Ionothermal synthesis of BiOCl Nanostructures via a long-chain ionic liquid precursor route

Article abstract of DOI:10.1021/cg900940s

Ultrathin BiOCl nanoflakes, nanoplate arrays, and curved nanoplates have been successfully synthesized via an ionothermal synthetic route by using an ionic liquid 1-hexadecyl-3-methylimidazolium chloride ([C₁₆Mim]Cl) as "all-in-one" solvent, simply adjusting reaction temperature. The samples are characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), high-resolution transmission electron microscopy (HR-TEM) and Fourier transform infrared spectroscopy (FT-IR), separately. Possible formation mechanisms of various nanostructures were proposed in terms of crystal growth habit and dynamics. In addition, the excellent adsorption performance of the as-prepared BiOCl nanoplates makes them useful with potential applications in the aspect of wastewater treatment.

Full text of DOI:10.1021/cg900940s

DOI: 10.1021/cg900940s
Ionothermal Synthesis of BiOCl Nanostructures via a Long-Chain Ionic
Liquid Precursor Route
2
010, Vol. 10
2522–2527
Jianmin Ma, Xiaodi Liu, Jiabiao Lian, Xiaochuan Duan, and Wenjun Zheng*
Department of Materials Chemistry, College of Chemistry, Nankai University, Tianjin, 300071,
P. R. China
Received August 9, 2009; Revised Manuscript Received April 28, 2010
ABSTRACT: Ultrathin BiOCl nanoflakes, nanoplate arrays, and curved nanoplates have been successfully synthesized via an
ionothermal synthetic route by using an ionic liquid 1-hexadecyl-3-methylimidazolium chloride ([C Mim]Cl) as “all-in-one”
1
6
solvent, simply adjusting reaction temperature. The samples are characterized by X-ray diffraction (XRD), scanning electron
microscopy (SEM), transmission electron microscopy (TEM), high-resolution transmission electron microscopy (HR-TEM)
and Fourier transform infrared spectroscopy (FT-IR), separately. Possible formation mechanisms of various nanostructures
were proposed in terms of crystal growth habit and dynamics. In addition, the excellent adsorption performance of the as-
prepared BiOCl nanoplates makes them useful with potential applications in the aspect of wastewater treatment.
1
. Introduction
of cylindrical mesopores using hydrothermal synthesis ap-
1
3
prouach, respectively. To the best of our knowledge, how-
ever, there is no report on long-chain ILs employed in
ionothermal synthesis as solvent and precursor.
Ionic liquids (ILs) have been widely used in various fields
not only due to their unique properties such as negligible
vapor pressure and thermal stability but also because of their
BiOCl has drawn considerable attention because of its optical
properties and promising inductrustrial applications, such as
1
tunable properties and designable structures. The designable
feature of ILs is very suitable to the synthesis of inorganic
nanomaterials, for inorganic chemical processes are extremely
diverse. In recent years, many IL-involved processes, includ-
14
catalysts and photocatalysts, ferroelectreic materials, pig-
15
16
17
ments, photoluminescence, and so on. Inspired by their
excellent properties, there is thus considerable interest in im-
proved BiOCl systems. Various nanostructures including: nano-
platelet, nanobelts, nanowires, and nanoflowers, have been fabri-
cated via varioussynthetic routes, suchashydro/solvothermal
2
3
ing electrodeposition, photochemical reduction, electron
4
5
6
beam irradiation, sol-gel, solvothermal, and ionothermal
route, have been developed to synthesize inorganic nanos-
7
tructures. Among them, ionothermal synthesis is one of the
most promising methods. Ionothermal synthesis has been
developed into a versatile and advantageous synthesis
18
19
method, low-temperature vapor-phase synthesis, electro-
14e
spinning,
20
and reverse micromulsions, sonochemical
21
synthesis. Although well-defined nanostructures of BiOCl
have been fabricated, it is still a big challenge to develop an
alternativeroute tofabricate BiOCl nanostructures with novel
morphologies and improved properties.
