Fabrication and Photoactivity of Hollow TiO2

Microspheres by Chemically Induced Self-

transformation

Jiaguo Yu

State Key Laboratory of Advanced Technology for Material

Synthesis and Processing, Wuhan University of Technology,
Luoshi Road 122#, Wuhan 430070, P.R. China.
E-mail address: jiaguoyu@yahoo.com.
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SCI Papers on photocatalysis published in recent 10 years

2000 International
China
Number of SCI Papers

1500

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500

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97 98 99 00 01 02 03 04 05 06 07
Publication Years 2
 Photocatalysis of TiO2 hollow microspheres

• due to its widely potential application in water and air

purification and solar energy conversion.
• Among various oxide semiconductor photocatalysts, titania
has proven to be the most suitable for widespread
environmental applications.
• Fabrication of TiO2 hollow microspheres has attracted a
great deal of attention because of their low density, high
surface area, good surface permeability, larger light-
harvesting efficiencies. higher energy conversion efficiency
and photocatalytic activity.
• Here, I will report fabrication and photocatalytic activity of
TiO2 hollow spheres by a chemically induced self-
transformation method, a environmentally friendly method.

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Preparation of TiO2 hollow microspheres
• chemically induced self-transformation method
• Crystalline mesoporous TiO2 hollow
microspheres are fabricated by hydrothermal
treatment of acidic Ti(SO4)2 aqueous solution in
the presence of NH4F at 200oC for 9 h. The molar
ratio of fluoride to titanium (R) varied from 0,
0.4, 1 to 2.
• The photocatalytic activity of the samples was
evaluated by measuring the photocatalytic
decomposition of acetone in air under UV
irradiation.
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 Scheme 1 Illustration of formation mechanism of hollow
TiO2 microspheres based on fluoride-induced self-
transformation strategy

Step 1: explosive multiplication of large numbers of metastable TiO2 nanoclusters;

Step 2: thermodynamically spontaneous organization of TiO2 nanoclusters into
amorphous spherical aggregates.
Step 3: heterogeneous nucleation of a crystalline thin shell around the amorphous
spherical aggregates.
Step 4: preferential dissolution of the amorphous particle interior and the continuous
deposition of a porous crystalline external shell, producing intact hollow
microspheres without modification in the bulk morphology.
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J. Yu, et al. Adv Funct Mater, 2006, 16, 2035
Fig. 1. TEM (a, b, c, f) and SEM (d, e) images of TiO2 samples prepared
with varying R at 200oC for 9 h: (a) 0; (b) 0.4; (c, d, e) 1; (f) 2.

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J. Yu, et al. J Catal, 2007, 249, 59
Fig. 2. EDX spectrum of anatase TiO2
hollow microspheres obtained with R
= 1 at 200oC for 9 h.
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Scheme 2. Illustration for the fluoride-mediated formation of hierarchical
porous TiO2 hollow microspheres and their morphology variations at
varying R
A
B
C

R=0 R = 0.4

Amorphous
Precursor
R=1 R=2

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A primary nanocrystal B secondary aggregate C triple aggregate
 0.09
R=0
200 R=0
R = 0.4
Adsorbed volume (cm /g)

R=1 R = 0.4
R=2 R=1
3

160

Pore volume (cm /g)

R=2
0.06

3
120

80
0.03
40

0
0.0 0.2 0.4 0.6 0.8 1.0 0.00
1 10 100
Relative pressure (P/P0) Pore diameter (nm)

Fig. 3. Nitrogen adsorption-desorption isotherms and

corresponding pore size distribution of TiO2 samples
prepared with varying R at 200oC for 9 h.
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Fig. 4. TEM images of TiO2 samples prepared with R = 1 at
200oC for different hydrothermal time: (a) 30 min; (b) 9 h; (c)
36 h. Inset in (a) shows the corresponding XRD pattern.

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 100
(A) (B)
Relative Intensity (a.u.)

