Journal of Colloid and Interface Science 408 (2013) 33–42

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Journal of Colloid and Interface Science

www.elsevier.com/locate/jcis

Hydrothermal formation of N-doped (BiO)2CO3 honeycomb-like

microspheres photocatalysts with bismuth citrate and dicyandiamide as
precursors
Qiuyan Li, Haitao Liu, Fan Dong ⇑, Min Fu ⇑
Chongqing Key Laboratory of Catalysis and Functional Organic Molecules, College of Environmental and Biological Engineering, Chongqing Technology and Business University,
Chongqing 400067, PR China

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

Article history: In order to develop efficient visible light driven photocatalysts for environmental application, novel
Received 24 April 2013 N-doped (BiO)2CO3 honeycomb-like hierarchical microspheres were fabricated by an one-pot and tem-
Accepted 18 July 2013 plate-free hydrothermal method, firstly using bismuth citrate and dicyandiamide as precursors. The
Available online 30 July 2013
as-prepared samples were characterized by XRD, SEM, FT-IR, PL, XPS, and UV–vis DRS in detail. The
results indicated that the crystal structure and morphology of the samples can be tuned by hydrothermal
Keywords: reaction temperature. The source of nitrogen doping was from dicyandiamide, which also played a key
Nitrogen doping
role in hydrolyzing bismuth citrate to produce bismuth ions and citrate ions. The ammonium ions from
Hydrothermal synthesis
Growth mechanism
the decomposition of dicyandiamide reacted with bismuth ions and carbonate ions from decomposition
Bismuth subcarbonate of citrate ions, producing in situ N-doped (BiO)2CO3 microspheres. The doped nitrogen substituted for
Visible light photocatalytic oxygen in (BiO)2CO3 and was responsible for the band gap reduction of N-doped (BiO)2CO3. The as-pre-
Hierarchical microspheres pared N-doped (BiO)2CO3 microspheres were applied for removal of NO in air and exhibited excellent vis-
ible light activity, exceeding that of N-doped TiO2 and C-doped TiO2. Time-dependent evolutions of
crystal structure, morphology, chemical composition, and optical property were investigated systemati-
cally to reveal the growth mechanism of the honeycomb-like (BiO)2CO3 microspheres. The growth pro-
cess involved multiple steps, including reaction, nucleation, crystallization, aggregation, and
recrystallization. The proposed growth mechanism could provide new insights into the design and fab-
rication of hierarchical materials with advanced properties.
Ó 2013 Elsevier Inc. All rights reserved.

1. Introduction efficient visible light driven photocatalysts is highly desirable. Re-

Nowadays, environmental pollution and energy crisis have be-
come global issues and attracted intensive attentions. Photocata-
lytic technology, which can potentially utilize solar light to
degrade contaminants and convert solar energy at mild conditions,
has turned out to be an ideal technology in pollution control and
energy conversion [1]. Recently, photocatalytic materials with
hierarchical structures were investigated widely due to their en-
hanced properties [2,3]. With the rapid development of nanotech-
nology, many novel nanostructured materials with functional
properties (optical, electrical, magnetic, catalytic, mechanical,
chemical, etc.) were fabricated, which are favorable for the
advancement of photocatalytic materials [2–5].
The traditional photocatalysts (such as TiO2) can only be excited
by UV light which only occupies 4% in solar light. In order to
initiate photocatalysts utilize visible light irradiation, developing
⇑ Corresponding authors. Fax: +86 23 62769785 605.
E-mail addresses: dfctbu@126.com (F. Dong), fumin1022@126.com (M. Fu).
cently, bismuth-containing materials with hollow or/and hierar-
chical structure have attracted intensive attention. These
bismuth-containing materials include BiOX (X = Cl, Br, I), BiVO4,
BiFeO3, Bi2Ti2O7, Bi2MoO6, Bi2WO6 and Bi2Sn2O7, which exhibited
high photocatalytic performance in degrading organic pollutants
due to their special morphological structure with respect to surface
areas, pore structure, light harvesting, and charge separation [6–
14]. The bismuth-containing materials can also be applied in other
areas, such as catalysis, drug delivery, energy conversion, and
nano-devices [2,3,15–17].
Very recently, (BiO)2CO3 as a new bismuth-containing material
was found to display interesting performance in antibacterial and
environmental applications [18–23]. Compared with other bis-
muth-containing materials, (BiO)2CO3 exhibited various micro/
nanostructures. Therefore, many researchers were devoted to the
synthesis and application of (BiO)2CO3 materials. Chen and
co-workers have prepared (BiO)2CO3 nanotubes [18], nanobars
[24], nanoplates [24], cube-like [24], and nanoparticles [19,25].
Xie’s group have synthesized various (BiO)2CO3 microstructures

