64 Egypt. J. Chem. 59, No.6 pp.

1061– 1068(2016)

Synthesis and Characterization of Multi-Walled

Carbon Nanotubes Decorated ZnO Nanocomposite
Eman, A. Mwafya, M. Dawya, A. Abouelsayedb, I. A.
Elsabbaghc and M. M. Elfassc
a
Physical Chemistry Department, Inorganic Chemical
Industries and Mineral Resources Division. bSpectroscopy
Department, Physics Division, National Research Centre, 33
ElBohouth st. (fromer El Tahrir st.), Dokki , Giza , P.O. 12622
and cChemistry Department, Faculty of Science, Al-Azhar
University, Cairo 11884, Egypt.

M ULTI-WALLED carbon nanotubes decorated Zinc oxide

..........(MWCNTs/ZnO) nanocomposites with ratio of (99: 1 wt %)
was prepared using sol gel method. Transmission Electron
Microscope (TEM) and The X-ray diffraction pattern (XRD)
showed that the MWCNTs/ZnO nanocomposites was synthesized
with particle size ranging from 2-7 nm and crystalline size about
7nm. The Field Emission Scanning Electron Microscopy (FESEM)
images demonstrate that ZnO had grown on the walls of MWCNTs
were uniformed layer in the shape of thin film layer of nanospheres
covering the surface of the tubes, also the energy dispersive X-ray
spectrum (EDX) and Fourier Transformed Infrared spectroscopy
(FTIR) prove the presence of ZnO without any impurities.

Keywords: MWCNT, MWCNTs/ZnO nanocomposites and Sol gel

method.

One-dimensional (1D) nanostructure materials had attracted a great interest due

to their incredible properties and high-potential technology applications in the
synthesis of nanoscale devices (1). Since their discovery in 1991(2), carbon
nanotubes (CNTs) are interesting 1D structure materials with high aspect ratio
(diameter to length) that has unique mechanical, electronic and chemical
properties (3). So, CNTs have been attracted much attention over the past few
years. Recently, CNTs-metal oxide based nanocomposite has a great attention
due to their potential applications as active elements in a wide range
applications including nanoelectronic and nano mechanical devices, super
capacitors, energy storage materials, catalyst supports and sensors (4).

The combination of the unique properties of both CNTs and semiconductor

nanostructures is creating a new class of nanocomposite materials that opens a
new broad range of applications in different areas of science (5,6). There are a lot
of researches about the growth of metal oxide nanoparticles using CNT as 1D
template. ZnO, TiO2, SnO2, CdS, CdSe, and CdTe nanoparticles decorated on
the wall surface of CNTs are attractive semiconductor due to their incredible
1062 Eman A. Mwafy et al .

properties that make them candidate in several applications as photo-

electrochemical solar cell, gas sensors and photo-detectors (7).

There is a fact that Zinc Oxide (ZnO), as an oxide, presents as a

semiconductor with a direct wide band gap (3.37 eV), and a large exciton
binding energy of 60 meV at room temperature (8), so it was expected that when
CNTs was coated with ZnO, they would be formed a composite with a
promising properties coupling the merits of both.

Various synthetic strategies based on chemical and physical processes to

obtain on a promising nanocomposite have been reported. With the recent
advance in the design of CNTs composites, sol gel method can be used to
deposit a variety of materials including oxides and metals on the surface of
CNTs with a small diameter at rather low temperatures.

In this paper, MWCNTs/ZnO nanocomposite with weight ratio of (99: 1 wt

%) was prepared by a sol-gel method and its properties were investigated by
using Transmission Electron microscope (TEM), X-ray diffraction pattern
(XRD), Fourier Transformed Infrared spectroscopy (FTIR) and The Field
Emission scanning electron microscopy (SEM) with the aid of energy dispersive
X-ray spectrum (EDX)

Experimental

Reagents and chemicals

Multi-walled carbon nanotubes (MWCNT) were previously prepared by the
Chemical Vapour Deposition (CVD) method with diameter of around 25 nm,
zinc nitrate dihydrate were purchased from Sigma-Aldrich. Citric acid was
purchased from Alnasr for Chemicals Company. Nitric acid (65%), HCl, poly
ethylene glycol and ammonium solution were obtained from Merck. All
chemical were used without any purification.

