Journal of Environmental Chemical Engineering 9 (2021) 105254

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Journal of Environmental Chemical Engineering

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

An investigation of transition metal doped TiO2 photocatalysts for the

enhanced photocatalytic decoloration of methylene blue dye under visible
light irradiation
Periyakaruppan Karuppasamy a, Nagoorkani Ramzan Nilofar Nisha b, Arivalagan Pugazhendhi c,
Sabariswaran Kandasamy d, Sakthivel Pitchaimuthu b, *
a
Department of Chemistry, Anna University Regional Campus-Tirunelveli, Tirunelveli 627 007, Tamil Nadu, India
b
Post Graduate and Research Department of Chemistry, Thiagarajar College, Madurai 625 009, Tamil Nadu, India
c
Innovative Green Product Synthesis and Renewable Environment Development Research Group, Faculty of Environment and Labour Safety, Ton Duc Thang University,
Ho Chi Minh City, Viet Nam
d
Institute for Energy Research, Jiangsu University, Zhenjiang, China

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

Editor: Dr. GL Dotto Photocatalytic decolouration of dyes/pollutants using semiconducting materials has grabbed great attention in
recent days. The current study focuses on a sol-gel method for preparing semiconducting materials such as TiO2
Keywords: (titanium oxide) and transition metal (Zn, Zr, Cu) doped TiO2, which were characterized by X-ray Powder
Sol-gel synthesis Diffraction (XRD), Scanning Electron Microscopy (SEM), UV–visible Diffuse Reflectance Spectroscopy (DRS) and
Metal-doped photocatalyst
UV–visible spectrophotometer, respectively. The photocatalytic behaviour of samples was tested with Methylene
Methylene blue
blue (MB) dye by observing the decolouration of the MB dye in aqueous solutions under visible light irradiation.
Degradation
Visible light The UV-DRS spectra showed that Zn doped TiO2 demonstrated a better photocatalytic efficiency than TiO2 and
Zr, Cu doped TiO2 catalysts. The effect of Zn doped TiO2 has a lesser band gap would probably lead to enhance
the MB dye degradation in aqueous solutions under visible light irradiation compared to TiO2 and Zr, Cu doped
TiO2 catalysts. UV–vis spectrum varied with the irradiation time between 10 and 60 min and the concentration of
MB decreased with the increasing irradiation time. UV–vis study revealed that the Zn (0.01) doped TiO2
exhibited 99.64% MB decolouration as compared to 90.4% by pure TiO2. The absorbance spectrum of Zn doped
TiO2 exhibited the lighter harvest in the visible light region, which facilitated more light energy for the utili­
zation of the photocatalytic activity for the decoloration of MB. Zn doped TiO2 catalyst exhibited a greater
photocatalytic activity than pure TiO2 and the other metal doped TiO2 catalysts.

1. Introduction in aquatic life [4]. Various methods including adsorption, ultrasonic

decomposition, electrocoagulation, advanced chemical oxidation,
Several countries are facing effluent treatment issues owing to chemical coagulation, nanofiltration, and sedimentation, adopted for
contamination of water by harmful organic dyes such as Methylene Blue treating textile pollutants in effluents, are combined with physical and
(MB). MB dye is not only used in dyeing but also in veterinary and chemical principles. The aforesaid techniques have some shortcomings
human medicine for several diagnostic and therapeutic purposes. As a such as high energy waste, high expensive, and production of secondary
result of its complex structure, hydrophilic nature, stability over light, pollutants during the treatment of industrial effluents [5,6]. So far,
temperature, chemicals, and water, it causes ample environmental various reports have demonstrated various catalysts for the degradation
pollution. The total global dye produced (~15%) is wasted during the of MB dye such as Pd-supported Cu-doped Ti-pillared montmorillonite
dyeing process and in industrial effluents [1–3]. The colored pollutant is catalyst [3,4], modified TiO2/BiVO4 photocatalysts [7], Mn-doped ZrO2
mixed with water, when released into the ecosystem and causes an nanoparticles [8], and MgO–SCCA-Zn catalyst [9], Fe3O4/TiO2 core/shell
ample basis of non-aesthetic pollution, eutrophication, and perturbation nanocubes [10], magnetic SrFe12O19 [11], ZnO/NiFe2O4 nanoparticles

