During the last decades, X-ray absorption spectroscopy (XAS) has become an indispensable method for probing the structure and composition of heterogeneous catalysts, revealing the nature of the active sites and establishing links between structural motifs in a catalyst, local electronic structure, and catalytic properties. Here we discuss the fundamental principles of the XAS method and describe the progress in the instrumentation and data analysis approaches undertaken for deciphering X-ray absorption near edge structure (XANES) and extended X-ray absorption fine structure (EXAFS) spectra. Recent usages of XAS in the field of heterogeneous catalysis, with emphasis on examples concerning electrocatalysis, will be presented. The latter is a rapidly developing field with immense industrial applications but also unique challenges in terms of the experimental characterization restrictions and advanced modeling approaches required. This review will highlight the new insight that can be gained with XAS on complex real-world electrocatalysts including their working mechanisms and the dynamic processes taking place in the course of a chemical reaction. More specifically, we will discuss applications of in situ and operando XAS to probe the catalyst’s interactions with the environment (support, electrolyte, ligands, adsorbates, reaction products, and intermediates) and its structural, chemical, and electronic transformations as it adapts to the reaction conditions.

中文翻译：

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X射线吸收光谱法原位/ Operando电催化剂表征

在过去的几十年中，X射线吸收光谱（XAS）成为探测非均相催化剂的结构和组成，揭示活性位点的性质并在催化剂的结构基序，局部电子结构和分子之间建立联系的必不可少的方法。催化性能。在这里，我们讨论了XAS方法的基本原理，并描述了仪器和数据分析方法的进展，这些方法用于解密近边缘结构（XANES）和扩展X射线吸收精细结构（EXAFS）光谱的X射线吸收。将介绍XAS在非均相催化领域的最新用法，重点是有关电催化的实例。后者是一个快速发展的领域，具有巨大的工业应用，但在实验表征限制和所需的高级建模方法方面也面临着独特的挑战。本文将重点介绍XAS可以对复杂的现实世界中的电催化剂获得的新见解，包括其工作机理以及在化学反应过程中发生的动态过程。更具体地说，我们将讨论以下方面的应用原位和操作XAS，以探查催化剂与环境（载体，电解质，配体，吸附物，反应产物和中间体）的相互作用及其适应于反应条件的结构，化学和电子转化。