Results in Physics 12 (2019) 1230–1237

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Results in Physics
journal homepage: www.elsevier.com/locate/rinp

Effect of operational parameters on the photocatalytic degradation of T

Methylene blue dye solution using manganese doped ZnO nanoparticles
L. Anju Chanua, W. Joychandra Singha, K. Jugeshwar Singhb, K. Nomita Devia,
⁎

a
Department of Physics, Manipur University, Canchipur, Imphal 795003, India
b
Talent Development Centre, Indian Institute of Science, Kudapura 577536, Karnataka, India

ARTICLE INFO ABSTRACT

Keywords: Photocatalytic degradation of aqueous solution of methylene blue dye under UV light illumination was studied
Manganese doped ZnO by using manganese doped ZnO (Zn1 x Mn x O, where x = 0.00, x = 0.02 and x = 0.05) nanoparticles as a pho-
Methylene blue dye tocatalyst. The nanophotocatalysts were synthesized by wet chemical co-precipitation method. The structural,
Photocatalytic activity morphological, and optical properties of the photocatalysts were done by X-ray diffraction (XRD), Scanning
Electron microscope (SEM), Energy Dispersive X-Ray (EDX), photoluminescence (PL), Fourier Transform
Infrared Ray (FTIR) and UV–visible spectroscopic techniques. An improved photocatalytic efficiency of ZnO was
observed upon doping with Mn and 2% Mn-doped ZnO exhibited the highest photocatalytic activity among the
doped samples. The effect of operating parameters such as amount of catalyst, the initial dye concentration, and
initial pH on the rate of dye degradation using 2% Mn-doped ZnO was studied. Under the optimum operation
conditions, approximately 99% of dye removal was achieved after 120 min of irradiation.

Introduction
Among the various environmental pollutions, wastewater from
textile dye industries poses a serious problem. The effluents produced
by the textile dye industry are complex consisting of dyes, organic and
inorganic salts, acids and heavy metals [1]. Usually the textile dyes are
difficult to decompose in water as they have composite molecular
structures which are resistant to biodegradation [2]. Because of this
non‐biodegradability and high solubility of dyes in water, other pri-
mary methods for dye removal have been found to be ineffective [3,4].
Photocatalysis is an alternative method which is used for the de-
gradation of dyes in wastewater [5]. The technique requires a high
energy light irradiation source and an oxidant to generate hydroxyl
radicals as the main process taking place is oxidation. In order to
generate hydroxyl radicals responsible for the degradation of dye,
electron-hole pairs are generated by irradiating the photocatalyst with a
high energy light source [6]. Many researchers reported the use of
semiconducting materials (TiO2, SrTiO3, ZnO, WO3, Fe2O3, etc) as
photocatalyst [7–9]. Among the various semiconductor materials, ZnO
is generally considered as a good photocatalyst for the degradation of
organic dyes because of its wide band gap energy 3.37 eV (bulk),
harmless nature, high photosensitivity [10]. But one of the major
drawbacks of ZnO as a photocatalyst is its high rate of electron-hole
recombination rate, which reduce the degradation efficiency [11]. To
overcome this problem, many researchers reported doping of ZnO with
impurity atoms to enhance the activity [12–15]. Doping of ZnO with
transition metal introduces new energy level where electrons are
trapped in this level inhibiting electron hole recombination during ir-
radiation [16]. Mn-doped ZnO has the potential to be a multifunctional
material with coexisting magnetic, semi-conducting, and optical prop-
erties and it is regarded as a promising material for photocatalytic de-
gradation of dyes [17,18]. Ullah et al. [16] reported an improved
photocatalytic activity of Mn doped ZnO compared to undoped ZnO
upon the degradation of MB under visible light. Dodd et al. [19] re-
ported the enhanced photocatalytic degradation of chemical waste with
Mn dopant compared to undoped ZnO under UV-irradiation. Barzgari
et al. [20] investigated the photocatalytic activity of Mn doped ZnO
towards the degradation of Orange G. The results demonstrated that
doping of Mn greatly improved the photocatalytic efficiency of ZnO and
6% Mn-doped ZnO nanostructure exhibited the highest photocatalytic
activity under an irradiation time of 1 h. Moreover, various operational
parameters such as pH of the wastewater, initial dye concentration and
catalyst loading affect the activity of the photocatalyst [21–24].
Sleiman et al. [16] reported the influence of pH on the photocatalytic
degradation of Metanil Yellow, an anionic dye with a sulphonate group,
by TiO2 photocatalyst under UV illumination. Konstantinou and Albanis
[24] also reported an enhanced degradation rates for optimum catalyst
loading up to 0.4–0.5 g/l.

