Thermodynamic Considerations for Optimizing Selective CO₂ Reduction by Molecular Catalysts

Energetically efficient electrocatalysts with high product selectivity are desirable targets for sustainable chemical fuel generation using renewable electricity. Recycling CO₂ by reduction to more energy dense products would support a carbon-neutral cycle that mitigates the intermittency of renewable energy sources. Conversion of CO₂ to more saturated products typically requires proton equivalents. Complications with product selectivity stem from competitive reactions between H⁺ or CO₂ at shared intermediates. We describe generalized catalytic cycles for H₂, CO, and HCO₂ ^- formation that are commonly proposed in inorganic molecular catalysts. Thermodynamic considerations and trends for the reactions of H⁺ or CO₂ at key intermediates are outlined. A quantitative understanding of intermediate catalytic steps is key to designing systems that display high selectivity while promoting energetically efficient catalysis by minimizing the overall energy landscape. For CO₂ reduction to CO, we describe how an enzymatic active site motif facilitates efficient and selective catalysis and highlight relevant examples from synthetic systems.