Powder Technology 253 (2014) 608–613

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Powder Technology
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Preparation and photocatalytic activity of B–N co-doped

mesoporous TiO2
Kui Zhang a, Xiangdong Wang a,⁎, Tianou He a, Xiaoling Guo b, Yaming Feng b
a
School of Science, Xi'an Jiaotong University, Xi'an 710049, Shaanxi, PR China
b
School of Textile and Materials, Xi'an Polytechnic University, Xi'an 710048, Shaanxi, PR China

a r t i c l e i n f o a b s t r a c t

Article history: B-doped and B–N co-doped mesoporous TiO2 photocatalysts were synthesized by a fast sol–gel method. The pre-
Received 18 July 2013 pared samples were characterized by X-ray diffraction (XRD), UV–vis diffuse reflectance spectrum (DRS), trans-
Received in revised form 30 November 2013 mission electron microscopy (TEM), N2 adsorption–desorption, and X-ray photoelectron spectroscopy (XPS). It is
Accepted 13 December 2013
found that the average crystallite size, pore size, and specific surface area of the co-doped TiO2 are 9.1 nm,
Available online 21 December 2013
16.8 nm, and 125.4 m2/g, respectively. Compared with that of the pure mesoporous TiO2, the absorption band
Keywords:
edge of B–N co-doped sample exhibits an evident red-shift and the absorption intensity of visible region increases
Mesoporous TiO2 obviously. The experimental results show that a structure of Ti–N–B–O is formed on the surface of the
B–N co-doping photocatalyst, indicating a synergistic effect of two dopants enhancing the photocatalytic activity, which was
Methyl blue evaluated by the degradation of methyl blue aqueous solution under UV and visible light irradiation.
Photocatalytic activity © 2013 Elsevier B.V. All rights reserved.

1. Introduction
Titanium dioxide (TiO2) is widely investigated because of its high
photocatalytic activity, non-toxicity, and chemical stability, which
make it functional in a wide range of areas such as dye-sensitized
solar cells [1,2], degradation of pollutant in water and air [3–5], and
hydrogen evolution [6]. Nevertheless, the application of conventional
TiO2 is very limited, mainly due to two problems: (1) the band gap of
anatase TiO2 is 3.2 eV, which leads it active only in UV region, account-
ing for less than 5% of the solar energy; (2) the low surface area of the
conventional TiO2, resulting in a low efficiency when absorbing and
reacting. It is, therefore, urgent to develop some modifications of TiO2
to gain the novel photocatalyst, which has high surface area and can
be activated by visible light.
Since the report by Asahi et al. [7] revealed that nitrogen doping
can significantly improve the photocatalytic activity of TiO2 under
visible light, it has been an effective means by doping non-metal ions
to narrow the band gap of TiO2, thus expand the light response
range to visible light region. Extensive efforts have been made in TiO2
doped with non-metal ions, such as B, C, N, S, F [8–12]. In recent years,
the TiO2 materials co-doped with two kinds of nonmetal atoms such
as S–N, C–N, F–N, and B–F [13–18], which are expected to get the syner-
gistic effect permitting tune the electronic structure and enhance the
photocatalytic activity, have drawn more and more attention. As the
co-doped elements, however, B–N co-doping has been less studied.
Liu et al. [19] and In et al. [20] reported that B–N co-doped TiO2 exhibits
enhanced photocatalytic activity under UV and visible lights irradiation,
⁎ Corresponding author.
E-mail address: wang90xd@163.com (X. Wang).
which is probably attributed to the synergistic effect between boron and
nitrogen, resulting the narrowing of the band gap. Owing to the
synergistic effect of B and N, B–N co-doped TiO2 is considered as a
much effective photocatalyst under visible light. Xing et al. [21]
prepared the B and N co-doped TiO2 by a novel double hydrothermal
method. They revealed that when nitrogen was introduced into the
material before boron, the synergistic effect maybe aroused by the for-
mation of Ti–B–N–Ti and Ti–N–B–O compounds on the surface of the
catalyst, while only Ti–N–B–O occurred when boron was introduced
into the material before nitrogen. Some studies have been performed
to investigate the synergistic effect of boron and nitrogen in the TiO2
catalysts [19–24], but few of these studies have focused on the modify-
ing the crystalline structure and improving the specific surface area.
Mesoporous materials have shown unparalleled advantages in pho-
tocatalytic application especially due to their high specific surface area,
which may produce numerous surface reaction sites for the adsorption
of the reactant molecular. In addition, for mesoporous TiO2, the small
grain size results in a shorter distance for the electrons and holes to
transfer to the reaction sites [25]. Since Antonelli and Ying [26] firstly
synthesized mesoporous TiO2 in 1995, many attempts have been
made to modify TiO2 by giving it mesopore structures [27–30]. Howev-
er, few studies reported the mesoporous TiO2 doped with other
elements [19,31]. In our previous work, we developed a fast sol–gel
method using polyacrylamide (PAM) and polyethylene (PEG) as the
templates to synthesis N-doped mesoporous TiO2 with high specific
surface area [32]. In the present work, B doped mesoporous TiO2 and
B–N co-doped mesoporous TiO2 photocatalysts were prepared by the
fast sol–gel method using the tetrabutyl titanate, urea, and boric acid
as Ti precursor, N source, and B source, respectively. The photocatalysts
with high specific surface area were characterized by X-ray diffraction