0021-9797/$ - see front matter Ó 2013 Elsevier Inc. All rights reserved.
http://dx.doi.org/10.1016/j.jcis.2013.07.040
34 Q. Li et al. / Journal of Colloid and Interface Science 408 (2013) 33–42
for degradation of aqueous dye RhB [20]. (BiO)2CO3 nanosheets and
flower-like structures were prepared by Huang et al. [21,22]. Cao’s
group have prepared persimmon-like (BiO)2CO3, exhibiting effi-
cient photocatalytic activity in degrading RhB and eosin sodium
salt under simulated solar irradiation [23]. Yu and co-workers re-
ported BiVO4/(BiO)2CO3 nanocompsites achieved by hydrothermal
treatment which exhibited enhanced visible light photocatalytic
activity [26]. (BiO)2CO3 hierarchical hollow microspheres were fab-
ricated by Dong’s group through a template-free method and
exhibited outstanding photocatalytic activity under both UV and
visible light irradiation [27,28]. However, the undoped (BiO)2CO3
cannot be excited by visible light due to its large band gap. In addi-
tion, the fabrication of N-doped (BiO)2CO3 honeycomb-like hierar-
chical microspheres using bismuth citrate and dicyandiamide as
precursors has not been reported until now.
In the present work, we developed a one-pot and template-free
hydrothermal method to fabricate N-doped (BiO)2CO3 hierarchical
microspheres, utilizing bismuth citrate and dicyandiamide as pre-
cursors. The as-prepared samples were characterized by various
techniques. The morphology and structure of (BiO)2CO3 can be
tuned by hydrothermal reaction temperature. The photocatalytic
activity test for removal of NO in air was carried out, and the as-
prepared N-doped (BiO)2CO3 honeycomb-like microspheres exhib-
ited excellent visible light photocatalytic activity due to nitrogen
doping and the special morphology. Time-dependent evolutions
of crystal structure, morphology, chemical compositions, and opti-
cal property were investigated systematically to reveal the growth
mechanism of honeycomb-like (BiO)2CO3 microspheres, which
could provide new insights into the design and fabrication of hier-
archical materials with advanced properties.
2. Experimental
2.1. Synthesis
All the reagents employed in this study were analytical grade
and were used without further purification. Distilled water was
used in all experiments. In a typical synthesis process, dicyandia-
mide (0.338 g) was first dissolved in distilled water (75 ml) in a
100 ml autoclave Teflon vessel and stirred for 10 min. Then, bis-
muth citrate (1.60 g) was added to the above solution and further
stirred for 30 min. The resulted precursor suspension was hydro-
thermally treated at a certain temperature for 24 h. After that,
the resulting solid was filtered, washed with water and ethanol
three times, and dried at 60 °C to get final N-doped (BiO)2CO3 sam-
ples. In order to investigate the effects of reaction temperature on
the formation of N-doped (BiO)2CO3, the temperature was con-
trolled at 150, 180 and 210 °C and the obtained samples were la-
beled as N-BOC-150 °C, N-BOC-180 °C and N-BOC-210 °C,
respectively. Undoped (BiO)2CO3 sample prepared without adding
dicyandiamide and was labeled as BOC [27]. C-doped TiO2 and N-
doped TiO2 were prepared according to previous report [29,30].
2.2. Characterization
The X-ray diffraction patterns of the samples were collected on
an X-ray diffractometer with Cu Ka radiation (XRD: model D/max
RA, Rigaku Co., Japan). FT-IR spectra were recorded on a Nicolet
Nexus spectrometer over the range of 400–4000 cm1. X-ray pho-
toelectron spectroscopy measurements were carried out to investi-
gate the surface chemical compositions, using Al Ka X-rays
(hm = 1486.6 eV) radiation source operated at 150 W (XPS: Thermo
ESCALAB 250, USA). In order to characterize the morphology of the
obtained products, a scanning electron microscope (SEM: JEOL
model JSM-6490, Japan) was used to collect the scanning electron
microscopy images. The UV–vis diffuse reflection spectra were ob-
tained for the dry-pressed disk samples with a Scan UV–vis spec-
trophotometer (UV–vis DRS: UV-2450, Shimadzu, Japan), using
BaSO4 as reflectance sample. The Photoluminescence (PL: F-7000,
HITACHI, Japan) was used to investigate the optical properties of
the obtained samples. Nitrogen adsorption–desorption isotherms
were obtained on a nitrogen adsorption apparatus (ASAP 2020,
USA) with all samples degassed at 100 °C for 12 h prior to
measurements.
2.3. Evaluation of photocatalytic activity
The photocatalytic activity of the as-prepared samples was
evaluated by removing NO at ppb level in a continuous flow reac-
tor. The volume of the reactor was 4.5 L (30 cm  15 cm  10 cm),
made of stainless steel, and covered with Saint-Glass. There was a
commercial tungsten halogen lamp (150 W) vertically placed out-
