Degradation of 2,4,6-Trichlorophenol and hydrogen production simultaneously by TiO2

nanotubes/graphene composite
Slamet, and Raudina

Citation: AIP Conference Proceedings 1904, 020074 (2017);

View online: https://doi.org/10.1063/1.5011931
View Table of Contents: http://aip.scitation.org/toc/apc/1904/1
Published by the American Institute of Physics
 Degradation of 2,4,6-Trichlorophenol and Hydrogen
Production Simultaneously by TiO2 Nanotubes/Graphene
Composite
Slameta) and Raudina

Chemical Engineering Department, Universitas Indonesia, Kampus Baru UI, Depok 16424, Indonesia
a)
Corresponding author: slamet@che.ui.ac.id

Abstract. Industrial waters in coal pyrolysis process, synthetic chemicals and oil and gas process contain phenol
derivatives that are dangerous to the environment and needs to be removed, one of them is 2,4,6-Trichlorophenol.
Degradation of 2,4,6-Trichlorophenol and hydrogen production simultaneously have been investigated using
TiNT/Graphene composite at various graphene loading and initial concentration of 2,4,6-Trichlorophenol. Optimal
graphene loading of 0.6 wt% was obtained in the simultaneous system with 89% elimination of 2,4,6-Trichlorophenol
and 986 μmol of hydrogen production. Test results showed that addition of 2,4,6-Trichlorophenol would subsequently
increased 2,4,6-Trichlorophenol conversion and enhanced hydrogen production linearly. 2.7 times greater hydrogen
production was found in addition of 50 ppm 2,4,6-Trichlorophenol.

INTRODUCTION
2,4,6-Trichlorophenol (2,4,6-TCP) is one of the four chlorophenols (2-CP, 2,4-DCP, 2,4,6-TCP and PCP) that
have been classified as priority pollutants by the U.S. Environmental Protection Agency (EPA) because of its high
toxicity, carcinogenic properties and bioaccumulation capability (Jin et al., 2006). 2,4,6-TCP and other phenol
derivatives are mainly found in industrial waters such as coal pyrolysis process, synthetic chemicals, oil and gas
process and others (Semple and Cain, 1996). Several methods to remove and degrade chlorophenols have been
widely developed using thermal, chemical and biological treatments which were restricted by the generation of toxic
by-product (Pera-Titus et al., 2004). Photocatalytic is one of the most effective method to degrade chlorophenols and
allows the efficient degradation of a variety of low concentration organic pollutants in aqueous wastes. In addition,
organic compounds, such as chlorophenols, could reduce recombination by acting as hole scavenger and as
hydrogen source that undergoes oxidation reaction which enhance hydrogen production (Luo et al., 2009).
Hydrogen is one of renewable energy that considered as an ideal energy source for the future for its clean and
high specific energy. This renewable energy source is hoping to replace fossil fuels in the near future. In the recent
years, hydrogen has commonly produced from natural gas, crude oil, biomass and others which are all fossil fuels.
Processes such as reforming and water electrolysis need high energy source because of its high temperature
operating condition and also produce CO2 gas. Due to its low economic cost and clean process, hydrogen production
from water by photocatalyst has been growing interest.
Titanium dioxide (TiO2) has been the most common photocatalyst in various applications such as environmental
pollution control, hydrogen production, solar energy and so on for its highly stable performance, wide bandgap and
compatibility in industrial scale. Recently, one-dimensional TiO2 materials such as TiO2 nanotubes (TiNT) have
attracted considerable attention due to its nanostructure, large specific surface area, good electron/proton
conductivity, high aspect ratio and ion exchange (Bavykin et al., 2006; Chen et al., 2011). However, the
photocatalytic activity of TiO2 remains quite limited due to its rapid recombination of electron/hole pairs and a
narrow light response range, which result in low efficiency in the utilization of solar energy. Numerous modification
have been done to improve the photocatalytic performance of TiO2 with carbonaceous materials, such as carbon

Proceedings of the 3rd International Symposium on Applied Chemistry 2017

AIP Conf. Proc. 1904, 020074-1–020074-7; https://doi.org/10.1063/1.5011931
Published by AIP Publishing. 978-0-7354-1594-2/$30.00

