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

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 CeO 2(111) surfaces, determined by single crystal adsorption calorimetry of gaseous Cu atoms onto slightly reduced CeO 2(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 CeO 2 surface and are thus considered representative of stoichiometric CeO 2(111) surfaces.
Authors:
 [1] ;  [1] ;  [1]
  1. Univ. of Washington, Seattle, WA (United States). Dept. of Chemistry
Publication Date:
Grant/Contract Number:
FG02-96ER14630
Type:
Published Article
Journal Name:
ACS Catalysis
Additional Journal Information:
Journal Volume: 5; Journal Issue: 10; Journal ID: ISSN 2155-5435
Publisher:
American Chemical Society (ACS)
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
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; 77 NANOSCIENCE AND NANOTECHNOLOGY; adsorption energy; catalysis; ceria; copper; nanoparticles; size effects
OSTI Identifier:
1213955
Alternate Identifier(s):
OSTI ID: 1438016

James, Trevor E., Hemmingson, Stephanie L., and Campbell, Charles T.. Energy of Supported Metal Catalysts: From Single Atoms to Large Metal Nanoparticles. United States: N. p., Web. doi:10.1021/acscatal.5b01372.
James, Trevor E., Hemmingson, Stephanie L., & Campbell, Charles T.. Energy of Supported Metal Catalysts: From Single Atoms to Large Metal Nanoparticles. United States. doi:10.1021/acscatal.5b01372.
James, Trevor E., Hemmingson, Stephanie L., and Campbell, Charles T.. 2015. "Energy of Supported Metal Catalysts: From Single Atoms to Large Metal Nanoparticles". United States. doi:10.1021/acscatal.5b01372.
@article{osti_1213955,
title = {Energy of Supported Metal Catalysts: From Single Atoms to Large Metal Nanoparticles},
author = {James, Trevor E. and Hemmingson, Stephanie L. and Campbell, Charles T.},
abstractNote = {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.},
doi = {10.1021/acscatal.5b01372},
journal = {ACS Catalysis},
number = 10,
volume = 5,
place = {United States},
year = {2015},
month = {8}
}