Stability and Effects of Subsurface Oxygen in Oxide-Derived Cu Catalyst for CO2 Reduction
Abstract
Here, oxide-derived copper (OD-Cu) catalysts are promising candidates for the electrochemical CO2 reduction reaction (CO2RR) due to the enhanced selectivity toward ethylene over methane evolution, which has been linked to the presence of subsurface oxygen (Osb). In this work, Osb is investigated with theoretical methods. Although Osb is unstable in slab models, it becomes stabilized within a “manually” reduced OD-Cu nanocube model which was calculated by self-consistent charge density functional tight binding (SCC-DFTB). The results obtained with SCC-DFTB for the full nanocube were confirmed with subcluster models extracted from the nanocube, calculated with both density functional theory (DFT) and SCC-DFTB. The higher stability of Osb in the nanocube is attributed to the disordered structure and greater flexibility. The adsorption strength of CO on Cu(100) is enhanced by Osb withdrawing electron density from the Cu atom, resulting in reduction of the σ-repulsion. Hence, the coverage of CO may be increased, facilitating its dimerization.
- Authors:
-
[1];
[1];
[3];
[1];
[1];
- Stockholm Univ., Stockholm (Sweden)
- Univ. Federal de Minas Gerais (Brazil)
- Stockholm Univ., Stockholm (Sweden); SLAC National Accelerator Lab., Menlo Park, CA (United States)
- Publication Date:
- Research Org.:
- SLAC National Accelerator Laboratory (SLAC), Menlo Park, CA (United States)
- Sponsoring Org.:
- USDOE
- OSTI Identifier:
- 1463400
- Grant/Contract Number:
- AC02-76SF00515; 348-2013-6723; KAW-2013.0020
- Resource Type:
- Accepted Manuscript
- Journal Name:
- Journal of Physical Chemistry. C
- Additional Journal Information:
- Journal Volume: 121; Journal Issue: 45; Journal ID: ISSN 1932-7447
- Publisher:
- American Chemical Society
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
Citation Formats
Liu, Chang, Lourenço, Maicon P., Hedström, Svante, Cavalca, Filippo, Diaz-Morales, Oscar, Duarte, Hélio A., Nilsson, Anders, and Pettersson, Lars G. M. Stability and Effects of Subsurface Oxygen in Oxide-Derived Cu Catalyst for CO2 Reduction. United States: N. p., 2017.
Web. doi:10.1021/acs.jpcc.7b08269.
Liu, Chang, Lourenço, Maicon P., Hedström, Svante, Cavalca, Filippo, Diaz-Morales, Oscar, Duarte, Hélio A., Nilsson, Anders, & Pettersson, Lars G. M. Stability and Effects of Subsurface Oxygen in Oxide-Derived Cu Catalyst for CO2 Reduction. United States. https://doi.org/10.1021/acs.jpcc.7b08269
Liu, Chang, Lourenço, Maicon P., Hedström, Svante, Cavalca, Filippo, Diaz-Morales, Oscar, Duarte, Hélio A., Nilsson, Anders, and Pettersson, Lars G. M. Tue .
"Stability and Effects of Subsurface Oxygen in Oxide-Derived Cu Catalyst for CO2 Reduction". United States. https://doi.org/10.1021/acs.jpcc.7b08269. https://www.osti.gov/servlets/purl/1463400.
