Article

pubs.acs.org/Langmuir

Visible-Light-Induced Self-Cleaning Property of Bi2Ti2O7‑TiO2

Composite Nanowire Arrays
Hang Liu,† Yajie Chen,† Guohui Tian,*,†,‡ Zhiyu Ren,† Chungui Tian,† and Honggang Fu*,†
†
Key Laboratory of Functional Inorganic Material Chemistry, Ministry of Education of the People’s Republic of China and ‡Key
Laboratory of Chemical Engineering Process & Technology for High-Efficiency Conversion, College of Heilongjiang Province,
School of Chemistry and Materials Science, Heilongjiang University, Harbin 150080, PR China
*
S Supporting Information

ABSTRACT: Bi2Ti2O7-TiO2 composite nanowire arrays were

prepared via a two-step sequential solvothermal and
subsequent calcination process. The morphology and structure
of the Bi2Ti2O7-TiO2 composite nanowire array composite
were characterized by X-ray diffraction, field emission scanning
electron microscopy, and transmission electron microscopy.
The UV−visible diffuse reflectance spectroscopy analysis
indicated that the absorption spectrum of the Bi2Ti2O7-TiO2
composite nanowire array composite was extended to the
visible-light region due to the existence of Bi2Ti2O7. The
Bi2Ti2O7-TiO2 composite nanowire arrays exhibit superhydrophilicity with water contact angles of 0° after irradiation with visible
light, and the superhydrophilic nature is retained for at least 15 days. This effect enables us to consider self-cleaning applications
that do not require permanent UV exposure. Compared to pure Bi2Ti2O7 and TiO2, the vertically aligned Bi2Ti2O7-TiO2
composite nanowire arrays showed more significant visible-light self-cleaning performance due to the synergistic effect of
superhydrophilicity and significant photocatalytic activity caused by effective electron−hole separation at the interfaces of the two
semiconductors, which was confirmed by the electrochemical analysis and surface photovoltage technique.

1. INTRODUCTION techniques to fabricate narrow band gap semiconductor/TiO2

The self-cleaning phenomenon is a special characteristic by
which material keeps itself free of dirt and grime,1−4 which
makes use of sunlight and natural rainfall to keep surfaces clean;
this is one of the most attractive and promising fields.5,6 The
self-cleaning coatings have been commercially attractive and are
available in the building industry because it can save significant
maintenance costs. In recent years, TiO2 thin films have
attracted much attention as photofunctional material for self-
cleaning.7,8 However, pure TiO2 films can be activated only
under UV light because of its large band gap (3.2 eV), which
limits its widespread application because UV light accounts for
only 5% of the solar spectrum. And the superhydrophilicity of
TiO2 surfaces generated by UV irradiation typically reconverts
to the initial state with rather high contact angles when stored
under dark conditions. When considering practical aspects, a
surface cannot permanently be irradiated by UV light.
Meanwhile, a high recombination rate of photogenerated
electron−hole pairs is another critical drawback in the
application of heterogeneous TiO2 films for photocatalysis.9 A
general method used to resolve the above problems is to
prepare the composite films consisting of bottom-layer TiO2
and another top layer semiconductor with a narrow band gap
because the built-in potential gradient at the interface in the
composite of semiconductors facilitates the separation of
electron and hole pairs and reduces the chance of
recombination.10−13 Thus, the development of suitable
bilayer films will be essential for practical applications of TiO2
films as photocatalysts for pollutant decomposition, self-
cleaning, and hydrophilic surface systems.
