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The synthesis of a novel magnetic demulsifier and

its application for the demulsification of oil-
Cite this: J. Mater. Chem. A, 2014, 2, 94
charged industrial wastewaters
Shuqiang Li,† Naixu Li,† Shanbo Yang, Fangyuan Liu and Jiancheng Zhou*

Water produced from alkaline–surfactant–polymer flooding technology is more difficult to treat than
Published on 11 October 2013. Downloaded on 29/08/2014 11:15:52.

Received 29th July 2013
Accepted 10th October 2013
DOI: 10.1039/c3ta12952g
www.rsc.org/MaterialsA
that from water flooding. In this study, a novel magnetic demulsifier, called M-5010, was synthesized
through the reaction of 5010, a type of demulsifier currently used in oilfields, and epoxy group
functionalized Fe3O4@SiO2 microspheres. The oil removal rates and effect of the demulsifier dosage
as well as the settling time were investigated. It was found that the oil removal rate of M-5010 was
higher than that of 5010 under the same conditions. In addition, M-5010 can be recycled and reused
by using an external magnetic field that acts as a material phase separator. Accordingly, we found that
M-5010 is still effective after being reused for 5 cycles. Our results indicate that the magnetic
demulsifier we fabricated can be used as an effective and recyclable material for the removal of oil
from oil contaminated wastewater.

consequence, it is necessary to nd a suitable method with

1 Introduction
At present, in China, alkaline–surfactant–polymer ooding
technology is widely used for oil extractions in order to improve
the recovery of oil, therefore more and more wastewater has
been generated.1 The water produced from this technology
contains residual chemicals and is more difficult to treat than
that from water ooding.2 Therefore, it is necessary to purify the
produced water so that it can be reused in order to protect the
environment. If the type of produced water has a high oil
content and rather small oil droplet size it is termed an oil-in-
water (O/W) emulsion.3 O/W emulsions, which are comprised of
oil droplets, surfactants and co-surfactants, are highly stable
because the surfactants reduce the oil–water interfacial tension
and zeta potential at the surface of the oil droplets.4 Polymers
can increase the viscosity of the aqueous phase,5 the produced
water forms a complex and stable O/W emulsion system and an
electrical double layer may exist at the surface of this O/W
emulsion.6 Thus, it is more difficult to dispose of the produced
water. As a result, this brings about a lot of environmental
problems. Considerable effort has been made to develop effec-
tive treatment techniques such as otation,7 chemical coagu-
lation coupled with otation,8 chemical and electrochemical
techniques,9 chemical demulsication,10 membrane separa-
tion11 and biotechnology.12 Although these methods have been
proven to be effective techniques, their use can not fully meet
the requirements for this type of produced water. As a
School of Chemistry and Chemical Engineering, Southeast University, Nanjing,
211189, China. E-mail: jczhou@seu.edu.cn
† These authors contributed equally to this work.
properties including a high oil removal rate and fast oil–water
separation.
Since magnetic materials possess special magnetic prop-
erties that allow them to be conveniently separated from
complex multiphase systems, these materials have attracted a
signicant amount of interest during the past decade.
Magnetic materials have been widely used in a variety of elds,
such as separation and purication,13 catalysis,14 drug
delivery,15 and contrast enhancement in magnetic resonance
imaging.16 Among these materials, magnetite (Fe3O4) is
considered to be an ideal candidate because of its low cyto-
toxicity and good biocompatibility.17 Y. F. Shen et al.18 added
Fe3O4 nanoparticles into wastewater contaminated with metal
ions and found that the contaminants could be effectively and
conveniently removed. However, during the process of appli-
cation, the chemical reactivity of the magnetite particles is not
satisfactory. From this point of view, it is necessary to develop
efficient strategies in order to improve the chemical reactivity
of magnetite particles. As previously reported,19 a common
protection strategy is the formation of a core–shell structure,
i.e., the magnetite particles form a core that is coated by a
shell. The shell can be divided into two types: organic shell
coatings, including surfactants and polymers, or inorganic
coating components, including silica, carbon and precious
metals. Moreover, a protective shell not only protects the
magnetite particles against oxidation, but can also be used for
further functionalization of the particles with functional
groups, such as amines, carboxyl groups and so on. Silica
coated core–shell magnetite nanoparticles, i.e., Fe3O4@SiO2,
are usually prepared because the SiO2 shell has abundant

