Limited dissolution of transition metals in the nanocrystalline cerium (IV) oxide

IF 5.1 2区 材料科学 Q1 MATERIALS SCIENCE, CERAMICS Ceramics International Pub Date : 2024-10-02 DOI:10.1016/j.ceramint.2024.10.004
Agata Ducka , Patryk Błaszczak , Marcin Zając , Adrian Mizera , Francesco d'Acapito , Beata Bochentyn
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Abstract

Nanocrystalline cerium (IV) oxides doped with transition metals have gained significant interest recently, mostly in the field of catalysis. Herein, we present the comprehensive studies on ceria doped with 10 mol.% of transition metals (Mn, Fe, Co, Ni or Cu) synthesized by the reverse microemulsion method. The aim of this work is to study the properties of those materials with the use of different complementary methods like XRD, SEM, TPR, and XPS and to determine the possibility of fabrication of single-phase materials with that doping level. Studies presented here prove that despite showing single-phase XRD patterns with high nanocrystallinity, in all obtained materials, the dopants are not fully incorporated in the ceria lattice. Spectroscopy studies show that additional transition metal oxides are present on the surface of all materials. Herein, we also present the analyses of L3,2-edges of transition metals in ceria, as well as high energy Ce K-edge to prove that 10 mol.% of any of those transition metals cannot be incorporated in the ceria host without the formation of additional phases. Using techniques presented here, it was found that the highest share of Mn can be dissolved in the lattice, while Cu is mostly present as a surficial Cu2O. Studies presented are an important contribution to the discussion about the solubility limits in nanocrystalline ceria and its properties which may be utilized for e.g various catalysts or as electrolytes.
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过渡金属在纳米晶氧化铈(IV)中的有限溶解
掺杂过渡金属的纳米晶铈(IV)氧化物近来引起了人们的极大兴趣,主要是在催化领域。在此,我们介绍了通过反向微乳液法合成的掺杂 10 mol.% 过渡金属(锰、铁、钴、镍或铜)的铈的综合研究。这项工作的目的是利用 XRD、SEM、TPR 和 XPS 等不同的辅助方法研究这些材料的特性,并确定利用该掺杂水平制造单相材料的可能性。本文介绍的研究证明,尽管所有获得的材料都显示出具有高纳米结晶度的单相 XRD 图样,但掺杂剂并没有完全融入铈晶格中。光谱研究表明,所有材料的表面都存在额外的过渡金属氧化物。在此,我们还介绍了陶瓷中过渡金属的 L3、2 边沿以及高能 Ce K 边沿的分析结果,以证明在不形成附加相的情况下,任何一种过渡金属中的 10 mol.% 都无法掺入到陶瓷宿主中。利用本文介绍的技术发现,锰在晶格中的溶解比例最高,而铜则主要以表面 Cu2O 的形式存在。这些研究对讨论纳米结晶铈的溶解度极限及其特性(可用于各种催化剂或电解质等)做出了重要贡献。
本文章由计算机程序翻译,如有差异,请以英文原文为准。
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来源期刊
Ceramics International
Ceramics International 工程技术-材料科学:硅酸盐
CiteScore
9.40
自引率
15.40%
发文量
4558
审稿时长
25 days
期刊介绍: Ceramics International covers the science of advanced ceramic materials. The journal encourages contributions that demonstrate how an understanding of the basic chemical and physical phenomena may direct materials design and stimulate ideas for new or improved processing techniques, in order to obtain materials with desired structural features and properties. Ceramics International covers oxide and non-oxide ceramics, functional glasses, glass ceramics, amorphous inorganic non-metallic materials (and their combinations with metal and organic materials), in the form of particulates, dense or porous bodies, thin/thick films and laminated, graded and composite structures. Process related topics such as ceramic-ceramic joints or joining ceramics with dissimilar materials, as well as surface finishing and conditioning are also covered. Besides traditional processing techniques, manufacturing routes of interest include innovative procedures benefiting from externally applied stresses, electromagnetic fields and energetic beams, as well as top-down and self-assembly nanotechnology approaches. In addition, the journal welcomes submissions on bio-inspired and bio-enabled materials designs, experimentally validated multi scale modelling and simulation for materials design, and the use of the most advanced chemical and physical characterization techniques of structure, properties and behaviour. Technologically relevant low-dimensional systems are a particular focus of Ceramics International. These include 0, 1 and 2-D nanomaterials (also covering CNTs, graphene and related materials, and diamond-like carbons), their nanocomposites, as well as nano-hybrids and hierarchical multifunctional nanostructures that might integrate molecular, biological and electronic components.
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