Dynamics in electrochemical organic oxidation reactions from in situ and operando techniques

Abstract

Electrochemical organic oxidation reactions (OORs) play a pivotal role in various industrial processes and sustainable chemical production, transforming small molecules into value-added products. Understanding electrode surface dynamics, catalyst structures, reaction intermediates and product selectivity during OOR is crucial for both fundamental knowledge and the design of high-performance electrocatalysts and economically valuable reactions. The advancement of in situ and operando techniques, especially X-ray absorption and Raman and infrared spectroscopies, as well as differential electrochemical mass spectrometry, provide powerful tools for studying OORs. In situ methods reveal catalyst structural changes under applied bias and reaction-relevant conditions, whereas operando techniques simultaneously monitor both structure and activity in real operating conditions. This Review addresses the achievements towards closing the knowledge gap between fundamental, lab-scale studies and industrial, large-scale applications using in situ and operando techniques to uncover bulk catalyst structures, catalyst–surface–electrolyte dynamics and local transient product formation during anodic OORs. It also highlights the underlying principles of these techniques, offering perspectives on future prospects and challenges for advancing OOR applications, particularly in discovering next-generation efficient catalysts. (Figure presented.)