Costentin, C., Daasbjerg, K. & Robert, M.

The development of supported molecular catalysts deposited at conductive electrodes has recently (re)opened a wide range of new possibilities to investigate CO2 reduction with the catalytic selectivity traditionally offered by molecules, and the increased stability usually encountered with heterogeneous materials. The various methods for immobilizing molecules (non-covalent, covalent, periodic systems) are detailed as well as the performances of the most typical hybrid electrodes so far investigated. As in homogeneous conditions, electrochemical techniques provide the tools for thorough mechanistic studies. Models are described toward these ends and typical systems are analysed. Remarkably, these supported catalytic systems offer the most intriguing and stimulating avenues to bridge and possibly merge homogeneous and heterogeneous catalysis.