Chemosphere 287 (2022) 132278

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Chemosphere
journal homepage: www.elsevier.com/locate/chemosphere

Modified TiO₂ nanotubes-zeolite composite photocatalyst: Characteristics,

microstructure and applicability for degrading triclocarban
Siti Nor Hidayah Arifin a, Radin Maya Saphira Radin Mohamed a, **, Adel Ali Al-Gheethi a, *,
Lai Chin Wei b, G. Yashni c, Nurina Fitriani d, Mu. Naushad e, Ahmad B. Albadarin f
a
Micropollutant Research Centre (MPRC), Faculty of Civil Engineering and Built Environment, Universiti Tun Hussein Onn Malaysia (UTHM), 86400, Parit Raja, Batu
Pahat, Johor, Malaysia
b
Nanotechnology & Catalysis Research Centre (NANOCAT), Institute of Postgraduate Studies (IPS), University of Malaya, 3rd Floor, Block A, 50603, Kuala Lumpur,
Malaysia
c
School of Applied Science, Faculty of Engineering, Science and Technology, Nilai University, 71800, Nilai, Negeri Sembilan, Malaysia
d
Biology Department, Faculty of Science and Technology, Universitas Airlangga, Kampus C Jl.Mulyorejo, Surabaya, 60115, Indonesia
e
Department of Chemistry, College of Science, King Saud University, P.O. Box 2455, Riyadh-11451, Saudi Arabia
f
Department of Chemical Sciences, Bernal Institute, University of Limerick, Limerick, Ireland

H I G H L I G H T S G R A P H I C A L A B S T R A C T

• The characteristics of modified TiO2

nanotubes with zeolite composite was
described.
• MTNZC exhibited 81.2% of the triclo­
carban degradation within 50 min.
• The reusability of MTNZC exhibited be­
tween 94.2 and 77.4% of TCC
degradation.

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

Handling Editor: Derek Muir The study explored the characteristics and effectiveness of modified TiO2 nanotubes with zeolite as a composite
photocatalyst (MTNZC) for the degradation of triclocarban (TCC) from the aqueous solution. MTNZC samples
Keywords: have been produced via electrochemical anodisation (ECA) followed by electrophoretic deposition (EPD). Three
Electrochemical anodisation independent factors selected include MTNZC size (0.5–1 cm2), pH (3–10), and irradiation time (10–60 min). The
Electrophoretic deposition
observation revealed that the surface of Ti substrate by the 40 V of anodisation and 3 h of calcination was
Photocatalytic degradation
covered with the array ordered, smooth and optimum elongated nanotubes with average tube length was
Triclocarban
Zeolite approximately 5.1 μm. EDS analysis proved the presence of Si, Mg, Al, and Na on MTNZC due to the chemical
composition present in the zeolite. The average crystallite size of TiO₂ nanotubes increased from 2.07 to 3.95 nm
by increasing anodisation voltage (10, 40, and 60 V) followed by 450 ◦ C of calcination for 1, 3, and 6 h,
respectively. The optimisation by RSM shows the F-value (36.12), the p-value of all responses were less than
0.0001, and the 95% confidence level of the model by all the responses indicated the model was significant. The
R2 in the range of 0.9433–0.9906 showed the suitability of the model to represent the actual relationship among

* Corresponding author.
** Corresponding author.
E-mail addresses: maya@uthm.edu.my (R.M.S. Radin Mohamed), adel@uthm.edu.my (A.A. Al-Gheethi).

