Modeling Chemical Microenvironments in Porous Copper Electrodes for CO2 Reduction at Elevated Current Densities

Abstract

Electrochemical CO2 reduction (CO2R) presents a promising pathway toward the reuse of CO2 emitted during the production of industrial commodities (e.g., cement, steel, and plastics) to form value-added commodities and fuels at ambient temperatures and pressures with renewably generated electrons. Copper (Cu) catalysts demonstrate the ability to convert CO2 to multicarbon (C2+) products. Additionally, 3-D structured porous Cu electrodes can facilitate the operation of CO2R to C2+ at significantly elevated current densities by enhancing the delivery of CO2 to catalytic active sites on Cu, offering the potential to translate lab-scale understanding to industrial operation. Nonetheless, there still exist selectivity limitations in porous electrode systems due to poor control of the chemical microenvironment, (i.e., the local pH, CO2 activity, and CO intermediate management), in these complex electrodes. Therefore, resolving microenvironment in porous Cu electrodes will be critical to advancing these systems towards industrialization.In this talk, we explore the use of continuum modeling to resolve and understand the effects of mass transfer and chemical environment in electrochemical CO2 reduction in porous Cu electrodes. We explore two scenarios of porous Cu electrodes performing electrochemical CO2 reduction. The first is the operation of a device employing a bipolar membrane (BPM) in reverse bias, wherein modeling reveals that the proton flux generated by the BPM substantially lowers the pH of the porous electrode and promotes selective CH4 and HCOOH generation. The second is the use of a micro-structured porous electrode that employs an anion-exchange membrane and more selectively generates C2+ products. 2-D modeling reveals heterogeneities in the porous electrode enable hotspots of increased pH that locally enhance C2+ selectivity. Ultimately, this talk underscores the powerful ability of continuum modeling to resolve microenvironments at spatial resolutions beyond what is achievable experimentally, as well as to link changes in microenvironment to changes in local selectivity. These simulations will rationalize and guide the engineering of microenvironment in next-generation porous electrodes for CO2 reduction to C2+ products at industrial scales.