Journal of Alloys and Compounds 597 (2014) 101–109

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Journal of Alloys and Compounds

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

Characterization and photocatalytic activity of large-area single

crystalline anatase TiO2 nanotube films hydrothermal synthesized
on Plasma electrolytic oxidation seed layers
Qiang Luo a, Qizhou Cai a,⇑, Xinwei Li a, Xidi Chen a,b

a
State Key Lab of Material Processing and Dies & Mould Technology, Huazhong University of Science and Technology, Wuhan 430074, China
b
Institute of Functional Materials, Wuyi University, Jiangmen 529020, China

articleinfo abstract

Article history: The layer produced by Plasma electrolytic oxidation technique was used as seed layer for hydrothermal
Received 14 November 2013 synthesis of large-area TiO2 nanotube film in this paper. The effects of hydrothermal parameters on the
Received in revised form 26 January 2014 surface morphologies of films were investigated by field emission scanning electron microscopy (FSEM).
Accepted 28 January 2014 The results showed that the surface morphologies of films can be easily changed by varying the NaOH
Available online 5 February 2014 concentration, reaction temperature and reaction time. In addition, the effect of calcination temperature
on the morphologies, crystal structure, photophysical properties and photocatalytic activity of the nano-
Keywords: tube films were also studied using field emission scanning electron microscopy (FSEM), transmission
TiO2 nanotube film electron microscopy (TEM), X-ray diffraction (XRD), UV–Vis spectrophotometry and Fluorescence spec-
Large-area trophotometry. Calcination resulted in crystallization of the nanotubes from amorphous state to sin- gle-
Hydrothermal crystalline anatase phase. Furthermore, the increase of calcination temperature was beneficial to the
Plasma electrolytic oxidation improvement of crystallization degree. However, the nanotubes completely collapsed to form short
Photocatalytic
nanorods when the calcination temperature increased to 700 °C. The TiO 2 nanotube film calcined at
600 °C exhibited the narrowest band gap energy, the strongest UV light absorption, the weakest band –
band PL intensity and the best photocatalytic activity.
© 2014 Elsevier B.V. All rights reserved.

1. Introduction
Titanium oxide (TiO 2) nanostructured materials have attracted
tremendous attention in a lot of fields, such as in photocatalysis
[1,2], dye-sensitized solar cell [3], water splitting catalysts for
hydrogen generation [4], and electrochemical sensing [5]. TiO2
nanotubes possess remarkably superior properties in these applica-
tions compared with other forms of nanocrystalline TiO 2 because of
their high surface area and charge transport property [6]. Further-
more, the tube-like structure can supply sufficiently reactive points
for the reaction [7]. Therefore, synthesis, properties and applications
of TiO2 nanotubes has been intensively investigated by scientists in
recent years [8]. A number of methods have been developed for pre-
paring TiO2 nanotubes, including anodic oxidation [9–12], template-
based approaches [13,14] and hydrothermal technique [15].
Since Kasuga et al. [16] firstly reported the preparation of TiO 2
nanotubes through hydrothermal method, the preparation of TiO 2
nanotubes by hydrothermal method has caught the attention of
⇑ Corresponding author.
E-mail address: caiqizhou@hust.edu.cn (Q. Cai).
the scientific community due to its simplicity and easy operation.
Wang et al. [17] investigated the formation mechanism of nano-
tubes, which can be explained as a process of three-dimensional
crystal transforming to lamellar structure and then rolling to form
nanotubes. Sreekantan and Wei [18] studied the effect of NaOH to
TiO2 ratio, reaction temperature, time and annealing temperature
on the structural characteristic of the nanotubes. The general prin-
ciple of this method is the reaction between the seeds and highly
concentrated NaOH aqueous solution under hydrothermal envi-
ronment, followed by acid treatment and calcination. However,
most of TiO2 nanotubes prepared by hydrothermal treatment are
obtained in powder form, which is difficult for practical application
due to that powder is hard to separate, recycle and reuse. There-
fore, the development of TiO2 nanotube film from the large-area
seed is very useful for practical application. Some scientists have
successfully synthesized the TiO2 nanotube film by hydrothermal
method in recent years. For example, Yang et al. [19] prepared
the nanotube-like TiO2 by oxidizing the surface of a titanium sheet
through calcining under an atmosphere of air to form rutile TiO2
and then treating it to form the tubular structure in NaOH aqueous
solution. Losilla et al. [20] prepared TiO2 nanotube films by pulsed

http://dx.doi.org/10.1016/j.jallcom.2014.01.216
0925-8388/© 2014 Elsevier B.V. All rights reserved.
102 Q. Luo et al. / Journal of Alloys and Compounds 597 (2014) 101–109

Table 1
Parameters of hydrothermal treatment and calcination.