side the reactor. UV cutoff filter (420 nm) was applied to remove
UV light for the test of visible light photocatalytic activity. The
as-prepared sample (0.20 g) was added in distilled water (50 ml)
in a beaker and then coated onto a glass dish with a diameter of
12.0 cm. The coated dish was pretreated at 70 °C to remove water
in the suspension and placed in the center of the reactor after cool-
ing to room temperature. The NO gas was acquired from a com-
pressed gas cylinder at a concentration of 100 ppm of NO (N2
balance, BOC gas) with traceable National Institute of Standards
and Technology (NIST) standard. The initial concentration of NO
was diluted to about 450 ppb by the air stream. The flow rate of
mixed stream of air and NO was controlled at 2.4 L min1 and
15 mL min1, respectively. Then, the two gas streams were pre-
mixed by a three-way valve. After the adsorption–desorption equi-
librium was achieved, the lamp was turned on. The concentration
of NO was measured by a NOx analyzer (Thermo Scientific, 42i-TL)
every 1 min, which monitors NO and NOx (NOx represents
NO + NO2). The removal ratio (g) of NO was calculated by g
(%) = (1  C/C0)  100%, C is outlet concentration of NO after reac-
tion for time t, and C0 represents the inlet concentration.
3. Results and discussion
3.1. Crystal structure
Fig. 1 shows the XRD patterns of the samples prepared at dif-
ferent reaction temperatures. The diffraction peaks of the samples
obtained at the temperature of 180 °C and 210 °C can be indexed
Fig. 1. XRD patterns of the samples obtained at 150, 180, and 210 °C for 24 h.
 Q. Li et al. / Journal of Colloid and Interface Science 408 (2013) 33–42
to (BiO)2CO3 (JCPDS-ICDD Card No. 41-1488). Meanwhile, the
intensified (1 1 0) diffraction peak means a preferential orienta-
tion along the (1 1 0) plane. However, when the reaction temper-
ature is set at 150 °C, the diffraction peaks are obviously different
from the other two, implying that the sample is not (BiO)2CO3.
Based on further observation, we can find that the diffraction
peaks of N-BOC-150 °C can be assigned to bismuth citrate itself
[27], which suggests that bismuth citrate cannot be hydrolyzed
under the temperature of 150 °C. A closer look in Fig. 1 shows
that the peak intensity becomes stronger as the reaction temper-
ature is increased from 180 °C to 210 °C, which indicates that the
higher reaction temperature will result in the better crystallinity.
Note that there is a minor diffraction peak at around 27.5° for N-
BOC-180 °C and N-BOC-210 °C which can be indexed to Bi2O3.
This result suggests that the as-prepared N-doped (BiO)2CO3 sam-
ples consist of minor phase of Bi2O3. According to the crystal
structure of (BiO)2CO3, the (Bi2O2)2+ layers and CO2 3 layers are
orthogonally inter-grown. The internal layered structure would
mediate lower growth rate along certain axis to form nanosheet
morphology [31,32].
3.2. Morphological structure
The morphology and microstructure of the N-doped (BiO)2CO3
samples were characterized by SEM. In Fig. 2, we can easily find
that the morphologies of the samples under different reaction tem-
peratures are obviously different. Accordingly, the reaction tem-
peratures can affect the morphology of the samples.
Fig. 2a and 2b shows SEM images of N-BOC-150 °C sample. It
can be seen that the surface of the sample is rough with
many small particles attached. According to the XRD result, N-
BOC-150 °C is actually bismuth citrate. The rough surface of the
N-BOC-150 °C indicates that the reaction has taken place on the
surface of bismuth citrate. When the temperature reaches 180 °C,
large amount of honeycomb-like hierarchical microspheres assem-
bled by nanosheets with an average diameter of 3–4 lm are pro-
duced as shown in Fig. 2c. Obviously, a large number of pores are
formed during the hydrothermal process due to the self-assembly
of nanosheets. Moreover, the surface becomes smooth compared
with N-BOC-150 °C sample (Fig. 2d). No other morphologies can
be detected, indicating a 100% yield of (BiO)2CO3 superstructure.
When the temperature is elevated to 210 °C, another type of mor-
phology (loose aggregates) is generated as shown in Fig. 2g and 2 h.
The hierarchical architectures are partly disappeared. The high-
magnification SEM images (Fig. 2b, d and h) reveal that the nano-
sheets become thicker as the temperature increased.
The morphological structures of the samples obtained at 180 °C
and 210 °C are further investigated by TEM. Fig. 2e shows the TEM
image of N-BOC-180 °C, and the entire microsphere is composed of
self-assembled nanosheets. Fig. 2i demonstrates that the N-BOC-
210 °C is composed of randomly aggregated nanosheets. The
HRTEM images of a single nanosheet of N-BOC-180 and N-BOC-
210 °C are shown in Fig. 2f and j. The lattice spacing of N-BOC-
