Acetaldehyde as an Intermediate in the Electroreduction of Carbon Monoxide to Ethanol on Oxide-Derived Copper

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

doi:10.1002/anie.201508851

Acetaldehyde as an Intermediate in the Electroreduction of Carbon Monoxide to Ethanol on Oxide-Derived Copper

Angew Chem Int Ed Engl. 2016 Jan 22;55(4):1450-4. doi: 10.1002/anie.201508851. Epub 2015 Dec 21.

Affiliations

¹ Department of Physics, Technical University of Denmark, 2800 Kgs., Lyngby, Denmark.
² Carlsberg Laboratory, Gamle Carlsberg vej 4, 1799, København V, Denmark.
³ SUNCAT Center for Catalysis and Interface Science, Department of Chemical Engineering, Stanford University, 443 Via Ortega, Stanford, CA, 94305, USA.
⁴ Department of Chemistry, Technical University of Denmark, 2800 Kongens, Lyngby, Denmark.
⁵ SUNCAT Center for Catalysis and Interface Science, SLAC National Accelerator Laboratory, 2675 Sand Hill Road, Menlo Park, CA, 94025, USA.
⁶ Department of Physics, Technical University of Denmark, 2800 Kgs., Lyngby, Denmark. [email protected].
⁷ Department of Mechanical Engineering, Massachusetts Institute of Technology (MIT), 77 Massachusetts Avenue, Cambridge, MA, 02319, USA. [email protected].
⁸ Department of Physics, Technical University of Denmark, 2800 Kgs., Lyngby, Denmark. [email protected].

Abstract

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 represent an important step towards understanding the CO reduction mechanism on OD-Cu electrodes.

Keywords: analytical chemistry; catalysis; electrochemistry; energy conversion; materials science.

Publication types

Research Support, Non-U.S. Gov't