Computational Design of an Electro-Organocatalyst for Conversion of CO2 into Long Chain Aldehydes

Density functional theory calculations employing a hybrid implicit/explicit solvation method were used to demonstrate that an electro-organocatalyst designed in our previous work for reducing CO₂ to formaldehyde could also be capable of coupling formaldehyde to form long chain aldehydes. The catalytic activity is enabled by an electron-rich vicinal enediamine (>N–C═C–N<) backbone that activates formaldehyde by reversing the polarity on the carbon atom, enabling it to act as a nucleophile in the subsequent aldol addition step. The catalyst then enables reductive dehydroxylation of the aldol addition product by facilitating outer-sphere electron transfer. The optimal pH as well as the limiting potential and formaldehyde concentration are identified and related to the kinetic balance between several rate limiting steps. Finally, the optimal conditions for coupling with the CO₂ reduction cycle are discussed, demonstrating that the electro-organocatalyst is capable of efficiently converting CO₂ into aldehyde products with a turnover frequency (per carbon atom) on the order of 0.1–1 s^–1.