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Title: The evolution of crystalline ordering for ligand-ornamented zinc oxide nanoparticles

Abstract

Recent total scattering experiments have opened up the possibility to study nanoparticle formation in situ and to observe the structural transformation from precursor clusters to adult particles. Organic ligand molecules interact with precursors of metal oxide nanoparticles, yet their influence onto the evolution of crystallinity during particle formation has not been addressed in detail; nor have in situ total scattering experiments ventured into the field of low-concentration, room-temperature syntheses in organic solvents to date. In this report, we follow the crystallization of ZnO nanoparticles in ethanol in the presence of different organic ligands. Low coordinated zinc precursor clusters rapidly polymerize upon base addition to particles of ca. 1 nm in diameter. In situ SAXS experiments reveal that the overall particle size increases to 2 to 4 nm with advancing reaction time. Complementary in situ PDF experiments show smaller crystalline domain sizes, which are only one third to half as large as the particle diameter. The ZnO particles thus feature a crystalline core surrounded by a disordered shell. Both, the core and the shell diameter are influenced by the different surface-bound organic ligands, which prevent an immediate relaxation to fully crystalline particles. A slow crystallization takes place in solution. We assumemore » a dynamic equilibrium of the ligand and solvent molecules at the particle surface, which enables gradual bond restructuring. With suitably adjusted synthesis conditions, in our case by a continuous base addition, we show how to bypass the disordered intermediates, allowing the spontaneous nucleation of fully crystalline nanoparticles.« less

Authors:
; ; ; ; ; ; ; ;
Publication Date:
Research Org.:
Argonne National Lab. (ANL), Argonne, IL (United States). Advanced Photon Source (APS)
Sponsoring Org.:
FOREIGN
OSTI Identifier:
1377906
Resource Type:
Journal Article
Journal Name:
CrystEngComm
Additional Journal Information:
Journal Volume: 18; Journal Issue: 12; Journal ID: ISSN 1466-8033
Publisher:
Royal Society of Chemistry
Country of Publication:
United States
Language:
ENGLISH
Subject:
36 MATERIALS SCIENCE; 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Citation Formats

Zobel, Mirijam, Windmüller, Anna, Schmidt, Ella M., Götz, Klaus, Milek, Theodor, Zahn, Dirk, Kimber, Simon A. J., Hudspeth, Jessica M., and Neder, Reinhard B. The evolution of crystalline ordering for ligand-ornamented zinc oxide nanoparticles. United States: N. p., 2016. Web. doi:10.1039/C5CE02099A.
Zobel, Mirijam, Windmüller, Anna, Schmidt, Ella M., Götz, Klaus, Milek, Theodor, Zahn, Dirk, Kimber, Simon A. J., Hudspeth, Jessica M., & Neder, Reinhard B. The evolution of crystalline ordering for ligand-ornamented zinc oxide nanoparticles. United States. doi:10.1039/C5CE02099A.
Zobel, Mirijam, Windmüller, Anna, Schmidt, Ella M., Götz, Klaus, Milek, Theodor, Zahn, Dirk, Kimber, Simon A. J., Hudspeth, Jessica M., and Neder, Reinhard B. Fri . "The evolution of crystalline ordering for ligand-ornamented zinc oxide nanoparticles". United States. doi:10.1039/C5CE02099A.
@article{osti_1377906,
title = {The evolution of crystalline ordering for ligand-ornamented zinc oxide nanoparticles},
author = {Zobel, Mirijam and Windmüller, Anna and Schmidt, Ella M. and Götz, Klaus and Milek, Theodor and Zahn, Dirk and Kimber, Simon A. J. and Hudspeth, Jessica M. and Neder, Reinhard B.},
abstractNote = {Recent total scattering experiments have opened up the possibility to study nanoparticle formation in situ and to observe the structural transformation from precursor clusters to adult particles. Organic ligand molecules interact with precursors of metal oxide nanoparticles, yet their influence onto the evolution of crystallinity during particle formation has not been addressed in detail; nor have in situ total scattering experiments ventured into the field of low-concentration, room-temperature syntheses in organic solvents to date. In this report, we follow the crystallization of ZnO nanoparticles in ethanol in the presence of different organic ligands. Low coordinated zinc precursor clusters rapidly polymerize upon base addition to particles of ca. 1 nm in diameter. In situ SAXS experiments reveal that the overall particle size increases to 2 to 4 nm with advancing reaction time. Complementary in situ PDF experiments show smaller crystalline domain sizes, which are only one third to half as large as the particle diameter. The ZnO particles thus feature a crystalline core surrounded by a disordered shell. Both, the core and the shell diameter are influenced by the different surface-bound organic ligands, which prevent an immediate relaxation to fully crystalline particles. A slow crystallization takes place in solution. We assume a dynamic equilibrium of the ligand and solvent molecules at the particle surface, which enables gradual bond restructuring. With suitably adjusted synthesis conditions, in our case by a continuous base addition, we show how to bypass the disordered intermediates, allowing the spontaneous nucleation of fully crystalline nanoparticles.},
doi = {10.1039/C5CE02099A},
journal = {CrystEngComm},
issn = {1466-8033},
number = 12,
volume = 18,
place = {United States},
year = {2016},
month = {1}
}

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