Acetaldehyde as an intermediate in the electroreduction of carbon monoxide to ethanol on oxide-derived copper

Bertheussen, Erlend; Verdaguer-Casadevall, Arnau; Ravasio, Davide; Montoya, Joseph H.; Trimarco, Daniel B.; Roy, Claudie; Meier, Sebastian; Wendland, Jürgen; Nørskov, Jens K.; Stephens, Ifan E.  L.; Chorkendorff, Ib

doi:10.1002/anie.201508851

Title: Acetaldehyde as an intermediate in the electroreduction of carbon monoxide to ethanol on oxide-derived copper

Journal Article · Mon Dec 21 00:00:00 EST 2015 · Angewandte Chemie (International Edition)

DOI:https://doi.org/10.1002/anie.201508851· OSTI ID:1240104

^[1]; Verdaguer-Casadevall, Arnau ^[1]; Ravasio, Davide ^[2]; Montoya, Joseph H. ^[3]; Trimarco, Daniel B. ^[1]; Roy, Claudie ^[1];

^[1];

^[4]; Nørskov, Jens K. ^[5];

^[6];

^[1]

Technical University of Denmark, Lyngby (Denmark)
Carlsberg Lab., KÃ¸benhavn V, (Denmark)
Stanford Univ., Stanford, CA (United States)
Carlsberg Lab., KÃ¸benhavn V (Denmark)
SLAC National Accelerator Lab., Menlo Park, CA (United States)
Technical University of Denmark, Lyngby (Denmark); Massachusetts Inst. of Technology (MIT), Cambridge, MA (United States)

Oxide-derived copper (OD-Cu) electrodes exhibit unprecedented CO reduction performance towards liquid fuels, producing ethanol and acetate with >50 % Faradaic efficiency at -0.3 V (vs. RHE). By using static headspace-gas chromatography for liquid phase analysis, we identify acetaldehyde as a minor product and key intermediate in the electroreduction of CO to ethanol on OD-Cu electrodes. Acetaldehyde is produced with a Faradaic efficiency of ≈5 % at -0.33 V (vs. RHE). We show that acetaldehyde forms at low steady-state concentrations, and that free acetaldehyde is difficult to detect in alkaline solutions using NMR spectroscopy, requiring alternative methods for detection and quantification. Our results indicate an important step towards understanding the CO reduction mechanism on OD-Cu electrodes.

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Research Organization:: SLAC National Accelerator Laboratory (SLAC), Menlo Park, CA (United States)

Sponsoring Organization:: USDOE Office of Science (SC)

Grant/Contract Number:: AC02-76SF00515

OSTI ID:: 1240104

Journal Information:: Angewandte Chemie (International Edition), Vol. 55, Issue 4; ISSN 1433-7851

Publisher:: WileyCopyright Statement

Country of Publication:: United States

Language:: English

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Cited by: 143 works

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References (29)

