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Title: Electrochemical Carbon Monoxide Reduction on Polycrystalline Copper: Effects of Potential, Pressure, and pH on Selectivity toward Multicarbon and Oxygenated Products

Abstract

Here by understanding the surface reactivity of CO, which is a key intermediate during electrochemical CO2 reduction, is crucial for the development of catalysts that selectively target desired products for the conversion of CO2 to fuels and chemicals. In this study, a custom-designed electrochemical cell is utilized to investigate planar polycrystalline copper as an electrocatalyst for CO reduction under alkaline conditions. Seven major CO reduction products have been observed including various hydrocarbons and oxygenates which are also common CO2 reduction products, strongly indicating that CO is a key reaction intermediate for these further-reduced products. A comparison of CO and CO2 reduction demonstrates that there is a large decrease in the overpotential for C–C coupled products under CO reduction conditions. The effects of CO partial pressure and electrolyte pH are investigated; we conclude that the aforementioned large potential shift is primarily a pH effect. Thus, alkaline conditions can be used to increase the energy efficiency of CO and CO2 reduction to C–C coupled products, when these cathode reactions are coupled to the oxygen evolution reaction at the anode. Further analysis of the reaction products reveals common trends in selectivity that indicate both the production of oxygenates and C–C coupled products aremore » favored at lower overpotentials. These selectivity trends are generalized by comparing the results on planar Cu to current state-of-the-art high-surface-area Cu catalysts, which are able to achieve high oxygenate selectivity by operating at the same geometric current density at lower overpotentials. Combined, these findings outline key principles for designing CO and CO2 electrolyzers that are able to produce valuable C–C coupled products with high energy efficiency.« less

Authors:
 [1];  [1];  [2];  [1]; ORCiD logo [1];  [1]; ORCiD logo [3]; ORCiD logo [3];  [3]; ORCiD logo [3]; ORCiD logo [3]
  1. Stanford Univ., Stanford, CA (United States)
  2. Technical Univ. of Denmark, Lyngby (Denmark)
  3. Stanford Univ., Stanford, CA (United States); SLAC National Accelerator Lab., Menlo Park, CA (United States)
Publication Date:
Research Org.:
SLAC National Accelerator Lab., Menlo Park, CA (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES)
OSTI Identifier:
1469211
Grant/Contract Number:  
SC0004993; AC02-76SF00515
Resource Type:
Accepted Manuscript
Journal Name:
ACS Catalysis
Additional Journal Information:
Journal Volume: 8; Journal Issue: 8; Related Information: The Supporting Information is available free of charge on the ACS Publications website at https://pubs.acs.org/doi/suppl/10.1021/acscatal.8b01200; Journal ID: ISSN 2155-5435
Publisher:
American Chemical Society (ACS)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; 32 ENERGY CONSERVATION, CONSUMPTION, AND UTILIZATION; carbon monoxide; carbon monoxide reduction; copper; overpotential; pH effect; selectivity

