DOE PAGES title logo U.S. Department of Energy
Office of Scientific and Technical Information

Title: Ligand induced shape transformation of thorium dioxide nanocrystals

Journal Article · · Physical Chemistry Chemical Physics. PCCP
DOI: https://doi.org/10.1039/C8CP00240A · OSTI ID:1524386

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.

Research Organization:
Los Alamos National Lab. (LANL), Los Alamos, NM (United States)
Sponsoring Organization:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22). Chemical Sciences, Geosciences & Biosciences Division; USDOE National Nuclear Security Administration (NNSA)
Grant/Contract Number:
89233218CNA000001; AC52-06NA25396
OSTI ID:
1524386
Alternate ID(s):
OSTI ID: 1434968
Report Number(s):
LA-UR--17-31042
Journal Information:
Physical Chemistry Chemical Physics. PCCP, Journal Name: Physical Chemistry Chemical Physics. PCCP Journal Issue: 26 Vol. 20; ISSN 1463-9076; ISSN PPCPFQ
Publisher:
Royal Society of ChemistryCopyright Statement
Country of Publication:
United States
Language:
English

References (57)

Kinetics of II-VI and III-V Colloidal Semiconductor Nanocrystal Growth:  “Focusing” of Size Distributions journal June 1998
Predicting Nanocrystal Shape through Consideration of Surface-Ligand Interactions journal February 2012
Synthesis of Monodisperse Spherical Nanocrystals journal August 2007
Thorium dioxide: Properties and nuclear applications journal November 1985
Bulk-nanocrystalline oxide nuclear fuels – An innovative material option for increasing fission gas retention, plasticity and radiation-tolerance journal March 2012
Non-aqueous Synthesis of Isotropic and Anisotropic Actinide Oxide Nanocrystals journal May 2012
Application of the Covalent Bond Classification Method for the Teaching of Inorganic Chemistry journal April 2014
Temperature Dependence of the Surface Energy of the Low Index Planes of UO2 and ThO2 journal April 2016
A model for the phase stability of arbitrary nanoparticles as a function of size and shape journal September 2004
The Thermodynamic Properties of the f -Elements and their Compounds. Part 2. The Lanthanide and Actinide Oxides journal March 2014
Thermodynamic stability of the UO 2 surfaces: Interplay between over-stoichiometry and polarity compensation journal March 2016
Nanomaterials and nanotechnologies in nuclear energy chemistry journal August 2012
The surface science of nanocrystals journal January 2016
Chemistry and Properties of Nanocrystals of Different Shapes journal April 2005
Metal-Free Carbon Nanomaterials Become More Active than Metal Catalysts and Last Longer journal June 2010
Controlled Synthesis of Thorium and Uranium Oxide Nanocrystals journal March 2013
Ligand Effect on the Growth and the Digestion of Co Nanocrystals journal March 2005
Shape control of CdSe nanocrystals journal March 2000
Actinide Dioxides in Water: Interactions at the Interface journal November 2011
Composition, structure, and stability of RuO 2 ( 110 ) as a function of oxygen pressure journal December 2001
Symmetry-Controlled Colloidal Nanocrystals:  Nonhydrolytic Chemical Synthesis and Shape Determining Parameters journal August 2005
Hydroxylation of the surface of PbS nanocrystals passivated with oleic acid journal May 2014
Efficiency of ab-initio total energy calculations for metals and semiconductors using a plane-wave basis set journal July 1996
Nanomaterials for Rechargeable Lithium Batteries journal April 2008
Formation of High-Quality CdS and Other II-VI Semiconductor Nanocrystals in Noncoordinating Solvents: Tunable Reactivity of Monomers journal July 2002
The bulk modulus of ThO2—an experimental and theoretical study journal November 2004
Über die Säurekatalyse der Wasserabspaltung aus Thioglykolsäure journal January 1953
Semiconductor Clusters, Nanocrystals, and Quantum Dots journal February 1996
Effects of irradiation on the microstructure and mechanical properties of nanostructured materials journal February 2005
Colloidal metal oxide nanocrystal catalysis by sustained chemically driven ligand displacement journal January 2016
Nano goes nuclear journal December 2006
Nanostructures and Nanomaterials book January 2004
Shape-Controlled Synthesis of Colloidal Metal Nanocrystals: Thermodynamic versus Kinetic Products journal June 2015
Synthesis of Monodisperse Spherical Nanocrystals journal June 2007
Mechanical and electronic properties of CeO 2 , ThO 2 , and ( Ce , Th ) O 2 alloys journal July 2009
The Heats of Combustion of Thorium and Uranium 1,2,3 journal July 1952
High-resolution X-ray luminescence extension imaging journal February 2021
Symmetry-Controlled Colloidal Nanocrystals: Nonhydrolytic Chemical Synthesis and Shape Determining Parameters journal November 2005
Nanoparticle shapes by using Wulff constructions and first-principles calculations journal January 2015
New mechanistic pathways for CO oxidation catalyzed by single-atom catalysts: Supported and doped Au1/ThO2 journal September 2016
Dissociative Binding of Carboxylic Acid Ligand on Nanoceria Surface in Aqueous Solution: A Joint In Situ Spectroscopic Characterization and First-Principles Study journal November 2013
Synthesis of Colloidal Uranium−Dioxide Nanocrystals journal December 2006
Molecular Rulers for Scaling Down Nanostructures journal February 2001
From ultrasoft pseudopotentials to the projector augmented-wave method journal January 1999
Generalized Gradient Approximation Made Simple journal October 1996
Mechanistic Aspects in the Formation, Growth and Surface Functionalization of Metal Oxide Nanoparticles in Organic Solvents journal May 2017
Ultra-large-scale syntheses of monodisperse nanocrystals journal November 2004
Prediction of TiO 2 Nanoparticle Phase and Shape Transitions Controlled by Surface Chemistry journal July 2005
Thorium/uranium mixed oxide nanocrystals: Synthesis, structural characterization and magnetic properties journal November 2013
Hydroxylation-induced surface stability of AnO2 (An=U, Np, Pu) from first-principles journal February 2013
Thermophysical properties of uranium dioxide journal March 2000
Reducing Dzyaloshinskii-Moriya interaction and field-free spin-orbit torque switching in synthetic antiferromagnets journal May 2021
SOWOS : an open-source program for the three-dimensional Wulff construction journal April 2013
Colloidal nanocrystal synthesis and the organic–inorganic interface journal September 2005
Semiempirical GGA-type density functional constructed with a long-range dispersion correction journal January 2006
Chemistry and Properties of Nanocrystals of Different Shapes journal July 2005
Formation of High-Quality CdS and Other II-VI Semiconductor Nanocrystals in Noncoordinating Solvents: Tunable Reactivity of Monomers journal July 2002

Cited By (2)

Structural properties of ultra-small thorium and uranium dioxide nanoparticles embedded in a covalent organic framework journal January 2020
Understanding the size effects on the electronic structure of ThO 2 nanoparticles journal January 2019