@article{osti_1463400,
title = {Stability and Effects of Subsurface Oxygen in Oxide-Derived Cu Catalyst for CO2 Reduction},
author = {Liu, Chang and Lourenço, Maicon P. and Hedström, Svante and Cavalca, Filippo and Diaz-Morales, Oscar and Duarte, Hélio A. and Nilsson, Anders and Pettersson, Lars G. M.},
abstractNote = {Here, oxide-derived copper (OD-Cu) catalysts are promising candidates for the electrochemical CO2 reduction reaction (CO2RR) due to the enhanced selectivity toward ethylene over methane evolution, which has been linked to the presence of subsurface oxygen (Osb). In this work, Osb is investigated with theoretical methods. Although Osb is unstable in slab models, it becomes stabilized within a “manually” reduced OD-Cu nanocube model which was calculated by self-consistent charge density functional tight binding (SCC-DFTB). The results obtained with SCC-DFTB for the full nanocube were confirmed with subcluster models extracted from the nanocube, calculated with both density functional theory (DFT) and SCC-DFTB. The higher stability of Osb in the nanocube is attributed to the disordered structure and greater flexibility. The adsorption strength of CO on Cu(100) is enhanced by Osb withdrawing electron density from the Cu atom, resulting in reduction of the σ-repulsion. Hence, the coverage of CO may be increased, facilitating its dimerization.},
doi = {10.1021/acs.jpcc.7b08269},
journal = {Journal of Physical Chemistry. C},
number = 45,
volume = 121,
place = {United States},
year = {Tue Oct 10 00:00:00 EDT 2017},
month = {Tue Oct 10 00:00:00 EDT 2017}
}
Free Publicly Available Full Text
Publisher's Version of Record
Other availability
Search WorldCat to find libraries that may hold this journal
Cited by: 79 works
Citation information provided by
Web of Science
Web of Science
Save to My Library
You must Sign In or Create an Account in order to save documents to your library.
Works referenced in this record:
New trends in the development of heterogeneous catalysts for electrochemical CO 2 reduction
journal, July 2016
- Kumar, Bijandra; Brian, Joseph P.; Atla, Veerendra
- Catalysis Today, Vol. 270
Electrode Build-Up of Reducible Metal Composites toward Achievable Electrochemical Conversion of Carbon Dioxide
journal, November 2015
- Lee, Seunghwa; Lee, Jaeyoung
- ChemSusChem, Vol. 9, Issue 4
Electrochemical CO2 Reduction on Metal Electrodes
book, January 2008
- Hori, Y.; Vayenas, Constantinos G.; White, Ralph E.
- Modern Aspects of Electrochemistry, p. 89-189
Electrochemical Reduction of CO2 Using Supported Cu2O Nanoparticles
journal, August 2013
- Bugayong, J.; Griffin, G. L.
- ECS Transactions, Vol. 58, Issue 2
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
Stable and selective electrochemical reduction of carbon dioxide to ethylene on copper mesocrystals
journal, January 2015
- Chen, Chung Shou; Handoko, Albertus D.; Wan, Jane Hui
- Catalysis Science & Technology, Vol. 5, Issue 1
High Selectivity for Ethylene from Carbon Dioxide Reduction over Copper Nanocube Electrocatalysts
journal, February 2015
- Roberts, F. Sloan; Kuhl, Kendra P.; Nilsson, Anders
- Angewandte Chemie, Vol. 127, Issue 17
Insights into an autonomously formed oxygen-evacuated Cu 2 O electrode for the selective production of C 2 H 4 from CO 2
journal, January 2015
- Kim, Dahee; Lee, Seunghwa; Ocon, Joey D.
- Physical Chemistry Chemical Physics, Vol. 17, Issue 2
Catalytic Reduction of CO[sub 2] to Ethylene by Electrolysis at a Three-Phase Interface
journal, January 2003
- Ogura, Kotaro; Yano, Hiroshi; Shirai, Fukutaro
- Journal of The Electrochemical Society, Vol. 150, Issue 9
Electrochemical CO 2 reduction on Cu 2 O-derived copper nanoparticles: controlling the catalytic selectivity of hydrocarbons
journal, January 2014
- Kas, Recep; Kortlever, Ruud; Milbrat, Alexander
- Phys. Chem. Chem. Phys., Vol. 16, Issue 24
Selective Electrochemical Reduction of Carbon Dioxide to Ethylene and Ethanol on Copper(I) Oxide Catalysts
journal, March 2015
- Ren, Dan; Deng, Yilin; Handoko, Albertus Denny
- ACS Catalysis, Vol. 5, Issue 5
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
Formation of Copper Catalysts for CO 2 Reduction with High Ethylene/Methane Product Ratio Investigated with In Situ X-ray Absorption Spectroscopy
journal, April 2016
- Eilert, André; Roberts, F. Sloan; Friebel, Daniel
- The Journal of Physical Chemistry Letters, Vol. 7, Issue 8
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
CO 2 Electroreduction with Enhanced Ethylene and Ethanol Selectivity by Nanostructuring Polycrystalline Copper
journal, April 2016
- Kwon, Youngkook; Lum, Yanwei; Clark, Ezra L.