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Paper
surface hydroxyl groups, which allow easy subsequent func-
tionalization of the magnetite nanoparticles.20 Recently, the
introduction of magnetic properties into functional materials
has attracted researchers’ attention. For example, Z. N. Liu
et al.21 synthesized Fe3O4 nanoparticles coated with dense
nonporous silica as an inter layer and mesoporous silica as an
outer layer and then functionalized the Fe3O4 nanoparticles
with poly methyl acrylate through a plasma polymerization
technique. These nanoparticles could remove most of
the pollutants from oileld wastewater. In contrast to this,
J. X. Peng et al.4 synthesized a novel magnetic demulsier by
graing ethyl cellulose onto the surface of amino-functional-
ized Fe3O4 nanoparticles coated with silica in order to remove
water from a diluted bitumen emulsion. P. Calcagnile et al.22
prepared a novel composite material based on polyurethane
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foam functionalized with colloidal magnetic iron oxide
nanoparticles, which efficiently separated oil from water.
However, the above materials can not effectively treat oileld
O/W wastewater.
In this study, Fe3O4 microspheres were rst coated with a
thin shell of amorphous silica. These Fe3O4@SiO2 microspheres
were then modied using the silane coupling agent, (3-glyci-
doxypropyl)trimethoxysilane. Subsequently, the epoxy group
modied Fe3O4@SiO2 microspheres were reacted with a
demulsier known as 5010, which is used in oilelds and is a
type of polyether polyol. The prepared novel magnetic demul-
sier was applied to O/W wastewater and the oil removal rate
was higher than that of the 5010 demulsier used in oilelds.
Moreover, this novel magnetic demulsier could be rapidly
separated in the presence of an external magnetic eld and then
reused, which means that the dosage of demulsier used to
treat the oileld wastewater could be reduced. To the best of our
knowledge, there are no reports concerning the treatment of
O/W wastewater from oilelds with this kind of magnetic
demulsier. This is the rst report on the synthesis of a
magnetically responsive demulsier applied to O/W emulsions
produced from oilelds.
2 Experimental methods
2.1 Chemicals
Anhydrous FeCl3, trisodium citrate, 4-dimethylaminopyridine
(DMAP), tetraethyl orthosilicate (TEOS), polyacrylic acid, ethylene
glycol, (3-glycidoxypropyl)trimethoxysilane (GPTMS), sodium
acetate, sodium dodecyl sulfate (SDS), ammonia (28 wt%), poly-
acrylamide, ethanol and toluene. All of the chemicals were
purchased from the Shanghai Chemical Reagent Company in
analytical grade, and were used as received without further
purication.
2.2 Procedure for the synthesis of the novel magnetic
demulsier
2.2.1 Synthesis of monodisperse Fe3O4 microspheres.
Monodisperse Fe3O4 microspheres were synthesized according
to the method reported by Zhao et al.17 with some modication.
Briey, FeCl3 (1.2 g) and trisodium citrate (0.5 g) were dissolved
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in ethylene glycol (60 mL) and NaAc (1.8 g) and polyacrylic acid
(0.02 g) were subsequently added. The mixture was stirred
