Because HO is thermally unstable, it seems to be difficult to synthesize peroxides at elevated temperatures. We describe here the in situ generation of peroxide that is incorporated in a new uranyl peroxo complex, HT-UPO1, through the hydrothermal treatment of uranyl nitrate at 150 °C in the presence of organic ligands. In this novel process, a highly conjugated aromatic carboxylate linker, ()-4-[2-(pyridin-4-yl)vinyl]benzoic acid (H), plays a crucial role by inducing the reduction of oxygen in air to form peroxide in situ and coordinating with uranyl to promote the preferred formation of thermally stable HT-UPO1. This work expands our knowledge on the speciation and chemistry of uranyl peroxide compounds and also sheds light on the possibility of their synthesis under more harsh conditions.
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http://dx.doi.org/10.1021/acs.inorgchem.0c03661 | DOI Listing |
HO produced from water radiolysis is expected to play a significant role in radiation induced oxidative dissolution of spent nuclear fuel under the anoxic conditions of a deep geological repository if the safety-barriers fail and ground water reaches the fuel. It was recently found that the coordination chemistry between U(vi), HCO and HO can significantly suppress HO induced dissolution of UO in 10 mM bicarbonate. This was attributed to the much lower reactivity of the U(vi)O-coordinated O as compared to free HO.
View Article and Find Full Text PDFJ Am Chem Soc
April 2024
Hainan Institute of East China Normal University, Shanghai Key Laboratory of Green Chemistry and Chemical Processes, State Key Laboratory of Petroleum Molecular & Process Engineering, School of Chemistry and Molecular Engineering, East China Normal University, 3663 North Zhongshan Road, Shanghai 200062, P.R. China.
The C-F bond is the strongest covalent single bond (126 kcal/mol) in carbon-centered bonds, in which the highest electronegativity of fluorine (χ = 4) gives rise to the shortest bond length (1.38 Å) and the smallest van der Waals radius ( = 1.47 Å), resulting in enormous challenges for activation and transformation.
View Article and Find Full Text PDFChemistry
July 2023
Department of Civil and Environmental Engineering and Earth Sciences, University of Notre Dame, Notre Dame, IN 46556, USA.
Electrospray ionization tandem mass spectrometry with collision-induced dissociation (ESI-MS/MS) was utilized to study the gas phase fragmentation of uranyl peroxide nanoclusters with hydroxo, peroxo, oxalate, and pyrophosphate bridging ligands. These nanoclusters fragment into uranium monomers and dimers with mass-to-charge (m/z) ratios in the 280-380 region. The gas phase fragmentation of each cluster studied yields a distinct UO anion attributed to the cleavage of a uranyl ion bound to 2 peroxide groups, along with other anions that can be attributed to the initial composition of the nanoclusters.
View Article and Find Full Text PDFInorg Chem
June 2022
Department of Chemistry, School of Engineering Sciences in Chemistry, Biotechnology and Health, KTH Royal institute of Technology, SE-10044 Stockholm, Sweden.
Hydrogen peroxide is produced upon radiolysis of water and has been shown to be the main oxidant driving oxidative dissolution of UO-based nuclear fuel under geological repository conditions. While the overall mechanism and speciation are well known for granitic groundwaters, considerably less is known for saline waters of relevance in rock salt or during emergency cooling of reactors using seawater. In this work, the ternary uranyl-peroxo-chloro and uranyl-peroxo-bromo complexes were identified using IR, Raman, and nuclear magnetic resonance (NMR) spectroscopy.
View Article and Find Full Text PDFACS Omega
May 2022
Department of Chemistry, KTH Royal Institute of Technology, Teknikringen 30, Stockholm SE-100 44, Sweden.
The interfacial radiation chemistry of UO is of key importance in the development of models to predict the corrosion rate of spent nuclear fuel in contact with groundwater. Here, the oxidative dissolution of UO induced by radiolytically produced HO is of particular importance. The difficulty of fitting experimental data to simple first-order kinetics suggests that additional factors need to be considered when describing the surface reaction between HO and UO.
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