Hindawi Publishing Corporation
Journal of Nanomaterials
Volume 2016, Article ID 3967156, 6 pages
http://dx.doi.org/10.1155/2016/3967156
Research Article
Modified Sol-Gel Synthesis of Carbon Nanotubes
Supported Titania Composites with Enhanced Visible
Light Induced Photocatalytic Activity
Quanjie Wang,1 Yanqing Wang,1,2 Baorong Duan,1 and Mengmeng Zhang1
1
Department of Light Industry of Technology and Engineering, College of Chemistry and Chemical Engineering,
Yantai University, Yantai 264005, China
2
Key Laboratory of Wetland Ecology and Environment, Northeast Institute of Geography and Agro-Ecology,
Chinese Academy of Sciences, Changchun 130102, China
Correspondence should be addressed to Quanjie Wang; [email protected] and Yanqing Wang; [email protected]
Received 28 July 2015; Revised 8 November 2015; Accepted 12 November 2015
Academic Editor: Xujie Lü
Copyright © 2016 Quanjie Wang et al. This is an open access article distributed under the Creative Commons Attribution License,
which permits unrestricted use, distribution, and reproduction in any medium, provided the original work is properly cited.
Multiwalled carbon nanotube (MWCNT) enhanced MWCNT/TiO2 nanocomposites were synthesized by surface coating of carbon
nanotube with mixed phase of anatase and rutile TiO2 through a modified sol-gel approach using tetrabutyl titanate as raw material.
The morphological structures and physicochemical properties of the nanocomposites were characterized by FT-IR, XRD, DTA-TG,
TEM, and UV-Vis spectra. The results show that TiO2 nanoparticles with size of around 15 nm are closely attached on the sidewall
of MWCNT. The nanocomposites possess good absorption properties not only in the ultraviolet but also in the visible light region.
Under irradiation of ultraviolet lamp, the prepared composites have the highest photodegradation efficiency of 83% within 4 hours
towards the degradation of Methyl Orange (MO) aqueous solution. The results indicate that the carbon nanotubes supported TiO2
nanocomposites exhibit high photocatalytic activity and stability, showing great potentials in the treatment of wastewater.
1. Introduction Carbon nanotube (CNT) is a new category of carbon
structure, which was founded in 1991 by Iijima [11]. The
Treatment of the industrial wastewater, especially the organic ideal carbon nanotubes own seamless, hollow tube structure
pollutants which are difficult to be biochemically degraded, rolled by graphite surfaces slice layer composed of hexagon
is currently viewed as an active research area [1, 2]. Titanium carbon atom. According to the number of graphite surface
dioxide (TiO2 ) is an environmental-friendly photocatalyst layers, they can be divided into single walled carbon nanotube
material due to its high catalytic activity, thermal stability, (SWCNT) and multiwalled carbon nanotube (MWCNT).
strong oxidizing power, and nontoxic, low cost, and other CNTs are considered to be ideal catalyst carriers due to
unique advantages [3–5]. However, its photoefficiency is not their huge specific surface area, remarkable chemical stability,
high enough and the speed of ultraviolet photoresponse is not unique electronic structure, nanoscale hollow tube property,
satisfactory [6, 7]. On the other hand, there is a measurable and good absorbability [12–15].
reduction in the photocatalytic activity for the recycled use of It was demonstrated in the paper that CNTs are regarded
the photocatalysts. The disadvantage of TiO2 semiconductor as the carrier of TiO2 nanoparticle with the aim of improving
is that it only absorbs a small portion of solar spectrum in the the photocatalytic activity effectively and make TiO2 easy to
ultraviolet region, which limits its applications. Therefore, the recycle. Herein, MWCNT/TiO2 nanocomposites were syn-
development of modified TiO2 with enhanced visible light thesized by surface coating of carbon nanotubes with anatase
induced properties is needed to increase the photocatalytic and rutile types TiO2 through a modified sol-gel approach
activity for the organic pollutants [8–10]. using tetrabutyl titanate as the raw material. The obtained
2 Journal of Nanomaterials
(a) (b)
Figure 1: Typical SEM morphology of (a) modified MWCNT and (b) MWCNT/TiO2 nanocomposites.