vigorously for 30 min and then sealed in a Teon-lined stain-
less-steel autoclave. The autoclave was heated to 200
C and
maintained at that temperature for 10 h. The autoclave was then
allowed to cool to room temperature naturally. The black
product was washed with ethanol and deionized water several
times. Finally, the product was stored in deionized water for
further use.
2.2.2 Synthesis of Fe3O4@SiO2 and the epoxy group-func-
tionalized Fe3O4@SiO2 microspheres. The Fe3O4 microspheres
were prepared through a modied Stober process as follows: an
aqueous solution (25 mL) containing Fe3O4 microspheres (0.5 g)
was added to a three-neck round-bottom ask, then mixed with
ethanol (100 mL) and an ammonia solution (1.0 mL, 28 wt%)
under vigorous mechanical stirring for 15 min at room
temperature. Aerwards, 0.5 mL of tetraethyl orthosilicate
(TEOS) was added, and the reaction was allowed to proceed for 6
h under mechanical stirring at room temperature. The resulting
Fe3O4@SiO2 microspheres were collected using a magnet and
then washed with ethanol several times. The nal Fe3O4@SiO2
microspheres were vacuum dried at 70
C for 8 h.
The epoxy group-functionalized Fe3O4@SiO2 microspheres
were prepared by surface functionalization of the Fe3O4@SiO2
microspheres using (3-glycidoxypropyl)trimethoxysilane
(GPTMS) as a silane coupling agent. Fe3O4@SiO2 microspheres
(0.6 g) and toluene (120 mL) were added to a four-neck round-
bottom ask and then ultrasonically dispersed for 30 min.
GPTMS (1.5 mL) was then added into the ask, and the mixture
was reuxed at 80
C with continuous mechanical stirring for 8
h under a ow of nitrogen. The functionalized Fe3O4@SiO2
microspheres were collected with a magnet then washed with
ethanol several times and vacuum dried at 60
C for 12 h. The
obtained product is hereaer referred to as Fe3O4@SiO2-epoxy.
2.2.3 Synthesis of the novel magnetic demulsier.
Fe3O4@SiO2-epoxy (0.2 g) and toluene (100 mL) were added to a
four-neck round-bottom ask and ultrasonically dispersed for
30 min. Demulsier 5010 (0.8 g) and DMAP (0.08 g) were then
added into the ask, and the mixture was reuxed at 120
C with
continuous mechanical stirring for 5 h under a ow of nitrogen.
The nal product was collected with a magnet and then washed
with ethanol several times. Finally, the product was vacuum
dried at 70
C for 8 h. The novel magnetic demulsier is here-
aer referred to as M-5010.
2.3 Preparation of the O/W emulsion
The O/W emulsion was prepared in the laboratory, using a
commercial oil (ExxonMobil Co. USA). Oil (0.5 g), SDS (0.001 g),
polyacrylamide (0.05 g) and 500 mL H2O were added into a
beaker. The mixture was stirred using a homogenizer operated
at 1500 rpm for 30 min, which caused disruption of the droplets
by a combination of turbulence and intense shear ow. In this
process, SDS, which has hydrophilic and hydrophobic groups,
was absorbed at oil–water interface forming a stable layer on the
surfaces of the droplets. By adsorbing at the interface, SDS can
reduce the free energy of the system and the interfacial
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Journal of Materials Chemistry A Paper

