Issue 4, 2025

Interactions of perrhenate (ReO4) and pertechnetate (TcO4) with the uranyl ion (UO22+) in acetonitrile solution: spectroscopy and theoretical calculations

Abstract

The co-extraction of pertechnetate (TcO4) along with the uranyl ion (UO22+) is a problematic issue that complicates the Plutonium Uranium Reduction EXtraction (PUREX) process for reprocessing spent nuclear fuel. Unfortunately, research on the interactions of TcO4 with UO22+ is very scarce. This work quantitatively investigated the interactions of TcO4 and its analog ReO4 with UO22+ in acetonitrile with 0.5% water content by spectrophotometric titrations including UV-Vis absorption and Raman spectroscopies. UO22+ and TcO4/ReO4 form complexes of 1 : 1 to 1 : 3 molar ratios, in which the stability constants of the UO22+–TcO4 complexes are slightly higher than those of the UO22+–ReO4 complexes. The structures of the complexes of UO22+ with TcO4/ReO4 are modeled by DFT calculations. The DFT calculations indicate that the TcO4/ReO4 anions are monodentate coordinated with UO22+. The UV-Vis and Raman spectra of the complexes are simulated, and it is found that the second solvation shell needs to be explicitly taken into account in the DFT calculations in order to obtain Raman spectra comparable to the experiments. The results in this work help understand the co-extraction behavior of TcO4 with UO22+ in spent nuclear fuel reprocessing.

Graphical abstract: Interactions of perrhenate (ReO4−) and pertechnetate (TcO4−) with the uranyl ion (UO22+) in acetonitrile solution: spectroscopy and theoretical calculations

Supplementary files

Article information

Article type
Paper
Submitted
15 Oct 2024
Accepted
28 Nov 2024
First published
02 Dec 2024

Dalton Trans., 2025,54, 1528-1540

Interactions of perrhenate (ReO4) and pertechnetate (TcO4) with the uranyl ion (UO22+) in acetonitrile solution: spectroscopy and theoretical calculations

H. Liu, S. Wei, X. Cheng, C. Xu, H. Hu and T. Sun, Dalton Trans., 2025, 54, 1528 DOI: 10.1039/D4DT02887B

To request permission to reproduce material from this article, please go to the Copyright Clearance Center request page.

If you are an author contributing to an RSC publication, you do not need to request permission provided correct acknowledgement is given.

If you are the author of this article, you do not need to request permission to reproduce figures and diagrams provided correct acknowledgement is given. If you want to reproduce the whole article in a third-party publication (excluding your thesis/dissertation for which permission is not required) please go to the Copyright Clearance Center request page.

Read more about how to correctly acknowledge RSC content.

Social activity

Spotlight

Advertisements