* Corresponding author.
E-mail addresses: pugal.smile@gmail.com (A. Pugazhendhi), sabari@ujs.edu.cn (S. Kandasamy), pitchaimuthu_chemsf@tcarts.in, spmmsc@gmail.com
(S. Pitchaimuthu).

https://doi.org/10.1016/j.jece.2021.105254
Received 13 October 2020; Received in revised form 12 February 2021; Accepted 17 February 2021
Available online 18 February 2021
2213-3437/© 2021 Elsevier Ltd. All rights reserved.
P. Karuppasamy et al. Journal of Environmental Chemical Engineering 9 (2021) 105254

[12], Co–Mn–Fe modified metal oxide catalyst [13], CdS [14], Ag Merck chemicals, India. All the chemicals were purchased as analytical
nanoparticle hybrid polymeric spheres [15] and Au/ZnO–CeO2[16]. The grade (AR) and used without further purification as such. Throughout
development of an inexpensive and greener method for the degradation the study, all the experimental solutions were prepared using double
of dyes/pollutants in contaminated water is an important problem now distilled water.
days.
Recent years, Zinc based semiconducting materials have been 2.2. Methods
focused in the research side because of it shows n-type semiconducting
property, high binding energy (60 meV), wide band gap (3.37 eV), The morphology of the catalytic materials was analyzed using SEM
enhanced optical property, ease preparation, high stability [17–19]. As a (FEI, QUANTA FEG-250, ThermoFischer Scientific, USA, Accelerating
result of these constructive properties, Zinc semiconducting materials voltage 200 V–30 kV, Operating Voltage 5–30 kV operating voltage,
are employed in various field of applications such as electronics, field Magnification: 30X- 300kX, 30 kV@High vacuum conditions: 1.2 nm,
emission displays, photocatalysis, sensors, solar cells, etc. [20,21]. In 30 kV Low vacuum conditions: 3.0 nm) microscopy carried out at an
recent years, Zinc materials have played a vital role in photocatalytic accelerated voltage of 200 V–30 kV with low vacuum conditions. X-ray
applications due to their stability and catalytic ability [22]. Many dyes diffraction pattern of the prepared powdered sample was recorded using
are used in industries for the colorization of materials, releasing 15% of a high-resolution powder X-ray diffractometer (PANalytical X′ Pert Pro-
total world production of dyes as textile effluents (colored waste) into MPD, Malvern Panalytical Ltd, United Kingdom, a short 2θscan over the
the water bodies [23]. These types of colored dye wastes discharged into region of interest: ROI, normal operating conditions (under 200 ◦ C) to
water sources make a eutrophication non-aesthetic pollution, and migrate predominantly via grain boundaries) with Cu Kα radiation. To
adverse effect to the bio-organisms. Discharge of toxic organic pollutants determine the optical property, UV–vis diffuse reflectance spectrum was
into water resources should affect the quality of water and create recorded with BaSO4 as the background between 200 and 700 nm in a
adverse effects on the biological species present in the aquatic system UV–visible spectrophotometer (Model No 2550PC, Shimadzu, Japan).
[24,25]. Among the existing oxidation processes, using heterogeneous UV–visible spectrum was recorded using a double beam UV–visible
photocatalysis for the oxidation/decolonization of dye pollutants is a spectrophotometer (UV–vis spectrophotometer-2375, ESICO, India,
pioneering technique for minimizing water pollution based on dye and Wavelength Range: 190–1100 nm, Spectral Bandwidth 1.0 nm, Optical
ease to provide a suitable mechanism for the oxidation of dye using System: Double beam, grating 1200 lines/mm, Scanning speed: HI,
photocatalysts [26–28]. MED, LOW, MAX. 3000 nm/min, Photometric accuracy: + 0.3%T or +
Among the aforementioned reported techniques, photocatalytic 0.002 A/h @ 1 A, Light source: Halogen and deuterium lamps, Pre-
