Spectroscopic Evidence of Size-Dependent Buffering of Interfacial pH by Cation Hydrolysis during CO2 Electroreduction

The support of the University of Aberdeen and the Leverhulme Trust (Grant No. RPG-2015-040) is gratefully acknowledged. OA acknowledges an Elphinstone Scholarship awarded by the University of Aberdeen.Peer reviewedPostprin

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

The field of electrochemical CO2 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 CO2 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 CO2 are reviewed, including challenges associated with the detection of reaction intermediates.</p

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

The field of electrochemical CO2 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 CO2 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 CO2 are reviewed, including challenges associated with the detection of reaction intermediates.Accepted Author ManuscriptChemE/Materials for Energy Conversion & StorageChemE/O&O groe