Kvashnina Kristina O
The Rossendorf Beamline at ESRF, The European Synchrotron, CS40220, 38043, Grenoble Cedex 9, France.
Institute of Resource Ecology, Helmholtz Zentrum Dresden Rossendorf, Dresden, 01328, Germany.
Chemistry. 2024 Aug 19;30(46):e202400755. doi: 10.1002/chem.202400755. Epub 2024 Aug 1.
Historically, cerium has been attractive for pharmaceutical and industrial applications. The cerium atom has the unique ability to cycle between two chemical states (Ce(III) and Ce(IV)) and drastically adjust its electronic configuration: [Xe] 4f5d6s in response to a chemical reaction. Understanding how electrons drive chemical reactions is an important topic. The most direct way of probing the chemical and electronic structure of materials is by X-ray absorption spectroscopy (XAS) or X-ray absorption near-edge structure (XANES) in high energy resolution fluorescence detection (HERFD) mode. Such measurements at the Ce L edge have the advantage of a high penetration depth, enabling in-situ reaction studies in a time-resolved manner and investigation of material production or material performance under specific conditions. But how much do we understand Ce L XANES? This article provides an overview of the information that can be extracted from experimental Ce L XAS/XANES/HERFD data. A collection of XANES data recorded on various cerium systems in HERFD mode is presented here together with detailed discussions on data analysis and the current status of spectral interpretation, including electronic structure calculations.
从历史上看，铈在制药和工业应用方面一直具有吸引力。铈原子具有在两种化学状态（Ce(III) 和 Ce(IV)）之间循环并根据化学反应大幅调整其电子构型：[Xe] 4f5d6s 的独特能力。理解电子如何驱动化学反应是一个重要的课题。探测材料化学和电子结构最直接的方法是在高能量分辨率荧光检测（HERFD）模式下通过X射线吸收光谱（XAS）或X射线吸收近边结构（XANES）。在Ce L边进行的此类测量具有高穿透深度的优势，能够以时间分辨的方式进行原位反应研究，并研究特定条件下的材料生产或材料性能。但是我们对Ce L XANES了解多少呢？本文概述了可以从实验性Ce L XAS/XANES/HERFD数据中提取的信息。这里展示了一组在HERFD模式下记录的各种铈体系的XANES数据，并对数据分析以及光谱解释的现状进行了详细讨论，包括电子结构计算。