oxidation has been considered as an efficient method for degrading the aligned, Power: 230 V + 10% AC, 50 Hz) in the range between 400
MB dye. Herein, TiO2 based semiconducting materials have been used and 700 nm.
for testing the photocatalytic behavior using the MB dye due to its
excellent photocatalytic activity, effectiveness, stability, reusability, 2.3. Preparation of catalyst
inexpensiveness, non-toxicity, easy availability and a wide bandgap
(3.2 eV) limit under visible light [1,3]. TiO2 has lesser quantum effi­ TiO2 and transition metal doped TiO2 sample catalysts were syn­
ciency (< 20%), which restricts the electron-hole separation and it thesized through a sol-gel method by using titanium tetra isopropoxide
produces reactive oxygen species (ROS) for degrading the pollutants [7]. (TTIP) and isopropanol solvent. Advantages of the sol-gel method in the
Recently, many researchers have tried to reduce the bandgap by adding catalyst preparation: Sol-gel process provides a novel procedure for
metals (Au, Cu, Ag, Ir and Ni) [29–35] and nonmetals (N, carbon preparing new catalytic materials. This method permits better control of
nanotubes, reductive graphene, etc.) [36–39] and semiconductors the structure, composition, homogeneity, porosity, purity, stability,
(MoS2, WO3, C3N4, CdS, etc.) [40–47] with TiO2 to enhance the pho­ particle size, optical transparency, chemical robustness, high surface
tocatalytic oxidation/reduction efficiency. The photocatalytic degrada­ area, incorporation of other materials, ease to obtain metal oxide cata­
tion of MB using photocatalysts is also an essential part for identifying lysts, synthesis of hybrid inorganic-organic materials, less energy utili­
the intermediates, products, and degradation paths of MB. The degra­ zation, and cost-effectiveness [52–55]. TTIP was mixed with
dation of MB occurs between the central aromatic ring and the methyl isopropanol (1:3 v/v ratio) and stirred well for 30 min and during the
substituent on the ambilateral aromatic ring [48,51], and also, stirring, acetic acid was added and the mixture was named as solution A.
numerous MB degradation pathways have been reported [9–16,29–32]. Zinc Nitrate 0.6 H2O, Zirconium Nitrate •H2O, and Copper Nitrate
Nevertheless, it is pertinent to propose a plausible mechanism for the •3H2O were used as the precursor of the Zn, Zr, Cu ions. To prepare 0.01
discoloration of the MB dye and to find an intermediate product during M of solution B, the above mentioned metal salts were dissolved and
the photocatalytic oxidation process. stirred well for 15 min in distilled water. The dropwise addition of So­
In the present work, synthesis of TiO2 (titanium oxide) and transition lution B in Solution A was carried out during stirring with a low speed
metal (Zn, Zr, Cu) doped TiO2semiconducting materials using sol-gel method for 1 h. The gel obtained from the aforesaid mixture was aged at
method have been reported and those materials were characterized by room temperature for 12 h and dried at 80 ◦ C using a hot air oven. The
spectral and analytical techniques. To improve the absorption spectra in dried sample was ground in agate mortar until a fine homogeneous
the visible light range, different transition metals (Zn, Zr, Cu) were powder was obtained. The obtained powder samples were washed with
doped with TiO2 and the photocatalytic activity of TiO2 and the effect of double distilled water (3–5 times), dried at 100 ◦ C, and calcinated at
transition metals doped with TiO2 on the photocatalytic degradation of 450 ◦ C for 2 h. Undoped TiO2 was prepared using the same method in
MB in aqueous solution under visible light irradiation, were also studied. the absence of solution B.

