From CO2 to fuels : electrons, protons and earth-abundant metal complexes for new, highly active catalytic systems – EClock

Our approach combines the design and synthesis of new catalysts, in-depth mechanistic studies using electrochemical methods such as cyclic voltammetry, in situ spectroscopic studies (infrared and mass), and also complementary theoretical calculations using DFT-type methods. We will study electrochemical catalysis in homogeneous media (catalyst and CO2 in solution), as well as supported catalysis with a catalyst immobilized on the electrode surface or embedded in a polymer film (for the implementation of electrolyzers or other devices). The mechanisms involved in the transformation of CO2 remain poorly understood and controlled, which hinders the development of efficient catalysts and electrolyzers.

We have developed highly efficient abundant metal electrocatalysts for the reduction in water of 2-electron CO2, especially in water, with 100% selectivity and very high currents. They can be inserted in flow cells, and the catalytic mechanisms have been studied.

New perspectives have also been opened with the discovery of a molecular catalyst capable of reducing CO2 into methanol, a liquid that can be directly used as a fuel or in a fuel cell. An international patent has been filed on this subject.

High impact international publications have been published in the framework of this project (notably J. Am. Chem. Soc; Angew. Chem. Int. Ed.; Chem. Soc. Rev.). The project has also led to the filing of an international patent, and to numerous international invitations in conferences.

The aim of Eclock is to develop new catalysts for the electro-driven reduction of CO2 and further design CO2-electrolyzers. The ultimate goal is to produce efficiently and selectively HCOOH (a liquid fuel that can be used directly in fuel cells), CO (a precursor to hydrocarbons and commodity chemicals like e.g. olefins), as well as more reduced fuels, including CH3OH and CH4, while using cheap, abundant metal based catalysts. New catalysts incorporating earth abundant Fe, Co, Ni have shown great promise in our preliminary studies. The electron used for the conversion may come from any intermittent, renewable energy source such as solar, wind, geothermal and marine energies, but also from surplus electricity. Such developments will in the end allow storing energies for further fuel production as well as making substrates for producing value added chemicals. Therefore, Eclock will contribute to the development of innovative solutions for the upcoming energetic transition and to the development of much needed, new valorization pathways for carbon dioxide.

We will in first place employ molecular catalysts, since they have the advantage of the selectivity towards a target molecule. Based on a promising family of flexible catalysts and electrochemical mechanistic tools we have recently developed, complemented by in situ spectroscopic studies and quantum chemical calculations, we will concentrate our efforts to advance the two electrons molecular electrochemical reduction of CO2 in both homogeneous and surface supported conditions (CO and HCOOH production). Based on these results, we will develop lab-scale CO2 electrolyzers, taking advantage of the experience of the consortium in that field. We will further combine the most active molecular catalysts with solid, metallic or semi-conductive materials (cooperative catalysis) so as to drive the reduction process beyond the two electron reduction so as to selectively obtain HCHO, CH3OH, CH4, or related products. By gathering complementary competences in molecular electrochemical catalysis, electrocatalysis, chemical engineering, spectroscopy, quantum calculations and molecular and coordination chemistry, we have set an international consortium unique in Europe and we will aim at exerting a leadership position in a very competitive international context.