https://doi.org/10.1016/j.chemosphere.2021.132278
Received 4 July 2021; Received in revised form 2 September 2021; Accepted 16 September 2021
Available online 18 September 2021
0045-6535/© 2021 Elsevier Ltd. All rights reserved.
S.N.H. Arifin et al.
the parameters. The photocatalytic degradation rate of TCC from the first and the fifth cycles were 94.2 and
77.4%, indicating the applicability of MTNZC to be used for several cycles.
1. Introduction
The continuous persistence of triclocarban (TCC) in rivers and
streams is a major issue to the environment and humankind due to the
toxicity of the substance and the hazardous effect on the ecosystem
(Rochester et al., 2017). TCC is an antimicrobial agent that has been
used in several personal care products, such as soap and toothpaste. Still,
it can end up in the food chain by discharging bathroom greywater
directly to the stream, neither regulated nor monitored. The European
Chemical Agency and British Environment Agency proposed triclo­
carban as an organic compound of potential concern because the TCC in
surface water was found to be at a risk level that needs to be controlled
(Vimalkumar et al., 2018). TCC potentially can impact aquatic life with
the level of 3 μg L− 1 to 10 μg L− 1 of concentration (Barros et al., 2017;
Musee, 2018). TCC is known to cause methemoglobinemia in humans,
cause cancer and baby blue syndrome, a condition of decreasing
oxygen-carrying capacity of haemoglobin in babies leading to death
(Bomar et al., 2017).
Electrochemical anodisation (ECA) is an electrolytic process that
produces an oxidised layer over a metallic surface such as Ti foil (Sahrin
et al., 2020; Lai and Sreekantan, 2011). Synthesis of TiO₂ nanotubes via
electrochemical anodisation method using appropriate electrolyte and
processing parameters could produce uniformly array ordered and
straight-up aligned TiO₂ nanotubes (Montakhab et al., 2020; Yoo et al.,
2018). The significant processing parameters of ECA are anodisation
voltage, processing time, type of electrolyte, countered electrodes
(anode and cathode), calcination temperature and time, and ramping
rate (Mazierski et al., 2016). By using Ti foil as substrate, TiO₂ nanotubes
are formed on Ti foil as a result of a process that begins with the
development of the first layer before the formation of a rather
well-defined nanotubes structure that could be formed after a complete
process of electrochemical anodisation (Yoo et al., 2018; Mazierski
et al., 2016; Macak et al., 2007) Generally, vertically uniform array
nanotubes promise a large specific surface area, which has tube struc­
tures with a circular nanotubular opening that could anchor
light-harvesting assemblies and provide a more active site of photo­
catalyst (Sahrin et al., 2020; Mazierski et al., 2016; Zakir et al., 2020;
Sun et al., 2010). The diameter of the nanotubular opening and the
length of the tube are depending on the processing parameter. The base
part of the nanotubes is called the barrier layer, which is the nanotubes
attached to the Ti foil with the typical shape of hexagonal or pentagonal
(Mohan et al., 2020; Mor et al., 2011; Paulose et al., 2007).
TiO₂ is one of the general photocatalysts applied in photocatalytic
degradation that plays the main role in the process (Hunge et al., 2021).
However, the TiO₂ photocatalyst alone is inadequate to degrade recal­
citrant compounds, especially TCC, because TiO₂ photocatalyst has high
recombination of electron-hole that could decrease the photocatalytic
performance activities (Nguyen et al., 2020). Consequently, unmodified
TiO₂ usually needs a solution to undertake practical applications of in­
dustrial and environmental interest (Daghrir et al., 2013). This phe­
nomenon could lead to the loss of some operation effects. The mentioned
issues could be prevented by selecting a significant cation-based mate­
rial for the TiO₂ nanotubes modification, such as zeolite. Titanium di­
oxide coated with cation—for example, zeolite—could upgrade the
exhibition of photocatalysis (Azizi-Lalabadi et al., 2019; Prakash et al.,
2019). Azizi-Lalabadi et al. (2019), Mao et al. (2017), and Zhang et al.
(2018) studied the modification of TiO₂ nanotubes to improve the
photocatalytic activities. The TiO₂ nanotubes coated with zeolite
hypothesised could widen the range of light absorption, improve the
redox potential of hydroxyl radical, and prevent the recombination of
electron-hole on the conduction and valence band (Mao et al., 2017;
2
Chemosphere 287 (2022) 132278
Zhang et al., 2018). Coating TiO₂ with zeolite could have significant
oxidation; either lower or higher oxidation states improve the electrical
conductivity. The lower oxidation state assists in achieving
electro-neutrality by removing electrons from the valence band (Prakash
et al., 2019).
Zeolite seems like an attractive candidate that could improve the
performance of TiO₂ nanotubes photocatalyst for photocatalytic degra­
dation due to its advantages (Prakash et al., 2019; Koohsaryan and
Anbia, 2016). The characteristic of zeolite has proven to have a unique
relationship with titania structures, and its modified morphologies are
promising for better photocatalytic activities. Zeolite has proven to have
the ability to accommodate a variety of ions which is cations including
K⁺, Na⁺, Mg2⁺, Ca2⁺ and more (Koohsaryan and Anbia, 2016;
Pérez-Ramírez et al., 2008). Freshly, zeolite involving positive transition
metal ions have potential in many research areas, especially to enhance
photocatalysis processes due to its ability to exchange within the process
for others in reaction solution (Wang et al., 2015).
Among the group of TiO2-modified photocatalysts, ions like zeolite
shows a great potential with the light irradiation (Wang et al., 2015).
Therefore, the study intends to propose modification on the photo­
catalyst, which requires metal cation (zeolite) as a precursor to be coated
on TiO₂ nanotubes to enhance the photocatalyst activity—in this case,
the photocatalytic degradation of TCC in water given that zeolite can
separate the recombination of electron-hole (Prakash et al., 2019;
Priyanka et al., 2020). The study aims to modify TiO₂ nanotubes pho­
tocatalyst by coating it with zeolite to efficiently degrade the TCC
through photocatalytic degradation to enhance the knowledge on pho­
tocatalysis degradation of wastewater systems. This approach attracts
much attention from researchers and scientists globally because the
benefits of an environmental-friendly approach have always been at the
forefront of sustainable development.
The current work aimed to enhance the photocatalyst performance
for photocatalytic degradation of TCC by synthesising a modified TiO₂
nanotubes-zeolite composite photocatalyst (MTNZC) and investigate its
characteristics, microstructure and applicability of degrading triclo­
carban in an aqueous solution. The degradation process was optimised
using response surface methodology (RSM), while the reusability of
MTNZC was investigated for 5 cycles.
2. Experimental procedures
2.1. Synthesis of MTNZC
The synthesis of TiO₂ Nanotubes was conducted as described in the
previous study (Arifin et al., 2021). In brief, the titanium substrate was
anodised in a two electrodes electrochemical setup using a platinum rod
(Nischk et al., 2016). The ethylene glycol was used as the electrolyte of
the electrochemical anodisation process with the mixture of fluoride
ions by 98% v/v of ethylene glycol, 2% v/v of H₂O, and 0.09 M of NH₄F.
The Ti foil substrate underwent an electrochemical anodisation process
for 1 h at 10, 40 and 60 V of the applied voltage using a DC power
supply. The TiO₂ nanotubes were rinsed using acetone, followed by
deionised water, dried at 80 ◦ C for 24 h and calcined at 450 ◦ C with 2
◦
C/min of heating rate for 6 h (Li et al., 2018) (Fig. 1a). The MTNZC was
produced using pure TiO₂ nanotubes modified with transition metal
nanoparticles (zeolite) by electrophoresis deposition (EPD) (Fig. 1b).
A fixed volume (100 mL) solution was prepared by the mixing of 98%
v/v of ethanol, 0.2 g of zeolite powder, 2% v/v of deionised water and
0.04 g of magnesium nitrate (Mg(NO₃)₂) as dispersing agent. The pre­
pared solution was ultrasonically cleaned and stirred by a magnetic
stirrer until all the mixture were concentrated. The EPD experimental
S.N.H. Arifin et al.
setup was conducted at room temperature within two counter elec­
trodes, which is TiO₂ nanotubes as a cathode (− ) and Pt rod as an anode
(+). Both electrodes were dipped into the 100 mL prepared solution with
a 1–1.5 cm gap between TiO₂ nanotubes and Pt rod. The samples were
electrophoresis deposited at 40 V of applied voltage for 60 s by using DC
power. The obtained samples were dried before cleaning to strengthen
the deposition of zeolite particles into the surface of the TiO₂ nanotubes.
After the samples were completely dried, distilled water followed by
acetone were used to rinse the samples and dried again at 80 ◦ C for 24 h
using a drying oven. Finally, the samples were calcined at 450 ◦ C for 3 h
within 5 ◦ C min− 1 of ramping time.
2.2. Characterisation of MTNZC
The morphology structure of MTNZC was described using Field
Emission-Scanning Electron Microscopy (FESEM), while the chemical
compositions were determined using energy-dispersive X-ray spectros­
copy (EDS) (Zhang et al., 2014; Yan and Zhou, 2011; Bessekhouad et al.,
2006). The micrographs from the scanned image were obtained to
analyse the microstructure of the TiO₂ nanotubes arrays. FESEM images
were obtained via JEOL/JAPAN microscope combines with Oxford
instrument/USA energy dispersive X-ray analyser. The accelerating
Fig. 1. a: Electrochemical anodisation process for TiO₂ Nanotubes. Fig. 1b: Electrophoresis deposition for MTNZC. Fig. 1c: Sample extraction procedures. Fig. 1d:
Schematic diagram of High-Performance Liquid Chromatography (HPLC).
3
Chemosphere 287 (2022) 132278
voltage was applied in the range of 5 kV at a working distance of 6 mm.
The surface elemental analysis focused on five different areas of sam­
pling aiming at composition and characteristic determination of the
samples. The chemical composition of the analysed materials was ob­
tained at a different energy level of excitation of the TiO₂ nanotubes
using the EDS spectrum. X-ray diffractometry (XRD) was used to
determine the chemical structure and the crystallinity of the MTNZC.
The XRD patterns are recorded using a PanAnalytical X-ray diffrac­
tometer with copper Kα target (40 kV, 30 mA, λ = 1.5404 Å). The
scanning range was applied in a range of 2θ = 20–80◦ at a scan step of
0.01◦ . Furthermore, the estimated crystal size was calculated according
to Sherrer’s formula (Ref).
2.3. Photocatalytic degradation setup for optimisation of TCC
degradation
The TCC degradation was optimised using a factorised central
composite design (FCCD) based on response surface methodology (RSM)
via Design-Expert 11. Table 1 shows experimental variables and levels in
the factorised central composite design. Three independent factors were
selected and included MTNZC size (0.5–1 cm2), pH (3–10) and irradia­
tion time (10–60 min), according to Farouq et al. (2018). A total of 20
S.N.H. Arifin et al. Chemosphere 287 (2022) 132278

