Journal of Alloys and Compounds 886 (2021) 161169

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Journal of Alloys and Compounds

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

Synthesis of TiO2@ZnO heterojunction for dye photodegradation and

wastewater treatment ]]
]]]]]]
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⁎
Hamouda M. Mousa a, , Jarah Fares Alenezi a, Ibrahim M.A. Mohamed b, Ahmed S. Yasin c,
Abdel-Fatah M. Hashem a, Abdalla Abdal-hay a,d
a
Department of Mechanical Engineering, Faculty of Engineering, South Valley University, Qena 83523, Egypt
b
Department of Chemistry, Faculty of Science, Sohag University, Sohag 82524, Egypt
c
Graduate School of Energy Science and Technology, Chungnam National University, 99 Daehak-ro, Yuseong-gu, Daejeon 34134, Republic of Korea
d
The University of Queensland, School of Dentistry, Herston, QLD 4006, Australia

a r t i cl e i nfo a bstr ac t

Article history: The presented work aims to synthesis and engineering a semiconductor-semiconductor (S–S) heterojunc­
Received 1 May 2021 tion with low bandgap energy. The synthesized material composed mainly from titanium dioxide (TiO2) and
Received in revised form 26 June 2021 zinc oxide (ZnO) as a photocatalytic nanoparticle (NPs). This strategy could highly enhance photo-de­
Accepted 12 July 2021
gradation properties and antibacterial properties for wastewater treatment. A composite cellulose acetate
Available online 14 July 2021
CA@TiO2 NPs (CTO) was fabricated via electrospinning technique to generate a core TiO2 NPs within a
polymeric matrix followed by immersion in ZnO NPs suspension solution to deposit ZnO NPs on the na­
Keywords:
Oxide materials nofiber surface (CTZO). Subsequently, the composite mat was subjected to a calcination/annealing process
Nanofabrication at 700 °C for 4 h to obtain composite S–S heterojunction nanostructure material (TZO). The morphological
Heterojunctions characteristics, thermal degradation, chemical composition, and phase structure of the synthesis material
Kinetics were investigated. In addition, antibacterial properties were evaluated using E-coli bacteria, whereas the
Semiconductors photocatalytic degradation efficiency was performed using both methylene blue (MB) and methylene red
Photocatalysis (MR) dyes under direct sunlight. The morphological properties showed that TiO2 NPs was well decorated
with ZnO NPs and form heterojunction structure. The resulted (TZO) has high antibacterial effect and
showed a 15 ± 0.8 mm of inhibition zone in gram (-ve) Bactria comparing to that of ZnO NPs (12 ± 0.2) mm.
Furthermore, photocatalytic degradation of the composite NPs showed high photodegradation properties
close to 25% and 13% for MB and MR dyes in direct sunlight, respectively. The increased dye photo­
degradation is attributed to the formation of S–S heterojunction structure with low bandgap energy
(1.17 eV) comparing to that of wide band gap energy (3.52 eV) of TiO2 that play role in enhancement of
electron transfer and thus photodegradation process. These results suggest that the resulted S–S hetero­
junction nanomaterial have a high potential in wastewater application.
© 2021 Elsevier B.V. All rights reserved.

1. Introduction and aromatic nature [2]. For example, microorganisms in water are
not capable to degrade dyes and show some carcinogenic substance
Recent progress and industrial development led to a variety of in decomposition process. In addition, physical techniques including
water contaminant which mainly include dyes. In textile industry, activated carbon adsorption [3], ultrafiltration [4], and reverse os­
organic dyes have been widely involved in textiles, papers and lea­ mosis [5]; are capable to transfer the organic compound to another
ther manufacturing which creates a large quantity of pollutant water phase which can cause a secondary pollution. The resulted sec­
[1]. Hence, wastewater should be treated for reuse application to ondary pollutants lead to solid waste management and require post-
face the increasing demand of water in industry and agriculture treatment process which subsequently means extra cost [6,7]. One of
field. Usually, physical and biological treatments are not effective to the promising, simple, and cost-effective solution is a photocatalysis
remove dyes from wastewater effectively due to their high stability degradation process which capable to remove pollutants from the
wastewater, especially dyes [8–11]. Metals oxides; especially semi­
conductors materials such as; ZnO and TiO2 [12] among others
⁎
Corresponding author.
[13–16] demonestrate a high potential in wastewater treatment due
E-mail address: hmousa@eng.svu.edu.eg (H.M. Mousa). to thier high photocatalytic properties under sunlight [17].

https://doi.org/10.1016/j.jallcom.2021.161169
0925-8388/© 2021 Elsevier B.V. All rights reserved.
H.M. Mousa, J.F. Alenezi, I.M.A. Mohamed et al. Journal of Alloys and Compounds 886 (2021) 161169

Scheme 1. Illustration of the proposed synthesized TiO2@ZnO S–S heterojunction and role of electrospinning in particles distribution in the formed heterojunction structure after
annealing process.