2. Experimental 2.4. Photocatalytic activity tests

2.1. Materials The photocatalytic decoloration of the MB dye in the absence and
presence of a catalyst was tested under visible light irradiation (Heber
Methylene blue (MB) dye (molecular formula: C16H18CIN3S, λmax = Annular (500W, OSRAM), HV AR MP-460 photoreactor was used as a
664 nm) was purchased from Loba Chemie, India. Titanium tetra iso­ light source), which inferred that there was no change in the concen­
propoxide (TTIP) and isopropyl alcohol were purchased from Avantor tration of MB in the absence of catalyst, indicating that MB is more
chemicals, India. Zinc Nitrate (ZnNO3•6H2O), Zirconium Nitrate stable. At the same time, when the photocatalyst was added, the con­
(ZrNO3•H2O), Copper Nitrate (CuNO3•3H2O) were purchased from centration of MB dye diminished resulting in the photocatalytic

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P. Karuppasamy et al. Journal of Environmental Chemical Engineering 9 (2021) 105254

were collected and labeled. The remained concentration of the MB dye

was determined by measuring its absorbance under visible light at
different time intervals. The absorption spectral changes of 0.1 g of 0.5
M sample showed an absorption peak at λmax = 664 nm for MB. It is
observed that the color of the MB dye changed gradually from dark blue
to colorless and the result indicated that the MB dye was oxidized.

3. Results and discussion

3.1. Powder X-ray diffraction

The Powder X-ray Diffraction Patterns (PXRD) of pure TiO2 and

transition metal doped TiO2 were examined in the 2θ range of 10–80◦ .
The PXRD patterns of TiO2 and transition metal doped TiO2was are
shown in Fig. 1. The diffraction peaks were corresponding to (110),
(101), (200), (111), (210), (211), (220), (002), (310), (301), (112) and
(202) crystal planes. The intense peak observed at 27.37◦ indicated the
anatase phase of TiO2(JCPDS Card No.21-1272) [13,16]. It had a
tetragonal unit cell, with unit cell parameters, a = b = 4.593 Å, and c =
2.959 Å, respectively (JCPDS Card No.21-1276) [13]. The Zn doped
TiO2, showed the diffraction peaks corresponding to (102), (112), (202),
Fig. 1. Powder X-ray Diffraction Patterns (PXRD) of TiO2 and Zn, Cu, Mn, Zr (212), (004), (310), (114), (204), (223), (105) and (224) crystal planes.
doped TiO2 catalysts. An intense peak for Zn was observed at 35.28◦ for the crystal plane
(211). It indicated the presence of the Zn with the tetragonal phase
reduction of the MB dye under visible light irradiation. The MB dye (JCPDS Card No.86-0158) [30–32,36,37] and rutile phase TiO2 (JCPDS
solutions containing the photocatalysts were prepared stoichiometri­ Card No. 89-8304). The diffraction peak of ZnO was intense, suggesting
cally and the photocatalytic decoloration was examined by the varia­ that ZnO nanocrystallites were formed. PXRD data of Zn (0.01) doped
tions in absorption maxima (λmax) concerning the irradiation time (t) TiO2 revealed that the sample exhibited the anatase phase of TiO2. Zn
using the UV–visible spectrum. The photocatalytic activity of TiO2 and showed a sharp, intense peak at 2θ = 32.72◦ corresponding to the (211)
transition metal doped TiO2 was investigated by measuring the decol­ crystal plane, representing that the synthesized nanomaterials were well
oration of MB in the presence of a 50 mL solution containing 0.1 g of the crystallized (JCPDS Card No. 85-0547). All the diffraction peaks ob­
catalyst. For attaining the adsorption-desorption equilibrium between tained from PXRD closely agreed with the reported data (JCPDS Card no.
the MB dye and the prepared catalysts, the abovementioned solution 21-1272) [13] for anatase of TiO2. The diffraction peak maxima shifted
mixture was kept in dark (no light) for 10 min before the irradiation towards smaller angles when increasing the Zn2+ concentration (Zn
process. The solutions were centrifuged well; the supernatant liquids (0.01) with TiO2) with TiO2 exhibiting better results due to a relatively

Fig. 2. (a,b) SEM image of pure TiO2 catalyst; (c,d) SEM image of Zn (0.01) doped TiO2 catalyst; (e,f) SEM image of Zr (0.01) doped TiO2 catalyst; (g,h) SEM image of
Zr (0.03) doped TiO2 catalyst. Blue, red, brown indicates TiO2, Zinc, Zirconium, respectively and (a), (b) indicates pure TiO2. (For interpretation of the references to
colour in this figure legend, the reader is referred to the web version of this article.)

