Cu deposited on CeOx-modified TiO2(110): Synergistic effects at the metal–oxide interface and the mechanism of the WGS reaction

Plata, Jose J.; Graciani, Jesús; Evans, Jaime; Rodriguez, José A.; Sanz, Javier Fernandez

doi:10.1021/acscatal.6b00948

Cu deposited on CeOx-modified TiO₂(110): Synergistic effects at the metal–oxide interface and the mechanism of the WGS reaction

Journal Article · Mon Jun 06 00:00:00 EDT 2016 · ACS Catalysis

DOI:https://doi.org/10.1021/acscatal.6b00948· OSTI ID:1326740

Plata, Jose J. ^[1]; Graciani, Jesús ^[1]; Evans, Jaime ^[2]; Rodriguez, José A. ^[3]; Sanz, Javier Fernandez ^[1]

Univ. de Sevilla, Sevilla (Spain)
Univ. Central de Venezuela, Caracas (Venezuela)
Brookhaven National Lab. (BNL), Upton, NY (United States)

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/CeO_x/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/CeO_x/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/CeO_x/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/CeO_x/TiO₂ illustrates the importance of optimizing the oxide phase when improving the performance of metal/oxide catalysts for the WGS.

View Accepted Manuscript (DOE)

Research Organization:: Brookhaven National Laboratory (BNL), Upton, NY (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)

OSTI ID:: 1326740

Report Number(s):: BNL--112631-2016-JA; KC0302010

Journal Information:: ACS Catalysis, Journal Name: ACS Catalysis Journal Issue: 7 Vol. 6; ISSN 2155-5435

Publisher:: American Chemical SocietyCopyright Statement

Country of Publication:: United States

Language:: English

References (65)