Citation Formats

Wang, Lei, Nitopi, Stephanie A., Bertheussen, Erlend, Orazov, Marat, Morales-Guio, Carlos G., Liu, Xinyan, Higgins, Drew C., Chan, Karen, Nørskov, Jens K., Hahn, Christopher, and Jaramillo, Thomas F. Electrochemical Carbon Monoxide Reduction on Polycrystalline Copper: Effects of Potential, Pressure, and pH on Selectivity toward Multicarbon and Oxygenated Products. United States: N. p., 2018. Web. doi:10.1021/acscatal.8b01200.
Wang, Lei, Nitopi, Stephanie A., Bertheussen, Erlend, Orazov, Marat, Morales-Guio, Carlos G., Liu, Xinyan, Higgins, Drew C., Chan, Karen, Nørskov, Jens K., Hahn, Christopher, & Jaramillo, Thomas F. Electrochemical Carbon Monoxide Reduction on Polycrystalline Copper: Effects of Potential, Pressure, and pH on Selectivity toward Multicarbon and Oxygenated Products. United States. https://doi.org/10.1021/acscatal.8b01200
Wang, Lei, Nitopi, Stephanie A., Bertheussen, Erlend, Orazov, Marat, Morales-Guio, Carlos G., Liu, Xinyan, Higgins, Drew C., Chan, Karen, Nørskov, Jens K., Hahn, Christopher, and Jaramillo, Thomas F. Wed . "Electrochemical Carbon Monoxide Reduction on Polycrystalline Copper: Effects of Potential, Pressure, and pH on Selectivity toward Multicarbon and Oxygenated Products". United States. https://doi.org/10.1021/acscatal.8b01200. https://www.osti.gov/servlets/purl/1469211.
@article{osti_1469211,
title = {Electrochemical Carbon Monoxide Reduction on Polycrystalline Copper: Effects of Potential, Pressure, and pH on Selectivity toward Multicarbon and Oxygenated Products},
author = {Wang, Lei and Nitopi, Stephanie A. and Bertheussen, Erlend and Orazov, Marat and Morales-Guio, Carlos G. and Liu, Xinyan and Higgins, Drew C. and Chan, Karen and Nørskov, Jens K. and Hahn, Christopher and Jaramillo, Thomas F.},
abstractNote = {Here by understanding the surface reactivity of CO, which is a key intermediate during electrochemical CO2 reduction, is crucial for the development of catalysts that selectively target desired products for the conversion of CO2 to fuels and chemicals. In this study, a custom-designed electrochemical cell is utilized to investigate planar polycrystalline copper as an electrocatalyst for CO reduction under alkaline conditions. Seven major CO reduction products have been observed including various hydrocarbons and oxygenates which are also common CO2 reduction products, strongly indicating that CO is a key reaction intermediate for these further-reduced products. A comparison of CO and CO2 reduction demonstrates that there is a large decrease in the overpotential for C–C coupled products under CO reduction conditions. The effects of CO partial pressure and electrolyte pH are investigated; we conclude that the aforementioned large potential shift is primarily a pH effect. Thus, alkaline conditions can be used to increase the energy efficiency of CO and CO2 reduction to C–C coupled products, when these cathode reactions are coupled to the oxygen evolution reaction at the anode. Further analysis of the reaction products reveals common trends in selectivity that indicate both the production of oxygenates and C–C coupled products are favored at lower overpotentials. These selectivity trends are generalized by comparing the results on planar Cu to current state-of-the-art high-surface-area Cu catalysts, which are able to achieve high oxygenate selectivity by operating at the same geometric current density at lower overpotentials. Combined, these findings outline key principles for designing CO and CO2 electrolyzers that are able to produce valuable C–C coupled products with high energy efficiency.},
doi = {10.1021/acscatal.8b01200},
journal = {ACS Catalysis},
number = 8,
volume = 8,
place = {United States},
year = {2018},
month = {7}
}

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Works referenced in this record:

Catalysis of the electrochemical reduction of carbon dioxide
journal, January 2013

  • Costentin, Cyrille; Robert, Marc; Savéant, Jean-Michel
  • Chem. Soc. Rev., Vol. 42, Issue 6
  • DOI: 10.1039/C2CS35360A

Electrochemical reduction of CO2 to hydrocarbons to store renewable electrical energy and upgrade biogas
journal, April 2007


Frontiers, Opportunities, and Challenges in Biochemical and Chemical Catalysis of CO 2 Fixation
journal, June 2013

  • Appel, Aaron M.; Bercaw, John E.; Bocarsly, Andrew B.
  • Chemical Reviews, Vol. 113, Issue 8
  • DOI: 10.1021/cr300463y

A comparative technoeconomic analysis of renewable hydrogen production using solar energy
journal, January 2016

  • Shaner, Matthew R.; Atwater, Harry A.; Lewis, Nathan S.
  • Energy & Environmental Science, Vol. 9, Issue 7
  • DOI: 10.1039/C5EE02573G

Synthesis of thin film AuPd alloys and their investigation for electrocatalytic CO 2 reduction
journal, January 2015