Table 1 sunlight irradiation for 60 min. The samples were analysed every 10 min
Experiment variables and level in the factorised central composite design. of time interval to identify the performance ability of MTNZC. In addi­
Symbols Variables Coded Level tion, before MTNZC was reused for the repeated experiment, it was
washed with acetone and rinsed with ultra-pure water. After that, the
− 1 0 +1
MTNZC catalyst was dried in a drying oven at 80 ◦ C within 24 h. The
A pH value 3 6.5 10 reused MTNZC were characterised by using FESEM and EDS.
B Irradiation Time (minutes) 10 35 60
C TNTs/Zeo Catalyst Size (cm2) 0.5 0.75 1.0
3. Results and discussion

experimental runs were performed; for each experimental run, a fixed 3.1. Morphological structure of MTNZC
volume (100 mL) of TCC solution was prepared by mixing 5 mL of TCC
stock solution and 95 mL of distilled water. The photocatalytic experi­ The diameter length and wall thickness of nanotube dimensions as
ments were conducted in triplicates to obtain accurate results for the determined using FESEM images are illustrated in Fig. 2 and Table 1.
degradation performance. The MTNZC with different concentrations The samples were set under 10, 40, and 60 V electrochemical anodisa­
was mixed with the TCC solution; pH was adjusted to the desired value tion within 1 h with ethylene glycol as electrolyte solution and calcined
using 0.1 N of HCl and 0.1 N of NaOH. The mixture was placed under the
natural sunlight radiation between 11 a.m. and 4 p.m., the mixture was
aerated throughout the photocatalysis process. A fixed volume (10 mL)
of the treated samples was collected after 10, 20, 30, 40, 50 and 60 min
of the photocatalysis process to determine the TCC degradation.

2.4. Sample extraction

The treated samples were extracted using disperse liquid-liquid

microextraction (DLLME). In this experiment, 10 mL of the sample
was transferred into a 60 mL QuEChErs tube and mixed with 10 mL of
sodium chloride (NaCl). A mixture of acetonitrile (4 mL) as extraction
solvent and hexane (1 mL) as dispersive solvent were rapidly injected
into the sample. The mixture was concentrated by gradually shaking the
sample tube and left the mixture to form the sedimentation phase. The
supernatant was transferred by micropipette into a clean QuEChErs tube
and mixed with calcium chloride (CaCl) as a drying agent to absorb the
moisture in the sample. The precipitate was transferred into a 2 mL vial,
sealed with aluminium foil and parafilm and stored below − 4 ◦ C for
preservation before high-performance liquid chromatography (HPLC)
analysis. The procedures of the DLLME of the sample were illustrated in
Fig. 1c.