CO Oxidation Catalyzed by Supported Gold: Cooperation between Gold and Nanocrystalline Rare-Earth Supports Forms Reactive Surface Superoxide and Peroxide Species Guzman, Javier; Carrettin, Silvio; Fierro-Gonzalez, Juan C. Angewandte Chemie International Edition, Vol. 44, Issue 30 https://doi.org/10.1002/anie.200500659	journal	July 2005
On the Issue of the Deactivation of Au–Ceria and Pt–Ceria Water–Gas Shift Catalysts in Practical Fuel-Cell Applications Deng, Weiling; Flytzani-Stephanopoulos, Maria Angewandte Chemie International Edition, Vol. 45, Issue 14 https://doi.org/10.1002/anie.200503220	journal	March 2006
Water Gas Shift Reaction on Cu and Au Nanoparticles Supported on CeO2(111) and ZnO(000): Intrinsic Activity and Importance of Support Interactions Rodriguez, José A.; Liu, Ping; Hrbek, Jan Angewandte Chemie International Edition, Vol. 46, Issue 8 https://doi.org/10.1002/anie.200603931	journal	February 2007
Shape and Crystal-Plane Effects of Nanoscale Ceria on the Activity of Au-CeO₂ Catalysts for the Water–Gas Shift Reaction Si, Rui; Flytzani-Stephanopoulos, Maria Angewandte Chemie International Edition, Vol. 47, Issue 15, p. 2884-2887 https://doi.org/10.1002/anie.200705828	journal	March 2008
Water-Gas Shift Reaction on a Highly Active Inverse CeO x /Cu(111) Catalyst: Unique Role of Ceria Nanoparticles Rodriguez, José A.; Graciani, Jesús; Evans, Jaime Angewandte Chemie International Edition, Vol. 48, Issue 43 https://doi.org/10.1002/anie.200903918	journal	October 2009
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 Carrasco, Javier; López-Durán, David; Liu, Zongyuan Angewandte Chemie International Edition, Vol. 54, Issue 13 https://doi.org/10.1002/anie.201410697	journal	February 2015
Preface Hutchings, Graham J.; Goodmann, Wayne Topics in Catalysis, Vol. 44, Issue 1-2 https://doi.org/10.1007/s11244-007-0273-0	journal	June 2007
Interaction of Au with titania: the role of reduced Ti Chen, M. S.; Goodman, D. W. Topics in Catalysis, Vol. 44, Issue 1-2 https://doi.org/10.1007/s11244-007-0276-x	journal	June 2007
Recent Advances in Catalysis for Hydrogen Production and Fuel Processing for Fuel Cells Song, Chunshan Topics in Catalysis, Vol. 49, Issue 1-2 https://doi.org/10.1007/s11244-008-9069-0	journal	May 2008
Gold catalysts prepared by coprecipitation for low-temperature oxidation of hydrogen and of carbon monoxide Haruta, M. Journal of Catalysis, Vol. 115, Issue 2 https://doi.org/10.1016/0021-9517(89)90034-1	journal	February 1989
A kinetic model of the water gas shift reaction Ovesen, C. V.; Stoltze, P.; Nørskov, J. K. Journal of Catalysis, Vol. 134, Issue 2 https://doi.org/10.1016/0021-9517(92)90334-E	journal	April 1992
Efficiency of ab-initio total energy calculations for metals and semiconductors using a plane-wave basis set Kresse, G.; Furthmüller, J. Computational Materials Science, Vol. 6, Issue 1, p. 15-50 https://doi.org/10.1016/0927-0256(96)00008-0	journal	July 1996
The interaction of water with solid surfaces: fundamental aspects revisited Henderson, M. Surface Science Reports, Vol. 46, Issue 1-8 https://doi.org/10.1016/S0167-5729(01)00020-6	journal	May 2002
A golden age of catalysis: A perspective Hutchings, Graham J.; Haruta, Masatake Applied Catalysis A: General, Vol. 291, Issue 1-2 https://doi.org/10.1016/j.apcata.2005.05.044	journal	September 2005
Performance enhancement in the water–gas shift reaction of platinum deposited over a cerium-modified TiO2 support González, I. D.; Navarro, R. M.; Álvarez-Galván, M. C. Catalysis Communications, Vol. 9, Issue 8 https://doi.org/10.1016/j.catcom.2008.02.005	journal	April 2008
Screening of bifunctional water-gas shift catalysts Thinon, O.; Diehl, F.; Avenier, P. Catalysis Today, Vol. 137, Issue 1 https://doi.org/10.1016/j.cattod.2008.01.001	journal	August 2008
Water-gas shift activity of Cu surfaces and Cu nanoparticles supported on metal oxides Rodriguez, J. A.; Liu, P.; Wang, X. Catalysis Today, Vol. 143, Issue 1-2 https://doi.org/10.1016/j.cattod.2008.08.022	journal	May 2009
A comparative study of the water gas shift reaction over platinum catalysts supported on CeO2, TiO2 and Ce-modified TiO2 González, I. D.; Navarro, R. M.; Wen, W. Catalysis Today, Vol. 149, Issue 3-4 https://doi.org/10.1016/j.cattod.2009.07.100	journal	January 2010
Density functional theory studies of the structure and electronic structure of pure and defective low index surfaces of ceria Nolan, Michael; Grigoleit, Sonja; Sayle, Dean C. Surface Science, Vol. 576, Issue 1-3 https://doi.org/10.1016/j.susc.2004.12.016	journal	February 2005
The electronic structure of oxygen vacancy defects at the low index surfaces of ceria Nolan, Michael; Parker, Stephen C.; Watson, Graeme W. Surface Science, Vol. 595, Issue 1-3 https://doi.org/10.1016/j.susc.2005.08.015	journal	December 2005
Understanding the Role of Oxygen Vacancies in the Water Gas Shift Reaction on Ceria-Supported Platinum Catalysts Vecchietti, Julia; Bonivardi, Adrian; Xu, Wenqian ACS Catalysis, Vol. 4, Issue 6 https://doi.org/10.1021/cs500323u	journal	April 2014