tension.23 Therefore, the obtained emulsion can be kept

stable. The resulting emulsion is hereaer referred to as the
O/W emulsion and the oil content in the O/W emulsion is
about 1000 mg L1.

2.4 Demulsication tests

Typically, different quantities of the M-5010 and 5010 demul-
siers were added to 25 mL of the O/W emulsion in a color-
imeter tube and the mixture was shaken 200 times by hand. The
mixture was then placed in a water bath and heated at 60
C for
a period of time. Subsequently, the solution at the bottom of
colorimeter tube was removed and the oil content in the solu-
tion was measured using a spectrophotometric technique. Each
sample was repeated 3 times and the oil content reported is the
average of the three repetitions. The demulsication perfor-
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mance is derived from the oil removal rate, which can be

calculated from the equation:
C0  C
R¼  100%
C0
where R (%) is the oil removal rate, C0 (mg L1) is the initial oil
content, and C (mg L1) represents the oil content aer the
demulsier was added.

2.5 Recycling tests

In order to evaluate the reusability of M-5010, the used M-5010
was separated from the solution using a magnet aer the Fig. 1 TEM images of (a) Fe3O4 and (b) Fe3O4@SiO2 microspheres.
demulsication test and thoroughly washed several times with
both petroleum ether and ethanol. The washed M-5010 was
vacuum dried at 50
C for 8 h for use in the next cycle. Similar to the microspheres have well dened core–shell structures. In
the above the demulsication test, the recycled M-5010 was this case, it should be noted that the uniform silica layer was
added to the O/W emulsion. In our study, 5 recycles were per- formed on the individual magnetite particle through a sol–gel
formed in order to test the reusability of this type of novel process involving the hydrolysis and condensation of tetraethyl
magnetic demulsier. orthosilicate (TEOS) in a mixture of deionized water, ethanol
and ammonia.24
2.6 Characterization In order to investigate the crystal structures of Fe3O4,
Fe3O4@SiO2 and Fe3O4@SiO2-epoxy, XRD experiments were
The morphology of the samples was characterized by trans- carried out. As shown in Fig. 2a, diffraction peaks at 2q values of
mission electron microscopy (TEM) with a Hitachi H-600
microscope operating at 120 kV. X-ray diffraction (XRD)
patterns were recorded using a Rigaku D/MAX-R diffractom-
eter with a copper target at 40 kV and 30 mA. Fourier transform
infrared (FT-IR) spectra were obtained with a Bruker Tensor 27
FT-IR spectrometer at room temperature using KBr pellets.
Thermal analysis experiments were collected using a TA Q-600
TGA apparatus operated at a heating rate of 10 K min1 under
a nitrogen atmosphere. Magnetic hysteresis loops were
measured using a vibrating sample magnetometer (VSM,
Lakeshore 7407) with an applied eld between 20 000 Oe and
20 000 Oe at 300 K.

3 Results and discussion

The morphology of the magnetite particles is shown in Fig. 1a.
As revealed by TEM, the magnetite particles are uniform and
nearly monodisperse spherical particles with a mean diameter Fig. 2 XRD patterns of the (a) Fe3O4, (b) Fe3O4@SiO2, and (c)
of about 420 nm. On the other hand, it is clear from Fig. 1b that Fe3O4@SiO2-epoxy microspheres.

96 | J. Mater. Chem. A, 2014, 2, 94–99 This journal is © The Royal Society of Chemistry 2014

