Journal of Alloys and Compounds 548 (2013) 70–76

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Journal of Alloys and Compounds

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Characterization and photocatalytic properties of N-doped BiVO4 synthesized

via a sol–gel method
Min Wang ⇑, Qiong Liu, Yinsheng Che, Lifang Zhang, Dong Zhang
College of Environmental and Chemical Engineering, Shenyang Ligong University, Shenyang 110165, China

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

Article history: A N-doped BiVO4 photocatalyst with high visible light activity was synthesized by the complexing sol–gel
Received 23 July 2012 method using citric acid as a chelate and hexamethylene tetramine (C6H12N4) as a nitrogen source. The
Received in revised form 20 August 2012 as-prepared N-doped BiVO4 samples were characterized by X-ray photoelectron spectroscopy (XPS),
Accepted 22 August 2012
X-ray diffraction (XRD), scanning electron microscopy (SEM), specific surface area (BET) and UV–Vis dif-
Available online 10 September 2012
fuse reflectance spectroscopy (DRS). The photocatalytic activity was evaluated by photocatalytic degra-
dation of methyl orange (MO) solution under visible light. This technique revealed that pure BiVO4
Keywords:
and all the N-doped samples were in a monoclinic phase; no peaks of any other phases or impurities were
BiVO4
Photocatalytic activity
detected. Nitrogen atoms were doped into the BiVO4 lattice and filled the atomic sites of oxygen to form
N-doped O–Bi–N–V–O bonds, which contributed to the appearance of the more active species V4+ and oxygen
Methyl orange solution vacancies. The doped nitrogen resulted in a red shift in the absorption edge. However, the N-doping only
slightly changed the morphologies and BET special surface areas of the samples. The photocatalytic activ-
ity of BiVO4 significantly depended on the N-doping content and the calcination temperature. The max-
imum activity was observed for the catalyst obtained via calcination at 500 °C, for which the molar ratio
of N to Bi was 0.20. Excess N-doping decreased the light absorption.
Ó 2012 Elsevier B.V. All rights reserved.

1. Introduction structure exhibits high photocatalytic activities due to its relatively

Currently, dye pollution is a major source of environmental
pollution in waste fields that is difficult to eliminate with conven-
tional water treatment technologies [1–4]. In recent decades, a
great deal of interest has been devoted to photocatalytic degrada-
tion of organic water pollutants by semiconductor particles [5–7].
Among these semiconductors, titanium oxide (TiO2) is the prefera-
ble material for its chemical stability, lack of toxicity and low cost.
However, the TiO2 photocatalyst has not been applied widely in
the field of environmental pollution control, given that its large
band-gap energy (Eg = 3.2 eV) considerably limits the use of natu-
ral solar light or artificial visible light. Therefore, the development
of high activity photocatalysts driven by visible light is now of
great importance, especially in view of serious energy shortages.
Recently, a large number of novel semiconductor photocatalysts
with visible light response have been developed. Bismuth vanadate
(BiVO4), one of the visible-light-driven semiconductor photocata-
lysts [8–14], has recently attracted considerable attention for its
photocatalytic activity in the degradation of organic compounds
[15] and organic dyes [16] and in water splitting for hydrogen
and oxygen evolution [17]. The photocatalytic properties strongly
depend on the crystal structure. BiVO4 with a monoclinic scheelite
⇑ Corresponding author. Tel./fax: +86 24 24680345.
E-mail address: minwang62@msn.com (M. Wang).
narrow band gap energy (2.4 eV) compared to BiVO4 with a tetrag-
onal phase (3.1 eV) [18]. However, the photocatalytic activity of
the monoclinic scheelite BiVO4 is not as strong because of its poor
adsorptive performance and low quantum yield caused by the dif-
ficult migration of photo-generated electron–hole pairs.
To remove such obstacles to high photocatalytic activity, doping
of nonmetals, metals and metal oxides is used to accelerate the sep-
aration of electron–hole pairs, as well as to efficiently extend the
usable region of visible light. Using the impregnation technique,
Long et al. [19] successfully synthesized Co3O4/BiVO4 composite
photocatalysts that exhibited high photocatalytic activity on the
degradation of phenol under visible-light irradiation. Zhang et al.
[15] investigated the silicon-doped BiVO4 film via the modified
metalorganic decomposition (MOD) method, for which the phenol
elimination rate on the Si-doped BiVO4 film electrode in the photo-
electrocatalytic process was 1.84 times greater than that on the
BiVO4 film electrode. Suo et al. [20] found that the Cu-doped BiVO4
catalyst exhibited improved photocatalytic activity for the degrada-
tion of toluene in the gas phase, which reached over 90% and
extended a red-shift. Chatchai et al. [21] studied the photoelectro-
chemical properties of a FTO/WO3/BiVO4 composite electrode con-
sisting of monoclinic WO3 and crystalline monoclinic BiVO4. WO3/
BiVO4 was observed to exhibit elevated photocurrent efficiencies,
reaching values ten times those of a bare BiVO4 electrode under
both UV and visible light irradiation. Ag–BiVO4 composites were

