skip to main content
DOE PAGES title logo U.S. Department of Energy
Office of Scientific and Technical Information

This content will become publicly available on July 24, 2020

Title: Selective reduction of CO to acetaldehyde with CuAg electrocatalysts

Abstract

Electrochemical CO reduction can serve as a sequential step in the transformation of CO 2 into multicarbon fuels and chemicals. In this study, we provide insights on how to steer selectivity for CO reduction almost exclusively toward a single multicarbon oxygenate by carefully controlling the catalyst composition and its surrounding reaction conditions. Under alkaline reaction conditions, we demonstrate that planar CuAg electrodes can reduce CO to acetaldehyde with over 50% Faradaic efficiency and over 90% selectivity on a carbon basis at a modest electrode potential of −0.536 V vs. the reversible hydrogen electrode. The Faradaic efficiency to acetaldehyde was further enhanced to 70% by increasing the roughness factor of the CuAg electrode. Density functional theory calculations indicate that Ag ad-atoms on Cu weaken the binding energy of the reduced acetaldehyde intermediate and inhibit its further reduction to ethanol, demonstrating that the improved selectivity to acetaldehyde is due to the electronic effect from Ag incorporation. These findings will aid in the design of catalysts that are able to guide complex reaction networks and achieve high selectivity for the desired product.

Authors:
ORCiD logo; ; ; ORCiD logo; ORCiD logo; ;
Publication Date:
Sponsoring Org.:
USDOE
OSTI Identifier:
1594223
Grant/Contract Number:  
SC0004993
Resource Type:
Published Article
Journal Name:
Proceedings of the National Academy of Sciences of the United States of America
Additional Journal Information:
Journal Name: Proceedings of the National Academy of Sciences of the United States of America; Journal ID: ISSN 0027-8424
Publisher:
Proceedings of the National Academy of Sciences
Country of Publication:
United States
Language:
English

Citation Formats

Wang, Lei, Higgins, Drew C., Ji, Yongfei, Morales-Guio, Carlos G., Chan, Karen, Hahn, Christopher, and Jaramillo, Thomas F. Selective reduction of CO to acetaldehyde with CuAg electrocatalysts. United States: N. p., 2020. Web. doi:10.1073/pnas.1821683117.
Wang, Lei, Higgins, Drew C., Ji, Yongfei, Morales-Guio, Carlos G., Chan, Karen, Hahn, Christopher, & Jaramillo, Thomas F. Selective reduction of CO to acetaldehyde with CuAg electrocatalysts. United States. doi:10.1073/pnas.1821683117.
Wang, Lei, Higgins, Drew C., Ji, Yongfei, Morales-Guio, Carlos G., Chan, Karen, Hahn, Christopher, and Jaramillo, Thomas F. Fri . "Selective reduction of CO to acetaldehyde with CuAg electrocatalysts". United States. doi:10.1073/pnas.1821683117.
@article{osti_1594223,
title = {Selective reduction of CO to acetaldehyde with CuAg electrocatalysts},
author = {Wang, Lei and Higgins, Drew C. and Ji, Yongfei and Morales-Guio, Carlos G. and Chan, Karen and Hahn, Christopher and Jaramillo, Thomas F.},
abstractNote = {Electrochemical CO reduction can serve as a sequential step in the transformation of CO 2 into multicarbon fuels and chemicals. In this study, we provide insights on how to steer selectivity for CO reduction almost exclusively toward a single multicarbon oxygenate by carefully controlling the catalyst composition and its surrounding reaction conditions. Under alkaline reaction conditions, we demonstrate that planar CuAg electrodes can reduce CO to acetaldehyde with over 50% Faradaic efficiency and over 90% selectivity on a carbon basis at a modest electrode potential of −0.536 V vs. the reversible hydrogen electrode. The Faradaic efficiency to acetaldehyde was further enhanced to 70% by increasing the roughness factor of the CuAg electrode. Density functional theory calculations indicate that Ag ad-atoms on Cu weaken the binding energy of the reduced acetaldehyde intermediate and inhibit its further reduction to ethanol, demonstrating that the improved selectivity to acetaldehyde is due to the electronic effect from Ag incorporation. These findings will aid in the design of catalysts that are able to guide complex reaction networks and achieve high selectivity for the desired product.},
doi = {10.1073/pnas.1821683117},
journal = {Proceedings of the National Academy of Sciences of the United States of America},
number = ,
volume = ,
place = {United States},
year = {2020},
month = {1}
}