ZnO is a semiconductor material that shows a promising future and semiconductor- metal (S–M) hetrojunction; semiconductor- carbon
has high surface reactivity and photosensitivity, economical price, anti­ materials including activated carbon, carbon nanotubes (CNT) and
bacterial effect, chemical stability, and wide bandgap energy (3.37 eV) graphne (S-C) heterojunction [37]; and finally (4) multicomponent
[18,19]. It has been widely reported in perovskite devices for green en­ heterojunction (all these cateogeries are reviewed in detailed by Huanli
ergy i.e solar cell [20–23] and quantum dots photodetectors [24]. In Wang, et al.[38]). The formation of hetrojunction can enhance photo­
wastewater, degradation of the organic pollutants degrades when ZnO generation process and cause electron transfer from ZnO CB to TiO2 CB
NPs exposure to UV light (< 400 nm) and produce a hydroxyl radical and thus hole transfer from TiO2 VB to ZnO VB gives a rise of higher
(OH•) which works as oxidizing agents in the photodegradation process. electron-hole transfer separation and lifetime. Several attempts have
However, ZnO has limitations such as lower stability during photo­ been performed to combine TiO2@ZnO NPs for photodegradation [39]
catalytic process due to the photo-corrosion effect and wide bandgap and water spilitting application [40]. However, photocatalytic materials
energy which can absorb about 5% of the ultraviolet sunlight [25]. Beside in a fiber-like structure with aligned morphology showed high photo­
of that, its rapid charge carrier recombination and its lower interfacial degradation properties [41].Therefore, the aims of our study is en­
charge transfer rate [26]. TiO2 is another promising photocatalytic ma­ gineering of TiO2@ZnO NPs S–S composite hetrojunction using the
terial that show good performance in wastewater treatment with wide electrospinning technique as a simple and cost-effective approach. To
band gap (3.2 eV). TiO2 has a three-phase structure which are anatase, obtain a composite hetrojuction photocatalytic, TiO2 NPs were loaded in
rutile, and brookite [27]. The brookite phase is known to be inactive in CA polymer (high generation of nanofiber) to form composite nanofiber
wastewater treatment comparing to the anatase and rutile phases. It is from CA@TiO2 in nanofiber form followed by immobilization of ZnO NPs
well known that the excitation wavelength that is required for TiO2 falls on the outer surface by dip coating in sonicated dispersion solution.The
in (300–390 nm) UV region [28]. Mainly, the surface hydroxyl group prepared mats were calcinated/annealed at 700 °C to form a S–S he­
(OH) concentration plays an important role in the photodegradation trojunction material. The role of nanofiber formation is to enable
process. Morovere, the higher the hydroxyl groups on the catalyst sur­ alighned TiO2 NPs distribution decorated with ZnO NPs on the outer
face (anatase) the higher the reaction rate and subsequently the de­ interface according to the illustritive Scheme (1). The resulted S–S he­
gradation process [29]. Several advantages of TiO2 was reported as a trojunction photocatalytic nanomaterial is expected to have an anti­
photocatalysts such as; economical, abundant, photostability, and en­ bacterial effect and low bandgap energy and thus high degradation rate
vironmentally safe, as well as it’s the best photocatalytic metal oxide for in direct sunlight.
wastewater and hydrogen production [30]. However, limitations such as
bandgap, overpotential, and recombination of photogenerated carriers 2. Materials and methods
retard its commercial photocatalytic properties [31].
The photocatalytic materials are incorporated as a photochemical 2.1. Materials
response of semiconductor's materials surface, which at any rate two
reactions happening once [32]. The first reaction including oxidation The following chemical & materials were purchased from Sigma-
from photo-induced positive holes and the second subsequent reaction Aldrich and utilized in this study without any further modifications:
including photo-induced negative electrons reduction [33]. To enhance cellulose acetate (average Mn ~50000 and 39.20–40.20 wt% of
photocatalytic activity and increase harvesting light several techniques acetyl), titanium dioxide nanoparticles (TiO2 NPs), zinc oxide na­
are introduced including coating, doping with other metals and semi­ noparticles (ZnO NPs), acetic acid, and acetone.
conductor materials [34]. Engineering of a hetrojunction two semi­
conductor materials provides a novel and efficient photocatalytic 2.2. Preparation of electrospinning solution
materials. This is contribute in accelerating the transfer of photoinduced
charge cariers and thus more surface of hydroxide groups [35]. Cellulose acetate (CA) powder was dissolved in a dual solvent
Synthesize of ZnO@TiO2 photocatalyst materials at the nanoscale composed of acetic acid: acetone in a mass ratio of 3:1 at 18 wt%
level received extraordinary interest from the research community as concentrations and under stirring at 200 rpm for 12 h at room
the foremost environmental solution for pollutant removal due to the temperature. The second condition of CA solution was mixed with
formation of hetrojunction with different bandgap energy [36]. There are 0.5 g TiO2 NPs into 18 wt% of the polymer solution to generate
four categories of photocatalytic hetrojunction named as; (1) semi­ composite nanofibers. The polymeric solution was stirred at 200 rpm
conductor- semiconductor materials (S-S) hetrojunction; (2) overnight, followed by 1 h sonication to enhance nanoparticle