180 and N-BOC-210 °C are determined to be 0.27 nm and
0.34 nm, respectively, matching the spacing of the (1 1 0) and
(0 0 4) crystal plane of (BiO)2CO3.
3.3. Specific BET Surface Areas and Pore Structure
Fig. 3 shows the nitrogen adsorption–desorption isotherms and
the corresponding pore size distribution curves of N-BOC-180 °C
and N-BOC-210 °C. According to the BDDT classification, the major-
ity of physisorption isotherms can be classified into six types. Typ-
ically, the N-BOC-180 °C has an isotherm of type IV, indicating the
presence of mesopores. The N-BOC-210 °C has type III curve, which
implies the presence of macropores. The corresponding pore size
35
distribution curves of the samples are shown in Fig. 3b. It can be
seen that the pore distribution range for N-BOC-180 °C is broad
in the range of 2–50 nm and bimodal with small mesopores
(3.2 nm) and larger ones (22.7 nm), confirming the formation of
mesopores. The smaller mesopores can be attributed to the pores
formed among stacked nanosheets in the microsphere, and the
large mesopores can be ascribed to the pores formed among the
stack of microspheres. The existence of macropores in N-BOC-
210 °C is further confirmed by the corresponding pore size distri-
bution (Fig. 3b). The pore size distribution is located in the range
of 50–150 nm with a peak at 93.8 nm. Such macropores can be
ascribed to the pores formed among the randomly aggregated
nanosheets (Fig. 2g). The BET areas of N-BOC-150, N-BOC-180,
and N-BOC-210 °C samples are 4, 18, and 11 m2/g, respectively.
The pore volumes of N-BOC-180 and N-BOC-210 °C are 0.106 and
0.069 cm3/g, respectively.
3.4. Chemical composition by FT-IR and XPS
FT-IR analysis was carried out to investigate the chemical com-
position of the as-prepared samples, as shown in Fig. 4. As we
know, the ‘‘free’’ CO23 ions have four internal vibration forms, con-
taining symmetric stretching mode m1, anti-symmetric stretching
mode m3, out-of-plane bending mode m2, and in-plane bending
mode m4. The peak at 1067 cm1 can be assigned to mode m1. While
the peaks at 846 and 820 cm1 can be attributed to mode m2, the
mode m3 can be detected at 1468 and 1391 cm1. The peaks at
698 and 670 cm1 are ascribed to mode m4. The band groups of
m1 + m4 at 1756 and 1730 cm1 can also be observed. In addition,
the peak intensity of CO2 3 ions increases with the increasing reac-
tion temperature. The broad peak at 1580 cm1 and 3500 cm1 can
be assigned to the vibrations of surface hydroxyl groups and the
adsorbed water molecules [32,33]. Fig. 4 shows that the peak
intensity at 1580 cm1 decreases as the reaction temperature is in-
creased from 180 to 210 °C. As the peak at 1580 cm1 can be as-
signed to the vibrations of hydroxyl groups from the adsorbed
water molecules, the decrease in hydroxyl groups with increased
reaction temperature can be attributed to the enhanced crystallin-
ity of the samples. As the crystallinity of the sample is enhanced,
the adsorbed water molecules are decreased, leading to the de-
creased hydroxyl groups. The band at 548 cm1 can be attributed
to the Bi-O stretching. The bands of N-BOC-150 °C are similar to
bismuth citrate, which is consistent with XRD.
The XPS measurement was used to confirm the chemical state
of the elements on the surface of N-BOC-180 °C and N-BOC-
210 °C samples, as shown in Fig. 5. The two strong peaks at
159.1 and 164.4 eV in the spectra (Fig. 5a) are assigned to Bi4f7/2
and Bi4f5/2, respectively, which is the feature of Bi3+ in (BiO)2CO3
[34]. Fig. 5b shows the C1s spectra of (BiO)2CO3. The spectra can
be fitted to four peaks at 284.78, 285.93, 287.59, and 288.7 eV,
respectively. The peaks at 284.78, 285.93, and 287.59 eV can be
attributed to adventitious carbon species, while the peak at
288.7 eV can be ascribed to the CO2 3 in (BiO)2CO3. Meanwhile,
the O1s spectra (Fig. 5c) can be fitted to three peaks at 529.9,
530.99, and 532.2 eV, respectively. The peak at 529.9 eV is charac-
teristic of Bi-O in (BiO)2CO3 [35], and the other two peaks at 530.99
and 532.2 eV can be assigned to CO2 3 and hydroxyl groups on the
surface. N1s spectra (Fig. 5d) were recorded. The binding energy
centered at 400 eV indicates that nitrogen substituted for oxygen
atom and doped into (BiO)2CO3 lattice during the hydrothermal
process. The atomic concentration of doped nitrogen in N-BOC-
180 and N-BOC-210 °C is determined to be 2.1% and 0.50%, respec-
tively, indicating that the amount of doped nitrogen is decreased as
the reaction temperature is increased. This nitrogen doping effect
in (BiO)2CO3 is in accordance with the reported N-doped TiO2 [30].
In our case, the only source of nitrogen doping is dicyandiamide.
36 Q. Li et al. / Journal of Colloid and Interface Science 408 (2013) 33–42