0925-8388/$ - see front matter Ó 2012 Elsevier B.V. All rights reserved.
http://dx.doi.org/10.1016/j.jallcom.2012.08.140
 M. Wang et al. / Journal of Alloys and Compounds 548 (2013) 70–76
prepared by Zhang et al. [22] through a photoreduction technique;
these composites showed visible-light activities superior to those of
pure BiVO4 in the decomposition of phenol. Yu et al. [23] fabricated
Co3O4 and CuO/BiVO4 by intense ultrasound irradiation at room
temperature. The composite photocatalysts exhibited much higher
photocatalytic activity than that of pure BiVO4 due to the high crys-
tallinity and the formed p–n heterojunction of Co3O4/BiVO4 or CuO/
BiVO4. These two factors can effectively suppress the recombina-
tion of photogenerated hole–electron pairs.
Although there have been many reports on nonmetal-, metal-
and noble metal-doping in BiVO4, the effect of N doping on the pho-
tocatalytic activity of BiVO4 for the photodegradation of organic
contaminants has seldom been reported, to the best of our knowl-
edge. Herein, we synthesized pure BiVO4 and N-doped BiVO4 phot-
ocatalysts through the sol–gel method and characterized them by
XPS, XRD, SEM, BET and DRS. The effects of N-doping concentration
and calcination temperature on the photocatalytic degradation of
methyl orange were investigated under visible-light irradiation.
Based on the results of photocatalyst characterization and activity
testing, the mechanism of the enhanced activity of N-doped BiVO4
composite catalysts was also discussed.
2. Experimental
2.1. Photocatalyst preparation
Bi(NO3)35H2O and NH4VO3 (Shenyang Chemical Company) were used as
received without further purification. All other chemicals used in experimentation
were of analytical grade.
In a typical preparation process, 0.01 mol Bi(NO3)35H2O was first dissolved in
50 mL of 10% (w/w) HNO3. The appropriate amount of citric acid was added until
the molar ratio of citric acid and Bi(NO3)3 was 2:1. Solution A was thereby obtained.
NH4VO3 was dissolved in 80 °C distilled water, and the solution was magnetically
stirred until the dissolution was complete. The appropriate amount of citric acid
was then added until the molar ratio of citric acid and NH4VO3 was 2:1. The mixture
was completely stirred to dissolve the solid, generating solution B. Solution A was
then added drop-wise into solution B with continual magnetic stirring until the
two solutions were mixed at a 1:1 M ratio to obtain solution C. A given amount
of C6H12N4 (C6H12N4 in strong acid solution is hydrolyzed when it is heated to more
than 100 °C) was then added to solution C. Under vigorous stirring, the pH of the
mixture was adjusted to approximately 6.5 using ammonia solution. The mixture
was stirred at 80 °C until the dark blue BiVO4 sol–gel was obtained and then dried
at 80 °C in a drying cabinet for 10 h to produce the BiVO4 precursor. The resulting
powder was collected and calcined in air at different temperatures (between 350
and 500 °C) for 5 h, cooled to room temperature, and then crushed to obtain a fine
powder. The sample was labeled as BVON-x, where x represents the initial molar
ratio of N to Bi (between 0.13 and 0.30). Pure BiVO4 was prepared by the same
method as N-BiVO4, except that the ‘solution C’ corresponding to pure BiVO4 did
not contain C6H12N4.
2.2. Photocatalyst characterization
XPS spectra were measured on a MULTILAB2000 X-ray photoelectron spectro-
scope equipped with Mg Ka excitation. Detailed scans were recorded for N 1s, V
2p, Bi 4f and O 1s. The C 1s peak, set at 285.0 eV, was used as an internal reference
for absolute binding energy. XRD patterns were measured on a Scintag-XDS-2000
diffractometer with Cu Ka radiation (k = 0.15418 nm). The morphologies and struc-
tures of the prepared samples were observed using scanning electron microscopy
(SEM), Hitachi S-3000 N. UV–Vis DRS spectra were obtained on a Hitachi U-3010