2.5. Analytical procedure

TCC concentration was measured using HPLC analysis. The chro­

matographic system used for HPLC was Agilent 1260 Infinity DAD HPLC
system, 1260 Quat Pump VL, 1260 ALS Auto-Injector, and ZORBAX
Eclipse Plus C18 column was used with the rapid resolution 4.6 × 100
mm, 35 μ. The mobile phase (flow rate 1 mL min⁻1) applied contained
80% acetonitrile and 20% deionised water by 25 min of stop time, 5 min
post-run, 25 ± 1 ◦ C column temperature, and 20 μL of sample injection
volume. HPLC analysis was conducted by 265 nm (10) of absorbance
wavelength, 360 nm (100) of absorbance reference wavelength and
190–400 nm spectrum (Fig. 1d). The degradation efficiency was calcu­
lated according to Eq. (1).
A0 − A
Degradation (%) = × 100 (1)
A0

Where;
A0 represents the TCC initial concentration (before the adsorption),
while A is the final concentration.

2.6. Reusability of MTNZC

The reusability assessment of the MTNZC was determined by

repeating TCC photocatalytic degradation experimental set up as
described in Section 2.4 several times. The photocatalytic degradation of
TCC was conducted by using the same MTNZC five times with the same Fig. 2. The influence of anodisation voltage on the morphology of the resulting
MTNZC in 5 ppm of TCC initial concentration and pH 11 under natural thin TiO₂ films: (a) 10V, (b) 40V, (c) 60V

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S.N.H. Arifin et al. Chemosphere 287 (2022) 132278

at 450 ◦ C for 1, 3, and 6 h with 2 ◦ C min− 1 of ramping rate. The obtained

pure TiO₂ nanotubes by the 10V anodisation have a very small nano­
tubes surface with the tube’s diameter of approximately 50 nm (Fig. 2a).
The smaller TiO₂ nanotubes formed due to less electric field dissolution
occurs at low voltage as 10 V, and the TiO₂ layer becomes compact with
not the smooth nanotubular structure can be observed as shown in
Fig. 2a. On the contrary, a well-defined TiO₂ nanotubes structure could
be seen when the voltage is high (Ozkan et al., 2017). However, it could
be noticed that the obtained nanotubes from 10 V anodisation are not in
uniform array order to be compared with 40 V and 60 V of TiO₂ nano­
tubes. The TiO₂ nanotubes obtained by 40 V anodisation were in uniform
array ordered and smooth structure due to the effect of electrolyte type
presented in Fig. 2a. It was shown that the morphology structure of the
TiO₂ nanotubes layer is influenced by the electrolyte solution composi­
tion, such as fluoride ions concentration and water content (Montakhab
et al., 2020). As reported by Macak et al. (2007), the anodic growth of
the oxidised layers on metal surfaces and the formation of tubes are
created by the reaction between anodisation and chemical dissolution
toward the metallic surface. The balance between water content and
fluoride concentration in electrolyte solution influenced the formation
rate of the nanotubes (Qin et al., 2021).
The differences of the TiO₂ nanotubes morphology structure affected
by calcination time within 450 ◦ C of calcination temperature by 40 V of
anodisation is shown in Fig. 3. The nanotubular structure of 3 h calci­
nation time has a smooth arrangement compared to 6 h of calcination.
The nanotubes formed in 40 V anodisation are much longer than those
prepared in 10 V anodisation, as shown in Fig. 4, and all dimensions’
details have presented in Table 1. The differences in tube length of TiO₂
nanotubes by 10–60 V of anodisation reached about 0.56 μm–20.64 μm,
respectively. Hence, the length of TiO₂ nanotubes is proportional to the

Fig. 4. The influence of anodisation voltage on the morphology of the resulting

on TiO₂ nanotubes length: (a) 10V, (b) 40V, (c) 60V

anodisation voltage. Furthermore, studies showed that the range of

Fig. 3. The influence of calcination time on the surface morphology of TiO₂
nanotubes at 40 V anodisation: (a) 3 h calcination, (b) 6 h calcination.
voltage forming TiO₂ nanotubes strongly relates to an electrolyte solu­
tion. The anodisation potential exhibits a significant influence on the
growth of TiO₂ nanotube arrays, which exhibited a slight influence in
non-aqueous electrolytes such as ethylene glycol electrolyte solution.
The voltage value significantly reduces non-aqueous electrolytes, which
is attributed to a large extent to the low conductivity of organic elec­
trolytes (Fu and Mo, 2018). However, Mor et al. (2006) mentioned that
with the longer length of the nanotubes, the base could no longer hold
the nanotubes root, and it ended up broken and formed another layer of
nanotubes. The higher anodisation voltage grows longer the length of
the nanotubes, and 60 V of anodisation gave substantial modification of
nanotubes base.
The FESEM image of MTNZC is presented in Fig. 5 (a, b). The
observation of FESEM images revealed that the TiO₂ nanotubes were