0032-5910/$ – see front matter © 2013 Elsevier B.V. All rights reserved.
http://dx.doi.org/10.1016/j.powtec.2013.12.024
 K. Zhang et al. / Powder Technology 253 (2014) 608–613 609

(XRD), transmission electron microscopy (TEM), X-ray photoelectron

spectroscopy (XPS), UV–vis spectroscopy, and N2 adsorption–desorp- (c)
tion. The photocatalytic activity of the catalysts is evaluated by the pho-
tocatalytic degradation of methyl blue (MB) in water under UV and
visible light irradiation.

Intensity (a.u.)
2. Experimental
(b)

2.1. Preparation of photocatalysts

A fast sol–gel preparation of the B and B-N co-doped mesoporous (a)

TiO2 was performed as follows. 10 mL tetrabutyl titanate was dissolved
into 20 mL anhydrous ethanol with stirring to obtain solution A. 10 mL
nitric acid (5 wt.%), H3BO3 (0.055, 0.091, 0.182 g corresponding to 0.03, 10 20 30 40 50 60 70
0.05, 0.10 of B/Ti molar ratios), and urea (0, 1.76 g corresponding to 0, 1 2θ (degree)
of N/Ti molar ratios) were added to the solution of 10 mL deionized
water and 280 mL anhydrous ethanol with stirring to obtain solution Fig. 1. XRD patterns of (a) pure TiO2, (b) (0.03B)-TiO2, and (c) (0.03B, 1.0N)-TiO2 .