No. NaOH Reaction Reaction Calcination

concentration temperature time (h) temperature (°C)
(mol dm—3) (°C)

1 1 180 10 —
2 4 180 10 —
3 7 180 10 —
4 10 180 10 —
5 7 120 10 —
6 7 150 10 —
7 7 210 10 —
8 7 180 1 —
9 7 180 4 —
10 7 180 7 —
11 7 180 13 —
12 7 180 10 400
13 7 180 10 500
14 7 180 10 600
15 7 180 10 700

laser deposition of P25 and P90 TiO 2 nanoparticles onto stainless

steel foils followed by a hydrothermal treatment. Finally, Bavykin
et al. [21] prepared the films of random titanate nanotubes ob-
tained from anodized TiO2 nanotubes array via hydrothermal route
in order to control over titanate nanotube agglomerates.
Plasma electrolytic oxidation (PEO) technique has been widely
used to prepare the oxide films on the valve metals such as Al,
Mg and Ti [22–25]. The distinct properties of oxide films formed
through PEO include porous structure, remarkable thickness and
well adhesion to the substrates [26], which allow the TiO 2 film pro-
duced through PEO to become a potential seed layer for the syn-
thesis of TiO 2 nanotube film. Therefore, a novel and useful
method to prepare TiO 2 nanotube films with well adhesion and
large-area through hydrothermal method on the seed layers pre-
pared by PEO technique was reported in this study. This method
is a hybrid technique which includes the initial nucleation of seed
layer controlled by PEO and subsequent growth of nanostructures
produced by the hydrothermal method. The effects of different
experimental conditions, such as NaOH concentration, reaction
temperature, reaction time and calcination temperature on the
morphology and crystal structure of the nanotube films were also
investigated. In addition, the effect of calcination temperation on
the photophysical properties and photocatalytic activity of TiO2
nanotube films was studied.
2. Experimental
2.1. Preparation of seed layers
Fig. 2. XRD pattern of the seed layer.
system, a cooling system and an exhaust system. The positive voltage, negative
voltage, frequency and duty cycle were 400 V,—50 V, 700 Hz and 0.3, respectively.
Na3PO4 aqueous solution with the concentration of 0.05 mol dm —3 was selected as
electrolyte. The treatment period was 10 min and the temperature of electrolyte
was kept under 40 °C. The prepared seed layers were rinsed with distilled water
and dried with hot air.
2.2. Preparation of nanotube films
The seed layers were placed against the wall of a 210 mL Teflon-lined stainless
steel autoclave filled with 100 mL of aqueous NaOH solution and then the sealed
autoclave was heated in an electric oven. After the hydrothermal treatment, the
as-synthesized films were washed with distilled water, immersed in 100 mL of
0.1 mol dm—3 HCl aqueous solution for 10 min and then washed with distilled
water again. Finally, the as-synthesized films were calcined at 400, 500, 600,
700 °C in air for 1 h. The parameters of hydrothermal treatment and calcination
are listed in Table 1.
2.3. Analysis of nanotube films
The morphologies of films were characterized by field emission scanning elec-
tron microscopy (FSEM, FEI Sirion 200, FEI Company, Eindhoven, Netherlands) and
transmission electron microscopy (TEM, JEM 2100, JEOL, Tokyo, Japan). The compo-
sition of the nanotube films were analyzed with energy dispersive X-ray (EDX)
detector incorporated into the FSEM. The crystal structure of nanotube films were
determined by using X-ray diffraction (XRD, X’Pert PRO, PANalytical B.V., Almelo,
Netherlands). The UV–Vis absorption spectra of TiO2 nanotube films were recorded
on UV–Vis spectrophotometer (UV-2550, Shimadzu, Kyoto, Japan) with an integrat-
ing sphere attachment. Photoluminescence spectra of TiO 2 nanotube films were
measured with Fluorescence spectrophotometer (FP-6500, Jasco, Tokyo, Japan).