⁎
Corresponding author.
E-mail address: kongkhamn@gmail.com (K. Nomita Devi).

https://doi.org/10.1016/j.rinp.2018.12.089
Received 1 December 2018; Received in revised form 29 December 2018; Accepted 30 December 2018
Available online 31 December 2018
2211-3797/ © 2018 Published by Elsevier B.V. This is an open access article under the CC BY-NC-ND license
(http://creativecommons.org/licenses/BY-NC-ND/4.0/).
L. Anju Chanu et al.
In this paper, the photocatalytic degradation of Methylene blue dye
solution in water by using Manganese (Mn) doped ZnO as a photo-
catalyst under the illumination of UV light is studied. A simple wet
chemical co-precipitation method is employed for the synthesis of Mn
doped ZnO nanoparticles. Chemical co-precipitation method has sev-
eral advantages such as use of cheap raw material, easy handling,
ambient processing temperatures, pressures and large scale production
compared to other synthesis methods like sol-gel, hydrothermal, auto
combustions etc. Moreover, the particle size and morphology can be
controlled by changing the synthesis parameter such as solvent, tem-
perature, pH etc. The effects of various operational parameters on
photocatalytic activity of Mn doped ZnO such as catalyst loading, initial
dye concentration and pH of the dye solution are also investigated.
Experimental
Materials
All the chemical reagents used are of analytical grade and are used
without further purification. Zinc Acetate dihydrate (Zn (CH3CO2)2
2H2O (Hi-Media)) and Manganese Acetate tetrahydrate (Mn (CH3CO2)2
4H2O (Sigma-Aldrich)) are used as precursor materials. Sodium hy-
droxide (NaOH (Merck)) is used as a precipitating agent. A solution of
Methylene blue dye (aqueous-Hi-media) in distilled water is used as a
model wastewater. All the glasswares used are procured from BOROSIL.
Synthesis of Mn doped ZnO
Manganese doped ZnO (Zn1 x Mn x O, where x = 0.00,
x = 0.02 and x = 0.05) were synthesized by wet chemical co-pre-
cipitation method. In a typical process, the appropriate amount of two
precursors of zinc acetate and manganese acetate were thoroughly
dissolved in 400 ml of distilled water under constant stirring for about
15 min. An equal molar solution of NaOH is prepared and added drop
by drop to the above solution and the solution is maintained at pH-11
for the reaction to take place. Then, the solution is again stirred for
another 2 h in order to complete the reaction and a precipitate is
formed. The obtained precipitates were washed with distilled water for
several times to remove insoluble impurities if present. It was filtered
and dried in an oven for 24 h, maintaining the temperature at 80 °C. The
dried precipitates were ground to obtain fine powder.
The overall chemical reactions are as follows
(1 x ) Zn (CH3 CO2 ) 2 + xMn (CH3 CO2 ) 2 + NaOH (1 x ) Zn (OH ) 2
+ xMn (OH ) 2 + Na (CH3 CO2 )
(1 x ) Zn (OH )2 + xMn (OH )2 Zn1 x Mn x O + H2 O
Characterization
The structural properties of the synthesized manganese doped ZnO
nanoparticles were characterized by using Phillip’s PANalytical X’PERT
PRO Diffractometer with Cu target (λ = 1.5405 Å). Rietveld
Refinement technique was used for fitting and analyzing the XRD pat-
tern using the FullProf Suite Program. The morphology and chemical
compositional analysis were carried out using Scanning electron mi-
croscope (FEI Quanta 250) equipped with an energy dispersive spec-