B. 0.05 g PAM and 8.8 g PEG was added to 20 mL anhydrous ethanol

with stirring to obtain solution C. Solution C was added to solution B
while stirring to get the mixture. Then solution A was added dropwise
to the mixture above under stirring. The resultant mixture was stirred
at room temperature for 1 h until a white gel was obtained. The gel
was dried at 30 °C for 16 h to gain the xerogel. The resultant xerogel
was crushed to obtain fine powder and further calcined in air at
400 °C for 4 h to obtain the catalyst. The samples were labeled as
(mB, nN)-TiO2, where m and n corresponded to the initial molar
ratios of B to Ti and N to Ti, respectively. For the comparison, undoped
TiO2 was prepared according to the above procedure in the absence of
solution B.
2.2. Characterizations
X-ray diffraction (XRD) patterns of photocatalysts were collected at
room temperature in the range 10–75° (2θ) using a Rigaku D/MAX 2550
diffractometer (Cu Kα radiation, λ = 1.5406 Å), operated at 40 kV and
100 mA. The crystalline size was estimated by applying the Scherrer
equation. N2 absorption isotherms were collected on an AUTOSORB-1
nitrogen adsorption apparatus at − 196 °C and all samples were
degassed at 120 °C for 2 h. The instruments employed for XPS analysis
was a PHI 5300 ESCA with an Mg K X-ray source at a power of 250 W.
The shift of binding energy due to relative surface charging was
corrected using the C1s lever at 284.6 eV as an internal standard. The
UV–vis absorbance spectra were obtained using a Shimadzu-2501 spec-
trophotometer. BaSO4 was the reference sample and the spectra were
recorded at room temperature in air within the range 200–900 nm.
TEM images were recorded on a JEM-2100F made in Japan.
2.3. Evaluation of photocatalytic activity
The photocatalytic activity of as-prepared samples was evaluated
by degradation of methyl blue in water (MB, 10 mg/L) under UV and
visible light irradiation. The catalyst (0.05 g) was added into a quartz re-
actor (100 mL), which contained 50 mL of MB solution. Prior to irradia-
tion, the suspension was magnetically stirred for 40 min in the dark to
reach an adsorption-desorption equilibrium. A 300 W high-pressure
mercury lamp was used as UV radiation with a peak of 365 nm and a
300 W xenon lamp through a UV-cutoff filter (≤400 nm) was used as
the visible light source. The lamp was cooled by flowing water in the
quartz jacket around the lamp during the photocatalytic reaction, thus
the ambient temperature would stay constant. The analytic suspension
(5 mL) was taken out of the reactor at regular intervals, which would be
centrifuged immediately and then filtered to separate TiO2 from the
solution. The residual concentration of the MB in the remaining clear
liquid was analyzed by a spectrophotometer (UV-7220, Beifenruili,
China) at 662 nm. The degradation ratio of MB can be calculated by
(A0 − A) / A0 × 100%.
3. Results and discussion
3.1. XRD and BET analysis
The XRD patterns of the as-synthesized pure TiO2, (0.03B)–TiO2, and
(0.03B, 1.0N)–TiO2 samples are presented in Fig. 1. All the diffraction
peaks can be ascribed to pure anatase phase TiO2 after calcination.
These test results indicate that there has been virtually no phase transi-
tion in TiO2 in the process of B-doping or B–N co-doping. The diffraction

140 0.025
a b
Adsorbed volumn (cm3/g,STP)

120
0.020
dV/dD (cm3/g-nm)

100
0.015
80

60 0.010

40 0.005

20
0.000
0
0.0 0.2 0.4 0.6 0.8 1.0 0 10 20 30 40 50 60 70 80
Relative pressure (p/p0) Pore diameter(nm)

Fig. 2. N2 adsorption-desorption isotherms (a) and the BJH corresponding pore size distribution curve (b) of (0.03B, 1.0N)-TiO2.
610 K. Zhang et al. / Powder Technology 253 (2014) 608–613

Table 1 sample were determined to be 125.4 m2/g and 0.1776 cm3/g. Other
The characterization results of different samples. samples have the similar nitrogen adsorption–desorption isotherms
Sample Crystallite sizea SBETb Pore sizec Pore volumed and BJH pore size distributions to the (0.03B, 1.0N)-TiO2 sample. Their
(nm) (m2/g) (nm) (cm3/g) textural properties are listed in Table 1. Considering the crystallite size
TiO2 12.9 121.6 16.9 0.1754 of the sample, the mesopores are believed to be formed by the agglom-
(0.03B)-TiO2 9.5 130.6 15.6 0.1804 eration and connection of adjacent nanoparticles in the sample [34].
(0.03B, 1.0N)-TiO2 9.1 125.4 16.8 0.1776 This network nanostructure offers more efficient transportation for
a
Evaluated by the Scherrer's equation. the reactant molecules to the active sites, which are expected to en-
b
Measured by the BET method. hance the photocatalytic activity [26].
c
Estimated from the Barrett-Joyner-Halenda (BJH) formula.
d
Estimated by the cryolac number of N2 adsorption at relative pressure of 0.99.
3.2. TEM analysis

