Cu deposited on CeOx-modified TiO2(110): Synergistic effects at the metal–oxide interface and the mechanism of the WGS reaction
Abstract
Experimental techniques and DFT calculations have been combined to study and compare the effect of the metal–substrate interaction in Cu/TiO2(110) and Cu/CeOx/TiO2(110) catalysts for the water–gas shift (WGS) reaction. Experiments and theory show that CeOx nanoparticles affect the dispersion of copper on titania, and on the formed copper–ceria interface, there are synergistic effects which favor water dissociation and the WGS reaction. The minimum energy path for the WGS reaction on the new highly active catalytic system Cu/CeOx/TiO2(110) has been predicted by theoretical calculations. Main steps such as adsorption–dissociation of water and *OCOH carboxyl intermediate formation–deprotonation have been characterized. In this very particular system, water splitting is no longer the rate-limiting step because it can dissociate overcoming an energy barrier of only 0.92 kcal/mol. One important insight of the present work is to show that easy full hydration of the ceria particles strongly lowers the reaction barrier for the deprotonation of the *OCOH intermediate and facilitates the evolution of the WGS reaction. For the first time, a system has been found on which the WGS reaction is able to work with all the involved energy barriers below 12 kcal/mol. This remarkable behavior makes the metal/CeOx/TiO2 family a potential candidate for industrialmore »
- Authors:
-
- Univ. de Sevilla, Sevilla (Spain)
- Univ. Central de Venezuela, Caracas (Venezuela)
- Brookhaven National Lab. (BNL), Upton, NY (United States)
- Publication Date:
- Research Org.:
- Brookhaven National Laboratory (BNL), Upton, NY (United States)
- Sponsoring Org.:
- USDOE Office of Science (SC), Basic Energy Sciences (BES)
- OSTI Identifier:
- 1326740
- Report Number(s):
- BNL-112631-2016-JA
Journal ID: ISSN 2155-5435; R&D Project: CO027; KC0302010
- Grant/Contract Number:
- SC00112704
- Resource Type:
- Accepted Manuscript
- Journal Name:
- ACS Catalysis
- Additional Journal Information:
- Journal Volume: 6; Journal Issue: 7; Journal ID: ISSN 2155-5435
- Publisher:
- American Chemical Society
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; carboxyl; ceria; copper; DFT; metallic clusters; titania; water gas shift reaction
Citation Formats
Plata, Jose J., Graciani, Jesús, Evans, Jaime, Rodriguez, José A., and Sanz, Javier Fernandez. Cu deposited on CeOx-modified TiO2(110): Synergistic effects at the metal–oxide interface and the mechanism of the WGS reaction. United States: N. p., 2016.
Web. doi:10.1021/acscatal.6b00948.
Plata, Jose J., Graciani, Jesús, Evans, Jaime, Rodriguez, José A., & Sanz, Javier Fernandez. Cu deposited on CeOx-modified TiO2(110): Synergistic effects at the metal–oxide interface and the mechanism of the WGS reaction. United States. https://doi.org/10.1021/acscatal.6b00948
Plata, Jose J., Graciani, Jesús, Evans, Jaime, Rodriguez, José A., and Sanz, Javier Fernandez. Mon .
"Cu deposited on CeOx-modified TiO2(110): Synergistic effects at the metal–oxide interface and the mechanism of the WGS reaction". United States. https://doi.org/10.1021/acscatal.6b00948. https://www.osti.gov/servlets/purl/1326740.