spectrophotometer equipped with an integrating sphere. Absorption spectra were
referenced to BaSO4. The BET specific surface area was measured using ASAPZOLOM
Micrometrics, with nitrogen as the adsorbent, at 196 °C. Prior to measurement, all
samples were degassed at 130 °C for 5 h.
2.3. Photocatalytic activity test
The photocatalytic activities of the samples were evaluated through the degra-
dation of MO under visible light. A 250 W halogen lamp was used as the visible light
source and was placed 16 cm from the reactor. A cut-off filter was placed under the
lamp to exclude all wavelengths lower than 400 nm to ensure irradiation with only
visible light (For visible light, k > 400 nm.). The experiments were performed as fol-
lows. Equal amounts (10 mg) of photocatalyst and 0.1 mL H2O2 (10%) were added to
50 mL of 10 mg/L MO solution. The solution was stirred for 20 min in the dark prior
to illumination to attain the adsorption–desorption equilibrium between the dye
and the catalyst surface under air-equilibrated room conditions. At given time
71
intervals, samples were collected from the mixtures, immediately centrifuged and
then filtered through a 0.45 lm Millipore filter to remove catalyst particles. The
filtrate concentration was determined by recording the absorbance at 464 nm using
a UV-1800 UV–Vis spectrophotometer (Puxi, China). The reproducibility of the
results, which was determined by repeating the measurements at least three times,
was within an acceptable limit (±5%).
3. Results and discussion
3.1. XPS analysis
The overall XPS spectra of BVO and BVON-20 samples are
shown in Fig. 1. Seven peaks corresponding Bi 5d, Bi 4f, Bi 4d5/2,
Bi 4d3/2, V 2p, O 1s, and C 1s appeared for both BVO and BVON-
20 powders. The N 1s peak at approximately 399.8 eV can be
detected obscurely for the BVON-20 compared with the pure
BiVO4, which was due to the presence of nitrogen from the sol–
gel precursor. The C 1s peak at 285 eV most likely originated from
the calcinated residue of the organic materials used and is used for
calibration. The total nitrogen concentration calculated from the
XPS spectrum was 2.87%. It indicated that the actual N-doping con-
centration in sample was only about 1/10 of the original doping
ratio. But for convenience, the N-doping concentration still used
the theoretical doping amount in text.
To investigate the doped nitrogen chemical states in the photo-
catalyst, the N 1s high resolution XPS spectrum was analyzed, as
shown in Fig. 2(a). As shown in Fig. 2(a), the N 1s peak was found
at 399.8 eV only; no other peaks appeared. The binding energy at
399.8 eV can be attributed to nitrogen replacing the common oxy-
gen in the crystal lattice of BiVO4 to form the O–Bi–N–V–O bond
[24]. This binding energy could not represent O–Bi–N or O–V–N
alone because both the binding energies of Bi 4f and V 2p, presented
in Fig. 2(b) and (c), changed to some degree. Therefore, the common
O atom in the O–Bi–O–V–O bond was most likely replaced by a N
atom. Furthermore, because the high electronegativity of oxygen
leads to the reduction of electron density on the nitrogen, a rela-
tively higher binding energy at 399.8 eV was observed compared
to V–N in VN (the N 1s binding energy is 397.4 eV [25]) or Bi–N
in BiN (the N 1s binding energy is 397.4 eV [25]). So, it can be con-
cluded that the doping N only replaced the O in the crystal lattice of
BiVO4, but did not form the VN and (or) BiN species in the N-doped
BiVO4 sample; this interpretation is further supported by the XRD
results.
Fig. 2(b) shows the XPS spectra for the Bi 4f region of BVO and
BVON-20. By fitting the curves, two strong symmetrical peaks were
O1s
Bi4f V2p
Bi4d3/2
Intensity/a.u.
Bi4d5/2 a
C1s
b
Bi5d
N1s
0 200 400 600 800 1000
Binding Energy/eV
Fig. 1. XPS spectra of (a) BVO and (b) BVON-20 calcined at 500 °C.
72 M. Wang et al. / Journal of Alloys and Compounds 548 (2013) 70–76

