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Title: Shell-Induced Ostwald Ripening: Simultaneous Structure, Composition, and Morphology Transformations during the Creation of Hollow Iron Oxide Nanocapsules

Abstract

The creation of nanomaterials requires simultaneous control of not only crystalline structure and composition but also crystal shape and size, or morphology, which can pose a significant synthetic challenge. Approaches to address this challenge include creating nanocrystals whose morphologies echo their underlying crystal structures, such as the growth of platelets of two-dimensional layered crystal structures, or conversely attempting to decouple the morphology from structure by converting a structure or composition after first creating crystals with a desired morphology. A particularly elegant example of this latter approach involves the topotactic conversion of a nanoparticle from one structure and composition to another, since the orientation relationship between the initial and final product allows the crystallinity and orientation to be maintained throughout the process. Here we report a mechanism for creating hollow nanostructures, illustrated via the decomposition of β-FeOOH nanorods to nanocapsules of α-Fe2O3, γ-Fe2O3, Fe3O4, and FeO, depending on the reaction conditions, while retaining single-crystallinity and the outer nanorod morphology. Using in situ TEM, we demonstrate that the nanostructured morphology of the starting material allows kinetic trapping of metastable phases with a topotactic relationship to the final thermodynamically stable phase.

Authors:
 [1];  [1]; ORCiD logo [2]; ORCiD logo [2];  [1]; ORCiD logo [2];  [1]; ORCiD logo [2]; ORCiD logo [1]
  1. Univ. of Kentucky, Lexington, KY (United States)
  2. Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)
Publication Date:
Research Org.:
Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)
Sponsoring Org.:
USDOE
OSTI Identifier:
1470842
Grant/Contract Number:  
AC05-00OR22725
Resource Type:
Accepted Manuscript
Journal Name:
ACS Nano
Additional Journal Information:
Journal Volume: 12; Journal Issue: 9; Journal ID: ISSN 1936-0851
Publisher:
American Chemical Society (ACS)
Country of Publication:
United States
Language:
English
Subject:
36 MATERIALS SCIENCE

Citation Formats

Yu, Lei, Han, Ruixin, Sang, Xiahan, Liu, Jue, Thomas, Melonie P., Hudak, Bethany M., Patel, Amita, Page, Katharine, and Guiton, Beth S. Shell-Induced Ostwald Ripening: Simultaneous Structure, Composition, and Morphology Transformations during the Creation of Hollow Iron Oxide Nanocapsules. United States: N. p., 2018. Web. doi:10.1021/acsnano.8b02946.
Yu, Lei, Han, Ruixin, Sang, Xiahan, Liu, Jue, Thomas, Melonie P., Hudak, Bethany M., Patel, Amita, Page, Katharine, & Guiton, Beth S. Shell-Induced Ostwald Ripening: Simultaneous Structure, Composition, and Morphology Transformations during the Creation of Hollow Iron Oxide Nanocapsules. United States. https://doi.org/10.1021/acsnano.8b02946
Yu, Lei, Han, Ruixin, Sang, Xiahan, Liu, Jue, Thomas, Melonie P., Hudak, Bethany M., Patel, Amita, Page, Katharine, and Guiton, Beth S. Thu . "Shell-Induced Ostwald Ripening: Simultaneous Structure, Composition, and Morphology Transformations during the Creation of Hollow Iron Oxide Nanocapsules". United States. https://doi.org/10.1021/acsnano.8b02946. https://www.osti.gov/servlets/purl/1470842.
@article{osti_1470842,
title = {Shell-Induced Ostwald Ripening: Simultaneous Structure, Composition, and Morphology Transformations during the Creation of Hollow Iron Oxide Nanocapsules},
author = {Yu, Lei and Han, Ruixin and Sang, Xiahan and Liu, Jue and Thomas, Melonie P. and Hudak, Bethany M. and Patel, Amita and Page, Katharine and Guiton, Beth S.},
abstractNote = {The creation of nanomaterials requires simultaneous control of not only crystalline structure and composition but also crystal shape and size, or morphology, which can pose a significant synthetic challenge. Approaches to address this challenge include creating nanocrystals whose morphologies echo their underlying crystal structures, such as the growth of platelets of two-dimensional layered crystal structures, or conversely attempting to decouple the morphology from structure by converting a structure or composition after first creating crystals with a desired morphology. A particularly elegant example of this latter approach involves the topotactic conversion of a nanoparticle from one structure and composition to another, since the orientation relationship between the initial and final product allows the crystallinity and orientation to be maintained throughout the process. Here we report a mechanism for creating hollow nanostructures, illustrated via the decomposition of β-FeOOH nanorods to nanocapsules of α-Fe2O3, γ-Fe2O3, Fe3O4, and FeO, depending on the reaction conditions, while retaining single-crystallinity and the outer nanorod morphology. Using in situ TEM, we demonstrate that the nanostructured morphology of the starting material allows kinetic trapping of metastable phases with a topotactic relationship to the final thermodynamically stable phase.},
doi = {10.1021/acsnano.8b02946},
journal = {ACS Nano},
number = 9,
volume = 12,
place = {United States},
year = {2018},
month = {8}
}

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