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Title: TiO{sub 2} nanotube arrays for photocatalysis: Effects of crystallinity, local order, and electronic structure

To furnish insight into correlations of electronic and local structure and photoactivity, arrays of short and long TiO{sub 2} nanotubes were synthesized by electrochemical anodization of Ti foil, followed by thermal treatment in O{sub 2} (oxidizing), Ar (inert), and H{sub 2} (reducing) environments. The physical and electronic structures of these nanotubes were probed with x-ray diffraction, scanning electron microscopy, and synchrotron-based x-ray absorption spectroscopy, and correlated with their photocatalytic properties. The photocatalytic activity of the nanotubes was evaluated by monitoring the degradation of methyl orange under UV-VIS light irradiation. Results show that upon annealing at 350 °C all as-anodized amorphous TiO{sub 2} nanotube samples partially transform to the anatase structure, with variations in the degree of crystallinity and in the concentration of local defects near the nanotubes' surface (∼5 nm) depending on the annealing conditions. Degradation of methyl orange was not detectable for the as-anodized TiO{sub 2} nanotubes regardless of their length. However, the annealed long nanotubes demonstrated detectable catalytic activity, which was more significant with the H{sub 2}-annealed nanotubes than with the Ar- and O{sub 2}-annealed nanotube samples. This enhanced photocatalytic response of the H{sub 2}-annealed long nanotubes relative to the other samples is positively correlated with the presence of amore » larger concentration of lattice defects (such as Ti{sup 3+} and anticipated oxygen vacancies) and a slightly lower degree of crystallinity near the nanotube surface. These physical and electronic structural attributes impact the efficacy of visible light absorption; moreover, the increased concentration of surface defects is postulated to promote the generation of hydroxyl radicals and thus accelerate the photodegradation of the methyl orange. The information obtained from this study provides unique insight into the role of the near-surface electronic and defect structure, crystal structure, and the local chemical environment on the photocatalytic activity and may be employed for tailoring the materials' properties for photocatalysis and other energy-related applications.« less
Authors:
; ;  [1] ;  [2] ; ;  [3] ;  [4]
  1. Department of Chemical Engineering, Northeastern University, Boston, Massachusetts 02115 (United States)
  2. Chemistry Department, Brookhaven National Laboratory, Upton, New York 11973 and Department of Chemistry, SUNY Stony Brook, Stony Brook, New York 117944 (United States)
  3. Department of Physics, Northeastern University, Boston, Massachusetts 02115 (United States)
  4. National Synchrotron Light Source, Brookhaven National Laboratory, Upton, New York 11973 (United States)
Publication Date:
OSTI Identifier:
22392133
Resource Type:
Journal Article
Resource Relation:
Journal Name: Journal of Vacuum Science and Technology. A, Vacuum, Surfaces and Films; Journal Volume: 33; Journal Issue: 2; Other Information: (c) 2014 American Vacuum Society; Country of input: International Atomic Energy Agency (IAEA)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY; ABSORPTION SPECTROSCOPY; ANNEALING; ANODIZATION; ELECTRONIC STRUCTURE; HYDROXYL RADICALS; METHYL ORANGE; NANOTUBES; PHOTOCATALYSIS; SCANNING ELECTRON MICROSCOPY; SURFACES; TITANIUM OXIDES; X-RAY DIFFRACTION; X-RAY SPECTROSCOPY