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P. Karuppasamy et al. Journal of Environmental Chemical Engineering 9 (2021) 105254

doped TiO2 was slightly smaller than that of pure TiO2 and the lattice
parameters also changed by doping. This indicated that Cu doped into
TiO2 lattice significantly inhibited the growth of crystallite, resulting in
a decrease of the crystallite size [29–32,36].

3.2. SEM analysis

The surface morphology and size of pure TiO2, Zn (0.01) doped TiO2,
Zr (0.01) doped TiO2, and Zr (0.03) doped TiO2 were examined by SEM.
The obtained SEM images are shown in Fig. 2a–d. Fig. 2a, b shows the
SEM image of pure TiO2 and the particles having a spherical shape and
large surface area. The SEM images of Zn (0.01) doped TiO2 are shown in
Fig. 2c, d. It had an even size, and less agglomeration than pure TiO2. Zr
(0.01) doped TiO2 SEM image is shown in Fig. 2e, f. The surface area was
less as compared with Zn (0.01) doped TiO2. If, the percentage of Zr
doping increased up to 0.03, the regular shape, and surface area of the Zr
Fig. 3. UV–vis DRS spectra of pure TiO2 (black line), Cu (0.01) doped TiO2 (0.03) doped TiO2 is decreasing [44]. Fig. 2g, h shows the flake like
(green line), Zr (0.03) doped TiO2 (dark blue line) and Zr (0.01) doped TiO2 structure of Zr (0.03) doped TiO2 [51,56,57].
(sky blue line) and Zn (0.01) doped TiO2 (red line). (For interpretation of the
references to colour in this figure legend, the reader is referred to the web
version of this article.)
3.3. UV–vis diffuse reflectance spectra

The UV–vis DRS spectra of pure TiO2, Cu (0.01) doped TiO2, Zr

high crystalline nature and the anatase nature of TiO2. However, (0.03)
(0.03) doped TiO2, Zr (0.01) doped TiO2, and Zn (0.01) doped TiO2ca­
Zn doped TiO2 had a low crystalline nature and it appeared in the rutile
talysts are shown in Fig. 3. The broad absorption spectrum in the visible
phase of TiO2. The obtained results manifested that the rutile phase
region (400–700 nm) was obtained for pure TiO2 and Zn doped TiO2
exhibited a quite different behaviour than the anatase phase of TiO2.
catalysts, which inferred that the catalysts were more efficient and
However, Zr (0.01) doped TiO2 showed one more intense broad peak at
visible light sensitive [56–58]. Zn doped TiO2 catalyst showed strong
2θ = 25.1◦ , 37.5◦ , 48.6◦ ,54.04◦ and 62.4◦ belonging to the anatase phase
and broader absorption between 400 nm and 700 nm, indicating that
TiO2 (JCPDS Card No.89-4921) [49,50], which corresponded to (101),
the catalyst effectively used the visible light irradiation. Zn (0.01) doped
(004), (200), (213), (204) and (107) crystal planes. However, Zr had a
TiO2 lead to a significant effect on the absorption of visible light and a
low intense peak at 2θ = 37.5◦ and it had (202) crystal plane, according
better photocatalytic activity. It was revealed that Zn doping might have
to the JCPDS Card No.73-0958. Zr doped TiO2 exhibited a decreasing
extended the absorption region of TiO2 in the visible region due to
crystalline nature with an increasing Zr content, which meant that Zr
electronic energy levels below the conduction band. The redshift of the
doping has retarded the amorphous anatase. Zr (0.03) doped TiO2
bandgap was found between the plot of (αhν)1/2 and hν. This revealed
showed one intense peak corresponds to (100) crystal plane, which
that the bandgap shifted from 3.0 eV for pure TiO2and to 2.8 eV for Zn
belonged to Zr (JCPDS Card No. 89-3045) and no other peaks were
doped TiO2. The redshift was obtained for the transition metal doped
obtained. Hence it revealed the absence of TiO2, it was not considered as
TiO2 due to the charge transfer that occurred between the impurity
an efficient catalyst in the present study. The PXRD pattern of Cu (0.01)
bands and the TiO2 conduction band. The bandgap of Zr (0.01) doped
doped TiO2 provided the peaks at 25.2◦ (major), 27.3◦ , 47.1◦ , and 56.6◦ ,
TiO2 is 3.3 eV, Cu doped TiO2 is 3.7 eV and Zr (0.03) doped TiO2 was
respectively. However, the PXRD peaks for the rutile phase (TiO2-R)
3.5 eV, and it revealed that the increase of bandgap did not affect the
appeared at 47.1◦ , 54.2◦ and 62.7◦ . PXRD peaks for copper species were
photocatalytic decoloration of MB. The bandgap diagrams of pure TiO2,
observed at 37.5◦ (JCPDS Card No. 701995). The diffraction peaks were
Cu (0.01) doped TiO2, Zr (0.03) doped TiO2, Zr (0.01) doped TiO2 and
indexed to (101), (103), (004), (112), (200), (105), (211), (204), (116),
Zn (0.01) doped TiO2 catalysts are shown in the Supporting Information
(220) and (215) planes of TiO2 (JCPDS Card No. 21-1272). The Cu
(Figs. S1–S5). For example, when comparing Zr (0.01) and Zr (0.03)