Fig. 2. SEM, TEM, and HRTEM images of the samples obtained at 150 °C (a, b), 180 °C (c, d, e, f), and 210 °C (g, h, i, j) for 24 h.

The dicyandiamide plays dual roles in the formation of (BiO)2CO3
microspheres, one is to hydrolyze bismuth citrate, and the other
is to behave as a doped nitrogen source. The DOS of VB is shown
in Fig. 5e, and the valence band maximum (VBM) is determined
to be 1.7 eV. Interestingly, the N-BOC-180 °C sample shows new
electronic states above the valence band edge, indicating the for-
mation of mid-gap. Such mid-gap can be ascribed to the nitrogen
doping and make (BiO)2CO3 microspheres absorb visible light.
Compared to N-BOC-180 °C, the N-BOC-210 °C sample shows little
change in VB due to the very low doping content of nitrogen.
 Q. Li et al. / Journal of Colloid and Interface Science 408 (2013) 33–42
Fig. 3. N2 adsorption–desorption isotherms (a) and pore size distribution curves (b) of N-BOC-180 and N-BOC-210 °C.
Fig. 4. FT-IR spectra of N-BOC-150, N-BOC-180, and N-BOC-210 °C samples in the range of 400–2000 cm1 (a) and 2000–4000 cm1 (b).
3.5. UV–vis DRS and PL
Fig. 6a shows the UV–vis DRS spectra of the as-prepared sam-
ples. Compared with undoped (BiO)2CO3, the absorption edges of
N-doped (BiO)2CO3 samples prepared at 180 °C and 210 °C both
show a red shift. The N-BOC-180 °C sample especially exhibits
strong visible light absorption and the absorption edge shifts from
360 nm to 535 nm as the content of doped nitrogen is high (2.1%).
However, compared to N-BOC-180 °C, the absorption edge of N-
BOC-210 °C is blue-shifted to 375 nm, which is caused by the lower
amount of doped nitrogen (0.50%). Such shift in absorption edge
can also be reflected by the change in color1 of the samples from
yellow to light gray. As shown in Fig. 6b, the band gap energies of
N-BOC-150 °C, N-BOC-180 °C, and N-BOC-210 °C samples are esti-
mated to be 3.16, 2.38, and 3.15 eV, respectively, which are lower
than that of undoped (BiO)2CO3 (3.33 eV) [27]. The reduction in
the band gap can be assigned to the in situ doped nitrogen in
(BiO)2CO3, which makes the samples absorb visible light. This result
is also consistent with new electronic states observed in VB XPS.
Similar effects have been widely observed in N-doped TiO2 [30].
The band gap of N-BOC-180 °C sample is greatly reduced to
2.38 eV, which indicates the potential excellent photocatalytic activ-
ity under visible light irradiation.
Fig. 7 shows the PL spectra of the N-BOC-150 °C, N-BOC-180 °C,
and N-BOC-210 °C samples with an excitation wavelength of
280 nm. It can be seen that the fluorescence emission peaks are
mainly centered at 325–400 nm and 450–500 nm, which represent
1
For interpretation of color in Fig. 6, the reader is referred to the web version of
this article.
37
UV and visible light region, respectively. The peak at UV region can
be ascribed to the intrinsic band-to-band transition of (BiO)2CO3
and the peak at visible region is due to the band-to-band transition
of N-doped (BiO)2CO3. Further observation implies that the peak
intensity of N-BOC-180 °C sample is the lowest in both UV and vis-
ible light region. This fact suggests that the recombination rate of
electron–hole pairs on N-BOC-180 °C is the lowest. Therefore, we
can infer that N-BOC-180 °C sample may exhibit the most efficient
photocatalytic activity.
3.6. Photocatalytic activity
NO is a representative indoor and outdoor air pollutant. The
photocatalytic activity of the as-prepared samples is evaluated by
removal of NO in gas phase. As previous reported, NO was very sta-
ble and cannot be photolyzed under light irradiation in the absence
of photocatalyst [34]. In the presence of the as-prepared samples,
NO reacted with the photogenerated reactive radicals to produce
HNO2 and HNO3 [33,34].
Fig. 8 shows the variation of NO concentration (C/C0%) with
irradiation time over N-BOC-150 °C, N-BOC-180 °C, and N-BOC-
210 °C samples under visible light irradiation with C-doped TiO2
and N-doped TiO2 as references. Obviously, the N-BOC-150 °C sam-
ple exhibits negligible visible light activity because N-BOC-150 °C
is actually bismuth citrate. The NO removal ratio of C-doped TiO2
and N-doped TiO2 is 25% and 36%, respectively. However,
N-BOC-180 °C sample shows outstanding visible light photocata-
lytic activity with a NO removal ratio of 41%, much higher than
that of C-doped TiO2 and N-doped TiO2, although the surface area
of N-BOC-180 °C (18 m2/g) is smaller than that of C-doped TiO2
38 Q. Li et al. / Journal of Colloid and Interface Science 408 (2013) 33–42

