Of the many challenges facing the development of artificial light harvesting, one of the most significant barriers is the development of selective, energy efficient, and economically viable catalysts that can facililate the electrochemical reduction of CO2 to higher energy content molecules, particularly those that are useful fuels. The first part of this talk will discuss development and implementation of an appropriate electronic structure approach for modeling electrocatalysis under applied bias, using a continuum description of solvent and salt, which we have implemented as a modification to a plane wave density functional theory program package. The second part will describe the application of this approach to model critical steps in the electrocatalysis of CO2 on a copper surface, whose activity for CO2 reduction is already experimentally well established. The use of potential-dependent electronic structure allows the direct calculation of experimental observables which are not readily accessible otherwise, and gives some new insights into the steps associated with the formation of higher hydrocarbons (C2 and above) on copper. It also serves as a useful validation of the methodology, which sets the stage for the third part, which is a progress report on efforts to rationally design new catalyst systems capable of yielding improved selectivity and energy efficiency. Our particular focus is breaking the well-accepted scaling relations between proton reduction and CO2 reduction by altering the catalyst chemistry.

Electronic structure theory applied to modeling catalysis of the CO2-reduction reaction for artificial light harvesting

251st National Meeting (2016)

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