trometer. FTIR spectra were recorded using FTIR Spectrophotometer
(Perkin Elmer, Spectrum Two) in the wavenumber range
4000–400 cm−1 with KBr pellet and the optical absorption spectra was
taken using UV–Vis Spectrophotometer (Ocean Optics 4000HR) in
aqueous dispersed solution and the band gaps were calculated. The
photoluminescence spectra were recorded with Horiba Fluoromax-4
Spectroflourometer.
Results in Physics 12 (2019) 1230–1237
Photocatalytic degradation experiment with Mn doped ZnO
The photocatalytic degradation of Methylene blue dye using Mn
doped ZnO as photocatalyst under the illumination of 8 W (UV-C,
254 nm) Mercury lamp (Phillips) was performed in a custom made
photoreactor. The photoreactor consists of a magnetic stirrer and a
source of UV light which is enclosed in a closed tight chamber. In a
typical process, 0.30 g/L of catalyst was suspended in model waste-
water of methylene blue dye solution. The solution was dispersed in an
ultrasonicator and kept at dark for 1 h in order to obtain absorption-
desorption equilibrium. The suspension was kept magnetically stirred
and illuminated with UV light and the samples were collected after a
regular interval of time. The degradation of the dye was monitored by
measuring the absorbance spectrum of the solution in an Ocean Optics
HR4000 Spectrophotometer. The percentage of degradation of the dye
was determined by using the following relation [25].
C0 C A0 At
%ofDegradation = × 100% = × 100%
C0 A0 (1)
where C0 and C are the initial dye concentration and concentration
after irradiation and A0 and At are corresponding initial absorbance and
absorbance after irradiation respectively.
Results and discussion
Fig. 1 shows the X-Ray Diffraction pattern of Zn1 x Mn x O
(x = 0.00, 0.02 and 0.05) . The diffraction peak from the planes (1 0 0),
(0 0 2), (1 0 1), (1 0 2), (1 1 0), (1 0 3), (2 0 0), (1 1 2), (2 0 1), (0 0 4)
and (2 0 2) were obtained. This confirms the formation of pure hex-
agonal wurtzite phase of ZnO. The XRD pattern are compared with
ICDD/PDF 2 database using X’PERT Highscore plus and found to be
well matched with the standard ICDD card No. 01-079-0205. In the
diffraction pattern of Zn1 x Mn x O (x = 0.02 and 0.05) , only the dif-
fraction peak from the planes of ZnO is obtained. No additional peak
corresponding to the metal manganese and its oxide phase is obtained.
This is due to the replacement of Zn ions by the Mn ions from the lattice
sites of ZnO without disturbing the hexagonal wurtzite phase of ZnO.
The crystallite size of the polycrystalline samples were calculated
from full width half maximum (FWHM) of the diffraction peak by using
the Scherer’s relation [26]
0.9
g=
cos (2)
where g is the crystallite size,K = 0.9 (shape factor), λ is the wavelength
of the X-ray used (1.54 Å for Cu k radiation), β is the observed FWHM
of the dominant peak (1 0 1) and is Bragg’s diffraction angle. The
calculated crystalline size of ZnO, Zn 0.98 Mn 0.02 O and Zn 0.95 Mn 0.05 O
(A)
are found to be 37 nm, 30 nm and 22 nm respectively. With the increase
Fig. 1. XRD pattern of ZnO, Zn 0.98 Mn 0.02 O and Zn 0.95 Mn 0.05 O .
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L. Anju Chanu et al. Results in Physics 12 (2019) 1230–1237

Table 1
Lattice parameter, cell Volume, atomic fractional position, reliability factor and
2
obtained from Rietveld Refinement analysis.
Sample ZnO Zn 0.98 Mn 0.02 O Zn 0.95 Mn 0.05 O