Fig. 4. Band gap energy diagram of pure TiO2, Zn (0.01) doped TiO2, Zr (0.01) doped TiO2, Cu (0.01) doped TiO2 and Zn (0.03) doped TiO2 catalysts Pure TiO2
catalyst and plausible mechanism of Photodecoloration of MB.

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P. Karuppasamy et al. Journal of Environmental Chemical Engineering 9 (2021) 105254

Fig. 5. (a) UV–vis absorption spectra of MB solution at different time durations in presence of Pure TiO2 catalyst; (b) UV–vis absorption spectra of MB solution at
different time durations in presence of Cu doped TiO2 catalyst; (c) UV–vis absorption spectra of MB solution at different time durations in presence of Zr (0.03) doped
TiO2 catalyst; (d) UV–vis absorption spectra of MB solution at different time durations in presence of Zn doped TiO2catalyst; (e) UV–vis absorption spectra of MB
solution at different time durations in presence of Zr (0.01) doped TiO2.

doped TiO2, upon increasing the dopant (Zr) concentration, the bandgap 3.4. Photocatalytic decoloration of MB
increased and the energy level between valance band and the conduc­
tion band was also too large but the photocatalytic activity did not Photocatalytic activity of pure TiO2 and Cu, Zr, and Zn doped TiO2
improve. However, the Zn (0.01) doped TiO2 band gap was very low; it for the degradation of MB dye was studied using a UV–vis spectropho­
provided better photocatalytic activity towards the decoloration of MB tometer under visible light irradiation. The increase of photocatalytic
[51]. The bandgap energy level diagrams of pure TiO2, Cu (0.01) doped activity of Zr, Cu, and Zn doped TiO2was attributed to a smaller crys­
TiO2, Zr (0.03) doped TiO2, Zr (0.01) doped TiO2 and Zn (0.01) doped talline size, higher surface area, reduced bandgap energy, lower
TiO2 catalysts with the band gap values (in eV) and the plausible electron-hole recombination rate and higher efficiency for the electron-
mechanism are depicted in the Supporting Information (Fig. 4). hole generation than pure TiO2. Zn doped TiO2 showed better photo­
catalytic activity with a doping concentration of 0.01%. The radical

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P. Karuppasamy et al. Journal of Environmental Chemical Engineering 9 (2021) 105254

Fig. 7. Kinetic Study ln (C0/Ct) with time (min).

