Although numerous techniques are developed to enable real‐time understanding of dynamic interactions at the solid–liquid interface during electrochemical reactions, further progress in the development of these methods over the last several decades has faced challenges. With the rapid development of high‐brilliance synchrotron sources, operando X‐ray spectroscopies have become increasingly popular for revealing interfacial features and catalytic mechanisms in electrocatalysis. Nevertheless, the resulting spectra are highly sensitive to factors such as X‐ray radiation, reaction environment, and acquisition procedures, all of which may potentially introduce artifacts that are often overlooked, leading to misinterpretations of electrocatalytic behaviors. In this perspective, several emerging hard X‐ray spectroscopies used in electrocatalysis research are reviewed, highlighting their electronic transition processes, detection modes, and functional complementarity. Significantly, based on a case study of operando X‐ray absorption spectroscopy at various beamlines, potential artifacts generated by X‐ray irradiation are systematically investigated through photon‐flux density‐, dose‐, and time‐dependent studies of typical copper electrocatalysts. Accordingly, a practical protocol for conducting reliable X‐ray spectroscopic measurements in operando electrocatalytic studies to minimize potential artifacts that can affect the resulting X‐ray spectra, thereby ensuring accurate interpretation and a deeper understanding of interfacial interactions and electrocatalytic mechanisms, is established.

中文翻译：

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通过原位 X 射线吸收光谱的进步解析电催化剂的动态行为：潜在的伪影和实用指南


尽管已经开发了许多技术来实时了解电化学反应过程中固液界面处的动态相互作用，但在过去几十年中，这些方法的进一步发展面临着挑战。随着高亮度同步加速器源的快速发展，原位 X 射线光谱在揭示电催化中的界面特征和催化机制方面越来越受欢迎。然而，所得光谱对 X 射线辐射、反应环境和采集程序等因素高度敏感，所有这些都可能引入经常被忽视的伪影，从而导致对电催化行为的误解。从这个角度来看，回顾了用于电催化研究的几种新兴的硬 X 射线光谱，强调了它们的电子跃迁过程、检测模式和功能互补性。值得注意的是，基于各种光束线上的原位 X 射线吸收光谱的案例研究，通过对典型铜电催化剂的光子通量密度、剂量和时间依赖性研究，系统地研究了 X 射线照射产生的潜在伪影。因此，建立了在原位电催化研究中进行可靠 X 射线光谱测量的实用方案，以最大限度地减少可能影响所得 X 射线光谱的潜在伪影，从而确保准确解释和更深入地了解界面相互作用和电催化机制。