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H.M. Mousa, J.F. Alenezi, I.M.A. Mohamed et al. Journal of Alloys and Compounds 886 (2021) 161169

Fig. 1. Scheme shows summary of the experimental route to obtain S–S heterojunction structure photocatalytic materials. (a) prepared CTO sample organic solution, (b) elec­
trospinning setup, (c) prepared mats dip coating in ZnO dispersion solution, and (d) calcination/ annealing process.

dispersions within the polymer solution. The resulted procedure 2.5. Materials characterizations
depends on the solution mixing technique where organic and in­
organic substitutes are bonded under hydrogen bonds and Van der Surface morphology of all samples was observed with scanning
Waals forces. electron microscopy (SEM, JOEL JSM 6360LA, Japan) at 15–20 kV after a
gold sputtering of samples. The samples chemical bonds were char­
2.3. Electrospinning setup acterized using Fourier transform infrared (FTIR) spectra (Shimadzu
FTIR-8400 S, Japan) within the range of 400 cm−1 to 4000 cm−1 at
Nanofibers were prepared by electrospinning apparatus. The transmittance mode. Samples were examined in a temperature range of
electrospinning set-up is shown in Fig. 1. The different parameters of 20–600 °C utilizing a thermogravimetric analyzer (TGA) (Shimadzu TGA-
electrospinning including syringe diameter, feed rate, collector dis­ 50, Japan) under nitrogen with a 10 °C/min heating rate and the flow rate
tance from needle is as the following: 0.52 mm inner diameter, was 20 ml/min. X-ray diffraction type (GA-XRD, Philips X′Pert, Holland)
1.0 ml/h, and 17 cm, respectively. Herein, alligator clips were used to was used for analyzing the crystal structure of the different samples
connect a positive charge as (anode) from a high voltage DC power using Cu Kα (k = 1.54056 A°) from 5° to 80° at operating condition of
supply, and a flat plate wrapped in aluminum foil (collector) was 40 Kv, 30 mA, and beam size of 20 µm.
fixed to the needle tip. The electrospinning technique depends
mainly on the applied voltage and surface tension of the polymer 2.6. Physical properties
solution on a Taylor cone which spins down the polymeric solution
as fiber to spread on the collector. A syringe pump (Supplier: Na­ The optical properties have been studied using vis-spectro­
noNC, South Korea) and a high voltage power supply (ESN-HV30/ photometer (model; U-3900, Hitachi, Japan). A Fluoromax-4 radiance
ESN-HV30N, NanoNC, South Korea) were used in the electrospinning spectrophotometer (JOBIN YVON, USA) was utilized to give the photo­
process with high voltage at 20 kV under room condition. luminescence spectra. The fluorescence conditions were set at 340 nm
excitation wavelength and a scan range of 200–600 nm with a scan rate
2.4. Deposition of ZnO NPs on the fabricated mats and calcination of 600 nm min−1. In addition, to evaluate bandgap energy, diffuse re­
flectance spectroscopy was performed for all samples in powder form
The composite CA/ TiO2 NPs mats were exposed to a sonication
bath with the ZnO NPs dispersed onto distilled water to fulfill the Table 1
porous structure of the membrane. The process was achieved as Samples codes and the corresponding composition.
follows: fabricated nanocomposite fibers mats were deposited with
Sample code Composition
ZnO NPs dispersed in distilled water at 70 °C in the sonication bath
TiO2 NPs Commercial TiO2 NPs.
for 2 min the coated membrane was exposed to drying conditions at
ZnO NPs Commercial ZnO NPs
130 °C for 1 h. The resulted composite (CA/TiO2 NPs)/ZnO NPs was CTO Cellulose acetate and TiO2 NPs solution via
calcined in an electric furnace (VULCAN 3 −550) at 700 °C for 4 h. To electrospinning.
generate a S-S heterojunction TiO2 NPs and ZnO NPs according to CTZO Sample CTO deposited with ZnO NPs dispersed into DI
Fig. 1. The different samples were coded according to Table 1 for easy water at 70 °C then dried under vacuum 60 °C.
TZO CTZO calcined and annealed under 700 °C.
following up.

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H.M. Mousa, J.F. Alenezi, I.M.A. Mohamed et al. Journal of Alloys and Compounds 886 (2021) 161169

Fig. 2. Samples morphology using SEM: (a) CTO, (b) CTZO, (c) TZO, (d) TiO2 NPs as received.

