Materials Research Bulletin 47 (2012) 39433946

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Materials Research Bulletin

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Cotton fibers nano-TiO2 composites prepared by as-assembly process and the

photocatalytic activities
J.H. Xia *, C.T. Hsu, D.D. Qin
School of Engineering, The Hong Kong University of Science and Technology, Hong Kong, PR China

A R T I C L E I N F O A B S T R A C T

Article history: This paper describes photocatalytic cotton fibers produced by a TiO2 nanoparticle self-assembly process
Received 30 November 2011 with the assistance of carboxylic groups. The carboxylic group was introduced by a displacement
Received in revised form 19 June 2012 reaction, the molecular structure of the glucose unit was studied by utilizing solid 13C NMR. The
Accepted 28 July 2012
appearance of the prepared fibers was observed by scanning electron microscopy, it was found that nano-
Available online 14 August 2012
TiO2 coated uniformly on the fiber surface. The loading amount of nano-TiO2 was depended on the
displacement degree of C-6-OH. UVVis experiments showed these coated fibers undergo photocatalysis
Keyword:
efficiently. The degradation reaction of Rhodamine 6G under UV light obeys the zero-order rate law.
A. Composites
! 2012 Elsevier Ltd. All rights reserved.
A. Surface
A. Nanostructures
C. Nuclear magnetic resonance (NMR)

1. Introduction nano-TiO2 quite heterogeneous distribution, this is because

Titanium dioxide nanoparticles (nano-TiO2) in the anatase form
are an effective type of photocatalyst. They efficiently absorb solar
energy to produce active superoxide anions and hydroxyl radicals,
which can decompose organic and biological species. Nano-TiO2 is
utilized by the textile industry to produce clothes with excellent
anti-bacteria and anti-fungus properties. For this purpose, nano-
TiO2 needs to be attached to the fiber firmly.
Cotton fiber is widely used to make soft textile. The main
ingredient of cotton fiber is cellulose, a linear polymer of D-glucose
with 3 hydroxyl groups on C-2, C-3 and C-6 in the 6-member cycle
chain. These polar groups can adsorb the nanoparticles via oxygen
bonding [1]. However, the carboxylic group is more polar than the
hydroxyl one, as well it has a stronger interaction with the hydroxylic
group on the nanoparticle surface [2,3]. The oxygen from the
hydroxyl group is a basic atom and a nucleophilic center, it easily
attacks the carbon and then a displacement reaction is carried out
after leaving the halide ion. This characteristic can be utilized to
convert OH into COOH. The newly formed COOH can be utilized to
anchor TiO2 to produce more stable nano-TiO2polymer composites.
The general strategy of coating nano-TiO2 on the fiber surface is
by a common dipping or dripping technique [46]. The coating
thickness is at the mm-scale even without repeated dipping
operation. For practical applications, these methods will lead to
* Corresponding author. Tel.: +852 23588808; fax: +852 23588719.
E-mail address: xiajianhan@163.com (J.H. Xia).
bundles and bundles fibers are used like a filter. However, it is
very important that the fibers retain their natural features after the
surface modification. Particle-loading is an important parameter
for this kind of material process. It is necessary to develop a
technique that can be carried out in room temperature without
heating to produce a thin film and tune the TiO2-loading.
In this paper, a thin layer of nano-TiO2 was developed by self-
assembling nanoparticles on the fiber surface.
2. Experiment
In this paper, TiOx (0 < x ! 2) nanoparticles were produced by
the arc discharge method. Nanoparticles were previously prepared
using arc discharge in a liquid medium, such as deionized water
[7,8], or ethanol [9]. The experiment was conducted with the
following parameters, a 1 mm diameter titanium wire as the
consumable anode, graphite cathode with a 3 mm diameter, and an
applied voltage of 130 V. The two electrodes were submerged into
a liquid medium in a glass beaker. The arc discharge was controlled
by a DC power and a stepping motor.
Before the experiment, cotton fiber was dipped into ethanol and
deionized water respectively in an ultrasonic bath for 3 times. The
carboxylic acid groups were introduced to the D-glucose unit via
chloroacetic acid reaction. Typically, cotton fiber was treated by a
strong alkali and chloroacetic acid. After the alkoxide has attacked
the carbon-chlorine bonds and left the chlorine atoms, carbox-
ymethyl cellulose was formed. Before further experiments, these
as-prepared fibers were washed 3 times in a deionized water bath.

