Herein, NG/SnO
2
hollow spheres hybrids were fabricated
using a hydrothermal method with SiO
2
act as sacricial
template, urea act as nitrogen source and reducing agent in
this work. The microwave absorption performance of NG/SnO
2
hollow sp heres hybrids was investigated in the frequency
range of 2–18 GHz. The high performance EM absorbing
mechanism of the NG/SnO
2
hollow spheres hybrids is further
discussed.
2. Experimental section
All the chemicals and reagents were used without further
purication. Graphene oxide (GO) was synthesized from natural
graphite by using a modied Hummers' method.
44
The silica
nanospheres with particle size of about 200 nm were prepared
via aSt
¨
ober method.
45
2.1. Preparation of SnO
2
hollow spheres
The SnO
2
hollow spheres were prepared by according to
previous method with some modication.
45,46
Typically, 100 mg
of as-prepared SiO
2
nanospheres were dispersed into 60 mL of
deionized water and ultrasound for 2 h. Then, 1.2 g of glucose
was added into the suspension and stirred for 10 min. Aer
that, 0.2 g SnCl
2
$2H
2
O was added into the suspension under
stirring. Aer stirring for 30 min, 0.044 g of NH
4
F was added
into the mixed suspension and stirred another 30 min. Aer
that, the mixed suspension was transferred into a Teon-lined
stainless steel autoclave, and then placed in an oil bath at
160
C with magnetic stirring for 10 h. Aer cooled down to
room temperature, the hollow SnO
2
@polysaccharides nano-
spheres were collected by centrifugation, washed with deion-
ized water and ethanol thoroughly, and dried in an oven at
60
C. Finally, the SnO
2
hollow spheres composite was obtained
by heat treatment at a temperature of 500
C for 3 h with
a ramping rate of 4
C min
1
in air.
2.2. Preparation of NG/SnO
2
hollow spheres hybrids
Amino-function SnO
2
hollow spheres (amino-SnO
2
) were ach-
ieved via a post-graing strategy. Typically, 100 mL of anhy-
drous toluene and 200 mg of SnO
2
hollow spheres was mixed
under ultrasound and mechanical stirring for 1 h. Then 0.5 mL
of APTES was added dropwise to the suspension and kept at
110
C with reux for 6 h. The amino-SnO
2
were collected by
centrifugation and washed for several times with ethanol and
deionized water and dried in an oven at 60
C. The NG/SnO
2
hollow spheres hybrids were prepared by using a hydrothermal
method. Briey, 100 mg GO was dispersed into 60 mL deionized
water and ultrasound for 2 h, 100 mg amino-SnO
2
hollow
spheres were added into the suspension with ultrasonic and
stirred for 1 h. Then 2 g urea was added into the suspension and
stirred for another 30 min. The suspension was transferred into
a stainless-steel autoclave and kept at 180
C for 6 h. The
product was collected by centrifugation and then washed with
ethanol and deionized water and dried at 60
C. The NG was
also prepared by using the same method without amino-SnO
2
.
2.3. Characterization
The crystal phase was investigated with X-ray powder diffrac -
tion (Em pyrean, PANalytical B.V.). Raman spectroscopy was
carried out on a LabRAM HR800 in via Raman microscope. X-
ray photoelectron spectroscopy (XPS) measurements were ob-
tained with an AXIS-ULTRA DLD-600W electron spectrometer
from Kratos. The morphology was examined by eld emission
scanning electron microscope (Gemini SEM 300) and trans-
mission electron microscope (TEM, Tecnai G2 20). The
measurements of FT-IR were performed with spectroscopy
(VERTEX 70) using the KBr pellet method at room tempera-
ture. The electromagnetic parameters of the samples were
measured by a vector network analyzer ( Agilent E5071C) within
2–18 GH z. The toroidal shape samples wit h an i nner diamet er
of 3.04 mm , out diam eter of 7 mm and thickness of 2 mm were
prepared by mixing the paraffinandsampleswithamassratio
of 6 : 4.
3. Results and discussion
The formation mechanism of NG/SnO
2
hollow spheres hybrids
is schematically illustrated in Fig. 1. First, polycrystalline SnO
2
hollow spheres were prepared by facile strategy of one-pot
hydrothermal following a subsequent heat treatment with
SiO
2
act as sacricial template. Second, amino-functional SnO
2
hollow spheres were obtained via a post-graing strategy with
reux. Third, amino-function SnO
2
hollow spheres anchored on
the GO sheets surface through electrostatic interaction and the
NG/SnO
2
hollow spheres hybrids were prepared by using
a hydrothermal method with urea as the nitrogen source and
reducing agent.
Fig. 2 shows the FT-IR spectra of the samples at each stages
of the experiments. The characteristic features of GO are the
adsorption bands corresponding to the C]O stretching vibra-
tion at 1723 cm
1
,C]C deformation vibration at 1613 cm
1
,C–
OH stretching at 1226 cm
1
and C–O stretching at 1053 cm
1
,
indicating that abundant oxygen functional groups (–COOH,
–OH) were introduced during the exfoliation of the graphene
sheet.
2
Compared the FT-IR spectrum of amino-function SnO
2
hollow spheres with SnO
2
hollow spheres, two new bonds were
found at 3373 and 1570 cm
1
correspond to the coupling of
N–H stretching vibration, suggesting that NH
2
group have
adhered to the surface of SnO
2
hollow spheres.
47
All samples
except for GO show strong absorption at 500–700 cm
1
corre-
sponding to characteristic vibration of O–Sn–O in the SnO
2
.
48
For NG/SnO
2
hollow spheres hybrids, the peaks at 1723, 1226
and 1503 cm
1
almost disappear, indicating that most oxygen
function groups have been removed.
2
There are three peaks at
1555, 1185 and 623 cm
1
can be assigned to the C]C, C–N(C–
O) and Sn–O stretching vibration in NG/SnO
2
hollow spheres
hybrids, indicating that the SnO
2
hollow spheres have been
successful anchored on the NG surface.
The XRD was utilized to investigate the phase structure of
GO, NG, SnO
2
hollow spheres and NG/SnO
2
hollow spheres
hybrids, as shown in Fig. 3(a). The GO shows a sharp peak at
10.9
, corresponding to its (001) crystal plane. The NG shows
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