The pure Ti sheet with thickness of 2 mm was selected as anode and the reac-
tion area was fixed as 20 × 20 mm. Prior to PEO, the Ti sheets were polished with
emery papers (#180 ~ #800 grit), degreased using acetone and then rinsed with
distilled water. The stainless steel plate was used as cathode. The equipment used
in the PEO process consisted of an AC power supply, an electrolyte cell, a stirring
2.4. Evaluation of photocatalytic activity
Photocatalytic activities of the TiO2 nanotube films were measured by monitor-
ing photodegradation of methylene blue (MB) in aqueous solution. Films were im-
mersed into 10 mL of the aqueous MB solution (10 mg dm —3) for 30 min prior to

Fig. 1. Surface morphology of the seed layer prepared by PEO process: (a) low magnification and (b) high magnification.
 Q. Luo et al. / Journal of Alloys and Compounds 597 (2014) 101–109 103

Fig. 3. Surface morphologies of films synthesized under different NaOH concentrations: (a) 1 M, (b) 4 M, (c) 7 M and (d) 10 M.
 Fig. 4. Surface morphologies of films synthesized at different reaction temperatures: (a) 120 °C, (b)150 °C, (c) 210 °C, (d) part A in (c) and (e) part B in (c).

104 Q. Luo et al. / Journal of Alloys and Compounds 597 (2014) 101–109
 Q. Luo et al. / Journal of Alloys and Compounds 597 (2014) 101–109 103

irradiation to reach adsorption/desorption equilibrium. An ultraviolet germicidal

lamp (40 W) with a maximum irradiation peak at 365 nm was used as light source
and the irradiation time was 300 min, a fixed quantity of solution was removed
every 60 min to measure the absorbance. The degradation rate of MB was
calculated from the height of peak at the wavelength of 664 nm in UV–Vis spectra
recorded on UV–Vis spectrophotometer.

3. Results and discussion

3.1. Characterization of the seed layers

Fig. 1 shows the surface morphology of the seed layer prepared

by PEO process. It can be found that the seed layer was porous,
these crater-like holes with size of micrometer and nanometer le-
vel were residual discharge channels which produced by plasma
discharge during the PEO process [26]. The XRD pattern of the seed
layer is shown in Fig. 2. The Ti peaks (JCPDS card No. 44-1294)
were detected from the Ti substrate and mixed anatase (JCPDS card
No. 71-1167) and rutile (JCPDS card No. 76-1939) phase appeared
in the seed layer.

3.2. The effect of NaOH concentration on the surface morphologies of

films

The surface morphologies of films synthesized under different

NaOH concentrations at 180 °C for 10 h are shown in Fig. 3. Many
small layered nanosheets could be observed on the surface of the
film under the 1 mol dm—3 NaOH concentration condition, as shown
in Fig. 3a. The nanosheets with large size and a few nanotubes
formed on the surface of the film under 4 mol dm—3 NaOH concen-
tration (Fig. 3b). A large number of nanotubes were synthesized on
Fig. 6. Surface morphology of nanotube film after acid treatment and EDX analysis
of nanotube films before and after acid treatment: (a) surface morphology of
nanotube film after acid treatment and (b) EDX analysis of nanotube films before
and after acid treatment.

the surface of the film and the nanosheets cannot be observed when
the NaOH concentration was increased to 7 mol dm—3, these nano-
tubes were randomly oriented and formed an intertexture-like
structured film, as shown in Fig. 3c. Furthermore, the nanotubes
prepared in 10 mol dm—3 NaOH solution (Fig. 3d) were thinner
and denser compared with the nanotubes prepared in 7 mol dm—3
NaOH solution. These observations indicate that the NaOH
concentration plays an important role in the formation of the nano-
tubes. The anisotropic swelling of TiO2 would occur at the beginning
stage of hydrothermal reaction [27] and then the nanosheets of
sodium titanate begin to form. Because growth of the nanosheets
of sodium titanate is a dissolution–crystallization reaction which
is reversible [28], the increase of NaOH concentration could be

