Energy of Supported Metal Catalysts: From Single Atoms to Large Metal Nanoparticles

James, Trevor E.; Hemmingson, Stephanie L.; Campbell, Charles T.

doi:10.1021/acscatal.5b01372

Title: Energy of Supported Metal Catalysts: From Single Atoms to Large Metal Nanoparticles

Journal Article · Fri Aug 14 00:00:00 EDT 2015 · ACS Catalysis

DOI:https://doi.org/10.1021/acscatal.5b01372· OSTI ID:1213955

James, Trevor E. ^[1]; Hemmingson, Stephanie L. ^[1]; Campbell, Charles T. ^[1]

Univ. of Washington, Seattle, WA (United States). Dept. of Chemistry

It is known that many catalysts consist of late transition metal nanoparticles dispersed across oxide supports. The chemical potential of the metal atoms in these particles correlate with their catalytic activity and long-term thermal stability. This chemical potential versus particle size across the full size range between the single isolated atom and bulklike limits is reported here for the first time for any metal on any oxide. The chemical potential of Cu atoms on CeO₂(111) surfaces, determined by single crystal adsorption calorimetry of gaseous Cu atoms onto slightly reduced CeO₂(111) at 100 and 300 K is shown to decrease dramatically with increasing Cu cluster size. The Cu chemical potential is ~110 kJ/mol higher for isolated Cu adatoms on stoichometric terrace sites than for Cu in nanoparticles exceeding 2.5 nm diameter, where it reaches the bulk Cu(solid) limit. In Cu dimers, Cu’s chemical potential is ~57 kJ/mol lower at step edges than on stoichiometric terrace sites. Since Cu avoids oxygen vacancies, these monomer and dimer results are not strongly influenced by the 2.5% oxygen vacancies present on this CeO₂ surface and are thus considered representative of stoichiometric CeO₂(111) surfaces.

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Research Organization:: Univ. of Washington, Seattle, WA (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences, and Biosciences Division

Grant/Contract Number:: FG02-96ER14630

OSTI ID:: 1213955

Alternate ID(s):: OSTI ID: 1438016

Journal Information:: ACS Catalysis, Journal Name: ACS Catalysis Vol. 5 Journal Issue: 10; ISSN 2155-5435

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

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Cited by: 67 works

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References (45)