(JASCO V-670, UV–VIS–NIR) in a wave range of 200–1100 cm−1, then respectively using UV–vis absorption peak. The following equation
Kubelka–Munk formula was used for estimation of band gap en­ was applied to estimate the rate of dye degradation,
ergy [42].
C
Degradation Efficiency (%) = 1 × 100%
2.7. Antibacterial properties C

The detailed experiment of the antibacterial properties of the Herein, Co is the initial or starting concentration and C is the dye
synthesis samples was performed according to our previous study concentration after different intervals of times at irradiation system.
[43]. Briefly, a gram-negative bacteria type E. coli was used to assess All the experiments were conducted in a sunny day (between 12 PM
the different materials in the present study. Muller- Hinton agar and 3 PM, April) at high-intensity solar light and average solar ra­
plate model and the plates were incubated at 37 °C for 24–48 h at diation of 25 MJ/m2) in atmospheric environment at faculty of en­
pH= 7.3 ± 0.1. The filtered paper disc with diameter of 6 mm was gineering, south valley university, Qena, Egypt.
sterilized by autoclaving at 121 °C for 20 min and concentration of
1.5 × 108 CFU/ml from different substance. The impregnated discs 3. Results and discussions
were incubated at 37 °C for 48 h and 30 mg/disc from Tetracycline
was used as positive control with the growth inhibition diameter 3.1. Morphological analysis
and the tested hybrid materials expressed in (mm).
Photocatalytic materials with a unique morphology with nanofiber
2.8. Photocatalytic activity have an important role in the photodegradation process due to of its
high surface area. Fig. 2 shows SEM images of the overall samples, SEM
The photocatalytic materials were assessed using two different images of the composite nanofiber CA@TiO2 (CTO) is shown in Fig. 2a.
dyes; methylene blue (MB) (10 ppm) [12] and methylene red (MR) The results showed the formation of nanofibers without beads which
(30 ppm) [44] dyes mixed in direct sunlight irradiation as a simple may be due to the optimized conditions and incorporated with TiO2 NPs.
photochemical reactor. The amount of fabricated photocatalytic na­ The composite CA@TiO2 shows an ultrafine nanofiber with a uniform
nomaterial’s initial concentration and the volume of the mixed so­ distribution. The second sample (CTZO) which was deposited with dis­
lution was equal during all the experiments. An amount of 10 mg of persed ZnO NPs solution was coated on the membrane nanofibers sur­
the fabricated materials was added to 15 ml of organic dyes solution face which was achieved with dip coating in a hot water bath at 70 °C
with (10 ppm) of concentrations in a 50-ml glass beaker. Before then dried at 130 °C for 1 h. SEM images of the resulted composites
using the mixed solution, it was subject to a stirring process for (CTZO) revealed the formation of nanoparticles on the top surface of the
30 min to reach desorption-absorption equilibrium in the dark. nanofibers. Interestingly, SEM images show that particles cover the
Thereafter, the mixed solution of dyes was assessed using spectro­ surface of nanofibers as shown in Fig. 2b. On the other hand, the calcined
photometer as initial concentrations. Then samples in the beakers composite mat (TZO), as clear in Fig. 2c the effect of calcination tem­
were exposed to direct sunlight. Thereafter, samples were assessed perature reveals surface morphology of the nanoparticle’s formations.
at different times with the amount of 1 ml then centrifuged and This investigates that a composite of two-phase formation from TiO2 NPs
measured the absorbance at λmax = 646 nm wavelength; then the and ZnO NPs and thus formation of S-S heterojunction on the surface of
efficiency of the photocatalyst material was estimated. The corre­ the two materials. Fig. 2d shows SEM images of as received TiO2 NPs,
sponding wavelength of both MB and MR was 646 nm and 464 nm SEM images show that TiO2 NPs are not uniform and contain irregularly

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H.M. Mousa, J.F. Alenezi, I.M.A. Mohamed et al. Journal of Alloys and Compounds 886 (2021) 161169

Fig. 3. TEM images of the different samples: (a) ZnO NPs, (b) calcined nanofibers at 700 °C, with lower and higher resolution (TZO sample), (c) EDX point of the TZO sample and
corresponding elemental weight and atomic %, and (d) EDX mapping resulted from TEM (colors: Ti (green), Zn (blue), O (red)).

shaped particles that are aggregations of tiny crystals. Fig. 3a shows TEM
image of the as-received ZnO NPs with hexagonal morphology and
Fig. 3b shows TEM images of the calcined TZO sample which is com­
posed of TiO2 NPs and ZnO NPs at a higher and lower resolution. As
clearly shown in Fig. 3b, the size of the TiO2 and ZnO nanoparticles was
determined by TEM. TiO2 tends to appear in the form of white spots and
ZnO appeared in the form of black arrows to measure the size of each
nanoparticle (size was ranging from 16 to 72 nm). The average particle
size was approximately 36.7 nm. In addition, EDS point and mapping
(Fig. 3c-d) show the elemental distribution of the TZO sample. Elements
weight percent show mainly 3.37% C, 1.34% O, 44.49%Ti, and 39.77% Zn.
Fig. 4 shows HR-TEM image of the composite TiO2@ZnO materials andD-
spacing in two different particles and resulted in 0.7–1.8 nm. In the same
image using ImageJ software about six measurements of D-spacing were
measured in the different locations and the average value found to be
0.78 nm which revealed the high crystallinity order. This was revealed
with the selected area of electron diffraction in the same figure.HR-TEM
indicate the bonding between the two-semiconductor material. For
more reveal, the presence of TiO2 and ZnO crystals in all samples were
subject to FTIR spectra analysis in transmission mode and by X-ray
diffraction test.