7
technique. Compared to traditional hydro/solvothermal
synthesis, ionothermal synthesis has two advantageous fea-
tures: the ionic reaction medium can uniquely influence the
course of chemical reactions; ionic liquids can act as “all-in-
one” solvent/template for the synthesis of inorganic materials,
which enables the synthesis of inorganic materials with novel
Herein, we have reported the ionothermal synthesis of the
ultrathin BiOCl nanoplatelets, nanoplate arrayes and curving
nanoplates at different reaction temperatures. Furthermore,
the formation mechanism of BiOCl nanostructures have been
rationally explained in terms of crystal growth habit and
dynamics. It is expected that this ionothermal synthesis using
long-chain ionic liquid could be used to fabricate other polar
nanomaterials with novel morphologies and improved prop-
erties in the fields of optics, electrochemistry, and catalysis.
Moreover, experimental results demonstrated that the as-
synthesized BiOCl nanoplates had a high adsorption capacity
and high adsorption effiecnce, compared with some other
nanomaterials in the neutral media. We expect that the as-
synthesized BiOCl nanoplates would be promisingly applied
to adsorp heavy metal ions in the field of wastewater treat-
ment.
8
and improved properties.
ILs derived from 1-alkyl-3-methylimidazolium are of par-
ticular interest because, by changing the alkyl chain length
or the anion, a wide variation of properties such as hydro-
phobicity, viscosity, density and salvation strength can be
obtained. The long-chain ILs display the behavior of both
1
lyotropic and thermotropic liquid crystalline, and the am-
phiphlic ILs’ derivatives could bring out ordered self-orga-
For example, Zhou et al. demonstrated
that the long-chain 1-hexadecyl-3-methylimidazolium chlo-
ride ([C Mim]Cl) displayed significantly stronger tendency
toward self-aggregation and supramolecular templating in the
preparation of supermicroporous lamellar silica by nanocast-
ing, owing to the distinct polarizability of the head groups and
the special high-concentration phases of those ILs. Wang
et al. and Adams et al. found thatlong-chainILs couldbeused
to generate mesoporous silica with a 2D hexagonal structure
9
0
1
0a,11
nized structures.
16
1
2
2
. Experimental Section
2
.1. Synthesis of Ionic Liquid 1-Hexadecyl-3-methylimidazolium
Chloride ([C16Mim]Cl). [C16Mim]Cl was synthesized according to
2
2
reported procedures, 0.25 mol of 1-hexadecyl chloride and 0.25
mol of 1-methylimidazole were mixed and refluxed at 363 K for 24 h,
*
Corresponding author. Phone: þ86-22-23507951. Fax: þ86-22-23502458.
E-mail: zhwj@nankai.edu.cn.
r
pubs.acs.org/crystal
Published on Web 05/11/2010
2010 American Chemical Society

Article
Crystal Growth & Design, Vol. 10, No. 6, 2010 2523
then cooled to room temperature to obtain a waxy white solid,
which was dispersed in THF to recrystallize, and then washed with
THF three times. A white powder product was collected and dried
under a vacuum at room temperature.
pH of 2.5. UV-vis adsorption spectra (Shimadzu UV-1601PC)
were recorded at different intervals to monitor the process.
3
. Results and Discussion
2
mmol of Bi(NO 5H O and 10 mmol of [C16Mim]Cl were mixed
.2. Synthesis of BiOCl Nanostructures. In a typical synthesis, 1.0
3
)
3
2
3.1. Characterization of Structure and Morphology. Figure 1
shows the typical XRD pattern of the as-synthesized 2D BiOCl
nanoplatelets. The experimental XRD profile taken from the as-
synthesized BiOCl samples shows that all of the peaks may be
3
together, then transferred into a 20 mL Teflon-lined stainless auto-
clave. The autoclave was heated at 180 °C for 12 h, and then naturally
cooled to room temperature. The resulting precipitates were collected
and washed with ethanol and deionized water thoroughly and dried at
˚
indexed as the tetragonal phase BiOCl (cell constants a=3.89 A,
˚
5
0 °C in air. To investigate the effect of reaction temperature, we also
conducted ionothermal reactions at 120 and 200 °C.
