Electrolyte-Guided Design of Electroreductive CO Coupling on Copper Surfaces

• Published in: ACS applied energy materials Vol. 4; no. 8; pp. 8201 - 8210
• Main Authors: Akhade, Sneha A, Jayathilake, Buddhinie S, Weitzner, Stephen E, Eshelman, Hannah V, Hamilton, Julie, Feaster, Jeremy T, Wakerley, David W, Wang, Lei, Lamaison, Sarah, Lee, Dong Un, Hahn, Christopher, Jaramillo, Thomas F, Duoss, Eric B, Baker, Sarah E, Varley, Joel B
• Format: Journal Article
• Language: English
• Published: United States American Chemical Society 23-08-2021; American Chemical Society (ACS)
• Subjects: catalysis; CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSICS; CO coupling; CO2 reduction; copper; density functional theory; electrical properties; electrochemical reduction; electrodes; electrolyte solutions; electrolytes; ENVIRONMENTAL SCIENCES; ions; MATERIALS SCIENCE; modeling; electrochemical reduction; modeling; density functional theory; copper; catalysis; CO2 reduction; CO coupling
• ISSN: 2574-0962; 2574-0962
• DOI: 10.1021/acsaem.1c01427

Engineering the interfacial distribution of electrolytic ions can aid in modulating the electrocatalyst performance and efficiency. Using a hybrid quantum-classical modeling approach, we describe how predictive tuning of the solution microenvironment on copper can enhance the efficiency of CO2 reduction (CO2R) to C2 products. We elucidate how competing electrolyte constituents in mixed electrolyte solutions stimulate restructuring of the electrochemical double layer (EDL) and stabilize the OCCO* dimer (* denotes surface adsorbed), with predictions validated in flow reactors using copper gas diffusion electrodes (Cu-GDEs). Our findings highlight how molecular-scale electrolyte engineering with informed models of the EDL can be leveraged to tailor CO2R activity and selectivity toward C2 products.