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30.4
, 35.5
, 43.3
, 57.4
and 62.8
were observed as for Fe3O4.
Obviously, these diffraction peaks could be easily indexed to the
reections of standard Fe3O4, which conrmed that the
magnetite microspheres were successfully synthesized. In
contrast, similar diffraction peaks are also found for the
samples of Fe3O4@SiO2 and Fe3O4@SiO2-epoxy, as shown in
Fig. 2b and c, suggesting that the Fe3O4 microspheres were well
retained in the silica layer. No diffraction peaks corresponding
to SiO2 were observed because silica is amorphous.
FTIR spectra of Fe3O4, Fe3O4@SiO2, Fe3O4@SiO2-epoxy,
5010 and M-5010 are shown in Fig. 3. Typical bands associated
with Fe–O stretching are visible at around 585 and 443 cm1.
For Fe3O4, Fe3O4@SiO2 and Fe3O4@SiO2-epoxy, the bands
observed at around 1635 and 1384 cm1 correspond to the
carboxylate group of trisodium citrate. Due to the citrate
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groups, the Fe3O4 microspheres have excellent dispersibility
in polar solvents, which is benecial for the SiO2 coating and
modication processes. In addition, as shown in Fig. 3a and b,
a new strong band appears around 1093 cm1 and can be
ascribed to Si–O–Si vibrations, indicating that there is a
coating of silica on the magnetite surface. Compared with
Fig. 3b, Fig. 3cshows new peaks at 2923 and 2856 cm1, cor-
responding to the –CH2– groups of GPTMS, which can provide
epoxy functionalities and exhibits many advantageous prop-
erties such as hydrophilicity, specic chemical reaction
behaviour and high reactivity. Due to its three-membered ring,
an epoxy group can react with different functional groups such
as amines or hydroxyl groups. Moreover, the peak at 885 cm1
can be assigned to the epoxy groups.25 In Fig. 3d, a broad band
around 3400 cm1 is observed that is caused by O–H stretch-
ing vibrations, reecting the fact that 5010 contains abundant
hydroxyl groups. This is because 5010 was synthesized using
an initial self-made agent in order to enable copolymerization
with ethylene oxide and propylene oxide. Therefore, the novel
magnetic demulsier can be prepared through the chemical
reaction between the epoxy functionalities of the micro-
spheres and the hydroxyl groups of 5010. Fig. 3e also indicates
that the reaction happens.
Fig. 3 FT-IR spectra of (a) Fe3O4, (b) Fe3O4@SiO2, (c) Fe3O4@SiO2-
epoxy, (d) M-5010, and (e) 5010.
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The amount of the organic compound on the surface of
the samples was determined using thermogravimetric anal-
ysis (TGA) under a nitrogen atmosphere. It is known that the
decomposition of an organic compound can occur when the
temperature is gradually increased. Therefore, the weight
loss of the samples can be determined. Fig. 4 shows the
variation of the weight of the sample versus temperature for
Fe3O4, Fe3O4@SiO2, Fe3O4@SiO2-epoxy and M-5010. With
regards to the Fe3O4 and Fe3O4@SiO2 samples, a weight loss
(4.58 wt%) is observed at temperatures below 300
C and this
phenomenon may be attributed to the desorption of water.
TGA analysis of Fe3O4@SiO2-epoxy shows a weight loss (11.69
wt%) from 0 to 800
C, which may indicate decomposition of
the hydration water and epoxy groups. In addition, a signif-
icant weight loss (48.64 wt%) is observed for M-5010, which
could mainly be attributed to the decomposition of 5010,
which is an organic compound. These results clearly imply
that 5010 has been successfully graed onto the surface of
Fe3O4@SiO2-epoxy.
The vibrating sample magnetization (VSM) curves for Fe3O4,
Fe3O4@SiO2, Fe3O4@SiO2-epoxy and M-5010 are shown in
Fig. 5. It can be seen that Fe3O4, Fe3O4@SiO2, Fe3O4@SiO2-
epoxy and M-5010 all exhibit ferromagnetic behavior at 300 K.
In these circumstances, the saturation magnetization (Ms)
values of Fe3O4, Fe3O4@SiO2, Fe3O4@SiO2-epoxy and M-5010
are 49.3 emu g1, 42.3 emu g1, 40.4 emu g1, 35.1 emu g1,
respectively. Compared with the bare Fe3O4 microspheres, the
other three sample exhibited lower saturation magnetization
values. It is likely that a silica coating formed on the Fe3O4
microspheres. Although the saturation magnetization of
M-5010 is decreased, M-5010 still remains magnetically
responsive. Therefore, M-5010 can be completely separated
from an O/W emulsion with the help of a magnet, as shown in
the photograph in Fig. 6. M-5010 was separately dispersed in
deionized water and an O/W emulsion before the demulsica-
tion test, as shown in Fig. 6a and b, respectively. Fig. 6c shows a
prepared O/W emulsion. Fig. 6d reveals the solution aer the
demulsication test was carried out using a magnet, which
