In‐Situ Infrared Spectroscopy Applied to the Study of the Electrocatalytic Reduction of CO2: Theory, Practice and Challenges

Abstract The field of electrochemical CO 2 conversion is undergoing significant growth in terms of the number of publications and worldwide research groups involved. Despite improvements of the catalytic performance, the complex reaction mechanisms and solution chemistry of CO 2 have resulted in a considerable amount of discrepancies between theoretical and experimental studies. A clear identification of the reaction mechanism and the catalytic sites are of key importance in order to allow for a qualitative breakthrough and, from an experimental perspective, calls for the use of in‐situ or operando spectroscopic techniques. In‐situ infrared spectroscopy can provide information on the nature of intermediate species and products in real time and, in some cases, with relatively high time resolution. In this contribution, we review key theoretical aspects of infrared reflection spectroscopy, followed by considerations of practical implementation. Finally, recent applications to the electrocatalytic reduction of CO 2 are reviewed, including challenges associated with the detection of reaction intermediates.