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Available at www.sciencedirect.com

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journal homepage: www.elsevier.com/locate/carbon

Janus graphene oxide nanosheets prepared via

Pickering emulsion template
Hao Wu, Wenyuan Yi, Zhe Chen, Haitao Wang *, Qiangguo Du
State Key Laboratory of Molecular Engineering of Polymers, Department of Macromolecular Science, Fudan University, Shanghai 200433,
PR China

A R T I C L E I N F O

A B S T R A C T

Article history:

Janus graphene oxide (GO) nanosheets functionalized by amino-containing chemicals were

Received 30 January 2015

prepared via Pickering emulsion template. A wax-in-water Pickering emulsion was used to

Accepted 23 May 2015

mask one side of GO nanosheets in order to achieve asymmetric chemical functionaliza-

Available online 29 May 2015

tion. Janus particles were obtained by removing the oil phase. The successful reaction of
epoxy groups on the surface of GO with amino-containing chemicals was confirmed by
Fourier transform infrared spectroscopy (FT-IR) and thermal gravimetric analysis (TGA).
The asymmetric surface structure of Janus GO nanosheets was detected by atomic force
microscope (AFM) and X-ray diffraction (XRD). The efficient stabilization of an oil-inwater Pickering emulsion by Janus GO was proved. Polymer microspheres fabricated by
using Janus GO as Pickering stabilizer had a more hydrophilic surface compared with those
stabilized by symmetrically modified GO.
2015 Elsevier Ltd. All rights reserved.

1.

Introduction

Particles possessing two sides of different structures and/or

chemical compositions are known as Janus particles [1],
which have attracted tremendous interests in various
research aspects of physics, chemistry, and biological science
in recent years [24]. Compared with homogeneous particles,
Janus particles can be designed to own unique amphiphilic
feature as well as anisotropic electrical, magnetic, or optical
properties due to their asymmetric structure [57].
Therefore, Janus particles have potential applications in a
broad range of fields such as medical target deliveries, biosensors, imaging nanoprobes, self-motile colloidal materials and
Pickering interfacial catalysts [812]. One of the most important applications of Janus particles is used as solid stabilizers
of emulsions and foams due to their truly amphiphilic structure [1315]. Binks et al. predicted by calculation that Janus

* Corresponding author: Fax: +86 21 65640293.

E-mail address: wanght@fudan.edu.cn (H. Wang).
http://dx.doi.org/10.1016/j.carbon.2015.05.083
0008-6223/ 2015 Elsevier Ltd. All rights reserved.

particles should possess a significantly higher adsorption

energy than uniform particles at the oil/water interface [16].
Plenty of methods have been developed for the preparation of Janus particles during the last decades [11,17], mainly
including masking technique [7,18,19], electrohydrodynamic
jetting [20,21], microfluidic technique [2224], phase separation [25,26], seeded emulsion polymerization [27] and selfassembly [28,29]. As a kind of masking technique, Pickering
emulsion template stabilized by solid particles instead of
molecular surfactants has intrigued particular interest [30].
Solidifiable oils can be used to prepare Pickering emulsions
in order to immobilize solid particles more firmly [31]. The
surface masked by solidified oil is protected from the subsequent chemical modification to achieve asymmetric structure, and finally, Janus particles are obtained by removing
the oil phase [19]. Tuning the functionalized areas can be
achieved via Pickering emulsion method, since embedding

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depth of particles in the droplet is controlled by the droplets

