Spectroelectrochemical mechanistic investigation of the electrocatalytic activation of CO2 with Co based macrocycles heterogenised at carbon

Noble metal-free molecular electrocatalysis for CO2 activation is a fast growing field. Thanks to their structural modularity, these molecular structures can lead to the fine understanding of the mechanisms involved in the catalytic process through the definition of structure-activity relationships. This understanding is the key toward the development of the earth-abundant based catalyst to be integrated to fuel cell and electrolysers for H2 production or CO2 valorisation. This proposal aims at studying, operando, a surface confined cobalt-based molecular catalyst for aqueous electrocatalytic CO2 reduction to CO. We will disclose the evolution of the molecular structure of the catalyst (geometry, nature of the ligands) as a function of the applied potential, in the presence or absence of the substrate. This will allow to precisely access to the real structure of the electroactive species and to apprehend potential degradation pathways.