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3944 J.H. Xia et al. / Materials Research Bulletin 47 (2012) 39433946
TiO2-coated cotton fibers (TCFs) were produced by soaking the
cotton fibers into the TiO2 suspension, and then left to dry in air for
24 h; the same procedure is typically repeated for 3 times.
The experiments of Rhodamine 6G (R6G) degradation by TCFs
were carried out in a UV irradiation chamber. Samples with an
initial concentration of 5 " 10#5 mol/L of R6G, the catalyst loading
1 g/kg, were irradiated with a 4 W UV lamp (peak wavelength
370 nm), bubbled air was fed into the dye solution at a flow rate of
$100 mL/min. The environment temperature throughout the
experiments was maintained at around 25 8C. Samples for UV
Vis testing were obtained at an interval of 30 min after
centrifugation. The intensity change of the absorption maximum
indicated the degree of R6G concentration varied according to
Beers law. The final concentrations of R6G were obtained from the
calibration curve of the standard solution.
Characterization. Scanning electron microscopy (SEM) was
carried out using ultra-high resolution SEM (1 nm at 15 kV and
2.2 nm at 1 kV, a cold field emission gun, and the model JSM-6700F).
The structural properties of TiO2 particles were analyzed by X-
ray diffraction (XRD). A PAnalytical powder X-ray diffractometer
was equipped with an Xpert Pro model, and a monochromatized
X-ray beam from the nickel-filtered CuKa radiation. For XRD
testing, the samples were deposited onto glass slides, followed by
vacuum-drying at room temperature.
The experiments were performed on a solid state nuclear
magnetic resonance spectrometer (Solid 13C NMR, Model NM-
ESH40MU, JEOL, frequency range 40162 MHz).
The degree of dye decoloration was measured with a
spectrophotometer (Perkin Elmer, Lambda 20, range 190
1100 nm, resolution 1 nm) at the peak intensity l = 526 nm.
3. Results and discussion
3.1. XRD analysis
Powder samples were produced by vaporizing the medium
followed by rinsing with ethanol and then deionized water, and
finally drying in a 50 8C vacuum oven to remove the water. The
powder samples were sintered at different temperatures to study
the amount of carbon removed and titanium atom oxidation. After
thermal post-treatment, crystals were formed and compositions of
as-synthesized nanoparticles were measured by XRD. In this paper,
the experiment temperature was raised to 450 8C and 600 8C and
maintained for 30 min. 2u were collected from 208 to 708, and the
Fig. 1. XRD patterns of TiO2. Reflections from anatase and rutile TiO2 are indicated
by A, R.
XRD patterns are shown in Fig. 1. Before thermal treatment, the
starting powder was assigned to TiC. The 450 8C-samples had main
composition mixing TiO2 and TiC, indicating that the sintering
temperature of 450 8C was not high enough to remove the carbon
and anatase TiO2 formation. However, the 600 8C-samples showed
a mixing phase of anatase and rutile. The results indicate that a
heating temperature of 600 8C is sufficient to oxidize Ti to TiO2 and
remove the carbon. The rutile appearance suggests transformation
from anatase to rutile occurred [10]. However, anatase TiO2 has a
better photocatalytic activity and stronger antibacterial property
than rutile. So in this paper, the treatment temperature was no
more than 600 8C.
3.2. NMR studies
Cotton fiber consists of many glucose units, 13C NMR can give the
spectrum of chemical shifts of C-1 to C-6 in the glucose units [11]. If a
chemical reaction occurs in the backbone unit to link some chemical
groups, there will be new peaks or a change in the intensity of the
signal. In this study, the spectra recorded by a solid state 13C NMR
spectrometer were studied by comparing before and after the
treatment of chloroacetic acid to characterize the formation of
carboxymethyl groups. Fig. 2.1 shows the typical spectra of cellulose
obtained, four main peaks were assigned to the chemical shifts of C-
1, C-4, C-2C-5, and C-6. Comparing the two samples (Figs. 2.1 and
2.2), the appearance of two new peaks with chemical shifts at
175.2 ppm and 44.5 ppm is noticed. The signal intensity of C-2 and
C-3 decreased slightly, and C-6 at 64.3 ppm shows a like broad peak
from 59.6 to 65.9 ppm; there is much difference to the original fibers
without treatment. For the R-COOH compounds, a typical position of
the carbonyl carbon is in the region of 160180 ppm. The 175.2 ppm
signal was assigned to the contribution of the carboxyl groups [12].
The new peak of 44.5 ppm was assigned to methylene. By
comparison, in the original cotton fiber (Fig. 2.1), the NMR spectra
changes correspond to the results that the displacement reaction of
hydroxyl mainly on C-2 and C-3 (COH) with carboxylmethyl group
underwent. By this way, the carboxylic groups (OCCOOH) were
introduced to the cotton fiber surface.
3.3. TEM observation
The main purpose of cotton fiber modification is to introduce
new features to the fabric. For a good anti-bacteria and anti-fungus
effect, as well as retaining the macroscopic properties of soft
textile, the fibers should be coated with no more than a single layer
7 C 2, 3, 5
5
Signal Intensity
C6 C1
4
65.9 ppm C4
3 59.6 ppm
-COOH
CH2 175.2 ppm
2
1 2
0 C6 64.3 ppm 1
0 20 40 60 80 100 120 140 160 180 200
Chemical Shift (ppm)
Fig. 2. 13C NMR spectra of cotton fiber before or after chloroacetic acid treatment.
(1) Original fiber, (2) the fiber after chloroacetic acid treatment.
 J.H. Xia et al. / Materials Research Bulletin 47 (2012) 39433946 3945