(m /g)
75

SBET
2
50
25
0.24

(cm /g)
R=2

PV
0.16

3
R=1 0.08

5 min R = 0.4 15

(nm)
APS
R=0 10

10 20 30 40 50 60 70 5
0 1 2
2 Theta (degree)
R

Fig. 5. (A): XRD patterns and (B): BET surface area (SBET ),
pore volume (PV) and average pore size (APS) of TiO2
samples with varying R at 200oC for 9 h.

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Fig. 6. The apparent rate constant of TiO2 samples prepared
at 200oC for 9 h with varying R, and their comparision with
that of P25.

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Rate constant (10 , min )

30 min
-1
-3

6
P25

0
R = 0 R = 0.4 R=1 R=2 12
Conclusions
Hollow anatase-phase TiO2 microspheres with bimodel
mesoporous shells can be easily fabricated on a
large scale.
fluoride induces the hollowing process of TiO2
microspheres, and the rate of such a process can be
readily tuned by changing R, a higher R results in a
greater hollowing rate.
chemically induced self-transformation is a
environmentally friendly method, can be used to
produce highly active photocatalytic materials.

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the added fluoride promotes the crystallization and
crystallite growth of anatase-phase TiO2 primary
nanocrystals, and thus the BET surface areas
decrease with increasing R. The as-prepared hollow
TiO2 microspheres generally exhibit bimodal
mesopore size distribution, finer intra-aggregated
pores and greater inter-aggregated pores, with their
maximum pore diameters in the range of 3-10 and
30-50 nm, respectively.
The positive effect of fluoride on enhancing the
crystallization and increasing the pore volume at
appropriate R is suggested to be the main
contribution of fluoride to the improvement of
photocatalytic activity of hollow TiO2 microspheres.
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 Fabrication of CaCO3 Hollow Microspheres by Chemically
Induced Self-Transformation

High-magnification SEM

Low-magnification SEM

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J. Yu, et al. Adv Funct Mater, 2006, 16, 2035
 Fabrication of CaCO3 Hollow Microspheres by Chemically
Induced Self-Transformation

TEM images
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J. Yu, et al. Adv Funct Mater, 2006, 16, 2035
 Formation Mechanism of CaCO3 Hollow Microspheres

30 min 2h 24 h

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J. Yu, et al. Adv Funct Mater, 2006, 16, 2035
 Spontaneous Formation of a Tungsten Trioxide Sphere-in-Shell
Superstructure by Chemically Induced Self-Transformation

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J. Yu, et al. Small, 2008, 4, 87
 Formation Mechanism of a Tungsten Trioxide Sphere-in-Shell
Superstructure

WO3·nH2O SrWO4

WO3·1/3H2O

WO3·nH2O

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J. Yu, et al. Small, 2008, 4, 87
Fabrication of SnO2 Hollow Structures by Chemically Induced Self-
Transformation

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J. Yu, et al. Adv Funct Mater, 2006, 16, 2035
A One-Pot Approach to Hierarchically Nanoporous Titania Hollow
Microspheres with High Photocatalytic Activity

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J. Yu, et al. Cryst. Growth Des, 2008, 8, 930
 Formation Mechanism of Hierarchically Nanoporous Titania
Hollow Microspheres

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J. Yu, et al. Cryst. Growth Des, 2008, 8, 930
Nitrogen adsorption–desorption isotherm (inset) and corresponding
pore-size distribution of TiO2 hollow spheres

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J. Yu, et al. Cryst. Growth Des, 2008, 8, 930
Hydrothermal Synthesis and Photocatalytic Activity of Zinc Oxide
Hollow Spheres

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J. Yu, et al. Environ Sci Tech, 2008, 42, 4902
Acknowledgment

• This work was supported by NSFC

(50625208, 20773097 and 20877061) and
973 program (No. 2007CB613302).

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 Important open Questions

1 Secondary pollution and separation of nanoparticles.

2 Stability of nanocatalysts in air, solution and solid.
3 Thermodynamically driven self-aggregation and self-
transformation of nanoparticles.
4 Preparation of nanostructured hollow microspheres.
5 Application of nanostructured hollow microspheres in
water and air purification.
6 Nano-pollution and its influence on health.

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Thank you
for
your attention!

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