Fig. 5. XPS spectra of N-BOC-180 and N-BOC-210 °C, Bi4f (a), C1s (b), O1s (c), N1s (d), and VB (e).

(123 m2/g) and N-doped TiO2 (63 m2/g). This result suggests that
N-doped (BiO)2CO3 microspheres are excellent visible light photo-
catalysts due to its intrinsic property. The hierarchical superstruc-
ture, which belongs to the intrinsic property, is in favor of the
diffusion of reaction intermediates to accelerate the reaction rate.
The special superstructure also allows multiple reflections of light,
which enhance the light-harvesting efficiency and increase the
quantity of photogenerated electrons and holes to participate in
the photocatalytic reaction, thus enhancing the photocatalytic
activity. The NO removal ratio of N-BOC-210 °C (33%) is lower than
that of N-BOC-180 °C, which can be attributed to the destroyed
hierarchical structures (Fig. 2g), the small surface areas and the
low amount of doped nitrogen (0.50%). In general, the visible light
photocatalytic activity of N-BOC-180 °C is the best due to the con-
tribution of hierarchical superstructure (Fig. 2c), strong visible
light absorption (Fig. 6), and low recombination rate of electron–
hole pairs (Fig. 7).
3.7. Growth mechanism of hierarchical microspheres
In order to investigate how to form such special hierarchical
nanosheet architectures, time-dependent experiment was carried
out to understand the detailed evolution process during hydrother-
mal reaction. The products obtained at different reaction times (6, 9,
12, 16, 24, and 48 h) were analyzed by several different characteriza-
tions. The reaction temperature was controlled at 180 °C with other
conditions unchanged. The resulted products at different reaction
times were labeled as N-BOC-6 h, N-BOC-9 h, N-BOC-12 h,
N-BOC-16 h, N-BOC-24 h, and N-BOC-48 h, respectively. Time-
dependent evolutions of phase structure, chemical composition,
 Q. Li et al. / Journal of Colloid and Interface Science 408 (2013) 33–42
Fig. 6. UV–vis DRS (a) and the plot of (ahm)1/2 vs. photon energy (b) of N-BOC-150, N-BOC-180, N-BOC-210 °C, and undoped (BiO)2CO3 samples.
Fig. 7. PL spectra of N-BOC-150 °C, N-BOC-180 °C, and N-BOC-210 °C samples.
Fig. 8. Visible light photocatalytic activity of N-BOC-150, N-BOC-180, N-BOC-
210 °C, C-doped TiO2, and N-doped TiO2 for the removal of NO in air.
morphological structure, and optical property were investigated
systematically to reveal the growth mechanism of such novel
superstructure.
3.7.1. Evolution of phase structure
Fig. 9a shows the XRD patterns of the samples prepared at
different reaction stages from 6 h to 48 h. It is obvious that the
39
diffraction peaks of the samples obtained at every stage are signif-
icantly different, indicating that the microstructures of the samples
grow gradually by prolonging the reaction time. When the reaction
time reaches 6 h, the diffraction peaks of the sample can be in-
dexed to bismuth citrate. Compared with Fig. 1, we can see that
the diffraction peak of N-BOC-6 h is similar to that of N-BOC-
150 °C. Therefore, N-BOC-6 h is determined to be bismuth citrate.
By extending the reaction time to 9 h, the peak intensity becomes
weaker compared with that of N-BOC-6 h, implying that bismuth
citrate starts to be hydrolyzed and intermediate product is formed.
Bismuth citrate is first hydrolyzed by a large amount of OH ions
provided by the dissolved NH3 which comes from the decomposi-
tion of dicyandiamide. The BiO+ and citrate ions are produced
simultaneously (reactions (1) and (2)). Under the hydrothermal
temperature of 180 °C, the citrate ions can be decomposed to pro-
duce carbonate ions (reaction (3)). However, bismuth citrate can-
not be hydrolyzed under the same conditions without
dicyandiamide, suggesting that dicyandiamide plays an important
role in hydrolyzing bismuth citrate to produce citrate ions.
NH3 þ H2 O ! NHþ4 þ OH ð1Þ
þ
BiðC6 H5 O7 Þ þ 3OH ! BiO þ C6 H5 O3
7 þH
þ
ð2Þ
C6 H5 O3 2
7 ! CO2 þ H2 O ! CO3 þ H
þ
ð3Þ
When the reaction time is prolonged to 12 h, all the diffraction
peaks are almost disappeared, suggesting that most of bismuth cit-
rate has been hydrolyzed. At this stage, there exist a large number
of ions in the solution which react with each other to form semi-
crystallized intermediate. By increasing the reaction time to 16 h,
the diffraction peaks become distinct and can be indexed to the
(BiO)4CO3(OH)2 phase (JCPDS-ICDD Card No. 38-0579), although
the crystallinity is not good. The (BiO)4CO3(OH)2 is produced by
the reaction (4) on the basis of previous reactions.
þ
4BiO þ CO2 
3 þ 2OH ! ðBiOÞ4 CO3 ðOHÞ2 ðSÞ ð4Þ
After reaction for 24 h, the diffraction peaks become stronger
and can be indexed to (BiO)2CO3 phase (JCPDS-ICDD Card No. 41-
1488). This result indicates that CO2 
3 substitutes for OH gradually
in (BiO)4CO3(OH)2 and the phase is transformed to (BiO)2CO3 be-
tween 16 and 24 h (reaction (5)). All the (BiO)4CO3(OH)2 interme-
diates are transformed to (BiO)2CO3 phase after reaction for 24 h.
The enlarged view (Fig. 9b) shows that the diffraction angle of
the dominant peaks at around 27–30° shifts slightly to higher val-
ues by increasing the reaction time. This fact suggests that the
phase transition from (BiO)4CO3(OH)2 to (BiO)2CO3 took place
40 Q. Li et al. / Journal of Colloid and Interface Science 408 (2013) 33–42

