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

Title: Subsurface oxide plays a critical role in CO 2 activation by Cu(111) surfaces to form chemisorbed CO 2, the first step in reduction of CO 2

Abstract

A national priority is to convert CO 2 into high-value chemical products such as liquid fuels. Because current electrocatalysts are not adequate, we aim to discover new catalysts by obtaining a detailed understanding of the initial steps of CO 2 electroreduction on copper surfaces, the best current catalysts. Using ambient pressure X-ray photoelectron spectroscopy interpreted with quantum mechanical prediction of the structures and free energies, we show that the presence of a thin suboxide structure below the copper surface is essential to bind the CO 2 in the physisorbed configuration at 298 K, and we show that this suboxide is essential for converting to the chemisorbed CO 2 in the presence of water as the first step toward CO 2 reduction products such as formate and CO. This optimum suboxide leads to both neutral and charged Cu surface sites, providing fresh insights into how to design improved carbon dioxide reduction catalysts.

Authors:
 [1]; ORCiD logo [2]; ORCiD logo [2]; ORCiD logo [2];  [1];  [1]
  1. Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
  2. California Inst. of Technology (CalTech), Pasadena, CA (United States)
Publication Date:
Research Org.:
Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
OSTI Identifier:
1408437
DOE Contract Number:  
AC02-05CH11231; SC0004993
Resource Type:
Journal Article
Journal Name:
Proceedings of the National Academy of Sciences of the United States of America
Additional Journal Information:
Journal Volume: 114; Journal Issue: 26; Journal ID: ISSN 0027-8424
Publisher:
National Academy of Sciences, Washington, DC (United States)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; CO2 reduction; suboxide copper; ambient pressure XPS; density functional theory; M06L

Citation Formats

Favaro, Marco, Xiao, Hai, Cheng, Tao, Goddard, William A., Yano, Junko, and Crumlin, Ethan J. Subsurface oxide plays a critical role in CO2 activation by Cu(111) surfaces to form chemisorbed CO2, the first step in reduction of CO2. United States: N. p., 2017. Web. doi:10.1073/pnas.1701405114.
Favaro, Marco, Xiao, Hai, Cheng, Tao, Goddard, William A., Yano, Junko, & Crumlin, Ethan J. Subsurface oxide plays a critical role in CO2 activation by Cu(111) surfaces to form chemisorbed CO2, the first step in reduction of CO2. United States. doi:10.1073/pnas.1701405114.
Favaro, Marco, Xiao, Hai, Cheng, Tao, Goddard, William A., Yano, Junko, and Crumlin, Ethan J. Mon . "Subsurface oxide plays a critical role in CO2 activation by Cu(111) surfaces to form chemisorbed CO2, the first step in reduction of CO2". United States. doi:10.1073/pnas.1701405114. https://www.osti.gov/servlets/purl/1408437.
@article{osti_1408437,
title = {Subsurface oxide plays a critical role in CO2 activation by Cu(111) surfaces to form chemisorbed CO2, the first step in reduction of CO2},
author = {Favaro, Marco and Xiao, Hai and Cheng, Tao and Goddard, William A. and Yano, Junko and Crumlin, Ethan J.},
abstractNote = {A national priority is to convert CO2 into high-value chemical products such as liquid fuels. Because current electrocatalysts are not adequate, we aim to discover new catalysts by obtaining a detailed understanding of the initial steps of CO2 electroreduction on copper surfaces, the best current catalysts. Using ambient pressure X-ray photoelectron spectroscopy interpreted with quantum mechanical prediction of the structures and free energies, we show that the presence of a thin suboxide structure below the copper surface is essential to bind the CO2 in the physisorbed configuration at 298 K, and we show that this suboxide is essential for converting to the chemisorbed CO2 in the presence of water as the first step toward CO2 reduction products such as formate and CO. This optimum suboxide leads to both neutral and charged Cu surface sites, providing fresh insights into how to design improved carbon dioxide reduction catalysts.},
doi = {10.1073/pnas.1701405114},
journal = {Proceedings of the National Academy of Sciences of the United States of America},
issn = {0027-8424},
number = 26,
volume = 114,
place = {United States},
year = {2017},
month = {6}
}

Works referenced in this record:

CO2 Reduction at Low Overpotential on Cu Electrodes Resulting from the Reduction of Thick Cu2O Films
journal, April 2012