(a) (b)
Figure 2: Typical TEM images of acid modified MWCNT coated with nanosized TiO2 materials in low magnification (a) and high magnifi-
cation (b).
photocatalysts exhibit higher performance for Methyl Orange tube-like aperture structure of carbon nanotubes with large
(MO) than pure TiO2 . surface area contributes to the adsorption of the organic
molecules. On the other hand, it is observed that the surfaces
of MWCNT were not fully covered by TiO2 nanoparticles,
2. Results and Discussion since the number of active sites on MWCNT generated by
The morphology and microstructure of the acid modi- the acid treatment is not sufficient for the full covering [16].
fied MWCNT and MWCNT/TiO2 nanocomposites were Figure 3 presents the Fourier transform infrared (FT-IR)
observed by Scanning Electron Microscope (SEM) and trans- spectroscopy spectrum of MWCNT/TiO2 nanocomposites.
mission electron microscope (TEM) investigations, respec- The appearance of two strong absorption peaks at 2920 cm−1
tively. As shown in Figure 1(a), the acid modified MWC- and 2850 cm−1 is attributed to symmetrical and asymmetric
NTs were dispersed uniformly with no or less aggregation. telescopic vibration of methylene group (-CH2 -) of carbon
The weaved interconnected networks of carbon nanotubes nanotubes, which indicates that the methylene structure of
contribute largely to the homogenous supporting of pho- carbon nanotubes is not destroyed. Two absorption peaks at
tocatalyst nanoparticles. After being supported by TiO2 1728 cm−1 and 1160 cm−1 demonstrate the formation of car-
photocatalysts, as shown in Figure 1(b), the interval space of boxyl groups and carbonyl groups in the modification stage
these weaved MWCNT networks was filled with nanosized [17]. Additionally, the band in the low wavenumber around
TiO2 . 670 cm−1 in the spectrum corresponds to the characteristic
In the TEM image with low magnification (Figure 2(a)), absorption peak of TiO2 [18].
MWCNTs coated with TiO2 nanoparticles are identified with In order to describe the crystalline structure of the
minor agglomeration of MWCNT. From the TEM image obtained nanocomposites, X-ray diffraction (XRD) spectra
with higher magnification (Figure 2(b)), it can be seen that were involved in the characterization. As shown in Figure 4,
the TiO2 nanoparticles with an average size of 15 nm are a characteristic diffraction peak at 2𝜃 = 26.23∘ is the typical
closely attached on the walls of MWCNT, which agrees feature of carbon nanotubes. In curve (b), the peaks at 2𝜃 =
with the XRD results below. Furthermore, the long and 25.33∘ and 27.48∘ are attributed to anatase and rutile structure
Journal of Nanomaterials 3
100 absorption in the region of visible light from 400 to 800 nm
with slight increase of absorption intensity between 700
and 800 nm in the wavelength. The composites have good
95
absorption properties not only in the ultraviolet area but also
Transmittance (%)
in the visible light region, which is of significance for us to
1728
662
exploit and utilize solar energy resources in the application
2850
90
1382
2920
of environmental remediation [22].
To explore the photocatalytic activity of MWCNT/TiO2
1160
85 nanocomposites, photocatalytic experiments are performed
1580
using MO as the model pollutant under irradiation of
3427
ultraviolet lamp. Figure 7 shows the relation of the irradiation
80 time and the degradation of MO by MWCNT/TiO2 , pure
4000 3500 3000 2500 2000 1500 1000
Wavenumbers (cm−1) TiO2 , and MWCNT. The prepared composites have higher
degradation efficiency than pure TiO2 , which is comparable
Figure 3: FT-IR spectrum of MWCNT/TiO2 nanocomposites. with the previous result that metal-doped TiO2 (P25) has a
much higher photocatalytic activity than pure TiO2 with a
degradation ratio of less than 10% under visible light and
around 30% even under a 500 W high-pressure Hg lamp
(a) [23]. Within 4 h, the highest photodegradation efficiency can
reach 83%. However, only about 53% and 34% of MO were
Intensity (a.u.)
degraded by using pure TiO2 and MWCNT, respectively.
The photocatalytic activities of TiO2 were largely improved
A(101)
through the addition of MWCNT. The reason can be con-
(b) A(200)
A(103) A(105) A(213) cluded as follows: firstly, MWCNT can absorb dissolved
R B oxygen and organic matter on the outside of its surface due to
the large surface area and special aperture structure; secondly,
20 30 40 50 60 70 MWCNTs are eminent electronic conductors that can orderly
2𝜃 (deg.) export electrons from the surface of TiO2 and quickly reduce
electronic accumulation on TiO2 [24, 25].
A: anatase
R: rutile
B: brookite 3. Experimental Section
Figure 4: XRD patterns of MWCNT (a) and MWCNT/TiO2 (b) na-
nocomposites.
3.1. Materials. MWCNT (diameter 10–20 nm, length 1-2 𝜇m,
purity: 98%, and ashes 0.2 wt.%) was purchased from
Nano Port of Shenzhen Inc.; tetrabutyl titanate (CP) and
other chemicals were purchased from Sinopharm Chemical
of TiO2 , respectively [19]. The main characteristic diffraction Reagent Limited Corporation.
peak of carbon nanotubes at 25.33∘ is overlapped with
characteristic feature of TiO2 . Furthermore, the obtained
TiO2 particles with around 15 nm were calculated by Scherrer 3.2. Purification of MWCNT. 1.0 g MWCNT were acidified
equation using the peak of 2𝜃 = 25.33∘ [20], which is in a mixed solution of concentrated sulfuric (98%) and
consistent with TEM images. nitric acids (65%–68%) with a volume ratio of 3 : 1 under
In order to evaluate and confirm the chemical compo- ultrasonication at 70∘ C for 3 h. Then, the MWCNTs were
sitions of the prepared samples, differential thermal anal- separated by filtration, followed by the washing with distilled
ysis and thermogravimetric (DTA-TG) analysis of carbon water until pH = 7. The purified MWCNTs were dried at 100∘ C
nanotubes and MWCNT/TiO2 nanocomposites is shown in and ground for the further using.
