Structural and physical investigation of ordered BaO-deficient Ba3PuO6

Ternary actinide compounds allow for a range of oxidation states and a rich but often not well-known chemistry. Here, a BaO-deficient plutonium-containing perovskite with a composition close to Ba 3 PuO 6 has been obtained via solid state synthesis. The compound was characterised using X-Ray Diffrac...

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Veröffentlicht in:Communications chemistry Jg. 8; H. 1; S. 270 - 12
Hauptverfasser: van Hattem, Andries, Popa, Karin, Wallez, Gilles, Boshoven, Jacobus, Colineau, Eric, Dahms, Eckhard, Griveau, Jean-Christophe, Hein, Herwin, Walter, Olaf, Schacherl, Bianca, Vitova, Tonya, Dardenne, Kathy, Pruessmann, Tim, Rothe, Jörg, Smith, Anna L., Konings, Rudy J. M.
Format: Journal Article
Sprache:Englisch
Veröffentlicht: London Nature Publishing Group UK 01.09.2025
Nature Publishing Group
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Schlagworte:
639/301/119/997
639/638/263/915
Absorption spectroscopy
Barium oxides
Chemistry
Chemistry and Materials Science
Chemistry/Food Science
Composition
Crystal structure
Crystallography
Energy resolution
Fine structure
Heat
Low temperature
Magnetic permeability
Magnetic properties
Oxidation
Paramagnetism
Perovskites
Phase transitions
Plutonium
Room temperature
Solid solutions
Solid state
Specific heat
Temperature dependence
Unit cell
Valence
X ray absorption
ISSN:2399-3669, 2399-3669
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Zusammenfassung:Ternary actinide compounds allow for a range of oxidation states and a rich but often not well-known chemistry. Here, a BaO-deficient plutonium-containing perovskite with a composition close to Ba 3 PuO 6 has been obtained via solid state synthesis. The compound was characterised using X-Ray Diffraction from room temperature up to 1473 K, revealing two phase transitions and ordered Ba-deficiency. X-ray Absorption Spectroscopy was performed at the Pu L 3 - and M 5 -edges. The XANES spectrum at the Pu L 3 -edge and the XANES in high-energy resolution mode at the Pu M 5 -edge both indicate a Pu(VI) oxidation state. Despite the rather complex crystallographic unit cell, Extended X-ray Absorption Fine Structure (EXAFS) spectroscopy at the Pu L 3 -edge yields Pu-O distances of 2.01(1) and 2.4(3) Å. The low-temperature heat capacity of Ba 2.875 PuO 5.875 was measured between 5 and 270 K. The heat capacity and standard entropy at 298.15 K were found to be C p = (251 ± 8) J⋅K −1 ⋅mol −1 and S m 0 = ( 318 ± 8 ) J ⋅ K − 1 ⋅ mol − 1 , respectively. The magnetic susceptibility was measured from 2 to 320 K and shows a temperature-independent paramagnetism, consistent with the hexavalent oxidation state of Pu. This article reports the first extended low-temperature heat capacity curve and a temperature-dependent magnetic susceptibility measurement in a [Rn]5 f 2 Pu-based system. The exact crystal chemistry of perovskites containing 5f elements has remained a matter of debate. Here, the authors synthesise a BaO-deficient Pu-based perovskite with a composition close to Ba3PuO6 and study the Pu oxidation state, the crystal structure and Ba/Pu ratio, reporting on thermodynamic and magnetic properties and offering new insights into Ba-Pu-O solid-state chemistry.
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ISSN:2399-3669
2399-3669
DOI:10.1038/s42004-025-01669-x