polarity and the particles amphiphilicity [31]. In addition,
Janus particles are able to be produced in large quantity
because Pickering emulsions are easily prepared and emulsion droplets normally have large surface area [11,3134].
Some Janus particles in different dimensions have been
successfully obtained via Pickering emulsion templates,
including zero-dimensional (0D) Janus spheres [3537] and
two-dimensional (2D) Janus discs [12,38,39]. 2D Janus particles
arouse intense interest in the field of emulsification for their
large adsorption energy and highly confined rotation at the
oilwater interface [12,15,40]. Graphene and its derivatives
are extremely thin 2D carbon materials with outstanding
properties which have attracted broad attention for wide
applications [4144]. Janus graphene nanosheets have been
fabricated via a two-step covalent reaction on each side
assisted by a poly(methyl methacrylate)-mediated transfer
approach [45]. In comparison to graphene, there are lots of
oxygen-containing groups on the surface of graphene oxide
(GO) nanosheets, which make GO more easily to be chemically modified [46]. Unlike the structure of single-layered
Janus graphene nanosheets, stacked GO and the hybrid films
with the thickness of several hundred nanometers or above
were functionalized to achieve macroscopic films with asymmetric surfaces [47,48]. Hydrophilic oxygen-containing
groups and hydrophobic basal plane endow GO with
amphiphilicity to act as Pickering stabilizer [49,50].
Monolayer Janus GO is expected to show excellent ability to
stabilize Pickering emulsions due to its asymmetric surface
wettability in comparison with homogeneous GO [14,16,51].
However, the fabrication of monolayer GO nanosheets with
asymmetric structure is usually difficult, for the reason that
GO is extremely thin in thickness and inclined to aggregate.
In this work, we utilize a wax-in-water Pickering emulsion
stabilized by GO nanosheets to protect one side of GO, and the
functionalization is performed by reacting amino-containing
chemicals with epoxy groups on the outer surface of GO.
Janus GO shows effective stabilization for Pickering emulsions compared with symmetrically modified GO. This paper
provides a facile method to design the surface structure of
GO to meet specific requirements for its applications.

2.

Experimental

2.1.

Materials

Sulfuric acid (98%), potassium permanganate (99%), sodium

nitrate (99%), hydrogen peroxide (30%), ethanol (99%),
hydrochloric acid (37%), sodium hydroxide (99%), styrene
(99%), azo-bisisobutyronitrile (AIBN, 99%), toluene (99%) and
chloroform (99%) were purchased from Sinopharm Chemical
Reagent Co. (China). Paraffin wax (with a melting point of
roughly 55 C), graphite powders (99.95%), and dodecylamine
(DDA, 98%) were supplied by Aladdin Chemistry Co. Ltd.
Poly(propylene glycol) bis(2-aminopropyl ether) with average
molecular weights of 2000 (D2000) was purchased from
Huntsman Chemical Co. Ltd. Styrene was distilled under vacuum and AIBN was recrystallized prior to use. Deionized
water was used throughout the experiments.

2.2.

Preparation of GO nanosheets

GO nanosheets were prepared via a modified Hummers

method from graphite [52]. The GO suspension was dialyzed
in deionized water for 1 week, followed by drying in a vacuum
oven at 50 C for 24 h. The dried GO was then dispersed in
water and sonicated for 1 h with the power of 300 W to form
the aqueous suspension (0.1 wt.%).

2.3.
Preparation of wax-in-water Pickering emulsions
stabilized by GO
The mixture of GO aqueous suspension (20.0 g), deionized
water (80.0 g) and hydrochloric acid aqueous solution (0.06 g,
37 %) was sonicated for 5 min in a 150 mL flask. Wax (20.0 g)
was then added to the aqueous phase and the flask was
placed in a 60 C water bath until wax melted, followed by
emulsification with an FJ200-S homogenizer at 12,000 rpm
for 10 min at 60 C. The emulsion was cooled at room temperature to obtain GO-coated wax microspheres through filtration. The spheres were then dispersed in NaOH aqueous
solution (50 mL, pH = 10) and sonicated for 5 min followed
by filtration.

2.4.
Preparation of D2000-modified Janus GO and DDA
modified Janus GO
GO-coated wax microspheres (10.0 g) and D2000 (100 mg)
were dispersed in 60.0 g of aqueous ethanol solution (1/1,
v/v), followed by mild stir at 30 C for 12 h. Wax was dissolved
in chloroform (1/5, m/m) to obtain D2000-modified Janus GO
by washing with ethanol using a centrifugation-sonication
cycle three times. In order to fabricate GO symmetrically
modified by D2000 for comparison, D2000 (100 mg) and GO
obtained from 10.0 g GO-coated wax microspheres after
removing wax were added to 60.0 g of aqueous ethanol solution (v/v, 1/1) and the mixture was stirred at 30 C for 12 h. The
modified GO was then washed with ethanol using a
centrifugation-sonication cycle three times. Asymmetric
DDAmodified GO (AMG) and symmetric DDAmodified GO
(SMG) were prepared in the same way, the mass ratio of
DDA to GO was 1. Symmetric DDAmodified GO (SMG-2)
was also prepared when the mass ratio of DDA to GO was 2.