Recycling of carbon dioxide to methanol and derived products – closing the loop Goeppert, Alain; Czaun, Miklos; Jones, John-Paul Chem. Soc. Rev., Vol. 43, Issue 23 https://doi.org/10.1039/C4CS00122B	journal	January 2014
Electrochemical CO₂ Reduction on Metal Electrodes Hori, Y.; Vayenas, Constantinos G.; White, Ralph E. Modern Aspects of Electrochemistry, p. 89-189 https://doi.org/10.1007/978-0-387-49489-0_3	book	January 2008
New insights into the electrochemical reduction of carbon dioxide on metallic copper surfaces Kuhl, Kendra P.; Cave, Etosha R.; Abram, David N. Energy & Environmental Science, Vol. 5, Issue 5 https://doi.org/10.1039/c2ee21234j	journal	January 2012
A new mechanism for the selectivity to C1 and C2 species in the electrochemical reduction of carbon dioxide on copper electrodes Schouten, K. J. P.; Kwon, Y.; van der Ham, C. J. M. Chemical Science, Vol. 2, Issue 10 https://doi.org/10.1039/c1sc00277e	journal	January 2011
Impurity Ion Complexation Enhances Carbon Dioxide Reduction Catalysis Wuttig, Anna; Surendranath, Yogesh ACS Catalysis, Vol. 5, Issue 7 https://doi.org/10.1021/acscatal.5b00808	journal	June 2015
The importance of surface morphology in controlling the selectivity of polycrystalline copper for CO2 electroreduction Tang, Wei; Peterson, Andrew A.; Varela, Ana Sofia Phys. Chem. Chem. Phys., Vol. 14, Issue 1 https://doi.org/10.1039/C1CP22700A	journal	January 2012
Aqueous CO ₂ Reduction at Very Low Overpotential on Oxide-Derived Au Nanoparticles Chen, Yihong; Li, Christina W.; Kanan, Matthew W. Journal of the American Chemical Society, Vol. 134, Issue 49 https://doi.org/10.1021/ja309317u	journal	November 2012
Efficient Reduction of CO ₂ to CO with High Current Density Using in Situ or ex Situ Prepared Bi-Based Materials Medina-Ramos, Jonnathan; DiMeglio, John L.; Rosenthal, Joel Journal of the American Chemical Society, Vol. 136, Issue 23 https://doi.org/10.1021/ja501923g	journal	May 2014
Active and Selective Conversion of CO ₂ to CO on Ultrathin Au Nanowires Zhu, Wenlei; Zhang, Yin-Jia; Zhang, Hongyi Journal of the American Chemical Society, Vol. 136, Issue 46 https://doi.org/10.1021/ja5095099	journal	November 2014
Robust carbon dioxide reduction on molybdenum disulphide edges Asadi, Mohammad; Kumar, Bijandra; Behranginia, Amirhossein Nature Communications, Vol. 5, Issue 1 https://doi.org/10.1038/ncomms5470	journal	July 2014
Metal-Doped Nitrogenated Carbon as an Efficient Catalyst for Direct CO ₂ Electroreduction to CO and Hydrocarbons Varela, Ana Sofia; Ranjbar Sahraie, Nastaran; Steinberg, Julian Angewandte Chemie International Edition, Vol. 54, Issue 37 https://doi.org/10.1002/anie.201502099	journal	July 2015
Metal-Doped Nitrogenated Carbon as an Efficient Catalyst for Direct CO ₂ Electroreduction to CO and Hydrocarbons Varela, Ana Sofia; Ranjbar Sahraie, Nastaran; Steinberg, Julian Angewandte Chemie, Vol. 127, Issue 37 https://doi.org/10.1002/ange.201502099	journal	July 2015
Activity Descriptors for CO ₂ Electroreduction to Methane on Transition-Metal Catalysts Peterson, Andrew A.; Nørskov, Jens K. The Journal of Physical Chemistry Letters, Vol. 3, Issue 2 https://doi.org/10.1021/jz201461p	journal	January 2012
CO₂ Reduction at Low Overpotential on Cu Electrodes Resulting from the Reduction of Thick Cu₂O Films Li, Christina W.; Kanan, Matthew W. Journal of the American Chemical Society, Vol. 134, Issue 17, p. 7231-7234 https://doi.org/10.1021/ja3010978	journal	April 2012
Electroreduction of carbon monoxide to liquid fuel on oxide-derived nanocrystalline copper Li, Christina W.; Ciston, Jim; Kanan, Matthew W. Nature, Vol. 508, Issue 7497 https://doi.org/10.1038/nature13249	journal	April 2014
Probing the Active Surface Sites for CO Reduction on Oxide-Derived Copper Electrocatalysts Verdaguer-Casadevall, Arnau; Li, Christina W.; Johansson, Tobias P. Journal of the American Chemical Society, Vol. 137, Issue 31 https://doi.org/10.1021/jacs.5b06227	journal	July 2015
Electrochemical Reduction of CO at a Copper Electrode Hori, Yoshio; Takahashi, Ryutaro; Yoshinami, Yuzuru The Journal of Physical Chemistry B, Vol. 101, Issue 36 https://doi.org/10.1021/jp970284i	journal	September 1997
Theoretical Insights into a CO Dimerization Mechanism in CO ₂ Electroreduction Montoya, Joseph H.; Shi, Chuan; Chan, Karen The Journal of Physical Chemistry Letters, Vol. 6, Issue 11 https://doi.org/10.1021/acs.jpclett.5b00722	journal	May 2015
Selective Formation of C2 Compounds from Electrochemical Reduction of CO ₂ at a Series of Copper Single Crystal Electrodes Hori, Yoshio; Takahashi, Ichiro; Koga, Osamu The Journal of Physical Chemistry B, Vol. 106, Issue 1 https://doi.org/10.1021/jp013478d	journal	January 2002
Ethanol, Acetaldehyde and Acetic Acid Adsorption/Electrooxidation on a Pt Thin Film Electrode under Continuous Electrolyte Flow: An in Situ ATR-FTIRS Flow Cell Study Heinen, M.; Jusys, Z.; Behm, R. J. The Journal of Physical Chemistry C, Vol. 114, Issue 21 https://doi.org/10.1021/jp101441q	journal	May 2010
Insights into CC Coupling in CO ₂ Electroreduction on Copper Electrodes Montoya, Joseph H.; Peterson, Andrew A.; Nørskov, Jens K. ChemCatChem, Vol. 5, Issue 3 https://doi.org/10.1002/cctc.201200564	journal	January 2013
Theoretical Considerations on the Electroreduction of CO to C ₂ Species on Cu(100) Electrodes Calle-Vallejo, Federico; Koper, Marc T. M. Angewandte Chemie International Edition, Vol. 52, Issue 28 https://doi.org/10.1002/anie.201301470	journal	June 2013
Theoretical Considerations on the Electroreduction of CO to C ₂ Species on Cu(100) Electrodes Calle-Vallejo, Federico; Koper, Marc T. M. Angewandte Chemie, Vol. 125, Issue 28 https://doi.org/10.1002/ange.201301470	journal	June 2013
Photocatalytic reduction of CO2: a brief review on product analysis and systematic methods Hong, Jindui; Zhang, Wei; Ren, Jia Analytical Methods, Vol. 5, Issue 5 https://doi.org/10.1039/c2ay26270c	journal	January 2013
Electrocatalytic Oxidation of Alcohols on Gold in Alkaline Media: Base or Gold Catalysis? Kwon, Youngkook; Lai, Stanley C. S.; Rodriguez, Paramaconi Journal of the American Chemical Society, Vol. 133, Issue 18 https://doi.org/10.1021/ja200976j	journal	May 2011
Experimental Aspects in Benchmarking of the Electrocatalytic Activity Čolić, Viktor; Tymoczko, Jakub; Maljusch, Artjom ChemElectroChem, Vol. 2, Issue 1 https://doi.org/10.1002/celc.201402295	journal	November 2014
An object-oriented scripting interface to a legacy electronic structure code Bahn, S. R.; Jacobsen, K. W. Computing in Science & Engineering, Vol. 4, Issue 3 https://doi.org/10.1109/5992.998641	journal	January 2002
Improved adsorption energetics within density-functional theory using revised Perdew-Burke-Ernzerhof functionals Hammer, B.; Hansen, L. B.; Nørskov, J. K. Physical Review B, Vol. 59, Issue 11 https://doi.org/10.1103/PhysRevB.59.7413	journal	March 1999
How copper catalyzes the electroreduction of carbon dioxide into hydrocarbon fuels Peterson, Andrew A.; Abild-Pedersen, Frank; Studt, Felix Energy & Environmental Science, Vol. 3, Issue 9 https://doi.org/10.1039/c0ee00071j	journal	January 2010