However, the self-cleaning performance of general composite
films with a dense, smooth surface is still moderate. This is
because self-cleaning treatments occur on the surfaces of
catalyst films and the surface morphology of the catalyst films
plays a key role in the self-cleaning property.14−16 The dense,
smooth surface can provide only a low surface area and a small
number of reaction active sites, thus leading to low perform-
ance. Therefore, controlling and optimizing surface morphol-
ogy may further enhance its performance.17,18
In recent years, one-dimensional (1D) nanoarray architec-
tures (nanowires, nanorods, and nanotubes) have been widely
studied,19−23 and aligned 1D nanoarray films have shown
controllable wettability (superhydrophobicity and superhydro-
philicity) under different conditions due to the cooperation of
the surface photosensitivity and the aligned nanostructure of
the films.24−28 Such controllable wettability will greatly extend
the applications of semiconductor nanoarray films. For
example, highly ordered 1D TiO2 nanoarrays have been widely
studied in photocatalysis and photoelectrochemical application
Received: February 8, 2015
Revised: April 14, 2015

© XXXX American Chemical Society A DOI: 10.1021/acs.langmuir.5b00516

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due to their high surface-to-volume ratio, effective electron
percolation pathways, and improved light scattering ability for
light harvesting.29−31 However, the sole UV light absorption of
TiO2 nanoarrays limits its performance. Recently, researchers
have started employing nonmetal doping (S, N, F, C) and
narrow band gap semiconductors such as CdS and CdSe in
quantum-dot-sensitized photoelectrochemical solar cells and
have achieved a remarkable enhancement in efficiency.32−36
However, the use of most of them is still limited by the
upsetting challenge of photochemical stability.37,38
Bismuth titanates, a large family that includes several phases
in the Bi−O-Ti system, are promising candidates for various
technological applications.39−42 Bi2Ti2O7 belongs to a family of
A2B2O7 compounds with pyrochlore structure.43−47 Previous
studies indicated Bi2Ti2O7 (Eg = 2.82 eV) had exhibited visible-
light photocatalytic activity and photochemical stability.48−50
However, the rapid recombination of photoinduced electron−
hole pairs seriously limits the energy-conversion efficiency. To
promote the separation of photogenerated carriers of Bi2Ti2O7,
designing a composite photocatalyst by coupling Bi2Ti2O7 with
a semiconductor with matched band potentials is a sensible
strategy. The well-established heterojunction structure could be
employed to restrict the recombination of the charge carriers
and enhance the quantum yield. As stimulated by promising
applications, coupling Bi2Ti2O7 with TiO2 showed synergistic
properties which differentiate Bi2Ti2O7 from TiO2 alone.51,52
Thus, the synthesis of the vertically aligned Bi2Ti2O7-TiO2
nanowire arrays with enhanced visible-light self-cleaning
properties is a subject of considerable research interest.
In the present work, the Bi2Ti2O7-TiO2 composite nanowire
array was prepared via a two-step sequential solvothermal and
subsequent calcination process. The TiO2 nanowire array
precursor was first synthesized using our previous method,53
and then it was used as a substrate precursor to fabricate the
Bi2Ti2O7-TiO2 nanowire array composite via an in situ
solvothermal and subsequent calcination process. In our
material-design strategy, employing a 1D nanostructured
morphology for Bi2Ti2O7-TiO2 offers the potential advantage
of improved charge transport over a flat surface while
simultaneously enhancing visible-light utilization. The self-
cleaning properties of the Bi2Ti2O7-TiO2 composite nanowire
array films were evaluated by changes in the contact angle of
water and their photocatalytic ability to decompose rhodamine
B and phenol under visible-light irradiation.
2. EXPERIMENTAL SECTION
2.1. Preparation of the TiO2 Nanowire Array Precursor. The
TiO2 nanowire array precursor was synthesized by solvothermal
growth reaction according to our previous study.53 Typically, 0.7 mL
of titanium isopropoxide (TTIP) and 5 mL of glycerol were
successively added to 25 mL of ethanol under magnetic stirring. The
resulting mixed solution was transferred to a 50 mL Teflon-lined
stainless steel autoclave. Then the thoroughly cleaned glass substrates
(10 × 70 × 1 mm3) were placed in a Teflon-lined stainless steel
autoclave at an angle of about 45°. The Teflon-lined stainless steel
autoclave containing a mixture solution was then heated to 180 °C and
maintained for 24 h. Subsequently, the autoclave was cooled naturally
to room temperature by switching off the furnace. The as-obtained
films were slightly rinsed with ethanol.
2.2. Fabrication of Bi2Ti2O7 and Bi2Ti2O7-TiO2 Nanowire
Arrays. In a typical case, 0.09976 g of Bi(NO3)3·5H2O was dissolved
in 5 mL of glycerol under magnetic stirring. Then 20 mL of ethanol
was slowly added to the above solution, followed by stirring for 10
min. The resulting clear solution was transferred into a 50 mL Teflon-
lined stainless steel autoclave. Then the prepared TiO2 nanowire array
B DOI: 10.1021/acs.langmuir.5b00516
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precursor glass substrates were placed in a Teflon-lined stainless steel
autoclave at an angle of about 45°. The mixture solution was then
heated to 180 °C and maintained for 12 h. Subsequently, the autoclave
was cooled naturally to room temperature by switching off the furnace.
The obtained glass substrates were slightly rinsed with ethanol and
dried at 80 °C. The as-obtained nanowire array precursor glass
substrates were then calcined at 550 °C for 2 h in air. For comparison,
a pure Bi2Ti2O7 nanowire array film was fabricated under the above-
mentioned experimental conditions by adjusting the quantity of
Bi(NO3)3·5H2O to 0.9976 g.
