Reversible and Selective CO₂ to HCO₂ ^- Electrocatalysis near the Thermodynamic Potential

Reversible catalysis is a hallmark of energy-efficient chemical transformations, but can only be achieved if the changes in free energy of intermediate steps are minimized and the catalytic cycle is devoid of high transition-state barriers. Using these criteria, we demonstrate reversible CO₂ /HCO₂ ^- conversion catalyzed by [Pt(depe)₂ ]²⁺ (depe=1,2-bis(diethylphosphino)ethane). Direct measurement of the free energies associated with each catalytic step correctly predicts a slight bias towards CO₂ reduction. We demonstrate how the experimentally measured free energy of each step directly contributes to the <50 mV overpotential. We also find that for CO₂ reduction, H₂ evolution is negligible and the Faradaic efficiency for HCO₂ ^- production is nearly quantitative. A free-energy analysis reveals H₂ evolution is endergonic, providing a thermodynamic basis for highly selective CO₂ reduction.