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Title: Anatase-TiO2 Nanomaterials: Morphological/Size Dependence of the Crystallization and Phase Behavior Phenomena

Abstract

Nanoparticulated TiO{sub 2} materials with anatase structure were synthesized by using a microemulsion method. Three different syntheses with varying surfactant-to-water molar ratio ({omega}) were used to obtain amorphous solid precipitates at room temperature. The structural characteristics of these solid precursors were studied by using X-ray absorption structure (X-ray absorption near-edge structure and extended X-ray absorption fine structure) and Raman spectroscopies, which showed that all lack 3D (tridimensional) order but contain a different degree of 2D-confined connectivity. While heating such solid precursors under dry air, marked differences appeared in the phase behavior; the onset temperature for anatase crystallization increases ca. 150 {sup o}C while the {omega} parameter decreases and only one of the samples shows the anatase-to-rutile transformation below 900 {sup o}C. In all cases, the crystallization of the anatase structure does not follow a traditional nucleation and growth mechanism and its analysis using the Avrami formalism gives conclusive evidence of a surface nucleation-dominated process. This appears as a distinctive feature of anatase-TiO{sub 2} nanomaterials, far from the corresponding behavior of microsized or bulk materials. After nucleation, the grain growth of anatase nanoparticles was found to follow the kinetic equation D{sup 2}-D{sub 0}{sup 2} = k{sub 0} exp(-E{sub a}/RT), where themore » activation energy is a function of several structural properties of the solid materials mainly related to the hydration characteristics of the surface layer. A combined in situ X-ray diffraction/Raman/infrared study aimed to unveil the physical basis of the phase behavior and to interpret key variables allowing control of the crystallization mechanism and morphological properties, particularly primary particle size, in the nanometer regime.« less

Authors:
; ; ; ;
Publication Date:
Research Org.:
Brookhaven National Laboratory (BNL) National Synchrotron Light Source
Sponsoring Org.:
Doe - Office Of Science
OSTI Identifier:
930326
Report Number(s):
BNL-81036-2008-JA
Journal ID: ISSN 1932-7447; TRN: US200904%%521
DOE Contract Number:
DE-AC02-98CH10886
Resource Type:
Journal Article
Resource Relation:
Journal Name: Journal of Physical Chemistry C; Journal Volume: 111; Journal Issue: 2
Country of Publication:
United States
Language:
English
Subject:
36 MATERIALS SCIENCE; 77 NANOSCIENCE AND NANOTECHNOLOGY; TITANIUM OXIDES; NANOSTRUCTURES; SYNTHESIS; PHASE STUDIES; CRYSTALLIZATION; PARTICLE SIZE; ACTIVATION ENERGY; GRAIN GROWTH; KINETIC EQUATIONS; national synchrotron light source