2.3. Characterization. The structure and morphology of the
obtained product was investigated by powder X-ray diffraction (XRD,
Bruker D8 Advance using Cu Kα radiation), scanning electron
microscopy (SEM, Hitachi S-4800, Japan), and transmission electron
microscopy (TEM, JEOL 2100, Japan). The optical properties of the
films were analyzed by UV−visible diffuse reflectance spectroscopy
recorded on a UV−visible spectrophotometer (Shimadzu UV-2550) at
room temperature. The surface photovoltage spectra (SPS) were
carried out on a laboratory-built surface photovoltage spectrometer. A
150 W xenon lamp with a monochromator was used as a light source.
The SPS was obtained by scanning the wavelength of monochromatic
light from the visible to the UV spectral region at a rate of about 30
nm min−1. A lock-in amplifier (SR830-DSP, made in the USA)
synchronized with a light chopper was employed to amplify the
photovoltage signal. The spectral resolution was 1 nm. The SPS
measurements were carried out with a solid-junction photovoltaic
substrate/sample/substrate sandwich structure. The generation of
photovoltage arose from the creation of electron−hole pairs followed
by the separation under a built-in electric field (the space charge layer).
Photoelectrochemical measurements of the obtained product films
were recorded by a BAS100B electrochemical analyzer (Bioanalytical
Systems Inc., USA) in a standard three-compartment cell consisting of
a working electrode, a Pt slice as the counter electrode, and saturated
Ag/AgCl as the reference electrode. N2-saturated 0.1 M NaOH in
water was used as an electrolyte. A 300 W Xe lamp (Oriel) equipped
with a 420 nm cutoff filter was used for excitation. Electrochemical
impedance spectroscopy (EIS) was carried out on an electrochemical
analyzer (Zahner, Germany) in the above-mentioned standard three-
electrode system. Impedance data were fitted with ZSimpWin software
(Princeton Applied Research). The contact angle measurements of the
films were conducted on an OCA20 goniometer from Dataphysics
with an experimental error of ±1° by the sessile drop method at room
temperature using a water droplet with a volume of about 1 μL.
2.4. Measurement of Photocatalytic Activity. Photocatalytic
activities of the photocatalysts were evaluated by the photocatalytic
degradation of rhodamine B (RhB) in an aqueous solution under
visible-light irradiation. A 150 W Xe lamp with a 420 nm cutoff filter
placed above the reactor to cut off UV light was used as the light
source to provide visible-light irradiation. In each experiment, the glass
slides on which Bi2Ti2O7-TiO2 films were prepared were cut to make
use of only the regions with assembled films. For consistency, the same
film areas were used for each set of experiments. The slides were
placed in a quartz cell (10 × 10 × 65 mm3) containing 2.5 mL of RhB
solution with a concentration of 10−5 mol L−1 at room temperature.
The quartz cell was covered with a quartz slide to minimize
evaporation. Prior to irradiation, the film was immersed in the
solution in the dark for 30 min to ensure the establishing of an
adsorption/desorption equilibrium between the photocatalyst and
RhB solution. Then the film immersed in the solution was irradiated
with a 150 W Xe lamp. At the intervals of given irradiation time, the
film was taken out of the cell, and a UV−vis spectrophotometer
(Shimadzu UV-2550) was used to obtain the absorption spectra of the
RhB aqueous solution as a function of the visible-light irradiation time.
The RhB aqueous solution was bubbled with O2 gas for 20 min prior
to irradiation, and the bubbling was continued during irradiation. For
this analysis, the absorbance at the peak (553 nm) was monitored to
determine the concentration change of the dye solution. For
comparison, the degradation of RhB solution under visible-light
irradiation without O2 bubbling was also tested.
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In addition, the phenol is chosen as the model pollutant in the

experiments, which is a typical contaminant without sensitizing as a
dye. The photocatalytic activity of the obtained film was also
investigated by nondye organic pollutant phenol degradation to
exclude the dye-sensitizing effect. The 150 W Xe lamp was used as a
light source with a cutoff filter to remove the irradiation wavelengths
below 420 nm. The slides were placed in a quartz cell (10 × 10 × 65
mm3) containing phenol solution (5 mg L−1, 2.5 mL) at room
temperature under the same experimental conditions used to degrade
phenol solution. At given time intervals, the concentration variations
of phenol were analyzed using HPLC (Shimadzu SPD-10A) at a
wavelength of 270 nm with a UV detector.