- ChemElectroChem, Vol. 3, Issue 6
Controlling the selectivity of CO2 electroreduction on copper: The effect of the electrolyte concentration and the importance of the local pH
journal, February 2016
- Varela, Ana Sofia; Kroschel, Matthias; Reier, Tobias
- Catalysis Today, Vol. 260
Mechanistic Explanation of the pH Dependence and Onset Potentials for Hydrocarbon Products from Electrochemical Reduction of CO on Cu (111)
journal, January 2016
- Xiao, Hai; Cheng, Tao; Goddard, William A.
- Journal of the American Chemical Society, Vol. 138, Issue 2
Atomistic Mechanisms Underlying Selectivities in C 1 and C 2 Products from Electrochemical Reduction of CO on Cu(111)
journal, December 2016
- Xiao, Hai; Cheng, Tao; Goddard, William A.
- Journal of the American Chemical Society, Vol. 139, Issue 1
Full atomistic reaction mechanism with kinetics for CO reduction on Cu(100) from ab initio molecular dynamics free-energy calculations at 298 K
journal, February 2017
- Cheng, Tao; Xiao, Hai; Goddard, William A.
- Proceedings of the National Academy of Sciences, Vol. 114, Issue 8
Bond-Making and Breaking between Carbon, Nitrogen, and Oxygen in Electrocatalysis
journal, October 2014
- Li, Hongjiao; Li, Yongdan; Koper, Marc T. M.
- Journal of the American Chemical Society, Vol. 136, Issue 44
Hydrolysis of Electrolyte Cations Enhances the Electrochemical Reduction of CO 2 over Ag and Cu
journal, September 2016
- Singh, Meenesh R.; Kwon, Youngkook; Lum, Yanwei
- Journal of the American Chemical Society, Vol. 138, Issue 39
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
CO-CO coupling on Cu facets: Coverage, strain and field effects
journal, December 2016
- Sandberg, Robert B.; Montoya, Joseph H.; Chan, Karen
- Surface Science, Vol. 654
Electric Field Effects in Electrochemical CO 2 Reduction
journal, September 2016
- Chen, Leanne D.; Urushihara, Makoto; Chan, Karen
- ACS Catalysis, Vol. 6, Issue 10
Structure-Sensitive CO 2 Electroreduction to Hydrocarbons on Ultrathin 5-fold Twinned Copper Nanowires
journal, January 2017
- Li, Yifan; Cui, Fan; Ross, Michael B.
- Nano Letters, Vol. 17, Issue 2
Electrochemical CO 2 Conversion Using Skeleton (Sponge) Type of Cu Catalysts
journal, July 2017
- Dutta, Abhijit; Rahaman, Motiar; Mohos, Miklos
- ACS Catalysis, Vol. 7, Issue 8
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
The influence of pH on the reduction of CO and 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
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
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
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
- Lee, Seunghwa; Kim, Dahee; Lee, Jaeyoung
- Angewandte Chemie, Vol. 127, Issue 49
Effect of Subsurface Oxygen on the Reactivity of the Ag(111) Surface
journal, September 2005
- Xu, Ye; Greeley, Jeff; Mavrikakis, Manos
- Journal of the American Chemical Society, Vol. 127, Issue 37
Effect of Subsurface Oxygen on Selective Catalytic Reduction of NO by H 2 on Pt(100): A First-Principles Study
journal, October 2015
- Huai, Li-yuan; Wang, Hui; He, Chao-zheng
- The Journal of Physical Chemistry C, Vol. 119, Issue 44
Hydrogen Activation on Silver: A Computational Study on Surface and Subsurface Oxygen Species
journal, February 2008
- Mohammad, Amjad B.; Yudanov, Ilya V.; Lim, Kok Hwa
- The Journal of Physical Chemistry C, Vol. 112, Issue 5
First-Principles Study of Carbon Monoxide Oxidation on Ag(111) in Presence of Subsurface Oxygen and Stepped Ag(221)
journal, April 2009
- Su, Hai-Yan; Zeng, Zhenhua; Bao, Xin-He
- The Journal of Physical Chemistry C, Vol. 113, Issue 19
CO Adsorption on Clean and Oxidized Pd(111)
journal, December 2013
- Martin, N. M.; Van den Bossche, M.; Grönbeck, H.