Crystal System Hexagonal Hexagonal Hexagonal

Space group P63mc (No. 186) P63mc (No. 186) P63mc (No. 186)

Lattice Parameters (Å)

a 3.257(3) 3.257(1) 3.256(1)
c 5.223(8) 5.220(7) 5.219(9)
3
Cell volume (Å ) 47.99(8) 47.96(4) 47.92(9)

Atomic positions
Zn (2b) (2b) (2b)
x 0.3333 0.3333 0.3333
y 0.6666 0.6666 0.6666
z 0.0000 0.0000 0.0000
O (2b) (2b) (2b)
x 0.3333 0.3333 0.3333
y 0.6666 0.6666 0.6666
z 0.3791(8) 0.3775(6) 0.3766(0)
Fig. 2. Rietveld refinement profile of ZnO.
RFactors
Rp 12.9 13.7 14.7
in dopant concentration, the crystallite size of the sample decreases. Rwp 18.0 18.6 20.7
Rexp 18.3 18.76 19.22
The decrease in crystallite size is due to the distortion in host ZnO
χ2 0.977 0.994 1.16
lattice caused by the addition of Mn2+ ions thereby decreasing grain RBragg 4.81 5.04 7.32
growth and nucleation of Mn doped ZnO nanoparticles [27,28]. RF 3.34 3.65 5.13
The Rietveld Refinement analysis of the doped ZnO was done with
FullProf Suite Program [29]. In the refinement method, Space group
P63mc was considered and pseudo-Voigt peak function was utilized to chemical stoichiometry within the expected error. From the EDX pat-
refine the several parameters such as scale factor, zero shifting, back- tern of doped ZnO samples, the presence of Manganese (Mn) atoms is
ground co-efficient, the lattice parameter, profile shape, width of the detected confirming the successful doping of Mn atoms in the lattice of
peak, preferred orientation, global thermal factor, asymmetric factor ZnO. The weight ratio of Mn/Zn atoms are obtained as 0.021 and 0.053,
and atomic co-ordinate of oxygen. Other factors like isothermal para- forZn 0.98 Mn 0.02 O and Zn 0.95 Mn 0.05 O respectively. The value of Mn/Zn
meter and occupancies of both zinc and oxygen are also taken as fixed atomic weight ratio is very close to their nominal ratios within the
during the refinement. A typical Rietveld Refinement profile of ZnO experimental error.
sample is shown in Fig. 2 in which the profile for the observed XRD FTIR spectroscopy was employed to study the vibrational mode of
pattern is found to be well matched with the calculated pattern of the the sample which provides the information related to functional group
space group P63mc. present in the sample, molecular geometry and intra and inter-mole-
The obtained refined parameter such as three lattice parameter, cell cular interaction. The FTIR spectra of the samples in the wavenumber
volume, atomic fractional position, the reliability factor range 400 cm 1 to 4000 cm 1 with a resolution of 1 cm 1 are shown in
(Rp , Rwp , R exp , RBragg and RF ) and goodness of the fitting ( 2) are re- Fig. 5. The prominent absorption peaks due to the stretching vibration
ported in the Table1. The slight higher value of R-factors is due to the mode of ZneO bond [34,35] are observed at 478 cm 1, 483 cm 1 and
nanocrystalline nature of the sample and such higher values are also 491 cm 1 for ZnO, Zn 0.98 Mn 0.02 O and Zn 0.95 Mn 0.05 O respectively. The
