Editors’ Choice—Rapid Deactivation Convolutes Electrochemical CO 2 Reduction Selectivity Measurements on Gold Rotating Ring Disk Electrodes

Kelly, Maria; Wnuk, Rachel A.; Kas, Recep; Teeter, Glenn; Kreider, Melissa E.; Smith, Wilson A.

doi:10.1149/1945-7111/adc553

Title: Editors’ Choice—Rapid Deactivation Convolutes Electrochemical CO ₂ Reduction Selectivity Measurements on Gold Rotating Ring Disk Electrodes

Journal Article · 08 April 2025 · Journal of the Electrochemical Society

DOI: https://doi.org/10.1149/1945-7111/adc553 · OSTI ID:2553109

; Wnuk, Rachel A.; Kas, Recep; Teeter, Glenn;

;

Voltammetric measurements of electrochemical CO ₂ reduction reaction (CO ₂ RR) selectivity on rotating ring disk electrodes (RRDE) are a rapid and sensitive method for quantifying an electrocatalyst’s selectivity, i.e. faradaic efficiency (FE). This method has been applied to polycrystalline Au electrocatalysts where a Au disk electrode catalyzes both the CO ₂ RR and hydrogen evolution reaction while the concentric Au ring electrode selectively senses CO by oxidizing CO back to CO ₂ . Such measurements enabled fundamental mechanistic studies but suffer from poor inter-laboratory reproducibility. This work identifies causes of variability in RRDE selectivity measurements by comparing protocols with different electrochemical methods, reagent purities, and glassware cleaning procedures. We observed FE _CO decrease by 56% during 5 min chronoamperometry measurements, a phenomenon that is not readily apparent in voltammetric scans due to their dynamic nature. Electroplating of electrolyte impurities onto the disk and ring surfaces were identified as a major contributor to Au deactivation. Additionally, the oxygen reduction reaction may lead to higher disk currents in inadequately purged electrolytes, causing an apparent underestimation of FE _CO at low overpotentials. Lastly, we propose operational bounds for CO ₂ RR selectivity measurements on Au using the RRDE method and provide suggestions on steps for improving the accuracy of this technique.

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Research Organization:: National Renewable Energy Laboratory (NREL), Golden, CO (United States)

Sponsoring Organization:: National Science Foundation (NSF); USDOE; USDOE Office of Science (SC), Basic Energy Sciences (BES); USDOE Office of Science (SC), Office of Workforce Development for Teachers & Scientists (WDTS)

Grant/Contract Number:: AC36-08GO28308; SC0021266

OSTI ID:: 2553109

Report Number(s):: NREL/JA--5900-93438

Journal Information:: Journal of the Electrochemical Society, Journal Name: Journal of the Electrochemical Society Journal Issue: 4 Vol. 172; ISSN 0013-4651

Publisher:: The Electrochemical SocietyCopyright Statement

Country of Publication:: United States

Language:: English

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37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
CO2 reduction
carbon dioxide
electrochemistry
rotating ring disk electrode
selectivity

Title: Editors’ Choice—Rapid Deactivation Convolutes Electrochemical CO 2 Reduction Selectivity Measurements on Gold Rotating Ring Disk Electrodes

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Title: Editors’ Choice—Rapid Deactivation Convolutes Electrochemical CO ₂ Reduction Selectivity Measurements on Gold Rotating Ring Disk Electrodes