- The Journal of Physical Chemistry C, Vol. 118, Issue 2
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
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
Plasma-Activated Copper Nanocube Catalysts for Efficient Carbon Dioxide Electroreduction to Hydrocarbons and Alcohols
journal, April 2017
- Gao, Dunfeng; Zegkinoglou, Ioannis; Divins, Nuria J.
- ACS Nano, Vol. 11, Issue 5
Improvement of the selectivity of the electrochemical conversion of CO2 to hydrocarbons using cupreous electrodes with in-situ oxidation by oxygen
journal, January 2017
- Engelbrecht, Andreas; Hämmerle, Martin; Moos, Ralf
- Electrochimica Acta, Vol. 224
Nature and Distribution of Stable Subsurface Oxygen in Copper Electrodes During Electrochemical CO 2 Reduction
journal, October 2017
- Cavalca, Filippo; Ferragut, Rafael; Aghion, Stefano
- The Journal of Physical Chemistry C, Vol. 121, Issue 45
Improved tangent estimate in the nudged elastic band method for finding minimum energy paths and saddle points
journal, December 2000
- Henkelman, Graeme; Jónsson, Hannes
- The Journal of Chemical Physics, Vol. 113, Issue 22
A climbing image nudged elastic band method for finding saddle points and minimum energy paths
journal, December 2000
- Henkelman, Graeme; Uberuaga, Blas P.; Jónsson, Hannes
- The Journal of Chemical Physics, Vol. 113, Issue 22, p. 9901-9904
Improved initial guess for minimum energy path calculations
journal, June 2014
- Smidstrup, Søren; Pedersen, Andreas; Stokbro, Kurt
- The Journal of Chemical Physics, Vol. 140, Issue 21
Real-space grid implementation of the projector augmented wave method
journal, January 2005
- Mortensen, J. J.; Hansen, L. B.; Jacobsen, K. W.
- Physical Review B, Vol. 71, Issue 3
Electronic structure calculations with GPAW: a real-space implementation of the projector augmented-wave method
journal, June 2010
- Enkovaara, J.; Rostgaard, C.; Mortensen, J. J.
- Journal of Physics: Condensed Matter, Vol. 22, Issue 25
Generalized Gradient Approximation Made Simple
journal, October 1996
- Perdew, John P.; Burke, Kieron; Ernzerhof, Matthias
- Physical Review Letters, Vol. 77, Issue 18, p. 3865-3868
Tight-Binding Density Functional Theory: An Approximate Kohn−Sham DFT Scheme †
journal, July 2007
- Seifert, G.
- The Journal of Physical Chemistry A, Vol. 111, Issue 26
Global Optimization of Adsorbate–Surface Structures While Preserving Molecular Identity
journal, October 2013
- Peterson, Andrew A.
- Topics in Catalysis, Vol. 57, Issue 1-4
Calculation of exchange-correlation potentials with auxiliary function densities
journal, August 2004
- Köster, Andreas M.; Reveles, J. Ulises; del Campo, Jorge M.
- The Journal of Chemical Physics, Vol. 121, Issue 8
Improved adsorption energetics within density-functional theory using revised Perdew-Burke-Ernzerhof functionals
journal, March 1999
- Hammer, B.; Hansen, L. B.; Nørskov, J. K.
- Physical Review B, Vol. 59, Issue 11
A new analysis of charge transfer and polarization for ligand–metal bonding: Model studies of Al 4 CO and Al 4 NH 3
journal, May 1984
- Bagus, Paul S.; Hermann, K.; Bauschlicher, Charles W.
- The Journal of Chemical Physics, Vol. 80, Issue 9
Bonding in metal–carbonyls: A comparison with experiment and calculations on adsorbed CO
journal, April 2006
- Nyberg, M.; Föhlisch, A.; Triguero, L.
- Journal of Molecular Structure: THEOCHEM, Vol. 762, Issue 1-3
On the uniqueness of the constrained space orbital variation (CSOV) technique
journal, August 1986
- Bauschlicher, Charles W.
