Leveraging Electrons for Electrochemical CO₂ Capture Using a Hemi-Labile Iron Complex

Climate change, driven by anthropogenic carbon emissions, demands urgent action to prevent a 2050 tipping point. With CO₂ levels at 427 ppm (50% above pre-industrial levels), deploying energy-efficient carbon capture technologies is crucial. Electrochemical carbon capture processes that have been touted to have the potential to meet these needs rely on the applied cell voltage, and electron utilization (CO₂ molecules separated per electron), which has generally been asserted to have a theoretical limit of one. Here, we introduce an electron-leveraging strategy to enhance electron utilization beyond this limit to 1.43 by employing Fe-EDDHA, a redox-active coordination complex having a ligand with multiple hemi-labile coordination sites. The reversibility and robustness of the system were enabled by the efficient prevention of CO₂ reduction upon the introduction of nicotinamide as a guardian of the iron(2+) center. The proof-of-concept cyclic system exhibits a minimum operational energy of 22.6 kJ_e mol^-1 and an average of 63.7 kJ_e mol^-1 over 29 cycles, using a simulated flue gas (15% CO₂). Our electron-leveraging strategy holds promise for advancing energy-efficient electrochemical carbon capture technologies, and offers an alternative to prevalent redox potential shifting methods proposed to mitigate undesired electron transfer reactions in redox-active materials across diverse operational conditions.