Fig. 5. Surface morphologies of films synthesized at different reaction time: (a) 1 h, (b) 4 h, (c) 7 h and (d) 13 h.
 Q. Luo et al. / Journal of Alloys and Compounds 597 (2014) 101–109 105

beneficial to the crystallization and growth of the nanosheets.
Therefore, higher NaOH concentration will result that bigger nano-
sheets are produced. Crystallization of dissolved titanates on nano-
sheets could result in mechanical tensions, which is enough to
initiate the curving and wrapping of nanosheets to nanotubes when
the NaOH concentration reaches to a certain value. Furthermore, it
is suggested that higher NaOH concentration will produce faster
rate of crystallization of dissolved titanates on nanosheets, which
results in greater mechanical tensions and faster rate of nanosheets
wrapping. Therefore, further increase of the NaOH concentration
will lead to thinner nanotubes.
3.3. The effect of reaction temperature on the surface morphologies of
films
The reaction temperature is also a very important influencing
factor of the morphologies of hydrothermal products. Fig. 4 shows
the surface morphologies of films synthesized at different reaction
temperatures with 7 mol dm —3 NaOH solution for 10 h. The
sheet-like structure was formed on the surface of the film at
120 °C, as shown in Fig. 4a. With increasing the temperature to
150 °C, a large number of nanotubes were synthesized and very
few nanosheets could be observed in Fig. 4b. These results indi-
cated that moderate increase of temperature was beneficial to
the formation of the nanotubes. With continuing to increase the
temperature to 210 °C, it could be observed that many micro-
spheres appeared on the surface of the film, as shown in Fig. 4c.
The parts A and B indicated in Fig. 4c are enlarged and shown in
Fig. 4d and e, respectively. Fig. 4d shows that a lot of adjacent
nanotubes were attached together and a bundle-like structure
was formed, which can be explained through the oriented attach-
ment mechanism [29]. Fig. 4e shows that the microspheres con-
sisted of nanosheets and a small amount of nanotubes. A high
hydrothermal temperature may result that the nanotubes assem-
ble into bundles and then aggregate to form the microspheres
accompanied by the transformation from bundles to nanosheets
in order to diminish the mechanical stress and the total free en-
thalpy of the system.

Fig. 7. Surface morphologies of nanotube films with acid treatment followed by calcination at different temperature: (a) 400 °C, (b) 500 °C, (c) 600 °C and (d) 700 °C.

Fig. 8. Cross-section morphologies of nanotube films: (a) before acid treatment and (b) after acid treatment and then calcination at 500 °C.
106 Q. Luo et al. / Journal of Alloys and Compounds 597 (2014) 101–109

3.4. The effect of reaction time on the surface morphologies of films
The surface morphologies of films synthesized at different reac-
tion time with 7 mol dm —3 NaOH solution at 180 °C are shown in
Fig. 5. After 1 h, the sheet-like structure was formed on the surface
of the film, as shown in Fig. 5a. After 4 h, the nanotubes have been
formed on the surface of the film, which indicated that the energy
generated by the hydrothermal reaction in our experiment was
sufficient to curve and wrap nanosheets into nanotubes in a very
short time. However, the length of nanotubes was short, as shown
in Fig. 5b. The nanotubes became longer and thinner with the in-
crease of reaction time (Figs. 3c, 5c and d) because the growth of
nanotubes along the length can be considered to take place after
the nanosheets transform to the nanotubes [30].
3.5. The effect of calcination temperature on morphologies of nanotube
films
analysis. Fig. 9a shows the XRD patterns of nanotubes before and
after acid treatment. The diffraction peaks of nanotubes before acid
treatment can be indexed to sodium titanium oxide, and the dif-
fraction peaks of the nanotubes after acid treatment can be in-
dexed as hydrogen titanium oxide or hydrogen titanium oxide
hydrate [7]. The low peak intensity and substantial peak widths
were attributed to the poor crystallinity and the nanoscale size
of the nanotubes. Fig. 9b shows the XRD patterns of nanotubes
with acid treatment followed by calcination at different tempera-
ture. It can be found that all the diffraction peaks of the nanotubes
calcined at 400–700 °C can be indexed as the anatase phase (JCPDS
card No. 71-1167). Furthermore, the peak intensities increased and
the widths of the peak became narrow with the increase of calcina-
tion temperature, indicating the improvement of crystallization
degree and the growth of grain size.
3.7. TEM, SAED and HRTEM analysis of nanotube films

