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Title: Ligand induced shape transformation of thorium dioxide nanocrystals

Abstract

Nanocrystals (NCs) with size and shape dependent properties are a thriving research field. Significant progress has been made in the controlled synthesis of NCs of stable elements in the past two decades; however, the knowledge of the NCs of actinide compounds has been considerably limited due the difficulties in handling them both experimentally and theoretically. Actinide compounds, especially actinide oxides, play a critical role in many stages of the nuclear fuel cycle. Recently, a non-aqueous surfactant assisted approach has been developed for the synthesis of actinide oxide NCs with different morphologies, but an understanding of its control factors is still missing to date. Herein we present a comprehensive study on the low index surfaces of thorium dioxide (ThO 2) and their interactions with relevant surfactant ligands using density functional calculations. A systematic picture on the thermodynamic stability of ThO 2 NCs of different sizes and shapes is obtained employing empirical models based on the calculated surface energies. It is found that bare ThO 2 NCs prefer the octahedral shape terminated by (111) surfaces. Oleic acid displays selective adsorption on the (110) surface, leading to the shape transformation from octahedrons to nanorods. Other ligands such as acetylacetone, oleylamine, and trioctylphosphine oxidemore » do not modify the equilibrium shape of ThO 2 NCs. This research provides atomic level insights into the anisotropic growth of ThO2 NCs that was recently observed in experiments, and thus may contribute to the controlled synthesis of actinide oxide NCs with well-defined size and shape for future applications.« less

Authors:
ORCiD logo [1]; ORCiD logo [1]; ORCiD logo [1]
  1. Los Alamos National Lab. (LANL), Los Alamos, NM (United States)
Publication Date:
Research Org.:
Los Alamos National Lab. (LANL), Los Alamos, NM (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22). Chemical Sciences, Geosciences & Biosciences Division; USDOE National Nuclear Security Administration (NNSA)
OSTI Identifier:
1524386
Alternate Identifier(s):
OSTI ID: 1434968
Report Number(s):
LA-UR-17-31042
Journal ID: ISSN 1463-9076; PPCPFQ
Grant/Contract Number:  
89233218CNA000001; AC52-06NA25396
Resource Type:
Journal Article: Accepted Manuscript
Journal Name:
Physical Chemistry Chemical Physics. PCCP (Print)
Additional Journal Information:
Journal Volume: 20; Journal Issue: 26; Journal ID: ISSN 1463-9076
Publisher:
Royal Society of Chemistry
Country of Publication:
United States
Language:
English

Citation Formats

Wang, Gaoxue, Batista, Enrique R., and Yang, Ping. Ligand induced shape transformation of thorium dioxide nanocrystals. United States: N. p., 2018. Web. doi:10.1039/C8CP00240A.
Wang, Gaoxue, Batista, Enrique R., & Yang, Ping. Ligand induced shape transformation of thorium dioxide nanocrystals. United States. doi:10.1039/C8CP00240A.
Wang, Gaoxue, Batista, Enrique R., and Yang, Ping. Mon . "Ligand induced shape transformation of thorium dioxide nanocrystals". United States. doi:10.1039/C8CP00240A. https://www.osti.gov/servlets/purl/1524386.
@article{osti_1524386,
title = {Ligand induced shape transformation of thorium dioxide nanocrystals},
author = {Wang, Gaoxue and Batista, Enrique R. and Yang, Ping},
abstractNote = {Nanocrystals (NCs) with size and shape dependent properties are a thriving research field. Significant progress has been made in the controlled synthesis of NCs of stable elements in the past two decades; however, the knowledge of the NCs of actinide compounds has been considerably limited due the difficulties in handling them both experimentally and theoretically. Actinide compounds, especially actinide oxides, play a critical role in many stages of the nuclear fuel cycle. Recently, a non-aqueous surfactant assisted approach has been developed for the synthesis of actinide oxide NCs with different morphologies, but an understanding of its control factors is still missing to date. Herein we present a comprehensive study on the low index surfaces of thorium dioxide (ThO2) and their interactions with relevant surfactant ligands using density functional calculations. A systematic picture on the thermodynamic stability of ThO2 NCs of different sizes and shapes is obtained employing empirical models based on the calculated surface energies. It is found that bare ThO2 NCs prefer the octahedral shape terminated by (111) surfaces. Oleic acid displays selective adsorption on the (110) surface, leading to the shape transformation from octahedrons to nanorods. Other ligands such as acetylacetone, oleylamine, and trioctylphosphine oxide do not modify the equilibrium shape of ThO2 NCs. This research provides atomic level insights into the anisotropic growth of ThO2 NCs that was recently observed in experiments, and thus may contribute to the controlled synthesis of actinide oxide NCs with well-defined size and shape for future applications.},
doi = {10.1039/C8CP00240A},
journal = {Physical Chemistry Chemical Physics. PCCP (Print)},
issn = {1463-9076},
number = 26,
volume = 20,
place = {United States},
year = {2018},
month = {4}
}

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