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Title: Influence of Atomic Surface Structure on the Activity of Ag for the Electrochemical Reduction of CO2 to CO

Abstract

The present work was undertaken to elucidate the facet-dependent activity of Ag for the electrochemical reduction of CO2 to CO. To this end, CO2 reduction was investigated over Ag thin films with (111), (100), and (110) orientations prepared via epitaxial growth on single-crystal Si wafers with the same crystallographic orientations. This preparation technique yielded larger area electrodes than can be achieved using single-crystals, which enabled the electrocatalytic activity of the corresponding Ag surfaces to be quantified in the Tafel regime. The Ag(110) thin films exhibited higher CO evolution activity compared to the Ag(111) and Ag(100) thin films, consistent with previous single-crystal studies. Density functional theory calculations suggest that CO2 reduction to CO is strongly facet-dependent, and that steps are more active than highly coordinated terraces. This is the result of both a higher binding energy of the key intermediate COOH as well as an enhanced double-layer electric field stabilization over undercoordinated surface atoms located at step edge defects. As a consequence, step edge defects likely dominate the CO2 reduction activity observed over the Ag(111) and Ag(100) thin films. The higher activity observed over the Ag(110) thin film is then related to the larger density of undercoordinated sites compared to themore » Ag(111) and Ag(100) thin films. Our conclusion that undercoordinated sites dominate the CO2 reduction activity observed over close-packed surfaces highlights the need to consider the contribution of such defects in studies of single-crystal electrodes.« less

Authors:
 [1];  [2];  [2];  [3]; ORCiD logo [4]; ORCiD logo [2]; ORCiD logo [4]; ORCiD logo [1]
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  1. Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States); Univ. of California, Berkeley, CA (United States)
  2. SLAC National Accelerator Lab., Menlo Park, CA (United States); Stanford Univ., CA (United States)
  3. Univ. of California, Berkeley, CA (United States)
  4. SLAC National Accelerator Lab., Menlo Park, CA (United States)
Publication Date:
Research Org.:
SLAC National Accelerator Laboratory (SLAC), Menlo Park, CA (United States); Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States)
Sponsoring Org.:
National Science Foundation (NSF); USDOE Office of Science (SC), Basic Energy Sciences (BES). Scientific User Facilities Division
OSTI Identifier:
1529376
Alternate Identifier(s):
OSTI ID: 1572005
Grant/Contract Number:  
AC02-76SF00515; SC0004993; AC02-05CH11231
Resource Type:
Accepted Manuscript
Journal Name:
ACS Catalysis
Additional Journal Information:
Journal Volume: 9; Journal Issue: 5; 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; electrocatalysis; carbon dioxide reduction; silver; atomic surface structure; step edge defects

Citation Formats

Clark, Ezra L., Ringe, Stefan, Tang, Michael, Walton, Amber, Hahn, Christopher, Jaramillo, Thomas F., Chan, Karen, and Bell, Alexis T. Influence of Atomic Surface Structure on the Activity of Ag for the Electrochemical Reduction of CO2 to CO. United States: N. p., 2019. Web. doi:10.1021/acscatal.9b00260.
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Clark, Ezra L., Ringe, Stefan, Tang, Michael, Walton, Amber, Hahn, Christopher, Jaramillo, Thomas F., Chan, Karen, & Bell, Alexis T. Influence of Atomic Surface Structure on the Activity of Ag for the Electrochemical Reduction of CO2 to CO. United States. https://doi.org/10.1021/acscatal.9b00260
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Clark, Ezra L., Ringe, Stefan, Tang, Michael, Walton, Amber, Hahn, Christopher, Jaramillo, Thomas F., Chan, Karen, and Bell, Alexis T. Tue . "Influence of Atomic Surface Structure on the Activity of Ag for the Electrochemical Reduction of CO2 to CO". United States. https://doi.org/10.1021/acscatal.9b00260. https://www.osti.gov/servlets/purl/1529376.
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@article{osti_1529376,
title = {Influence of Atomic Surface Structure on the Activity of Ag for the Electrochemical Reduction of CO2 to CO},
author = {Clark, Ezra L. and Ringe, Stefan and Tang, Michael and Walton, Amber and Hahn, Christopher and Jaramillo, Thomas F. and Chan, Karen and Bell, Alexis T.},
abstractNote = {The present work was undertaken to elucidate the facet-dependent activity of Ag for the electrochemical reduction of CO2 to CO. To this end, CO2 reduction was investigated over Ag thin films with (111), (100), and (110) orientations prepared via epitaxial growth on single-crystal Si wafers with the same crystallographic orientations. This preparation technique yielded larger area electrodes than can be achieved using single-crystals, which enabled the electrocatalytic activity of the corresponding Ag surfaces to be quantified in the Tafel regime. The Ag(110) thin films exhibited higher CO evolution activity compared to the Ag(111) and Ag(100) thin films, consistent with previous single-crystal studies. Density functional theory calculations suggest that CO2 reduction to CO is strongly facet-dependent, and that steps are more active than highly coordinated terraces. This is the result of both a higher binding energy of the key intermediate COOH as well as an enhanced double-layer electric field stabilization over undercoordinated surface atoms located at step edge defects. As a consequence, step edge defects likely dominate the CO2 reduction activity observed over the Ag(111) and Ag(100) thin films. The higher activity observed over the Ag(110) thin film is then related to the larger density of undercoordinated sites compared to the Ag(111) and Ag(100) thin films. Our conclusion that undercoordinated sites dominate the CO2 reduction activity observed over close-packed surfaces highlights the need to consider the contribution of such defects in studies of single-crystal electrodes.},
doi = {10.1021/acscatal.9b00260},
journal = {ACS Catalysis},
number = 5,
volume = 9,
place = {United States},
year = {Tue Mar 19 00:00:00 EDT 2019},
month = {Tue Mar 19 00:00:00 EDT 2019}
}
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Works referenced in this record:

