BICEPS - Bridging Innovative Coordination complexes of Earth-abundant metals for efficient PhotocatalysiS
The BICEPS project led by Clémence QUEFFELEC focuses on the development of innovative solutions for transforming CO2 into carbon monoxide (CO), a molecule useful in industry. The aim is to use visible light as an energy source, and to create systems capable of carrying out this transformation using elements that are abundant on Earth, such as copper (Cu) and nickel (Ni). Few current systems make effective use of these non-noble metals. We are seeking to fill this gap by developing catalysts - chemical species that make particularly energy-intensive reactions possible - that can capture and use the energy of light to convert CO2 in a sustainable and economical way.
Project summary
Carbon Dioxide (CO2) is a renewable feedstock for the production of chemicals and energy-rich fuels. Its transformation is however challenging because if its chemical inertness. There is a pressing need for the development of efficient, robust, and economically viable CO2-reduction catalysts. In this BICEPS program, we aim to develop molecular systems based on Earth abundant elements for use in reducing CO2 to CO, a high-value molecule, using visible light as the primary energy source.
There are few efficient molecular photocatalytic systems based entirely on non-noble metals. We aim to fill this gap by designing and synthesizing molecular photocatalysts based on Cu and Ni coordination complexes. Built on our prior accomplishments, homoleptic Cu(I)-phenanthroline complexes and macrocyclic Ni(II) complexes are chosen as model photosensitizers (PS) and molecular catalysts (MC), respectively, which will be effectively coupled by covalent linkers. We hypothesize that the rational design of the covalent linkers uniting PS and MC will enable the tuning of photo-induced charge separation and multi-electron CO2 reduction steps.
Our hypothesis will be tested by the following research tasks:
- Preparing a set of PS-Linker-MC dyads based only on Earth abundant elements where molecular structures of the linkers between PS and MC will be varied systematically;
- Studying the structures and photocatalytic properties of the PS-Linker-MC systems;
- Investigating photocatalytic mechanisms using a combination of in-situ infrared spectroelectrochemistry, and time-resolved X-ray absorption spectroscopies.
This project highlights an international collaboration between the CEISAM Lab at Nantes University in France and the Photocatalysis Group at the University of New Hampshire (UNH) in USA. The two teams collaborate to provide complementary expertise needed for this project. In particular, the CEISAM Lab will lead on ligand synthesis and derivatization, while the UNH team will focus on photocatalysis and spectroscopic investigation.