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Title: Trends in Adhesion Energies of Metal Nanoparticles on Oxide Surfaces: Understanding Support Effects in Catalysis and Nanotechnology

Abstract

Nanoparticles on surfaces are ubiquitous in nanotechnologies, especially in catalysis, where metal nanoparticles anchored to oxide supports are widely used to produce and use fuels and chemicals, and in pollution abatement. Here we show that for hemispherical metal particles of the same diameter, D, the chemical potentials of the metal atoms in the particles (μ M) differ between two supports by approximately –2( E adh,AE adh,B) V m/ D, where E ad,i is the adhesion energy between the metal and support i, and V m is the molar volume of the bulk metal. This is consistent with calorimetric measurements of metal vapor adsorption energies onto clean oxide surfaces where the metal grows as 3D particles, which proved that μ M increases with decreasing particle size below 6 nm and, for a given size, decreases with E adh. Since catalytic activity and sintering rates correlate with metal chemical potential, it is thus crucial to understand what properties of catalyst materials control metal/oxide adhesion energies. Trends in how E adh varies with the metal and the support oxide are presented. For a given oxide, E adh increases linearly from metal to metal with increasing heat of formation of the mostmore » stable oxide of the metal (per mole metal), or metal oxophilicity, suggesting that metal–oxygen bonds dominate interfacial bonding. For the two different stoichiometric oxide surfaces that have been studied on multiple metals (MgO(100) and CeO 2(111), the slopes of these lines are the same, but their offset is large ( ~2 J/m 2). Adhesion energies increase as MgO(100) ≈ TiO 2(110) < α-Al 2O 3(0001) < CeO 2(111) ≈ Fe 3O 4(111).« less

Authors:
 [1]; ORCiD logo [1]
  1. Univ. of Washington, Seattle, WA (United States). Dept. of Chemistry
Publication Date:
Research Org.:
Univ. of Washington, Seattle, WA (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22). Chemical Sciences, Geosciences & Biosciences Division
OSTI Identifier:
1534920
Grant/Contract Number:  
FG02-96ER14630
Resource Type:
Journal Article: Accepted Manuscript
Journal Name:
ACS Nano
Additional Journal Information:
Journal Volume: 11; Journal Issue: 2; Journal ID: ISSN 1936-0851
Publisher:
American Chemical Society (ACS)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; Chemistry; Science & Technology - Other Topics; Materials Science; nanoparticles; adhesion energy; catalyst support; metal catalyst; sintering; oxide surface; gold on MgO(100)

Citation Formats

Hemmingson, Stephanie L., and Campbell, Charles T. Trends in Adhesion Energies of Metal Nanoparticles on Oxide Surfaces: Understanding Support Effects in Catalysis and Nanotechnology. United States: N. p., 2016. Web. doi:10.1021/acsnano.6b07502.
Hemmingson, Stephanie L., & Campbell, Charles T. Trends in Adhesion Energies of Metal Nanoparticles on Oxide Surfaces: Understanding Support Effects in Catalysis and Nanotechnology. United States. https://doi.org/10.1021/acsnano.6b07502
Hemmingson, Stephanie L., and Campbell, Charles T. Tue . "Trends in Adhesion Energies of Metal Nanoparticles on Oxide Surfaces: Understanding Support Effects in Catalysis and Nanotechnology". United States. https://doi.org/10.1021/acsnano.6b07502. https://www.osti.gov/servlets/purl/1534920.
@article{osti_1534920,
title = {Trends in Adhesion Energies of Metal Nanoparticles on Oxide Surfaces: Understanding Support Effects in Catalysis and Nanotechnology},
author = {Hemmingson, Stephanie L. and Campbell, Charles T.},
abstractNote = {Nanoparticles on surfaces are ubiquitous in nanotechnologies, especially in catalysis, where metal nanoparticles anchored to oxide supports are widely used to produce and use fuels and chemicals, and in pollution abatement. Here we show that for hemispherical metal particles of the same diameter, D, the chemical potentials of the metal atoms in the particles (μM) differ between two supports by approximately –2(Eadh,A – Eadh,B)Vm/D, where Ead,i is the adhesion energy between the metal and support i, and Vm is the molar volume of the bulk metal. This is consistent with calorimetric measurements of metal vapor adsorption energies onto clean oxide surfaces where the metal grows as 3D particles, which proved that μM increases with decreasing particle size below 6 nm and, for a given size, decreases with Eadh. Since catalytic activity and sintering rates correlate with metal chemical potential, it is thus crucial to understand what properties of catalyst materials control metal/oxide adhesion energies. Trends in how Eadh varies with the metal and the support oxide are presented. For a given oxide, Eadh increases linearly from metal to metal with increasing heat of formation of the most stable oxide of the metal (per mole metal), or metal oxophilicity, suggesting that metal–oxygen bonds dominate interfacial bonding. For the two different stoichiometric oxide surfaces that have been studied on multiple metals (MgO(100) and CeO2(111), the slopes of these lines are the same, but their offset is large ( ~2 J/m2). Adhesion energies increase as MgO(100) ≈ TiO2(110) < α-Al2O3(0001) < CeO2(111) ≈ Fe3O4(111).},
doi = {10.1021/acsnano.6b07502},
url = {https://www.osti.gov/biblio/1534920}, journal = {ACS Nano},
issn = {1936-0851},
number = 2,
volume = 11,
place = {United States},
year = {2016},
month = {12}
}

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Works referencing / citing this record:

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