Generalized Gradient Approximation Made Simple Perdew, John P.; Burke, Kieron; Ernzerhof, Matthias Physical Review Letters, Vol. 77, Issue 18, p. 3865-3868 https://doi.org/10.1103/PhysRevLett.77.3865	journal	October 1996
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
Atomic processes in crystal growth Venables, John A. Surface Science, Vol. 299-300, p. 798-817 https://doi.org/10.1016/0039-6028(94)90698-X	journal	January 1994
Ag Nanoparticles on Reducible CeO ₂ (111) Thin Films: Effect of Thickness and Stoichiometry of Ceria Hu, Shanwei; Wang, Yan; Wang, Weijia The Journal of Physical Chemistry C, Vol. 119, Issue 7 https://doi.org/10.1021/jp511691p	journal	February 2015
Highly active copper-ceria and copper-ceria-titania catalysts for methanol synthesis from CO2 Graciani, J.; Mudiyanselage, K.; Xu, F. Science, Vol. 345, Issue 6196 https://doi.org/10.1126/science.1253057	journal	July 2014
PHYSICS: The Active Site in Nanoparticle Gold Catalysis Campbell, C. T. Science, Vol. 306, Issue 5694 https://doi.org/10.1126/science.1104246	journal	October 2004
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
Origin of the High Activity of the Ceria-Supported Copper Catalyst for H ₂ O Dissociation Yang, Zongxian; Xie, Luogang; Ma, Dongwei The Journal of Physical Chemistry C, Vol. 115, Issue 14 https://doi.org/10.1021/jp200005r	journal	March 2011
Energetics of Cu Adsorption and Adhesion onto Reduced CeO ₂ (111) Surfaces by Calorimetry James, Trevor E.; Hemmingson, Stephanie L.; Ito, Tsuyoshi The Journal of Physical Chemistry C, Vol. 119, Issue 30 https://doi.org/10.1021/acs.jpcc.5b04621	journal	July 2015
Copper clusters on Al2O3/NiAl(110) studied with STM Worren, T.; Højrup Hansen, K.; Lægsgaard, E. Surface Science, Vol. 477, Issue 1 https://doi.org/10.1016/S0039-6028(01)00703-8	journal	April 2001
Electronic interactions and charge transfers of metal atoms and clusters on oxide surfaces Pacchioni, Gianfranco Physical Chemistry Chemical Physics, Vol. 15, Issue 6 https://doi.org/10.1039/c2cp43731g	journal	January 2013
CO Adsorption and Oxidation on Ceria Surfaces from DFT+U Calculations Huang, Min; Fabris, Stefano The Journal of Physical Chemistry C, Vol. 112, Issue 23 https://doi.org/10.1021/jp709898r	journal	May 2008
Self-limiting growth of copper islands on TiO2(110)-(1×1) Chen, D. A.; Bartelt, M. C.; Hwang, R. Q. Surface Science, Vol. 450, Issue 1-2 https://doi.org/10.1016/S0039-6028(99)01251-0	journal	April 2000
Atom-Resolved Imaging of Dynamic Shape Changes in Supported Copper Nanocrystals Hansen, P. L. Science, Vol. 295, Issue 5562 https://doi.org/10.1126/science.1069325	journal	March 2002
Physisorbed, Chemisorbed, and Oxidized CO on Highly Active Cu−CeO ₂ (111) Yang, Zongxian; He, Bingling; Lu, Zhansheng The Journal of Physical Chemistry C, Vol. 114, Issue 10 https://doi.org/10.1021/jp909174u	journal	March 2010
Accurate spin-dependent electron liquid correlation energies for local spin density calculations: a critical analysis Vosko, S. H.; Wilk, L.; Nusair, M. Canadian Journal of Physics, Vol. 58, Issue 8 https://doi.org/10.1139/p80-159	journal	August 1980
Copper-ceria interaction: A combined photoemission and DFT study Szabová, Lucie; Skála, Tomáš; Matolínová, Iva Applied Surface Science, Vol. 267 https://doi.org/10.1016/j.apsusc.2012.04.098	journal	February 2013
Tuning selectivity in catalysis by controlling particle shape Lee, Ilkeun; Delbecq, Françoise; Morales, Ricardo Nature Materials, Vol. 8, Issue 2 https://doi.org/10.1038/nmat2371	journal	January 2009
Thermodynamic, electronic and structural properties of Cu/CeO2 surfaces and interfaces from first-principles DFT+U calculations Szabová, Lucie; Camellone, Matteo Farnesi; Huang, Min The Journal of Chemical Physics, Vol. 133, Issue 23 https://doi.org/10.1063/1.3515424	journal	December 2010
Gold supported on well-ordered ceria films: nucleation, growth and morphology in CO oxidation reaction Lu, J. -L.; Gao, H. -J.; Shaikhutdinov, S. Catalysis Letters, Vol. 114, Issue 1-2 https://doi.org/10.1007/s10562-007-9039-3	journal	February 2007
Anchored metal nanoparticles: Effects of support and size on their energy, sintering resistance and reactivity Campbell, Charles T.; Sellers, Jason R. V. Faraday Discussions, Vol. 162 https://doi.org/10.1039/c3fd00094j	journal	January 2013
Engineering atomic and molecular nanostructures at surfaces Barth, Johannes V.; Costantini, Giovanni; Kern, Klaus Nature, Vol. 437, Issue 7059 https://doi.org/10.1038/nature04166	journal	September 2005
Density Functional Theory Study of the Interaction of Cu, Ag, and Au Atoms with the Regular CeO ₂ (111) Surface Branda, María Marta; Hernández, Norge C.; Sanz, Javier Fdez. The Journal of Physical Chemistry C, Vol. 114, Issue 4 https://doi.org/10.1021/jp910782r	journal	January 2010