Fig. 9. XRD patterns of the samples obtained at 180 °C for different reaction times from 6 to 48 h (a), enlarged view of (1 0 3) and (1 1 0) diffraction region (b).

during this reaction process. When the reaction time is prolonged 3.7.3. Evolution of morphological structure
to 48 h, the peak intensity becomes stronger and the pure (BiO)2- SEM analysis was carried out to directly observe the morpho-
CO3 phase with good crystallinity is obtained. During the forma- logical evolution of the samples between 6 h and 48 h. As shown
tion, crystalline ðBiOÞ2 CO3 ; NHþ
4 is simultaneously doped into the in Fig. 11, the morphological structure at every stage is signifi-
lattice of (BiO)2CO3, subsequently modifying its band structure. cantly different. Specifically, the growth process of (BiO)2CO3 hier-
archical superstructures includes the following stages:
ðBiOÞ4 CO3 ðOHÞ2 ðSÞ þ CO2
3 ! ðBiOÞ2 CO3 ðSÞ þ 2OH

ð5Þ Initially, the precursor suspension is composed of bismuth cit-
rate and dicyandiamide. After hydrothermal treatment for 6 h, sub-
stantial irregular particles are obtained as shown in Fig. 11a and b.
3.7.2. Evolution of chemical composition
According to the results of XRD and FT-IR, these irregular particles
In order to investigate the evolution of chemical composition of
are bismuth citrate. When the reaction time reaches 9 h, the SEM
the samples during the hydrothermal process, FT-IR analysis was
images (Fig. 11c and d) obviously show that the microstructures
carried out. The spectra of the samples obtained at different reac-
become loose, indicating that bismuth citrate starts to be hydro-
tion stages are shown in Fig. 10. At first sight, we can find that
lyzed (reaction 2). The XRD pattern of N-BOC-9 h can also prove it.
the bands of the samples obtained at 6 h and 9 h are distinctly dif-
After reaction for 12 h, the microstructures become looser as
ferent from other samples. Based on further observation, the dif-
shown in Fig. 11e. Some semi-crystallized irregular particles cir-
fraction peaks of N-BOC-6 h are similar to that of bismuth citrate,
cled in Fig. 11f are produced during the stage due to the subse-
consistent with the result of XRD. When the reaction time is in-
quent process of reaction, nucleation, aggregation, and
creased to 9 h, the bands of bismuth citrate become weaker. Some
crystallization. A large number of ions came from the hydrolysis
peaks at 846 cm1 and 670 cm1 appeared and can be ascribed to
of bismuth citrate react with each other in the solution to form nu-
CO2
3 . The result implies that bismuth citrate starts to be hydro-
cleus. Then, the nucleus continues to crystallize and small particles
lyzed and CO2 3 ions are gradually formed. From 12 h to 16 h, the
are generated. These small particles dissolve and recrystallize to
peak intensity of CO23 becomes stronger. When the reaction time
form large particles. The consumption of small particles and gener-
is increased to 24 h, the peak intensity of hydroxyl groups in
ation of large particles are complied with the well-known ‘‘Ost-
(BiO)4CO3(OH)2 decreases rapidly and the peak intensity of carbon-
wald ripening’’ mechanism [36,37].
ate ions increases quickly with the prolonged reaction time,
After reaction for 16 h, a large amount of honeycomb-like
which can be ascribed to the CO2 
3 substitutes for OH and makes
microspheres are obtained as shown in Fig. 11g. While they are
(BiO)4CO3(OH)2 transform into (BiO)2CO3. Combining the result of
stacked together and interconnected by the un-dissolved matter,
XRD with FT-IR, it can be concluded that (BiO)4CO3(OH)2 is an
some small particles are still adhered to the surface of the sample
important intermediate on the way to form (BiO)2CO3.

