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Abstract
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 in enabled by an electron-rich >N−C=C−N< (enediamine) 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 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.
Supplementary materials
Title
Supporting Information for Computational Design of an Electro-Organocatalyst for Conversion of CO2 into Long Chain Aldehydes
Description
Technical Details of the DFT Calculations
Description of the hybrid solvation method
Method for finding electron transfer transition states
Corrections to DFT energies
Free energy contributions of intermediates and ransition states
The pH dependence of the total barriers of all other steps in the catalytic cycle (Figure S1)
The kinetic dependence of the chain growth cycle on formaldehyde concentration at pH of 7.78 (Figure S2)
Coupling of the chain growth and CO2 reduction cycles (Figure S3)
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