.3. Characterization. The X-ray diffraction (XRD) patterns of
c=7.37 A; JCPDS File No. 06-0249). No peaks of any other
2
phases were detected, indicating that the products are very high-
purity, single-phase samples. In addition, the intense and sharp
diffraction peaks suggest that the as-synthesized products are
well-crystallized. The corresponding energy-dispersive X-ray
spectrum (EDS) (see Figure S1 in the Supporting Information)
further indicates that the products consist of Bi, O and Cl with a
ratio of about 1:1:1, which is consistent with the stoichiometric
BiOCl.
the products were recorded with Rigaku D/max Diffraction System
using a Cu KR source (λ = 0.15406 nm). The scanning electron
microscopy (SEM) images were taken with a JEOLJSM-6700F
field-emission scanning electron microscope (15 kV). The high-
resolution transmission electron microscopy (HR-TEM) images
were taken on a JEOL 2010 high-resolution transmission electron
microscope performed at 200 kV. The specimen of HR-TEM
measurement was prepared via spreading a droplet of ethanol
suspension onto a copper grid, coated with a thin layer of amor-
phous carbon film, and allowed to dry in air.
The morphology of as-prepared BiOCl nanoflakes were
characterized by SEM and TEM technique. Images a and b
in Figure 2show the morphology of as-prepared BiOCl
nanoflakes. As shown in Figure 2a, the sample is composed
of almost uniform nanoplates. Further investigation found
that the average thickness of BiOCl nanoflakes was about
2
.4. Water Treatment Experiments. The adsorption studies were
performed by mixing 0.1 g BiOCl nanoplates with 50 mL of
Cr solution in a 100 mL stopper conical flask. Standard acid
of 0.1 M HNO solution was used for pH adjustment. All the
K
2
2 7
O
3
adsorption experiments were carried out at room temperature and
1
8 nm and the edge is not very smooth, as shown in
Figure 2b. The delicate structure of BiOCl nanoflakes was
further characterized by TEM. Figure 2c shows the ultrathin
BiOCl nanoflakes. The corresponding fast Fourier transfor-
mation (FFT) image of BiOCl (inset of Figure 3d) indicates
that the layered structure is perpendicular to the c axis. The
HRTEM image of a single BiOCl nanoflake (Figure 3d)
exhibits good crystalline and clear lattice fringes. The inter-
planar spacing is 0.275 nm corresponding to the {110} planes
of the tetragonal system of BiOCl. The HRTEM observation
confirms that these BiOCl lamellae are perpendicular to the
c axis, which is well according to the XRD result.
3.2. Formation Mechanism of BiOCl nanoplates. Although
plates are typically observed for BiOCl, the ultrathin nanoplate
Figure 1. XRD pattern of BiOCl nanoplates obtained at 180 °C for
2
4 h.
Figure 2. (a, b) SEM images; (c) TEM image and (d) HR-TEM image of BiOCl nanoplates obtained at 180 °C for 24 h. Inset: its corresponding
fast Fourier transform (FFT) image.

2
524 Crystal Growth & Design, Vol. 10, No. 6, 2010
Ma et al.
Figure 3. (a) Clinographic projection of the unit cell of BiOCl; (b) clinographic projection of the coordination polyhedron around Bi.
is not easily obtained. Therefore, template effect of [C Mim]Cl
should be taken into account. Under this synthetic condi-
tion, [C Mim]Cl not only acts as reactant and solvent, but
Scheme 1. Schematic Illustration of the Interaction of Biocl
Crystal Planes and the Head Parts of [C16Mim]Cl
16
1
6
may also play a crucial role on the shape of the BiOCl as a
soft template and a capping agent. In recent years, based on
the special molecular structure and properties of the long-
chain ILs, some IL-crystal precursors containing organic
2
3
matrix have been used as templates in the synthesis system.