a:N1s 399.8eV Bi4f7/2 159.7eV

b:Bi4f
Bi4f5/2 165.0eV

Intensity/a.u.
Intensity/a.u.

Bi4f7/2 159.1eV
Bi4f5/2 164.4eV

BVON-20

BVO

385 390 395 400 405 410 154 156 158 160 162 164 166 168 170
Binding Energy/eV Binding Energy/eV

c1:V2p c2:V2p

516.8eV
516.6eV
Intensity / a.u.

Intensity/a.u.
516.1eV 515.8eV

512 514 516 518 520 513 514 515 516 517 518 519
Binding Energy / eV Binding Energy/eV

d2:O1s
d1:O1s 529.6eV

529.1eV
Intensity/a.u.

529.9eV
Intensity / a.u.

531.4eV

526 528 530 532 534 536 526 528 530 532 534 536
Binding Energy / eV Binding Energy/eV

Fig. 2. N 1s (a), Bi 4f (b), V 2p (c) and O 1s (d) XPS spectra of BVO and BVONF-6 samples. (1) BVO and (2) BVONF-6.

obtained at 159.1 and 164.4 eV, corresponding to the Bi 4f7/2 and Bi
4f5/2 signals of BVO; peaks at 159.7 and 165.0 eV corresponded to
the Bi 4f7/2 and Bi 4f5/2 signals of BVON-20, respectively, which
were characteristic of the Bi3+ species [26]. We can conclude that
N-doping had no effect on the chemical state of the bismuth ion
in BiVO4. However, the banding energy of Bi 4f increased by
0.6 eV when compared with the pure sample. This result reveals
that doping N can lead to a decrease of electron density on Bi
due to the lower electronegativity of nitrogen compared to that
of oxygen [27].
From Fig. 2(c), the asymmetric V 2p3/2 signals were decomposed
into two peaks at Eb = 515.1 and 516.8 eV for BVO and Eb = 515.8
and 516.6 eV for BVON-20, attributable to the surface V4+ and V5+
species, respectively [28,29]. This result indicated that the banding
energy of V changed after N-doping. In addition, the molar ratio of
surface V4+/V5+ of the N-doped BiVO4 sample was higher than that
of the undoped BiVO4 sample. This result is shown in Table 1.
According to the electroneutrality principle, the BiVO4 samples
were oxygen-deficient, and the amount of nonstoichiometric
oxygen at the surface was dependent on the molar ratio of surface
 M. Wang et al. / Journal of Alloys and Compounds 548 (2013) 70–76 73

Table 1
Analysis of O 1s and V 2p of BVO and BVON-20 samples.

Samples Binding energy (eV) Relative content Binding energy (eV) Relative content
5+ 4+
Lattice oxygen Hydroxyl oxygen Lattice oxygen Hydroxyl oxygen V V V5+ V4+
BVO 529.6 531.4 0.88 0.12 516.8 516.1 0.54 0.46
BVON-20 529.1 529.9 0.62 0.38 516.6 515.8 0.50 0.50

