process is to adjust Np(VI) to Np(V) by free-salt reductants, such as hydrazine and its derivatives. Recently, carbohydrazide (CO(N 2 H 3 ) 2 ), a derivative of hydrazine and urea, has received much attention, which can reduce Np(VI) to Np(V) in the extraction reprocessing of spent nuclear fuel. Herein, according to the experimental observations, we examine the reduction mechanism of four Np(VI) by one carbohydrazide molecule using multiple theoretical calculations. The fourth Np(VI) reduction with a 22.26 kcal mol −1 energy barrier is the rate-determining step, which is in accordance with the experimental observations (20.54 ± 1.20 kcal mol −1 ). The results of spin density reflect that the reduction of the first and third Np(VI) ion is an outer-sphere electron transfer, while that of the second and fourth Np(VI) ion is the hydrogen transfer. Localized molecular orbitals (LMOs) uncover that the breaking of the N−H bond and formation of the O yl −H bond are accompanied by the reaction from initial complexes (ICs) to intermediates (INTs). This work offers basic perspectives for the reduction mechanism of Np(VI) to Np(V) by CO(N 2 H 3 ) 2 , which is also expected to design excellent free-salt Np(VI) reductants for the separation of Np in the advanced PUREX process.

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Section: Methodsmentioning

confidence: 99%

Insights into the Reduction Mechanisms of Np(VI) to Np(V) by Carbohydrazide

Wang

et al. 2023

J. Phys. Chem. A

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“…Based on the best-substituted site, as discussed below, we explored the effect of electron-withdrawing (Br, CF 3 ) and electron-donating (OH) groups on Am(III)/Eu(III) separation (displayed in Scheme ). Computational chemistry can provide reliable results for the more complicated calculations in actinide chemistry, thanks to its exciting development. − We theoretically explored different substituent groups of Et-Tol-DAPhen and evaluated the Am(III)/Eu(III) separation performance. This work can provide useful information in understanding the role of electron-withdrawing and electron-donating groups in tuning the selectivity of Et-Tol-DAPhen derivatives and pave the way for designing new ligands modified by substituted groups with better An(III)/Ln(III) selectivity.…”

Section: Introductionmentioning

confidence: 99%

Theoretical Insights into the Substitution Effect of Phenanthroline Derivatives on Am(III)/Eu(III) Separation

Lei

Wang

et al. 2023

Inorg. Chem.

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Separation of trivalent actinides (An(III)) and lanthanides (Ln(III)) poses a huge challenge in the reprocessing of spent nuclear fuel due to their similar chemical properties. N,N′-Diethyl-N,N′-ditolyl-2,9-diamide-1,10-phenanthroline (Et-Tol-DAPhen) is a potential ligand for the extraction of An(III) from Ln(III), while there are still few reports on the effect of its substituent including electron-withdrawing and electron-donating groups on An(III)/Ln(III) separation. Herein, the interaction of Et-Tol-DAPhen ligands modified by the electron-withdrawing groups (CF3, Br) and electron-donating groups (OH) with Am(III)/Eu(III) ions was investigated using scalar relativistic density functional theory (DFT). The analyses of bond order, quantum theory of atoms in molecules (QTAIM), and molecular orbital (MO) indicate that the substitution groups have a slight effect on the electronic structures of the [M(L-X)(NO3)3] (X = CF3, Br, OH) complexes. However, the thermodynamic results suggest that a ligand with the electron-donating group (L-OH) improves the extraction ability of metal ions, and the ligand modified by the electron-withdrawing group (L-Br) has the best Am(III)/Eu(III) selectivity. This work could render new insights into understanding the effect of electron-withdrawing and electron-donating groups in tuning the selectivity of Et-Tol-DAPhen derivatives and pave the way for designing new ligands modified by substituted groups with better extraction ability and An(III)/Ln(III) selectivity.

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“…In addition, to evaluate the role of preorganization of the ligand on Am(III)/Eu(III) selectivity, L 3 is further preorganized with the amide group on the basis of L 2 . With the rapid development of actinide computational chemistry, ,− theoretical calculations can provide reliable results to elucidate the solvent extraction of An(III)/Ln(III) ions. ,− Here, we explore the electronic structures of L 1 – L 4 as well as their coordination modes, bonding properties, and extraction reactions with Am(III) and Eu(III) using scalar relativistic density functional theory (DFT). This study provides valuable information for understanding the mechanism by which the combination of N and O donor modes affects Am(III)/Eu(III) selectivity and further guides us to design excellent ligands with a higher An(III)/Ln(III) separation factor.…”

Section: Introductionmentioning

confidence: 99%

Heterocyclic Ligands with Different N/O Donor Modes for Am(III)/Eu(III) Separation: A Theoretical Perspective

Su,

Wu,

Wang

et al. 2023

Inorg. Chem.

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Excellent "CHON" compatible ligands based on a heterocyclic skeleton for the separation of trivalent actinides [An(III)] from lanthanides [Ln(III)] have been widely explored, the aim being spent nuclear fuel reprocessing. The combination mode of a soft/hard (N/O) donor upon the coordination chemistry of An(III) and Ln(III) should play a vital role with respect to the performance of ligands. As such, in this work, two typical experimentally available phenanthroline-derived tetradentate ligands, CyMe 4 -BTPhen (L 1 ) and Et-Tol-DAPhen (L 4 ), and two theoretically designed asymmetric tetradentate heterocyclic ligands, L 2 and L 3 , with various N/O donors were investigated using scalar relativistic density functional theory. We have evaluated the electronic structures of L 1 −L 4 and their coordination modes, bonding properties, and extraction reactions with Am(III) and Eu(III). We found that the Am/Eu−N interactions play a more important role in the orbital interactions between the ligand and Am(III)/Eu(III) ions. Compared with those of L 1 , the coordinated O atoms of L 2 and L 4 weaken the metal−N bonds. The Am(III)/Eu(III) selectivity follows the order L 1 > L 2 > L 4 based on the change in Gibbs free energy, reflecting the fact that the Am(III)/Eu(III) selectivity of the ligand is affected by the number of coordinated N atoms. In addition, L 3 displays the strongest binding ability for Am(III)/Eu(III) ions and the smallest Am(III)/ Eu(III) selectivity among the four ligands, due to its structural preorganization. This work clarifies the influence of the number of coordinated N and O atoms of ligands on Am(III)/Eu(III) selectivity, which provides valuable fundamental information for the design of efficient ligands with N and O donors for An(III)/Ln(III) separation.

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Theoretical prediction of a graphene-like 2D uranyl material with p-orbital antiferromagnetism

Abstract: Versatile graphene-like two-dimensional materials with s-, p- and d-block elements have aroused significant interests because of their extensive applications while there is a lack of f-block one. Herein we report...

Cited by 3 publications

References 88 publications

Insights into the Reduction Mechanisms of Np(VI) to Np(V) by Carbohydrazide

Insights into the Reduction Mechanisms of Np(VI) to Np(V) by Carbohydrazide

Theoretical Insights into the Substitution Effect of Phenanthroline Derivatives on Am(III)/Eu(III) Separation

Heterocyclic Ligands with Different N/O Donor Modes for Am(III)/Eu(III) Separation: A Theoretical Perspective

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