Fig. 10. FT-IR spectra of the samples obtained at 180 °C for different reaction times from 6 to 48 h in the range of 400–2000 cm1 (a) and 2000–4000 cm1 (b).
 Q. Li et al. / Journal of Colloid and Interface Science 408 (2013) 33–42
Fig. 11. SEM images of samples obtained at 180 °C for different reaction time, 6 h
(a, b), 9 h (c, d), 12 h (e, f), 16 h (g, h), 24 h (i, j), and 48 h (k, l).
as circled in Fig. 11g, indicating that the sample is not transformed
into (BiO)2CO3 completely, which can be proved by the XRD pat-
tern of N-BOC-16 h. Enlarged view in Fig. 11h shows that the
microstructure of the sample is hierarchical microsphere self-
assembled by many nanosheets. Given such a tremendous change,
a series of reactions must take place between 12 h and 16 h (reac-
tion 4 and 5). The production of the nanosheets is at the expense of
large particles. Then, the nanosheets gradually aggregated together
to form microspheres.
41
Fig. 12. UV–vis DRS spectra of the samples obtained at 180 °C for different reaction
time from 6 to 48 h.
After reaction for 24 h, the honeycomb-like hierarchical micro-
spheres with an average diameter of 3–4 lm are dispersed from
the stacks as shown in Fig. 11i. All the small particles attached to
the surface are disappeared. The enlarged view (Fig. 11j) shows
that the nanosheets become thicker compared with the sample ob-
tained at 16 h, indicating that the nanosheets continue to grow be-
tween 16 h and 24 h. The disappeared small particles take part in
the dispersion and anisotropic growth of the microspheres. Well-
defined (BiO)2CO3 hierarchical microspheres self-assembled by
nanosheets are obtained at this stage. The XRD pattern and FT-IR
spectra of N-BOC-24 h can prove it. When the reaction time is in-
creased to 48 h, the morphological structures have little change,
suggesting that 24 h is an appropriate time to prepare (BiO)2CO3
hierarchical microspheres.
3.7.4. Evolution of optical property
In order to investigate the evolution of optical property of N-
doped (BiO)2CO3, UV–vis DRS analysis was carried out, as shown
in Fig. 12. It can be seen that the samples display strong absorption
in the UV–visible region from 220 to 600 nm. When the reaction
time is 6 h, the absorption edge of the sample is at about
450 nm. By extending the reaction time from 9 to 16 h, the absorp-
tion edge of the samples shows an obvious red shift, indicating that
band gap transition took place during this stage due to nitrogen
doping. Finally, the absorption edge of N-BOC-24 h reaches
550 nm which is much larger than that of undoped (BiO)2CO3.
Interestingly, the spectra of the samples obtained at 9, 12, and
16 h show two absorption edges, suggesting that the samples con-
tain two semiconductors during the reaction process. Combining
the result with XRD and FT-IR, we can find that one of the semicon-
ductors is (BiO)4CO3(OH)2, which has been identified as an impor-
tant intermediate. When the reaction time reaches 24 h, the
spectra display only one absorption edge, suggesting that
(BiO)4CO3(OH)2 has completely transformed into N-doped
(BiO)2CO3. When the reaction time is prolonged to 48 h, the visible
light absorption of the sample is weakened, suggesting that 24 h is
an optimized reaction time.
4. Conclusion
In summary, we have successfully fabricated novel N-doped
(BiO)2CO3 honeycomb-like hierarchical microspheres. The synthe-
sis was based on a hydrothermal treatment of bismuth citrate and
42 Q. Li et al. / Journal of Colloid and Interface Science 408 (2013) 33–42

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