V4+/V5+. N3 substituting for O2 must cause partial electron trans-
formation from the N3 to another cation (Bi3+ or V5+) due to the
structure of the O–Bi–N–V–O bond. From the former XPS analysis
of Bi 4f, there was no Bi2+ appearing after N-doping, confirming
that there was no electron transfer to Bi3+; therefore, it is likely
that the electron transfer only occurred from V5+ to form more
V4+ sites in the crystal lattice. As for the O 1s XPS spectra
(Fig. 2(d)), the asymmetric peak centered at approximately 530
eV decomposed into two components at Eb = 529.6 and 531.4 eV
for undoped BiVO4 and at Eb = 529.1 and 529.9 eV for BVON-20;
these peaks were due to the surface lattice oxygen (Olatt) and the
adsorbed oxygen (Oads) species, respectively [30]. This result indi-
cates that the concentration of surface oxygen vacancies increases
after N-doping.
The above results show that nitrogen is incorporated into the
lattice and is substituted for oxygen. As this process occurs, the
additional oxygen vacancies and V4+ sites would become the active
sites for BiVO4, both of which are advantageous for the enhance-
ment of photocatalytic performance of BiVO4.
of the pure BiVO4 and N-doped BiVO4 series photocatalysts. The dif-
fraction peaks of all samples conform to the reference data for
monoclinic BiVO4 (JCPDS cards No. 75-1866). Compared with that
of the pure BiVO4, there were no impurity peaks arising in the
diffraction pattern of the N-doped BiVO4, which indicated that
N-doping did not change the crystal type of BiVO4. Additionally,
no significant peaks characteristic of nitrogen oxides were detected.
This may be attributed to low concentrations of N species in these
samples existing beyond the detection limit of the XRD technique.
The average crystallite sizes of these samples were estimated
according to the line width analysis of the (1 2 1) diffraction peak
based on the Scherrer formula and were summarized in Table 2.
As shown in Table 2, the crystallite sizes of N-doped BiVO4 are
slightly bigger than those of pure BiVO4; it can therefore be pro-
posed that N-doping may lead to a slight lattice distortion in the
structure of BiVO4. To further investigate the effect of N-doping
on the crystal structure of BiVO4, the lattice parameters of all
N-doped samples calculated using Bragg’s law (2dsinh = k) and the
 
2
formula dl2 ¼ h aþk
2 2
þ cl 2 , which is applicable to tetragonal systems,
2

were listed in Table 2. These data reveal that the crystallite sizes and
3.2. XRD analysis
the lattice parameter increased with the amount of N-doping when
the initial molar ratio of N/Bi was less than 0.2, whereas the crystal-
XRD was carried out to investigate the effect of N-doping on the
lite sizes and crystal lattice volumes decreased with increasing
phase structure of BiVO4. Fig. 3 shows the XRD diffraction patterns
N-doping when the molar ratio of N/Bi was greater than 0.2.

e
Intensity/a.u.

e
Intensity / a.u.

d
d
c
c
b
b
a
a

0 20 40 60 80 0 10 20 30 40 50 60 70 80 90
2-Theta/degrees 2-Theta / degrees

Fig. 3. XRD patterns of BiVO4 products: (a) BVO; (b) BVON-13; (c) BVON-20; Fig. 4. XRD patterns of BVON-20 sample under different calcination temperatures:
(d) BVON-25 and (e) BVON-30. (a) 350, (b) 400, (c) 450, (d) 500 and (e) 550 °C.

Table 2
Some selected properties of BiVO4.

Sample Crystal size/nm Crystal lattice parameter Band gap/eV BET/m2 g1 Absorption rate%
a/nm b/nm c/nm V/nm3
BVO 49.52 5.19202 5.09148 11.69728 309.21 2.29 2.09 7.83
BVON-13 50.14 5.19284 5.09331 11.70429 309.56 2.27 2.91 10.06
BVON-20 49.84 5.19237 5.09447 11.69839 309.62 2.23 3.03 12.43
BVON-25 49.43 5.19298 5.09427 11.69986 309.51 2.25 3.15 12.41
BVON-30 45.90 5.18104 5.09178 11.69552 308.89 2.26 3.63 13.20
74 M. Wang et al. / Journal of Alloys and Compounds 548 (2013) 70–76

