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prepared via Pickering emulsion template. A wax-in-water Pickering emulsion was used to
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.
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1.
Introduction
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2.
Experimental
2.1.
Materials
2.2.
Preparation of GO nanosheets
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.
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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2.7.
Characterization
3.
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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.)
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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.
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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.)
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479
Fig. 9 Size distribution of (a) pristine GO, (b) AMG and (c)
SMG dispersed in water.
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Fig. 11 FE-SEM images 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).
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