5
S.N.H. Arifin et al. Chemosphere 287 (2022) 132278

by the supporting material applied in the EDS analysis. The relative

amounts of Ti and O regarding P and C content, as estimated by EDS
analysis in Table 2. It was noted that only 40 V anodisation voltage of
TiO₂ shows the presence of Si, which might be related to the unwanted
element; however, it does not affect the characterisation of TiO₂. The
amount of Ti weight percentages was decreased by the increase of the
anodisation voltage. Table 2 shows the differences of Ti loading on the
sample, which decreases with the amount from 52.36 of weight per­
centage (10 V) to 49.19 of weight percentage (60 V). Its atomic per­
centage pattern also has a similar pattern to the weight percentage.
However, the weight of O remains almost similar with only a bit dif­
ference of amount that can be concluded that anodisation voltage is not
the only factor that can affect the loading of O in TiO₂ nanotubes.
The deposition of zeolite on the MTNZC was confirmed by EDS
analysis by the performed modifiers as 30s_40V, 60s_40V, 30s_60V,
60s_60V. Table 3 shows the elements of chemical composition. It was
noted that the presence of Si, Mg, Al, and Na might be due to the ele­
ments present in the zeolite. The amount of zeolite deposition must be
combined with the entire element together. However, the amount of the
deposited zeolite on samples at the 30 s was much lower than the 60 s
samples with 4.11% and 5.11% for the 30 s zeolite deposition times and
17.16% and 18.02% of the 60 s deposition time. The atomic ratios on
samples at the 30 s were much lower than the 60 s samples within 3.68%
and 4.4% for the 30 s zeolite deposition times and 12.84% and 13.34%
of the 60 s deposition time. The deposition of zeolite into TiO₂ nanotubes
was depended on the deposition time and voltage applied. Deposition
time significantly influenced the zeolite deposition where only 30 s gap
has given a big difference in weight percentage and atomic percentage of
the element. However, the applied voltage also strongly impacted this
deposition technique, proven by the amount differences between 40 V
and 60 V applied voltages. The 60 V applied has a bit higher weight and
atomic amount on the samples, as shown in Table 3.
Fig. 5. Homogeneous distribution of zeolite on the surface of TiO₂ nanotubes: The crystalline composition of MTNZC is depicted in Fig. 6. The re­
(a) NT_40V_30s, (b) NT_60V_30s. sults illustrate the outcomes of XRD measurement analysis for the ob­
tained MTNZC by applying ECA in ethylene glycol as electrolyte solution
uniformly array of ordered, elongated nanotubes formed, smooth at 10, 40 and 60 V of applied anodisation voltage calcined at 450 ◦ C
nanotube walls, and covered zeolite for the modification. The length, within 1, 3 and 6 h. The pattern of the TiO₂ nanotubes are also revealed
inner diameter, and wall thickness of the tubes were approximately 5.1 in Fig. 8 (a, b, c). The form of anatase and rutile of the TiO₂ nanotubes
μm, 120.3 nm, and 14.5 nm, respectively. The electrophoresis deposi­ has been confirmed by the XRD pattern analysis consisting of the re­
tion process for zeolite deposition has directed to the size-changing of flexes to both mentioned forms. In Fig. 8c, the rutile form could be seen
the tubes for fewer nanometres due to the presence of metal nano­ at the 2Ɵ = 25◦ where the presence of a bump in the pattern from
particles in zeolite by not greater than 1.2 nm in additional (Macak et al., samples anodised at 10 V and 6 h of calcination time. The event might be
2007; Ge et al., 2016). The electrophoresis voltage applied on the due to the changing formation at the TiO₂ state form anatase to rutile
charged particles (zeolite) is the product of electric field strength and the between 430 and 450 ◦ C of calcination temperature range (Yoo et al.,
surface charge of particles. Therefore, the deposition rate generally 2018).
increased with the increased applied deposition voltage and The increasing of anodisation voltage and calcination time (Fig. 7 a.
time-related (Zaidi et al., 2020). By the intense observation, the zeolite b.c) increases the intensity of the anatase reflexes. It is caused by the
particles possibly deposited pointedly on the wall of TiO₂ nanotubes at gaining thickness of the nanotubes’ walls. 10 V anodisation voltage of
60 V within 30 s of the electrophoresis process. samples shows the synthesis not reached to TiO₂ and the Ti shows all
The EDS analysis of MTNZC is presented in Table 2, which revealed over the pattern. After 6 h of the calcination time, the rutile reflex was
the presence of Ti and O elements. The presence of P and C were caused located at the beginning of 2Ɵ. All patterns show more than 45% crys­
tallinity, from 49.9% to 75.3%, which is predicted as an anatase state.
The crystallisation occurs during the calcination process and it is
Table 2
Dimension measurement of obtained TiO₂ nanotubes.
Sample Nanotubes’ Approximated Approximated wall Table 3
Label diameter, d (nm) nanotubes’ length, L, thickness, b (nm) Chemical composition elements detected on TiO₂ nanotubes by EDS analysis.
(μm)
Element 10 V 40 V 60 V
NT_10V_1hr 30.3 ± 0.4 0.76 ± 0.05 11.1 ± 0.11
Weight Atomic Weight Atomic Weight Atomic
NT_40V_1hr 93.9 ± 1.66 3.31 ± 0.01 12.8 ± 0.32
(%) (%) (%) (%) (%) (%)
NT_60V_1hr 116.5 ± 0.49 17.5 ± 0.34 13.8 ± 0.22
NT_10V_3hr 25.6 ± 0.52 0.64 ± 0.04 11.3 ± 0.2 Ti 52.36 26.93 50.07 25.22 49.19 24.55
NT_40V_3hr 120.3 ± 0.49 5.1 ± 0.12 14.5 ± 0.11 O 44.58 68.65 44.58 67.23 46.86 70.02
NT_60V_3hr 132.2 ± 1.92 19.3 ± 0.23 19.1 ± 0.33 C 1.57 3.23 2.20 4.42 1.96 3.90
NT_10V_6hr 26.1 ± 0.27 0.56 ± 638.7 10.5 ± 0.6 P 1.49 1.19 1.40 1.09 1.98 1.53
NT_40V_6hr 104.1 ± 0.58 4.5 ± 0.01 14 ± 0.3 Si ND ND 0.45 0.39 ND ND
NT_60V_6hr 121.2 ± 3.7 20.64 ± 0.09 18.9 ± 0.3 F ND ND 1.30 1.65 ND ND

