Materials Today: Proceedings 20 (2020) 482–487

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Materials Today: Proceedings

journal homepage: www.elsevier.com/locate/matpr

Methylene blue photocatalytic degradation by TiO2 nanoparticles

supported on PET nanofibres
Suhad A. Yasin, Jamal A. Abbas, Manaf M. Ali, Ibtisam A. Saeed, Idrees H. Ahmed
College of Science, University of Duhok, Duhok, Iraq

a r t i c l e i n f o a b s t r a c t

Article history: Polyethylene terephthalate (PET) nanofibers were synthesized by electrospinning and then composited
Received 7 July 2019 with TiO2 nanoparticles. In this study, PET nanofibres were dipped into TiO2 nanoparticles, which were
Received in revised form 17 September then operated for the photocatalytic degradation of methylene blue (MB) in an aqueous solution. A
2019
Fourier transform infrared spectroscopy (FTIR) and a scanning electron microscopy were used to study
Accepted 29 September 2019
the surface of the nanofibre morphology. UV–visible spectrophotometry was applied to define the methy-
Available online 22 October 2019
lene blue (MB) concentration after photodegradation. The photodegradation of MB in this study showed
that the degradation efficiency was affected by time. The results have proved that TiO2/PET nanofibres
Keywords:
Nanofibres
acquired high photodegradation efficiency 88% of the dye at 10 min. The activity is principally attributed
Electrospinning to the availability of more active binding sites exposed on the surface of TiO2.
Photocatalytic Ó 2019 Elsevier Ltd. All rights reserved.
Methylene blue Selection and peer-review under responsibility of the scientific committee of the 2nd International Con-
Polyethylene terephthalate (PET) ference on Materials Engineering & Science.

1. Introduction efficiency degradation, and non-selective degradation [8].

Nearly 0.8 million tons of organic dyes are manufactured yearly
worldwide. Moreover, in these industries, more than10,000 various
pigments and dyes are applied. Research indicates that around 15%
of the synthetic dyes produced each year have been lost through-
out processing operations involving the manufacture and handling
of numerous organic compounds that are dangerous to human
health [1]. Various technology for removing dyes from wastewater
include membrane filtration, precipitation, flocculation [2], photo-
catalytic degradation [3] and adsorption [4].
Electrospinning is an easy and cost-effective way to fabricate
nanofibrous polymers with diameters from several micrometers
to several hundred nanometers using a high-voltage (KV) power
supply [5]. Nanofibres with their structural features such as supe-
rior porosity, distinguished surface area to volume ratio and inter-
connectivity as new materials are suited for many applications [6].
Photocatalysis nanofibres are a form of green technology
regarded as a favorable technique for the photodegradation of
organic pollutants in polluted wastewater [7]. Photocatalytic
degradation system has a vast research concern due to its low cost,
Nanoparticles-polymer combinations have lately gained much
consideration for numerous application such as photodegradation
dyes from wastewater [9] with using a different light sources.
Titanium nanoparticles TiO2 have superior properties such as
mechanical strength and high efficiency for photodegradation of
organic dyes as well as availability, which have made them essen-
tial for various applications as sensors, catalysts and super-strong
materials [10].
In this work, TiO2 nanoparticles dispersed on PET nanofibres
showed active degradation of organic MB dye. MB dye is chosen
due to its chemical structure, which allows for good adsorption
onto a solid surface, which is important in the industry. The degra-
dation experiments of MB were examined by a UV–vis spectropho-
tometer. PET polymers are extensively used for their outstanding
properties; for example, chemical resistance, mechanical strength,
and transparency [11].
The choice of nanofibres is outstanding to the large surface area,
which may help with the better diffusion of TiO2 nanoparticles.
2. Materials and methods

Abbreviations: PET, Polyethylene terephthalate; MB, Methylene blue; TiO2,

The polymer PET as a waste material was used after cleaning
Titanium oxide; TFA, Trifluoroacetic acid; DCM, Dichloromethane. and then dried. The chemicals trifluoroacetic acid (TFA 98%),
E-mail address: suhad.yasin@uod.ac (S.A. Yasin) dichloromethane (DCM) and titanium oxide nanoparticles (TiO2

https://doi.org/10.1016/j.matpr.2019.09.174
2214-7853/Ó 2019 Elsevier Ltd. All rights reserved.
Selection and peer-review under responsibility of the scientific committee of the 2nd International Conference on Materials Engineering & Science.
 S.A. Yasin et al. / Materials Today: Proceedings 20 (2020) 482–487 483