2.5.
Preparation of Pickering emulsions stabilized by
DDAmodified GO
Aqueous suspension of DDAmodified Janus GO (0.3 g,
0.1 wt.%) was mixed with deionized water (8.0 g) by sonication. Toluene (0.5 g) was then added to the mixture, followed
by emulsification with a homogenizer at 20,000 rpm for 5 min.
Pickering emulsion stabilized by symmetric DDAmodified
GO was also prepared in the same method.

2.6.

Preparation of GO-coated PS microspheres

DDAmodified Janus GO (3 mg) was dispersed in NaOH aqueous solution (15.0 g, pH = 9). Styrene (1.0 g) and AIBN (0.01 g)
were mixed with the aqueous phase in a three-necked flask

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equipped with a magnetic stirrer and purged with N2 for

30 min. Polystyrene (PS) microspheres coated by DDAmodified Janus GO were obtained after the polymerization at
65 C for 10 h. Symmetric DDAmodified GO was also utilized
to produce PS microspheres in the same method for
comparison.

2.7.

Characterization

The morphologies of wax microspheres and PS microspheres

were observed using field-emission scanning electron microscope (FE-SEM, Zeiss Ultra 55). These microspheres were
diluted with deionized water and dried on mica substrates,
followed by spraying with gold before the test. Atomic force
microscope (AFM) images of GO, symmetric and asymmetric
D2000-modified GO were obtained using a Multimode 8 in
the tapping mode. The pristine GO and asymmetric D2000modified GO were dispersed in water and symmetric D2000modified GO was dispersed in dimethyl formamide before
test. The samples for AFM imaging were prepared by spin
coating onto freshly cleaved mica substrates. An X Pert PRO
(PANalytical) with Cu Ka radiation (k = 0.154 nm) was used
for the X-ray diffraction (XRD) analysis. Pristine GO and modified GO were dried at 50 C for 24 h before characterization.
The chemical structure of modified GO were characterized
using Fourier transform infrared spectroscopy (FT-IR,
Thermofisher Nicolet 6700). The samples were pressed into
KBr pellets for FT-IR measurements. The thermal stability of
surface-modified GO was measured by thermal gravimetric
analysis (TGA, PerkinElmer Pyris 1 TGA) at a heating rate of
20 C/min from 100 to 500 C under a nitrogen atmosphere.
Microscopy images of Pickering emulsion droplets were taken
by a digital microscope (EV5680). Canon Ixus 850IS digital
camera was used to take the photographs of the samples.
The particle size distributions of the pristine and modified
GO suspensions were measured by the Malvern Zetasizer
Nano ZS instrument, and the curves were normalized after
smooth. The concentration of GO suspension was 0.1 wt.%.
Sonication was conducted on samples before test. Water contact angle measurements (CA, Dataphysics OCA 40) were used
to characterize the surface wettability of GO-coated PS microspheres. The samples were dispersed in water and the suspensions were dropped onto glass slides and placed at room
temperature for 3 days to form films. A water droplet was
added to the surface of sample, and the static contact angle
was recorded when the droplet had stopped spreading.
Three measurements were performed for each sample.

3.