3.2. The phase structure of the syntesized samples

Fig. 5 shows X-ray diffraction patterns of TiO2 NPs, ZnO NPs, CTO, Fig. 4. HR-TEM images of the composite TiO2@ZnO S–S heterojunction structure:
CTZO, and TZO samples. TiO2 XRD analysis shows different peaks nanoparticles with d-spacing and selected area of electron diffraction in TZO sample.

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H.M. Mousa, J.F. Alenezi, I.M.A. Mohamed et al. Journal of Alloys and Compounds 886 (2021) 161169

Fig. 5. XRD patterns analysis of the different samples: (a) TiO2 NPs, (b) ZnO NPs, (c) CTO, (d) CTZO, and (e) TZO.

between 2θ = 10–80° attributed to the different planes. TiO2 character­ composite S-S heterojunction. The crystallite size, D, has been de­
istics peaks at different crystal planes shows crystal planes as following; termined using Debye–Scherrer equation as follows [48,49]:
(101), (004), (200), (105), and (204). The resulted reflection peaks at 2θ
D = 0.9 λ /β cosθ (1)
= 25.3° is attributed to tetragonal structure and anatase phase of TiO2
according to (JCPDS card No. 00-021-1272) [45]. This is give extra ad­ Where λ is the wavelength of the used X-ray (1.54060 Å), β is the angular
vantage in the present application where, anatase structure has higher peak width at half maximum in radians and θ is Bragg’s diffraction angle
photocatalysis performance than rutile crystals which belong to its large and the summary of the different samples are appended in Table 2 at
bandgap [46]. XRD analysis of ZnO NPs shows the following crystal­ corresponding pane of (101). The crystallite sizes for the fabricated
lographic planes with sharp intensity peaks; (100), (002), (101), (102), materials were 17.18 ± nm, 16.98 ± nm, and 18.23 ± nm for TiO2 NPs,
(110), (103), and (112). The XRD analysis of the composite CA@TiO2 fibers CTO, and TZO materials at the highest 2θ of anatase TiO2 phase (around
(CTO) shows expansive peaks below 2θ = 20° which are attributed to 25°). For ZnO, the crystallite sizes were about 20.90 nm and 21.55 nm for
pure CA, and this related to the semi-crystalline structure behavior of CA. ZnO NPs, and TZO materials, respectively at the highest 2θ of ZnO
Furthermore, the peak intensity has a place with the CA segment of the (around 36°) [50]. The enhancement of crystal size in the case of the TZO
composite nanofibers were progressively and disappear of TiO2. This is sample was attributed to the annealing and/or calcination step at 700 °C
also good indication of a successful dispersion of TiO2 NPs within the CA for 4 h [51].
polymeric matrix. The deposited CTZO sample shows reflection peaks at
2θ = 34°, 36° which were attributed to ZnO beside that of CA semi-crystal
structure between 2θ = (15° −25°) [47]. As a result, ZnO NPs have suc­ 3.3. Interfacial bonding at the molecular level
cessfully deposited on the fibers surface. Finally, the target sample TZO
shows combinations of TiO2 NPs and ZnO NPs phases and this could be Fig. 6 shows FTIR spectrum of the prepared samples (CTO, CTZO, and
clear in TZO XRD that all characteristic peaks of both TiO2, and ZnO are TZO). FTIR spectroscopy of CTO samples shows a wide bands at
observed. This is revealed doping of ZnO and TiO2 and formation of 3425 cm−1 attributed to adsorbtion of water due to the hydrophilic

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H.M. Mousa, J.F. Alenezi, I.M.A. Mohamed et al. Journal of Alloys and Compounds 886 (2021) 161169

Table 2
The lattice parameters, D-spacing and crystal size of prepared samples.

Materials D-spacing (Å), FWHM Crystallite The corresponding

(deg) size (nm) Plane

TiO2 NPs 3.54 0.47 17.18 (101)

ZnO NPs 2.49 0.40 20.90 (101)
CTO (TiO2) 3.51 0.48 16.98 (101)
TZO (TiO2) 3.56 0.45 18.23 (101)
TZO (ZnO) 2.49 0.39 21.55 (101)