6
S.N.H. Arifin et al.
Fig. 6. XRD patterns for the samples obtained with the use of ethylene glycol-
based electrolyte and anodisation voltage in different conditions: (a) 1 h, (b) 3
h, (c) 6 h.
dependent on the calcination temperature and time (Sahrin et al., 2020).
It can be seen that calcination influenced the intensity, the intensity
ratio and the width of the (1 0 1) and (0 0 4) reflexes of anatase (Nischk
et al., 2016). It verified that the nanotubes were significantly in uniform
array ordered and the growth of nanotubes direction is at (1 0 1) di­
rection. The best crystallinity percentage up to 68.6% has been revealed
by XRD pattern analysis from 40 V of anodisation voltage and 450 ◦ C of
calcination temperature within 3 h of TiO₂ nanotubes. The effect of the
calcination time on the structure of the nanotubes has been demon­
strated in Fig. 7 (a, b, c). It can be observed in Table 4 that calcination
time and anodisation voltage influence the intensity and crystallinity of
7
Chemosphere 287 (2022) 132278
Fig. 7. XRD pattern of TiO₂ Nanotubes modified with zeolite with different
deposition voltage and deposition time: (a) 40 V and 60 V at 30s, (b) 40 V and
60 V at 60s.
TiO₂ nanotubes which shows 40 V anodisation and 3 h of calcination
time is the most significant to be compared with other samples. Based on
the literature data, the structure crystalline is energetically relying on
the specific electrochemical anodisation parameters involving applied
voltage, anodisation time, or ramping rate of the calcination. The low
anodisation voltage applied in the range below 20 V has been reported
to produce amorphous TiO₂ nanotubes on Ti foil. In order to form a
crystalline structure, a higher anodisation voltage should be applied.
The crystal structure of the TiO₂ nanotubes was revealed to be anatase,
the mixture of anatase and rutile or rutile influenced by ECA parameters
condition (Sahrin et al., 2020; Zakir et al., 2020; Nischk et al., 2016).
The average crystallite size of MTNZC increased from 2.07 nm to
3.95 nm by the increasing of anodisation voltage (10 V, 40 V and 60 V)
followed by 450 ◦ C of calcination for 1, 3, and 6 h, respectively. It was
proven that the samples calcined for 3 h give significantly larger crys­
tallite sizes compared with 6 h of calcination. The 3 h of calcination time
showed the largest crystallite size with 40 V of anodisation from 2.57 nm
(1 h) up to 3.53 nm (3 h) and went down to 2.07 ± 5 nm (6 h). According
to Lai and Sreekantan (Yoo et al., 2018), the crystallinity of the samples
prepared by ECA depends on the explicit anodisation factors, such as the
anodisation voltage, anodisation time, calcination temperature, calci­
nation time, and ramping time. Due to the factors, it has been reported
that the structure of the TiO₂ can be amorphous at a low voltage as lower
than 10 V. Meanwhile, the higher anodisation voltage could affect the
crystallisation of the TiO₂ nanotubes. Regarding to the electrochemical
anodisation condition, the crystalline structure could be predicted as
anatase with the mixture of rutile (Lai et al., 2014).
The XRD patterns of modified TiO₂ nanotubes with zeolite (MTNZC)
S.N.H. Arifin et al.
Fig. 8. Response surface methodology of TCC degradation using MTNZC.
are shown in Fig. 9. Ti foil contained primarily pure titanium with a
small amount of crystallinity. According to Grimes (Mazierski et al.,
2016), the increasing nanotubes length and wall thickness could in­
crease the growth rate of the crystallites of TiO₂ nanotubes anatase
formed. The crystallites size of MTNZC were determined by using
Scherrer’s formula (Macak et al., 2007; Robin et al., 2014). Based on the
data presented in Table 5, 38.1–40.1 nm of anatase crystallites size was
in the range for all obtained MTNZC, indicating that the chosen oper­
ating factors for electrophoresis deposition of zeolite has significantly
affected the crystallinity properties of the samples (Awad et al., 2018).
8
Chemosphere 287 (2022) 132278
3.2. Optimisation of TCC degradation using MTNZC
The screening for TCC degradation using MTNZC is illustrated in
Table 6. The maximum TCC removal (92%) was recorded at pH 6.5, after
35 min and with 0.75 cm2 of MTNZC, while the minimum degradation
efficiency (62.79%) was obtained at pH 3, after 10 min and with 0.5 cm2
of MTNZC. The ANOVA analysis indicated that the photocatalytic
degradation process of TCC was most suitably described with a
quadratic model (p < 0.05). The Lack of Fit F-value of all responses
implied the non-significant Lack of Fit relative to the pure error. The
model showed a non-significant lack of fit that indicated the significance
of the model and the model is applicable. The F-value (36.12) of the
model for all responses presented the model was significant. The p-value
of all responses was less than 0.0001, and the model was statistically
significant at the 95% confidence level. A quite high coefficient of
determination, with R2 in the range of 0.9433–0.9906, showed the
suitability of the model to represent the actual relationship among the
parameters (Chaibakhsh et al., 2016) (see Table 7).
The actual and coded equations for all responses’ models are pre­
sented in Eqs. (2) and (3).
yactual = 90.379 − 0.804x1 + 3.814x2 + 4.428x3 − 1.53625x1 x2 − 0.98625x1 x3
+ 0.19125x1 x3 − 10.9264x12 − 3.25636x22 − 2.30636x23
(2)
ypredicted = − 0.262283 + 12.8255x1 + 0.60844x2 + 79.32015x3
− 0.01756x1 x2 − 1.12714x1 x2 + 0.0306x1 x3 − 0.891948x12 − 0.00521x22
− 36.90182x32
(3)
( ( ))
x1 (pH), x2 (time, min), x3 MTNZC size cm2 , y (TCC regredation %)
The three-dimensional surface plots of interaction between pH value
versus irradiation time are graphical representations of the regression
equation for the optimisation of reaction conditions and are the most
useful approaches in revealing the conditions of the reaction system.
Fig. 8 shows the eight plots of 3-D response surface that illustrate the
interaction between pH value and irradiation time affecting TCC
degradation rate. The relationship of pH and time is depicted in Fig. 8a.
It was noted that the interaction effects of pH value and irradiation time
on the reduction of TCC depicts a canopy-like surface. With the
increasing pH value and irradiation time to the optimum points, the
reduction rate of TCC approaches the maximum level. In the literature,
the authors claimed that irradiation time has the greatest impact on
photocatalytic activity, followed by oxidant concentration and photo­
catalyst amount (Dostanić et al., 2013).
The interaction between pH and MTNZC loading on the removal rate
of TSS show a half-cylindrical response shape (Fig. 8b). The pH and
MTNZC loads exhibited a synergistic interaction that significantly
improved the TSS degradation rate (p < 0.05). Chaibakhsh et al. (2016)
indicated that the molecule is broken into smaller pieces and de­
composes completely at higher pH due to the hydroxyl radicals. The pH
value of the solution could influence photocatalytic degradation due to
the effect of hydroxyl radical formation (Zulfiqar et al., 2019). The
significant TCC degradation due to the higher pH can be identified by
the characteristic of the photocatalyst surface charge. By increasing the
pH values, the number of negative charge sites gradually increase
(Farrokhi-Rad et al., 2018). The positive effect of MTNZC catalyst size in
alkaline solution may reduce the recombination of electrons hole-pair
on catalyst surface by taking the electrons from the conduction band.
Hence, both pH values of the alkaline region resulted in an increase in
TCC photocatalytic degradation rate.
The 3-D surface plot of photo-degradation of TCC as an interaction of
catalyst loading size MTNZC and irradiation time is shown in Fig. 8c.
The elliptical shape of the contour plot indicated that the interaction of
S.N.H. Arifin et al. Chemosphere 287 (2022) 132278