Results and discussion

Pickering emulsions have been widely used as template to

produce Janus particles via immobilizing solid particles at
the interface, followed by the surface modification to achieve
asymmetric structure [30]. It has been proved that amphiphilic graphene oxide (GO) nanosheets can be utilized to stabilize
Pickering emulsions [49,50]. The morphology of GO
nanosheets was observed by AFM, as shown in Fig. 1. The
height of the prepared GO nanosheets is about 0.9 nm,

475

indicating that full exfoliation is achieved. The size of the

GO nanosheets ranges from 100 to 1000 nm.
The extreme hydrophilicity of GO nanosheets leads to the
instability of Pickering emulsions, and thus HCl was added to
restrict the ionization of carboxyl groups. Herein, a wax-inwater Pickering emulsion stabilized by GO nanosheets was
prepared and the photograph of emulsion was taken after
homogenizing and cooling for 5 h as shown in Fig. 2a. The
surface of wax microspheres is covered by wrinkled GO
nanosheets (Fig. 2b and c). Compared with pure wax
(Fig. S1a), XRD result of GO-coated wax microspheres
(Fig. 3a) shows a new diffraction peak at 11.2, which is in
agreement with dried GO nanosheets seen from Fig. S1b.
The appearance of the new peak is due to the stack of GO
nanosheets. GO aggregates on the surface of wax may be
induced by the insufficient charge repulsion at lower pH value
and strong pp stacking interaction. It is difficult to fabricate
Janus GO nanosheets via Pickering emulsion template if
multi-layered GO nanosheets are covered on the surface of
wax microspheres, for the reason that the internal GO
nanosheets cannot be modified during the following chemical
functionalization and only the outermost ones may have
asymmetric structure.
It has been reported that the amphiphilicity of GO could be
tuned reversibly by changing the pH value. Even if an emulsion stabilized by GO at pH 2 has already formed, the droplets
coalesce into a continuous phase and GO is extracted back to
water when pH value is increased to 10. This may be induced
by the high hydrophilicity of GO and sufficient charge repulsion provided by the ionization of carboxyl groups [49,53].
Thus, wax microspheres were washed with NaOH aqueous
solution in our work to extract GO aggregates on the surface
to water. Besides, powerful sonication was performed to
ensure the redundant GO to be washed off thoroughly. The
color of the solution changes to light yellow (Fig. 2d), indicating that GO nanosheets are successfully washed into water.
From Fig. 2e, a smooth surface of wax microspheres can be
seen after the treatment rather than a wrinkled one caused
by stacking GO. Moreover, the borderline between GO
nanosheets and the exposed wax is found clearly (marked
with arrows) from the magnified FE-SEM image (Fig. 2f).
These results illustrate that the GO aggregates have been
washed off at the elevated pH value, while the innermost layers still cover on the surface of microspheres because of the
strong fixation of wax.
XRD characterization was performed to clarify the surface
structure of wax microspheres. The diffraction peak at 11.2
corresponds to the (0 0 1) reflection of pristine GO, which is
induced by the stack of GO on the surface (Fig. 3a).
Nevertheless, this diffraction peak disappears after alkalineliquor wash and sonication treatment as shown in Fig. 3b,
which further confirms that GO aggregates are exfoliated into
water and only the innermost layers fixed by wax are left over.
According to this strategy, monolayer GO nanosheets protected by wax microspheres are obtained, and thus, asymmetric surface structure of GO nanosheets may be achieved
via the subsequent chemical functionalization.
In generally, wax needs to be removed to obtain Janus particles after the chemical reaction. The adsorption of wax on

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Fig. 1 (a) Tapping-mode AFM image and (b) height profile of pristine GO. (A color version of this figure can be viewed online.)

Fig. 2 Photographs of wax-in-water Pickering emulsion stabilized by GO (a) before and (d) after washing with NaOH aqueous
solution. FE-SEM images of GO-coated wax microspheres (b and c) before and (e and f) after washing. (A color version of this
figure can be viewed online.)