Aeroxide P-25) were applied as received without additional purifi- The TiO2/PET nanofibre mat was split from the aqueous medium
cation. Solution preparations and washing processes three times and washed then dried at 40 °C in an oven. Then the TiO2/PET
were done by using deionized water (Reverse Osmosis Pure Water nanofibre mat was balanced, the quantity of the TiO2 adsorbed
System for Lab, Deionized Water Plant For Laboratory). An SEM onto the nanofibre was calculated from the weight of PET previ-
(scanning electron microscope, Cam Scan 3200LV with high volt- ously and afterward treatment with TiO2 (nearly 0.0032 g of TiO2
age 25Kv, 15 nm) on a gold layer was used. adsorbed).
The photodegradation study was done by using a UV–visible The TiO2/PET nanofibre and 10 ml of a 10 mg/L MB solution
spectrophotometer (Jenway, 7315, spectrophotometer). A Fourier were shaken for 30 min at 25 °C in the dark; the test tube is cov-
transform infrared spectroscopy (Shimadzu, FTIR) confirmed the ered by an Aluminum foil, (covered from any source of light) to
functional surface of the composite nanofibres in the range of let the adsorption-desorption equilibrium to be touched. The com-
400–4000 cm
1. bination of the reaction was then irradiated beneath a xenon lamp
(100 W) as a function of reaction time. During illumination, the
2.1. Preparation of electrospun solutions volume (2 ml) of the solution was deducted from the conical at
organized. When the exact irradiation time, the PET nanofibre
The preparation of nanofibres from waste PET was done in our and the TiO2/PET nanofibre were split by centrifugation, then
previous work, in which a solution was prepared by mixing absorption was measured by spectrophotometer [14].
dichloromethane (DCM) and trifluoroacetic acid (TFA) in a 3:1 The following equations calculate the percent degradation of
ratio. The solution was agitated (4 h) at room temperature, and MB in an aqueous solution [15]:
then the solutions were placed in a glass syringe (500 mL) which Co
C
was attached to a stainless-steel needle [12]. The ideal electrospin- Degradation rateð%Þ ¼  100 ð1Þ
Co
ning factors were regulated to be as follows: 1 ml/h flow rate,
15 cm distance between the needle tip and the collector, 5% PET AO
A
concentration and 9 kV for the operating voltage [13]. Degradation rateð%Þ ¼  100 ð2Þ
AO


2.2. Photodegradation study of (MB) where theinitialconcentrationoforganicdyeisC o mg , C is the organic

L
dye concentration mg L
after irradiation. AO and A are the initial
The mat of the PET nanofibre (0.011 g), TiO2 (0.008 g) and DI organic dye absorbance and the absorbance after irradiation,
water (6 ml) occupied a glass beaker and agitated for one hour. respectively.

Fig. 1. SEM images and the distribution equivalent of (a) PET nanofiber and (b) TiO2/PET nanofibre.
484 S.A. Yasin et al. / Materials Today: Proceedings 20 (2020) 482–487

Fig. 2. IR spectrum of (a) PET nanofibre and (b) TiO2/PET nanofibre.

Fig. 3. Photodegradation of MB with (a) PET nanofibres and (b) TiO2/PET nanofibres.
 S.A. Yasin et al. / Materials Today: Proceedings 20 (2020) 482–487
3. Results and discussion
3.1. Morphological results of nanofibres
The morphological results with the distribution equivalent of
the PET nanofibres and TiO2/PET nanofibres are presented in
Fig. 1. Fig. 1(a) revealed that the PET electrospun nanofibre had a
diameter less than 100 nm. Fig. 1(b) indicated the existence of
TiO2 particles on the surface of the PET nanofibres. The image of
SEM also revealed that the TiO2 appeared in an agglomerated
shape on the surface of the PET nanofibres [16] This result reveals
that the TiO2 nanoparticles are extremely attached on the PET
nanofibers, and (5–30 nm) were the diameters ranging of the TiO2.
The FT-IR spectra of PET and TiO2/PET are given in Fig. 2(a)–(b).
IR absorption at 1719 cm
1 is due to carbonyl stretching (CO);
2957 cm
1 and 2887 cm
1 are due to CH2 group (C–H) stretching
(Fig. 1[a]). The intense band appearing at 1261 cm
1 can be
assigned to CO–O stretching. Furthermore, the peak at 1098 cm
1
seems to correspond to a gauche C–O stretching vibration (Fig. 1
[a]) [17]. Comparing the IR spectrum of TiO2/PET nanofibres with
that of the pure PET nanofibre reveals the development of other
adsorption peaks. The broadband in TiO2 at 583 cm
1 is given to
the Ti–O vibration stretching and the broad bands at (3441–
3450) cm
1 in catalysts appoint to the functional groups of hydro-
xyl (OH) stretching vibrations[18]. Water molecular hydroxyl
groups form a peak at 1629 cm
1. These results indicate that the
functional groups of PET nanofibres can be susceptible to the inter-
action with TiO2.
Fig. 4. Photocatalytic degradation % of MB using TiO2/PET nanofibers.
Fig. 5. Photodegradation efficiency (with light) of (a) PET nanofibres and (b) TiO2/PET nanofibres on MB.
485
3.2. Photodegradation study of MB
The MB photodegradation was deliberate by the intensity of the
UV–visible spectra, which at 664 nm is the highest absorbance. The
TiO2 nanoparticles embedded in the PET nanofibres illustrated that
the degradation of (MB) steadily rose with irradiation time.
TiO2/PET nanofibres degraded further than 88% of the dye at
10 min, while the PET nanofibres degraded about 56% of MB under
a similar experimental situation, and after 60 min the dye degrada-
tion was almost constant as shown in Figs. 3 and 4. As shown in
Fig. 5 the high-level photodegradation of MB in aquatic media is
a result of the TiO2 nanoparticles on the surface of the PET nanofi-
bres. Fig. 5 displays the degradation rate of MB as a function of
light irradiation time without any catalyst (the blank test) and over
the photocatalysts. On the other hand, Fig. 6 represents the little
effect when MB is adsorbed on the PET nanofibres after 180 min,
without photocatalytic degradation system. These results show
the photodegradation study is more efficient than the adsorption
study. Table 1 lists the maximum photodegradation capacities of
MB on TiO2/PET nanofibers and other related adsorbents reported
in the literature. The data indicates that the prepared TiO2/PET
nanofibers show higher adsorption capacity of MB, and it is a
new adsorbent did not study before.
3.3. Kinetic study
The photocatalytic kinetics of the prepared MB samples were
evaluated by monitoring the degradation of MB solution.
The kinetic study of MB photodegradation in an aqueous solu-
tion vs. PET nanofibres and TiO2 nanoparticles embedded on PET
nanofibres was fitted well using a commonly applied pseudo-
first-order equation [19].
 
