The oxygen evolution reaction is crucial to sustainable electro- and photo-electrochemical approaches to chemical energy production (for example, H₂). Although mechanistic descriptions of the oxygen evolution reaction have been proposed, the frontier challenge is to extract the molecular details of its elementary steps. Here we discuss how advances in spectroscopy and theory are allowing for configurations of reaction intermediates to be elucidated, distinguishing between experimental approaches (static and dynamic) across a range of surface oxygen binding energies on catalysts (from ruthenium to titanium oxides). We outline how interpreting X-ray and optical spectra relies on established and newly implemented computational techniques. A key emphasis is on detecting adsorbed oxygen intermediates at the oxide/water interface by their chemical composition, electronic and vibrational levels and ion–electron kinetic pathways. Integrating the computational advances with the experimental spectra along these lines could ultimately resolve the elementary steps, elucidating how each intermediate leads to another during oxygen evolution reaction.

析氧反应对于化学能（例如H ₂ ）生产的可持续电化学和光电化学方法至关重要。尽管已经提出了析氧反应的机理描述，但前沿挑战是提取其基本步骤的分子细节。在这里，我们讨论光谱学和理论的进步如何阐明反应中间体的配置，区分催化剂上一系列表面氧结合能（从钌到氧化钛）的实验方法（静态和动态）。我们概述了解释 X 射线和光谱如何依赖于已建立的和新实施的计算技术。重点是通过化学成分、电子和振动水平以及离子-电子动力学途径检测氧化物/水界面处吸附的氧中间体。将计算进展与实验光谱相结合，最终可以解决基本步骤，阐明在析氧反应过程中每个中间体如何导致另一个中间体。