Size controllable synthesis and photocatalytic performance of mesoporous TiO2 hollow spheres

doi:10.1016/j.jmst.2020.03.013

摘要/Abstract

Abstract:

Hollow mesoporous TiO₂ spheres (THs) were prepared via template-directed deposition of TiO₂ nanoparticles on the surface of carbon spheres. The carbon spheres were used as hard templates. Their diameters were controlled by pH adjustment prior to a hydrothermal process. Physical properties, such as crystallinity, optical characteristics, microstructure and surface morphology of the samples were characterized. The results showed that the diameter of the carbon template could be well controlled in the range of 397-729 nm by adjusting the initial pH value of the dextrose solution from 3 to 10. Hollow TiO₂ spheres with average diameters ranging from 171 to 668 nm and shell thicknesses ranging from 28 to 47 nm formed by heat treatment at 450 °C. The photocatalytic performance of hollow TiO₂ spheres and TiO₂ nanoparticles was examined under UVA irradiation using a methyl orange aqueous solution as an artificial dye. The study revealed that the THs synthesized using a dextrose solution at pH 7 had a higher photocatalytic activity compared to other samples since it had the lowest shell thickness and the proper optical band gap of 3.12 eV with the longest lifetime of electron-hole pair separation.

Key words: TiO₂, Photocatalytic activity, Mesoporous titania, Hydrothermal method, Precipitation mechanism

. [J]. 材料科学与技术, 2020, 48(0): 105-113.

Nattakan Kanjana, Wasan Maiaugree, Phitsanu Poolcharuansin, Paveena Laokul. Size controllable synthesis and photocatalytic performance of mesoporous TiO₂ hollow spheres[J]. J. Mater. Sci. Technol., 2020, 48(0): 105-113.

图/表 13

Fig. 1. SEM images and the corresponding size distribution histograms of carbon spheres prepared using dextrose solutions at various pH values (a) pH 3, (b) pH 7 and (b) pH 10.

Fig. 2. TG/DSC curves of as-prepared CS-pH7 and CS@TiO2-pH7.

Fig. 3. X-ray diffraction patterns of the hollow TiO2 spheres synthesized using various carbon templates compared to the prepared TiO2 nanoparticles.

Fig. 4. FESEM micrographs (left) and corresponding higher magnification images (right) of the prepared TiO2 hollow spheres (a) THs-pH3, (b) THs-pH7 and (c) THs-pH10.

Fig. 5. Schematic illustration of the formation of TiO2 hollow spheres.

Fig. 6. TEM, HRTEM and the corresponding SAED patterns of THs-pH3 (a, b, and c), THs-pH7 (d, e, and f), and THs-pH10 (g, h, and i).

Fig. 7. N2 adsorption-desorption isotherms and the corresponding pore size distribution curves (inset) of the THs samples compared to TiO2 nanoparticles.

Table 1 Summary of diameter and shell thickness, specific surface area, pore-volume, optical absorption edge, band gap energy (Eg), rate constant and degradation efficiency of as-prepared samples.

Sample	Diameter (nm)	Shell thickness (nm)	Surface area (m²/g)	Pore volume (cm³/g)	Absorption edge (nm)	E_g (eV)	Rate constant (min^-1)	Degradation (%)
TNPs	n/a	n/a	4.27	0.03	402	2.98	1.38 × 10^-3	21.81
THs-pH3	667.98 ± 22.27	46.98 ± 8.30	138.07	0.89	409	2.88	5.21 × 10^-3	62.22
THs-pH7	327.03 ± 22.12	28.36 ± 6.63	101.98	0.58	394	3.12	10.43 × 10^-3	89.76
THs-pH10	170.91 ± 37.86	32.62 ± 6.00	54.53	0.47	397	3.05	8.34 × 10^-3	76.10

Fig. 8. UV-vis absorption spectra of TNPs and THs samples. The inset contains plots of (αhν)1/2 versus photon energy (hν) of the THs samples compared to TiO2 nanoparticles.

Fig. 9. EIS Nyquist plots and (inset) the corresponding equivalent circuit (a) and room temperature PL spectra of the TNPs and THs samples (b).

Fig. 10. Schematic illustration of the mechanism of methyl orange degradation under UVA irradiation on the surface of hollow TiO2 spheres.

Fig. 11. (a) Photocatalytic degradation of MO, (b) the degradation rate of all samples, (c) absorbance of MO dye by the THs and TiO2 nanoparticles after 140 min of photocatalytic degradation and (d) variations of ln(C0/C) as a function of irradiation time.

Fig. 12. Stability test on THs-pH7 for the degradation of MO.

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Size controllable synthesis and photocatalytic performance of mesoporous TiO₂ hollow spheres

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