Figure 5. There is an obviously exothermic peak at 650∘ C,
which is attributed to the peak of carbon nanotube. TG curve 3.3. Preparation of MWCNT/TiO2 Composites. In a typical
shows that a weight loss happens at 600∘ C and it can be sup- experiment for the preparation of composites, titanium
posed that the framework of carbon nanotubes was destroyed dioxide coated MWCNT was prepared by the following pro-
and then volatilized. The loading amount of MWCNT in the cedure. A precursor solution was prepared by the mixing of
MWCNT/TiO2 nanocomposites is about 12 wt.%, which is in 5 mL of ethanol and 1.5 mL of glacial acetic acid as inhibitors.
agreement with the results of previous reports that the low 20 mL of tetrabutyl titanate as a TiO2 precursor was added
ratio of carbon-based supporter contributes to the dispersion dropwise to the solution under stirring. The resulting solution
of catalysts on the supporters [21]. was designated as A. 20 mg of surface modified carbon
Figure 6 shows the UV-Vis spectra of the pure TiO2 , nanotubes was dispersed in a mixture solution of nitric acid,
MWCNT, and MWCNT/TiO2 nanocomposites. The absorp- deionized water, and ethanol. After ultrasonic vibration for
tion spectrum for the composites in 400 nm is much higher 20 min, the obtained suspension was mixed with solution A
than that of pure TiO2 . The composites also have stable under constant stirring until the gel formation. The gel was
4 Journal of Nanomaterials
30 20 25 5
25 0 20
20 15 0
−20
Mass loss (%)
Mass loss (%)
15 10
DTA (𝜇V)
DTA (𝜇V)
−40
10 5 −5
−60
5 0
−80
0 −5 −10
−5 −100
−10
−10 −120 −15
0 100 200 300 400 500 600 700 800 0 200 400 600 800
Temperature (∘ C) Temperature (∘ C)
(a) (b)
Figure 5: DTA-TG curves of MWCNT (a) and MWCNT/TiO2 (b) nanocomposites.
100
TiO2 1.0
80
0.8
Reflectivity (%)
60
0.6
C/C0
40 MWCNT/TiO2
0.4
20
0.2
CNT
0
0.0
300 400 500 600 700 800 0 1 2 3 4
Wavelength (nm) Time (h)
MWCNT/TiO2
Figure 6: UV-Vis absorption spectra of pure TiO2 , MWCNT, and TiO2
MWCNT/TiO2 nanocomposites. MWCNT
Figure 7: Effect of photocatalytic decomposition of Methyl Orange
aged for 48 h at room temperature, followed by the drying with irradiation time.
in air at 105∘ C for about 8 h and the further grinding to a
powder. The powder was then calcined at 450∘ C in air for 2 h
to produce MWCNT/TiO2 nanocomposites. determine the concentration of the sample. The concentra-
tion of the MO dye was monitored by UV-Vis spectroscopy
3.4. Photocatalytic Degradation Experiment. 200 mg nano- by recording the absorbance of the characteristic peak of MO
composites were added into 250 mL Methyl Orange (MO) at 465 nm. The change of MO concentration was regarded as
solution with concentration of 20 mg/L. After the pH value the evaluation of photocatalytic activity of the composites.
of degradation solution was adjusted to about 3, the solution
under vigorous stirring was irradiated by 200 W medium 3.5. Characterization and Testing. The FT-IR spectra were
mercury lamp with a main wavelength of 365 nm (Beijing recorded on a Shimadzu IR-440 infrared spectrometer. The
Institute of Light Sources). The dispersion was kept in the morphology of the particles was observed by JEM-1230
dark for 60 min for dark adsorption experiments, after which transmission electron microscope and JSM-5610LV scanning
photodegradation was carried out. The dark adsorption was electron microscope. DTA-TG measurement was carried
designed to be 60 min because the adsorption results indicate out in static air condition at room temperature. The X-ray
that MO molecules were absorbed to saturation on the diffraction (XRD) patterns were recorded by a PANalytical
surface of catalysts (data not shown). A certain amount of X’Pert PRO diffractometer operating at 50 kV with Cu k𝛼
aliquots (3 mL) was taken from solutions every 30 min to radiation. The XRD intensity was measured by step scanning
Journal of Nanomaterials 5
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