Citation Formats

Fernandez-Garcia,M., Wang, X., Belver, C., Hanson, J., and Rodriguez, J. Anatase-TiO2 Nanomaterials: Morphological/Size Dependence of the Crystallization and Phase Behavior Phenomena. United States: N. p., 2007. Web. doi:10.1021/jp065661i.
Fernandez-Garcia,M., Wang, X., Belver, C., Hanson, J., & Rodriguez, J. Anatase-TiO2 Nanomaterials: Morphological/Size Dependence of the Crystallization and Phase Behavior Phenomena. United States. doi:10.1021/jp065661i.
Fernandez-Garcia,M., Wang, X., Belver, C., Hanson, J., and Rodriguez, J. Mon . "Anatase-TiO2 Nanomaterials: Morphological/Size Dependence of the Crystallization and Phase Behavior Phenomena". United States. doi:10.1021/jp065661i.
@article{osti_930326,
title = {Anatase-TiO2 Nanomaterials: Morphological/Size Dependence of the Crystallization and Phase Behavior Phenomena},
author = {Fernandez-Garcia,M. and Wang, X. and Belver, C. and Hanson, J. and Rodriguez, J.},
abstractNote = {Nanoparticulated TiO{sub 2} materials with anatase structure were synthesized by using a microemulsion method. Three different syntheses with varying surfactant-to-water molar ratio ({omega}) were used to obtain amorphous solid precipitates at room temperature. The structural characteristics of these solid precursors were studied by using X-ray absorption structure (X-ray absorption near-edge structure and extended X-ray absorption fine structure) and Raman spectroscopies, which showed that all lack 3D (tridimensional) order but contain a different degree of 2D-confined connectivity. While heating such solid precursors under dry air, marked differences appeared in the phase behavior; the onset temperature for anatase crystallization increases ca. 150 {sup o}C while the {omega} parameter decreases and only one of the samples shows the anatase-to-rutile transformation below 900 {sup o}C. In all cases, the crystallization of the anatase structure does not follow a traditional nucleation and growth mechanism and its analysis using the Avrami formalism gives conclusive evidence of a surface nucleation-dominated process. This appears as a distinctive feature of anatase-TiO{sub 2} nanomaterials, far from the corresponding behavior of microsized or bulk materials. After nucleation, the grain growth of anatase nanoparticles was found to follow the kinetic equation D{sup 2}-D{sub 0}{sup 2} = k{sub 0} exp(-E{sub a}/RT), where the activation energy is a function of several structural properties of the solid materials mainly related to the hydration characteristics of the surface layer. A combined in situ X-ray diffraction/Raman/infrared study aimed to unveil the physical basis of the phase behavior and to interpret key variables allowing control of the crystallization mechanism and morphological properties, particularly primary particle size, in the nanometer regime.},
doi = {10.1021/jp065661i},
journal = {Journal of Physical Chemistry C},
number = 2,
volume = 111,
place = {United States},
year = {Mon Jan 01 00:00:00 EST 2007},
month = {Mon Jan 01 00:00:00 EST 2007}
}
  • Nanoparticulated TiO2 materials with anatase structure were synthesized by using a microemulsion method. The structural characteristics of the amorphous solid precursors and their evolution during thermal treatments were studied by using X-ray absorption structure (X-ray absorption near edge structure XANES and extended X-ray absorption fine structure EXAFS), XRD-PDF (X-ray diffraction-pair distribution function), and infrared spectroscopy. Concerning the precursor materials, XANES and EXAFS showed a local order closely related to that of the anatase structure but containing defective, undercoordinated Ti5c4+ species in addition to normal Ti6c4+ species. The PDF technique detects differences among samples in the local order (below 1 nm)more » and showed that primary particle size varies throughout the amorphous precursor series. The physical interpretation of results concerning the amorphous materials and their evolution under thermal treatment gives conclusive evidence that local, intraparticle ordering variations determine the temperature for the onset of the nucleation process and drive the solid behavior through the whole crystallization process. The significance of this result in the context of current crystallization theories of oxide-based nanocrystalline solids is discussed.« less
  • Single-phase anatase-TiO2 nanomaterials with a size of ca. 10 nm and variable quantities of anion impurities were prepared using a novel pathway based on the use of amorphous ammonium Ti-oxychloride precursors synthesized using Ti/Cl initial ratios between 1 and 6. The precursor nature and evolution under thermal treatment were studied using chemical analysis, XRD, XPS, DRIFTS, and mass spectrometry. The nature and concentration of anatase-TiO2 materials anion impurities were analyzed by XPS and DRIFTS. It is shown that negatively charged impurities located in substitutional positions of the anatase network are maximized for a sample synthesized using a Ti/Cl 1:1 atomicmore » ratio and are responsible for the elimination of liquid-phase (phenol) and gas-phase (isopropanol or methylcyclohexane) pollutants under sunlight excitation. A link is established among the initial chemical characterization of the precursors, the final morphological, structural, and chemical composition of the oxide materials, and their photochemical properties.« less
  • We demonstrate that x-ray absorption spectroscopy (XAS) can be used as an unconventional characterization technique to determine the proportions of different crystal phases in polymorphic samples. As an example, we show that ratios of anatase and rutile phases contained in the TiO{sub 2} samples obtained by XAS are in agreement with conventional x-ray diffraction (XRD) measurements to within a few percent. We suggest that XAS measurement is a useful and reliable technique that can be applied to study the phase composition of highly disordered or nanoparticle polymorphic materials, where traditional XRD technique might be difficult.