Synthesis of MWCNTs/ZnO (99:1 wt%) nanocomposite

A typical experimental procedure was followed. Firstly, the MWCNTs were
purified from any remaining catalyst by washing with 5M HCl solution, then
the surface of tubes was functionalized and opened by oxidation with nitric acid
solution (65%) and refluxing for 6 hr, then the treated MWCNTs were washed
with distilled water several times until the pH reached 7 and dried at 90°C for
an overnight. Secondly 1 wt% of ZnNO3 was dissolved in 10 ml of distilled
water, followed by adding to a solution of acid treated MWCNTs dispersed in
distilled water using ultrasound bath for 2 hr, then 0.5 gm of citric acid and 5ml
of ethylene glycol solution were added and the mixture was stirred for another 2
hr at room temperature then dropwise of ammonia solution was added until the
PH reached to 7 then the temperature was raised up to 80°C to evaporate the
solvent. Finally, the mixture was dried at 80°C then calcinated at 350°C for 4
hr.

Egypt. J. Chem. 59, No. 6 (2016)

 Synthesis and Characterization of Multi-Walled Carbon... 1063

Characterization techniques
The size and shape of CNT/ZnO nanocomposite were observed on a high
resolution transmission electron microscope (HRTEM) JEOL–JEM-1011,
Japan. Images were recorded at a rate of 200 kV. For each sample, low
concentration of suspension dispersion was deposited on a carbon copper grid
and left to dry at room temperature. Field emission scanning electron
microscope (FE-SEM) on a Quanta FEG 250 (Czech Republic) was used to
investigate the morphology analysis cooped with Energy Dispersive X-ray
spectroscopy analysis (TEAM –EDX Model).

The crystalline structure of samples was characterized using X-ray (XRD)

diffractometer (Schimadzu 7000, Japan) operating with Cu Kα radiation
(λ=0.154060 nm) generated at 30 kV and 30 mA with scanning rate of 4º min-1
for 2θ values between 10 and 80 degrees. Raman measurement was carried out
with BRUKER SENNTRRY, Micro Raman spectroscopy operating at 532 nm
laser, and embedded wavelength 88 to 4000 cm-1 spectral range and up to 3 cm-1
resolution.

A Fourier-transform infrared spectroscopy (JASCO FTIR 6100

spectrometer, 64 scans with 4 cm-1 resolution) was employed to demonstrate the
chemical composition of nanomaterials in the range of 4000–400 cm-1.

Results and Discussion

The XRD patterns of the pure MWCNTs and the MWCNTs/ZnO (99:1
wt%) nanocomposites are shown in Fig.1. From Fig.1, the characteristic peak at
2θ=26° and 43° represents graphite peak that corresponding to the carbon of the
MWCNTs and reveals the crystallinity of the MWCNTs (9). Moreover, the
diffractions of both MWCNTs and ZnO with ratio of (99:1 wt%) clearly
observed that other peaks are appeared in the profile rather than the peak
corresponding to the C of the MWCNTs at 26°, these peaks reveal a good
agreements with ZnO (JCPDS 36-1451).

Fig. 1. XRD patterns of MWCNTs and MWCNTs /ZnO nanocomposites.

Egypt. J. Chem. 59, No. 6 (2016)
1064 Eman A. Mwafy et al .