@article{osti_1326740,
title = {Cu deposited on CeOx-modified TiO2(110): Synergistic effects at the metal–oxide interface and the mechanism of the WGS reaction},
author = {Plata, Jose J. and Graciani, Jesús and Evans, Jaime and Rodriguez, José A. and Sanz, Javier Fernandez},
abstractNote = {Experimental techniques and DFT calculations have been combined to study and compare the effect of the metal–substrate interaction in Cu/TiO2(110) and Cu/CeOx/TiO2(110) catalysts for the water–gas shift (WGS) reaction. Experiments and theory show that CeOx nanoparticles affect the dispersion of copper on titania, and on the formed copper–ceria interface, there are synergistic effects which favor water dissociation and the WGS reaction. The minimum energy path for the WGS reaction on the new highly active catalytic system Cu/CeOx/TiO2(110) has been predicted by theoretical calculations. Main steps such as adsorption–dissociation of water and *OCOH carboxyl intermediate formation–deprotonation have been characterized. In this very particular system, water splitting is no longer the rate-limiting step because it can dissociate overcoming an energy barrier of only 0.92 kcal/mol. One important insight of the present work is to show that easy full hydration of the ceria particles strongly lowers the reaction barrier for the deprotonation of the *OCOH intermediate and facilitates the evolution of the WGS reaction. For the first time, a system has been found on which the WGS reaction is able to work with all the involved energy barriers below 12 kcal/mol. This remarkable behavior makes the metal/CeOx/TiO2 family a potential candidate for industrial application as catalysts in the WGS reaction. In conclusion, the change in the metal–support interactions when going from Cu/TiO2 to Cu/CeOx/TiO2 illustrates the importance of optimizing the oxide phase when improving the performance of metal/oxide catalysts for the WGS.},
doi = {10.1021/acscatal.6b00948},
journal = {ACS Catalysis},
number = 7,
volume = 6,
place = {United States},
year = {Mon Jun 06 00:00:00 EDT 2016},
month = {Mon Jun 06 00:00:00 EDT 2016}
}
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Works referenced in this record:
25 Years of Catalytic Automotive Pollution Control: A Collaborative Effort
journal, January 2001
- Webster, D. E.
- Topics in Catalysis, Vol. 16/17, Issue 1/4, p. 33-38
Recent Advances in Catalysis for Hydrogen Production and Fuel Processing for Fuel Cells
journal, May 2008
- Song, Chunshan
- Topics in Catalysis, Vol. 49, Issue 1-2
Preface
journal, June 2007
- Hutchings, Graham J.; Goodmann, Wayne
- Topics in Catalysis, Vol. 44, Issue 1-2
A golden age of catalysis: A perspective
journal, September 2005
- Hutchings, Graham J.; Haruta, Masatake
- Applied Catalysis A: General, Vol. 291, Issue 1-2
Gold catalysts for pure hydrogen production in the water–gas shift reaction: activity, structure and reaction mechanism
journal, January 2006
- Burch, Robbie
- Phys. Chem. Chem. Phys., Vol. 8, Issue 47
Screening of bifunctional water-gas shift catalysts
journal, August 2008
- Thinon, O.; Diehl, F.; Avenier, P.
- Catalysis Today, Vol. 137, Issue 1
Gold catalysts prepared by coprecipitation for low-temperature oxidation of hydrogen and of carbon monoxide
journal, February 1989
- Haruta, M.
- Journal of Catalysis, Vol. 115, Issue 2
Onset of Catalytic Activity of Gold Clusters on Titania with the Appearance of Nonmetallic Properties
journal, September 1998
- Valden, M.
- Science, Vol. 281, Issue 5383
The Structure of Catalytically Active Gold on Titania
journal, October 2004
- Chen, M. S.
- Science, Vol. 306, Issue 5694
Active Nonmetallic Au and Pt Species on Ceria-Based Water-Gas Shift Catalysts
journal, August 2003
- Fu, Q.
- Science, Vol. 301, Issue 5635
Water Gas Shift Reaction on Cu and Au Nanoparticles Supported on CeO2(111) and ZnO(000): Intrinsic Activity and Importance of Support Interactions
journal, February 2007
- Rodriguez, José A.; Liu, Ping; Hrbek, Jan
- Angewandte Chemie International Edition, Vol. 46, Issue 8
CO Oxidation Catalyzed by Supported Gold: Cooperation between Gold and Nanocrystalline Rare-Earth Supports Forms Reactive Surface Superoxide and Peroxide Species
journal, July 2005
- Guzman, Javier; Carrettin, Silvio; Fierro-Gonzalez, Juan C.
- Angewandte Chemie International Edition, Vol. 44, Issue 30
On the Issue of the Deactivation of Au–Ceria and Pt–Ceria Water–Gas Shift Catalysts in Practical Fuel-Cell Applications
journal, March 2006
- Deng, Weiling; Flytzani-Stephanopoulos, Maria
- Angewandte Chemie International Edition, Vol. 45, Issue 14
Shape and Crystal-Plane Effects of Nanoscale Ceria on the Activity of Au-CeO2 Catalysts for the Water–Gas Shift Reaction
journal, March 2008
- Si, Rui; Flytzani-Stephanopoulos, Maria
- Angewandte Chemie International Edition, Vol. 47, Issue 15, p. 2884-2887
Interaction of Au with titania: the role of reduced Ti
journal, June 2007
- Chen, M. S.; Goodman, D. W.
- Topics in Catalysis, Vol. 44, Issue 1-2
CHEMISTRY: Oxygen Vacancies and Catalysis on Ceria Surfaces
journal, July 2005
- Campbell, C. T.
