Protonated aromatic nitrogen heterocycles have been found to catalyze the electrochemical reduction of carbon dioxide at low overpotential to highly reduced products including methanol (Ea ~70kJ/mol for pyridinium). The reaction mechanism may be further investigated using aromatic amines with lower energy LUMOs and less basic nitrogen atoms. In this study, aromatic amines with expanded p-systems are investigated for their kinetic properties in carbon dioxide reduction on metal electrodes. Cyclic voltammetry with digital simulation and UV-Vis spectroscopy are used to probe the kinetics of charge transfer to the amine followed by CO2 binding to the electrogenerated radical. Product distributions in bulk electrolysis provide further mechanistic insight into the reactivity of reduced heterocycles with CO2. Our results indicate that the nature of the amine not only affects the kinetics and yield of the reaction, but also impacts the distribution of products.

Aromatic nitrogen heterocycle catalysts for CO<sub>2</sub> reduction: Key mechanistic studies of the multielectron pathway

244th National Meeting (2012)

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Aromatic nitrogen heterocycle catalysts for CO2 reduction: Key mechanistic studies of the multielectron pathway

Aromatic nitrogen heterocycle catalysts for CO₂ reduction: Key mechanistic studies of the multielectron pathway