Operando characterization of continuous flow CO₂ electrolyzers: current status and future prospects

The performance of continuous-flow CO2 electrolyzers has substantially increased in recent years, achieving current density and selectivity (particularly for CO production) meeting the industrial targets. Further improvement is, however, necessary in terms of stability and energy efficiency, as well as in high-value multicarbon product formation. Accelerating this process requires deeper understanding of the complex interplay of chemical-physical processes taking place in CO2 electrolyzer cells. Operando characterization can provide these insights under working conditions, helping to identify the reasons for performance losses. Despite this fact, only relatively few studies have taken advantage of such methods up to now, applying operando techniques to characterize practically relevant CO2 electrolyzers. These studies include X-ray absorption- and Raman spectroscopy, fluorescent microscopy, scanning probe techniques, mass spectrometry, and radiography. Their objective was to characterize the catalyst structure, its microenviroment, membrane properties, etc., and relate them to the device performance (reaction rates and product distribution). Here we review the current state-of-the-art of operando methods, associated challenges, and also their future potential. We aim to motivate researchers to perform operando characterization in continuous-flow CO2 electrolyzers, to understand the reaction mechanism and device operation under practically relevant conditions, thereby advancing the field towards industrialization.