Greatly facilitated oxygen vacancy formation in ceria nanocrystallites Migani, Annapaola; Vayssilov, Georgi N.; Bromley, Stefan T. Chemical Communications, Vol. 46, Issue 32 https://doi.org/10.1039/c0cc01091j	journal	January 2010
Ag Adsorption on Reduced CeO ₂ (111) Thin Films Farmer, Jason A.; Baricuatro, Jack H.; Campbell, Charles T. The Journal of Physical Chemistry C, Vol. 114, Issue 40 https://doi.org/10.1021/jp104593y	journal	July 2010
Enhanced Bonding of Gold Nanoparticles on Oxidized TiO2(110) Matthey, D.; Wang, J. G.; Wendt, S. Science, Vol. 315, Issue 5819 https://doi.org/10.1126/science.1135752	journal	March 2007
The Active Site of Methanol Synthesis over Cu/ZnO/Al₂O₃ Industrial Catalysts Behrens, M.; Studt, F.; Kasatkin, I. Science, Vol. 336, Issue 6083, p. 893-897 https://doi.org/10.1126/science.1219831	journal	April 2012
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
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
XPS Study of the reduction of cerium dioxide Romeo, M.; Bak, K.; El Fallah, J. Surface and Interface Analysis, Vol. 20, Issue 6 https://doi.org/10.1002/sia.740200604	journal	May 1993
A novel single-crystal adsorption calorimeter and additions for determining metal adsorption and adhesion energies Stuckless, J. T.; Frei, Nathan A.; Campbell, Charles T. Review of Scientific Instruments, Vol. 69, Issue 6 https://doi.org/10.1063/1.1148971	journal	June 1998
Interaction of Gold with Cerium Oxide Supports: CeO ₂ (111) Thin Films vs CeO _x Nanoparticles Baron, M.; Bondarchuk, O.; Stacchiola, D. The Journal of Physical Chemistry C, Vol. 113, Issue 15 https://doi.org/10.1021/jp9001753	journal	March 2009
Growth mode of ultrathin copper overlayers on ${TiO}_{2}$ (110) Diebold, U.; Pan, J. -M.; Madey, T. E. Physical Review B, Vol. 47, Issue 7 https://doi.org/10.1103/PhysRevB.47.3868	journal	February 1993
Clusters and islands on oxides: from catalysis via electronics and magnetism to optics Freund, Hans-Joachim Surface Science, Vol. 500, Issue 1-3 https://doi.org/10.1016/S0039-6028(01)01543-6	journal	March 2002
The Energetics of Supported Metal Nanoparticles: Relationships to Sintering Rates and Catalytic Activity Campbell, Charles T. Accounts of Chemical Research, Vol. 46, Issue 8 https://doi.org/10.1021/ar3003514	journal	April 2013
Ion scattering spectroscopy intensities for supported nanoparticles: The hemispherical cap model Campbell, Charles T.; James, Trevor E. Surface Science, Vol. 641 https://doi.org/10.1016/j.susc.2015.06.013	journal	November 2015
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
Pyroelectric detector for single-crystal adsorption microcalorimetry: analysis of pulse shape and intensity Stuckless, J. Todd; Frei, Nathan A.; Campbell, Charles T. Sensors and Actuators B: Chemical, Vol. 62, Issue 1 https://doi.org/10.1016/S0925-4005(99)00371-8	journal	January 2000
Identification of Active Gold Nanoclusters on Iron Oxide Supports for CO Oxidation Herzing, A. A.; Kiely, C. J.; Carley, A. F. Science, Vol. 321, Issue 5894 https://doi.org/10.1126/science.1159639	journal	September 2008
Adsorption calorimetry during metal vapor deposition on single crystal surfaces: Increased flux, reduced optical radiation, and real-time flux and reflectivity measurements Sellers, Jason R. V.; James, Trevor E.; Hemmingson, Stephanie L. Review of Scientific Instruments, Vol. 84, Issue 12 https://doi.org/10.1063/1.4832980	journal	December 2013
Subnanometre platinum clusters as highly active and selective catalysts for the oxidative dehydrogenation of propane Vajda, Stefan; Pellin, Michael J.; Greeley, Jeffrey P. Nature Materials, Vol. 8, Issue 3 https://doi.org/10.1038/nmat2384	journal	February 2009
The Effect of Size-Dependent Nanoparticle Energetics on Catalyst Sintering Campbell, C. T. Science, Vol. 298, Issue 5594 https://doi.org/10.1126/science.1075094	journal	October 2002
Electronic and Atomistic Structures of Clean and Reduced Ceria Surfaces Fabris, Stefano; Vicario, Gianpaolo; Balducci, Gabriele The Journal of Physical Chemistry B, Vol. 109, Issue 48 https://doi.org/10.1021/jp0511698	journal	December 2005
Ceria Maintains Smaller Metal Catalyst Particles by Strong Metal-Support Bonding Farmer, J. A.; Campbell, C. T. Science, Vol. 329, Issue 5994 https://doi.org/10.1126/science.1191778	journal	August 2010
Electronic states of metal (Cu, Ag, Au) atom on CeO2(111) surface: The role of local structural distortion Tang, Yuanhao; Zhang, Hua; Cui, Lixia Journal of Power Sources, Vol. 197 https://doi.org/10.1016/j.jpowsour.2011.09.026	journal	January 2012

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Title: Energy of Supported Metal Catalysts: From Single Atoms to Large Metal Nanoparticles

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