On the Mechanism of Low-Temperature Water Gas Shift Reaction on Copper Gokhale, Amit A.; Dumesic, James A.; Mavrikakis, Manos Journal of the American Chemical Society, Vol. 130, Issue 4 https://doi.org/10.1021/ja0768237	journal	January 2008
The Entropies of Adsorbed Molecules Campbell, Charles T.; Sellers, Jason R. V. Journal of the American Chemical Society, Vol. 134, Issue 43 https://doi.org/10.1021/ja3080117	journal	October 2012
Intrinsic Diffusion of Hydrogen on Rutile TiO ₂ (110) Li, Shao-Chun; Zhang, Zhenrong; Sheppard, Daniel Journal of the American Chemical Society, Vol. 130, Issue 28 https://doi.org/10.1021/ja8012825	journal	July 2008
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 Park, Joon B.; Graciani, Jesus; Evans, Jaime Journal of the American Chemical Society, Vol. 132, Issue 1 https://doi.org/10.1021/ja9087677	journal	January 2010
Reduction of NO ₂ on Ceria Surfaces Nolan, Michael; Parker, Stephen C.; Watson, Graeme W. The Journal of Physical Chemistry B, Vol. 110, Issue 5 https://doi.org/10.1021/jp055624b	journal	February 2006
The Nature of Water Nucleation Sites on TiO ₂ (110) Surfaces Revealed by Ambient Pressure X-ray Photoelectron Spectroscopy Ketteler, Guido; Yamamoto, Susumu; Bluhm, Hendrik The Journal of Physical Chemistry C, Vol. 111, Issue 23 https://doi.org/10.1021/jp068606i	journal	June 2007
Hydrogen Cycle on CeO ₂ (111) Surfaces: Density Functional Theory Calculations Watkins, Matthew B.; Foster, Adam S.; Shluger, Alexander L. The Journal of Physical Chemistry C, Vol. 111, Issue 42 https://doi.org/10.1021/jp071715s	journal	October 2007
First-Principles Assessment of H ₂ S and H ₂ O Reaction Mechanisms and the Subsequent Hydrogen Absorption on the CeO ₂ (111) Surface Marrocchelli, Dario; Yildiz, Bilge The Journal of Physical Chemistry C, Vol. 116, Issue 3 https://doi.org/10.1021/jp205573v	journal	November 2011
Water on Rutile TiO ₂ (110) and Au/TiO ₂ (110): Effects on Au Mobility and the Isotope Exchange Reaction Wu, Tianpin; Kaden, William E.; Anderson, Scott L. The Journal of Physical Chemistry C, Vol. 112, Issue 24 https://doi.org/10.1021/jp800521q	journal	May 2008
Methanol and Water Dissociation on TiO ₂ (110): The Role of Surface Oxygen Oviedo, Jaime; Sánchez-de-Armas, Rocío; San Miguel, Miguel Ángel The Journal of Physical Chemistry C, Vol. 112, Issue 46 https://doi.org/10.1021/jp805759y	journal	October 2008
Density Functional Theory Comparison of Water Dissociation Steps on Cu, Au, Ni, Pd, and Pt Phatak, Abhijit A.; Delgass, W. Nicholas; Ribeiro, Fabio H. The Journal of Physical Chemistry C, Vol. 113, Issue 17 https://doi.org/10.1021/jp810216b	journal	April 2009
High Water−Gas Shift Activity in TiO ₂ (110) Supported Cu and Au Nanoparticles: Role of the Oxide and Metal Particle Size Rodríguez, José A.; Evans, Jaime; Graciani, Jesús The Journal of Physical Chemistry C, Vol. 113, Issue 17 https://doi.org/10.1021/jp900483u	journal	April 2009
Role of Coverage and Surface Oxidation Degree in the Adsorption of Acetone on TiO ₂ (110). A Density Functional Study Márquez, Antonio M.; Plata, José J.; Sanz, Javier Fdez. The Journal of Physical Chemistry C, Vol. 113, Issue 46 https://doi.org/10.1021/jp906643h	journal	October 2009
25 Years of Catalytic Automotive Pollution Control: A Collaborative Effort Webster, D. E. Topics in Catalysis, Vol. 16/17, Issue 1/4, p. 33-38 https://doi.org/10.1023/A:1016618411613	journal	January 2001
Gold catalysts for pure hydrogen production in the water–gas shift reaction: activity, structure and reaction mechanism Burch, Robbie Phys. Chem. Chem. Phys., Vol. 8, Issue 47 https://doi.org/10.1039/B607837K	journal	January 2006
Density functional studies of model cerium oxide nanoparticles Loschen, Christoph; Migani, Annapaola; Bromley, Stefan T. Physical Chemistry Chemical Physics, Vol. 10, Issue 37 https://doi.org/10.1039/b805904g	journal	January 2008
The mechanism of the water-gas shift reaction on Cu/TiO2(110) elucidated from application of density-functional theory Peng, Shih-Feng; Ho, Jia-Jen Physical Chemistry Chemical Physics, Vol. 13, Issue 45 https://doi.org/10.1039/c1cp21975h	journal	January 2011
Kinetics and mechanism of the water-gas shift reaction catalysed by the clean and Cs-promoted Cu(110) surface: a comparison with Cu(111) Nakamura, Junji; Campbell, Joseph M.; Campbell, Charles T. Journal of the Chemical Society, Faraday Transactions, Vol. 86, Issue 15 https://doi.org/10.1039/ft9908602725	journal	January 1990
A climbing image nudged elastic band method for finding saddle points and minimum energy paths Henkelman, Graeme; Uberuaga, Blas P.; Jónsson, Hannes The Journal of Chemical Physics, Vol. 113, Issue 22, p. 9901-9904 https://doi.org/10.1063/1.1329672	journal	December 2000
Water-gas-shift reaction on metal nanoparticles and surfaces Liu, Ping; Rodriguez, José A. The Journal of Chemical Physics, Vol. 126, Issue 16 https://doi.org/10.1063/1.2722747	journal	April 2007