Based on the XPS analysis, we know the N ion is likely to be
incorporated into the interstitial BiVO4 structure and to lead to an
increasing V4+/V5+ molar ratio, creating more V4+ sites in an
N-doped BiVO4 lattice than in that of undoped BiVO4. This means
that when the initial molar ratio of N/Bi was less than 0.2, the
N-doped BiVO4 samples had larger crystallite sizes and crystal lat-
tice volumes because the radius of V4+ (0.074 nm) is larger than that
of V5+ (0.059 nm), and the radius of N3 (0.171 nm) is larger than
that of O2 (0.140 nm). When N-doping content increased further,
however, the crystallite sizes and crystal lattice volumes of samples
decreased. This may be attributed to the probable separation of N
ions from the BiVO4 lattice as other nitrogen phases appeared.
Moreover, as these phases are generated within minutes, their
timescale may be below the detection limit of the XRD technique.
The XRD patterns of BVON-20 catalyst samples calcined at dif-
ferent temperatures are shown in Fig. 4. The diffraction peaks of
all as-prepared samples fit well with the standard Joint Committee
on Powder Diffraction Standards (JCPDS 75-1866) card for mono-
clinic scheelite BiVO4 with space group I2/b. No diffraction peak
of the VN and (or) BiN3 phases are observed, which may be attrib-
uted to the nitrogen concentration existing below the level of
detection. According to the line width analysis of the (1 2 1) diffrac-
tion peak based on the Scherrer formula, the average crystallite
sizes of these samples are as follows: 36.62, 35.93, 42.30, 49.84,
and 50.76 nm. Thus, it appears that the crystal sizes of the samples
increase with the calcination temperature, implying that high tem-
peratures favored grain growth in accordance with the theory of
thermodynamic nucleation and growth.
3.3. Scanning electron microscopy (SEM) and BET specific surface area
Fig. 5 shows the morphologies of the BVO, BVON-13, BVON-20
and BVO-25 photocatalysts. A spherical structure can be observed
for all samples and the particles were uniform in size. There is little