  • Hahn, Christopher; Abram, David N.; Hansen, Heine A.
  • Journal of Materials Chemistry A, Vol. 3, Issue 40
  • DOI: 10.1039/C5TA04863J

Nickel–Gallium-Catalyzed Electrochemical Reduction of CO 2 to Highly Reduced Products at Low Overpotentials
journal, February 2016

  • Torelli, Daniel A.; Francis, Sonja A.; Crompton, J. Chance
  • ACS Catalysis, Vol. 6, Issue 3
  • DOI: 10.1021/acscatal.5b02888

How copper catalyzes the electroreduction of carbon dioxide into hydrocarbon fuels
journal, January 2010

  • Peterson, Andrew A.; Abild-Pedersen, Frank; Studt, Felix
  • Energy & Environmental Science, Vol. 3, Issue 9
  • DOI: 10.1039/c0ee00071j

PRODUCTION OF CO AND CH 4 IN ELECTROCHEMICAL REDUCTION OF CO 2 AT METAL ELECTRODES IN AQUEOUS HYDROGENCARBONATE SOLUTION
journal, November 1985

  • Hori, Yoshio; Kikuchi, Katsuhei; Suzuki, Shin
  • Chemistry Letters, Vol. 14, Issue 11
  • DOI: 10.1246/cl.1985.1695

A review of the aqueous electrochemical reduction of CO2 to hydrocarbons at copper
journal, August 2006


Understanding Selectivity for the Electrochemical Reduction of Carbon Dioxide to Formic Acid and Carbon Monoxide on Metal Electrodes
journal, June 2017


Catalysts and Reaction Pathways for the Electrochemical Reduction of Carbon Dioxide
journal, September 2015

  • Kortlever, Ruud; Shen, Jing; Schouten, Klaas Jan P.
  • The Journal of Physical Chemistry Letters, Vol. 6, Issue 20
  • DOI: 10.1021/acs.jpclett.5b01559

Electroreduction of carbon monoxide to methane and ethylene at a copper electrode in aqueous solutions at ambient temperature and pressure
journal, August 1987

  • Hori, Yoshio; Murata, Akira; Takahashi, Ryutaro
  • Journal of the American Chemical Society, Vol. 109, Issue 16
  • DOI: 10.1021/ja00250a044

Electrochemical Reduction of CO at a Copper Electrode
journal, September 1997

  • Hori, Yoshio; Takahashi, Ryutaro; Yoshinami, Yuzuru
  • The Journal of Physical Chemistry B, Vol. 101, Issue 36
  • DOI: 10.1021/jp970284i

Structure Sensitivity of the Electrochemical Reduction of Carbon Monoxide on Copper Single Crystals
journal, April 2013

  • Schouten, Klaas Jan P.; Pérez Gallent, Elena; Koper, Marc T. M.
  • ACS Catalysis, Vol. 3, Issue 6
  • DOI: 10.1021/cs4002404

Two Pathways for the Formation of Ethylene in CO Reduction on Single-Crystal Copper Electrodes
journal, June 2012

  • Schouten, Klaas Jan P.; Qin, Zisheng; Pérez Gallent, Elena
  • Journal of the American Chemical Society, Vol. 134, Issue 24
  • DOI: 10.1021/ja302668n

A DEMS Study of the Reduction of CO2, CO, and HCHO Pre-Adsorbed on Cu Electrodes: Empirical Inferences on the CO2RR Mechanism
journal, January 2015

  • Javier, Alnald; Chmielowiec, Brian; Sanabria-Chinchilla, Jean
  • Electrocatalysis, Vol. 6, Issue 2
  • DOI: 10.1007/s12678-015-0246-1

Electroreduction of carbon monoxide to liquid fuel on oxide-derived nanocrystalline copper
journal, April 2014

  • Li, Christina W.; Ciston, Jim; Kanan, Matthew W.
  • Nature, Vol. 508, Issue 7497
  • DOI: 10.1038/nature13249

Probing the Active Surface Sites for CO Reduction on Oxide-Derived Copper Electrocatalysts
journal, July 2015