Electrochemical reduction of carbon dioxide at various series of copper single crystal electrodes
journal, May 2003

Electrochemical Reduction of CO 2 Using Copper Single-Crystal Surfaces: Effects of CO* Coverage on the Selective Formation of Ethylene
journal, February 2017

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

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

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

Electrochemical reduction of CO2 on single crystal electrodes of silver Ag(111), Ag(100) and Ag(110)
journal, December 1997

  • Hoshi, Nagahiro; Kato, Makiko; Hori, Yoshio
  • Journal of Electroanalytical Chemistry, Vol. 440, Issue 1-2, p. 283-286
  • DOI: 10.1016/S0022-0728(97)00447-6

Mechanistic Insights into the Electrochemical Reduction of CO 2 to CO on Nanostructured Ag Surfaces
journal, June 2015

Structural effect on the rate of CO2 reduction on single crystal electrodes of palladium
journal, January 1997

  • Hoshi, Nagahiro; Noma, Makiko; Suzuki, Toshitake
  • Journal of Electroanalytical Chemistry, Vol. 421, Issue 1-2
  • DOI: 10.1016/S0022-0728(96)01023-6

CO2 Reduction on Rh single crystal electrodes and the structural effect
journal, October 1995

  • Hoshi, Nagahiro; Ito, Hiroki; Suzuki, Toshitake
  • Journal of Electroanalytical Chemistry, Vol. 395, Issue 1-2, p. 309-312
  • DOI: 10.1016/0022-0728(95)04267-R

Trends in electrochemical CO2 reduction activity for open and close-packed metal surfaces
journal, January 2014

  • Shi, Chuan; Hansen, Heine A.; Lausche, Adam C.
  • Physical Chemistry Chemical Physics, Vol. 16, Issue 10
  • DOI: 10.1039/c3cp54822h

Structure effects on the energetics of the electrochemical reduction of CO2 by copper surfaces
journal, August 2011

Grain-Boundary-Dependent CO 2 Electroreduction Activity
journal, April 2015

  • Feng, Xiaofeng; Jiang, Kaili; Fan, Shoushan
  • Journal of the American Chemical Society, Vol. 137, Issue 14
  • DOI: 10.1021/ja5130513

Tuned Chemical Bonding Ability of Au at Grain Boundaries for Enhanced Electrochemical CO 2 Reduction
journal, June 2016

Selective increase in CO 2 electroreduction activity at grain-boundary surface terminations
journal, November 2017

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

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

Electrocatalytic process of CO selectivity in electrochemical reduction of CO2 at metal electrodes in aqueous media
journal, August 1994

  • Hori, Yoshio; Wakebe, Hidetoshi; Tsukamoto, Toshio
  • Electrochimica Acta, Vol. 39, Issue 11-12, p. 1833-1839
  • DOI: 10.1016/0013-4686(94)85172-7

Insights into the electrocatalytic reduction of CO 2 on metallic silver surfaces
journal, January 2014

  • Hatsukade, Toru; Kuhl, Kendra P.; Cave, Etosha R.
  • Phys. Chem. Chem. Phys., Vol. 16, Issue 27
  • DOI: 10.1039/C4CP00692E