Journal Article:
Free Publicly Available Full Text
This content will become publicly available on July 24, 2020
Publisher's Version of Record

Save / Share:

Works referenced in this record:

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

Electrochemical CO 2 reduction to CO on dendritic Ag–Cu electrocatalysts prepared by electrodeposition
journal, September 2016


A Highly Selective Copper-Indium Bimetallic Electrocatalyst for the Electrochemical Reduction of Aqueous CO 2 to CO
journal, December 2014

  • Rasul, Shahid; Anjum, Dalaver H.; Jedidi, Abdesslem
  • Angewandte Chemie International Edition, Vol. 54, Issue 7
  • DOI: 10.1002/anie.201410233

Polymerization of acetaldehyde and crotonaldehyde catalyzed by aliphatic tertiary amines
journal, December 1951


Electroreduction of Carbon Dioxide to Hydrocarbons Using Bimetallic Cu–Pd Catalysts with Different Mixing Patterns
journal, December 2016

  • Ma, Sichao; Sadakiyo, Masaaki; Heima, Minako
  • Journal of the American Chemical Society, Vol. 139, Issue 1
  • DOI: 10.1021/jacs.6b10740

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

Electrochemical Reduction of Carbon Dioxide at Various Metal Electrodes in Aqueous Potassium Hydrogen Carbonate Solution
journal, September 1990

  • Noda, Hidetomo; Ikeda, Shoichiro; Oda, Yoshiyuki
  • Bulletin of the Chemical Society of Japan, Vol. 63, Issue 9, p. 2459-2462
  • DOI: 10.1246/bcsj.63.2459

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

Electrocatalytic Conversion of Carbon Dioxide to Methane and Methanol on Transition Metal Surfaces
journal, August 2014

  • Kuhl, Kendra P.; Hatsukade, Toru; Cave, Etosha R.
  • Journal of the American Chemical Society, Vol. 136, Issue 40
  • DOI: 10.1021/ja505791r

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


Particle Size Effects in the Catalytic Electroreduction of CO 2 on Cu Nanoparticles
journal, May 2014

  • Reske, Rulle; Mistry, Hemma; Behafarid, Farzad
  • Journal of the American Chemical Society, Vol. 136, Issue 19
  • DOI: 10.1021/ja500328k

CO 2 Reduction Selective for C ≥2 Products on Polycrystalline Copper with N-Substituted Pyridinium Additives
journal, July 2017


Tuning of Silver Catalyst Mesostructure Promotes Selective Carbon Dioxide Conversion into Fuels
journal, November 2016

  • Yoon, Youngmin; Hall, Anthony Shoji; Surendranath, Yogesh
  • Angewandte Chemie International Edition, Vol. 55, Issue 49
  • DOI: 10.1002/anie.201607942

Controllable Hydrocarbon Formation from the Electrochemical Reduction of CO 2 over Cu Nanowire Arrays
journal, April 2016

  • Ma, Ming; Djanashvili, Kristina; Smith, Wilson A.
  • Angewandte Chemie International Edition, Vol. 55, Issue 23
  • DOI: 10.1002/anie.201601282

Nanoporous Copper–Silver Alloys by Additive-Controlled Electrodeposition for the Selective Electroreduction of CO 2 to Ethylene and Ethanol
journal, April 2018

  • Hoang, Thao T. H.; Verma, Sumit; Ma, Sichao
  • Journal of the American Chemical Society, Vol. 140, Issue 17
  • DOI: 10.1021/jacs.8b01868