  • Li, Christina W.; Kanan, Matthew W.
  • Journal of the American Chemical Society, Vol. 134, Issue 17, p. 7231-7234
  • DOI: 10.1021/ja3010978

Bent valence excited states of CO 2
journal, December 1992

  • Spielfiedel, A.; Feautrier, N.; Cossart‐Magos, C.
  • The Journal of Chemical Physics, Vol. 97, Issue 11
  • DOI: 10.1063/1.463408

Practical algorithm for background subtraction
journal, June 1989


Activation of carbon dioxide at bismuth, gold and copper surfaces
journal, June 1991


Interactions of O2, CO, CO2, and D2 with the stepped CU(311) crystal face: Comparison to CU(110)
journal, February 1992


Control of the Charge State of Metal Atoms on Thin MgO Films
journal, March 2007


Investigation of solid/vapor interfaces using ambient pressure X-ray photoelectron spectroscopy
journal, January 2013

  • Starr, D. E.; Liu, Z.; Hävecker, M.
  • Chemical Society Reviews, Vol. 42, Issue 13
  • DOI: 10.1039/c3cs60057b

Microscopic View on a Chemical Vapor Deposition Route to Boron-Doped Graphene Nanostructures
journal, April 2013

  • Cattelan, Mattia; Agnoli, Stefano; Favaro, Marco
  • Chemistry of Materials, Vol. 25, Issue 9
  • DOI: 10.1021/cm302819b

Powering the planet: Chemical challenges in solar energy utilization
journal, October 2006

  • Lewis, N. S.; Nocera, D. G.
  • Proceedings of the National Academy of Sciences, Vol. 103, Issue 43, p. 15729-15735
  • DOI: 10.1073/pnas.0603395103

LMM Auger primary excitation spectra of copper
journal, December 2014


Predicting finite-temperature properties of crystalline carbon dioxide from first principles with quantitative accuracy
journal, January 2016

  • Heit, Yonaton N.; Nanda, Kaushik D.; Beran, Gregory J. O.
  • Chemical Science, Vol. 7, Issue 1
  • DOI: 10.1039/C5SC03014E

Surface Chemistry of Cu in the Presence of CO 2 and H 2 O
journal, September 2008

  • Deng, Xingyi; Verdaguer, Albert; Herranz, Tirma
  • Langmuir, Vol. 24, Issue 17
  • DOI: 10.1021/la8011052

Bonding, structure, and magnetism of physisorbed and chemisorbed O 2 on Pt(111)
journal, November 1990


Activation of Cu(111) surface by decomposition into nanoclusters driven by CO adsorption
journal, January 2016


A new local density functional for main-group thermochemistry, transition metal bonding, thermochemical kinetics, and noncovalent interactions
journal, November 2006

  • Zhao, Yan; Truhlar, Donald G.
  • The Journal of Chemical Physics, Vol. 125, Issue 19, Article No. 194101
  • DOI: 10.1063/1.2370993

Quantitative model of electron energy loss in XPS
journal, July 1997


Relativistic compact effective potentials and efficient, shared-exponent basis sets for the third-, fourth-, and fifth-row atoms
journal, February 1992

  • Stevens, Walter J.; Krauss, Morris; Basch, Harold
  • Canadian Journal of Chemistry, Vol. 70, Issue 2
  • DOI: 10.1139/v92-085

Copper (sub)oxide formation: a surface sensitive characterization of model catalysts
journal, January 2000

  • Schedel-Niedrig, Thomas; Neisius, Thomas; Böttger, Ingolf
  • Physical Chemistry Chemical Physics, Vol. 2, Issue 10
  • DOI: 10.1039/b000253o

Investigation of the L 3 -M 45 M 45 Auger spectra of Cu, Cu 2 O and CuO
journal, September 1992


Surface chemistry of carbon dioxide
journal, January 1996


Improved hybrid functional for solids: The HSEsol functional
journal, January 2011

  • Schimka, Laurids; Harl, Judith; Kresse, Georg
  • The Journal of Chemical Physics, Vol. 134, Issue 2
  • DOI: 10.1063/1.3524336

The interaction of carbon dioxide with Cu(100)
journal, May 1992


NO 2 Adsorption on Ag(100) Supported MgO(100) Thin Films: Controlling the Adsorption State with Film Thickness
journal, April 2009

  • Starr, David E.; Weis, Christoph; Yamamoto, Susumu
  • The Journal of Physical Chemistry C, Vol. 113, Issue 17
  • DOI: 10.1021/jp900410v

