Engineering Catalyst–Electrolyte Microenvironments to Optimize the Activity and Selectivity for the Electrochemical Reduction of CO₂ on Cu and Ag

The electrochemical reduction of carbon dioxide (CO₂R) driven by renewably generated electricity (e.g., solar and wind) offers a promising means for reusing the CO₂ released during the production of cement, steel, and aluminum as well as the production of ammonia and methanol. If CO₂ could be removed from the atmosphere at acceptable costs (i.e., <$100/t of CO₂), then CO₂R could be used to produce carbon-containing chemicals and fuels in a fully sustainable manner. Economic considerations dictate that CO₂R current densities must be in the range of 0.1 to 1 A/cm² and selectivity toward the targeted product must be high in order to minimize separation costs. Industrially relevant operating conditions can be achieved by using gas diffusion electrodes (GDEs) to maximize the transport of species to and from the cathode and combining such electrodes with a solid-electrolyte membrane by eliminating the ohmic losses associated with liquid electrolytes. Additionally, high product selectivity can be attained by careful tuning of the microenvironment near the catalyst surface (e.g., the pH, the concentrations of CO₂ and H₂O, and the identities of the cations in the double layer adjacent to the catalyst surface).We begin this Account with a discussion of our experimental and theoretical work aimed at optimizing catalyst microenvironments for CO₂R. We first examine the effects of catalyst morphology on the production of multicarbon (C₂₊) products over Cu-based catalysts and then explore the role of mass transfer combined with the kinetics of buffer reactions in the local concentration of CO₂ and pH at the catalyst surface. This is followed by a discussion of the dependence of the local CO₂ concentration and pH on the dynamics of CO₂R and the formation of specific products over both Cu and Ag catalysts. Next, we explore the impact of electrolyte cation identity on the rate of CO₂R and the distribution of products. Subsequently, we look at utilizing pulsed electrolysis to tune the local pH and CO₂ concentration at the catalyst surface. The last part of the discussion demonstrates that ionomer-coated catalysts in combination with pulsed electrolysis can enable the attainment of very high (>90%) selectivity to C₂₊ products over Cu in an aqueous electrolyte. This part of the Account is then extended to consider the difference in the catalyst-nanoparticle microenvironment, present in the catalyst layer of a membrane electrode assembly (MEA), with respect to that of a planar electrode immersed in an aqueous electrolyte.