Unraveling the Origin of Visible Light Capture by Core–Shell TiO2 Nanotubes

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Department of Chemistry and Soochow University-Western University Centre for Synchrotron Radiation Research, University of Western Ontario, 1151 Richmond Street, London, Ontario N6A 5B7, Canada
Institute of Functional Nano and Soft Materials (FUNSOM) and Soochow University-Western University Joint Centre for Synchrotron Radiation Research, Soochow University, Suzhou, Jiangsu 215123, Peoples’ Republic of China
§ Department of Mechanical and Material Engineering, University of Western Ontario, London, Ontario N6A 5B9, Canada
Advanced Light Source, Lawrence Berkeley National Laboratory, Berkeley, California 94720, United States
Department of Physics, Tamkang University, New Taipei City 25137, Taiwan, The Republic of China
# Department of Chemistry and Biochemistry, University of California, Santa Cruz, California 95064, United States
Cite this: Chem. Mater. 2016, 28, 12, 4467–4475
Publication Date (Web):May 24, 2016
Copyright © 2016 American Chemical Society
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A black TiO2 nanotube (NT) heterostructure with an anatase-core and an amorphous-shell has been synthesized by NH3 annealing of amorphous NT grown by the anodization of a Ti substrate. Remarkable photoabsorption behavior of these black TiO2 NTs is observed: strong absorption throughout the entire optical wavelength region from ultraviolet to near-infrared. X-ray absorption near-edge structure (XANES), X-ray photoelectron spectroscopy (XPS) and resonant inelastic X-ray scattering (RIXS) have been used to elucidate the origin of this spectacular light capture phenomenon. Surface-sensitive XANES recorded in total electron yield and XPS show that the surface layer is amorphous with a chemical composition approaching that of Ti4O7. Bulk-sensitive XANES using X-ray partial fluorescence yield and Ti 2p RIXS confirm the presence of a rich amount of Ti3+ in the crystalline bulk (core of the NT with anatase structure) of black TiO2 NTs, which exhibits a dispersive d-d energy loss at ∼2 eV corresponding to the broad visible light absorption at ∼600 nm. Our results suggest that the extraordinary photoabsorption behavior of these black TiO2 NTs is due to the stabilization of Ti3+ in this special N-doped core–shell assembly having structure varying between TiO2 (bulk anatase) and Ti4O7 (surface, amorphous).

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The Supporting Information is available free of charge on the ACS Publications website at DOI: 10.1021/acs.chemmater.6b01673.

  • SEM results (Figure S1), absorbance after air aging (Figure S2), O K-edge XANES analysis (Figure S3), overlay of Ti L3,2-edge and O K-edge XANES (Figure S4), XPS fitting results of Ti 2p (Figure S5) and O 1s (Figure S6), N K-edge XANES analysis (Figure S7), and C 1s XPS spectra of as-grown and annealed samples (Figure S8) (PDF)

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