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dc.contributor.author
Mao, Zhongtian
dc.contributor.author
Lustemberg, Pablo German
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Rumptz, John R.
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Ganduglia Pirovano, Maria Veronica
dc.contributor.author
Campbell, Charles T.
dc.date.available
2021-10-18T20:07:49Z
dc.date.issued
2020-05
dc.identifier.citation
Mao, Zhongtian; Lustemberg, Pablo German; Rumptz, John R.; Ganduglia Pirovano, Maria Veronica; Campbell, Charles T.; Ni Nanoparticles on CeO 2 (111): Energetics, Electron Transfer, and Structure by Ni Adsorption Calorimetry, Spectroscopies, and Density Functional Theory; American Chemical Society; ACS Catalysis; 10; 9; 5-2020; 5101-5114
dc.identifier.issn
2155-5435
dc.identifier.uri
http://hdl.handle.net/11336/144161
dc.description.abstract
The morphology, interfacial bonding energetics, and charge transfer of Ni clusters and nanoparticles on slightly reduced CeO2-x(111) surfaces at 100-300 K have been studied using single-crystal adsorption calorimetry (SCAC), low-energy ion scattering spectroscopy (LEIS), X-ray photoelectron spectroscopy (XPS), low-energy electron diffraction (LEED), and density functional theory (DFT). The initial heat of adsorption of Ni vapor decreased with the extent of pre-reduction (x) of CeO2-x(111), showing that stoichiometric ceria adsorbs Ni more strongly than oxygen vacancies. On CeO1.95(111) at 300 K, the heat dropped quickly with coverage in the first 0.1 ML, attributed to nucleation of Ni clusters on stoichiometric steps, followed by the Ni particles spreading onto less favorable terrace sites. At 100 K, the clusters nucleate on terraces due to slower diffusion. Adsorbed Ni monomers are in the +2 oxidation state, and they bind more strongly by ∼45 kJ/mol to step sites than terraces. The measured heat of adsorption versus average particle size on terraces is favorably compared to DFT calculations. The Ce 3d XPS line shape showed an increase in Ce3+/Ce4+ ratio with Ni coverage, providing the number of electrons donated to ceria per Ni atom. The charge transferred per Ni is initially large but strongly decreases with increasing cluster size for both experiments and DFT, and it shows large differences between clusters at steps versus terraces. This charge is localized on the interfacial Ni and Ce atoms in their atomic layers closest to the interface. This knowledge is crucial to understanding the nature of the active sites on the surface of Ni/CeO2 catalysts, for which metal-oxide interactions play a very important role in the activation of O-H and C-H bonds. The changes in these interactions with Ni particle size (metal loading) and the extent of reduction of ceria help to explain how previously reported catalytic activity and selectivity change with these same structural details.
dc.format
application/pdf
dc.language.iso
eng
dc.publisher
American Chemical Society
dc.rights
info:eu-repo/semantics/openAccess
dc.rights.uri
https://creativecommons.org/licenses/by-nc/2.5/ar/
dc.subject
CALORIMETRY
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CATALYST
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DFT
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METAL ADSORPTION
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NANOPARTICLES
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NICKEL/CERIA
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SIZE EFFECT
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Otras Ciencias Químicas
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Ciencias Químicas
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CIENCIAS NATURALES Y EXACTAS
dc.title
Ni Nanoparticles on CeO 2 (111): Energetics, Electron Transfer, and Structure by Ni Adsorption Calorimetry, Spectroscopies, and Density Functional Theory
dc.type
info:eu-repo/semantics/article
dc.type
info:ar-repo/semantics/artículo
dc.type
info:eu-repo/semantics/publishedVersion
dc.date.updated
2021-09-06T21:03:46Z
dc.identifier.eissn
2155-5435
dc.journal.volume
10
dc.journal.number
9
dc.journal.pagination
5101-5114
dc.journal.pais
Estados Unidos
dc.journal.ciudad
Washington D. C.
dc.description.fil
Fil: Mao, Zhongtian. University of Washington; Estados Unidos
dc.description.fil
Fil: Lustemberg, Pablo German. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Rosario. Instituto de Física de Rosario. Universidad Nacional de Rosario. Instituto de Física de Rosario; Argentina. Consejo Superior de Investigaciones Científicas. Instituto de Catálisis y Petroleoquímica; España
dc.description.fil
Fil: Rumptz, John R.. University of Washington; Estados Unidos
dc.description.fil
Fil: Ganduglia Pirovano, Maria Veronica. Consejo Superior de Investigaciones Científicas. Instituto de Catálisis y Petroleoquímica; España
dc.description.fil
Fil: Campbell, Charles T.. University of Washington; Estados Unidos
dc.journal.title
ACS Catalysis
dc.relation.alternativeid
info:eu-repo/semantics/altIdentifier/url/https://pubs.acs.org/doi/10.1021/acscatal.0c00333
dc.relation.alternativeid
info:eu-repo/semantics/altIdentifier/doi/http://dx.doi.org/10.1021/acscatal.0c00333
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