peak at 25.4°, corresponding to characteristic peak of crystal plane (101)
of anatase phase TiO2, became broader and the relative intensity de-
creased after boron and nitrogen are introduced into TiO2, suggesting
the decrease of the crystal size. According to Scherrer equation, the av-
erage crystallite sizes of pure TiO2, (0.03B)–TiO2, and (0.03B, 1.0N)–TiO2
samples are estimated to be about 10.9, 9.5, and 9.1 nm, respectively,
corresponding to (a), (b), and (c) in Fig. 1. It confirms that the boron
and nitrogen doping can decrease the crystal size mainly due to the de-
formation of lattice and oxygen vacancies left by the substitution of O
atoms for B or N atoms [19]. The size decreases from (b) to (c) maybe
aroused by the new structure Ti–N–B–O formed at the internal surface
of TiO2 [21].
Fig. 2 shows the nitrogen adsorption–desorption isotherms and pore
size distribution curves of the (0.03B, 1.0N)-TiO2 sample. As shown in
Fig. 2(a), the N2 sorption isotherm of the sample is consistent with
type IV of hysteresis loops, which is a typical mesoporous structure of
the material according to the IUPAC classification. There is a hysteresis
loop appearing at the relatively low pressure (0.4 b P/P0 b 0.8), indicat-
ing a small range of pore size distribution, which is centered at 16.8 nm
estimated by the Barrett–Joyner–Halenda (BJH) approach (Fig. 2(b)).
The mesopores allow light to scatter inside their pore channel, thus en-
hancing the harvesting of light [33]. According to the liner part of the
sorption isotherm, the specific surface area and pore volume of the
The microstructure of the (0.03B, 1.0N)-TiO2 sample was investigat-
ed with transmission electron microscopy (TEM) and high-resolution
transmission electron microscopy (HRTEM). TEM images of the sample
are shown in Fig. 3(a) and (b). As estimated from the TEM images,
grains are all round-shaped with a uniform size of about 10 nm,
which are in agreement with the XRD analysis. In addition, it is clearly
seen that the sample has a typical mesopore structure with a
wormhole-like framework. As observed in Fig. 3(b), the pore size is
about 15–20 nm, which is consistent with N2 sorption analysis. The
Debye rings showed in Fig. 3(d) suggest a sequence of diffraction rings
consistent with what is expected for anatase TiO2 as the nanocrystal of
the mesoporous sample. The average inter planar space is determined
to be 0.35 nm (Fig. 3(c)), which is assigned to the anatase TiO2 facet
(101) from the corresponding wide-angle XRD pattern [35,36].
3.3. UV–vis DRS of catalysts
The UV–vis diffraction reflectance spectra of (mB)-TiO2 samples are
shown in Fig. 4. It is found that the amount of boron doped into TiO2
affects the optical absorption of the sample both in the UV and visible
regions. The (0.1B)-TiO2 sample exhibits the strong absorption in visible
region, and the (0.03B)-TiO2 exhibits the strongest response to light in
wavelength N 550 nm. Furthermore, it can be clearly observed that the

Fig. 3. TEM characterization: (a, b) TEM images, (c) HRTEM images, (d) SAED pattern.

