Synthesis and Photocatalysis Property of Ultra-small TiO2 Nanoclusters in Aqueous Media

doi:10.15541/jim20160625

Abstract

Abstract:

Atomic clusters are of significant interest in catalysis. Ultra-small TiO₂ nanoclusters, a stable Ti-O cluster with diameters of a few nanometers or less, can exhibit fascinating reactive, optical and electronic properties. In this work, ~2 nm TiO₂ ultra-small nanoclusters were obtained by peptizing hydrolysate of tetrabutyl titanate (TPT) at 80℃. HRTEM and XRD were used to characterize microstructure of the ultra-small TiO₂nanoclusters, which was verified to have crystalline phase anatase. XPS demonstrated that the valence state of Ti atom was Ti⁴⁺ and no oxygen vacancy existed. Optical absorption properties were determined by UV-Vis spectroscopy and demonstrated that the ultra-small TiO₂ nanoclusters had extraordinary strong absorption in the light wavelength range from 235 nm to 340 nm. According to the transmission spectrum, the optical band gap was calculated to be 3.56 eV, indicating an appreciable size-base quantum effect. The specific surface area was analyzed to be 269.28 m²/g for Langmuir surface area and 186.90 m²/g for multi-point BET surface area, respectively. Photocatalytic reduction of Cr⁶⁺ to Cr³⁺ in ultra-small TiO₂ aqueous sol was investigated to estimate the photocatalytic activity. It demonstrated that the reduction rate of Cr⁶⁺ to Cr³⁺ by ultra-small TiO₂ nanoclusters was four times faster than that by widely used nano-crystals one. And owing to extraordinary strong ultraviolet absorption of the former, Cr⁶⁺ was completely reduced to Cr³⁺ under sunlight illumination.

Key words: atom cluster, ultra-small, titanium dioxide, photocatalysis, hexavalent chromium

CLC Number:

TQ174

LIN Jing-Cheng, TANG Xiao, CHU Wan-Yi. Synthesis and Photocatalysis Property of Ultra-small TiO₂ Nanoclusters in Aqueous Media[J]. Journal of Inorganic Materials, 2017, 32(8): 863-869.

Figures/Tables 10

Fig. 1 Standard concentration-absorbance curve of Cr6+

Fig. 2 Process of synthesizing ultra-small TiO2 nanoclusters(a) Tetrabutyl titanate (TPT) added into water to produce white precipitation hydrolysis products, and then (b) the hydrolysate peptized into transparent sol

Fig. 3 XRD patterns of (a) anatase nanocrystals, (b) resulting ultra-small nanoclusters and (c) TBT hydrolysates

Fig. 4 HR-TEM images of the ultra-small TiO2 nanoclusters (left) and the corresponding live FFT results (right)

Fig.5 XPS spectrum of ultra-small TiO2 nanocluster

Fig. 6 N2 adsorption and desorption isotherm and BET specific surface area analysis results of the ultra-small TiO2 nanocluster

Fig. 7 UV-Vis absorption spectra of (a) 2 nm sized ultra-small TiO2 nanoclusters and (b) 20 nm sized TiO2 nanocrystals

Fig.8 (a) UV-Vis transmissiom spectra of the ultra-small TiO2 nanocluster and (b) its absorption onset value of the first allowed transition

Fig. 9 (a) Mixtures of K2Cr2O7 solution with the sol of ultra- small TiO2 nanocluster (A) and that of the TiO2 nanocrystal (B) before sunlight irradiating; (b) after sunlight irradiating for 3 d

Fig. 10 Change of Cr6+ concentration with irradiating time for the ultra-small TiO2 nanocluster system (A) and TiO2 nanocrystal system (B) under UV irradiation

References 17

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Synthesis and Photocatalysis Property of Ultra-small TiO₂ Nanoclusters in Aqueous Media

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