Table 4
Chemical composition elements detected on TiO₂ Nanotubes-Zeolite Composite.
Element 30s_40V 60s_40V 30s_60V 60s_60V

Weight (%) Atomic (%) Weight (%) Atomic (%) Weight (%) Atomic (%) Weight (%) Atomic (%)

Ti 47.82 23.91 24.51 10.55 44.24 21.49 22.33 9.56

O 45.97 68.82 55.08 71.02 48.25 70.19 57.34 73.50
C 1.28 2.55 3.25 5.58 1.39 2.69 1.75 2.99
F 0.81 1.02 ND ND 1.01 1.23 0.56 0.61
Na ND ND 0.01 0.01 ND ND ND ND
Mg 1.31 1.29 2.05 1.74 1.28 1.23 1.80 1.51
Si 2.80 2.39 15.07 11.07 3.83 3.17 16.00 11.69
Al ND ND 0.04 0.03 ND ND ND ND
P ND ND − 0.01 − 0.01 ND ND 0.22 0.14

Table 5
Crystallinity properties of obtained TiO₂ nanotubes.
Sample Label Crystallinity (%) Average Crystallite Size (nm)

NT_10V_1hr 49.90 3.95

NT_40V_1hr 54.30 2.57
NT_60V_1hr 75.30 3.53
NT_10V_3hr 63.10 2.83
NT_40V_3hr 68.60 3.53
NT_60V_3hr 63.40 2.64
NT_10V_6hr 57.60 3.86
NT_40V_6hr 68.50 2.07
NT_60V_6hr 69.10 2.36

Table 6
Crystallinity properties of obtained TiO₂ Nanotubes-Zeolite Composite.
Sample Deposition Deposition Crystallite Crystallinity
Label Voltage (V) Time (s) size (nm) (%)

NT_40V_30s 40 30 38.1 71
NT_40V_60s 40 60 39.5 56.3
NT_60V_30s 60 30 40.1 60
NT_60V_60s 60 60 36.5 69.8

Table 7
The RSM FCCD responses to the TCC photocatalytic degradation.
Run x1 x2 x3 y

1 6.5 35 0.5 85.63

2 6.5 35 1 91.06
3 10 10 0.5 68.34
4 6.5 35 0.75 91.19
5 6.5 35 0.75 90.6
6 10 35 0.75 78.43
7 6.5 10 0.75 82.69
8 3 35 0.75 81.02
9 3 60 0.5 74.53
10 10 10 1 73.83
11 6.5 35 0.75 89.04
12 3 10 0.5 62.79
Fig. 9. TCC photocatalytic degradation versus irradiation time by the different 13 3 60 1 84.73
size of MTNZC loading (A); MTNZC applicability performance in TCC photo­ 14 10 60 1 80.19
15 6.5 35 0.75 91.85
catalytic degradation and its reusability (B).
16 6.5 60 0.75 92.1
17 3 10 1 75.96
MTNZC size and irradiation time was effective towards photo- 18 10 60 0.5 70.2
degradation of TCC, a significant interaction (p < 0.05) was recorded 19 6.5 35 0.75 86.06
20 6.5 35 0.75 92.44
between MTNZC size and time, which enhanced the photocatalytic
degradation of TCC. RSM has been used to optimise the photocatalytic x1 (pH), x2 (time, min), x3 (MTNZC size (cm2)), y (TCC regredation %).
performance of TiO₂ in the degradation of pollutants under simulated
sunlight (Dostanić et al., 2013). Based on the RSM analysis, the size of catalyst loading size could enhance the TCC degradation rate because
the MTNZC catalyst has great interaction with the TCC molecule and more active sites will be available to treat the TCC molecules. The au­
hydroxyl radical, where the adequate size of the photocatalyst active thors claimed that irradiation time has the greatest impact on photo­
sites enhance the TCC photocatalytic degradation rate along with catalytic activity, followed by photocatalyst size loading. This
reduction of electron-hole recombination. Hence, increasing the MTNZC phenomenon could be explained as the longer irradiation time and the