Fig. 5. SEM micrographs of (a) and (b) for BVO; (c) and (d) for BVON-13; (e) and (f) for BVON-20; (e) and (f) for BVON-20; (g) and (h) for BVON-25.
 M. Wang et al. / Journal of Alloys and Compounds 548 (2013) 70–76
difference in the morphologies and particle shapes of the samples,
which means that N-doping has little effect on the morphology of
BiVO4. The BET specific surface areas of as-prepared samples were
measured by a nitrogen adsorption BET method (shown in Table 2).
All of the powders showed relatively small BET surface areas,
although the specific areas of N-doped samples were slightly high-
er than that of the pure BiVO4. The BET results of this work indicate
that N-doping has little impact on increasing the specific surface
area, which is consistent with the increased particle grain sizes
confirmed by XRD results.
3.4. UV–visible diffuse reflectance spectroscopy (DRS) analysis
The UV–Vis diffuse reflectance spectra for the pure BiVO4 and
N-doped BiVO4 samples are shown in Fig. 6. All the samples
showed a strong absorption in the UV- and visible-light regions;
this visible light absorption was due to the bandgap transition.
N-doping caused a red shift in the BiVO4 adsorption edge. The
sharp peaks of the spectra indicated that the visible light adsorp-
tion is due to the band gap transition [31]; the prolonged absorp-
tion tail extending to approximately 600 nm may be the result of
the oxygen vacancies formed and the increased presence of V4+
sites that occurred as the nitrogen concentration increased [32].
The band gaps of the samples were calculated from the DRS; the
absorption onsets of the samples were measured by linear extrap-
olation from the inflection point of the curve to the baseline, reach-
ing a quantitative estimate of the band gap energies. The band gap
energy (Eg, eV) values for the different samples were calculated
from the UV–Vis spectra using the equation Eg (eV) = 1240/k
(nm), where k represents the wavelength of the absorption onset
[33]. As shown in the spectra, the absorption onsets located at dif-
ferent wavelengths and their corresponding band gap energies are
summarized in Table 2. A reduction in the band gap energy for
N-doped samples occurred, compared to the undoped BiVO4. The
band gap energy values of N-doped BiVO4 photocatalyst decreased
with increasing N-doping content when the initial N/Bi molar ratio
reached values below 0.2. On the other hand, the band gap energy
values decreased when the molar ratio was above 0.2. The absorp-
tion of BVON-20 is the highest and corresponds to the lowest band
gap energy of 2.23 eV. In accordance with the XPS and XRD data,
this result might be due to the N atom and the increased presence
of oxygen vacancies in the crystal lattice. Because its band gap lies
within the visible-light region and caused considerable light
1.0
0.4
Absorbance
b 80
0.8 e 0.2
Absorbance
0.6 0.0
500 520 540
Wavelength/nm
0.4
0.2
0.0
400 500 600 700
Wavelength/nm
Fig. 6. UV–Vis spectra of different samples calcined at 500 °C: (a) BVO; (b) BVON-
13; (c)BVON-20; (d) BVON-25; (e) BVON-30.
75
absorption to occur, significant photocatalytic activity can be
expected from N-doped BiVO4 under visible light irradiation.
3.5. Photocatalytic activity
The photocatalytic activity of N-doped BiVO4 was evaluated by
measuring the decomposition of MO solution under visible light
irradiation. No degradation of MO was observed in the absence
of photocatalyst or illumination. To determine the effect of calcina-
tion temperature of the BiVO4 precursor on the photocatalytic
activity of N-doped BiVO4, the calcination temperature of BiVO4
was varied from 350 to 550 °C while holding the molar ratio of
N/Bi at 0.2. Fig. 7 shows that the MO decomposition rates de-
pended on the calcination temperature of BiVO4. The photocata-
lytic activity of N-doped BiVO4 increased when the calcination
temperature was as low as 500 °C; however, the catalytic activity
remarkably decreased when the calcination temperature reached
550 °C. In the latter case, the high temperature heat treatment
may have resulted in grain growth, which can lower photocatalytic
activity. The catalyst calcined at 500 °C exhibits the highest photo-
catalytic activity because of its highly crystallized phase. In con-
trast, the calcination temperature above 500 °C promotes further
grain growth, potentially leading to lower photocatalytic activity.
Therefore, the optimum calcination temperature was found to be
500 °C.
Fig. 8 shows the effect of N dopant concentration on the photo-
catalytic activity of BiVO4 catalysts calcined at 500 °C for MO
decomposition. The degradation rate of MO on the pure BiVO4
under visible light irradiation was very low, approximately 38%
in 50 min. Obviously, the photocatalytic activity of N-doped BiVO4
is superior to that of pure BiVO4 for degradation of MO. The photo-
catalytic activities of the photocatalysts increased with heightened
N-doping in cases where the initial molar ratio of N/Bi was less
than 0.2; whereas the activities decreased at greater initial molar
ratios of N/Bi. The highest photocatalytic activity resulted in a
MO degradation rate reaching approximately 85% at the optimum
N/Bi molar ratio of 0.2. The higher photocatalytic activity of nitro-
gen-modified BiVO4 herein observed may be attributed to the fol-
lowing reasons. On the one hand, the enhanced photocatalytic
activity of N-doped BiVO4 may be attributed to the increasing mo-
lar ratio of V4+/V5+ and the increasing amount of oxygen vacancies,
as confirmed by XPS results; this may create a shallow trap for the
photogenerated electron and hole, inhibiting recombination and
extending the lifetime of charge carriers [34]. Meanwhile, the
90
70
Decoloration rate%
60
560 580 600 50
40
30
350
c 20 400
d 450
a 10 500
0 550
800 -10
0 10 20 30 40 50
Irradiation time/ min
Fig. 7. Photocatalytic activity of BVON-20 calcined at different temperatures.
76 M. Wang et al. / Journal of Alloys and Compounds 548 (2013) 70–76

100 of N-doped BiVO4 photocatalysts extended a red shift when com-

BVO
pared with that of pure BiVO4. These were the main reasons that
BVON-13
the appropriate concentration of N dopant can significantly increase
BVON-20
80 the photocatalytic activity. However, the photocatalytic activity was
BVON-25
BVON-30 found to decrease with excessive N-doping. In addition, the some-
Decoloration rate%

what improved adsorption ability of MO molecules to the catalytic

60
surfaces after N-doping affected the photocatalytic activity slightly.

40
Acknowledgements

The authors gratefully thank the financially supports of the Na-

20 tional Natural Science Foundation of China (21207093), Education
Department of Liaoning Province (L2010471) and the Doctoral In-
novation Fund of Shenyang Ligong University, China
0 (2010BS0605).

0 10 20 30 40 50 References
Irradiation time/min
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