First-principles calculations of hydrogen diffusion on rutile TiO2(110) surfaces Kajita, Seiji; Minato, Taketoshi; Kato, Hiroyuki S. The Journal of Chemical Physics, Vol. 127, Issue 10 https://doi.org/10.1063/1.2768951	journal	September 2007
Tuning LDA+U for electron localization and structure at oxygen vacancies in ceria Castleton, C. W. M.; Kullgren, J.; Hermansson, K. The Journal of Chemical Physics, Vol. 127, Issue 24 https://doi.org/10.1063/1.2800015	journal	December 2007
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 Graciani, Jesús; Plata, José J.; Sanz, Javier Fdez. The Journal of Chemical Physics, Vol. 132, Issue 10 https://doi.org/10.1063/1.3337918	journal	March 2010
High catalytic activity of Au/CeOx/TiO2(110) controlled by the nature of the mixed-metal oxide at the nanometer level Park, J. B.; Graciani, J.; Evans, J. Proceedings of the National Academy of Sciences, Vol. 106, Issue 13 https://doi.org/10.1073/pnas.0812604106	journal	March 2009
Atoms, molecules, solids, and surfaces: Applications of the generalized gradient approximation for exchange and correlation Perdew, John P.; Chevary, J. A.; Vosko, S. H. Physical Review B, Vol. 46, Issue 11 https://doi.org/10.1103/PhysRevB.46.6671	journal	September 1992
Ab initiomolecular dynamics for liquid metals Kresse, G.; Hafner, J. Physical Review B, Vol. 47, Issue 1, p. 558-561 https://doi.org/10.1103/PhysRevB.47.558	journal	January 1993
Projector augmented-wave method Blöchl, P. E. Physical Review B, Vol. 50, Issue 24, p. 17953-17979 https://doi.org/10.1103/PhysRevB.50.17953	journal	December 1994
Electron-energy-loss spectra and the structural stability of nickel oxide: An LSDA+U study Dudarev, S. L.; Botton, G. A.; Savrasov, S. Y. Physical Review B, Vol. 57, Issue 3, p. 1505-1509 https://doi.org/10.1103/PhysRevB.57.1505	journal	January 1998
From ultrasoft pseudopotentials to the projector augmented-wave method Kresse, G.; Joubert, D. Physical Review B, Vol. 59, Issue 3, p. 1758-1775 https://doi.org/10.1103/PhysRevB.59.1758	journal	January 1999
Linear response approach to the calculation of the effective interaction parameters in the LDA + U method Cococcioni, Matteo; de Gironcoli, Stefano Physical Review B, Vol. 71, Issue 3 https://doi.org/10.1103/PhysRevB.71.035105	journal	January 2005
Reply to “Comment on ‘Taming multiple valency with density functionals: A case study of defective ceria' ” Fabris, Stefano; de Gironcoli, Stefano; Baroni, Stefano Physical Review B, Vol. 72, Issue 23 https://doi.org/10.1103/PhysRevB.72.237102	journal	December 2005
Modeling of Ce O 2 , Ce 2 O 3 , and Ce O 2 − x in the LDA + U formalism Andersson, D. A.; Simak, S. I.; Johansson, B. Physical Review B, Vol. 75, Issue 3 https://doi.org/10.1103/PhysRevB.75.035109	journal	January 2007
First-principles LDA + U and GGA + U study of cerium oxides: Dependence on the effective U parameter Loschen, Christoph; Carrasco, Javier; Neyman, Konstantin M. Physical Review B, Vol. 75, Issue 3 https://doi.org/10.1103/PhysRevB.75.035115	journal	January 2007
Hybrid functionals applied to rare-earth oxides: The example of ceria Da Silva, Juarez L. F.; Ganduglia-Pirovano, M. Verónica; Sauer, Joachim Physical Review B, Vol. 75, Issue 4 https://doi.org/10.1103/PhysRevB.75.045121	journal	January 2007
First-principles study of the Pt ∕ Ce O 2 ( 111 ) interface Yang, Zongxian; Lu, Zhansheng; Luo, Gaixia Physical Review B, Vol. 76, Issue 7 https://doi.org/10.1103/PhysRevB.76.075421	journal	August 2007
Stability of the Ce 2 O 3 phases: A DFT + U investigation Da Silva, Juarez L. F. Physical Review B, Vol. 76, Issue 19 https://doi.org/10.1103/PhysRevB.76.193108	journal	November 2007
Evidence of Subsurface Oxygen Vacancy Ordering on Reduced CeO 2 ( 111 ) Torbrügge, Stefan; Reichling, Michael; Ishiyama, Atsushi Physical Review Letters, Vol. 99, Issue 5 https://doi.org/10.1103/PhysRevLett.99.056101	journal	August 2007
Active Nonmetallic Au and Pt Species on Ceria-Based Water-Gas Shift Catalysts Fu, Q. Science, Vol. 301, Issue 5635 https://doi.org/10.1126/science.1085721	journal	August 2003
The Structure of Catalytically Active Gold on Titania Chen, M. S. Science, Vol. 306, Issue 5694 https://doi.org/10.1126/science.1102420	journal	October 2004
Electron Localization Determines Defect Formation on Ceria Substrates Esch, F. Science, Vol. 309, Issue 5735 https://doi.org/10.1126/science.1111568	journal	July 2005
CHEMISTRY: Oxygen Vacancies and Catalysis on Ceria Surfaces Campbell, C. T. Science, Vol. 309, Issue 5735 https://doi.org/10.1126/science.1113955	journal	July 2005
Activity of CeOx and TiOx Nanoparticles Grown on Au(111) in the Water-Gas Shift Reaction Rodriguez, J. A.; Ma, S.; Liu, P. Science, Vol. 318, Issue 5857 https://doi.org/10.1126/science.1150038	journal	December 2007
Onset of Catalytic Activity of Gold Clusters on Titania with the Appearance of Nonmetallic Properties Valden, M. Science, Vol. 281, Issue 5383 https://doi.org/10.1126/science.281.5383.1647	journal	September 1998
Catalysis by Ceria and Related Materials Trovarelli, Alessandro Catalytic Science Series https://doi.org/10.1142/p249	book	January 2002

