Deciphering the Ce3+ to Ce4+ Evolution: Insight from X-ray Raman Scattering Spectroscopy at Ce N4,5 Edges.

IF 2.3 3区 化学 Q3 CHEMISTRY, PHYSICAL Chemphyschem Pub Date : 2024-10-31 DOI:10.1002/cphc.202400742
Soumya K Das, Alessandro Longo, Eugenio Bianchi, Claudio V Bordenca, Christoph J Sahle, Maria Pia Casaletto, Alessandro Mirone, Francesco Giannici
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Abstract

Cerium oxide, or ceria, (CeO2) is one of the most studied materials for its wide range of applications in heterogeneous catalysis and energy conversion technologies. The key feature of ceria is the remarkable oxygen storage capacity linked to the switch between Ce4+ and Ce3+ states, in turn creating oxygen vacancies. Changes in the electronic structure occur with oxygen removal from the lattice. Accordingly, the two valence electrons can be accommodated by the reduction of support cations where the electrons can be localized in empty f states of Ce4+ ions nearby. Quantifying the different oxidation states in situ is crucial to understand and model the reaction mechanism. Beside the different techniques to quantify Ce3+ and Ce4+ states, we discuss the use of X-ray Raman Scattering (XRS) spectroscopy as an alternative method. In particular, we show that XRS can observe the oxidation state changes of cerium directly in the bulk of the materials under realistic environmental conditions. The Hilbert++ code is used to simulate the XRS spectra and quantify accurately the Ce3+ and Ce4+ content. These results are compared to those obtained from in situ X-ray Diffraction (XRD) collected in parallel and the differences arising from the two different probes are discussed.

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解密 Ce3+ 到 Ce4+ 的演变:Ce N4,5 边缘的 X 射线拉曼散射光谱透视。
氧化铈(CeO2)是研究得最多的材料之一,因为它在异相催化和能源转换技术中有着广泛的应用。铈的主要特点是具有显著的储氧能力,这与 Ce4+ 和 Ce3+ 状态之间的切换有关,而 Ce4+ 和 Ce3+ 状态的切换又会产生氧空位。从晶格中去除氧气后,电子结构会发生变化。因此,支持阳离子的还原可以容纳两个价电子,电子可以定位在附近 Ce4+ 离子的空 f 态。现场量化不同的氧化态对于理解和模拟反应机制至关重要。除了量化 Ce3+ 和 Ce4+ 状态的不同技术外,我们还讨论了使用 X 射线拉曼散射(XRS)光谱作为替代方法。特别是,我们展示了 XRS 可以在现实环境条件下直接观察材料主体中铈的氧化态变化。我们使用 Hilbert++ 代码模拟 XRS 光谱,并准确量化了 Ce3+ 和 Ce4+ 的含量。将这些结果与同时采集的原位 X 射线衍射 (XRD) 所获结果进行比较,并讨论两种不同探针所产生的差异。
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来源期刊
Chemphyschem
Chemphyschem 化学-物理:原子、分子和化学物理
CiteScore
4.60
自引率
3.40%
发文量
425
审稿时长
1.1 months
期刊介绍: ChemPhysChem is one of the leading chemistry/physics interdisciplinary journals (ISI Impact Factor 2018: 3.077) for physical chemistry and chemical physics. It is published on behalf of Chemistry Europe, an association of 16 European chemical societies. ChemPhysChem is an international source for important primary and critical secondary information across the whole field of physical chemistry and chemical physics. It integrates this wide and flourishing field ranging from Solid State and Soft-Matter Research, Electro- and Photochemistry, Femtochemistry and Nanotechnology, Complex Systems, Single-Molecule Research, Clusters and Colloids, Catalysis and Surface Science, Biophysics and Physical Biochemistry, Atmospheric and Environmental Chemistry, and many more topics. ChemPhysChem is peer-reviewed.
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