CO Adsorption Dynamics during CO2 Electrolysis in Aprotic Organic Electrolytes
Francesco Longhin1, Maria Rodrigues Pinto1, Qiucheng Xu2
1Surface Physics and Catalysis (SurfCat), Department of Physics, Technical University of Denmark, 2800 Kongens, Lyngby, Denmark.
ACS Applied Materials & Interfaces
|June 12, 2025
Summary
Investigating carbon dioxide electrolysis (CO2E) in organic electrolytes, this study reveals unique CO adsorption dynamics on copper surfaces. Different electrolyte salts significantly alter CO adsorption behavior, impacting CO2E product selectivity.
Area of Science:
- Electrochemistry
- Surface Science
- Catalysis
Background:
- Carbon dioxide electrolysis (CO2E) in aprotic organic electrolytes produces oxalate, CO, and carbonate.
- Understanding CO adsorption is crucial for optimizing CO2E selectivity and efficiency.
- Previous studies on CO adsorption have been conducted in different electrolyte systems.
Purpose of the Study:
- To investigate the CO adsorption dynamics in the CO adsorption region (COAR) during CO2E.
- To elucidate the influence of electrolyte composition on CO adsorption behavior on copper surfaces.
- To characterize the nature of CO adsorption using in-situ spectroscopy.
Main Methods:
- Attenuated total reflectance surface-enhanced infrared absorption spectroscopy (ATR-SEIRAS) was employed.
- Experiments were conducted on polycrystalline copper electrodes in DMSO/DMF-based electrolytes.
- Electrochemical potentials were varied to study CO adsorption onset and behavior.
Main Results:
- A distinct vibrational feature at 2007 cm⁻¹ emerged during CO2E, attributed to CO adsorption on copper.
- This band's shape and shift suggest a convolution of CO adsorption on higher and lower-coordinated Cu sites.
- Replacing TBAPF₆ with CsClO₄ in the electrolyte eliminated the ~2000 cm⁻¹ band and introduced a new band at ~1800 cm⁻¹, indicating bridged CO adsorption.
Conclusions:
- The CO adsorption environment in organic electrolytes during CO2E is unique and influenced by electrolyte-adsorbate interactions.
- The specific electrolyte salt (e.g., CsClO₄ vs. TBAPF₆) dramatically alters CO adsorption modes and surface species.
- These findings provide critical insights into the reaction mechanisms and selectivity of CO2E in aprotic organic media.
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