3. RESULTS AND DISCUSSION

3.1. Characterization of the Bi2Ti2O7-TiO2 Composite
Nanowire Array. The crystalline phases of the obtained
different films were determined by XRD (Figure 1). The
Figure 2. SEM images of the top surface (A) and edge surface (B) of
the vertically aligned Bi2Ti2O7-TiO2 composite nanowire array films.
TEM (C) and HRTEM (D) images of the vertically aligned Bi2Ti2O7-
TiO2 composite nanowire arrays.

TEM image (Figure 2C). The HRTEM image in Figure 2D

Figure 1. XRD patterns of the obtained different samples: (a) TiO2,
(b) Bi2Ti2O7, and (c) Bi2Ti2O7-TiO2.
strong, sharp peaks indicate that the as-obtained products are
highly crystallized. In the XRD pattern (Figure 1c) of the
Bi2Ti2O7-TiO2 film, all of the peaks could be well-indexed to a
pure cubic phase of Bi2Ti2O7 (Figure 1b), the distinctive peaks
at 2θ = 14.97, 30.2, 34.63, 37.8, 49.66, and 59.23° can be
indexed to (222), (444), (800), (662), (880), and (1244)
planes of the pure cubic phase of Bi2Ti2O7 (PDF no. 32-118).
The other diffraction peaks can be attributed to anatase TiO2
(Figure 1a). The results indicate that the calcination of the
precursor leads to the formation of Bi2Ti2O7 and TiO2. No
impurity peaks were detected from this pattern by XRD
analysis. Thus, XRD result could infer that the obtained
nanowire array film is composed of Bi2Ti2O7 and TiO2. In the
Bi2Ti2O7-TiO2 formation process, Bi3+ does not substitute for
Ti to access the TiO2 lattice but reacts with part of the TiO2
precursor to forge the Bi2Ti2O7-TiO2 composite under
calcination. The synthesis procedure of the Bi2Ti2O7-TiO2
nanowire array composite is illustrated in Figure S1.
The as-synthesized vertically aligned Bi2Ti2O7-TiO2 nano-
wire arrays on glass substrates were characterized by SEM and
TEM (Figure 2). The top- ,and cross-sectional-view SEM
images of the Bi2Ti2O7-TiO2 films in Figure 2A,B show that
there are many vertically aligned nanowires. For comparison,
SEM images of pure TiO2 and Bi2Ti2O7 films are also shown in
Figure S2. It can be seen that the whole morphologies of
Bi2Ti2O7 and Bi2Ti2O7-TiO2 films are similar to that of the
TiO2 nanowire array film, indicating that the in situ reaction did
not change the nanowire array morphology. To further study
the crystal structural information on the nanowire array films,
TEM and HRTEM analyses were also conducted. Each
nanowire in these arrays is composed of nanoparticles with
uniform diameters of around 10 nm, which can be seen from
C DOI: 10.1021/acs.langmuir.5b00516
(the magnification of the white square part in Figure 2C) shows
that the spacings of adjacent lattice planes are consistent with
the interplanar distance (0.298 nm) of the (444) plane of the
cubic phase of Bi2Ti2O7 and the interplanar distance (0.352
nm) of the (101) plane of anatase TiO2.52 The results indicated
the formation of heterojunctions, which can benefit from better
charge separation and transfer within the hybrid structure
compared to pure Bi2Ti2O7 and TiO2.
3.2. Optical Properties. The UV−vis diffuse reflectance
spectra of the different samples are shown in Figure 3.
Figure 3. UV−visible diffuse reflectance spectra of (a) TiO2, (b)
Bi2Ti2O7, and (c) Bi2Ti2O7-TiO2 composite nanowire arrays.
According to the spectrum, bare TiO2 presents the photo-
response property in the UV-light region. Compared to the
TiO2 nanowire array, the visible-light absorption ability of the
composite is significantly enhanced, and wide absorption was
observed from 400 to 600 nm, which indicates that Bi2Ti2O7/
TiO2 and Bi2Ti2O7 nanowire arrays have the potential ability
for the photocatalytic decomposition of pollutants under
visible-light irradiation. It is interesting that Bi2Ti2O7-TiO2
composites showed stronger visible-light absorption and a
narrower band gap than pure Bi2Ti2O7. In the Bi2Ti2O7-TiO2
composite, the formed internal electric field between Bi2Ti2O7
and TiO2 causes the Fermi levels of the two materials to move
each other and eventually reach the same potential value
(Figure S3).54 The positive movement of the Fermi level of
Bi2Ti2O7 will also promote the positive movement of its
conduction band. The decrease in the band gap may lead to the
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extension of the visible-light absorption edge of the composite.