Absorbance (a.u.)
300 400 500
Wavelength (nm)
Fig. 4. UV–vis absorption spectra of (mB)-TiO2 samples.
absorption edge, which is decided by the intercept on the wavelength
axis for a tangent drawn on absorption spectra, of all samples doped
with boron extend into visible light from about 420 to 480 nm. Taking
into account of the absorption intensities in UV and visible regions,
the amount of boron doped of the (0.03B)-TiO2 sample is appropriate.
The relative atomic concentration of boron in the sample is about 1.23
atom % determined by the XPS data. This relative atomic concentration
of boron is approximately the maximized amount of boron doped
(about 1.13 atom %), which was demonstrated to be the very significant
activity for B doped sample [20].
Fig. 5 shows a description about the UV–vis diffraction reflectance
spectra of pure TiO2, (0.03B)-TiO2, and (0.03B, 1.0N)-TiO2. Compared
with the pure TiO2, the absorption of B-doped sample extends some-
what into the visible region. Further, it is clear that the absorption
edge of B-N co-doped sample exhibits an evident red-shift, indicating
a possible synergistic effect of the two dopants. The plots of transformed
Kubelka-Munk function versus the energy of absorbed light give the
band gap of the samples [25]. The band gap energies are estimated to
be 3.18, 3.02, and 2.86 eV for pure TiO2, (0.03B)-TiO2, and (0.03B,
1.0N)-TiO2, respectively. The narrowed band gap arises from the contri-
butions of B–N co-doping atoms, which formed the Ti–N–B–O structure
demonstrated by the XPS tests. The results confirm that both dopants
will make the band gap of TiO2 narrow and therefore improve the visi-
ble light photocatalytic activity.
3.4. XPS analysis
The XPS spectra of (0.03B, 1.0N)-TiO2 sample is shown in Fig. 6. The
obvious peaks of titanium, oxygen, nitrogen, boron, and carbon can be
detected in Fig. 6(a), and the binding energies of Ti2p, O1s, N1s, B1s,
Absorbance (a.u.)
200 300
Fig. 5. UV–vis absorption spectra of pure TiO2, (0.03B)-TiO2, and (0.03B, 1.0N)-TiO2.
K. Zhang et al. / Powder Technology 253 (2014) 608–613 611
and C1s are 459.0, 531.0, 400.5, 192.1, and 284.6 eV, respectively,
(0.1B)-TiO2
which are approximately in agreement with the previous data by
(0.03B)-TiO2 other researchers [20–23]. The C1s peak (284.6 eV) is usually associated
(0.05B)-TiO2 with the residual carbon from precursor solution and the adventitious
hydrocarbon from XPS instrument itself. The relative atomic concentra-
(0.02B)-TiO2
tions of boron and nitrogen in the sample, estimated from the XPS data,
were determined to be about 1.23 and 1.78 atom%, respectively.
Fig. 6(b) shows the high-resolution XPS spectra for B1s. Four XPS
peaks at 187.3, 189.2, 192.1, and 193.7 eV were observed. According
to the previous literature, the peak at 193.7 eV is attributed to the
bond of B–O [37]. The peaks at 187.3 and 192.1 eV are ascribed to the
structures of Ti–B and Ti–O–B [20,38], respectively. The peak at
189.2 eV is attributed to the bond of B\N, which is supposed to exist
in forms of Ti–B–N or Ti–N–B [19]. To make sure of the structural
600 700 800 forms of B and N existing in the sample, the N1s XPS spectra of the sam-
ple are measured and the high-resolution XPS spectra of N1s are shown
in Fig. 6(c). As seen from Fig. 6(c), three peaks at 399.1, 400.5, and
401.5 eV appeared on the spectra. The peak at 400.5 eV is attributed
to the structure of Ti–O–N [20]. The peak at 401.5 eV may be attributed
to the bond of Ti–N–O [25,39]. The peak at 399.1 eV indicates a structure
of Ti–N–B [21] rather than Ti–B–N, in which the binding energies of B1s
and N1s are 190.5 and 398.1 eV, respectively [19]. Taking the spectra of
B1s and N1s into account in this work, we may conclude that the dop-
ants of boron and nitrogen form a structure of Ti–N–B–O in the sample.
The high-resolution XPS spectrum of Ti2p, shown as Fig. 6(d), can
further verify the existence of this Ti–N–B–O structure. As seen from
Fig. 6(d), the characterization peak shifts from 458.2 eV, which is the
normal binding energy usually for pure TiO2, to 459 eV, the binding en-
ergy for TiO2 co-doped with boron and nitrogen [19–21]. This change of
the binding energy should be attributed to the electronegativity of O in
Ti–N–B–O structure, which is a good agreement with the results of other
literature [21].
3.5. Photocatalytic activity
The UV-light and visible light photocatalytic activities of pure meso-
porous TiO2, (0.03B)-mesoporous TiO2, and (0.03B, 1.0N)-mesoporous
TiO2 were evaluated by photocatalytic degradation of MB aqueous solu-
tion (shown in Fig. 7). Fig. 7(a) shows a comparison of photocatalytic
activity of the samples under UV-light irradiation. As seen from the fig-
ure, although all the samples exhibit high photocatalytic activity under
UV irradiation, it has somewhat difference for the samples. It can be
seen that the doped TiO2 exhibit a higher photocatalytic activity, espe-
cially for (0.03B, 1.0N)-TiO2, which may be because the doped samples
have higher absorption intensity than pure TiO2, as shown in Fig. 5(a).
The photocatalytic activity of samples under visible light was shown
in Fig. 7(b). Compared with pure mesoporous TiO2, doped mesoporous
TiO2 photocatalysts showed obviously enhancing effect on the photo-
catalytic activity, especially for the B–N co-doped mesoporous TiO2. As
(0.03B, 1.0N)-TiO2 a (0.03B, 1.0N)-TiO2
b
(0.03B)-TiO2 (0.03B)-TiO2
TiO 2 TiO2
(αEphoto)2 (a.u.)
400 500 600 700 800 2.6 2.8 3.0 3.2 3.4 3.6 3.8 4.0
Wavelength (nm) Ephoto (eV)
612 K. Zhang et al. / Powder Technology 253 (2014) 608–613

a O1s b 192.1eV
B1s
Ti2p

Intensity (a.u.)

