Visible light absorption of TiO{sub 2} materials impregnated with tungstophosphoric acid ethanol–aqueous solution at different pH values. Evidence about the formation of a surface complex between Keggin anion and TiO{sub 2} surfaces

Journal Article · Wed Jan 01 00:00:00 EST 2014 · Materials Research Bulletin

DOI:https://doi.org/10.1016/J.MATERRESBULL.2013.09.043· OSTI ID:22341869

Blanco, Mirta N.

Graphical abstract: - Highlights: • TPA impregnation on TiO{sub 2} particles was done at different initial pH values. • Powders characterization evidenced the possible existence of TPA–TiO{sub 2} complexes. • Keggin anion complexed on TiO{sub 2} would be responsible of visible light absorption. - Abstract: TiO{sub 2} particles prepared by the sol–gel method were impregnated at different pH values (1.0, 2.0, 5.0 and 10.0) with a water–ethanol solution (50% V/V) of tungstophosphoric acid (TPA) (0.012 M). Similar preparation was carried out to synthesize TiO{sub 2} impregnated with [WO{sub 4}]{sup 2−} (TiW). These materials were characterized by different techniques such as UV–vis diffuse reflectance spectroscopy (UV–vis DRS), magic angle spinning nuclear magnetic resonance of {sup 31}P ({sup 31}P MAS NMR), X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FT-IR), Fourier transform Raman spectroscopy (FT-Raman). Results revealed that TPA–TiO{sub 2} materials exhibit visible light absorption only when impregnation was done at pH 1.0 (TiTPA1) and 2.0 (TiTPA2). TiW powder did not show visible light absorption. XRD patterns show the presence of peaks at 2θ = 25.4° (1 0 1), 37.9° (0 0 4), 47.8° (2 0 0) and 54.3° associated to the anatase phase. Solid NMR, FT-IR and FT-Raman characterization showed that TiTPA1 and TiTPA2 samples contain Keggin ([PW{sub 12}O{sub 40}]{sup 3−}) and lacunary anions ([PW{sub 11}O{sub 39}]{sup 7−}) respectively. On the other hand, FT-Raman results revealed a blue shifting and broadening of the band at 141 cm{sup −1} corresponding to anatase TiO{sub 2} and moreover, a broadening of bands at 900–1100 cm{sup −1} attributed to Keggin structures of TPA. Both spectral changes could be related to the formation of a surface complex between the Keggin anion of TPA and TiO{sub 2} surfaces. This interaction should be responsible for visible light absorption.

• OSTI ID: 22341869
• Journal Information: Materials Research Bulletin, Vol. 49; Other Information: Copyright (c) 2013 Elsevier Science B.V., Amsterdam, The Netherlands, All rights reserved.; Country of input: International Atomic Energy Agency (IAEA); ISSN 0025-5408
• Country of Publication: United States
• Language: English

Related Subjects

36 MATERIALS SCIENCE
ABSORPTION
ANIONS
AQUEOUS SOLUTIONS
ETHANOL
FOURIER TRANSFORM SPECTROMETERS
FOURIER TRANSFORMATION
INFRARED SPECTRA
INTERACTIONS
NANOSTRUCTURES
NUCLEAR MAGNETIC RESONANCE
OPTICAL PROPERTIES
PARTICLES
PEAKS
POWDERS
RAMAN SPECTROSCOPY
SOL-GEL PROCESS
SOLIDS
TITANIUM OXIDES
TUNGSTATES
X-RAY DIFFRACTION