The enhanced light absorption of the composite arrays led to
the production of more electron−hole pairs under the same
visible-light irradiation, which subsequently results in higher
photocatalytic activity.
Surface photovoltage spectroscopy (SPS) is an effective
technique for studying the photophysics of excited states
generated by photon absorption and can effectively reflect
information about the separation and recombination of
photoinduced charge carriers. Therefore, the surface photo-
voltage technique was employed to characterize the behavior of
photogenerated charge carriers in the system. As shown in
Figure 4, for pure Bi2Ti2O7 and TiO2, the SPV response bands
Figure 4. Surface photovoltage spectra of (a) TiO2, (b) Bi2Ti2O7, and
(c) Bi2Ti2O7-TiO2 composite nanowire arrays.
were obtained in the ranges of 320−580 and 300−400 nm,
respectively, which were due to the band−band transition
(electrons transition from the valence band to the conduction
band).54 There was no SPV response for TiO2 under visible-
light irradiation. However, the Bi2Ti2O7-TiO2 nanowire array
composite displayed a similar SPV response range to Bi2Ti2O7,
suggesting that the photovoltage response of the composite in
the visible region mainly resulted from Bi2Ti2O7. Under visible-
light irradiation, the response intensity of pure Bi2Ti2O7 was
weaker than the response intensity of the Bi2Ti2O7-TiO2
nanowire array composite. In the UV response region, the
SPV response intensity of the Bi2Ti2O7-TiO2 nanowire array
composite was not the simple addition of pure Bi2Ti2O7 and
TiO2. Because the photovoltage response intensity was related
to the charge separation efficiency, which signified a stronger
SPV response intensity, there was a greater separation efficiency
of photoinduced charges. The SPV results implied that the
Bi2Ti2O7-TiO2 nanowire array composite had a higher
separation efficiency of photoinduced charges than pure
Bi2Ti2O7 or TiO2 due to the addition of Bi2Ti2O7.55 Because
the separation efficiency of photoinduced charges was one of
the most important factors influencing the photocatalytic
activity, it was reasonable to deduce that the photogenerated
electrons are injected with high efficiency from the conduction
band of Bi2Ti2O7 to the conduction band of TiO2 because of
the intimate contact between the two semiconductors,
contributing to the improvement in photocatalytic activity.
3.3. Photoelectrochemical Characteristics. The semi-
conducting nature of the Bi2Ti2O7-TiO2 nanowire arrays makes
it suitable for the development of photoelectrochemical cells
and photocatalysts. In order to evaluate the properties of the
Bi2Ti2O7-TiO2 nanowire arrays and further illustrate the
enhanced electron transfer in the Bi2Ti2O7-TiO2 nanowire
array composites, some photoelectrochemical characteristics
were carried out by choosing FTO conduction glass for the
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substrate. The photoelectrochemical behavior of TiO2,
Bi2Ti2O7, and Bi2Ti2O7-TiO2 electrodes was studied by
recording linear sweep voltammetry (LSV) measurements
under visible-light irradiation (Figure 5A). The TiO2 nanowire
Figure 5. (A) Linear sweep voltammetric curves recorded for the
different samples: (a) TiO2, (b) Bi2Ti2O7, and (c) Bi2Ti2O7-TiO2
nanowire arrays at a scan rate of 10 mV/s under visible light at 100
mW/cm2. (B) Transient photocurrent density vs time plotted for the
different samples: (a) TiO2, (b) Bi2Ti2O7, and (c) Bi2Ti2O7-TiO2
composite nanowire arrays under a visible-light pulse of 100 s.
arrays exhibited weak photocurrent values during the measure-
ment. However, the Bi2Ti2O7 and Bi2Ti2O7-TiO2 nanowire
arrays showed significant photocurrent generation under
visible-light irradiation. Among these, the Bi2Ti2O7-TiO2
nanowire arrays exhibited a maximum photocurrent density
of 0.95 mA/cm2. The results showed that all photocurrents
were attributed to electrons generated from Bi2Ti2O7 to further
improve the performance of LSV. The linear sweep
voltammetry life cycle performance test of the Bi2Ti2O7-TiO2
composite nanowire array electrode under visible-light
irradiation (Figure S4) showed that photocurrent after different
cycles (400, 800, and 1200 cycles) showed slight decreases.
