The depletion of current petrochemical reserves and the geographic and strategic importance of securing adequate energy production prioritize the development of alternative fuel sources. A favorable approach involves utilizing carbon dioxide (CO2) as a carbon feedstock for fuels and fuel precursors in the hopes of developing a carbon neutral energy cycle. This process can be driven electrochemically to produce the more synthetically useful products of carbon monoxide and formic acid. It is challenging to reductively activate the highly stable C=O double bonds of CO2, presenting a continuing challenge to the field for developing molecular electrocatalysts capable of high selectivity and efficiency. Previous success has been observed with N4 macrocyclic complexes such as porphyrins and cyclam derivatives. Our approach involves the modification of the macrocyclic ligand frameworks to incorporate both steric bulk and a pendent proton source for CO2 reduction with first row transition metals. The incorporation of a pendent proton will allow for secondary sphere interactions that can drive the C–O bond cleavage forward with concerted electron transfer from the metal center, which is commonly the rate determining step in this class of catalytic process. Furthermore, the addition of Brønsted acids such as phenol will be examined to enhance the relay effect of the pendent proton sources.

Development of molecular electrocatalyst for CO2 reduction based on nitrogen-based macrocyclic ligands

2019 Fall National Meeting

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