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nanotubes (Yao et al., 2008; Woan et al., 2009) and carbon nanofibers (Yang et al., 2012). Apart from these
materials, graphene, a single layer of sp2-bonded carbon atoms arranged in a honeycomb network, has recently
received the most attention in the field of material science because of its properties, which include unique optical,
electrical and electrochemical properties such as high electron mobility, high transparency and large specific surface
area (Adán-Más and Wei, 2013; Morozov et al., 2008; Aliofkhazraei et al., 2016).
Several approaches have been reported in the literature for degradation of organic compounds and hydrogen
production using TiO2/Graphene. Organic compounds such as methyl orange (Anjusree et al., 2013), formaldehyde
(Huang et al., 2013), bisphenol A (Bai et al., 2014) and bromate (Huang et al., 2014) have been degraded using
TiO2/Graphene. Hydrogen also produced from water using several sacrificial reagents such as Na2S and Na2SO3
(Haldorai et al., 2014; Zhang et al., 2011) and methanol (Dang et al., 2013). However, all approaches have been
done separately between the degradation of organic compounds and hydrogen production.
To the best of our knowledge, the TiNT/Graphene composite were at the first time used in the degradation of
2,4,6-Trichlorophenol and hydrogen production simultaneously. In the present work, TiNT/Graphene composite
were prepared by hydrothermal and sonication method and its performance were investigated and discussed. There
were two variations in this research which are graphene loading and initial concentration of 2,4,6-Trichlorophenol.
The effect of graphene loading to composite’s performance will be evaluated along with the effect of 2,4,6-
Trichlorophenol initial concentration to its effect on hydrogen production.

EXPERIMENTAL

Materials
TiO2 (P25, 21% rutile and 79% anatase) was commercially obtained from Evonic Industries. Single layer
graphene was obtained from ACS Material. Commercial sodium hydroxide pellets (NaOH, analytical grade), nitric
acid (HNO3, 65%) and 2,4,6-Trichlorophenol (98%) were purchased from Merck. Hydrogen chloride (HCl, 37%)
was kindly purchased from Mallinckrodt. Distilled water was used for aqueous solution preparation. All reagents
were used as received without further purification.

Synthesis of TiO2 Nanotubes (TiNT)

TiNT was synthesized by dispersing 6 g of TiO2 P25 in 300 ml of 10 M NaOH and sonicated for 30 min,
followed by hydrothermal treatment at 130 °C in a Teflon-lined autoclave for 6 h. The precipitates were washed
thoroughly with 0.2 M HCl until the pH value of the washing solution was approximately 2, then further rinsed with
distilled water until the pH value of the washing solution was lower than 7. The final products were obtained
through centrifugation and further dried at 120 °C then calcined at a very high temperature of 500 °C for 2 h.

Synthesis of TiNT/Graphene Composite

A certain amount of graphene (0.2 wt%, 0.4 wt%, 0.6 wt%, 0.8 wt% and 1 wt% loading with 1 g uncalcined
TiNT as base) were suspended in 100 ml of pH 3 solution prepared with HNO3. Then, the suspension was sonicated
for 10 min and refluxed at 130 °C for 30 min. After refluxed, the uncalcined TiNTs were suspended in 100 ml of pH
3 solution and sonicated along with graphene in different container. Both uncalcined TiNT and graphene suspension
then mixed in the same container and sonicated for 20 min. The final products were obtained through drying at 120
°C then calcined at a very high temperature of 500 °C for 2 h.

Photocatalyst Performance Test

The photocatalytic activities of the samples were evaluated by the degradation of 2,4,6-Trichlorophenol and
hydrogen production simultaneously. 2,4,6-Trichlorophenol solution was prepared by dissolving powdered 2,4,6-
Trichlorophenol in 175 ml of distilled water. Samples were then added to the solution with a loading of 1 g/l. The
test was performed in a closed reactor placed inside a closed test box lined with aluminium foil. The box contained
two mercury lamps of Philips HPL-N 250 W as a photon source (17% of UV, 83% of visible light) and a blower to
control the temperature inside the box. The reactor was equipped with a magnetic stirrer, which was turned on

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during the performance test to homogenize the reactant. Prior to irradiation, the reactor was purged by argon for
approximately 30 minutes to eliminate air that may affect hydrogen production and to test the leakage of the reactor.
After purging, the liquid sample (2,4,6-Trichlorophenol) were drawn to see the effect of adsorption before
irradiation begun. The test was conducted for 180 minutes irradiation and liquid samples (2,4,6-Trichlorophenol)
were drawn from periodically (every 30 min) to determine its concentration using UV-Vis spectrophotometry
Spectroquant Pharo 300. The hydrogen produced were also analyzed periodically at the same time as liquid samples
by gas chromatography (GC), using a Shimadzu GC-2014 equipped with a Thermal Conductivity Detector (TCD)
that was used to record the hydrogen peak.

