Unfolding the Anatase-to-Rutile Phase Transition in TiO2 Nanotubes Using X-ray Spectroscopy and Spectromicroscopy

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Department of Chemistry, University of Western Ontario, Chemistry Building, 1151 Richmond Street, London, Ontario Canada N6A 5B7
Canadian Light Source Inc., University of Saskatchewan, Saskatoon, Canada S7N 2 V3
Soochow University-Western University Centre for Synchrotron Radiation Research, University of Western Ontario, London, Canada N6A 5B7
*E-mail: [email protected]. Phone: 519-661-2111, ext. 86341.
Cite this: J. Phys. Chem. C 2016, 120, 38, 22079–22087
Publication Date (Web):August 31, 2016
https://doi.org/10.1021/acs.jpcc.6b07613
Copyright © 2016 American Chemical Society
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Abstract

This work reports a study of the anatase-to-rutile phase transition (ART) in a highly ordered TiO2 nanotube (NT) specimen fabricated using an electrochemical process followed by thermal annealing at 750 °C (NT750). Two-dimensional X-ray absorption near-edge structure–X-ray excited optical luminescence spectroscopy reveals the hierarchically two-layered structure of NT750 by resolving the surface anatase luminescence and bulk rutile optical emission. Scanning transmission X-ray microscopy analysis of a sliced NT750 lamella spatially differentiates the top nanotubular anatase structure from the denser rutile bottom layer with a gradual ART interface layer. On the basis of these results together with the known behavior of size and anisotropy dependence of ART in TiO2 nanocrystal, we propose the “bottom-up” mechanism for ART in anodic TiO2 NTs. This result is particularly relevant to the fundamental understanding of phase transition in nanostructures as well as the fabrication of desired TiO2 NT mixed-phase composite with an excellent control of the anatase/rutile phase ratio.

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The Supporting Information is available free of charge on the ACS Publications website at DOI: 10.1021/acs.jpcc.6b07613.

  • Detailed STXM sample preparation, characterization, and the associated data analysis; the setup for XANES and XEOL measurements (Figure S1); calculated attenuation length of X-rays for bulk anatase and rutile TiO2 (Figure S2); schematic views of X-ray penetration depth in porous NT750 (Figure S3); STXM examinations on the top nanotubular region (Figures S4 and S5); XRD analysis of various NT samples (Figure S6); and XANES analysis of NT800 and NT900 (Figure S7) (PDF)

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