Co
ln ¼ Kat ð3Þ
C
where the initial concentration of MB is C◦, C is the concentration of
MB at a specific time and the rate constant of the pseudo-first-order
model is Ka (min
1). Fig. 7 Pseudo-first order rate constant for the


photocatalytic degradation of the organic dyes (MB). From the CCo
values of all the solution samples after the dark reaction, the
adsorption of TiO2/PET is more noticeable than the other. In general,
better adsorption ability will indicate better photocatalytic showing
in a type of photocatalyst [20].
486 S.A. Yasin et al. / Materials Today: Proceedings 20 (2020) 482–487

Fig. 6. Adsorption study and removal% of MB on PET nanofibres with different times (without light).

Table 1
Comparison of maximum MB photodegradation.

Adsorbent Dyes Concentration mg/l Irradiation light Equilibrium time (min) References
CA–CNT/TiO2–NH2 10 UV 40 W 300 Salama et al. [21]
PAN–CNT/TiO2–NH2 10 UV 100 W 30 Mohamed et al. [3]
carbon-doped TiO2 coating on MWCNTs 20 Visible light 500 W 360 Cong et al. [22]
TiO2 Nanoparticles 10 UV 120 W 600 Bubacz et al. [23]
CNT-embedded hollow TiO2 10 UV 800 W 70 Jung et al. [24]
–
TiO2/PET nanofibers 10 xenon lamp 80 This study
PET nanofibers 10 xenon lamp 100 This study

Fig. 7. (a) Effect of contact time on MB removal efficiency by PET nanofibres and TiO2/PET nanofibres (b) Fitting of pseudo-first-order of PET nanofibres and TiO2/PET
nanofibres.

The photodegradation of the dye in the solution is initiated by The hydroxyl reactive radical (OH) is an additional intermedi-
the photoexcitation of the TiO2 as a semiconductor, followed by ate that is accountable for the degradation. It is produced by the
the production of an electron-hole pair on the surface of the TiO2 decomposition of H2O or via the reaction of OH
with the hole as
catalyst (Eq. (4)). The high oxidative potential of the hole (h+VB) in shown in Eqs. (6) and (7). The hydroxyl radical (OH) is an effective,
the catalyst allows the immediate oxidation of the organic dye non-selective oxidant
(MB) to reactive intermediates (Eq. (5)). (Eo = +3.06 V), which directs to the fractional or complete min-
eralization of numerous synthesis organic chemicals [19].
   
MO MO

þ
þ hv ! e
CB þ hVB ð4Þ hVB þ H2 O ! Hþ þ OH ð6Þ
MO2 MO2
þ
hVB þ OH
! OH ð7Þ
Metaloxide
þ þ
hVB þ dye ! dye ! oxidation of the dye ð5Þ OH þ dye ! degradation of the dye ð8Þ
 S.A. Yasin et al. / Materials Today: Proceedings 20 (2020) 482–487
4. Conclusion
The PET nanofibres were dipped into the TiO2 nanoparticles to
fabricate TiO2/PET nanofibers, and then their structure and mor-
phology were studied. The images of SEM have clearly shown that
the fiber diameter increased 250 nm after fabricated. Also, the
results of FTIR have shown that the new peaks are due to the add-
ing of TiO2 to the PET nanofibres. This composite nanofibre has a
superior photocatalytic under xenon lamp irradiation. TiO2/PET
nanofibres degraded further than 88% of the dye at 10 min. Finally,
modification of nanofibers can be presented as a capable efficient
visible photocatalyst for elimination of MB from wastewater in a
short time.
Acknowledgments
The authors are grateful for the financial support by Partner-
ships for Enhanced Engagement in Research (PEER). It was admin-
istered by the U.S. National Academies of Sciences, Engineering and
Medicine (NASEM), PEER/Iraq project/cycle 6.
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