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Enhanced photodegradation of methyl orange with TiO2 nanoparticles using a triboelectric

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2013 Nanotechnology 24 295401

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IOP PUBLISHING NANOTECHNOLOGY
Nanotechnology 24 (2013) 295401 (6pp) doi:10.1088/0957-4484/24/29/295401

Enhanced photodegradation of methyl

orange with TiO2 nanoparticles using
a triboelectric nanogenerator
Yuanjie Su1,2,4 , Ya Yang1,4 , Hulin Zhang1 , Yannan Xie1 , Zhiming Wu2 ,
Yadong Jiang2 , Naoki Fukata3 , Yoshio Bando3 and Zhong Lin Wang1,3
1
School of Materials Science and Engineering, Georgia Institute of Technology, Atlanta,
GA 30332-0245, USA
2
State Key Laboratory of Electronic Thin Films and Integrated Devices, School of Optoelectronic
Information, University of Electronic Science and Technology of China (UESTC), Chengdu 610054,
People’s Republic of China
3
MANA, International Center for Materials Nanoarchitectonics, National Institute for Materials
Science, 1-1 Namiki, Tsukuba, 305-0044, Japan

E-mail: zlwang@gatech.edu

Received 14 April 2013, in final form 21 May 2013

Published 27 June 2013
Online at stacks.iop.org/Nano/24/295401
Abstract
Methyl orange (MO) can be degraded by a photocatalytic process using TiO2 under UV
irradiation. The photo-generated holes and electrons can migrate to the surface of TiO2
particles and serve as redox sources that react with adsorbed reactants, leading to the
formation of superoxide radical anions, hydrogen peroxide and hydroxyl radicals involved in
the oxidation of dye pollution. Here, we fabricated a polytetrafluoroethylene–Al based
triboelectric nanogenerator (TENG) whose electric power output can be used for enhancing
the photodegradation of MO with the presence of TiO2 nanoparticles, because the TENG
generated electric field can effectively boost the separation and restrain the recombination of
photo-generated electrons and holes. Due to the photoelectrical coupling, the degradation
percentages of MO for 120 min with and without TENG assistance are 76% and 27%,
respectively. The fabricated TENGs have potential applications in wastewater treatment, water
splitting, and pollution degradation.
S Online supplementary data available from stacks.iop.org/Nano/24/295401/mmedia
(Some figures may appear in colour only in the online journal)

1. Introduction mobility of water systems in the environment, wastewater

treatment and liquid pollutant degradation can be a vital
Wastewater treatment, pollution degradation and energy issue for the whole of society [19]. Not only does the
shortage are among the most crucial problems that humanity wastewater treatment affect human health and hygiene, but
has to solve. Currently, based on piezoelectric [1–3], tribo- also it has a great influence on the entire ecosystem for all
electric [4, 5], and pyroelectric [6, 7] effects, nanogenerators creatures. Consequently, a green, energy-saving and low cost
have been extensively fabricated for applications in driving method for purifying water sources is desired. In general,
electronic devices [8, 9], self-powered nanosystems [10–12], wastewater from textile manufacturing, including aromatic
and sensors [13–18]. Owing to the enormous distribution and compounds and organic dyes, presents a potential hazard to
the environment that must be dealt with before the wastewater
4 These authors contributed equally to the work. can be discharged [20]. Titanium dioxide (TiO2 ) is one of

0957-4484/13/295401+06$33.00 1 c 2013 IOP Publishing Ltd Printed in the UK & the USA

