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Title: Support and Oxidation Effects on Subnanometer Palladium Nanoparticles

The effect of cluster size, oxidation state, and the support upon the structures and energetics of subnanometer palladium nanoparticles is investigated within a density functional framework. Gas phase global minima of Pd-4 and Pd-10 along with their suboxide counterparts are determined using a genetic algorithm and deposited upon MgO (001) and a high-index alumina surface. It is observed that there is an oxidation-dependent transition in the smaller clusters from three-dimensional to two-dimensional structures both in the gas phase and when supported by a surface. MgO strongly promotes a change from tetrahedral- and icosahedral-based structures toward cubic forms, while alumina induces significant distortion of the cluster and the breaking of Pd-Pd bonds. Increased oxygenation contributes cooperatively to these effects, causing disruption of the Pd-Pd bond network, favoring the incorporation of oxygen into the cluster structure, further complicating unambiguous structure prediction.
Authors:
 [1] ;  [2] ;  [1]
  1. Univ. of Birmingham (United Kingdom)
  2. Argonne National Lab. (ANL), Argonne, IL (United States); Yale Univ., New Haven, CT (United States)
Publication Date:
Grant/Contract Number:
AC02-06CH11357
Type:
Accepted Manuscript
Journal Name:
Journal of Physical Chemistry. C
Additional Journal Information:
Journal Volume: 118; Journal Issue: 7; Journal ID: ISSN 1932-7447
Publisher:
American Chemical Society
Research Org:
Argonne National Lab. (ANL), Argonne, IL (United States)
Sponsoring Org:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
OSTI Identifier:
1357189

Heard, Christopher J., Vajda, Stefan, and Johnston, Roy L.. Support and Oxidation Effects on Subnanometer Palladium Nanoparticles. United States: N. p., Web. doi:10.1021/jp411019t.
Heard, Christopher J., Vajda, Stefan, & Johnston, Roy L.. Support and Oxidation Effects on Subnanometer Palladium Nanoparticles. United States. doi:10.1021/jp411019t.
Heard, Christopher J., Vajda, Stefan, and Johnston, Roy L.. 2014. "Support and Oxidation Effects on Subnanometer Palladium Nanoparticles". United States. doi:10.1021/jp411019t. https://www.osti.gov/servlets/purl/1357189.
@article{osti_1357189,
title = {Support and Oxidation Effects on Subnanometer Palladium Nanoparticles},
author = {Heard, Christopher J. and Vajda, Stefan and Johnston, Roy L.},
abstractNote = {The effect of cluster size, oxidation state, and the support upon the structures and energetics of subnanometer palladium nanoparticles is investigated within a density functional framework. Gas phase global minima of Pd-4 and Pd-10 along with their suboxide counterparts are determined using a genetic algorithm and deposited upon MgO (001) and a high-index alumina surface. It is observed that there is an oxidation-dependent transition in the smaller clusters from three-dimensional to two-dimensional structures both in the gas phase and when supported by a surface. MgO strongly promotes a change from tetrahedral- and icosahedral-based structures toward cubic forms, while alumina induces significant distortion of the cluster and the breaking of Pd-Pd bonds. Increased oxygenation contributes cooperatively to these effects, causing disruption of the Pd-Pd bond network, favoring the incorporation of oxygen into the cluster structure, further complicating unambiguous structure prediction.},
doi = {10.1021/jp411019t},
journal = {Journal of Physical Chemistry. C},
number = 7,
volume = 118,
place = {United States},
year = {2014},
month = {1}
}