The main dominant peaks for ZnO were identified at 2θ=31.75°, 34.41°,
36.20°, 47.47°, 56.45°, 62.72°, 66.25°, 67.85° and 68.91°, that could be indexed
as (100), (002), (101), (102), (110), (103), (200), (112), (201) planes of ZnO
nanoparticles, respectively(10). There were not any other diffraction peaks
observed related to any impurities, it means that the resulted MWCNTs/ZnO
nanocomposite was pure.

The diameter (D) of ZnO nanoparticles was calculated using Debye Scherrer
formula D = Kλ/(βcosθ), where K is the Scherrer constant (equal to 0.9) , β is
the peak width at half maximum, λ is the X-ray wave length and θ is the Bragg
diffraction angle(11). The XRD pattern peaks showed that the ZnO nanoparticles
had a diameter of about 7 nm. Furthermore, the dominant peaks of ZnO were
more intensive and narrower, which means that a good crystalline nature of the
ZnO has been grown on the surface of MWCNTs.

Fig. 2. HRTEM of (a) MWCNTs and (b) MWCNTs/ZnO (99:1 wt%)

nanocomposite.

Figure 2(a) displays TEM images of the typical morphology of MWCNTs

prior to deposition indicating that most of the nanotubes are multiwalled tubes,
while Fig. 2(b) showed the morphology of decorated MWCNTs/ ZnO (99:1)
nanocomposite indicating that the deposition of ZnO nanocrystals is uniformed
distribution along the walls of the tubes with an average diameter around 2-7
nm and this result is in a good agreement with the result obtained from XRD.

As shown in Fig. 3, typical FTIR spectra of MWCNTs and MWCNTs/ZnO

nanocomposites can be clarify briefly. There is a band at 1569.5 cm-1 is
associated with the vibration of the carbon skeleton of the carbon nanotubes.
The two bands at about 2368.7 and 2337.6 cm-1 are corresponding to the C=C
double bonds stretch vibration, originated from the surface of tubes(12).

Egypt. J. Chem. 59, No. 6 (2016)

 Synthesis and Characterization of Multi-Walled Carbon... 1065

Fig. 3. FT-IR spectra of MWCNTs and MWCNTs/ZnO (99:1 wt%) nanocomposite.

The two bands at 1706, 1130 cm-1 indicate the existence of carboxylic
groups on the tubes surface (13). While IR spectra of the resulted MWNTs/ZnO
nanocomposites reveal the different surface chemistry of MWCNTs and the
MWNTs/ZnO nanocomposites. It can be observed that there are another two
weak peaks around 3516 and 3948 cm-1, which can be assigned to the stretching
vibrations of OH groups (14-16) . Compared with the IR spectra of MWCNTs, the
two peaks at 2368 and 2337 cm-1 became narrower and the two bands around
1706, 1130 cm-1 are lower in the composite than those of pure MWCNTs. The
result suggested that the surface of MWCNTs has been covered almost of
surface active sites by ZnO. Furthermore, the peak observed at about 460 cm -1
in Fig. 3 is assigned to the formation of ZnO.

Figure 4 shows the typical FESEM images of MWCNTs/ZnO

nanocomposites. In Fig. 4(a), the walls are composed of graphite sheets aligned
to the tube axis. The structures of individual MWCNTs are middle hollow,
while in Fig. 4(b) it is shown that ZnO nanoparticles have grown as a thin
nanosheet film layer on the surface of the MWCNTs because the diameter of
the tubes increase a few tens in nanometer.

Fig.4. FESEM of (a) MWCNTs and (b) MWCNTs/ZnO (99:1 wt%) nanocomposite.

Egypt. J. Chem. 59, No. 6 (2016)

1066 Eman A. Mwafy et al .

Fig. 5. EDX of MWCNTs/ZnO (99:1 wt%) nanocomposite.

In Fig. 5, EDX analysis was performed in order to confirm the elements

which presented in the resulted MWCNTs/ZnO nanocomposite, and the analysis
reveals the presence of Zn, O and C which emphasize the successful of
decoration process with ZnO nanoparticles. Also it was noted that there is no
any remaining catalyst in the composite improving the successful purification
process of the MWCNTs.