reported by many researchers [30–33]. The low value of 2 indicates absorption peaks are shifted to the higher wavenumber with the in-
goodness of the fitting. crease in Mn concentration. The additional absorption peak at
Fig. 3 shows the scanning electron micrograph of the undoped and 440 cm 1 appear in the FTIR Spectra of the doped ZnO sample which
doped ZnO samples. From the SEM image of undoped ZnO, it is ob- might be due to the band bending vibration of MneO bond [36]. A
served that the particles are well separated and has a homogenous weak absorption peak at 831 cm 1 is related to the metal-oxygen bend
distribution. The undoped ZnO possess a mixed type of particles of both vibration due to the microstructural changes in the sample [34,37]. The
spindle shaped and some distorted spherical shaped particles. The broad absorption band at 3346 cm 1 and a weak band at 1506 cm 1
average length of the spindle shaped particle is about 633 nm and are assigned to the OeH bond stretching and bending vibration re-
diameter is 315 nm. The distorted spherical shaped particle has an spectively which might be due to the presence of absorbed water on the
average size of 250 nm. The SEM images of doped ZnO samples reveals sample. Two weak absorption peaks at 2832 cm 1 and 2885 cm 1 are
that the particle size decreases upon doping with Mn and is in agree- due to the bond bending and stretching vibration of CeH bond which
ment with the observed decrease in crystallite size with Mn doping from indicates the presence of adsorbed group on the surface of the nano-
XRD measurement. The spherical shaped particle becomes more pro- crystal. The absorption peaks at 1394 cm 1, 1558 cm 1 and
minent with the increase in dopant concentration and also the ag- 1048 cm 1 are assigned as symmetrical, asymmetrical and deforma-
glomeration of the particle increases. Thus, the incorporation of Mn tion of C]O bonds which might be due to the Bronstead and Lewis
atoms in the lattice sites of ZnO influenced the size and morphology of acidity [38,39].
the particle in the synthesized sample. Fig. 6 shows the UV–Visible absorption spectrum of the samples. All
The quantitative analysis of the presence of Zinc, Oxygen and the samples showed a good absorption of light in the UV region. A well
Manganese in the synthesized sample is studied by EDX analysis and its excitonic absorption peak due to the optical transition of electron from
images are shown in Fig. 4. From the EDX pattern of undoped ZnO, only the valence band to the conduction band was obtained. The optical
the emission of X-rays corresponding to the atoms of Zinc and oxygen band gap energy of the sample are directly calculated from the ab-
hc
are observed. This shows that no impurity atoms are present in the sorption peak using the relation Eg = , where Eg is the band gap en-
undoped ZnO. From the quantitative analysis, it is also confirmed that ergy, h is planck’s constant, c is the speed of light and is the wave-
the presence of Zinc and Oxygen are according to their nominal length of the corresponding absorption peak. All the calculated band

