We propose a novel and general reaction mechanism based on observations from recent computational and experimental studies of pyridinium-catalyzed CO2 reduction to rationalize its unique performance towards CO2 reduction. We report pKas and standard reduction potentials derived from first principles quantum chemistry for homogeneously solvated species and species adsorbed on GaP photoelectrodes. On GaP surfaces, neither pyridinium reduction nor proton reduction is energetically favorable, even at very negative electrode potentials. However, the calculated redox potential for converting a surface-bound pyridine into the 2e� reduced species, dihydropyridine, suggests this may be feasible at less negative applied potentials. Such 2e� reduced species also happen to share a similar chemical moiety as some enzyme catalysts that facilitate hydride-transfer (e.g. NADH). Their redox potentials are also coincidentally similar to redox potentials that could carry out CO2 reduction to a variety of products, suggesting these species may be important intermediates in molecular-promoted CO2 reduction.

First-principles descriptors for molecular heterocycles that promote CO<sub>2 </sub>?reduction

247th National Meeting (2014)

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First-principles descriptors for molecular heterocycles that promote CO2 ?reduction

First-principles descriptors for molecular heterocycles that promote CO₂?reduction