skip to main content
DOE PAGES title logo U.S. Department of Energy
Office of Scientific and Technical Information

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 (μM) differ between two supports by approximately –2(Eadh,AEadh,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 thatmore » 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).« 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:
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. doi: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. doi: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},
journal = {ACS Nano},
number = 2,
volume = 11,
place = {United States},
year = {2016},
month = {12}
}

Journal Article:
Free Publicly Available Full Text
Publisher's Version of Record

Citation Metrics:
Cited by: 48 works
Citation information provided by
Web of Science

Save / Share:

Works referencing / citing this record:

Interaction trends between single metal atoms and oxide supports identified with density functional theory and statistical learning
journal, July 2018

  • O’Connor, Nolan J.; Jonayat, A. S. M.; Janik, Michael J.
  • Nature Catalysis, Vol. 1, Issue 7
  • DOI: 10.1038/s41929-018-0094-5

Interaction trends between single metal atoms and oxide supports identified with density functional theory and statistical learning
journal, July 2018

  • O’Connor, Nolan J.; Jonayat, A. S. M.; Janik, Michael J.
  • Nature Catalysis, Vol. 1, Issue 7
  • DOI: 10.1038/s41929-018-0094-5

Predicting metal–metal interactions. I. The influence of strain on nanoparticle and metal adlayer stabilities
journal, March 2020

  • Streibel, Verena; Choksi, Tej S.; Abild-Pedersen, Frank
  • The Journal of Chemical Physics, Vol. 152, Issue 9
  • DOI: 10.1063/1.5130566

Direct In Situ TEM Visualization and Insight into the Facet‐Dependent Sintering Behaviors of Gold on TiO 2
journal, December 2018


Oxide‐Supported Gold Clusters and Nanoparticles in Catalysis: A Computational Chemistry Perspective
journal, September 2018


Design of Ceria Catalysts for Low‐Temperature CO Oxidation
journal, October 2019


Theoretical Investigation of Metal-Support Interactions on Ripening Kinetics of Supported Particles
journal, April 2018


Thermal stability of oxide-supported gold nanoparticles
journal, May 2019


Control of metal-support interactions in heterogeneous catalysts to enhance activity and selectivity
journal, November 2019

  • van Deelen, Tom W.; Hernández Mejía, Carlos; de Jong, Krijn P.
  • Nature Catalysis, Vol. 2, Issue 11
  • DOI: 10.1038/s41929-019-0364-x

The physical chemistry and materials science behind sinter-resistant catalysts
journal, January 2018

  • Dai, Yunqian; Lu, Ping; Cao, Zhenming
  • Chemical Society Reviews, Vol. 47, Issue 12
  • DOI: 10.1039/c7cs00650k

Catalytic oxidation of propane over palladium alloyed with gold: an assessment of the chemical and intermediate species
journal, January 2018

  • Kareem, Haval; Shan, Shiyao; Wu, Zhi-Peng
  • Catalysis Science & Technology, Vol. 8, Issue 23
  • DOI: 10.1039/c8cy01704b

Interplay between the metal-support interaction and stability in Pt/Co 3 O 4 (111) model catalysts
journal, January 2018

  • Lykhach, Yaroslava; Faisal, Firas; Skála, Tomáš
  • Journal of Materials Chemistry A, Vol. 6, Issue 45
  • DOI: 10.1039/c8ta08142e

CeO 2 (111) electronic reducibility tuned by ultra-small supported bimetallic Pt–Cu clusters
journal, January 2019

  • Paz-Borbón, Lauro Oliver; Buendía, Fernando; Garzón, Ignacio L.
  • Physical Chemistry Chemical Physics, Vol. 21, Issue 28
  • DOI: 10.1039/c9cp01772k

The influence of support materials on the structural and electronic properties of gold nanoparticles – a DFT study
journal, January 2019

  • Engel, Julien; Francis, Samantha; Roldan, Alberto
  • Physical Chemistry Chemical Physics, Vol. 21, Issue 35
  • DOI: 10.1039/c9cp03066b

Preparation of isolated Co 3 O 4 and fcc-Co crystallites in the nanometre range employing exfoliated graphite as novel support material
journal, January 2019

  • Wolf, Moritz; Fischer, Nico; Claeys, Michael
  • Nanoscale Advances, Vol. 1, Issue 8
  • DOI: 10.1039/c9na00291j

Complex oscillatory decrease with size in diffusivity of {100}-epitaxially supported 3D fcc metal nanoclusters
journal, January 2019


Ultimate dispersion of metallic and ionic platinum on ceria
journal, January 2019

  • Tovt, Andrii; Bagolini, Luigi; Dvořák, Filip
  • Journal of Materials Chemistry A, Vol. 7, Issue 21
  • DOI: 10.1039/c9ta00823c

Understanding chemical and physical mechanisms in atomic layer deposition
journal, January 2020

  • Richey, Nathaniel E.; de Paula, Camila; Bent, Stacey F.
  • The Journal of Chemical Physics, Vol. 152, Issue 4
  • DOI: 10.1063/1.5133390

Predicting metal–metal interactions. II. Accelerating generalized schemes through physical insights
journal, March 2020

  • Choksi, Tej S.; Streibel, Verena; Abild-Pedersen, Frank
  • The Journal of Chemical Physics, Vol. 152, Issue 9
  • DOI: 10.1063/1.5141378

Quick-start guide for first-principles modelling of semiconductor interfaces
journal, November 2018

  • Park, Ji-Sang; Jung, Young-Kwang; Butler, Keith T.
  • Journal of Physics: Energy, Vol. 1, Issue 1
  • DOI: 10.1088/2515-7655/aad928