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L. Anju Chanu et al. Results in Physics 12 (2019) 1230–1237

a b c

Fig. 3. SEM images of a) ZnO, b) Zn 0.98 Mn0.02 O and c ) Zn0.95 Mn 0.05 O .

gap energy and its absorption peak are tabulated in Table 2. 200
The band gap energy of pure ZnO is found to be 3.31 eV which is Zn0.95Mn0.05O
slightly lower than its bulk value. This may be due to the presence of
oxygen vacancy in the sample [38,40]. With Mn doping the band gap 160

Transmittance(T) (AU)
energy increases which is expected as the band gap energy of bulk MnO Zn0.98Mn0.02O
is 4.2 eV. The increase in band energy may also be attributed to Bur-
120
stein-Moss band filling effect [41].
Photoluminescence (PL) spectroscopy is an important spectroscopic
technique to study the defect states in the semiconductor which pro- 80
vides the energy states of defects and impurities and is helpful in un- ZnO
derstanding the structural defects in the semiconductor. The room C=O
C-H
temperature PL spectra of the samples measured under the excitation of 40 O-H
325 nm are shown in Fig. 7. In the PL spectra, both UV and Visible
emission is observed. The broad PL spectrum is due to the presence of Zn-O
defects states and recombination sites such as Oxygen Vacancy(VO ) , 0
4000 3500 3000 2500 2000 1500 1000 500
Zinc vaccancy(VZn) , Oxygen interstitials(Oi ) and Zinc interstitials (Zni ) .
The weakly resolved near band edge emission (NBE) indicates the Wavenumber (cm-1)
dominated defects related emission over the NBE. The intensity of the Fig. 5. FTIR Spectrum of ZnO, Zn 0.98 Mn 0.02 O and Zn 0.95 Mn 0.05 O .
PL decreases with the increase in Mn concentration in the ZnO nano-
particles indicating the decrease in the rate of the electron-hole re-
in the VB is responsible for blue emission at ∼450 nm.
combination [28,42,43]. The incorporation of Manganese atom does
The Violet-blue emission at 467 nm is the defects related emission
not alter the shape of the emission spectrum but there is slight shift in
due to the positively charged VZn. The emission at ∼482 nm is due to
the position of the NBE peak towards shorter wavelength. The blue shift
the surface defects related emission. The Green emission at ∼492 nm is
in the NBE is attributed to Mn impurity introducing impurity level in
in accordance with the energy interval between CB and VO (∼2.5 eV).
the band gap of ZnO [44,45]. This is also in agreement with the ob-
The recombination of excited electron from the localized states just
served blue shifting of the band gap energy upon Mn doping in the UV
below the conduction band (CB) and hole trapped in the deep VO re-
visible absorption spectra.
sponsible for the emission at ∼502 nm. Recombination of electron-
The PL spectra are deconvulated into ten peaks using Gaussian
holes from Zni to VO is responsible for the yellow emission at 561 nm.
function and the deconvulated spectra are shown in Fig. 8. The NBE due
The yellow-Orange emission at ∼577–590 nm may be due to the ra-
to the recombination of excited electron from the localized states just
diative recombination between the states just below the CB and singly
below the conduction band(CB) and hole at Valence Band (VB) are
ionized Oi [28,38,41–43,46–48].
obtained at 393 nm, 391 nm and 389 nm for ZnO , Zn 0.98 Mn 0.02 O and
The photocatalytic performances of the undoped and doped ZnO
Zn 0.95 Mn 0.05 O respectively. The emission peak at ∼419 nm (Violet) is
samples were investigated under UV light irradiation. The percentage of
assigned to the transition from shallow donor level Zni to VB. The
degradation is calculated using relation (1) and is shown graphically in
Violet-blue emission at ∼437 nm may be originated from the transition
Fig. 9 (a). An enhanced photocatalytic activity was observed upon
of electrons from CB to VZn as it is in accordance with the energy in-
doping of Manganese. This might be due to decrease in electron-hole
terval between these two states (2.85 eV). The radiative recombination
recombination rate as evident from the PL spectroscopy. Among the
of electron from doubly negative ionized zinc vacancy VZn 2
with the hole

Fig. 4. The EDX pattern for ZnO, Zn 0.98 Mn 0.02 O and Zn 0.95 Mn 0.05 O .

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L. Anju Chanu et al. Results in Physics 12 (2019) 1230–1237

the surface of the photoctalyst powder thereby degrading the dye into
intermediate products. The degradation of the intermediate products
into colourless product is indicated by the second plot [30,51]. The
reaction rate constants k1 and k2 were calculated from the slopes of the
C
plot of ln C0 against t.
Catalyst loading is an important parameter to obtain an efficient
photocatalytic degradation process. An increase in the amount of cat-
alyst increases the number of active sites on the catalyst surface, which
in turn increase the number of hydroxyl and superoxide radicals [52].
Therefore, in order to understand the correlation between photo-
degradation efficiency and the catalyst loading, degradation of 10 ppm
of Methylene blue dye solution using Zn0.98 Mn0.02O under UV irra-
diation was investigated in the present work. Fig. 10 shows the semilog
plot of the samples with different catalyst loading-0.25 g/L, 0.30 g/L
and 0.35 g/L. Among the different catalyst loading, higher degradation
rate is achieved for 0.30 g/L and is graphically depicted in Fig. 10. With
further increase in the concentration of the catalyst, the degradation
Fig. 6. UV–Visible Absorption spectra for ZnO, Zn 0.98 Mn 0.02 O and Zn 0.95 Mn 0.05 O .
rate decreases. This might be due to the interception of the light by the
suspension [53]. Hence, there is a limit of catalyst concentration to be
used for the degradation of a particular pollutant in wastewater, above
Table 2 which the rate of degradation will eventually decrease.
Absorption peak and optical band gap energy of undoped and Mn doped ZnO.
Sample ZnO Zn 0.98 Mn 0.02 O Zn 0.95 Mn 0.05 O a) Dye concentration

