Operando Studies for CO₂/CO Reduction in Flow‐Based Devices

Abstract Electrocatalytic CO₂ reduction reaction (CO₂RR) conducted in a flow‐based device exhibits a substantial enhancement in Faradaic efficiency and catalytic current density compared to a conventional H‐type configuration. This highlights the distinct catalytic environment and behavior inherent in flow cells as opposed to H cells. To investigate the authentic properties of a catalyst within a flow‐based device, customized flow cells have been specifically devised for operando techniques during CO₂RR and CORR, rather than resorting to an in‐situ three‐electrode H‐type configuration with its disparate catalytic environment and performance. This approach ensures a catalytic environment identical to that employed in electrochemical measurements. This review delineates the disparities between H‐type and flow‐based cells as well as the operando techniques tailored for flow‐based devices, including X‐ray absorption spectroscopy and Raman spectroscopy, preserving a consistent catalytic environment. It also compiles recent findings on copper‐based systems using operando flow‐based devices. The operando insights reveal a significant augmentation in catalytic current density, impacting both chemical properties and crystal structures. Furthermore, the observation of various catalytic intermediates enriches our comprehension. In essence, the application of operando techniques to flow‐based devices furnishes a comprehensive understanding of the catalytic behavior exhibited by diverse systems, propelling progress toward achieving Net Zero emissions.