For the investigation on the effect of acid treatment and calcina- The samples were scraped from the titanium substrate and then
tion temperature, the nanotube film synthesized with 7 mol dm —3 dispersed in ethanol through ultrasound prior to TEM, SAED and
NaOH solution at 180 °C for 10 h was used. Fig. 6a shows the sur- HRTEM analysis. After hydrothermal treatment with 7 mol dm —3
face morphology of nanotube film immersed with 100 mL of NaOH solution at 180 °C for 10 h, nanotubes had approximate
0.1 mol dm—3 HCl aqueous solution for 10 min, which was similar
to that of film without acid treatment (Fig. 3c). The EDX analysis
of nanotube films before and after acid treatment is shown in (a)
Fig. 6b. Na element appeared in the nanotube films prepared by
hydrothermal treatment without acid treatment. However, after
acid treatment, Na element could not be detected in the nanotube
films, which indicated that Na has been removed completely.
The surface morphologies of nanotube films with acid treat-
ment followed by calcination at different temperature for 1 h are
shown in Fig. 7. Apparently, the surface morphologies of the nano-
tube films calcined at 400 °C (Fig. 7a) and 500 °C (Fig. 7b) were
similar to that of nanotube film without calcination (Fig. 6a). How-
ever, the nanotubes began to crumble when the calcination tem-
perature was increased to 600 °C, as shown in Fig. 7c. At 700 °C,
the nanotubes completely collapsed to form short nanorods
(Fig. 7d). The dehydration of interlayered OH group would occur
at high calcination temperature, which results in the destruction
of the tubes structures [31]. Therefore, the nanotubes finally trans-
formed to nanorods at high calcination temperature.
Fig. 8 shows the cross-section morphologies of nanotube films,
which indicates that there was no obvious discontinuity between
the nanotube films and the underlying substrate. It proved that the
nanotube films were well adhered to the titanium substrate, which
is beneficial to long-term degradation of organic com- pounds. Fig. (b)
8a shows the cross-section morphology of nanotube film before
acid treatment, it could be found that the nanotubes were arranged
nearly perpendicular to the titanium substrate in the inner layer.
There are a large number of tiny discharge channels throughout the
seed layer prepared by PEO technique, NaOH solu- tion is able to
enter the discharge channels under the effect of the high
temperature and pressure environment generated by the
hydrothermal process, resulting that the nanosheets may grow
along the discharge channels and eventually curl to form the nano-
tubes which are nearly perpendicular to the titanium substrate in
the inner layer. Fig. 8b shows the cross-section morphology of
nanotube film with acid treatment followed by calcination at
500 °C for 1 h, it could be found that the oriented nanotubes were
partly destroyed because of the dehydration of interlayered OH
group during the calcination process [31].