the surface of GO nanosheets due to their huge surface area

may affect the application of the material. Thus, the morphology of GO nanosheets is observed by AFM after removing wax
using chloroform. From Fig. S2, it can be seen that no wax
residues on the surface of GO nanosheets and the height is
nearly the same as that of pristine GO. Therefore, in the following experiments, the products after the surface functionalization are all treated by this method to obtain Janus GO
nanosheets.
There are several functional groups such as hydroxyl, carbonyl and epoxy groups on the basal plane and carboxylic
groups mainly at the edges of GO nanosheets [46]. In order

to avoid wax melting, a reaction between amino and epoxy

groups is selected because it can occur at room temperature
[54,55]. In addition, Janus GO nanosheets may be produced
via the graft of compounds containing the amino group as
epoxy groups are on the basal plane. As we know, the asymmetric structure of Janus particles is commonly difficult to be
characterized, especially for extremely thin 2D particles
because they tend to stack to conceal their surface during
drying. It has been reported that the thickness of
polyetheramine-modified GO is affected by the length of polymer chains according to XRD measurements [5658]. Herein,
poly(propylene glycol) bis(2-aminopropyl ether) with average

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Fig. 3 XRD patterns of GO-coated wax microspheres (a)

before and (b) after washing with NaOH aqueous solution.
The inset shows the range from 9.0 to 13.0.

molecular weights of 2000 (D2000) was chosen to functionalize GO nanosheets. The successful modification of GO with
D2000 is confirmed by FT-IR spectra as shown in Fig. S3b.
After removing wax by washing with chloroform, XRD
characterization was employed to clarify the surface structure of modified GO nanosheets. Both symmetric and asymmetric
D2000-modified
GO
were
investigated
for
comparison, as shown in Fig. 4. Single diffraction peak of
symmetrically modified GO with D2000 appears at 2.2, indicating that the interlayer spacing becomes larger after the
graft of D2000 on the surface of GO nanosheets [56].
Interestingly, two peaks at 2.2 and 9.1 are clearly seen for
the sample of asymmetrically modified GO, which is similar
with the diffraction peak of symmetrically modified GO and
unmodified GO, respectively. This is induced by the asymmetric surface structure of GO nanosheets, a D2000-grafted side
and a virgin side. The peak at 2.2 corresponds to the interlayer spacing between two modified sides of GO, and the peak
at 9.1 is ascribed to the distance between unmodified sides.

Fig. 4 XRD patterns of (a) symmetric and (b) asymmetric

D2000-modified GO.

477

The XRD result indicates that Janus GO nanosheets can be

successfully prepared by Pickering emulsion template.
Symmetric and asymmetric D2000-modified GO were
observed by AFM (Fig. 5) to clarify their surface morphology.
A distinct increase in thickness is found in both samples compared with the pristine GO (0.9 nm). The average height of the
symmetric
D2000-modified
GO
is
about
4.5 nm
(Fig. 5a and b), which is in consistent with the reported
result [56]. However, Janus GO is merely 2.7 nm high because
only one side of GO is available for functionalization
(Fig. 5c and d).
On the basis of successful preparation of D2000-modified
Janus GO nanosheets, dodecylamine (DDA) containing an
alkyl chain was used to tune the amphiphilicity of GO in order
to fabricate stable Pickering emulsions. The FT-IR result indicates the successful chemical reaction between DDA and
epoxy groups on the surface of GO nanosheets (Fig. S3c).
TGA tests of pristine GO and asymmetric DDAmodified
GO (AMG) were performed to verify the chemical graft of
DDA on the surface of GO, and symmetric DDAmodified GO
(SMG) was also characterized for comparison. From Fig. 6a,
an obvious weight loss from 180 to 250 C is found for pristine
GO, which is induced by the decomposition of labile oxygencontaining functional groups (carboxylic, hydroxyl and epoxy
groups) on the surface [55]. AMG and SMG have similar thermal decomposition behavior, while their weight loss is less
than pristine GO because some epoxy groups have been consumed by the graft of DDA (Fig. 6b and c). This can be proved
by the reported result that an improvement in thermal stability of GO is achieved by the reaction of carboxylic and epoxy
groups with 3-aminopropyltriethoxysilane [54]. Furthermore,
the weight loss of AMG and SMG is very close, indicating that
the amount of DDA grafted on the surface of GO is nearly the
same because epoxy groups on one side of GO nanosheets are
enough to react with DDA. It is proved by the further improvement in thermal stability of modified GO after doubling the
amount of DDA (Fig. 6d).
The surface structure of SMG and AMG was also clarified
with XRD characterization (Fig. 7). In comparison with
D2000-modified GO, a larger diffraction angle at 3.0 is found
on account of the shorter chain length of DDA as shown in
Fig. 7a [59]. Two diffraction peaks for AMG appearing at 3.0
and 9.3 indicate its asymmetric surface structure.
The structure of AMG and SMG was studied by dispersing
them in water, as shown in Fig. 8. A clear and yellowbrown
solution is found for AMG. However, SMG tends to form flocculation in water and the color of the suspension is lighter,
which can also be found in surfactant-modified GO [60,61].
Since the amount of DDA on the surface of GO is similar
based on TGA results of AMG and SMG, the obvious difference
of the dispersibility between two samples can only be induced
by their structure. The hydrophobic interaction of SMG
nanosheets causes the formation of flocculation because both
sides of GO are grafted by DDA.
Though DLS result of two-dimensional particles shows
their effective hydrodynamic diameter of an equivalent
sphere, it is still useful for comparative purposes as reported
[62,63]. The samples were sonicated before the DLS characterization and the result is displayed in Fig. 9. Pristine GO, AMG
and SMG show similar polydispersity index of 0.228, 0.206 and