Intensity (a.u.)
C1s 193.7eV 187.3eV
N1s B1s 189.2eV

600 500 400 300 200 100 195 194 193 192 191 190 189 188 187 186
Binding energy (eV) Binding energy (eV)

c 400.5eV d 459.0eV
N1s Ti2p
Intensity (a.u.)

Intensity (a.u.)
401.5eV
399.1eV

398 399 400 401 402 403 450 455 460 465 470 475
Binding energy (eV) Binding energy(eV)

Fig. 6. (a) XPS spectra of (0.03B, 1.0N)-TiO2, (b) high-resolution XPS spectra of B1s, (c) high-resolution XPS spectra of N1s, (d) high-resolution XPS spectra of Ti2p.

we can see from the data shown in Fig. 7(b), (0.03B)-doped and (0.03B,
1.0N) co-doped TiO2 photocatalysts can improve the degradation rate of
MB under visible light. It is obvious that the photocatalytic activity of B–
N co-doped TiO2 is better than that of B-doped TiO2, which is largely due
to the outstanding synergistic effect of boron and nitrogen co-doping by
forming the structure of Ti–N–B–O [21]. The result is in great agreement
with the UV–vis DRS analysis.
Compared with Fig. 7(a) and Fig. 7(b), it is evident that the photocat-
alytic activities of all samples in UV region are higher than in visible
region. This is because the absorption in UV region is stronger than in
the visible region, which has been shown in Fig. 5. It is also found that
the enhancement of photocatalytic activity by boron and nitrogen in
UV region seems to be negligible compared with that in visible region.
This may be ascribed to the structure of Ti–N–B–O formed on the sur-
face of the sample. To our best knowledge, the UV light irradiation will
produce a lot of electrons and holes, which will be recombined by the
excess amount of B–N species on the surface of the sample [21,40]
and therefore affect the photocatalytic activity.
4. Conclusions
In summary, mesoporous TiO2 photocatalyts co-doped with boron
and nitrogen were successfully prepared by using the fast sol–gel
method. The B–N co-doped catalyst has a specific surface area of
125.4 m2/g and the average pore size is decided to be 16.8 nm, which
implies a typical mesopore structure. The XPS analysis shows that a
structure of Ti–N–B–O was formed on the surface of the co-doped sam-
ple. The special structure greatly improves the photocatalytic activity
under visible light, suggesting a synergistic effect of boron and nitrogen.
The absorption band edge of the B–N co-doped mesoporous TiO2

1.0 a TiO2
1.0 b
(0.03B, 1.0N)-TiO 2
0.8 (0.03B)-TiO2 0.8

0.6 0.6
C/C0

C/C0

0.4 0.4 (0.03B)-TiO2

(0.03B, 1.0N)-TiO2
0.2 0.2
TiO2

0.0 0.0
0 20 40 60 80 100 0 60 120 180 240
Time (min) Time (min)

Fig. 7. Photocatalytic degradation kinetics of MB solutions under irradiation of (a) UV light and (b) visible light.
 K. Zhang et al. / Powder Technology 253 (2014) 608–613
sample exhibits an evident red-shift and its absorption intensity of vis-
ible region is higher than that of the undoped sample, which is respon-
sible for B–N co-doping that make the energy gap of TiO2 narrower.
Compared with the un-doped sample, B–N co-doped mesoporous TiO2
appears to have higher photocatalytic activity under irradiation of visi-
ble light.
Acknowledgment
This work has been supported by the Science and Technology
Planning Project of Shaanxi Province (2013K09-04) and the Scientific
Research Project of the Provincial College Key Laboratory of Shaanxi
Province (2010JS007).
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