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Capturing the Elusive: A Snapshot of the Pu(IV) Hexanuclear Cluster Intermediate in the Birth of PuO2 Colloidal Nanoparticles

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Title: Capturing the Elusive: A Snapshot of the Pu(IV) Hexanuclear Cluster Intermediate in the Birth of PuO2 Colloidal Nanoparticles
Authors: Cot-Auriol, Manon, Dourdain, Sandrine, Dumas, Thomas, Tamain, Christelle, Menut, Denis, Hunault, Myrtille, Solari, Pier, Moisy, Philippe, Nikitenko, Sergey, Virot, Matthieu
Contributors: Guilbaud, Philippe
Source: Inorganic Chemistry. 64:17178-17188
Publisher Information: American Chemical Society (ACS), 2025.
Publication Year: 2025
Subject Terms: [CHIM.THEO] Chemical Sciences/Theoretical and/or physical chemistry, [CHIM] Chemical Sciences, [CHIM.RADIO] Chemical Sciences/Radiochemistry
Description: While recent studies have provided a wealth of information about the structure of oxide nanoparticles resulting from Pu(IV) hydrolysis, little is known about their formation mechanism. This article describes the stabilization and characterization of a reaction intermediate observed during the formation of PuO 2 colloidal nanoparticles in aqueous solution. The intermediate was captured by a kinetic blocking of the started hydrolysis reaction by dilution of the reacting medium into DOTA (pH 3.5), glycine (pH 2.0), or acetic acid (pH 1.1) aqueous solutions. Such an approach stopped the hydrolysis and condensation processes by complexation and allowed for stabilization of hexameric polynuclear structures of Pu(IV) that were thoroughly characterized using laboratory and synchrotron techniques (UV-vis, small angle X-ray scattering, L 3 -edge X-ray absorption spectroscopy, and M 4 -edge high energy resolution fluorescence detected-X-ray absorption near edge structure). Beyond the new insight given about the contribution of the [Pu 6 O 4 (OH) 4 ] 12+ cluster during the aqueous formation of colloidal PuO 2 nanoparticles in aqueous conditions, this study confirms the added value of synchrotron radiation for the characterization of very dilute and strongly radioactive nanostructures, paving the way for further research in the domain.
Document Type: Article
File Description: application/pdf
Language: English
ISSN: 1520-510X
0020-1669
DOI: 10.1021/acs.inorgchem.5c01938
Access URL: https://cea.hal.science/cea-05224468v1/document
https://cea.hal.science/cea-05224468v1
https://doi.org/10.1021/acs.inorgchem.5c01938
Rights: STM Policy #29
Accession Number: edsair.doi.dedup.....b6aa7c3a8e8b2b75e7a05949f41903c6
Database: OpenAIRE
Description
Abstract:While recent studies have provided a wealth of information about the structure of oxide nanoparticles resulting from Pu(IV) hydrolysis, little is known about their formation mechanism. This article describes the stabilization and characterization of a reaction intermediate observed during the formation of PuO 2 colloidal nanoparticles in aqueous solution. The intermediate was captured by a kinetic blocking of the started hydrolysis reaction by dilution of the reacting medium into DOTA (pH 3.5), glycine (pH 2.0), or acetic acid (pH 1.1) aqueous solutions. Such an approach stopped the hydrolysis and condensation processes by complexation and allowed for stabilization of hexameric polynuclear structures of Pu(IV) that were thoroughly characterized using laboratory and synchrotron techniques (UV-vis, small angle X-ray scattering, L 3 -edge X-ray absorption spectroscopy, and M 4 -edge high energy resolution fluorescence detected-X-ray absorption near edge structure). Beyond the new insight given about the contribution of the [Pu 6 O 4 (OH) 4 ] 12+ cluster during the aqueous formation of colloidal PuO 2 nanoparticles in aqueous conditions, this study confirms the added value of synchrotron radiation for the characterization of very dilute and strongly radioactive nanostructures, paving the way for further research in the domain.
ISSN:1520510X
00201669
DOI:10.1021/acs.inorgchem.5c01938