- Science, Vol. 309, Issue 5735
Electron Localization Determines Defect Formation on Ceria Substrates
journal, July 2005
- Esch, F.
- Science, Vol. 309, Issue 5735
Evidence of Subsurface Oxygen Vacancy Ordering on Reduced
journal, August 2007
- Torbrügge, Stefan; Reichling, Michael; Ishiyama, Atsushi
- Physical Review Letters, Vol. 99, Issue 5
Activity of CeOx and TiOx Nanoparticles Grown on Au(111) in the Water-Gas Shift Reaction
journal, December 2007
- Rodriguez, J. A.; Ma, S.; Liu, P.
- Science, Vol. 318, Issue 5857
High catalytic activity of Au/CeOx/TiO2(110) controlled by the nature of the mixed-metal oxide at the nanometer level
journal, March 2009
- Park, J. B.; Graciani, J.; Evans, J.
- Proceedings of the National Academy of Sciences, Vol. 106, Issue 13
High Water−Gas Shift Activity in TiO 2 (110) Supported Cu and Au Nanoparticles: Role of the Oxide and Metal Particle Size
journal, April 2009
- Rodríguez, José A.; Evans, Jaime; Graciani, Jesús
- The Journal of Physical Chemistry C, Vol. 113, Issue 17
Water-Gas Shift Reaction on a Highly Active Inverse CeO x /Cu(111) Catalyst: Unique Role of Ceria Nanoparticles
journal, October 2009
- Rodriguez, José A.; Graciani, Jesús; Evans, Jaime
- Angewandte Chemie International Edition, Vol. 48, Issue 43
In Situ and Theoretical Studies for the Dissociation of Water on an Active Ni/CeO 2 Catalyst: Importance of Strong Metal-Support Interactions for the Cleavage of O-H Bonds
journal, February 2015
- Carrasco, Javier; López-Durán, David; Liu, Zongyuan
- Angewandte Chemie International Edition, Vol. 54, Issue 13
Density Functional Theory Comparison of Water Dissociation Steps on Cu, Au, Ni, Pd, and Pt
journal, April 2009
- Phatak, Abhijit A.; Delgass, W. Nicholas; Ribeiro, Fabio H.
- The Journal of Physical Chemistry C, Vol. 113, Issue 17
Water-gas-shift reaction on metal nanoparticles and surfaces
journal, April 2007
- Liu, Ping; Rodriguez, José A.
- The Journal of Chemical Physics, Vol. 126, Issue 16
Methanol and Water Dissociation on TiO 2 (110): The Role of Surface Oxygen
journal, October 2008
- Oviedo, Jaime; Sánchez-de-Armas, Rocío; San Miguel, Miguel Ángel
- The Journal of Physical Chemistry C, Vol. 112, Issue 46
Water on Rutile TiO 2 (110) and Au/TiO 2 (110): Effects on Au Mobility and the Isotope Exchange Reaction
journal, May 2008
- Wu, Tianpin; Kaden, William E.; Anderson, Scott L.
- The Journal of Physical Chemistry C, Vol. 112, Issue 24
The Nature of Water Nucleation Sites on TiO 2 (110) Surfaces Revealed by Ambient Pressure X-ray Photoelectron Spectroscopy
journal, June 2007
- Ketteler, Guido; Yamamoto, Susumu; Bluhm, Hendrik
- The Journal of Physical Chemistry C, Vol. 111, Issue 23
Intrinsic Diffusion of Hydrogen on Rutile TiO 2 (110)
journal, July 2008
- Li, Shao-Chun; Zhang, Zhenrong; Sheppard, Daniel
- Journal of the American Chemical Society, Vol. 130, Issue 28
First-principles calculations of hydrogen diffusion on rutile TiO2(110) surfaces
journal, September 2007
- Kajita, Seiji; Minato, Taketoshi; Kato, Hiroyuki S.
- The Journal of Chemical Physics, Vol. 127, Issue 10
Understanding the Role of Oxygen Vacancies in the Water Gas Shift Reaction on Ceria-Supported Platinum Catalysts
journal, April 2014
- Vecchietti, Julia; Bonivardi, Adrian; Xu, Wenqian
- ACS Catalysis, Vol. 4, Issue 6
Gold, Copper, and Platinum Nanoparticles Dispersed on CeO x /TiO 2 (110) Surfaces: High Water-Gas Shift Activity and the Nature of the Mixed-Metal Oxide at the Nanometer Level
journal, January 2010
- Park, Joon B.; Graciani, Jesus; Evans, Jaime
- Journal of the American Chemical Society, Vol. 132, Issue 1
Performance enhancement in the water–gas shift reaction of platinum deposited over a cerium-modified TiO2 support
journal, April 2008
- González, I. D.; Navarro, R. M.; Álvarez-Galván, M. C.
