There is great interest in developing and engineering chemical processes that generate renewable commodity chemicals, and a key challenge is understanding how to transfer protons and electrons selectively in an energetically efficient manner. To help identify and better understand efficient electrochemical conversions, we used first-principles quantum chemistry to determine pH and electrode potential dependent energies for various classes of aromatic N-heterocycles that are found in electrochemical, photochemical, and biological processes. With these calculated data, we locate Pourbaix diagram triple points that denote the electrochemical conditions where these molecules would facilitate energetically efficient proton and/or hydride shuttling. Within quite reasonable accuracy, the calculated molecular Pourbaix diagram triple points correspond to experimental conditions under which molecular-promoted CO2 reduction has been observed. This indicates that such calculable descriptors may have use in high-throughput computational screening to predict molecular co-catalysts and their ideal reaction conditions for catalysis of renewable commodity chemicals.

Redox potential and pKa descriptors for exploring the catalysis of renewables

250th National Meeting (2015)

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