Conclusion

In summary, MWCNTs/ZnO (99:1 wt%) nanocomposite had been

successfully synthesized via a sol-gel method. TEM micrographs confirmed that
nanocomposite which is composed of carbon nanotubes coated evenly by ZnO
particles with a particle size of ZnO ranging from 2—7 nm and this result was
supported by the results obtained from XRD analysis. The morphology of
nanocomposite demonstrates that ZnO had grown on the walls of MWCNTs as
uniformed layer in the shape of thin film layer of noanspheres covering the
surface of the tubes. Also it was proved from EDX analysis that the resulted
nanocomposite was pure.

References
1. Milunovic, S., and Roy, M.A.J., An Introduction to Nanotechnology: The Next
Small Thing, Merrill Lynch (2001).
2. Iijima, S., Helical microtubules of graphitic carbon. Nature, 354(6348), 56–58
(1991).
3. Zhang, Y., Zhang, Q., Li, Y. B., Wang, N., and Zhu, J., Coating of carbon
nanotubes with tungsten by physical vapor deposition. Solid State Communications,
115 (1), 51–55 (2000).
4. Hongwei Bai, Xiaoli Zan, Lilin Zhang and Darren Delai Sun, Multi-
functional CNT/ZnO/TiO2 nanocomposite membrane for concurrent filtration and
photocatalytic degradation, Separation and Purification Technology, 156, Part 3,
922-930 (2015).

Egypt. J. Chem. 59, No. 6 (2016)

 Synthesis and Characterization of Multi-Walled Carbon... 1067

5. Georgakilas, V., Gournis, D., Tzitzios, V., Pasquato, L., Guldie, D.M. and
Prato, M., Decorating carbon nanotubes with metal or semiconductor
nanoparticles. J. Mater. Chem. 17, 2679–2694 (2007).
6. Ye, X. R., Lin, Y. and Wai, C. M., Decorating catalytic palladium nanoparticles on
carbon nanotubes in supercritical carbon dioxide. Chem. Commun. 9, 642 (2003).
7. Ji Qi, Neeva Benipal, Changhai Liang and Wenzhen Li, PdAg/CNT catalyzed
alcohol oxidation reaction for high-performance anion exchange membrane direct
alcohol fuel cell (alcohol = methanol, ethanol, ethylene glycol and glycerol).
Applied Catalysis B: Environmental, 199, 494-503 (2016).
8. Chien-Sheng Huang, Chun-Yu Yeh, Yung-Huang Chang, Yi-Min Hsieh,
Chien-Yeh Ku and Quan-Ting Lai, Field emission properties of CNT–
ZnO composite materials. Diamond and Related Materials, 18(2–3), 452-456
(2009).
9. Papitchaya Woointranont and Wisanu Pecharapa, Effects of Surface
Modification of Carbon Nanotubes on the Deposition of NiO/CNTs
Nanocomposites. Journal of the Microscopy Society of Thailand, 4(2), 116-119
(2011).
10. Pooya Azadi, Ramin Farnood and Emanuel Meier, Preparation of Multiwalled
Carbon Nanotube-Supported Nickel Catalysts Using Incipient Wetness Method. J.
Phys. Chem. A, 114, 3962–3968 (2010).
11. Jayaprakash Khanderi, Rudolf C. Hoffmann and Jorg J. Schneider, A 3D
monolithic CNT block structure as a reductant, support and scavenger for
nanoscopic gold, platinum and zinc oxide. Nanoscale, 2, 613–622 (2010).
12. Kuo-Yuan Hwa and Boopathi Subramani, Synthesis of zinc oxide nanoparticles
on graphene-carbon nanotube hybrid for glucose biosensor applications. Biosensors
& Bioelectronics, 62, 127–133 (2014).
13. Hamadanian,M., Jabbari,V., Shamshiri,M., Asad,M. and Mutlay,I., Preparation
of novel hetero-nanostructures and high efficient visible light-active photocatalyst
using incorporation of CNT as an electron-transfer channel into the support TiO2
and PbS. Journal of the Taiwan Institute of Chemical Engineers, 44, 748–757
(2013).
14. Xiaoya Yuan, Chao Zhou, Qiuye Jing, Qi Tang, Yuanhua Mu and An-ke Du,
Facile Synthesis of g-C3N4 Nanosheets/ZnO Nanocomposites with Enhanced
Photocatalytic Activity in Reduction of Aqueous Chromium(VI) under Visible
Light. Nanomaterials, 6, 173 (2016).
15. Alagar Ramar, Thiagarajan Soundappan, Shen-Ming Chen, Muniyandi
Rajkumar and Saraswathi Ramiah, Incorporation of Multi-Walled Carbon
Nanotubes in ZnO for Dye Sensitized Solar Cells. Int. J. Electrochem. Sci., 7,
11734 – 11744 (2012).
16. Chunyang Zhang, Yahong Xie, Junhong Ma, Jing Hu, Cancan Zhang,
Composite Catalyst of Reduced Black TiO2-x /CNT: Highly Efficient Counter
Electrode for ZnO-Based Dye-Sensitized Solar Cells. ChemComm., 00, 1-3 (2015).

