Recent results will be presented regarding our attempts to unravel the mechanism by which carbon dioxide is selectively reduced to methanol under visible light irradiation of gallium phosphide electrodes, in the presence of an electrolyte consisting of pyridine in acidified water.  Given the inherent experimental difficulties with probing molecular species at the semiconductor electrodes immersed in water, our calculations offer the means to fill the knowledge gap regarding, e.g., the relative stability of various electrochemical intermediates, both in solution and at the semiconductor-liquid junction.  Armed with such knowledge, it has been possible to exclude certain mechanisms while suggesting others for further testing. Secondly, via calculating the electrochemical thermodynamics and kinetics of electron and proton transfer for homogeneous bpyRe and bpyMn catalysts, we have uncovered the origins of selectivity associated with CO2 reduction to CO by these complexes. The insights offer suggestions into further optimization of these electrocatalysts.

Mechanisms for heterogeneous and homogeneous reduction of carbon dioxide from first principles

248th National Meeting (2014)

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