of nano-TiO2. The appearance of the experimental fibers before and
after nano-TiO2 was coated on the cotton fibers was analyzed and
compared using SEM images.
In Fig. 3, the SEM images show the fibers were coated uniformly
with nano-TiO2. There were also some uncoated surfaces on the
fibers. This is beneficial for lowering the nano-TiO2-loading and
retaining the original physical properties of the fibers. The nano-
TiO2 covered not only the surface of the fiber sheet but also the area
between individual fibers. This phenomenon can be explained by
the fact that the carboxylic groups have existed along the polymer
fibers. The strong polar carboxylic groups could anchor the nano-
TiO2 anywhere on the fibers surface via chemical interaction. This
is quite different from the simple soaking method. The method
adopted in this paper contributed to the nano-TiO2 self-assembly
process on the fiber surface. At the same time, this chemical
interaction led to monolayer formation and mitigated the problem
of large amounts of excess TiO2 nanoparticle deposition on the
fiber surface.
From the NMR results, we found that OCCOOH was formed
by HCl elimination. The hydroxylic groups were more active in
adsorbing TiO2 by interaction with TiOH and OCCOOH. As a
result of this reaction, inorganic nanoparticles attached easily onto
the fiber surface. The schematic of the process is shown in Fig. 4.
One particle can react with a few carboxylic groups. The conversion
yield of COH to OCCOOH is not 100%, this is the reason why
there was an uncoated area (Fig. 3A). Increasing the treatment time
of chloroacetic acid reaction increased the conversion yield of
COH to OCCOOH. So, there were more COOH per unit surface
area of fiber, which resulted in an increase in the amount of
attached particles (Fig. 3E and B). This is a practical and easy way to

Fig. 3. SEM images of (A) naked cotton fibers, (B, C, E) TiO2-coated cotton fibers, (D) enlarged image of selected area in image B.

Fig. 4. Schematic model of TiO2 self-assembled on the surface of cotton fibers.

3946 J.H. Xia et al. / Materials Research Bulletin 47 (2012) 39433946

R6G Decoloration under UV

In the same figure, degradation degree y C 0 # C t =C 0 , x axis is
0.5 h
80 the degradation time. The degradation degree increased with time.
A linear trend line was simulated and can be described by the
equation y k ( x b. The results show the degradation rate is
y = 20.357x - 4.5 almost constant, k = 20.3 h#1. That means the degradation reaction
R6G Degradation (%)

60 2
R = 0.9646 obeys the zero-order rate law. After 3.5 h, nearly 70% of the R6G
3.5 h was decomposed.

40
4. Conclusions

500 600 y = 2.8204x - 0.2635 Cotton fiber modified by a polar carboxylic group can plant
20 2 nano-TiO2 by a self-assembly process to produce TiO2 compo-
R = 0.9516
sites. The most interesting feature of this process is nano-TiO2
loading can be controlled by the number of carboxylic groups
0 per unit area of the fiber surface. Photocatalyst performance was
0 0.5 1 1.5 2 2.5 3 3.5 4 studied using R6G as a photodegradation goal, under 370 nm of
Time (h) UV light. After 3.5 h, around 70% of the R6G was decomposed. By
calculation, the degradation reaction obeys the zero-order rate
Fig. 5. Kinetics of the photocatalytic degradation of aqueous solutions of R6G under
UV irradiation. (a, ^ TCFs), (b, & naked cotton fiber without TiO2). Absorbance
law. The photocatalytic activities show potential for practical
values at 526 nm were measured to calculate the concentration of R6G. The inset applications in the antibacterial textile industry.
shows the absorption spectra of the R6G solution at various time intervals after
ultracentrifugation (105 rpm). Acknowledgements

We are grateful to Hong Kong ITC Project (GHP/028/08SZ) for

control the inorganic nanoparticle loading by changing the degree financial support. We would also like to thank MCPF for material
of COH displacement. properties characterization.

3.4. Photocatalytic activities experiments References

Optical absorption depends on the concentration of conju-
gated chromophore in a molecular structure. R6G is a common
dye to determine the nano-TiO2 photodegradation activities
[10]. For R6G, absorption at 526 nm was assigned to the
response of the conjugated xanthene ring in a molecule
structure. So the reduction in the absorption maximum indicates
partial decomposition of the R6G. In this case, under UV
illumination, hydroxyl radicals were formed on the nano-TiO2
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A useful method to determine the degradation rate of R6G is to
measure absorbance values at the peak position at series time
intervals of UV irradiation. In Fig. 5 the inset shows the absorbance
change as a function of UV irradiation time. The R6G concentration
decreased with illumination time during the degradation process.
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