  • Verdaguer-Casadevall, Arnau; Li, Christina W.; Johansson, Tobias P.
  • Journal of the American Chemical Society, Vol. 137, Issue 31
  • DOI: 10.1021/jacs.5b06227

Acetaldehyde as an Intermediate in the Electroreduction of Carbon Monoxide to Ethanol on Oxide-Derived Copper
journal, December 2015

  • Bertheussen, Erlend; Verdaguer-Casadevall, Arnau; Ravasio, Davide
  • Angewandte Chemie International Edition, Vol. 55, Issue 4
  • DOI: 10.1002/anie.201508851

New insights into the electrochemical reduction of carbon dioxide on metallic copper surfaces
journal, January 2012

  • Kuhl, Kendra P.; Cave, Etosha R.; Abram, David N.
  • Energy & Environmental Science, Vol. 5, Issue 5
  • DOI: 10.1039/c2ee21234j

Effects of temperature and gas–liquid mass transfer on the operation of small electrochemical cells for the quantitative evaluation of CO 2 reduction electrocatalysts
journal, January 2016

  • Lobaccaro, Peter; Singh, Meenesh R.; Clark, Ezra Lee
  • Physical Chemistry Chemical Physics, Vol. 18, Issue 38
  • DOI: 10.1039/C6CP05287H

Structure- and Potential-Dependent Cation Effects on CO Reduction at Copper Single-Crystal Electrodes
journal, November 2017

  • Pérez-Gallent, Elena; Marcandalli, Giulia; Figueiredo, Marta Costa
  • Journal of the American Chemical Society, Vol. 139, Issue 45
  • DOI: 10.1021/jacs.7b10142

One-step electrosynthesis of ethylene and ethanol from CO2 in an alkaline electrolyzer
journal, January 2016


CO 2 electroreduction to ethylene via hydroxide-mediated copper catalysis at an abrupt interface
journal, May 2018


Initial and later stages of anodic oxide formation on Cu, chemical aspects, structure and electronic properties
journal, August 2001


Competition between CO 2 Reduction and H 2 Evolution on Transition-Metal Electrocatalysts
journal, September 2014

  • Zhang, Yin-Jia; Sethuraman, Vijay; Michalsky, Ronald
  • ACS Catalysis, Vol. 4, Issue 10
  • DOI: 10.1021/cs5012298

“Deactivation of copper electrode” in electrochemical reduction of CO2
journal, September 2005


Electroreduction of CO on Polycrystalline Copper at Low Overpotentials
journal, February 2018


Theoretical Insights into a CO Dimerization Mechanism in CO 2 Electroreduction
journal, May 2015

  • Montoya, Joseph H.; Shi, Chuan; Chan, Karen
  • The Journal of Physical Chemistry Letters, Vol. 6, Issue 11
  • DOI: 10.1021/acs.jpclett.5b00722

Theoretical Considerations on the Electroreduction of CO to C 2 Species on Cu(100) Electrodes
journal, June 2013

  • Calle-Vallejo, Federico; Koper, Marc T. M.
  • Angewandte Chemie International Edition, Vol. 52, Issue 28
  • DOI: 10.1002/anie.201301470

The Importance of Cannizzaro-Type Reactions during Electrocatalytic Reduction of Carbon Dioxide
journal, January 2017

  • Birdja, Yuvraj Y.; Koper, Marc T. M.
  • Journal of the American Chemical Society, Vol. 139, Issue 5
  • DOI: 10.1021/jacs.6b12008

A new mechanism for the selectivity to C1 and C2 species in the electrochemical reduction of carbon dioxide on copper electrodes
journal, January 2011

  • Schouten, K. J. P.; Kwon, Y.; van der Ham, C. J. M.
  • Chemical Science, Vol. 2, Issue 10
  • DOI: 10.1039/c1sc00277e

Surface reconstruction of pure-Cu single-crystal electrodes under CO-reduction potentials in alkaline solutions: A study by seriatim ECSTM-DEMS
journal, November 2016


