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胶体性质如何驱动锕系元素与羧酸表面活性剂在溶胶中的相互作用:迈向具有介孔纳米多孔锕系氧化物材料。

How colloid nature drives the interactions between actinide and carboxylic surfactant in sol: Towards a mesostructured nanoporous actinide oxide material.

机构信息

Institut de Chimie Séparative de Marcoule, CEA, UMR 5257 CEA-CNRS-UM-ENSCM, 30207 Bagnols-sur-Cèze, France.

Institut de Chimie Séparative de Marcoule, CEA, UMR 5257 CEA-CNRS-UM-ENSCM, 30207 Bagnols-sur-Cèze, France.

出版信息

J Colloid Interface Sci. 2023 May;637:207-215. doi: 10.1016/j.jcis.2023.01.087. Epub 2023 Jan 21.

Abstract

HYPOTHESIS

The key to prepare a mesostructured porous material by a soft-template route coupled to a colloidal sol-gel process is to control the surfactant-colloid interface. In the case of tetravalent actinide ions, their high reactivity in aqueous media always leads to uncontrolled and irreversible condensation. The addition of a complexing agent to the sol may moderate these reactions and enhances the interaction between the colloids and the surfactant to in fine prepare a mesostructured nanoporous actinide oxide material.

EXPERIMENTS

Several colloidal sols were prepared without and with formic acid as complexing agent by varying the molar ratios between thorium, carboxylic surfactant and pH. Small and Wide Angle X-ray Scattering were used to characterize the nature of the colloids, their interaction with the surfactant and the final ThO materials.

FINDINGS

Depending on the colloid nature, hexagonal or worm-like hybrid mesophase is formed. The thermal treatment of the worm-like mesophase with a sufficient amount of Th-formic acid hexameric species coated at the surface of surfactant micelles generates micrometric ThO nanofibers. This material having an accessible porosity opens new perspectives to be impregnated with minor actinide solutions offering a promising safety method for the fabrication of mixed oxide nuclear fuel and the minor actinide transmutation.

摘要

假设

通过软模板途径与胶体溶胶-凝胶过程相结合来制备介孔多孔材料的关键是控制表面活性剂-胶体界面。对于四价锕系元素离子,它们在水介质中的高反应性总是导致不可控制和不可逆的缩合。在溶胶中加入络合剂可以调节这些反应,并增强胶体与表面活性剂之间的相互作用,最终制备出具有介孔纳米多孔锕系氧化物材料。

实验

通过改变钍、羧酸表面活性剂和 pH 值之间的摩尔比,在没有和有甲酸作为络合剂的情况下制备了几种胶体溶胶。小角和广角 X 射线散射用于表征胶体的性质、它们与表面活性剂的相互作用以及最终的 ThO 材料。

结果

根据胶体的性质,形成了六方或蠕虫状混合中间相。在表面活性剂胶束表面涂有足够量的 Th-甲酸六聚体的蠕虫状中间相的热处理下,生成了微米级的 ThO 纳米纤维。这种具有可及孔隙率的材料为注入少量锕系元素溶液开辟了新的前景,为混合氧化物核燃料的制造和少量锕系元素嬗变提供了一种有前途的安全方法。

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