Nanotechnology 24 (2013) 295401 Y Su et al

the most investigated photocatalysts and has been found to the back electrode of PTFE. The layer of Al plays dual roles
be capable of decomposing a wide variety of organics and of electrode and triboelectric materials. The Al foil and Cu
inorganics in both liquid and gas phases [21]. The basic film was pasted on the PET substrates to protect the generator
principle of TiO2 photocatalysis involves photo-generated from mechanical impact. The microstructure of the TENG
electrons and holes migrating to the surface of TiO2 particles layer was characterized by scanning electron microscopy
and serving as redox sources that can react with adsorbed (SEM) as shown in figure S3 (available at stacks.iop.org/
reactants, leading to the formation of superoxide radical Nano/24/295401/mmedia). Figure S3(a) (available at stacks.
anions, hydrogen peroxide and hydroxyl radicals. The reactive iop.org/Nano/24/295401/mmedia) demonstrates Al foil to be
hydroxyl radical enables oxidation of organic compounds the electrode layer. Figures S3(b) and (c) (available at stacks.
in aqueous solution, mineralizing them to CO2 and H2 O. iop.org/Nano/24/295401/mmedia) shows the PTFE film layer
Although TiO2 photocatalytic degradation is a promising and the Cu foil, respectively. Figure S3(d) (available at stacks.
means for degradation of dyes, the low separation efficiency iop.org/Nano/24/295401/mmedia) illustrates the Cu foil under
and relatively high recombination of photo-generated carriers PTFE as one electrode for conducting the inductive charges.
limit the quantum efficiency of photodegradation. Here, According to figure S3 (available at stacks.iop.org/Nano/24/
we demonstrate that the photodegradation of MO can be 295401/mmedia), the thicknesses of Al foil, Cu film and PTFE
effectively enhanced by using a triboelectric nanogenerator film are about 96.5 µm, 171.3 µm, 30.2 µm, respectively.
(TENG). The TENG was fabricated by using polytetraflu- The PET was from DURA with a thickness of 220 nm.
oroethylene (PTFE) and an Al layer as the triboelectric The contact electrode (Al) and back electrode (Cu) of the
materials to harvest the mechanical energy based on the TENG were connected to the Pt electrodes in MO solution
triboelectric effect [22, 23]. By converting mechanical energy in order to produce an electric field. In addition, the Pt
into electricity, the TENG yields an electric field in the electrodes were covered by polydimethylsiloxane (PDMS)
MO solution to promote the separation and inhibit the film to prevent the current conduction in MO solution. The
recombination of photo-generated electrodes and holes for the TENG was mechanically triggered by a linear motor that
photocatalytic oxidation of dye pollutants. provided dynamic impact with controlled speed, force and
frequency. A rectifying bridge was connected to the TENG to
2. Experimental details convert the alternating current (AC) to direct current signals.
The output performance of the TENG was measured using
TiO2 nanopowders (Anatase, Evonik) were sonicated using Stanford Research Systems. SR560 and SR570 low noise
Branson Transonic 2510 and placed in the reactor. Methyl current amplifiers were used to record voltage and current,
orange (SIGMA-ALDRICH, ACS reagent, dye content 85%) respectively.
was placed in the reaction vessel and the mixture was placed
at the same position all the time for the UV irradiation
3. Results and discussion
and absorption measurement. With plenty of deionized water
filled in the reaction vessel, the concentration of TiO2 is
0.6 g l−1 and the concentration of MO is 20 mg l−1 . Figure 1(a) shows a scanning electron microscopy (SEM)
Prior to irradiation, the solution was stirred in the dark at image of TiO2 nanoparticles, indicating that the diameter
a speed of 6000 rev min−1 for 20 min. The methyl orange of the particles ranges from 20 to 40 nm. As displayed
(MO) was irradiated with a solar simulator (500 W model in figure S1 (available at stacks.iop.org/Nano/24/295401/
91160, Newport) with an AM 1.5 spectrum distribution mmedia), an x-ray diffraction (XRD) pattern of TiO2
(100 mW cm−2 ). In this work, the photocatalytic degradation illustrates a dominance of the anatase over the rutile form
of MO using TiO2 nanoparticle was conducted without O2 in a ratio of 6:1. The phase and crystal structure of the
bubbling. Every 30 min during the photodegradation process, TiO2 particles were confirmed by the lattice TEM image in
a small amount of MO suspension was taken out and then figure 1(b). The high magnification TEM image in the inset
stirred for 10 min in order to precipitate the particles in of figure 1(b) demonstrates that the distance between lattice
solution. Subsequently, the absorption spectra of MO were fringes is 0.35 nm, which can be attributed to (101) of the
measured using a UV–visible spectrophotometer (JASCO anatase TiO2 phase.
V-630). Figure 1(c) reveals absorption spectra of MO decom-
The morphology and nanostructure of TiO2 particles posed in the presence of TiO2 photocatalyst under UV
were characterized using a LEO 1530 field emission scanning irradiation. The spectrum ranges from 350 to 600 nm with
electron microscope (SEM) operated at 10 kV and a a peak at the wavelength of 464 nm. It can be seen that the
transmission electron microscope (TEM) TF30 operated at characteristic absorption peak intensity of MO decreases with
300 kV. Phase identification of TiO2 was conducted by means increasing degradation time. After 420 min of UV irradiation,
of x-ray diffraction (XRD) using a PANalytical X’Pert PRO the degradation of MO is up to 97% and the absorption peak is
diffractometer. totally removed. Figure 1(d) displays the decoloration of MO
The TENG consists of polyethylene terephthalate (PET) suspension at different degradation times. The color change
film, a Cu film, a PTFE film, and an Al foil, where PET film from dark orange to colorless indicates that the MO has been
was selected for the substrates at the top and bottom of the degraded by the TiO2 nanoparticles under UV irradiation. The
TENG. PTFE film serves as the contact layer. Cu film acts as mechanism of the photodegradation of MO by using TiO2