- Catalysis Communications, Vol. 9, Issue 8
A comparative study of the water gas shift reaction over platinum catalysts supported on CeO2, TiO2 and Ce-modified TiO2
journal, January 2010
- González, I. D.; Navarro, R. M.; Wen, W.
- Catalysis Today, Vol. 149, Issue 3-4
A theoretical insight into the catalytic effect of a mixed-metal oxide at the nanometer level: The case of the highly active metal/CeOx/TiO2(110) catalysts
journal, March 2010
- Graciani, Jesús; Plata, José J.; Sanz, Javier Fdez.
- The Journal of Chemical Physics, Vol. 132, Issue 10
From ultrasoft pseudopotentials to the projector augmented-wave method
journal, January 1999
- Kresse, G.; Joubert, D.
- Physical Review B, Vol. 59, Issue 3, p. 1758-1775
Projector augmented-wave method
journal, December 1994
- Blöchl, P. E.
- Physical Review B, Vol. 50, Issue 24, p. 17953-17979
Atoms, molecules, solids, and surfaces: Applications of the generalized gradient approximation for exchange and correlation
journal, September 1992
- Perdew, John P.; Chevary, J. A.; Vosko, S. H.
- Physical Review B, Vol. 46, Issue 11
Ab initiomolecular dynamics for liquid metals
journal, January 1993
- Kresse, G.; Hafner, J.
- Physical Review B, Vol. 47, Issue 1, p. 558-561
Efficiency of ab-initio total energy calculations for metals and semiconductors using a plane-wave basis set
journal, July 1996
- Kresse, G.; Furthmüller, J.
- Computational Materials Science, Vol. 6, Issue 1, p. 15-50
Role of Coverage and Surface Oxidation Degree in the Adsorption of Acetone on TiO 2 (110). A Density Functional Study
journal, October 2009
- Márquez, Antonio M.; Plata, José J.; Sanz, Javier Fdez.
- The Journal of Physical Chemistry C, Vol. 113, Issue 46
Electron-energy-loss spectra and the structural stability of nickel oxide: An LSDA+U study
journal, January 1998
- Dudarev, S. L.; Botton, G. A.; Savrasov, S. Y.
- Physical Review B, Vol. 57, Issue 3, p. 1505-1509
Reply to “Comment on ‘Taming multiple valency with density functionals: A case study of defective ceria' ”
journal, December 2005
- Fabris, Stefano; de Gironcoli, Stefano; Baroni, Stefano
- Physical Review B, Vol. 72, Issue 23
Linear response approach to the calculation of the effective interaction parameters in the method
journal, January 2005
- Cococcioni, Matteo; de Gironcoli, Stefano
- Physical Review B, Vol. 71, Issue 3
Tuning LDA+U for electron localization and structure at oxygen vacancies in ceria
journal, December 2007
- Castleton, C. W. M.; Kullgren, J.; Hermansson, K.
- The Journal of Chemical Physics, Vol. 127, Issue 24
Modeling of , , and in the formalism
journal, January 2007
- Andersson, D. A.; Simak, S. I.; Johansson, B.
- Physical Review B, Vol. 75, Issue 3
Density functional theory studies of the structure and electronic structure of pure and defective low index surfaces of ceria
journal, February 2005
- Nolan, Michael; Grigoleit, Sonja; Sayle, Dean C.
- Surface Science, Vol. 576, Issue 1-3
The electronic structure of oxygen vacancy defects at the low index surfaces of ceria
journal, December 2005
- Nolan, Michael; Parker, Stephen C.; Watson, Graeme W.
- Surface Science, Vol. 595, Issue 1-3
Reduction of NO 2 on Ceria Surfaces
journal, February 2006
- Nolan, Michael; Parker, Stephen C.; Watson, Graeme W.
- The Journal of Physical Chemistry B, Vol. 110, Issue 5
Hydrogen Cycle on CeO 2 (111) Surfaces: Density Functional Theory Calculations
journal, October 2007
- Watkins, Matthew B.; Foster, Adam S.; Shluger, Alexander L.
- The Journal of Physical Chemistry C, Vol. 111, Issue 42
First-principles study of the interface
journal, August 2007
- Yang, Zongxian; Lu, Zhansheng; Luo, Gaixia
- Physical Review B, Vol. 76, Issue 7
Stability of the phases: A investigation
journal, November 2007
- Da Silva, Juarez L. F.
