Materials Research Bulletin 45 (2010) 1850–1854

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Materials Research Bulletin

journal homepage: www.elsevier.com/locate/matresbu

Effect of different doping methods on microstructure and photo-catalytic

activity of Ag2O–TiO2 nanofibers
Yang You a, Long Wan a,*, Shiying Zhang b, Difa Xu b
a
College of Material Science and Engineering, Hunan University, Hunan 410082, PR China
b
Department of Biological and Environmental Science, Changsha University, Hunan 410003, PR China

A R T I C L E I N F O A B S T R A C T

Article history: Ag+ doping TiO2 nanofibers were prepared by in-situ and immersion methods (named as SI-TiO2 and IM-
Received 27 April 2010 TiO2 nanofibers, respectively). This paper assesses the effects of the two different doping methods on the
Received in revised form 3 August 2010 material properties. Results show that the two kinds of nanofibers with the diameter of about 20 nm are
Accepted 12 September 2010
micron-sized length, and covered by nano-balls of Ag2O with the diameter of 2–5 nm. Compared to IM-
Available online 17 September 2010
TiO2 nanofibers, the SI-TiO2 nanofibers have fewer Ag2O particles. Thus, the photo-catalytic activity of
IM-TiO2 nanofibers is higher than SI-TiO2 nanofibers, which is also proved in photo-catalysis experiment
Keywords:
(the degradation ratio of IM-TiO2 catalyst is 100%, and the degradation ratio of SI-TiO2 catalyst is 95%).
A. Nanostructures
ß 2010 Elsevier Ltd. All rights reserved.
B. Chemical synthesis
D. Catalytic properties
D. Microstructure

1. Introduction region to visible light or enhance the photo-catalytic activity [13–

17]. The recombination rate of electron/hole pairs decreased for
A great deal of attention has aroused on contaminants the charge separation mechanism after the load of noble metal.
degradation for environmental efficiency. Photo-catalysis of semi- Noble metal and semiconductor have different Fermi levels what
conductor is a promising technology and is able to produce highly bring the transfer from semiconductor to metal up to the equation
efficient catalysts that destroy not only bacteria but also a large of Fermi levels of them. According to the aggregation of noble
variety of chemical contaminants in air and water [1–3]. A lot of metal, the change of semiconductor surface property will improve
effective semiconductors for contamination degradation have been the photo-catalytic activity of catalyst.
synthesized, such as CdS, TiO2 and ZnO [4]. But CdS and ZnO are The aim of this paper is to mainly assess the effects of the two
unstable under light irradiation because of the ions on their surface different Ag-doping ways on microstructure and photo-catalytic
with biologic toxicity caused by photo-anode corrosion. TiO2 is activity of TiO2 nanofibers. Firstly, the morphology of two types of
perhaps the most prospecting photo-catalyst in various different TiO2 nanofibers will be reported using TEM, and the surface
semiconductors due to its lack of toxicity, chemical stability, characterization of the two nanofibers will be analyzed by XPS and
corrosion resistance and superior photo-catalytic activity [5–7]. DRS. Secondly, using the methylene blue as target pollutant, the
It is well known that a high rate of recombination between photo-catalytic activity of the two types of TiO2 nanofibers is
excited electron–hole pairs result in a low quantum yield rate and investigated under the ultraviolet-light radiation.
also a limited photo-oxidation rate. Consequently, it is important
to study how to develop the spectral response of TiO2 nanomater- 2. Experimental
ials as catalysts and increase the photo-catalysis reaction ratio [8–
10]. Whilst various methods, such as noble metal precipitation and 2.1. TiO2 nanofiber prepared by in-situ method (named as SI-TiO2
surface modification [11,12], have been reported to enhance the nanofibers)
photo-catalytic efficiency of TiO2 nanomaterials. Recently, meth-
ods for synthesizing TiO2 one-dimensional materials doped with C, In a typical synthesis, at room temperature, solution A was
N, S, Gd3+ and Zr have been found to improve the photo-catalytic prepared by dispersing tetrabutyl orthotitanate (10 g) into
cyclohexanol (50 mL). Solution B was prepared by mixing
cyclohexanol (50 mL) with a solution of hexadecyl trimethyl
* Corresponding author. Tel.: +86 731 88823540; fax: +86 731 88823540.
ammonium bromide (CTAB) and AgNO3 (2% molar ratio) in
E-mail addresses: [email protected] (L. Wan), [email protected] distilled water (20 mL). Solution A was dropped into solution B
(S. Zhang). with continually stirring for 18 h, followed by trithylamine

0025-5408/$ – see front matter ß 2010 Elsevier Ltd. All rights reserved.
doi:10.1016/j.materresbull.2010.09.015
[(Fig._1)TD$IG] Y. You et al. / Materials Research Bulletin 45 (2010) 1850–1854 1851

Fig. 1. XPS spectra of the samples prepared by different methods: (a) SI-TiO2 nanofibers and (b) IM-TiO2 nanofibers.