Fig. 6. Bar diagram of % removal of MB with time under visible light irradi­
ation using pure TiO2 and Zn, Cu, Zr doped TiO2 catalyst. Table 2
Pseudo first order (k, min− 1) rate constant and correlation coefficient (R2) for
decolorization of MB dye with various photocatalysts.
Table 1 Catalysts Amount of [MB] Pseudo first order Correlation
Efficiency removal % of MB dye using various photo catalysts. catalysts, mg/ dye, rate constant, k coefficient (R2)
L mg/L (min− 1)
Time Removal % of MB dye
(min) TiO2 1 5 0.0408 0.93
TiO2 Cu doped Zr (0.03) Zr (0.01) Zn (0.01)
1 10
TiO2 doped TiO2 doped TiO2 doped TiO2
1 15
10 8.73 1.24 1.64 39.45 39.75 1 20
20 46.64 10.9 3.57 42.42 74.11 Zn (0.01) 1 5 0.0193 0.98
30 50.23 17.99 5.48 44.67 79.0 doped 1 10
40 66.16 20.87 11.84 47.55 84.86 TiO2 1 15
50 73.77 29.14 17.6 65.35 91.64 1 20
60 89.69 27.5 39.42 81.9 99.64 Zr (0.01) 1 5 0.0616 0.94
doped 1 10
TiO2 1 15
scavenging test results showed that O−2 (superoxide) free radical and 1 20
Cu (0.01) 1 5 0.0321 0.99
holes lead the photocatalytic decoloration of MB.
doped 1 10
Potassium iodide (5 mmol/L), terephthalic acid (5 mmol/L), and TiO2 1 15
quinone (5 mmol/L) were added to the decoloration of the MB system 1 20
for reacting with OH, H+, and O−2 free radicals. The photocatalytic ac­ Zr (0.03) 1 5 0.0715 0.92
doped 1 10
tivity was lowered with potassium iodide due to reduce the hole by
TiO2 1 15
hydroxyl free radical. Then the O−2 free radical may be shared with 1 20
quinone and also reduce the photocatalytic activity. However, quinone
exhibited a better MB decoloration than potassium iodide and tereph­
thalic acid, which indicated that the O−2 free radical and the holes lead to time. The bar diagram of % removal of MB by pure TiO2 and Zr, Cu, and
the photocatalytic decoloration of MB. Doping of Zn, caused the for­ Zn doped TiO2 under visible light irradiation is shown in the Supporting
mation of superoxide anion radicals, and improved the effective sepa­ Information (Fig. 6). It was perceived that the decoloration of MB was
ration of electrons and holes. The pairs adversely affected the 99.64% using Zn (0.01) doped TiO2 whereas pure TiO2, it was 90.4%. Zn
photocatalytic activity of the Zn doped TiO2. Zr doped TiO2 showed doped TiO2 catalyst exhibited a more significant photocatalytic activity
significant photocatalytic activity for the decoloration of MB but when than pure TiO2 and the other metal-doped TiO2 catalysts. The efficiency
Zr concentration was increased there is a decreased or no significant of the photocatalysts is presented in Table 1.
change in the photocatalytic effect. The photocatalytic activity of Zn The photocatalytic decolorization of MB dye was studied under
doped TiO2 was higher than pure TiO2 due to the following reasons. (a). pseudo first order condition with excess of dye concentration. The rate
The absorbance spectrum of Zn doped TiO2 exhibited the lighter harvest of decolorization in the presence of photocatalysts is directly propor­
in the visible light region, which facilitated more light energy for the tional to MB dye concentration. The plot of ln(C0/Ct) vs. time is linear,
utilization of the photocatalytic activity for the decoloration of MB. (b). which indicates that the decolorization of MB dye using photocatalysts
Zn has a smaller bandgap pure TiO2, hence, the electron might have follows pseudo first order reaction Fig. 7. From the plot, we can easily
been easily transferred from the conduction band of TiO2 to metallic zinc evaluate the regression coefficient (R2), first order rate constant (k)
ion. The photocatalytic activity of Zn doped TiO2 was determined to be using the kinetic equation ln (C0/Ct) = kt [62–64]. Here, k is the
the highest than the other photocatalysts and the UV–vis spectrum is first-order rate constant, C0 is the initial concentration of MB dye, Ct is
presented in Fig. 5(a–e). Cu and Zr (0.03) doped TiO2 showed the lesser the concentration of MB dye at time t (in mins). The evaluated kinetic
photocatalytic activities as compared to pure TiO2 and Zn doped TiO2 data are summarized in Table 2. The higher rate constant values are
[51,56–61]. Irradiation time played an essential role in the photo­ evaluated using metal-doped TiO2 photocatalysts compared with TiO2.
catalytic decoloration of MB. In the present work, the UV–vis spectrum The k values indicate that the Zn (0.01) doped TiO2 catalyst has
was varied for the irradiation time between 10 and 60 min. The con­ exhibited a higher rate constant value than Zr, Cu doped TiO2
centration of MB decreased while increasing the visible light irradiation photocatalysts.