Therefore, the durability of the Bi2Ti2O7-TiO2 composite
nanowire array electrode is very high. The photocurrent
responses of TiO2, Bi2Ti2O7, and Bi2Ti2O7-TiO2 composite
electrodes were recorded for several on−off cycles of visible-
light irradiation. Figure 5B shows a comparison of the
photocurrent−time (I−t) curves for the aforementioned three
samples with several on−off cycles of intermittent visible-light
irradiation. It can be seen that photocurrent values rapidly
decrease to zero as soon as the irradiation of light ceases, and
the photocurrent returns to a constant value when the light is
on again, which is reproducible. The Bi2Ti2O7-TiO2 electrode
has a strong instant photoresponse to visible-light irradiation,
provides a stable photocurrent (0.86 mA/cm2), and hence is
considered to be superior to the TiO2 electrode (0.08 mA/cm2)
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and Bi2Ti2O7 electrode (0.40 mA/cm2). The magnitude of the
photocurrent represents the charge collection efficiency of the
electrode surface. This indicates that the Bi2Ti2O7-TiO2
composite nanowire arrays implied improved charge separation.
Moreover, the photoelectrochemical response was identical,
confirming that the improvement in photocurrent solely stems
from the coupling between Bi2Ti2O7 and TiO2. In the present
case, the significant enhancement of photocurrent also indicates
the efficient separation of photogenerated electron−hole pairs
for the Bi2Ti2O7-TiO2 composites at the interface between
Bi2Ti2O7 and TiO2, leaving more charge carriers to form
reactive species which in turn results in the highest photo-
current response.
Electrochemical impedance spectroscopy provides a powerful
method for the study of charge transfer and the recombination
process. Typical EIS Nyquist plots for the prepared TiO2,
Bi2Ti2O7, and Bi2Ti2O7-TiO2 composite nanowire arrays are
shown in Figure 6, and the electrochemical impedance spectra
Figure 6. Nyquist plots of the EIS data of the as-made different
nanowire arrays: (a) TiO2, (b) Bi2Ti2O7, and (c) Bi2Ti2O7-TiO2.
(EIS) analysis revealed that the semicircle diameter in the plot
was reduced with the introduction of Bi2Ti2O7, which indicated
a decrease in the interface resistance and the charge-transfer
resistance on the surface.56 The first semicircle part in the plot
reflected the charge-transfer process, and the electron-transfer
resistance could be evaluated by measuring its diameter. The
diameter of the Bi2Ti2O7-TiO2 composite nanowire array
electrode was less than that of the Bi2Ti2O7 and TiO2
electrodes, indicating that the Bi2Ti2O7-TiO2 composite
nanowire array was more efficient for photoinduced charge
separation and transfer than single Bi2Ti2O7 or TiO2. It revealed
that the charge-transfer resistance of the Bi2Ti2O7-TiO2
composite nanowire array decreased in the presence of
Bi2Ti2O7. Therefore, it can be concluded the Bi2Ti2O7 was
helpful in the charge transfer from the EIS results. Thus, the
charge transfer across the interface between the semiconductor
and solution becomes easy. Overall, Bi2Ti2O7 may act as a
sensitizer and transporter in the Bi2Ti2O7-TiO2 composite
nanowire array, and thereby improved photoelectrochemical
properties and higher photocatalytic performance would be
achieved compared to those of single Bi2Ti2O7 or TiO2.
3.4. Superhydrophilic and Photocatalytic Properties.
The self-cleaning phenomenon is related to the surface contact
angle. Contact angle measurements play a pivotal role in the
characterization of hydrophilic films. To evaluate the self-
cleaning properties of the prepared TiO2, Bi2Ti2O7, and
Bi2Ti2O7-TiO2 composite nanowire array films under visible-
light irradiation, the contact angle measurements were
performed as shown in Figure 7. The water contact angles of
E DOI: 10.1021/acs.langmuir.5b00516
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Figure 7. Water contact angle photographs of (A) TiO2, (B) Bi2Ti2O7,
and (C) Bi2Ti2O7-TiO2 composite nanowire arrays. (D) Change in the
water contact angle of the Bi2Ti2O7-TiO2 composite nanowire array
under visible-light irradiation.
the TiO2 and Bi2Ti2O7 nanowire arrays are 38.2 and 12.4°,
respectively. However, the surface of the obtained Bi2Ti2O7-
TiO2 composite nanowire array is superhydrophilic with a
water contact angle of 0°, and the water droplet spreads quickly
as soon as it contacts the surface. Moreover, the super-
hydrophilicity is maintained for at least 15 days (Figure 7D). A
major factor causing such improved and prolonged super-
hydrophilicity is mainly due to its nanowire array surface
morphology and heterostructure between Bi2Ti2O7 and TiO2 in
the composite, which could generate a capillary force that
attracts water into the pores in the nanowire arrays and leads to
a low contact angle.57
To achieve self-cleaning, a film not only must be super-
hydrophilic but also must be able to induce photocatalytic
oxidative decomposition.58 The photocatalytic activity of the as-
prepared Bi2Ti2O7-TiO2 composite nanowire array was
evaluated by the degradation of RhB solution under visible-
light irradiation. As shown in Figure 8A, the photocatalytic
activity of the TiO2 nanowire array in the degradation of RhB is
negligible because of its large band gap (3.2 eV). The
photodegradation rate of RhB by the Bi2Ti2O7 nanowire
array reaches only 37% after 360 min of visible-light irradiation.