addition to adjust the pH (pH 8.5). The sample was washed, dried at and the relative content of Ti3+ is lower than that of Ti4+. A second
60 8C and then calcined at 550 8C. The calcined sample was energy level appears in the band gap of the surface state of Ti3+,
dispersed in KOH solution (10 mol/L) and submitted to hydrother- which is the capturing place for photo-generated electrons [18].
mal synthesis at 150 8C for 72 h. Then the product was washed by The Ti 2p1/2 and Ti 2p3/2 spin-orbital splitting photoelectrons
acetone, dried at 80 8C and further calcined at 450 8C for 2 h to yield for both nanofibers are located at binding energies of 464.21 eV,
SI-TiO2 nanofiber. 464.11 eV and 458.48 eV, 458.40 eV, respectively. The peak
separation between the two cases is around 5.7 eV [19], suggesting
2.2. TiO2 nanofiber prepared by immersion method (named as IM- that the TiO2 nanofibers are high purity. Compared to the standard
TiO2 nanofibers) electron binding energy (458.7 eV) of Ti 2p3/2 [20], the electron
binding energy of IM-TiO2 was chemically shifted. This indicates
IM-TiO2 nanofiber prepared by hydrothermal method was that the chemical environment around Ti in the IM-TiO2 nanofibers
dispersed into distilled water (10 mL). After 10 min, alcohol (5 mL) altered, leading to an oxidation reaction between Ag+ and O2.
was added and the solution processed in an ultrasonic bath until Two diffraction peaks (2u = 32.88 and 63.38), corresponding to
the pH was 8.5. After stirring for 30 min, AgNO3 (2% molar ratio) the (1 1 1) and (1 0 5) crystal planes of Ag2O respectively, are
was added to the mixture and heat-treated in a water bath at 50 8C observed in the XRD pattern of the IM-TiO2 nanofibers (Fig. 2). The
for 8 h. The product was washed by acetone, dried at 80 8C, and appearance of Ag2O as a secondary phase indicates that Ag2O was
then calcined at 450 8C for 2 h to yield IM-TiO2 nanofiber. doped into the TiO2 nanofibers. In the IM-TiO2 sample, the Ag+ on
the surface has a higher work function (4.6 eV) than TiO2 (4.2 eV),
2.3. Photo-catalytic experiment which means the minimum energy of electrons transfer in Ag+ is
higher than that of TiO2. This leads to a transfer of electrons from
The SI-TiO2 and IM-TiO2 nanofibers were used as catalysts and TiO2 to Ag+ when the Ag2O particles are in contact with TiO2 until
methylene blue (MB) as the target pollutant. The following are the Fermi energy of the two matters is equal. And Schottky barrier
typical experimental conditions for the photo-catalysis: initial for electron transfer is created at the junction between Ag2O and
concentration of MB was 2 mg/L, the power of ultraviolet light with [(Fig._2)TD$IG] 2 [21], which prevents the recombination of generated
TiO
254 nm center wavelength was 25 W, the catalyst concentration
was 2 g/L, aeration speed was 3 L/min, and the pH was 6.0.

2.4. Characterization

Nanofiber morphology was characterized by high-resolution

transmission electron microscopy (HRTEM, JEM-3010, Japan). X-
ray diffraction (XRD, Bruker D8-Advance, Germany) and diffuse
reflection spectra (DRS, 2450 type, Japan) were used to investigate
crystalline structure. X-ray photoelectron spectra (XPS, AXIS-Ultra,
Kratos Analytical) were used to elucidate the surface chemical
composition and the oxidation state for the as-synthesized
samples. The spectrophotometer (722 type, shanghai, China)
was used to investigate the absorbency of the photo-catalytic
product. The type of UV lamp is ZWS (made in China).

3. Results and discussion

3.1. Structure and chemical composition

XPS spectra of the Ti 2p peaks of the two TiO2 nanofibers are

presented in Fig. 1. The major Ti valences are split into Ti4+ and Ti3+, Fig. 2. XRD patterns of the samples prepared by different methods.
1852 [(Fig._3)TD$IG]
Y. You et al. / Materials Research Bulletin 45 (2010) 1850–1854

electron–hole and increases the photo-catalytic activity of IM-TiO2

nanofiber. The high work function of IM-TiO2 sample causes a
corresponding increase in electron concentration on the surface of
the TiO2 nanofiber [22]. This also creates conditions favorable for
the capture of O2 from air and formation of OH. One peak
(2u = 63.38) of Ag2O phase is detected in the XRD pattern of SI-TiO2
sample (Fig. 2).
DRS patterns show that the absorption strength of both types of
nanofibers in the ultraviolet region is similar (Fig. 3). Compared
with SI-TiO2 nanofibers, the color of the IM-TiO2 nanofibers have
more gray, resulting in that the IM-TiO2 nanofibers have a stronger
absorptivity in the visible light area (Fig. 3). The introduction of
Ag2O reduces the excitation energy of surface atoms and enhances
the utilization ratio for visible light. In addition, the band gaps of
the samples are calculated with the formula [23]:

hc
Eg ¼ ¼ 1240=l0 (1)
l0 Fig. 3. DRS patterns of the samples prepared by different methods.