RESULTS AND DISCUSSION

The photocatalytic degradation of 2,4,6-Trichlorophenol and hydrogen production simultaneously using
TiNT/Graphene composite at various graphene loading was evaluated, and the results are presented in Fig. 1a and
1b. As shown in Fig. 1a, with 2,4,6-Trichlorophenol initial concentration of 50 ppm, after 30 min of adsorption and
180 min of irradiation, the final concentration of 2,4,6-Trichlorophenol are 8.5 ppm, 7.9 ppm, 7.4 ppm, 5.4 ppm,
11.12 ppm and 11.14 ppm with TiNT/Graphene 0%, TiNT/Graphene 0.2%, TiNT/Graphene 0.4%, TiNT/Graphene
0.6%, TiNT/Graphene 0.8% and TiNT/Graphene 1% composites, respectively. Adsorption process shows that the
higher graphene loading, the lower final concentration of 2,4,6-Trichlorophenol achieved. This result occurred
because of the large surface area of graphene, increasing the adsorption capacity of TiNT/Graphene composite.
Then, 2,4,6-Trichlorophenol will be reducted by •OH radicals into H2O and CO2 through photodegradation process.
Figure 1b shows the amount of hydrogen produced which are 515 μmol, 516 μmol, 654 μmol, 986 μmol, 378 μmol
and 373 μmol with TiNT/Graphene 0%, TiNT/Graphene 0.2%, TiNT/Graphene 0.4%, TiNT/Graphene 0.6%,
TiNT/Graphene 0.8% and TiNT/Graphene 1% composites, respectively. It shows that adsorption process did not
contribute to hydrogen production. Whereas in the photodegradation process, the water splitting reaction occurs and
produced hydrogen.
Figure 2 shows the synergism between degradation of 2,4,6-Trichlorophenol and hydrogen production at various
graphene loading. There is an increase for both degradation of 2,4,6-Trichlorophenol and hydrogen production until
graphene loading of 0.6%, then continue to decreases until graphene loading of 1%. In graphene loading of 0.2%,
0.4% and 0.6%, graphene role in conductivity increment is less than the light absorption of TiNT, resulting a good
photon absorption and increasing the number of electron excitation while also increasing the conductivity. In these
loadings, graphene acts as electron trapper that helped photodegradation process by creating π-π bond with its
delocalized electron and reduce recombination. Water molecule reacts with hole (h+), producing •OH radicals and
H+, where •OH radicals will reduced 2,4,6-Trichlorophenol into H2O and CO2 and H+ will reduced into hydrogen.
The major reaction steps in this mechanism are described in the following equations:

TiO2  hv  TiO2 (h   e  ) (1)

h   e   graphene ( e  )  TiO 2 (2)
H 2 O  TiO2 (h  )  OH  H   TiO2 (3)
 OH  2,4,6  TCP  H 2 O  CO2 (4)
1
H   graphene(e  )  H 2 (5)
2

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 (a)

(b)
FIGURE 1. (a) Degradation of 2,4,6-Trichlorophenol and (b) hydrogen production with various graphene loading (2,4,6-TCP
initial concentration = 50 ppm)

As for graphene loading of 0.8% and 1%, graphene role in conductivity increment dominates the light absorption
of TiNT, resulting a decrease in light absorption and therefore reduce the final concentration of 2,4,6-
Trichlorophenol and hydrogen production. The few layers of graphene that stacked in the surface of TiNT can also
reduce the amount of light absorbed to TiNT. In higher concentration of graphene, shading effect occurred due to
the number of graphene layers wrapped in TiNT surface, resulting lowered excitonic resonance and interrupt
electronic conductivity (Mak et al., 2011).