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Nanotechnology 24 (2013) 295401 Y Su et al

Figure 1. (a) SEM image of TiO2 nanoparticles. (b) TEM image of the TiO2 nanoparticles. Inset: high magnification TEM for the lattice
image of TiO2 . (c) Absorption spectra of MO degraded by TiO2 under UV irradiation. (d) Decoloration of MO at different photodegradation
times.

nanoparticles is proposed as follows [24]: the system for degradation of MO by photocatalytic oxidation.
The TENG is connected to Pt electrodes in MO solution
TiO2 + hν → TiO2 (e− , h+ ), (1)
to form parallel built-in electric field. The rectifying bridge
+ −
h + OH → ·OH, (2) circuit was used to convert the ac output into dc. UV light
e − + O2 → 2,
O− (3) source was placed 10 cm above the level of MO. Due
to the insulating property of the contacting material, the
dye + O−
2 or ·OH → peroxylated or hydroxylated intermedi- triboelectric charges stored in a single layer can be retained
ates → degraded products. for hours or even days [25]. Therefore, the fabricated TENG
UV irradiation of TiO2 excites electrons from a filled
photocatalysis system can work with high performance for
valence band to an empty conduction band, giving rise to
several years at least. Figure 2(b) shows a schematic diagram
electron–hole pairs. The valence band holes (h+ ) can migrate
of the TENG. In this study, the TENG was made of PET, a
to surfaces of TiO2 particles and react with adsorbed OH−
to produce hydroxyl radicals (·OH), whereas the conduction Cu layer, PTFE film, and Al foil. PET was selected as the
band electrons (e− ) migrate to the surfaces and react with material for substrates owing to its flexibility, light weight,
adsorbed electron acceptors, such as O2 . Although TiO2 and low cost. PTFE is the triboelectric contact layer. The Cu
photocatalysis is an attractive approach for decomposing the layer between the PET substrate and contact layer of PTFE
organic compounds and dye pollution, there are some factors acts as a back electrode. The layer of Al plays dual roles
that restrain the performance of photodegradation, such as of electrode and contact surface. The working mechanism
separation rate, migration of photo-generated carriers, and of the TENG is based on the triboelectric effect [5]. When
recombination. The low migration speed of photo-generated PTFE is in contact with the aluminum layer, electrons are
holes and electrons, poor separate efficiency, and relatively transferred from Al into PTFE due to the different triboelectric
high recombination rate suppress the quantum efficiency coefficients. Once the two surfaces are separated, the electric
of TiO2 photocatalytic degradation. In order to solve this potential difference is produced, leading to an open-circuit
problem, we use the TENG to yield an electric field in voltage [26]. The output voltage can be given by
the solution of MO so as to accelerate the separation
and migration of photo-generated carriers and inhibit their σd
recombination. Figure 2(a) indicates a schematic diagram of Voc = (4)
ε0
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Nanotechnology 24 (2013) 295401 Y Su et al

Figure 2. (a) Schematic diagram of TENG assisted photodegradation of MO. (b) Schematic diagram of the fabricated triboelectric
nanogenerator (TENG). Inset: photograph of a fabricated TENG. (c) Open-circuit voltage of the TENG with forward connection.
(d) Open-circuit voltage of the TENG with reverse connection.

