Nickel Oxide Selectively Deposited on the {101} Facet of Anatase TiO2 Nanocrystal Bipyramids for Enhanced Photocatalysis

  • Shun Kashiwaya
    Shun Kashiwaya
    Institut des Sciences Moléculaires, UMR 5255 CNRS, Université de Bordeaux, 351 Cours de la Libération, 33 405 Talence, France
    Fachbereich Material- und Geowissenshaften, Technische Universität Darmstadt, Petersenstr. 23, 64287 Darmstadt, Germany
  • Céline Olivier
    Céline Olivier
    Institut des Sciences Moléculaires, UMR 5255 CNRS, Université de Bordeaux, 351 Cours de la Libération, 33 405 Talence, France
  • Jérôme Majimel
    Jérôme Majimel
    ICMCB UMR 5026, CNRS, Univ. Bordeaux INP, F-33600 Talence, France
  • Andreas Klein
    Andreas Klein
    Fachbereich Material- und Geowissenshaften, Technische Universität Darmstadt, Petersenstr. 23, 64287 Darmstadt, Germany
  • Wolfram Jaegermann
    Wolfram Jaegermann
    Fachbereich Material- und Geowissenshaften, Technische Universität Darmstadt, Petersenstr. 23, 64287 Darmstadt, Germany
  • , and 
  • Thierry Toupance*
    Thierry Toupance
    Institut des Sciences Moléculaires, UMR 5255 CNRS, Université de Bordeaux, 351 Cours de la Libération, 33 405 Talence, France
    *E-mail: [email protected]
Cite this: ACS Appl. Nano Mater. 2019, 2, 8, 4793–4803
Publication Date (Web):July 17, 2019
https://doi.org/10.1021/acsanm.9b00729
Copyright © 2019 American Chemical Society
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Abstract

Facet-engineered anatase TiO2 with NiO nanoparticles heterocontacts were successfully prepared by selective photodeposition of NiO nanoparticles onto the {101} facet of the top-truncated bipyramidal TiO2 anatase nanocrystals coexposed with {001} and {101} facets. The morphology and electronic properties of the resulting 0.1–10 wt % NiO-decorated TiO2 were investigated by X-ray diffraction, high-resolution electron microscopy, N2 sorption analysis, and UV–vis spectroscopy. Furthermore, a careful determination of the energy band alignment diagram was conducted by a model experiment using XPS and UPS to verify charge separation at the interface of the NiO−TiO2 heterostructure. The model experiment was performed by stepwise deposition of NiO onto oriented TiO2 substrates and in-situ photoelectron spectroscopy measurements without breaking vacuum. Core levels showed shifts of 0.58 eV toward lower binding energies, meaning an upward band bending in TiO2 at the NiO–TiO2 interface. Furthermore, 0.1 wt % NiO–TiO2 exhibited 50% higher activities than the pure TiO2 for methylene blue (MB) photodecomposition under UV irradiation. This enhanced photocatalytic activity of NiO–TiO2 nanocomposites was related to the internal electric field developed at the p–n NiO−TiO2 heterojunction, leading to vectorial charge separation. Finally, mechanistic studies conducted in the presence of carrier or radical scavengers revealed that holes dominantly contributed to the photocatalytic reactions in the case of NiO–TiO2 photocatalysts while electrons played the main role in photocatalysis for the pure TiO2 materials.

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The Supporting Information is available free of charge on the ACS Publications website at DOI: 10.1021/acsanm.9b00729.

  • N2 adsorption–desorption isotherms along with complementary SEM/TEM images and XPS-UPS data (PDF)

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