Spectroscopic Observation of a Hydrogenated CO Dimer Intermediate During CO Reduction on Cu(100) Electrodes
journal, February 2017

  • Pérez-Gallent, Elena; Figueiredo, Marta C.; Calle-Vallejo, Federico
  • Angewandte Chemie International Edition, Vol. 56, Issue 13
  • DOI: 10.1002/anie.201700580

The influence of pH on the reduction of CO and CO 2 to hydrocarbons on copper electrodes
journal, March 2014

  • Schouten, Klaas Jan P.; Pérez Gallent, Elena; Koper, Marc T. M.
  • Journal of Electroanalytical Chemistry, Vol. 716
  • DOI: 10.1016/j.jelechem.2013.08.033

Understanding trends in electrochemical carbon dioxide reduction rates
journal, May 2017

  • Liu, Xinyan; Xiao, Jianping; Peng, Hongjie
  • Nature Communications, Vol. 8, Issue 1
  • DOI: 10.1038/ncomms15438

Engineering Cu surfaces for the electrocatalytic conversion of CO 2 : Controlling selectivity toward oxygenates and hydrocarbons
journal, May 2017

  • Hahn, Christopher; Hatsukade, Toru; Kim, Youn-Geun
  • Proceedings of the National Academy of Sciences, Vol. 114, Issue 23
  • DOI: 10.1073/pnas.1618935114

The importance of surface morphology in controlling the selectivity of polycrystalline copper for CO2 electroreduction
journal, January 2012

  • Tang, Wei; Peterson, Andrew A.; Varela, Ana Sofia
  • Phys. Chem. Chem. Phys., Vol. 14, Issue 1
  • DOI: 10.1039/C1CP22700A

Improving the hydrogen oxidation reaction rate by promotion of hydroxyl adsorption
journal, February 2013

  • Strmcnik, Dusan; Uchimura, Masanobu; Wang, Chao
  • Nature Chemistry, Vol. 5, Issue 4
  • DOI: 10.1038/nchem.1574

Competition between Hydrogen Evolution and Carbon Dioxide Reduction on Copper Electrodes in Mildly Acidic Media
journal, May 2017


Potential Dependence of Electrochemical Barriers from ab Initio Calculations
journal, April 2016


Low-Overpotential Electroreduction of Carbon Monoxide Using Copper Nanowires
journal, June 2017


Electrocatalytic Production of C3-C4 Compounds by Conversion of CO 2 on a Chloride-Induced Bi-Phasic Cu 2 O-Cu Catalyst
journal, October 2015


Subsurface Oxygen in Oxide-Derived Copper Electrocatalysts for Carbon Dioxide Reduction
journal, December 2016

  • Eilert, André; Cavalca, Filippo; Roberts, F. Sloan
  • The Journal of Physical Chemistry Letters, Vol. 8, Issue 1
  • DOI: 10.1021/acs.jpclett.6b02273

Plasma-Activated Copper Nanocube Catalysts for Efficient Carbon Dioxide Electroreduction to Hydrocarbons and Alcohols
journal, April 2017


Is Subsurface Oxygen Necessary for the Electrochemical Reduction of CO 2 on Copper?
journal, January 2018

  • Garza, Alejandro J.; Bell, Alexis T.; Head-Gordon, Martin
  • The Journal of Physical Chemistry Letters, Vol. 9, Issue 3
  • DOI: 10.1021/acs.jpclett.7b03180

The effects of currents and potentials on the selectivities of copper toward carbon dioxide electroreduction
journal, March 2018


Works referencing / citing this record:

What would it take for renewably powered electrosynthesis to displace petrochemical processes?
journal, April 2019


Rational catalyst and electrolyte design for CO2 electroreduction towards multicarbon products
journal, March 2019


Enhanced Electroreduction of Carbon Dioxide to Methanol Using Zinc Dendrites Pulse‐Deposited on Silver Foam
journal, February 2019