where σ is the triboelectric charge density, ε0 is the vacuum the absorption peak at 464 nm under different degradation
permittivity, and d is the distance between two contacting times, indicating that the TENG does boost the speed of
surfaces. According to equation (4), an AC open-circuit photodegradation of MO and shorten the duration required for
voltage is achieved by periodic separation and contact completely mineralizing the dye.
between the PTFE and Al films, which was triggered by Figure 3(d) illustrates the photodegradation rate of MO
a mechanical press. Parts (c) and (d) of figure 2 show the assisted by the TENG under different frequencies. The TENG
output performance of the fabricated TENG under the forward was driven by a linear motor that provides mechanical impact
and reversed connections, where the output voltage is up with controlled frequency. According to figure 3(d), the
to 30 V. The left part in figures 2(c) and (d) is the output degradation rate is proportional to the output frequency of
of the TENG without a rectifying bridge circuit while the the TENG and all the degradation percentages assisted by
right part is the output rectified by a rectifying bridge circuit. the TENG are much higher than that without the assistance
Owing to the insulation of the PDMS film covered on the
of the TENG at the same time. The voltage peak value and
Pt electrodes, no current was detected in the MO solution.
pulse shape under the different frequencies were found to
The MO decomposition is based on the TiO2 photocatalytic
be almost the same in figure S2 (available at stacks.iop.org/
process rather than conduction of current between electrodes,
Nano/24/295401/mmedia); more voltage peaks in a unit time
which is the main factor in electrocatalytic degradation.
Figure 3(a) illustrates the absorption spectrum of MO period means higher effective voltage, that can give rise to
photodegradation with TiO2 under the electric field triggered a stronger effective electric field intensity. The electric field
by the TENG. The characteristic absorption peak decreases in the MO solution not only accelerates the migration and
with increasing degradation time. With the assistance of the the separation of photo-generated carriers, but also restrains
TENG, the characteristic absorption peak of MO goes down recombination. A larger electric field will push more holes
more quickly than the one without the TENG assistance. towards adsorbed OH− and thus produce more hydroxyl
The decoloration in figure 3(b) displays color changing of radicals (·OH) for the degradation reaction with MO. In
the MO solution during the photocatalysis process, indicating consequence, the speed of photodegradation is increased with
that the TENG assisted photodegradation can be finished in increasing output frequency of the TENG.
only 240 min, which is almost half the time for the one The mechanism for the TENG enhancing the photocat-
without TENG assistance. Figure 3(c) shows the value of alytic degradation of MO is demonstrated in figure 4. Part (a)

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Nanotechnology 24 (2013) 295401 Y Su et al

Figure 3. (a) Absorption spectra of MO in photodegradation assisted by the TENG. (b) Decoloration of MO at different photodegradation
times. (c) Plot of the absorption peak at 464 nm versus the photodegradation time. (d) Plot of the degradation percentage versus the time
under the frequencies of 2, 3, and 4 Hz with a control without TENG assistance.

Figure 4. (a) Mechanism of the TiO2 photocatalytic degradation of MO under UV irradiation. (b) Mechanism of the TiO2 photocatalytic
degradation of MO under UV irradiation assisted by the TENG.

and (b) of figure 4 are cross-section views for the photodegra- once the electric field was generated in MO by the TENG
dation of MO without and with TENG assistance respectively. in figure 4(b), the photo-generated electrons and holes were
As revealed in figure 4(a), photo-generated holes and elec- driven to separate at once and flow in opposite directions by
trons cannot react with OH− and O2 until they migrate to the the electric force, which can increase the rate of separation of
surface of TiO2 particles where these reactants are adsorbed. electron–hole pairs and inhibit the recombination. Moreover,
Furthermore, the photo-excited electrons and holes on the instead of migration, the photo-excited carriers were pushed
surface of TiO2 cannot separate immediately when they are towards the surface of TiO2 or even directly to adsorbed
created, having the probability of recombination. However, OH− and O2 for oxidation, which can increase the speed

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Nanotechnology 24 (2013) 295401 Y Su et al

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