where Eg is the band gap, h is Plank’s constant, c is velocity of light,

and l0 is wavelength (vacuum). The band gaps of P25, IM-TiO2 and 3.2. Morphology of TiO2 nanofibers
SI-TiO2 are about 3.2 eV [24], 3.58 eV and 3.54 eV respectively. It is
clearly shown that the band gaps of the TiO2 nanofibers TEM images show that two different nanofiber samples have
synthesized are higher than that of Degussa P25 TiO2. different surface morphology (Fig. 4). There are numerous particles

[(Fig._4)TD$IG]

Fig. 4. TEM images of the samples prepared by different methods: (a) and (b) IM-TiO2 nanofibers, and (c) and (d) SI-TiO2 nanofibers.
 [(Fig._6)TD$IG]
Y. You et al. / Materials Research Bulletin 45 (2010) 1850–1854 1853

on their surfaces of IM-TiO2 nanofibers (Fig. 4a and b), and the

particle diameters are uniformly distribute around approximately
2–5 nm. However, SI-TiO2 nanofibers have smoother surfaces
(Fig. 4c and d) and fewer particles. The microstructure differences
can be attributed to the selective adsorbance of Ag2O on the two
nanofibers. Crystal lattice stripes in both kinds of nanofibers are
clear and singular (Fig. 4b and d), indicating that nanofibers have
excellent crystallization. According to the coordination number of
O2 ion of Ti4+ is 6 in the TiO2 crystal, the radius of Ti4+ ion is
74.5 pm [25]. The Ag2O is hard to enter the crystal lattice of TiO2
due to the Ag+ ion’s bigger radius. Therefore, some Ag2O
agglomerates will be formed on the surface of TiO2 in the
condition of low concentration of doping ions [26].

3.3. Photo-catalytic activity

To evaluate the photo-catalytic activity of IM-TiO2 and SI-TiO2

nanofibers, the decomposition of MB dye in solution has been
examined using the IM-TiO2 and SI-TiO2 nanofibers under
ultraviolet-light irradiation. Prior to irradiation, the MB solution
over the catalyst is kept in the dark for 30 min to obtain the
equilibrium adsorption state. The degradation of the MB solution is
finished after 200 min when IM-TiO2 nanofibers are used as the
catalyst (Fig. 5). In the same photo-catalysis condition, the
degradation ratio of the MB solution is only 95% when SI-TiO2
nanofibers are used as the catalyst (Fig. 5). The degradation ratio of
two nanofibers is higher than that of P25 (Degussa TiO2
nanocrystals with 25 nm diameter). For IM-TiO2 nanofibers,
Ag2O particles are adsorbed on the surface of the TiO2 nanofibers.
On absorbing a photon, a Ag2O particle generates an electron and a
hole, and subsequently the photo-generated electron combines
with an Ag+ ion to form an Ag atom. The adsorptive O2 on IM-TiO2
nanofibers act as electron acceptors to capture photo-generated
electrons and decrease the recombination of electrons and holes, as
described by the following equations:

e þ O2 ! O
2 (2) Fig. 6. The photo-catalytic degradation curve of MB during reusing the Ag2O–TiO2
nanofibers: (&) 3rd trial, (*) 5th trial, (~) 8th trial, (^) 12th trial, ([TD$INLE] ) 15th trial
Agþ þ e ! Ag (3)

Under the same photo-catalysis condition, IM-TiO2 nanofibers

and SI-TiO2 nanofibers are reused as photo-catalysts, as shown in nanofibers show excellent stability to use again, and 90% of initial
Fig. 6. The degradation ratio of IM-TiO2 nanofibers and SI-TiO2 activity still remains after 5 cycle usages. After repeating 15 times,
nanofibers after 3 recycles for the MB solution is 100% and 95% the degradation ratio of IM-TiO2 nanofibers and SI-TiO2 nanofibers
respectively, and the photo-catalysis time is 200 min. The two is 85.1% and 84.3% respectively. Therefore, IM-TiO2 nanofibers and
SI-TiO2 nanofibers have high photo-catalytic activity and are easy
[(Fig._5)TD$IG] to be reused.

4. Conclusion

In summary, Ag-doping TiO2 nanofibers with micron-level size

are successfully prepared by both immersion and in-situ methods.
The structure and properties of these two nanofibers have been
compared. A lot of Ag2O particles of approximately 2–5 nm
diameters are adsorbed on the surface of IM-TiO2 nanofibers,
while the surface of SI-TiO2 nanofibers has fewer Ag2O particles.
Photo-catalytic activity of IM-TiO2 nanofibers is higher than that
of SI-TiO2 nanofibers. The two nanofibers show excellent stability
to use again. After repeating 15 times, the degradation ratio of IM-
TiO2 nanofibers and SI-TiO2 nanofibers is 85.1% and 84.3%
respectively.

Acknowledgments

This work was supported by the National Natural Science

Foundation of China (50872014) and the Research Fund of
Fig. 5. Methylene blue solution photodegradation by different catalysts. Changsha University (SF030505).
1854 Y. You et al. / Materials Research Bulletin 45 (2010) 1850–1854

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