nature of the nanoparticles [52,53]. In our previous work [54], pure CA

nanofiber showed the follwing peaks; 3480 cm−1 (corresponding to
–OH), 1752 cm−1 (C–O) and 1236 cm−1 for (-C–O–). Herein, incorporation
of TiO2 NPs (sample, CTO), a similar peaks were observed and corros­
ponding to the similar funcational group. Further analyis of (sample,
CTZO) shows a characteristic band at 460 cm−1, 1384 cm−1, and
1600 cm−1 which attributed to ZnO, indicates the successful deposition
of ZnO NPs onto the surface of nanofiber [55,56]. The FTIR spectra of TZO
sample confirm the surface bonds of the calcined nanofibers. The ab­
sorbtion peaks at 3440 cm−1 attributed to (-OH) physically adsorbed
water [57] and band at 1400 cm−1 is corosponding to C–O bonds
Fig. 7. TGA analysis of the samples: (a) CTO, (d) CTZO, and (e) TZO.
stretching vibration [58]. In addation, absorption peaks at 550 cm−1 and
650 cm−1 attributed to stretching vibrations of ^Ti–O–Ti^ and vibration
mode of −Zn–O–Ti^ groups, respectivley [57]. These results confirm a which means sample loss 95% of its weight and the reminaing 5% of the
succsuful formation of a homogenous CA@TiO2 composite nanofiber mat total weight. This indicates that sample loss most of its weight between
(CTO), well deposition of ZnO NPs on the mat surface (CTZO), and doping 280.7 °C to 442.26 °C. Deposition of ZnO NPs on the composite mat
of the two semiconductor materials by calcined/annealed sample (TZO) which denoted by (CTZO) shows thermal degradation in TGA curve in
and thus formation of a composite S-S hetrojunction structure material. five stages as follwing: (1) from 28.72 °C to 64.07 °C; the weight loss was
about 2.992%; (2) from 64.07 °C to 259.73 °C; the weigh loss 2.327%; (3)
from 259.73 °C to 378.77 °C; the weigh loss 68.088%; (4) 378.77 °C to
3.4. Thermal performance
463.31 °C; weight loss 12.3%; and finally stage (5) 463.31 °C to 599.88 °C
shows weight loss of 1.975%. This suggested that sample loss about
Thermal stability of the prepared samples; CTO, CTZO, and TZO were
87.682% of the total weight which means about 12.318% of the sample
evaluated by TGA analysis as shown in Fig. 7. CTO sample shows de­
weigh converted to ash. The third sample (TZO), the sample only de­
composition temperature started at 350 °C, which higher than the re­
grade in two stages; the first one start from 31.59 °C to 57.47 °C with
ported to that of pure CA nanofiber which showed a degradation strated
weight loss 0.769%. The second stage start from 57.47 °C to 599.89 °C and
from 270 °C [54]. This confirms the successful incorporation of TiO2 NPs
sample show highly thermal degradation resistance with only 2.406%.
and thus improving of thermal degradation of CA. CTO sample shows six
This conclude that sample,TZO loss only 3.175% of the total weight; and
stages of degradation (i.e wight loss) as follwing; (1) between (30.31 °C
about 96.825% of the sample is still remining. Overall, thermal perfor­
to 73.17 °C) the weight loss was about 4.159%; (2) from 73.17 °C to
mance of the different samples are as following TZO (96.852%),CTZO
280.7 °C; weight loss 2.429%; (3) 280.7 °C to 373.18 °C the sample lost
(12.318%), and CTO (5.016%) in terms of the remining weight through the
about 52.587% of the total weight; (4) 373.18 °C to 442.26 °C the weight
TGA experiment. The huge difference of the thermal performance of the
loss was 22.54%; (5) 442.26 °C to 535.59 °C degratuion rate was 12.88;
three materials is mainly due to TZO is composed totally from composite
and finally (6) from 535.59 °C to 599.88 °C degradation rate was 0.384%
heterojunction ceramic materials which has higher thermal perfor­
mance comparing to composite materials from polymer and ceramic.

3.5. Optical properties (UV) & bandgap energy

Optical properties is the key element in the photocatalytic applica­

tion. To evaluate the optical response, UV-Vis absorption and reflectance
spectra measurements were performed. The obtained results are shown
in Fig. 8a. As can be seen, the absorption band edge of the TiO2 NPs is
observed at ~350 nm wavelength. The UV absorbance of ZnO NPs finds a
band peak between 300 and 400 nm wavelength. On the other hand, the
composite CA@TiO2 NPs find a similar peak to TiO2 NPs at approximately
320 nm and scattering peaks between 200 and 300 nm which attributed
to the CA polymer phase as shown in Fig. 8a. In CTZO sample, curve a
sharp peak attributed to ZnO NPs covers the outer surface of the
membrane at 320 nm wavelength. The absorbance of UV was decreased
in the formed two-phase nanomaterials which could be attributed to
more ZnO content on the compound as shown in the TZO curve. In
addation, The UV–visible absorbance near 320 nm is attributed to the
atmosphere pollution [59]. The diffused reflectance of the powder ma­
terials is an optimum tool to characterize the optical properties of ma­
terials. Where, energy from the incident beam that penetrates one or
Fig. 6. FTIR analysis of the different samples: (a) CTO, (d) CTZO, and (e) TZO. more particles is reflected in all directions and named diffused