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Fig. 5 (a and c) Tapping-mode AFM images and (b and d) height profiles of (a and b) symmetric and (c and d) asymmetric
D2000-modified GO. (A color version of this figure can be viewed online.)

Fig. 6 TGA curves of (a) pristine GO, (b) SMG, (c) AMG and (d)
SMG-2. (A color version of this figure can be viewed online.)

0.217 respectively. The average size of AMG increases from

310 nm for pristine GO to 450 nm due to the asymmetric graft
of DDA on the surface. SMG has a much larger size of above
700 nm, which is caused by the graft of DDA on both sides
of GO nanosheets. Furthermore, the formation of flocculation

Fig. 7 XRD patterns of (a) symmetric and (b) asymmetric

DDAmodified GO.

ascribed to hydrophobic interaction may also be responsible

for a larger particle size.
Janus particles can normally stabilize Pickering emulsions
more efficiently than homogeneous particles because of their

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479

Fig. 8 Photographs of aqueous suspensions of (a) AMG and

(b) SMG after standing for 0.5 h. (A color version of this figure
can be viewed online.)

Fig. 10 (a and c) Photographs and (b and d) optical

microscopy images of emulsions stabilized by (a and b) AMG
and (c and d) SMG. The photographs of emulsions were
taken after homogenizing and standing for 10 min. (A color
version of this figure can be viewed online.)

Fig. 9 Size distribution of (a) pristine GO, (b) AMG and (c)
SMG dispersed in water.

unique asymmetric structure [14,51]. A toluene-in-water

Pickering emulsion can be well stabilized by AMG with the
droplet size of 515 lm (Fig. 10) and shows good stability
against coalescence for at least 3 weeks. However, an unstable
emulsion is produced when SMG is utilized as Pickering stabilizer, even if the lipophilicity of GO is improved by the graft of
DDA. The excellent ability of AMG to stabilize emulsions can
only be attributed to the truly amphiphilic structure of GO
nanosheets.
In our previous paper, it has been reported that GO-coated
PS microspheres can be prepared via Pickering emulsion polymerization when GO nanosheets are used as the stabilizer
[64]. Herein, AMG and SMG were also utilized to fabricate PS
microspheres (Fig. 11). Two kinds of polymer microspheres

have similar morphology with the size ranging from 100

to150 nm. The wrinkled surface illustrates that GO
nanosheets cover on PS microspheres. The mechanism of
the polymerization has been mentioned in our previous work
[64]. Briefly, formed PS oligomers precipitate from monomer
phase due to their poor solubility. Then they adsorb on the
surface of GO because of the huge surface area of these
nanosheets and the interaction between GO and PS. The
nuclei produced by the aggregation of GO grows in size, and
finally, polymer microspheres are obtained.
PS microspheres stabilized by AMG and SMG have similar
morphology because they undergo the same polymerization
mechanism. However, their surface structure may be different, which is induced by the location of the adsorption of PS
oligomers precipitated from monomer phase. When AMG is
used as Pickering stabilizer, polymer oligomers are more
prone to adsorb on the surface grafted by DDA due to their
hydrophobic interaction. After polymerization, the relatively
hydrophilic surface of GO nanosheets without alkyl chains
is left outside PS microspheres. As for SMG, the adsorption
of PS oligomers are unselective ascribed to its homogeneous