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

Selective Formation of C2 Compounds from Electrochemical Reduction of CO 2 at a Series of Copper Single Crystal Electrodes
journal, January 2002

  • Hori, Yoshio; Takahashi, Ichiro; Koga, Osamu
  • The Journal of Physical Chemistry B, Vol. 106, Issue 1
  • DOI: 10.1021/jp013478d

Porous dendritic copper: an electrocatalyst for highly selective CO 2 reduction to formate in water/ionic liquid electrolyte
journal, January 2017

  • Huan, Tran Ngoc; Simon, Philippe; Rousse, Gwenaëlle
  • Chemical Science, Vol. 8, Issue 1
  • DOI: 10.1039/C6SC03194C

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

Brass and Bronze as Effective CO 2 Reduction Electrocatalysts
journal, November 2017

  • He, Jingfu; Dettelbach, Kevan E.; Huang, Aoxue
  • Angewandte Chemie International Edition, Vol. 56, Issue 52
  • DOI: 10.1002/anie.201709932

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

Promoter Effects of Alkali Metal Cations on the Electrochemical Reduction of Carbon Dioxide
journal, August 2017

  • Resasco, Joaquin; Chen, Leanne D.; Clark, Ezra
  • Journal of the American Chemical Society, Vol. 139, Issue 32
  • DOI: 10.1021/jacs.7b06765

New design paradigm for heterogeneous catalysts
journal, April 2015

  • Vojvodic, Aleksandra; Nørskov, Jens K.
  • National Science Review, Vol. 2, Issue 2
  • DOI: 10.1093/nsr/nwv023

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

Defining a Materials Database for the Design of Copper Binary Alloy Catalysts for Electrochemical CO 2 Conversion
journal, January 2018

  • Lee, Chan Woo; Yang, Ki Dong; Nam, Dae-Hyun
  • Advanced Materials, Vol. 30, Issue 42
  • DOI: 10.1002/adma.201704717

Self-Cleaning Catalyst Electrodes for Stabilized CO 2 Reduction to Hydrocarbons
journal, September 2017

  • Weng, Zhe; Zhang, Xing; Wu, Yueshen
  • Angewandte Chemie International Edition, Vol. 56, Issue 42
  • DOI: 10.1002/anie.201707478

Size-Dependent Electrocatalytic Reduction of CO 2 over Pd Nanoparticles
journal, March 2015

  • Gao, Dunfeng; Zhou, Hu; Wang, Jing
  • Journal of the American Chemical Society, Vol. 137, Issue 13
  • DOI: 10.1021/jacs.5b00046

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

Tuning the Selectivity of Carbon Dioxide Electroreduction toward Ethanol on Oxide-Derived Cu x Zn Catalysts
journal, November 2016


Product Selectivity Affected by Cationic Species in Electrochemical Reduction of CO 2 and CO at a Cu Electrode
journal, January 1991

  • Murata, Akira; Hori, Yoshio
  • Bulletin of the Chemical Society of Japan, Vol. 64, Issue 1
  • DOI: 10.1246/bcsj.64.123

Progress and Perspectives of Electrochemical CO 2 Reduction on Copper in Aqueous Electrolyte
journal, April 2019


Mesoporous palladium–copper bimetallic electrodes for selective electrocatalytic reduction of aqueous CO 2 to CO
journal, January 2016

  • Li, Mu; Wang, Junjie; Li, Peng
  • Journal of Materials Chemistry A, Vol. 4, Issue 13
  • DOI: 10.1039/C6TA00487C

CO 2 reduction to acetate in mixtures of ultrasmall (Cu) n ,(Ag) m bimetallic nanoparticles
journal, December 2017

  • Wang, Ying; Wang, Degao; Dares, Christopher J.
  • Proceedings of the National Academy of Sciences, Vol. 115, Issue 2
  • DOI: 10.1073/pnas.1713962115