However, the Bi2Ti2O7-TiO2 composite nanowire array exhibits
a much higher photodegradation rate of RhB than pure TiO2
and Bi2Ti2O7 nanowire arrays, which suggests a remarkable
enhancement in photocatalytic activity.59 In particular, 90% of
RhB is photocatalytically degraded by the Bi2Ti2O7-TiO2
nanowire array. Furthermore, the kinetic linear simulation
curves of RhB photocatalytic degradation with TiO2, Bi2Ti2O7,
and Bi2Ti2O7-TiO2 nanowire arrays are shown in Figure 8B. It
is clear that the curves with irradiation time as the abscissa and
ln(C0/C) as the vertical ordinate are close to linear curves,
which confirms that the photocatalytic degradation of RhB on
the Bi2Ti2O7 and Bi2Ti2O7-TiO2 composite nanowire arrays
follows first-order kinetics. The determined reaction constant k
values for the Bi2Ti2O7 and Bi2Ti2O7-TiO2 composite nanowire
arrays are 0.0013 and 0.0064 min−1, respectively, indicating the
higher photocatalytic performance of the Bi 2Ti2O7-TiO2
composite nanowire array compared to that of the pure
Bi2Ti2O7 nanowire array. Their linearly dependent coefficients
(R) are 0.997 and 0.999, respectively, suggesting good linear
dependence relationships. The enhanced photocatalytic activity
under visible-light irradiation can be attributed to the
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Figure 8. (A) Comparison of photocatalytic activities of different
catalysts in the degradation of RhB under visible-light irradiation: (a)
TiO2, (b) Bi2Ti2O7, and (c) and Bi2Ti2O7-TiO2 composite nanowire
arrays. (B) Pseudo-first-order kinetics curves of RhB degradation over
different catalysts: (a) TiO2, (b) Bi2Ti2O7, and (c) Bi2Ti2O7-TiO2.
synergistic effect between Bi2Ti2O7 and TiO2. The vertically
aligned Bi2Ti2O7-TiO2 composite nanowire arrays can increase
the separation efficiency of the electron−hole pairs compared
to single Bi2Ti2O7 or TiO2 nanowire arrays, which is confirmed
by the results of SPV and electrochemical measurements
(Figures 4−6). Under visible-light exposure (Figure S3), only
Bi2Ti2O7 is excited, and TiO2 cannot be excited because it is
not capable of absorbing visible light, and the generated
electrons in the conduction band of Bi2Ti2O7 would be driven
to the conduction band of TiO2 because the conduction band
energy level of TiO2 is inferior to that of Bi2Ti2O7. Because the
valence band of Bi2Ti2O7 is situated above the valence band of
TiO2, the holes in the valence band of Bi2Ti2O7 could not
migrate to the valence band of TiO2.60−62 The photogenerated
electrons transferred between Bi2Ti2O7 and TiO2 effectively
suppress the recombination chances of electrons and holes,
resulting in an improvement of the visible-light catalytic activity
of the Bi2Ti2O7-TiO2 composite nanowire array.
To study the impact of bubbling O2 on RhB degradation, the
photocatalytic activity of the as-prepared Bi2Ti2O7-TiO2
composite nanowire arrays was evaluated by the degradation
of RhB solution without O2 bubbling under visible-light
irradiation. As shown in Figure S5, the reductions of RhB are
about 28 and 79% after 360 min of visible-light irradiation in
the presence of the Bi2Ti2O7 and Bi2Ti2O7-TiO2 nanowire
arrays, respectively. Compared to results without O2 bubbling,
it is obvious that bubbling O2 plays a positive role in the
improvement of the photocatalytic activity. Enough molecular
oxygen can provide more chances to react with photogenerated
electrons from •O2− that can further oxidize RhB.