- Chemical Physics, Vol. 106, Issue 3
Fundamental Concepts in Heterogeneous Catalysis
book, January 2014
- Nørskov, Jens K.; Studt, Felix; Abild-Pedersen, Frank
- John Wiley & Sons, Inc.
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, Vol. 125, Issue 28
How Carbon Monoxide Adsorbs in Different Sites
journal, October 2000
- Föhlisch, A.; Nyberg, M.; Hasselström, J.
- Physical Review Letters, Vol. 85, Issue 15
The bonding of CO to metal surfaces
journal, January 2000
- Föhlisch, A.; Nyberg, M.; Bennich, P.
- The Journal of Chemical Physics, Vol. 112, Issue 4
A Molecular Perspective on the d-Band Model: Synergy Between Experiment and Theory
journal, October 2013
- Pettersson, Lars Gunnar Moody; Nilsson, Anders
- Topics in Catalysis, Vol. 57, Issue 1-4
Chemical bonding on surfaces probed by X-ray emission spectroscopy and density functional theory
journal, October 2004
- Nilsson, Anders; Pettersson, Lars Gunnar Moody
- Surface Science Reports, Vol. 55, Issue 2-5
Molecular Orbital View of Chemisorbed Carbon Monoxide
journal, October 1964
- Blyholder, George
- The Journal of Physical Chemistry, Vol. 68, Issue 10
Works referencing / citing this record:
Strategies for Designing Nanoparticles for Electro‐ and Photocatalytic CO 2 Reduction
journal, December 2019
- Choi, Ji Yong; Choi, Woong; Park, Joon Woo
- Chemistry – An Asian Journal, Vol. 15, Issue 2
Selective CO 2 Electroreduction to Ethylene and Multicarbon Alcohols via Electrolyte‐Driven Nanostructuring
journal, November 2019
- Gao, Dunfeng; Sinev, Ilya; Scholten, Fabian
- Angewandte Chemie, Vol. 131, Issue 47
Selective CO 2 Electroreduction to Ethylene and Multicarbon Alcohols via Electrolyte‐Driven Nanostructuring
journal, November 2019
- Gao, Dunfeng; Sinev, Ilya; Scholten, Fabian
- Angewandte Chemie International Edition, Vol. 58, Issue 47
Synergistic enhancement of electrocatalytic CO2 reduction to C2 oxygenates at nitrogen-doped nanodiamonds/Cu interface
journal, January 2020
- Wang, Hongxia; Tzeng, Yan-Kai; Ji, Yongfei
- Nature Nanotechnology, Vol. 15, Issue 2
Electrochemical reduction of CO 2 on defect-rich Bi derived from Bi 2 S 3 with enhanced formate selectivity
journal, January 2018
- Zhang, Ying; Li, Fengwang; Zhang, Xiaolong
- Journal of Materials Chemistry A, Vol. 6, Issue 11
Electrochemical CO 2 Reduction into Chemical Feedstocks: From Mechanistic Electrocatalysis Models to System Design
journal, December 2018
- Kibria, Md Golam; Edwards, Jonathan P.; Gabardo, Christine M.
- Advanced Materials, Vol. 31, Issue 31
Cuprous ions embedded in ceria lattice for selective and stable electrochemical reduction of carbon dioxide to ethylene
journal, January 2018
- Wu, Di; Dong, Cunku; Wu, Deyao
- Journal of Materials Chemistry A, Vol. 6, Issue 20
From CO 2 methanation to ambitious long-chain hydrocarbons: alternative fuels paving the path to sustainability
journal, January 2019
- Marques Mota, Filipe; Kim, Dong Ha
- Chemical Society Reviews, Vol. 48, Issue 1
CO 2 electroreduction to ethylene via hydroxide-mediated copper catalysis at an abrupt interface
journal, May 2018
- Dinh, Cao-Thang; Burdyny, Thomas; Kibria, Md Golam
- Science, Vol. 360, Issue 6390
Selective $CO_{2}$ Electroreduction to Ethylene and Multicarbon Alcohols via Electrolyte-Driven Nanostructuring
text, January 2019
- Gao, Dunfeng; Sinev, Ilya; Scholten, Fabian
- Deutsches Elektronen-Synchrotron, DESY, Hamburg