3.6. XRD analysis of nanotube films

The XRD patterns of nanotubes are shown in Fig. 9. All of the Fig. 9. XRD patterns of nanotubes: (a) before and after acid treatment and (b) after
acid treatment and then calcination at different temperature.
samples were scraped from the titanium substrate prior to XRD
 Q. Luo et al. / Journal of Alloys and Compounds 597 (2014) 101–109
outer diameters of 9–12 nm and inner diameters of 4–5 nm with
the distance between the adjacent layers of approximate 1 nm,
as shown in Fig. 10a. The responding SAED pattern presented in
the inset of Fig. 10a nearly showed a halo pattern, implying that
these nanotubes were identified as amorphous, which was in
agreement with the result of XRD analysis. The TEM and HRTEM
results of the nanotubes with acid treatment followed by calcina-
tion at 500 °C for 1 h are presented in Fig. 10b and c, respectively.
It can be found from Fig. 10b that the inner diameters became
smaller compared with that of the nanotubes with hydrothermal
treatment. Furthermore, some defects appeared on the surface of
the nanotubes. Those can be attributed to the dehydration of inter-
layered OH group during the calcination process [31]. The HRTEM
image shown in Fig. 10c suggests that the obtained TiO 2 nanotubes
were single-crystalline anatase. The nanotubes had the interplanar
distance of approximate 0.35 nm, corresponding to the interplanar
distance of the (101) crystal plane of anatase.
3.8. UV–Vis absorption spectra of TiO2 nanotube films
The UV–Vis absorption spectra of TiO 2 nanotube films calcined
at different temperatures are shown in Fig. 11a. A significant in-
crease in the absorption at wavelengths shorter than 375 nm can be
assigned to the intrinsic band gap absorption of TiO 2. Further-
more, not only the absorption edges of nanotube films shifted
gradually towards longer wavelength but also the optical absorp-
tion ability of nanotube films increased with the increase of the
calcination temperature, which can be ascribed to the increase of
grain size and surface roughness of nanotubes [32]. However, not
only the absorption edge shifted towards shorter wavelength but
also the optical absorption ability decreased when the calcination
Fig. 10. TEM, SAED and HRTEM analysis of nanotubes: (a) TEM and SAED of nanotubes after hydrothermal treatment, (b) TEM of the nanotubes with acid treatment followed
by calcination at 500 °C and (c) HRTEM of the nanotubes with acid treatment followed by calcination at 500 °C.
107
temperature increased to 700 °C. According to the analysis of sur-
face morphology, the nanotubes completely collapsed to form
short nanorods when the calcination temperature increased to
700 °C. The decrease of particle size can result in the increase of
the internal stress. The effect of quantum size may be less than that
of the particle internal stress. Therefore, the blue shift of absorp-
tion edges and weaker optical absorption occur with further in-
crease of the calcination temperature [33]. Assuming that the
fundamental absorption of TiO2 possesses an indirect transition
[34], the band gap energies of TiO2 nanotube films calcined at dif-
ferent temperatures were obtained by plotting (ahm)1/2 versus hm
(where a is the absorbance and hm is the photon energy) and
extrapolating the straight line portion to intersect the x axis, as
shown in Fig. 11b, which indicates that the band gap energies of
TiO2 nanotube films calcined at 400, 500, 600 and 700 °C were
about 3.28, 3.24, 3.18 and 3.27 eV, respectively.
3.9. Photoluminescence spectra of TiO 2 nanotube films
The PL emission analysis is commonly used to evaluate the
extent of transfer and separation, as well as trapping of charge
carriers within an activated semiconductor photocatalyst. The
transfer behavior of photoinduced electron and hole pairs can also
be interpreted from the spectra since recombination of these free
charges contribute significantly to emission signals [35]. According
to the attributes and formation mechanism of PL, there are two
types of PL phenomenon: the band–band PL and the excitonic PL
[36,37]. Generally, the band–band PL spectrum connects to the
separation situation of photo-generated charge carriers. But the
excitonic PL spectrum cannot directly reflect the separation
situation of photo-induced carriers. It can reveal some important
108 Q. Luo et al. / Journal of Alloys and Compounds 597 (2014) 101–109

(a)

Fig. 12. PL spectra of TiO2 nanotube films calcined at different temperatures.

(b)
Fig. 11. UV–Vis absorption spectra and (ahm)1/2 versus hm curve of TiO2 nanotube
films calcined at different temperatures: (a) UV–Vis absorption spectra and (b) (ahm)1/2
versus hm curve.
information about surface defects, oxygen vacancies and surface
states, which strongly influence photocatalytic reactions [38].
The PL spectra of TiO 2 nanotube films calcined at different
temperatures and excited at 300 nm are presented in Fig. 12. It
can be seen that the PL peak positions of four samples were similar
except for the change of PL peak intensity. The major emission
peaks at the wavelength range from 370 to 395 nm were attributed
to the band–band PL phenomenon with the energy of light approx-
imately equal to the band gap energy of anatase [38]. Furthermore,
the band–band PL intensity of TiO2 nanotube film calcined at
600 °C was weakest, indicating that this film should have a lowest
recombination rate of electrons and holes under UV light irradia-
tion. In addition, there were four peaks at the wavelength range
from 440 to 500 nm. These PL signals were attributed to excitonic
PL, which mainly resulted from surface oxygen vacancies and de-
fects of the TiO 2 nanotube films [38]. It could be found that the
TiO2 nanotube film calcined at 700 °C had the strongest excitonic
PL intensity, indicating that this film should have the most surface
oxygen vacancies and defects due to high calcination temperature.
removal ratio with the calcination temperature was small. Further-
more, the photocatalytic activity of the TiO 2 nanotube films in-
creased and then decreased with the increase of the calcination
temperature. About 74% of MB solution was degraded on the TiO2
nanotube film calcined at 600 °C, which displayed the stronger pho-
tocatalytic activity compared with the other films. This result was in
agreement with the strongest UV light absorption and the weakest
band–band PL intensity of the TiO2 nanotube film calcined at
600 °C. It is believed that with increasing calcination temperature
the photocatalytic activity of the TiO 2 nanotube films increases
due to the enhancement of crystallization of anatase [39]. However,
with increasing calcination temperature the surface oxygen vacan-
cies and defects of the TiO 2 nanotube films would increase due to
the dehydration of interlayered OH group, which would result that
the recombination centers of photogenerated electrons and holes in-
creased and the photocatalytic activity of the TiO 2 nanotube films
decreased [18]. Therefore, the variation of the photocatalytic activity
of the TiO 2 nanotube films with the increase of the calcination tem-
perature may be determined by the two competing factors: the
enhancement of crystallization of anatase and the increase of the
surface oxygen vacancies and defects. When the calcination temper-
ature is low, the enhancement of crystallization of anatase is the
main factor. However, the increase of the surface oxygen vacancies
and defects will became the main factor when the calcination tem-
perature is high and exceeds the optimal value. Therefore, the