  • Low, Qi Hang; Loo, Nicholas Wei Xian; Calle‐Vallejo, Federico
  • Angewandte Chemie International Edition, Vol. 58, Issue 8
  • DOI: 10.1002/anie.201810991

Advances and challenges in electrochemical CO 2 reduction processes: an engineering and design perspective looking beyond new catalyst materials
journal, January 2020

  • Garg, Sahil; Li, Mengran; Weber, Adam Z.
  • Journal of Materials Chemistry A, Vol. 8, Issue 4
  • DOI: 10.1039/c9ta13298h

Enhanced Electroreduction of Carbon Dioxide to Methanol Using Zinc Dendrites Pulse-Deposited on Silver Foam
journal, January 2019

  • Low, Qi Hang; Loo, Nicholas Wei Xian; Calle-Vallejo, Federico
  • Angewandte Chemie, Vol. 131, Issue 8
  • DOI: 10.1002/ange.201810991

Double layer charging driven carbon dioxide adsorption limits the rate of electrochemical carbon dioxide reduction on Gold
journal, January 2020


Formation of carbon–nitrogen bonds in carbon monoxide electrolysis
journal, August 2019


pH effects on the electrochemical reduction of CO(2) towards C2 products on stepped copper
journal, January 2019


Mechanistic reaction pathways of enhanced ethylene yields during electroreduction of CO2–CO co-feeds on Cu and Cu-tandem electrocatalysts
journal, October 2019


Hydroxide Is Not a Promoter of C 2+ Product Formation in the Electrochemical Reduction of CO on Copper
journal, January 2020

  • Li, Jing; Wu, Donghuan; Malkani, Arnav S.
  • Angewandte Chemie International Edition, Vol. 59, Issue 11
  • DOI: 10.1002/anie.201912412

Two-dimensional copper nanosheets for electrochemical reduction of carbon monoxide to acetate
journal, April 2019


Selective reduction of CO to acetaldehyde with CuAg electrocatalysts
journal, January 2020

  • Wang, Lei; Higgins, Drew C.; Ji, Yongfei
  • Proceedings of the National Academy of Sciences, Vol. 117, Issue 23
  • DOI: 10.1073/pnas.1821683117

Hydroxide Is Not a Promoter of C 2+ Product Formation in the Electrochemical Reduction of CO on Copper
journal, March 2020


Constraining CO coverage on copper promotes high-efficiency ethylene electroproduction
journal, November 2019


Cu nanowire-catalyzed electrochemical reduction of CO or CO 2
journal, January 2019

  • Zhang, Hongyi; Zhang, Yinjia; Li, Yuyang
  • Nanoscale, Vol. 11, Issue 25
  • DOI: 10.1039/c9nr03170g

Selectivity of Chemical Conversions: Do Light‐Driven Photoelectrocatalytic Processes Hold Special Promise?
journal, November 2019


Hydrogen bonding steers the product selectivity of electrocatalytic CO reduction
journal, April 2019

  • Li, Jingyi; Li, Xiang; Gunathunge, Charuni M.
  • Proceedings of the National Academy of Sciences, Vol. 116, Issue 19
  • DOI: 10.1073/pnas.1900761116

New aspects of operando Raman spectroscopy applied to electrochemical CO 2 reduction on Cu foams
journal, January 2019

  • Jiang, Shan; Klingan, Katharina; Pasquini, Chiara
  • The Journal of Chemical Physics, Vol. 150, Issue 4
  • DOI: 10.1063/1.5054109

Anomalous hydrogen evolution behavior in high-pH environment induced by locally generated hydronium ions
journal, October 2019


Electrochemically converting carbon monoxide to liquid fuels by directing selectivity with electrode surface area
journal, June 2019


Cover Picture: Hydroxide Is Not a Promoter of C 2+ Product Formation in the Electrochemical Reduction of CO on Copper (Angew. Chem. Int. Ed. 11/2020)
journal, January 2020

  • Li, Jing; Wu, Donghuan; Malkani, Arnav S.
  • Angewandte Chemie International Edition, Vol. 59, Issue 11
  • DOI: 10.1002/anie.202000873