Hydrodynamics Change Tafel Slopes in Electrochemical CO₂ Reduction on Copper
The hydrodynamics of electrochemical CO₂ reduction (CO₂R) systems is an insufficiently investigated area of research that has broad implications on catalyst activity and selectivity. While most previous reports are limited to laminar and CO₂-sparged systems, herein we address a wide range of hydrodynamics via electrolyte recirculation systems. We find that increased hydrodynamics at the electrode surface results directly in changes to the ethylene and methane Tafel slopes, demonstrating that mass transport is on equal footing with catalyst active sites in determining reaction mechanisms and the ensuing product distribution. Mass transport is traditionally considered to be in the purview of systems-level engineering, yet the present work shows that CO₂R mechanistic work must be considered in the context of the mass transport conditions. We extend our analysis to organic coatings, demonstrating that the films shield the active sites from variability in hydrodynamics and increase the residence time of CO so that it may be further reduced to desirable products.
© 2023 The Authors. Published by American Chemical Society. Attribution 4.0 International (CC BY 4.0). This material is based on work performed by the Liquid Sunlight Alliance, which is supported by the U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences, Fuels from Sunlight Hub under Award Number DE-SC0021266. The Resnick Sustainability Institute at Caltech is acknowledged for its support of enabling infrastructure and facilities. We thank Dr. Ian Sullivan for many productive conversations and Annette Boehme for initial insights into COMSOL calculations of the cells investigated. N.B.W. and Z.J.S. contributed equally to this work. The authors declare no competing financial interest.
Published - acsenergylett.3c00442.pdf
Supplemental Material - nz3c00442_si_001.pdf