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Structure‐Sensitivity and Electrolyte Effects in CO ₂ Electroreduction: From Model Studies to Applications Sebastián‐Pascual, Paula; Mezzavilla, Stefano; Stephens, Ifan E. L. ChemCatChem, Vol. 11, Issue 16 https://doi.org/10.1002/cctc.201900552	journal	June 2019
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AuCu Alloy Nanoparticle Embedded Cu Submicrocone Arrays for Selective Conversion of CO ₂ to Ethanol Shen, Sibo; Peng, Xianyun; Song, Lida Small, Vol. 15, Issue 37 https://doi.org/10.1002/smll.201902229	journal	June 2019
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Surface strategies for catalytic CO ₂ reduction: from two-dimensional materials to nanoclusters to single atoms Wang, Liming; Chen, Wenlong; Zhang, Doudou Chemical Society Reviews, Vol. 48, Issue 21 https://doi.org/10.1039/c9cs00163h	journal	January 2019
Solar driven reduction of CO ₂ using Pt–Cu/C as a catalyst in a photoelectrochemical cell: experiment and mechanism study Xuan, Xiaoxu; Cheng, Jun; Yang, Xiao RSC Advances, Vol. 9, Issue 19 https://doi.org/10.1039/c9ra00176j	journal	January 2019
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Selective reduction of CO to acetaldehyde with CuAg electrocatalysts Wang, Lei; Higgins, Drew C.; Ji, Yongfei Proceedings of the National Academy of Sciences, Vol. 117, Issue 23 https://doi.org/10.1073/pnas.1821683117	journal	January 2020
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