(Received 22/11/2016 ;
accepted 30/11/2016 )

Egypt. J. Chem. 59, No. 6 (2016)

‫‪1068‬‬ ‫‪Eman A. Mwafy et al .‬‬

‫تحضير وتوصيف متراكب مه اوابيب الكربون الىاوومترية المطعم باكسيد الزوك‬

‫ايمان عبدالصادق احمد موافي‪ ، 1‬ماجدي ضوي بدري‪ ، 1‬احمد صبحي محمد مرسي‪، 2‬‬
‫‪3‬‬
‫ايىاس عبدالعزيز الضباغ‪ 3‬و ماجدي محمد محمود الفص‬
‫‪ 1‬قظى انكًٍٍبء انفٍشٌقٍخ – ‪2‬قظى انزحهٍم انطٍفً‪ -‬انًزكش انقٕيً نهجحٕس – انجٍشح ٔ قظى‬
‫‪3‬‬

‫انكًٍٍبء – كهٍخ انعهٕو – جبيعخ األسْز‪ -‬انقبْزح – يصز‪.‬‬

‫‪،‬‬
‫رى رحضٍز يززاكت يٍ اَبثٍت انكزثٌٕ انُبَٕيززٌخ انًطعى ثبكظٍد انشَك ثطزٌفخ انًحهٕل‬
‫انجٍالرًٍُ‪ٔ .‬اظٓزد َزبئج انًٍكزٔطكٕة االنكززٔرً انُبفذ ٔرشزذ االشعخ انظٍٍُخ ثبٌ ْذا‬
‫انًززاكت رى رحضٍزِ ثحجى جشٌئً ٌززأح يب ثٍٍ ‪ 2‬انى ‪َ 7‬بَٕيزز‪ .‬كًب اظٓزد َزبئج‬
‫انًٍكزٔطكٕة االنكززٔرً انًبطخ اٌ اكبطٍد انشَك ًَذ عهى جدراٌ اَبثٍت انكزثٌٕ‬
‫انُبٔيززٌخ ثزجبَض عبنى عهى شكم طجقخ رقٍقّ يُزظًّ عهى ططخ االَبثٍت‪ .‬ثبالضبفخ انى اٌ‬
‫رحهٍم انعُبصز اكد اٌ انًززاكت َقً ٔال ٌحزٕي عهى اي شٕائت ْٔذا يب اكدِ اٌضب يقٍبص‬
‫االشعخ رحذ انحًزاء‬

‫)‪Egypt. J. Chem. 59, No. 6 (2016‬‬