Hydrothermal Transformation of Titanate Scrolled Nanosheets to Anatase over a Wide pH Range and Contribution of Triethanolamine and Oleic Acid to Control the Morphology

  • Qingguo Bai
    Qingguo Bai
    ICMCB, CNRS, Université Bordeaux, UMR 5026, 33608 Pessac, France
    LOMA, Université Bordeaux, CNRS, UMR 5798, 33405 Talence, France
    More by Qingguo Bai
  • Magali Lavenas
    Magali Lavenas
    ICMCB, CNRS, Université Bordeaux, UMR 5026, 33608 Pessac, France
  • Laetitia Vauriot
    Laetitia Vauriot
    ICMCB, CNRS, Université Bordeaux, UMR 5026, 33608 Pessac, France
    LOMA, Université Bordeaux, CNRS, UMR 5798, 33405 Talence, France
  • Quentin Le Tréquesser
    Quentin Le Tréquesser
    ICMCB, CNRS, Université Bordeaux, UMR 5026, 33608 Pessac, France
  • Junjie Hao
    Junjie Hao
    ICMCB, CNRS, Université Bordeaux, UMR 5026, 33608 Pessac, France
    LOMA, Université Bordeaux, CNRS, UMR 5798, 33405 Talence, France
    More by Junjie Hao
  • Francois Weill
    Francois Weill
    ICMCB, CNRS, Université Bordeaux, UMR 5026, 33608 Pessac, France
  • Jean-Pierre Delville
    Jean-Pierre Delville
    LOMA, Université Bordeaux, CNRS, UMR 5798, 33405 Talence, France
  • , and 
  • Marie-Helene Delville*
    Marie-Helene Delville
    ICMCB, CNRS, Université Bordeaux, UMR 5026, 33608 Pessac, France
    *E-mail: [email protected]
Cite this: Inorg. Chem. 2019, 58, 4, 2588–2598
Publication Date (Web):February 1, 2019
https://doi.org/10.1021/acs.inorgchem.8b03197
Copyright © 2019 American Chemical Society
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Abstract

Mild hydrothermal conditions used for the treatment of titanate scrolled nanosheets (SNSs) suspensions (140 °C, 72 h) resulted in a large variety of anatase TiO2 anisotropic nano-objects depending on the studied parameters: influence of the medium pH and the presence or not of structuring agents (SAs). The present work shows that such a hydrothermal treatment of the SNSs, whatever the pH, resulted in the formation of single-crystalline anatase nanoneedles (NNs) with a specific crystal-elongation direction and a pH-dependent morphological anisotropy with aspect ratios (ARs) from 1 to 8. The SNSs suspensions were prepared by the conventional ultrabasic treatment of TiO2 with NaOH, followed by washing with HNO3 to different pH values. The crystal size of the anatase TiO2 obtained from this hydrothermal treatment increased with the pH of the suspensions, from 15 nm nanoparticles (NPs; AR = 1) at pH 2.2 to 500 nm NNs (AR = 8) at a pH 10.8 with a long axis systematically along the anatase [001] direction. Triethanol amine and oleic acid were used as SAs. Their respective influence, when acting on their own, had little influence on the control of the size, shape, or polydispersity of the NNs. However, their concomitant use provided a much better control of not only the size and polydispersity, which was strongly reduced, but also on (i) the shape and morphology giving rise to a controlled access to well-defined nanorods as opposed to nanoneedles and (ii) the crystal phase purity eliminating the few percent brookite still visible in the X-ray diffraction patterns of samples prepared in SA-free conditions. This approach offers an on-demand control over the production of anatase morphologies with defined aspect ratios.

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(The Supporting Information is available free of charge on the ACS Publications website at DOI: 10.1021/acs.inorgchem.8b03197.

  • XRD patterns of TiO2 anatase NNs prepared at different initial pH values. TEM images of nanoparticles prepared with 500 μL of oleic acid (OA) at an initial pH of 2. TEM images of the result of nanoneedles synthesis using 500 μL of TEOA at initial pH 10.7 and (a) 0, (b) 500, and (c) 800 μL of OA showing the adverse effect of the concomitant use of high pH and oleate structuring agent (PDF)

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This article is cited by 7 publications.

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  2. Siqi Yu, Bing Han, Yunchao Lou, Guodong Qian, Zhiyu Wang. Nano Anatase TiO2 Quasi-Core–Shell Homophase Junction Induced by a Ti3+ Concentration Difference for Highly Efficient Hydrogen Evolution. Inorganic Chemistry 2020, 59 (5) , 3330-3339. https://doi.org/10.1021/acs.inorgchem.0c00277
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