Electrochemical reduction of carbon dioxide on flat metallic cathodes
journal, January 1997

  • Jitaru, M.; Lowy, D. A.; Toma, M.
  • Journal of Applied Electrochemistry, Vol. 27, Issue 8, p. 875-889
  • DOI: 10.1023/A:1018441316386

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

Electrochemical CO2 Reduction on Metal Electrodes
book, January 2008

A selective and efficient electrocatalyst for carbon dioxide reduction
journal, January 2014

  • Lu, Qi; Rosen, Jonathan; Zhou, Yang
  • Nature Communications, Vol. 5, Issue 1
  • DOI: 10.1038/ncomms4242

Effect of Chloride Anions on the Synthesis and Enhanced Catalytic Activity of Silver Nanocoral Electrodes for CO 2 Electroreduction
journal, August 2015

Selective and Efficient Reduction of Carbon Dioxide to Carbon Monoxide on Oxide-Derived Nanostructured Silver Electrocatalysts
journal, July 2016

  • Ma, Ming; Trześniewski, Bartek J.; Xie, Jie
  • Angewandte Chemie International Edition, Vol. 55, Issue 33
  • DOI: 10.1002/anie.201604654

Enhanced Carbon Dioxide Electroreduction to Carbon Monoxide over Defect-Rich Plasma-Activated Silver Catalysts
journal, August 2017

  • Mistry, Hemma; Choi, Yong-Wook; Bagger, Alexander
  • Angewandte Chemie International Edition, Vol. 56, Issue 38
  • DOI: 10.1002/anie.201704613

Preferentially Oriented Ag Nanocrystals with Extremely High Activity and Faradaic Efficiency for CO 2 Electrochemical Reduction to CO
journal, January 2018

  • Peng, Xiong; Karakalos, Stavros G.; Mustain, William E.
  • ACS Applied Materials & Interfaces, Vol. 10, Issue 2
  • DOI: 10.1021/acsami.7b16164

Standards and Protocols for Data Acquisition and Reporting for Studies of the Electrochemical Reduction of Carbon Dioxide
journal, May 2018

Effects of electrolyte, catalyst, and membrane composition and operating conditions on the performance of solar-driven electrochemical reduction of carbon dioxide
journal, January 2015

  • Singh, Meenesh R.; Clark, Ezra L.; Bell, Alexis T.
  • Physical Chemistry Chemical Physics, Vol. 17, Issue 29
  • DOI: 10.1039/C5CP03283K

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

The Central Role of Bicarbonate in the Electrochemical Reduction of Carbon Dioxide on Gold
journal, March 2017

  • Dunwell, Marco; Lu, Qi; Heyes, Jeffrey M.
  • Journal of the American Chemical Society, Vol. 139, Issue 10
  • DOI: 10.1021/jacs.6b13287

Impurity Ion Complexation Enhances Carbon Dioxide Reduction Catalysis
journal, June 2015

QUANTUM ESPRESSO: a modular and open-source software project for quantum simulations of materials
journal, September 2009

  • Giannozzi, Paolo; Baroni, Stefano; Bonini, Nicola
  • Journal of Physics: Condensed Matter, Vol. 21, Issue 39, Article No. 395502
  • DOI: 10.1088/0953-8984/21/39/395502

CO and CO2 Hydrogenation to Methanol Calculated Using the BEEF-vdW Functional
journal, December 2012

Special points for Brillouin-zone integrations
journal, June 1976

  • Monkhorst, Hendrik J.; Pack, James D.
  • Physical Review B, Vol. 13, Issue 12, p. 5188-5192
  • DOI: 10.1103/PhysRevB.13.5188

Ab initio study of BaTiO 3 and PbTiO 3 surfaces in external electric fields
journal, May 2001

Formation of copper silicides from Cu(100)/Si(100) and Cu(111)/Si(111) structures
journal, January 1990

  • Chang, Chin‐An
  • Journal of Applied Physics, Vol. 67, Issue 1
  • DOI: 10.1063/1.345194

Epitaxial growth of Cu on Si by magnetron sputtering
journal, November 1998

  • Jiang, H.; Klemmer, T. J.; Barnard, J. A.
  • Journal of Vacuum Science & Technology A: Vacuum, Surfaces, and Films, Vol. 16, Issue 6
  • DOI: 10.1116/1.581489

Epitaxial growth of Cu(111) films on Si(110) by magnetron sputtering: orientation and twin growth
journal, March 1998

Surface morphology and electric conductivity of epitaxial Cu(100) films grown on H‐terminated Si(100)
journal, May 1996