FIGURE 2. Degradation of 2,4,6-Trichlorophenol and hydrogen production simultaneously with various graphene loading
(2,4,6-TCP initial concentration = 50 ppm, irradiation time = 180 min)

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 The photocatalytic performance test shows that the optimum loading of graphene in TiNT/Graphene composite
is 6%. The TiNT/Graphene 0.6% composite are then tested for the degradation of 2,4,6-Trichlorophenol and
hydrogen production simultaneously at various initial concentration of 2,4,6-Trichlorophenol, and the results are
presented in Fig. 3a and 3b. As shown in Fig. 3a, after 30 min of adsorption and 180 min of irradiation, the final
concentration of 2,4,6-Trichlorophenol are 5.4 ppm, 4.3 ppm, 3.1 ppm dan 1.7 ppm with initial concentration of
2,4,6-Trichlorophenol 50 ppm, 30 ppm, 10 ppm and 5 ppm, respectively. It shows that along with 2,4,6-
Trichlorophenol initial concentration increment, the final concentration of 2,4,6-Trichlorophenol are reduced. It is
presumably caused by the reduction of active sites availability to form •OH radicals because of the adsorption of
2,4,6-Trichlorophenol in the catalyst surface and absorption of light into 2,4,6-Trichlorophenol that both reduce the
amount of photon received in the catalyst surface (Wong et al., 2011). And with the constant amount of catalyst
loading, reaction time and photon intensity, the increment of 2,4,6-Trichlorophenol will reduced catalyst
performance.
Figure 3b shows the amount of hydrogen produced which are 986 μmol, 631 μmol, 445 μmol, 405 μmol and 360
μmol with with initial concentration of 2,4,6-Trichlorophenol 50 ppm, 30 ppm, 10 ppm, 5 ppm and 0 ppm,
respectively. In addition of 50 ppm 2,4,6-Trichlorophenol, hydrogen production increased by 626 μmol (360 μmol
to 986 μmol) due to the role of 2,4,6-Trichlorophenol. In hydrogen production mechanism, 2,4,6-Trichlorophenol
acts as hole scavenger that could reduce recombination and therefore increase the number of excited electron to
reduce H+ to hydrogen. H2O produced from the reduction of 2,4,6-Trichlorophenol could also plays part in hydrogen
production accumulation, but the role is relatively small since the concentration of 2,4,6-Trichlorophenol are only in
part per million (ppm).

(a)

(b)
FIGURE 3. (a) Degradation of 2,4,6-Trichlorophenol and (b) hydrogen production with various initial concentration of 2,4,6-
Trichlorophenol (Catalyst used: TiNT/Graphene 0.6% composite)

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 Figure 4 shows the synergism between degradation of 2,4,6-Trichlorophenol and hydrogen production at various
initial concentration of 2,4,6-Trichlorophenol. There is an increase for both 2,4,6-Trichlorophenol conversion and
hydrogen production along with the increment of 2,4,6-Trichlorophenol initial concentration. Integration of 2,4,6-
Trichlorophenol conversion and hydrogen production occurred by electron and hole produced during electron
excitation. 2,4,6-Trichlorophenol acts as hole scavenger and reduce recombination, whereas H+ will be reduced by
electron to produce hydrogen. The higher 2,4,6-Trichlorophenol initial concentration, the bigger amount of electron
available for hydrogen production and created linear correlation. 2,4,6-Trichlorophenol conversion also increase due
to the increasing amount of •OH radicals produced to reduce 2,4,6-Trichlorophenol.

FIGURE 4. Degradation of 2,4,6-Trichlorophenol and hydrogen production simultaneously with various initial concentration of
2,4,6-Trichlorophenol (Catalyst used: TiNT/Graphene 0.6% composite, irradiation time = 180 min)

CONCLUSION
TiNT/Graphene composite has been successfully synthesized and showed good performance on 2,4,6-
Trichlorophenol degradation and hydrogen production simultaneously. Its performance were obtained under various
graphene loading and initial concentration of 2,4,6-Trichlorophenol. TiNT/Graphene 0.6% composite is the optimal
catalyst used in this study to degrade 2,4,6-Trichlorophenol and produce hydrogen simultaneously compared to
other catalysts. TiNT/Graphene 0.6% composite was able to degrade 2,4,6-Trichlorophenol by 89% and produce
986 μmol of hydrogen with 2,4,6-Trichlorophenol initial concentration of 50 ppm due to graphene as electron
trapper by creating π-π bond with its delocalized electron and reduce recombination. Higher initial concentration of
2,4,6-Trichlorophenol resulted in higher conversion of 2,4,6-Trichlorophenol, and also increased hydrogen
production simultaneously because of its role as hole scavenger. Addition of 2,4,6-Trichlorophenol by 50 ppm could
increase hydrogen production by 2.7 times greater.

ACKNOWLEDGEMENT
The authors would like to thank Universitas Indonesia and Directorate General of Higher Education (DGHE)
Indonesian Ministry of National Education through Program Kreativitas Mahasiswa-Penelitian Eksaktsa (PKM-PE)
2017 for the financial support of this research.

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