9
S.N.H. Arifin et al.
greater the MTNZC size devoted to the reaction, the more exposure the
MTNZC surface to visible light.
The best operating parameters for TCC degradation was recorded at
pH 10.11, after 50 min using 1 cm2 of the MTNZC size. An additional
experiment was conducted within the suggested optimum conditions to
compare the predicted and experimental values. The TCC degradation
was 81.2 vs 79.29% of the actual and predicted results, respectively. The
error values of the actual and predicted value were below 5% indicates
that the experimental values were closely agreed to the predicted values.
3.3. Performance of MTNZC in TCC photocatalytic degradation
The effectiveness of a catalyst defines the stability of the catalyst and
effectiveness of its photocatalytic performance. The trend of TCC pho­
tocatalytic degradation as a response for the MTNZC size and time is
presented in Fig. 9a. The results revealed that 0.75 cm2 and 1 cm2 of
MTNZC size exhibited a similar effect toward the TCC photocatalytic
degradation. The TCC degradation rate has slightly different, which is
92.0% for 1 cm2 and 94.2% for 0.75 cm2 of MTNZC. However, the
remained concentration of TCC after photocatalytic degradation treat­
ment by the 0.75 cm2 was 0.29 ppm compared to 1 cm2, which is the
remaining TCC concentration was 0.36 ppm. It proves that the larger
size of MTNZC does not affect the TCC photocatalytic degradation
process. The obtained results indicate that the performance of photo­
catalytic degradation of TCC improved in the alkaline condition of so­
lution regarding to the highest degradation rate of TCC by 95.2% with
1.0 cm2 in size of MTNZC at pH 11 in 5 ppm of TCC initial concentration
within 60 min of irradiation with the remain TCC concentration 0.24
ppm respectively. In alkaline solutions, the reactivity of the amino
groups is induced due to the protonation that occurred because the pH
level was above pKa of the functional group (Ding et al., 2015). It also
can be hypothesised the improvement of photocatalytic degradation of
TCC in alkaline conditions was due to the structural orientation of
substrate is significant for the attack of the reactive species under this
condition alongside protonation (Ji et al., 2013).
In order to verify the reusability of MTNZC on TCC photocatalytic,
the same experiments were repeated five times with the same MTNZC in
5 ppm of TCC initial concentration at pH 11 under natural sunlight
irradiation for 60 min. Before MTNZC was reused for the repeated
experiment, it was washed with acetone and rinsed using ultra-pure
water. After that, the MTNZC was dried in a drying oven at 80 ◦ C
within 24 h. The maintained high reactivity of MTNZC size after the fifth
cycle is presented in Fig. 9b. The photocatalytic degradation rate of TCC
from the fifth cycle was 77.4%, where it still can be considered a sig­
nificant degradation rate (Wang et al., 2016). The result demonstrated
the MTNZC has a stable and effective performance for TCC photo­
catalytic degradation and exhibited good recycle ability.
4. Conclusion
The preparation of the MTNZC depended on anodisation voltage and
calcination time. The TiO₂ nanotubes prepared by 40 V of anodisation
and 3 h of calcination process were the most significant catalyst due to
its smooth and uniformly ordered nanotubes with average tube’s length
was approximately 5.1 μm. The inner diameter and wall thickness were
120.3 and 14.5 nm, respectively and the zeolite particles possibly
deposited pointedly on the wall of TiO₂ nanotubes. The presence of el­
ements Al, Mg, Si and Na has been confirmed by EDS analysis, indicating
that zeolite’s deposition into TiO₂ nanotubes has significantly occurred.
TiO₂ nanotubes obtained from 3 h of calcination time shows the highest
crystallite size with 40 V of anodisation from 2.57 nm (1 h) up to 3.53
nm (3 h) and went down to 2.07 ± 5 nm (6 h). 38.1–40.1 nm of anatase
crystallites size was recorded in obtained by 40 and 60 V of electro­
phoresis voltage of MTNZC within 30 s, indicating that the chosen
operating factors for electrophoresis deposition of zeolite has signifi­
cantly affected the crystallinity properties of the samples. Based on the
10
Chemosphere 287 (2022) 132278
RSM analysis regarding optimisation of TCC photocatalytic degradation,
the ANOVA analysis with a quadratic model (p < 0.05) and the coeffi­
cient rate (R2) of the model operation is in the range of 0.9433–0.9906,
indicating that the optimisation of the process was significant. The best
operating parameters for TCC degradation was recorded at pH 10.11,
after 50 min and with 1 cm2 of the MTNZC size, where 81.2 vs. 79.29%
of the actual and predicted degradation were obtained. The photo­
catalytic degradation rate of TCC from the first and the fifth cycles was
94.2% and 77.4%, indicating the applicability of MTNZC for several
cycles.
Credit author statement
Siti Nor Hidayah Arifin: Methodology Investigation, Writing draft
manuscript, Radin Maya Saphira Radin Mohamed; Conceptualization,
Supervision, Writing - review & editing, Adel Ali Al-Gheethi; Concep­
tualization, Supervision, Writing - review & editing, Lai Chin Wei;
Conceptualization, Supervision, Writing - review & editing, G. Yashni:
software and data analysis, Nurina Fitriani: writing—review and edit­
ing. Mu. Naushad: writing—review and editing. Ahmad B. Albadarin;
writing—review and editing.
Declaration of competing interest
The authors declare that they have no known competing financial
interests or personal relationships that could have appeared to influence
the work reported in this paper.
Acknowledgement
This research was supported by the Ministry of Higher Education,
Malaysia (MOHE) through the Fundamental Research Grant Scheme:
FRGS/1/2018/WAB05/UTHM/02/2 (An Insight of Xenobiotic Organic
Compounds (XOCs) Degradation in Greywater via Photocatalytic
Enhancement for Water Resources Protection) vot K090 and Universiti
Tun Hussein Onn Malaysia for GPPS grant, vot U777 for the financial
support to this project. Mu. Naushad is grateful to the Researchers
Supporting Project number (RSP-2021/8), King Saud University,
Riyadh, Saudi Arabia, for the support.
Appendix A. Supplementary data
Supplementary data to this article can be found online at https://doi.
org/10.1016/j.chemosphere.2021.132278.
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