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H.M. Mousa, J.F. Alenezi, I.M.A. Mohamed et al. Journal of Alloys and Compounds 886 (2021) 161169

reflectance, this was detailed discussed by several authors [60,61]. Table 3

Antibacterial inhibition zone results of Escherichia coli (E-Coli).
(F (R) hv n
(αhv) = ( ) = A (hv -Eg) ,
t Bacterial growth inhibition zone diameter (mm)
Where; A is an energy-independent constant, Eg is the optical band gap Sample Gram (-Ve) bacteria Gram (+Ve) Bacteria
energy, n is a constant which determine the type of optical transitions E.Coli (mm) Enterococcus-facials (mm)
and for directly allowed transition n = 0.5, and t is samples thickness TiO2 NPs 10 ± 0.3 11 ± 0.1
(0.5 mm), and hv= 0 when extrapolating the linear portion of these plots ZnO NPs 12 ± 0.2 11 ± 0.1
to photon energy. Fig. 8(b) shows the optical band gap energy of the TZO 15 ± 0.8 14 ± 0.6
Tetracycline (30 mg) 30 ± 2.1 22 ± 1.0
different samples determined by plotting (F(R) hv/t)2 as a function of
photon energy hv. TZO sample shows a linear behavior with band gap
energy of 1.17 eV, when comparing to the other pure TiO2 and ZnO NPs ZnO, TZO samples are shown in Fig. 9. The results indicate that the
that have 3.52 eV and 3.27 eV bandgap, respectively as shown in Fig. 8(c). samples of composite hetrojunction materials have a the highest in­
Delong Li, et al. [62] show that ZnO/TiO2 hetereojunction material has a hibition zone i.e (15 ± 0.8 mm) among the samples (TiO2 NPs=
higher photocurrent compared to the mono-oxide materials and this 10 ± 0.3 mm, ZnO NPs= 12 ± 0.2 mm) in gram (-ve) bactria test, how­
was attributed to the tight heterojunction between ZnO and TiO2. ever, Tetracycline as control has a 30 mm inhibition zone. This concludes
Moreovere, formation of heterojunction structure can achieve much that the syntesized sample has around 50% of the reported tetracycline
more charge sepration and increase life time of charge carriers and thus which means that composite TiO2@ZnO NPs has formed a new com­
adsorbance of substrates can be effeciently enhanced, the photo current posite with higher antibacterial activity. The key advantages of the re­
response of the ZnO/TiO2 hetrojunction in thin film design was higher 5 sulted inorganic antimicrobial material are due to its biocidal action
times than that of TiO2 as concluded by Sujun Yuan,et al. [63]. against bacterial (i.e Escherichia coli) resulted in zone inhibition and
killing of bacteria. The antibacterial activity mechansim explained with
materials contact with bacterial cells membrane in the presence of
3.6. Antibacterial activity moisture produce reactive oxygen species such as hydroxyl radicals,
superoxide, and H2O2 [25]. The negatively charged particles presence
Wastewater is rich with living organisms such as microbial and other within OH• radicals and/or superoxide can penetrate the cell membrane
contaminations. Herein, ZnO has great role towards antibacterial activity and remains on the outer surface of bacteria and subsequently damage
to eliminate and disinfection of the wastewater from the living organ­ proteins, lipids, and DNA. In contrast, H2O2 penetrates the cell mem­
isms. The results of antibacterial test using E-Coli bacteria are shown in brane and kills the bacteria as a result works as disinfection material for
Table 3 and the optical image of the inhibition zone of control, TiO2 NPs, the wastewater in the photocatalytic treatment process [64].

Fig. 8. (a) optical properties of the different samples: CTO, CTZO, TZO, TiO2 NPs, and ZnO NPs. (b) plotting of (F (R) hv/t)2 versus the photon energy of TZO NPs, TiO2 NPs, and ZnO
NPs. (c) histogram of band gap energy of the different samples.

8
H.M. Mousa, J.F. Alenezi, I.M.A. Mohamed et al. Journal of Alloys and Compounds 886 (2021) 161169

Fig. 9. Optical images of antibacterial inhibition zone results of the control, TiO2 NPs, ZnO NPs, and TZO sample.

3.7. Photocatalytic activity has a good photodegradation ability along with 120 min of sunlight in­
tensity. To investigate the chemical kinetics of MB and MR dye de­
Fig. 10 shows the performance of the photodegradation of MB and gradation, the pseudo-first-order Eq. (2) was utilized to fit the obtained
MR dyes. The photodegradation curve in terms of the final concentration data from different dyes of MB and MR:
to the initial concentration aginast the exposed time of sunlight
ln (C/C0) = -kt (2)
(120 min) was investigated by the addition of the photocatalytic nano­
materials 15 ml of MB and MR into DI water at direct sunlight. Therafter, Where; k is the rate constant, and t is the time.
assessment of the photocatalytic materials (TZO) with UV spectrometer Fig. 11 displayes the ln (C/C0) versus degradation time (min) plots
absorbance was performed at 646 nm and 464 nm wavelength for MB for both degradation of MB and MR dyes. The rate constants values
and MR, respectively. The results of dye degradation are shown in Fig. 10. were 0.00127 ± min−1 and 0.00138 ± min−1 for MB and MR, re­
For both MB and MR degradation, the prepared composite nanomaterial spectively. It was found that the rate constant of MR is higher than

Fig. 10. Photodegradation catalysis of the synthesized sample (TZO) using methylene Fig. 11. Plots of ln(C/C0) versus time for the prepared photocatalyst against de­
blue (MB) and methyl red (MR) in different interval of time under direct sunlight. gradation of MB or MR of the synthesized sample (TZO).

