Importance of Site Diversity and Connectivity in Electrochemical CO Reduction on Cu

Electrochemical CO2 reduction on Cu is a promising approach to produce value-added-chemicals using renewable feedstocks, yet various Cu preparations have led to differences in activity and selectivity towards single and multi-carbon products. Here, we find, surprisingly, that the effective catalytic activity towards ethylene improves when there is a larger fraction of less active sites acting as reservoirs of *CO on the surface of Cu nanoparticle electrocatalysts. In an adaptation of chemical transient kinetics to electrocatalysis, we measure the dynamic response of a gas diffusion electrode (GDE) cell when the feed gas is abruptly switched between Ar (inert) and CO. When switching from the Ar to CO, CO reduction (COR) begins promptly, but when switching from CO to Ar, COR can be maintained for several seconds (delay time), despite the absence of the CO reactant in the gas phase. A three-site microkinetic model captures the observed dynamic behavior and shows that Cu catalysts exhibiting delay times have a less active *CO reservoir that exhibits fast diffusion to active sites. The observed delay times and the estimated *CO reservoir sizes are affected by catalyst preparation, applied potential, and microenvironment (electrolyte cation identity, electrolyte pH, and CO partial pressure). Notably, we estimate that the *CO reservoir surface coverage can be as high as 88±7% on oxide-derived (OD-Cu) at high overpotentials (-1.52 V vs. SHE) and that increases in reservoir coverage coincide with increased turnover frequencies to ethylene. We also estimate that *CO can travel substantial distances (up to 10s of nm) prior to desorption or reaction. It appears that active C-C coupling sites, by themselves, do not control selectivity to C2+ products in electrochemical COR; the supply of CO to those sites is also a crucial factor. More generally, the overall activity of Cu electrocatalysts cannot be approximated from linear combinations of individual site activities. Future designs must consider the diversity of the catalyst network and account for inter-site transportation pathways

Data from: Importance of Site Diversity and Connectivity in Electrochemical CO reduction on Cu

<p><strong>Microkinetic Modeling</strong></p><ul><li>Contains raw ipynb files to generate graphs used in this work</li></ul><p><strong>EC-Lab Potentiosat Data</strong></p><ul><li>Contains potentiostat I-V data, organized in folder by date of acquisition</li></ul><p><strong>Mass flow and product quantification</strong></p><ul><li>Mass flow measurements, gas chromatography, and nuclear magnetic resonance spectroscopy</li></ul><p><strong>Overview of all experiments</strong></p><ul><li>Spreadsheets listing all experiments</li></ul><p><strong>Cell Design</strong></p><ul><li>Files for the 1 cm2 gas diffusion electrodes used in this work.</li></ul><p>This work was supported by the Clean Energy Manufacturing Program, U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences, Chemical Sciences, Geosciences, and Biosciences Division, in under Contract No. DE-AC02-05CH11231. Research on microkinetic modeling was supported as part of the Center for Closing the Carbon Cycle, an Energy Frontier Research Center funded by the U.S. Department of Energy (DOE), Office of Science, Basic Energy Sciences (BES), under Award Number DE-SC0023427. </p&gt