  • Krastev, E. T.; Voice, L. D.; Tobin, R. G.
  • Journal of Applied Physics, Vol. 79, Issue 9
  • DOI: 10.1063/1.361508

Optimum Cu buffer layer thickness for growth of metal overlayers on Si (111)
journal, October 2002

  • Pedersen, Kjeld; Kristensen, Thomas B.; Pederser, Thomas G.
  • Physical Review B, Vol. 66, Issue 15
  • DOI: 10.1103/PhysRevB.66.153406

Epitaxial growth of thin Ag and Au films on Si(111) using thin copper silicide buffer layers
journal, July 2003

  • Pedersen, Kjeld; Morgen, Per; Pedersen, Thomas G.
  • Journal of Vacuum Science & Technology A: Vacuum, Surfaces, and Films, Vol. 21, Issue 4
  • DOI: 10.1116/1.1564035

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

Direct Observation of the Local Reaction Environment during the Electrochemical Reduction of CO 2
journal, April 2018

  • Clark, Ezra L.; Bell, Alexis T.
  • Journal of the American Chemical Society, Vol. 140, Issue 22
  • DOI: 10.1021/jacs.8b04058

Probing the Reaction Mechanism of CO 2 Electroreduction over Ag Films via Operando Infrared Spectroscopy
journal, December 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

Understanding Trends in the Electrocatalytic Activity of Metals and Enzymes for CO 2 Reduction to CO
journal, January 2013

  • Hansen, Heine A.; Varley, Joel B.; Peterson, Andrew A.
  • The Journal of Physical Chemistry Letters, Vol. 4, Issue 3
  • DOI: 10.1021/jz3021155

Origin of the Overpotential for Oxygen Reduction at a Fuel-Cell Cathode
journal, November 2004

  • Nørskov, J. K.; Rossmeisl, J.; Logadottir, A.
  • The Journal of Physical Chemistry B, Vol. 108, Issue 46
  • DOI: 10.1021/jp047349j

Mechanistic insights into electrochemical reduction of CO 2 over Ag using density functional theory and transport models
journal, October 2017

  • Singh, Meenesh R.; Goodpaster, Jason D.; Weber, Adam Z.
  • Proceedings of the National Academy of Sciences, Vol. 114, Issue 42
  • DOI: 10.1073/pnas.1713164114

Inhibited proton transfer enhances Au-catalyzed CO 2 -to-fuels selectivity
journal, July 2016

  • Wuttig, Anna; Yaguchi, Momo; Motobayashi, Kenta
  • Proceedings of the National Academy of Sciences, Vol. 113, Issue 32
  • DOI: 10.1073/pnas.1602984113

Trends in the Exchange Current for Hydrogen Evolution
journal, January 2005

  • Nørskov, J. K.; Bligaard, T.; Logadottir, A.
  • Journal of The Electrochemical Society, Vol. 152, Issue 3
  • DOI: 10.1149/1.1856988

Electric Field Effects in Electrochemical CO 2 Reduction
journal, September 2016

A Pore-Scale Model of Oxygen Reduction in Ionomer-Free Catalyst Layers of PEFCs
journal, January 2011

  • Chan, Karen; Eikerling, Michael
  • Journal of The Electrochemical Society, Vol. 158, Issue 1
  • DOI: 10.1149/1.3505042

The electrochemical double layer on sp metal single crystals
journal, March 1983

  • Hamelin, A.; Vitanov, T.; Sevastyanov, E.
  • Journal of Electroanalytical Chemistry and Interfacial Electrochemistry, Vol. 145, Issue 2
  • DOI: 10.1016/S0022-0728(83)80085-0

Anomalously low dielectric constant of confined water
journal, June 2018

Work function measurements on (110), (100) and (111) surfaces of silver
journal, April 1982

The dependence of the potential of zero charge of silver electrodes on the crystallographic orientation of the surface
journal, March 1986

  • Bachetta, M.; Trasatti, S.; Doubova, L.
  • Journal of Electroanalytical Chemistry and Interfacial Electrochemistry, Vol. 200, Issue 1-2
  • DOI: 10.1016/0022-0728(86)90073-2

Influence of the crystallographic orientation of the surface on the potential of zero charge of silver electrodes
journal, July 1988

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

Structure Sensitivity in the Electrocatalytic Reduction of CO 2 with Gold Catalysts
journal, February 2019

  • Mezzavilla, Stefano; Horch, Sebastian; Stephens, Ifan E. L.
  • Angewandte Chemie International Edition, Vol. 58, Issue 12
  • DOI: 10.1002/anie.201811422

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

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