Knowledge-guided improvement of electrocatalytic materials is facilitated by insight in determinants of activity, selectivity, and stability. Catalyst re-construction, surface adsorbates and reaction intermediates, and the mechanistic role of the electrolyte can be addressed by operando (= in situ) Raman spectroscopy, where Raman scattering is detected during electrochemical operation. After outlining the basic experimental technology and addressing the light-damage problem, selected applications in electrocatalysis research are reviewed: (1) Redox-state changes of the catalyst material induced by electrode potentials are traced by operando Raman spectroscopy. (2) Surface-bound (adsorbed) educt, products and reaction intermediates are detected using surface-enhanced Raman spectroscopy (SERS). (3) Local-pH values are determined at the catalyst–electrolyte interface, with spatial resolution at the visible-light diffraction limit.

深入了解活性、选择性和稳定性的决定因素有助于以知识为导向的电催化材料改进。催化剂重建、表面吸附物和反应中间体以及电解质的机械作用可以通过操作（= 原位）拉曼光谱来解决，其中拉曼散射在电化学操作期间被检测到。在概述了基本实验技术并解决了光损伤问题后，回顾了在电催化研究中的选定应用：（1）通过操作拉曼光谱追踪由电极电位引起的催化剂材料的氧化还原状态变化。(2) 使用表面增强拉曼光谱 (SERS) 检测表面结合（吸附）的离析物、产物和反应中间体。