Real-time detection of acetaldehyde in electrochemical CO reduction

Yu Qiao^a, Brian Seger^a, Ib Chorkendorff^a, Degenhart Hochfilzer^a

^aTechnical University of Denmark, Department of Physics, Fysikvej, 312, Kongens Lyngby, Denmark

Materials for Sustainable Development Conference (MATSUS)
Proceedings of MATSUS Fall 2023 Conference (MATSUSFall23)

#CO2X - Frontier developments in Electrochemical CO2 reduction and the utilization

Torremolinos, Spain, 2023 October 16th - 20th

Organizers: Alexander Bagger and Yu Katayama

Oral, Yu Qiao, presentation 022
DOI: https://doi.org/10.29363/nanoge.matsus.2023.022
Publication date: 18th July 2023

Copper is the only monometallic material that produces C₂ hydrocarbons and oxygenates from electrochemical CO₂ and CO reduction (eCO2RR and eCORR) [1]. Previous studies have found ethylene (C₂H₄) and ethanol (EtOH) share the same formation pathway after C-C coupling [2], which is the rate-limiting step of C₂ product formation [3]. However, their bifurcation point remains unclear. It has been reported that acetaldehyde (AcH) is the direct precursor of EtOH, and the earliest bifurcation happens between C₂H₄ and AcH during eCO2RR [4]. Considering the experimentally observed similar product distribution in eCORR as in eCO2RR process [5], the above finding was extrapolated as that AcH is the direct precursor of EtOH and that the earliest branching happens between C₂H₄ and AcH in both eCORR and eCO2RR processes [6]. However, since eCO2RR is normally conducted in neutral pH whereas eCORR is operated in alkaline electrolytes where AcH is unstable [7], the above extrapolation fails to take alkaline-induced AcH chemical conversion into account. Moreover, AcH as a liquid product is usually detected and measured separately from gas products with ex situ techniques. As a consequence, the validation and precision of analysis on the AcH/EtOH vs. C₂H₄ generation mechanism during eCORR are questionable.

In this work, we investigated the AcH chemistry in alkaline electrolytes and thus manifested the necessity of real-time detection of AcH during eCORR, followed by its operando simultaneous measurement with other gas products (H₂, CH₄, and C₂H₄) during eCORR realized on our electrochemistry-mass spectrometry (EC-MS) system [8] with deliberately modified mass spectrometer (MS) parameters. With the high sensitivity and high time resolution, operando AcH production on both polycrystalline and single crystal Cu electrodes during eCORR under low overpotentials (> -0.6 V) is presented for the first time. The presented work provides valuable insights into the facet-dependent AcH/EtOH and C₂H₄ bifurcation during eCORR.

References:

[1] Y. Hori, “Electrochemical CO2 Reduction on Metal Electrodes,” in Modern Aspects of Electrochemistry, New York, NY: Springer New York, 2008, pp. 89–189.

[2] R. Kortlever, J. Shen, K. J. P. Schouten, F. Calle-Vallejo, and M. T. M. Koper, “Catalysts and Reaction Pathways for the Electrochemical Reduction of Carbon Dioxide,” J. Phys. Chem. Lett., vol. 6, no. 20, pp. 4073–4082, 2015.

[3] Y. Kim et al., “Time-resolved observation of C-C coupling intermediates on Cu electrodes for selective electrochemical CO2reduction,” Energy Environ. Sci., vol. 13, no. 11, pp. 4301–4311, 2020.

[4] K. P. Kuhl, E. R. Cave, D. N. Abram, and T. F. Jaramillo, “New insights into the electrochemical reduction of carbon dioxide on metallic copper surfaces,” Energy Environ. Sci., vol. 5, no. 5, pp. 7050–7059, 2012.

[5] Y. Hori, R. Takahashi, Y. Yoshinami, and A. Murata, “Electrochemical reduction of CO at a copper electrode,” J. Phys. Chem. B, vol. 101, no. 36, pp. 7075–7081, 1997.

[6] K. J. P. Schouten, Y. Kwon, C. J. M. Van Der Ham, Z. Qin, and M. T. M. Koper, “A new mechanism for the selectivity to C1 and C2 species in the electrochemical reduction of carbon dioxide on copper electrodes,” Chem. Sci., vol. 2, no. 10, pp. 1902–1909, 2011.

[7] E. Bertheussen et al., “Acetaldehyde as an Intermediate in the Electroreduction of Carbon Monoxide to Ethanol on Oxide-Derived Copper,” Angew. Chemie - Int. Ed., vol. 55, no. 4, pp. 1450–1454, 2016.

[8] [1] Y. Hori, “Electrochemical CO2 Reduction on Metal Electrodes,” in Modern Aspects of Electrochemistry, New York, NY: Springer New York, 2008, pp. 89–189. [2] R. Kortlever, J. Shen, K. J. P. Schouten, F. Calle-Vallejo, and M. T. M. Koper, “Catalysts and Reaction Pathways for the Electrochemical Reduction of Carbon Dioxide,” J. Phys. Chem. Lett., vol. 6, no. 20, pp. 4073–4082, 2015, doi: 10.1021/acs.jpclett.5b01559. [3] Y. Kim et al., “Time-resolved observation of C-C coupling intermediates on Cu electrodes for selective electrochemical CO2reduction,” Energy Environ. Sci., vol. 13, no. 11, pp. 4301–4311, 2020, doi: 10.1039/d0ee01690j. [4] K. P. Kuhl, E. R. Cave, D. N. Abram, and T. F. Jaramillo, “New insights into the electrochemical reduction of carbon dioxide on metallic copper surfaces,” Energy Environ. Sci., vol. 5, no. 5, pp. 7050–7059, 2012, doi: 10.1039/c2ee21234j. [5] Y. Hori, R. Takahashi, Y. Yoshinami, and A. Murata, “Electrochemical reduction of CO at a copper electrode,” J. Phys. Chem. B, vol. 101, no. 36, pp. 7075–7081, 1997, doi: 10.1021/jp970284i. [6] K. J. P. Schouten, Y. Kwon, C. J. M. Van Der Ham, Z. Qin, and M. T. M. Koper, “A new mechanism for the selectivity to C1 and C2 species in the electrochemical reduction of carbon dioxide on copper electrodes,” Chem. Sci., vol. 2, no. 10, pp. 1902–1909, 2011, doi: 10.1039/c1sc00277e. [7] E. Bertheussen et al., “Acetaldehyde as an Intermediate in the Electroreduction of Carbon Monoxide to Ethanol on Oxide-Derived Copper,” Angew. Chemie - Int. Ed., vol. 55, no. 4, pp. 1450–1454, 2016, doi: 10.1002/anie.201508851. [8] D. B. Trimarco et al., “Enabling real-time detection of electrochemical desorption phenomena with sub-monolayer sensitivity,” Electrochim. Acta, vol. 268, pp. 520–530, 2018.

Acknowledgements:

B.S. and Y.Q. acknowledge European Union’s Horizon 2020 research and innovation programme under grant agreement no. 85144, (SELECT-CO2).

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