Fig. 4 TGA curves of (a) Fe3O4, (b) Fe3O4@SiO2, (c) Fe3O4@SiO2-
epoxy, and (d) M-5010.
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Fig. 5 Magnetization curves of (a) Fe3O4, (b) Fe3O4@SiO2, (c)
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Fe3O4@SiO2-epoxy, and (d) M-5010.
Fig. 6 Photographs of (a) M-5010 dispersed in deionized water, (b) M-
5010 dispersed in an O/W emulsion, (c) an O/W emulsion, and (d) the
solution after the demulsification test was carried out using a hand magnet.
conrms that M-5010 can be separated from the solution using
an external magnetic eld.
Fig. 7 shows the effect of the demulsier dosage on the oil
removal rate. To this end, the demulsier dosage with respect to
Fig. 7 The effect of demulsifier dosage on oil removal rate in O/W
emulsions.
98 | J. Mater. Chem. A, 2014, 2, 94–99
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the total volume of the O/W emulsion was varied from 72 mg L1
to 198 mg L1. In addition, the settling time was kept constant at
3 h together with the temperature (60
C). It can be seen that the
oil removal rate increases with the increasing demulsier
dosage. However, the oil removal rate does not obviously change
if the demulsier dosage continuously increases. The maximum
oil removal rate is achieved when the dosage of demulsier is
about 198 mg L1, at which point some oil droplets are observed
suspended in the water. The maximum oil removal rate of M-
5010 (which is as high as 97.3%) can be observed in Fig. 7.
Obviously, M-5010 has a higher oil removal rate than 5010 under
the same conditions. This is probably because the electrical
double layer can be compressed further when M-5010 is added.
The relationship between the settling time and oil removal
rate was also studied. Different settling times, i.e., 0.5 h, 1 h,
1.5 h, 2 h, 2.5 h and 3 h, were tested while the amount of
demulsier (162 mg L1) and the temperature (60
C) were kept
constant. As exhibited in Fig. 8, the oil removal rate increases
with the increase in settling time. Aer 3 h settling time, the oil–
water separation was more efficient when M-5010 was used
rather than 5010. The oil removal rate of M-5010 was 94.9%,
showing its better performance in oil–water separation.
In contrast to the conventional demulsier 5010, M-5010
can be recycled by using a magnet and can be reused aer
demulsication, which is a unique feature of this magnetic
demulsier. The recycled M-5010 was washed with petroleum
ether and ethanol several times in order to remove any residue
of the emulsion and then used for a subsequent demulsi-
cation test. In the recycle test, the dosage of recycled M-5010
was 162 mg L1, the temperature was 60
C and the settling
time was 3 h. The demulsication test procedure described
above was repeated up to 5 cycles. The oil removal rate of the
recycled M-5010 was studied during each cycle, as shown in
Fig. 9. Although the oil removal rate gradually decreases for
each recycle, the oil removal rate of the last cycle is still above
70.4%. Our study indicates that M-5010 may potentially be an
excellent demulsier for produced wastewater containing O/W
emulsions.
Fig. 8 The effect of settling time on the oil removal rate in an O/W
emulsion.
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Fig. 9 Oil removal rate in different cycles by M-5010.
4 Conclusions
In summary, a novel magnetic demulsier M-5010 was synthe-
sized using the reaction between 5010 and epoxy group func-
tionalized Fe3O4@SiO2 microspheres. The obtained M-5010 and
5010 were applied to O/W emulsions and the inuence of
varying the dosage of demulsier and the settling time were
studied. Furthermore, the oil removal rates of M-5010 and 5010
were compared. The results show that the oil removal rate
increases with increasing dosage and settling time within a
specic range. In addition, the maximum oil removal rate of M-
5010 is 97.3% when the dosage is 198 mg L1 and settling time
is 3 h, which shows a better performance in oil–water separation
than 5010, which is used in oilelds, under the same condi-
tions. Furthermore, the demulsier M-5010 can be recycled and
reused with the help of a magnet because of its high saturation
magnetization (35.1 emu g1) and the oil removal rate remains
above 70.4% aer recycling 5 times. This excellent performance
allows us to draw the primary conclusion that this novel
magnetic demulsier may hold great promise for the treatment
of O/W wastewater from oilelds.
Acknowledgements
This work is funded by the National Natural Science Foundation
of China (31070517).
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