In the present case, the formation of the ultrathin flakelike
BiOCl can be possibly explained from the view of crystal
growth habit and dynamics. The BiOCl has a tetrahedron
structure (the unit cell of BiOCl shown in Figure 3a), which
2
4
can derive from the fluorite (CaF ) structure. Figure 3b
2
shows the clinographic projection of the coordination poly-
hedron around Bi. In Figure 3b, each Bi atom is eight-
coordinated by four O atoms and four Cl atoms in the form
of an asymmetric decahedron. The decahedra are linked to
each other by a common O- Cl edge along the a and b axes
forming infinite layers. Figure 3b also shows the coordina-
tion of O and Cl. Each O atom is linked to four Bi atoms,
forming a tetragonal pyramid with the O atom at its apex.
Also each Cl atoms forms with the neighboring Bi atoms. A
tetragonal pyramid with the Cl atom at its apex. Neighboring
decahedra form layers along (001), which are connected by
common O-Cl edges. Neighboring layers of decahedra are
connected by common O-O or Cl-Cl edges. The [BiOCl]
layers are stacked together by the van der Waals forces
chlorine source being replaced by distilled water and
1 mmol of [C16Mim]Cl. The experimental results indicate
that ionothermal process is vital to obtain ultrathin BiOCl
nanoplates.
3.3. Influence of Reaction Temperature. Reaction tempera-
ture played a crucial role in determining the morphologies of
BiOCl nanostructures. Curved nanoplates (Figure 4a,b) could
be obtained when the reaction was performed at 200 °C while
other condition kept constant. In images a and b in Figure 4,
the average thickness of curved nanoplates is about 14 nm,
which is thinner than that of nanoplates synthesized at 180 °C.
The curving of BiOCl nanoplates could be well-explained
as follows: as we know, the lamellar BiOCl possessed two-
dimensional layered structures. The edges of the lamellar
products might have many atoms with dangling bonds, and
they should possess enough energy to destabilize the two-
dimensional structures. To minimize the total surface energy,
the lamellar BiOCl tends to bend to form curved nanoplates
by saturating these dangling bonds, which is similar to the
1
4f
through the Cl atoms along the c-axis. Therefore, the
structure is not closely packed in this direction, and the ab
plane of BiOCl is favorable by the preferred adsorption of
þ
[
the solvent and a structure-directing agent for the crystal-
C Mim] cations. The alkyl imidazolium ion is part of
1
6
-
þ
lization. Along with the Cl , [C Mim] will be also aligned
1
6
and arrayed along the BiOCl layer, driven by the coulomb
coupling force with the Cl. It is reasonable to deduce that
the [C Mim]Cl, which is therefore a supramolecular solvent
1
6
23a,25
26
that has ordered structures similar to those in literatures,
is
reported literature.
selectively adsorbed on the (001) plane of BiOCl to effec-
tively inhibit crystalline growth in the [001] direction. There-
fore, the growth of BiOCl crystals are inhibited along the
c-axis to form thin BiOCl nanoflakes. The interaction be-
tween BiOCl crystal planes and the heads of [C Mim]Cl can
be schematically illustrated in Scheme 1. To investigate the
role of ionothermal parameters, controlled experiment was
conducted under hydrothermal condition. BiOCl nanoplates
with a thickness of about 50 nm (see Figure S2 in the
Supporting Information) can be obtained when reaction
other parameters kept the same except the solvent and
One the other hand, nanoplate arrays (Figure 5a, b) could
be obtained when reaction was conducted at low tempera-
ture (120 °C). In Figure 5b, the thickness of nanoplates of
nanoplate arrays is about 32 nm. The formation of nanoplate
arrays might be attributed to the state of ionic liquid
[C16Mim]Cl at lower temperature. It is well accepted that
[C16Mim]Cl is one of special liquid crystals. The liquid
crystal phase has properties and characteristics of the solid
state and of the liquid state. In a liquid crystal, the molecules
are oriented around a preferred direction. When reaction
temperature was carried out at low temperature (120 °C), the
1
6

Article
Crystal Growth & Design, Vol. 10, No. 6, 2010 2525
Figure 4. (a, b) SEM images, and (c) XRD pattern of as-synthesized BiOCl curved nanoplates.