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P. Karuppasamy et al. Journal of Environmental Chemical Engineering 9 (2021) 105254

Table 3
Comparison of photocatalytic degradation of MB dye with other reported photocatalysts.
Method of synthesis Photocatalyst Decoloration efficiency (in %) Reaction conditions Ref.

[MB] [Catalyst] Light source used

Sol-gel Zn doped TiO2 99.64 0.5 × 10− 5 M 0.1 g Visible light Present work*
Sol-gel ZnO NPs/rGO 99.5 10 mg/L 10 mg Hg lamp [52]
Sol-gel ZnO NPs 63 10 mg/l 10 mg Hg lamp [52]
Sol-gel ZnO 65.6 2 × 10− 5 M 0.01 g/L Xenon lamp [53]
Sol-gel Ag/ZnO 82.6 2 × 10− 5 M 0.01 g/L Xenon lamp [53]
sol–gel 2%Fe–ZnO 92 20 mg/L 1 g/L UV light [54]
sol–gel Fe2TiO5 97 10 mg/ l 50 mg/l Visible light [55]
Solvothermal ZnO@GO 98.5 0.5 mM 10 mg UV lamp [65]
Solvothermal ZnO/grapheme 100 20 mg/L 30 mg Visible light [66]
Solvothermal rGo/TiO2/ZnO 92 0.3 mg/L 0.1 g/L Xenon lamp [67]
Solvothermal rGo/TiO2 68 0.3 mg/L 0.1 g/L Xenon lamp [67]
Ultrasonication/ hydrothermal ZnO/CNTs 99 20 mg/L 0.5 g/L Hg lamp [68]
Microwave hydrothermal N doped ZnO 97.1 20 mg/L 50 mg Xenon lamp [69]
Ultrasonication rGO/TiO2 91.3 20 ppm 2 g/L Sun light [70]
Ultrasonic dispersion GO/TiO2 99 5 mg/L 0.1 g/L UV light [63]
Modified-impregnation method Fe-Ti/SF 94.2 10 ppm 0.2 g Xenon lamp [71]
Greener synthesis Sb-ZnO 98.6 50 μM 0.05 mg/mL UV lamp [72]

This work has been compared with already reported literature Acknowledgment
[52–55,63,65–72], and a Table of comparison is given in Table 3. It was
perceived that, Zn doped TiO2 catalyst prepared by this work exhibited a Dr. S. Pitchaimuthu thanks the University Grants Commission (UGC),
remarkable photocatalytic efficiency. New Delhi, India for providing financial support through UGC–Minor
research project, F.No. 6450/2016(SR) dated. 30.06.2017 and Post
4. Conclusion Graduate and Research Department of Chemistry, Thiagarajar College,
Madurai – 625 009, Tamil Nadu, India for providing laboratory facilities
A novel and straightforward sol-gel method was employed for syn­ to carry out the present work.
thesizing TiO2 and transition metal (Cu, Zr. Zn) doped TiO2 catalysts.
The characterization techniques such as PXRD, SEM, and UV–vis DRS Appendix A. Supporting information
are supported to determine the prepared catalysts’ structural insights.
Among the photocatalysts, Zn (0.01) doped TiO2 was exhibited better Supplementary data associated with this article can be found in the
photocatalytic activity for the decoloration of MB dye due to its n-type online version at doi:10.1016/j.jece.2021.105254.
semiconducting property, high binding energy (60 meV), wide band gap
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