- Physical Review B, Vol. 76, Issue 19
Hybrid functionals applied to rare-earth oxides: The example of ceria
journal, January 2007
- Da Silva, Juarez L. F.; Ganduglia-Pirovano, M. Verónica; Sauer, Joachim
- Physical Review B, Vol. 75, Issue 4
First-principles and study of cerium oxides: Dependence on the effective U parameter
journal, January 2007
- Loschen, Christoph; Carrasco, Javier; Neyman, Konstantin M.
- Physical Review B, Vol. 75, Issue 3
Density functional studies of model cerium oxide nanoparticles
journal, January 2008
- Loschen, Christoph; Migani, Annapaola; Bromley, Stefan T.
- Physical Chemistry Chemical Physics, Vol. 10, Issue 37
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
Kinetics and mechanism of the water-gas shift reaction catalysed by the clean and Cs-promoted Cu(110) surface: a comparison with Cu(111)
journal, January 1990
- Nakamura, Junji; Campbell, Joseph M.; Campbell, Charles T.
- Journal of the Chemical Society, Faraday Transactions, Vol. 86, Issue 15
A kinetic model of the water gas shift reaction
journal, April 1992
- Ovesen, C. V.; Stoltze, P.; Nørskov, J. K.
- Journal of Catalysis, Vol. 134, Issue 2
On the Mechanism of Low-Temperature Water Gas Shift Reaction on Copper
journal, January 2008
- Gokhale, Amit A.; Dumesic, James A.; Mavrikakis, Manos
- Journal of the American Chemical Society, Vol. 130, Issue 4
The mechanism of the water-gas shift reaction on Cu/TiO2(110) elucidated from application of density-functional theory
journal, January 2011
- Peng, Shih-Feng; Ho, Jia-Jen
- Physical Chemistry Chemical Physics, Vol. 13, Issue 45
First-Principles Assessment of H 2 S and H 2 O Reaction Mechanisms and the Subsequent Hydrogen Absorption on the CeO 2 (111) Surface
journal, November 2011
- Marrocchelli, Dario; Yildiz, Bilge
- The Journal of Physical Chemistry C, Vol. 116, Issue 3
Water-gas shift activity of Cu surfaces and Cu nanoparticles supported on metal oxides
journal, May 2009
- Rodriguez, J. A.; Liu, P.; Wang, X.
- Catalysis Today, Vol. 143, Issue 1-2
The Entropies of Adsorbed Molecules
journal, October 2012
- Campbell, Charles T.; Sellers, Jason R. V.
- Journal of the American Chemical Society, Vol. 134, Issue 43
Works referencing / citing this record:
Ceria-based model catalysts: fundamental studies on the importance of the metal–ceria interface in CO oxidation, the water–gas shift, CO 2 hydrogenation, and methane and alcohol reforming
journal, January 2017
- Rodriguez, José A.; Grinter, David C.; Liu, Zongyuan
- Chemical Society Reviews, Vol. 46, Issue 7
Alloying copper and palladium nanoparticles by pulsed laser irradiation of colloids suspended in ethanol
journal, January 2018
- Gal, Gyora; Monsa, Yaakov; Ezersky, Vladimir
- RSC Advances, Vol. 8, Issue 58
Black TiO 2−x with stable surface oxygen vacancies as the support of efficient gold catalysts for water-gas shift reaction
journal, January 2018
- Li, Lei; Song, Li; Zhu, Longfeng
- Catalysis Science & Technology, Vol. 8, Issue 5
Understanding the Photocatalytic Properties of Pt/CeO x /TiO 2 : Structural Effects on Electronic and Optical Properties
journal, May 2019
- Plata, J. J.; Remesal, E. R.; Graciani, Jesús
- ChemPhysChem, Vol. 20, Issue 12
Theoretical Study of the Water–Gas Shift Reaction on a Au/Hematite Model Catalyst
journal, May 2019
- Fuente, Silvia A.; Zubieta, Carolina; Ferullo, Ricardo M.
- Topics in Catalysis, Vol. 62, Issue 12-16
Improving the activity of gold nanoparticles for the water-gas shift reaction using TiO 2 –Y 2 O 3 : an example of catalyst design
journal, January 2018
- Plata, Jose J.; Romero-Sarria, Francisca; Amaya Suárez, Javier
- Physical Chemistry Chemical Physics, Vol. 20, Issue 34