Cited By (6)

Understanding the Photocatalytic Properties of Pt/CeO _x /TiO ₂ : Structural Effects on Electronic and Optical Properties Plata, J. J.; Remesal, E. R.; Graciani, Jesús ChemPhysChem, Vol. 20, Issue 12 https://doi.org/10.1002/cphc.201900141	journal	May 2019
Theoretical Study of the Water–Gas Shift Reaction on a Au/Hematite Model Catalyst Fuente, Silvia A.; Zubieta, Carolina; Ferullo, Ricardo M. Topics in Catalysis, Vol. 62, Issue 12-16 https://doi.org/10.1007/s11244-019-01174-1	journal	May 2019
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 Rodriguez, José A.; Grinter, David C.; Liu, Zongyuan Chemical Society Reviews, Vol. 46, Issue 7 https://doi.org/10.1039/c6cs00863a	journal	January 2017
Black TiO _2−x with stable surface oxygen vacancies as the support of efficient gold catalysts for water-gas shift reaction Li, Lei; Song, Li; Zhu, Longfeng Catalysis Science & Technology, Vol. 8, Issue 5 https://doi.org/10.1039/c7cy02429k	journal	January 2018
Improving the activity of gold nanoparticles for the water-gas shift reaction using TiO ₂ –Y ₂ O ₃ : an example of catalyst design Plata, Jose J.; Romero-Sarria, Francisca; Amaya Suárez, Javier Physical Chemistry Chemical Physics, Vol. 20, Issue 34 https://doi.org/10.1039/c8cp03706j	journal	January 2018
Alloying copper and palladium nanoparticles by pulsed laser irradiation of colloids suspended in ethanol Gal, Gyora; Monsa, Yaakov; Ezersky, Vladimir RSC Advances, Vol. 8, Issue 58 https://doi.org/10.1039/c8ra07067a	journal	January 2018

Similar Records

High Water−Gas Shift Activity in TiO2(110) Supported Cu and Au Nanoparticles: Role of the Oxide and Metal Particle Size

Journal Article · Wed Dec 31 23:00:00 EST 2008 · Journal of Physical Chemistry C · OSTI ID:980233

Gold, Copper and Platinum Nanoparticles Dispersed on CeOx/TiO2(110) Surfaces: High Water-Gas Shift Activity and the Nature of the Mixed-Metal Oxide at the Nanometer Level

Journal Article · Tue Jan 12 23:00:00 EST 2010 · Journal of American Chemical Society · OSTI ID:1041153

Gold, Copper, and Platinum Nanoparticles Dispersed on CeOx/TiO2(110) Surfaces: High Water-Gas Shift Activity and the Nature of the Mixed-Metal Oxide at the Nanometer Level

Journal Article · Thu Dec 31 23:00:00 EST 2009 · Journal of the American Chemical Society · OSTI ID:1019827

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
DFT
carboxyl
ceria
copper
metallic clusters
titania
water gas shift reaction