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Fig. 11 FE-SEM images of PS microspheres stabilized by (a) AMG and (b) SMG.

Fig. 12 (a and c) Photographs and (b and d) FE-SEM images

of PS microspheres stabilized by (a and b) AMG and (c and d)
SMG. (A color version of this figure can be viewed online.)

Fig. 13 Water contact angle measurements of films of PS

microspheres stabilized by (a) AMG and (b) SMG.

structure. The surface of obtained SMG-coated PS microspheres is hydrophobic because DDA is also grafted on the
outside surface of GO. Therefore, AMG-coated PS microspheres can well disperse in water, while serious aggregation
is found when SMG is used as Pickering stabilizer as shown in
Fig. 12.
Water contact angle measurements were conducted to further reveal the surface structure of polymer microspheres by
dropping water droplets on the films of two kinds of PS microspheres. As shown in Fig. 13, the contact angle of AMG-coated
PS is 68 2, which is comparable with the reported data of
GO films [65]. The film composed of PS microspheres stabilized by SMG shows a higher water contact angle of 100 3,
indicating that a more hydrophobic outer surface of GO
nanosheets is formed due to symmetric graft of DDA on both
sides. On this basis, we can expect that Janus GO has the
potential to tailor the surface structure of functionalized
materials.
In this paper, a facial strategy is proposed to produce Janus
GO nanosheets in large scale via Pickering emulsion template,
as shown in Fig. 14. Considering of the excessive hydrophilicity of GO, HCl is used to adjust the amphiphilicity to prepare
a wax-in-water Pickering emulsion. Nevertheless, decreased
charge repulsion at lower pH value and strong pp stacking
interaction lead to the aggregation of GO nanosheets on the
surface of wax microspheres. NaOH aqueous solution is thus
utilized to wash these wax microspheres. Outer GO
nanosheets are exfoliated into water because of the sufficient
charge repulsion provided by the ionization of carboxyl
groups. Wax microspheres covered by monolayer GO
nanosheets are obtained for the reason that innermost GO
is fixed by wax. The epoxy groups on the bare side of GO
are then reacted with amino-containing chemicals (e.g.,
DDA) in the mild conditions to achieve the asymmetric surface structure. After removing wax by dissolving microspheres in chloroform, Janus GO nanosheets are successful
collected.

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481

Fig. 14 Schematic illustration of the preparation of Janus GO nanosheets via Pickering emulsion template. (A color version of
this figure can be viewed online.)

4.

Conclusions

A wax-in-water Pickering emulsion stabilized by GO is prepared at low pH value and wax microspheres covered by
monolayer GO are obtained after alkaline-liquor wash and
sonication treatment. The asymmetric structure of Janus GO
is achieved by the graft of amino-containing chemicals on
the outer surface. Janus GO is thinner than symmetrically
modified GO because one surface is well protected from the
reaction, which also leads to two diffraction peaks in XRD
pattern. DDA-grafted Janus GO can stabilize an oil-in-water
Pickering emulsion effectively due to its truly amphiphilic
structure. PS microspheres prepared using Janus GO modified
by DDA as Pickering stabilizer show more hydrophilic surface
compared with those stabilized by uniform particles, and
thus can well disperse in water. This study provides a facile
method for the structure design of GO to meet its application
requirements.

Acknowledgment
This work was financially supported by the National Natural
Science Foundation of China (NSFC) (No. 51373038).

Appendix A. Supplementary data

Supplementary data associated with this article can be found,
in the online version, at http://dx.doi.org/10.1016/j.carbon.
2015.05.083.
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