Figure 5. (a, b) SEM images, and (c) XRD pattern of samples synthesized at 120 °C.
reaction solvent temperature [C Mim]Cl is more preferred to
keep characteristics of its solid state, in which the ionic liquid is
relative fixed and can not freely move. Therefore, when reac-
16
-
3þ
tants and product such as Cl , Bi , H O, and final products
2
are transferred more slower, the aggregated phenomenon
would appear, and thus nanoplate arrays would be produced.
Furthermore, the XRD data (Figure 5c) shows that the as-
synthesized samples are composed of a series of bismuth oxide
chlorides including: Bi O Cl (PDF: 41-0658), Bi O Cl
4
5
2
3 4
(36-0760), and BiOCl (PDF: 06-0249). In summary, influ-
ence of the reaction temperature on the morphology and
compositions of BiOCl is closely related to the state of ionic
liquid [C Mim]Cl.
2 2 7
Figure 6. UV-vis absorption spectra of K Cr O solutions after
treated with BiOCl nanoplates at different time intervals.
16
3
.4. Application in Water Treatment. In recent years,
considerable attention has been paid to the environmental
problems involving water treatment. Compared with the
traditional methods, the development of nanoscience and
nanotechnology offers an alternative by using nanosorbents,
nanocatalysts, bioactive nanoparticles, catalytic membranes
with nanostructures, and so on for the resolution or ameli-
oration of current water-treatment problems. Because of the
good chemical stability, low cost, and large surface area of
the as-synthesized BiOCl product, we expect it to be useful in
the water treatments. Moreover, because the size of the
BiOCl nanoplates was not too small, the solid/liquid separa-
tion would be easily realized by a facile method such as
centrifugation.
can be seen from the curve that the adsorption is rapid
2-
initially, and nearly 40% of the Cr O
2
can be absorbed
7
in a short time. Calculated from the patterns, the removal
capacities of Cr(VI) are 32 mg/g for the BiOCl nanoplates.
The experimental results demonstrate that the adsorption
2-
performance of BiOCl nanoplates for Cr O
2
is better than
7
28
that of mesoporous flowerlike NiO. The difference is
attributed to the different pH, for lower pH was favored by
the adsorption. The mechanism for the removal of the
2-
Cr O
2
contaminant can be explained from the perspective
7
of surface chemistry in aqueous phase. The surfaces of metal
oxides are generally covered with hydroxyl groups that vary
in forms at different pH. The surface charge is neutral at
pHzpc. Belowthe pHzpc, the adsorbent surface is positively
Herein, we used the as-obtained BiOCl nanoplates to
investigate their applications in water treatments. Potassium
dichromate (K Cr O ) is considered highly toxic pollutants
29
charged, anion adsorption occurs. These phenomena
further proved that the adsorption of the metal ions may
be a surface absorption process.
2
2
2
7
7
in water resources, and their efficient removal from water is
of great importance. In our experiments, 0.1 g of the as-
obtained BiOCl nanoplates was added into 50 mL solutions
with the initial concentrations of Cr(VI) being set at 40 mg/L
and adjusted to pH 2.5 at room temperature (25 °C). Figure 6
4
. Conclusion
In conclusion, this paper present a novel procedure for the
synthetic BiOCl with different nanostructures, such as ultrathin
2
7
-
shows the changes of Cr O
concentration versus time. It
2

2
526 Crystal Growth & Design, Vol. 10, No. 6, 2010
Ma et al.
nanoplates, curved nanoplates and nanoplate arrays. Reac-
tion temperature was found to play a crucial role in determin-
ing the morphologies of BiOCl nanostructures. This iono-
thermal synthetic route using long-chain ionic liquid has
potential application in fabricating other polar nanomaterials
with novel morphologies and improved properties in aspects
of optics, electrochemistry, and catalysis. Moreover, the as-
synthesized BiOCl nanoplates would be promisingly applied
to adsorp heavy metal ions in the field of wastewater treat-
ment.
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