(Invited) First-Principles CO2 Reduction Catalyst Design at Electrified Solid-Liquid Interfaces

Abstract

Electrocatalysis at electrified solid-liquid interfaces is the key to sustainable storage and conversion of energy. In the search for more active electrocatalysts, first-principles calculations based on Density Functional Theory have become a state-of-the-art means, which, however generally, ignore the presence of the interface. In this talk, we revisit the implications of this approximation at the example of electrocatalytic CO2 reduction. In contrast to previous believes, we find the interfacial electric field to be significant and even determine the product selectivity and conversion rate on Gold and Copper catalysts. From experimental and theoretical studies, we then derive novel interface-aware design principles and apply them for material and electrical engineering towards highly optimized energy conversion systems. We also use the concepts to initiate a descriptor-based screening of catalyst materials for CO2 reduction and highlight critical differences to previous studies. Finally, we extend the approach by including also mass transport effects which enables the design of electrode materials on all relevant time and size scales.