In addition, the photocatalytic activities of the different
obtained nanowire arrays were also investigated by nondye
organic pollutant phenol degradation to exclude the dye-
sensitizing effect. Figure S6 shows the photocatalytic
degradation rates of phenol as a function of irradiation time
with TiO2, Bi2Ti2O7, and Bi2Ti2O7-TiO2 nanowire arrays under
F DOI: 10.1021/acs.langmuir.5b00516
Article
visible-light irradiation. As shown in Figure S6A, the decrease in
phenol concentration in the presence of pure TiO2 is small.
The reductions in phenol are about 58 and 81% after 360 min
of visible-light irradiation in the presence of the Bi2Ti2O7 and
Bi2Ti2O7-TiO2 nanowire arrays, respectively. It is obvious that
the Bi2Ti2O7-TiO2 nanowire array exhibits a much higher
photocatalytic degradation efficiency than pure Bi2Ti2O7. The
pseudo-first-order rate constants of the Bi2Ti2O7 and Bi2Ti2O7-
TiO2 nanowire arrays in Figure S6B are 0.0024 and 0.0046
min−1, respectively. These results clearly indicate that the
Bi2Ti2O7-TiO2 nanowire array has significantly enhanced
visible-light photocatalytic activity compared to single TiO2
and Bi2Ti2O7 nanowire arrays.
It is worth pointing out that the stability of a photocatalyst
during photoreaction is a crucial factor in its practical
applications. In this study, the photocatalytic durability of the
Bi2Ti2O7-TiO2 nanowire array was also tested. Figure S7 shows
the cyclic photodegradation of RhB over the Bi2Ti2O7-TiO2
composite nanowire array under visible-light irradiation. After
five cycles, the Bi2Ti2O7-TiO2 composite nanowire array
maintained a relatively high photocatalytic activity, and there
was no obvious catalyst deactivation. A similar result can also be
obtained from the cyclic photodegradation experiment of
phenol (Figure S8), indicating high stability. Therefore, the
Bi2Ti2O7-TiO2 composite nanowire array with excellent
photocatalytic activity and stability provided a probability for
the long visible-light self-cleaning applications.
4. CONCLUSIONS
A new strategy has been developed for the preparation of a
Bi2Ti2O7-TiO2 composite nanowire array film for self-cleaning
applications. The vertically aligned Bi2Ti2O7-TiO2 composite
nanowire arrays were fabricated on glass substrates through a
two-step solvothermal and subsequent calcination process. The
heterostructure in Bi2Ti2O7-TiO2 composite nanowire arrays
can effectively increase the photogenerated charge separation
efficiency; meanwhile, the existence of Bi2Ti2O7 can extend its
spectral response range, thus improving the visible-light
catalytic activity. Most importantly, the Bi 2 Ti 2 O 7 -TiO 2
composite nanowire arrays exhibited a significant visible-light
self-cleaning property and good stability. Such a significant self-
cleaning property of Bi2Ti2O7-TiO2 composite nanowire arrays
may be applied to a large area and has the potential to be an
economic route for industrial production. In addition, the
Bi2Ti2O7-TiO2 composite nanowire arrays have potential in
other areas such as photovoltaic cells and photoelectrochemical
sensors.
■
*
ASSOCIATED CONTENT
S Supporting Information
Additional schematic illustration of the synthesis procedure and
the energy band structure and electron−hole pair separation of
the Bi2Ti2O7-TiO2 composite nanowire array. SEM images.
Linear sweep voltammetric curves. Comparison of the
photocatalytic activities of different catalysts in the degradation
of RhB without bubbling O2. Stability evaluation of the
photocatalytic activities of the catalysts. The Supporting
Information is available free of charge on the ACS Publications
website at DOI: 10.1021/acs.langmuir.5b00516.
Langmuir XXXX, XXX, XXX−XXX
Langmuir
■ AUTHOR INFORMATION
Corresponding Authors
*E-mail: tiangh@hlju.edu.cn. Tel: +86 451 8660 4330. Fax: +86
451 8667 3647.
*E-mail: fuhg@vip.sina.com.
Notes
The authors declare no competing financial interest.
■ ACKNOWLEDGMENTS
This research was supported by the National Natural Science
Foundation of China (51272070, 21031001, 20971040,
21001042, and 21101060), the Cultivation Fund of the Key
Scientific and Technical Innovation Project, Ministry of
Education of China (no. 708029), Natural Science Foundation
of Heilongjiang Province of China (E201455), Research Fund
for the Doctoral Program of Higher Education of China
(20112301110002), and the Postdoctoral Science-Research
Developmental Foundation of Heilongjiang Province (LBH-
Q13136).
■
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H DOI: 10.1021/acs.langmuir.5b00516
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