Mechanism of CO 2 Reduction at Copper Surfaces: Pathways to C 2 Products
journal, January 2018

  • Garza, Alejandro J.; Bell, Alexis T.; Head-Gordon, Martin
  • ACS Catalysis, Vol. 8, Issue 2
  • DOI: 10.1021/acscatal.7b03477

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

Cu–Sn Bimetallic Catalyst for Selective Aqueous Electroreduction of CO 2 to CO
journal, April 2016

  • Sarfraz, Saad; Garcia-Esparza, Angel T.; Jedidi, Abdesslem
  • ACS Catalysis, Vol. 6, Issue 5
  • DOI: 10.1021/acscatal.6b00269

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

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


General Techno-Economic Analysis of CO 2 Electrolysis Systems
journal, February 2018

  • Jouny, Matthew; Luc, Wesley; Jiao, Feng
  • Industrial & Engineering Chemistry Research, Vol. 57, Issue 6
  • DOI: 10.1021/acs.iecr.7b03514

Ionic Liquid-Mediated Selective Conversion of CO2 to CO at Low Overpotentials
journal, September 2011

  • Rosen, B. A.; Salehi-Khojin, A.; Thorson, M. R.
  • Science, Vol. 334, Issue 6056, p. 643-644
  • DOI: 10.1126/science.1209786

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


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


Electrochemical CO 2 Reduction over Compressively Strained CuAg Surface Alloys with Enhanced Multi-Carbon Oxygenate Selectivity
journal, October 2017

  • Clark, Ezra L.; Hahn, Christopher; Jaramillo, Thomas F.
  • Journal of the American Chemical Society, Vol. 139, Issue 44
  • DOI: 10.1021/jacs.7b08607

Enhanced electrocatalytic CO2 reduction via field-induced reagent concentration
journal, August 2016


Activity Descriptors for CO 2 Electroreduction to Methane on Transition-Metal Catalysts
journal, January 2012

  • Peterson, Andrew A.; Nørskov, Jens K.
  • The Journal of Physical Chemistry Letters, Vol. 3, Issue 2
  • DOI: 10.1021/jz201461p

Effect of Cations on the Electrochemical Conversion of CO2 to CO
journal, November 2012

  • Thorson, M. R.; Siil, K. I.; Kenis, P. J. A.
  • Journal of the Electrochemical Society, Vol. 160, Issue 1, p. F69-F74
  • DOI: 10.1149/2.052301jes

Gas-Diffusion Electrodes for Carbon Dioxide Reduction: A New Paradigm
journal, December 2018


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


Using a One-Electron Shuttle for the Multielectron Reduction of CO2 to Methanol: Kinetic, Mechanistic, and Structural Insights
journal, August 2010

  • Barton Cole, Emily; Lakkaraju, Prasad S.; Rampulla, David M.
  • Journal of the American Chemical Society, Vol. 132, Issue 33, p. 11539-11551
  • DOI: 10.1021/ja1023496

Guiding Electrochemical Carbon Dioxide Reduction toward Carbonyls Using Copper Silver Thin Films with Interphase Miscibility
journal, November 2018


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

Electroreduction of Carbon Monoxide Over a Copper Nanocube Catalyst: Surface Structure and pH Dependence on Selectivity
journal, February 2016

  • Roberts, F. Sloan; Kuhl, Kendra P.; Nilsson, Anders
  • ChemCatChem, Vol. 8, Issue 6
  • DOI: 10.1002/cctc.201501189

Combining theory and experiment in electrocatalysis: Insights into materials design
journal, January 2017


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

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

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

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


Selectivity of CO 2 Reduction on Copper Electrodes: The Role of the Kinetics of Elementary Steps
journal, January 2013

  • Nie, Xiaowa; Esopi, Monica R.; Janik, Michael J.
  • Angewandte Chemie, Vol. 125, Issue 9
  • DOI: 10.1002/ange.201208320

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