(Invited) The Role of Structural Inhomogeneity in the Promotion of Electrochemical CO2 Conversion on Pristine and Doped Ligand-Protected Au Nanoparticle

Abstract

The tremendous progress made in the first-principles mechanistic studies of the CO2 reduction process in ligand protected gold nanocluster and its various doped counterparts will be described. A significant finding is that the active form of the catalysts does not correspond to the fully ligand protected version because of the weak adsorption of relevant intermediates. Our calculations reveal that the reduction process is facilitated by a structurally inhomogeneous reaction center. Instead of an exposed metal center, it features a more thermodynamically favorable sulfur site which binds the intermediates in such a way that the process can occur at lower over-potentials. The results affirm the role of structural disorder in the surface region for this class of materials as a critical factor in the promotion of CO2 recycling under electrochemical environment. In the last segment, the application of an in-house micro-kinetic modeling code to analyze heterogeneously catalyzed electrochemical CO2 reduction process will be presented.