9
H.M. Mousa, J.F. Alenezi, I.M.A. Mohamed et al. Journal of Alloys and Compounds 886 (2021) 161169

Fig. 12. Proposed photocatalytic mechanism and electron transfer in the pure and S-S heterojunction photocatalytic materials under direct sun light: (a) pure ZnO, (b) TiO2, (c)
composite TiO2 @ZnO S-S heterojunction TZO sample.

Table 4
A comparison study of heterojunction/nanocomposite ZnO@TiO2 photocatalysts material.

Synthesis method Heterojunction type/ Light source Target pollutant photocatalytic Remarks Ref.
nanocomposite performance

Chemical co- Precipitation Nanocomposite 18 W UV-lamp MB 59.56% (ZnO@TiO2) 1/25 [69]

Hydrothermal process (TiO2- Hybrid nanostructure UV-irradiation MB enhanced photocatalytic [70]
doped ZnO)
Electrospinning followed by Nanocomposite UV irradiation MB enhanced photocatalytic Carbon nanofibers decorated with [71]
hydrothermal the heterojunction
Sol-gel method Nanocomposites Solar light MB and brilliant enhanced photocatalytic – [72]
irradiation green (BG)
ball milling p-n junction Photoreactor MO 42.8% reduction higher photocatalytic reduction, [73]
26.1% oxidation lower photocatalytic oxidation
Both at 2.0 wt% p-ZnO activity
Electrospinning- calcination S-S heterojunction Solar light MB and MR 25% and 13% – Present work
irradiation

that of MB. This indicates that the photodegradation ability of MR is summary of the heterojunction/nanocomposite photocatalysts
better than that of MB. The proposed photocatalysis mechanism is based ZnO@TiO2 based on the different techniques, junction type,
mainly based on the photon energy which excites the electrons from polutant type, exposed light source, and phtocatalytic performance.
the VB or energy shell to the higher CB and thus keep a holes in its The present work show S-S heterojunction photocatalytic comparing
origin bands. Both resulted electrons and holes can then initiate to the other reported one with high effeciency in direct sun light due
radical groups from specific redox reactions with some molecular to the lower band gap energy.
species which can further adsorbed on the catalyst surface [65,66].
Fig. 12 illustrate scheme of the mechanism of both MO and MR dyes 4. Conclusions
under sunlight. Deposition of the Zn2+ in the outer surface instead of
Ti3+ can create many oxygen vacancies. The composite nanoparticles A composite (S–S) hetrojunction from TiO2@ZnO NPs have been
photocatalytic enhancement is attributed to charge transfer between successfully syntesized with a simple route as a photocatalytic ma­
ZnO and TiO2. Therfore, the charge carrier was generated by the terials with aid of electrospinning technique and calcination and/or
excitation of solar light and accumulated on the CB and VB of both annealing process. The results revealed a uniform and crystalline
ZnO and TiO2, respectively [67]. Yi Zhou et al. [25] showed that nanoparticles with hetrojunction structure formation. The obtained
charge transfer from ZnO surface to TiO2 surface followed a direct Z- (S–S) hetrojunction TiO2@ZnO nanomaterials has strong thermal
scheme photocatalytic mechanism due to the higher band CB of the properties after calcination comparing to the other samples due to
TiO2. At the same time, the transferred electrons to TiO2 recombine the highest ceramic content. Furthermore, the syntesized TiO2@ZnO
with the holes on the VB of the TiO2 and thus enhance dyes pho­ NPs resulted in an effective photocatalytic material for wastewater
todegradation. These electrons are accumulated and react with treatment containing MB and MR dyes due to the lower band gap
oxygen molecules which are absorbed on the surface and produce energy TZO (1.67 eV). In addation, the formed (S-S) hetrojunction
superoxide radical (•O2-) and the holes are accumulated on the induced a strong antibacterial effect which is essential in wastewater
surface of ZnO (h+). Both MR and MB are degraded by the active treatment in terms of water disinfection from living organisms. This
substances (•O2-, h+) to form tinny molecules. The better rate of MR property is attributed to the incorporation of ZnO NPs in the final
than MB can attributed to the difference in chemical structure and structure of the syntesized hetrojunction composite NPs with higher
their interaction with the oxide material. The higher degradability antibacterial activity.Interesting that the obtained hetrojunction
rate of MR could be attributed to the existence of a carboxylic group structure showed a fast photocatalytic dye degradation efficiency
which can easily react via a photo-Kolbe reaction [68]. Additionally, after 120 min in direct sunlight which accounts to different reseaons
to interpret the difference of the photo reactivities of these two including; presence of different rutile and antast structure of TiO2,
different dyes (MR and MB) could also be their ability to be interact ZnO, photocatalytic, lower ban gap, and (S-S) heterojunction for­
or adsorb over the introduced semiconductor. Table 4 shows mation.

10
H.M. Mousa, J.F. Alenezi, I.M.A. Mohamed et al. Journal of Alloys and Compounds 886 (2021) 161169

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