3.10. Photocatalytic activity of TiO 2 nanotube films

No detectable degradation of MB occurred without TiO 2 nano-

tube films under UV radiation. The photodegradation of MB in the
presence of TiO 2 nanotube films calcined at different temperatures
Fig. 13. Photodegradation of MB in the presence of TiO 2 nanotube films.
is summarized in Fig. 13. It can be seen that the variation of the
 Q. Luo et al. / Journal of Alloys and Compounds 597 (2014) 101–109
photocatalytic activity of the TiO 2 nanotube films increased and
then decreased with the increase of the calcination temperature.
We believed that the optimum photocatalytic activity of the TiO2
nanotube film calcined at 600 °C was explained by the combined ef-
fects of appropriate crystallinity and surface states.
4. Conclusions
Large-area single crystalline anatase TiO 2 nanotube films were
successfully synthesized through hydrothermal method on the
seed layer prepared by Plasma electrolytic oxidation technique.
The effects of NaOH concentration, reaction temperature and reac-
tion time on the surface morphologies of films were investigated.
The small layered nanosheets were synthesized on the surface of
the film under the 1 mol dm —3 NaOH concentration condition.
With the NaOH concentration of 4 mol dm —3, the nanosheets with
large size and a few nanotubes formed on the surface of the film.
Further increase of the NaOH concentration (7 mol dm —3 and 10
mol dm—3) resulted in the formation of nanotubes on the sur- face
of the film. The sheet-like structure was formed on the surface of
the film at 120 °C and the nanotubes were obtained on the sur- face
of the film at 150 °C and 180 °C. Further increase of the reac- tion
temperature resulted in the formation of microspheres on the
surface of the film. The nanotubes can form in a very short time un-
der the effect of sufficient energy, further increase of reaction time
resulted in the growth of nanotubes along the length. In addition,
the effect of calcination temperature on the morphologies, crystal
structure, photophysical properties and photocatalytic activity of
the nanotube films were also studied. Calcination resulted in
crystallization of the nanotubes from amorphous state to single-
crystalline anatase phase. Furthermore, the increase of calcination
temperature was beneficial to the improvement of crystallization
degree. However, the nanotubes completely collapsed to form
short nanorods when the calcination temperature increased to
700 °C. It was also revealed that the TiO2 nanotube film calcined
at 600 °C exhibited narrower band gap energy, the stronger UV
light absorption and the weaker band–band PL intensity compared
with the other TiO 2 nanotube films. Furthermore, the TiO 2 nano-
tube film calcined at 600 °C also showed the best photocatalytic
activity due to the combined effects of appropriate crystallinity
and surface states. As a consequence, the investigation in this
paper will provide an appropriate and novel method to synthesize
TiO2 nanotubes for practical applications, such as the treatment of
environmental pollutants.
Acknowledgement
The authors would gratefully acknowledge analytical and test-
ing center in Huazhong University of Science and Technology for
the tasks of test.
109
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