Effect of Oxygen Content on the Photoelectrochemical Activity of Crystallographically Preferred Oriented Porous Ta3N5 Nanotubes

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Instituto de Física, UFRGS, Av Bento Goncalves 9500 PO Box -15051 91501-970, POA-RS, Brazil
Instituto de Física de São Carlos, Universidade de São Paulo, CP 369, São Carlos 13560−970, SP Brazil
§ Instituto de Quimica, UFRGS, Av Bento Goncalves 9500 PO Box -15051 91501-970, POA-RS, Brazil
Department of Chemistry, University of Victoria, Victoria, BC V8W 3 V6, Canada
School of Chemistry, University of Nottingham, University Park, Nottingham NG7 2RD, U.K.
*E-mail: [email protected]. Phone: +55-51-33086498.
Cite this: J. Phys. Chem. C 2015, 119, 34, 19906–19914
Publication Date (Web):July 31, 2015
Copyright © 2015 American Chemical Society
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Crystallographically preferred oriented porous Ta3N5 nanotubes (NTs) were synthesized by thermal nitridation of vertically oriented, thick-walled Ta2O5 NTs, strongly adhered to the substrate. The adherence on the substrate and the wall thickness of the Ta2O5 NTs were fine-tuned by anodization, thereby helping to preserve their tubular morphology for nitridation at higher temperatures. Samples were studied by scanning electron microscopy, high-resolution electron microscopy, X-ray diffraction, Rietveld refinements, ultraviolet–visible spectrophotometry, X-ray photoelectron spectroscopy, photoluminescence spectra, and electrochemical techniques. Oxygen content in the structure of porous Ta3N5 NTs strongly influenced their photoelectrochemical activity. Structural analyses revealed that the nitridation temperature has crystallographically controlled the preferential orientation along the (110) direction, reduced the oxygen content in the crystalline structure and the tubular matrix, and increased the grain size. The preferred oriented porous Ta3N5 NTs optimized by the nitridation temperature presented an enhanced photocurrent of 7.4 mA cm–2 at 1.23 V vs RHE under AM 1.5 (1 Sun) illumination. Hydrogen production was evaluated by gas chromatography, resulting in 32.8 μmol of H2 in 1 h from the pristine porous Ta3N5 NTs. Electrochemical impedance spectroscopy has shown an effect of nitridation temperature on the interfacial charge transport resistance at the semiconductor–liquid interface; however, the flat band of Ta3N5 NTs remained unchanged.

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  • Details of experimental methods and characterizations; SEM images, XPS spectra, LSV curves, SAED patterns, PL spectra, and Mott–Schottky plots; and tables displaying data on the geometrical dimensions of the NTs, Rietveld refinement, and PEC parameters. (PDF)

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