Catalyst Chemical State during CO Oxidation Reaction on Cu(111) Studied with Ambient-Pressure X-ray Photoelectron Spectroscopy and Near Edge X-ray Adsorption Fine Structure Spectroscopy
journal, August 2015

  • Eren, Baran; Heine, Christian; Bluhm, Hendrik
  • Journal of the American Chemical Society, Vol. 137, Issue 34
  • DOI: 10.1021/jacs.5b07451

Methanol Oxidation on a Copper Catalyst Investigated Using in Situ X-ray Photoelectron Spectroscopy
journal, September 2004

  • Bluhm, Hendrik; Hävecker, Michael; Knop-Gericke, Axel
  • The Journal of Physical Chemistry B, Vol. 108, Issue 38
  • DOI: 10.1021/jp040080j

Curve synthesis and optimization procedures for X-ray photoelectron spectroscopy
journal, February 1991


Cu/ZnO(0001̄) and ZnOx/Cu(111): Model catalysts for methanol synthesis
journal, April 1987


Dissociative Carbon Dioxide Adsorption and Morphological Changes on Cu(100) and Cu(111) at Ambient Pressures
journal, June 2016

  • Eren, Baran; Weatherup, Robert S.; Liakakos, Nikos
  • Journal of the American Chemical Society, Vol. 138, Issue 26
  • DOI: 10.1021/jacs.6b04039

Ambient pressure photoelectron spectroscopy: A new tool for surface science and nanotechnology
journal, April 2008


Highly selective plasma-activated copper catalysts for carbon dioxide reduction to ethylene
journal, June 2016

  • Mistry, Hemma; Varela, Ana Sofia; Bonifacio, Cecile S.
  • Nature Communications, Vol. 7, Issue 1
  • DOI: 10.1038/ncomms12123

Quantification of plasmon excitations in core-level photoemission
journal, January 2005


C RYSTAL14 : A program for the ab initio investigation of crystalline solids
journal, March 2014

  • Dovesi, Roberto; Orlando, Roberto; Erba, Alessandro
  • International Journal of Quantum Chemistry, Vol. 114, Issue 19
  • DOI: 10.1002/qua.24658

A synchrotron-based spectroscopic study of the electronic structure of N-doped HOPG and PdY/N-doped HOPG
journal, April 2016


New ambient pressure photoemission endstation at Advanced Light Source beamline 9.3.2
journal, May 2010

  • Grass, Michael E.; Karlsson, Patrik G.; Aksoy, Funda
  • Review of Scientific Instruments, Vol. 81, Issue 5
  • DOI: 10.1063/1.3427218

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

Does CO 2 dissociatively adsorb on Cu surfaces?
journal, October 1989

  • Nakamura, J.; Rodriguez, J. A.; Campbell, C. T.
  • Journal of Physics: Condensed Matter, Vol. 1, Issue SB
  • DOI: 10.1088/0953-8984/1/SB/026

Resolving overlapping peaks in ARXPS data: The effect of noise and fitting method
journal, January 2012

  • Muñoz-Flores, Jaime; Herrera-Gomez, Alberto
  • Journal of Electron Spectroscopy and Related Phenomena, Vol. 184, Issue 11-12
  • DOI: 10.1016/j.elspec.2011.08.004

The adsorption of oxygen on copper surfaces
journal, June 1982


A consistent and accurate ab initio parametrization of density functional dispersion correction (DFT-D) for the 94 elements H-Pu
journal, April 2010

  • Grimme, Stefan; Antony, Jens; Ehrlich, Stephan
  • The Journal of Chemical Physics, Vol. 132, Issue 15
  • DOI: 10.1063/1.3382344

In-Situ Carbon Doping of TiO 2 Nanotubes Via Anodization in Graphene Oxide Quantum Dot Containing Electrolyte and Carburization to TiO x C y Nanotubes
journal, February 2015

  • Favaro, Marco; Leonardi, Silvia; Valero-Vidal, Carlos
  • Advanced Materials Interfaces, Vol. 2, Issue 5
  • DOI: 10.1002/admi.201400462

A review of catalysts for the electroreduction of carbon dioxide to produce low-carbon fuels
journal, January 2014

  • Qiao, Jinli; Liu, Yuyu; Hong, Feng
  • Chem. Soc. Rev., Vol. 43, Issue 2
  • DOI: 10.1039/C3CS60323G