Absorption Peak (nm)
Band gap, Eg (eV)
375 367 362 In order to study the effect of initial dye concentration on the
3.31 3.38 3.43
photocatalytic activity of Zn 0.98 Mn 0.02 O , experiment is carried out by
adding 0.30 g/L (fixed) of catalysts to the different initial dye con-
centration viz 8 ppm, 10 ppm, and 12 ppm maintaining the dye solution
( )
C
at pH 7. The plot of the ln C0 Vs t of irradiation for different initial dye
degradation is shown in Fig. 11 and the maximum degradations ob-
tained at 10 ppm.
The rate of the photodegradation of dyes depends on the probability
of the formation of OH% radical on the surface of catalyst and the re-
action of dye molecules with the OH% radical. The initial increase in the
degradation rate with increase in initial dye concentration in Fig. 11
might be attributed to an increase in the probability of the reaction
between the dye molecules and OH% radical [53]. However, further
increase in dye concentration decreases the activity of the catalyst. This
might be due to the inhibition of the reaction between the dye mole-
cules and OH% radical as more dye molecules are adsorbed on the cat-
alyst surface at high dye concentration thereby reducing the formation
of OH% radical [54].

b) Effect of pH:
Fig. 7. Room temperature PL spectra of the ZnO, Zn 0.98 Mn 0.02 O
The pH of a solution is an important parameter for studying the
and Zn 0.95 Mn0.05 O .
photocatalytic activity of a catalyst as it provides the information of
surface charge properties of the catalyst [53,55]. Therefore, degrada-
doped samples, Zn 0.98 Mn 0.02 O photocatalyst showed higher activity tion of MB Dye solution at different pH values 5, 7, 10 and 12 was
which can degrade upto 99% of the dye within 4hrs of UV light irra- investigated. The pH of the dye solution was varied by adding HCl and
diation. However, further increase in the doping concentration, the NaOH to the dye solution. The semilog plot of the photodegradation
photocatalytic activity decreases as the creation of excess oxygen va- activity of Zn0.98Mn0.02O sample on degrading 10 ppm of MB at pH-5, 7,
cancies and dopant (Mn) species provides the recombination centers for 10 and 12 is shown in Fig. 12.
photo induced electrons and holes [49]. The Photodegradation percentage calculated using Eq. (1) is shown
C
The relationship between ln C0 and irradiation time t is shown in in Table 3. The degradation efficiency increases with the increase in pH
Fig. 9 (b) and is nearly a linear relationship showing that the de- from 5 to 12. At acidic pH, the removal efficiency is less due to the
gradation reaction of MB corresponds to first-order reaction kinetics dissolution of ZnO. The zero point charge of ZnO is at pH-9. Above this
[5,50]. The presence of two linear regions in the plot can be explained pH value, ZnO surface is negatively charged and in aqueous solution,
by the reaction mechanism given below: MB has positive charge. Due to electrostatic interaction between the
k1 negatively charged ZnO surface and positively charged MB dye, better
Organic Dyes Adsorption Intermediate Product photodegradation efficiency is obtained in alkaline solution. Optimum
k2
Colourless Product degradation of Methylene blue dye is obtained at pH-10 which degrades
the dye upto 99% under the irradiation time of 2 h.
The first linear plot indicates the absorption of the organic dye on

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L. Anju Chanu et al. Results in Physics 12 (2019) 1230–1237

Fig. 8. Deconvulated PL emission peak with Gaussian fitting of ZnO, Zn 0.98 Mn 0.02 O and Zn 0.95 Mn 0.05 O .

ZnO 99% 6
105 (a) ZnO (b)
Zn0.98Mn0.02O

r.
5 Zn0.98Mn0.02O

rh
90 94%
% of degradation

Zn0.95Mn0.05O

pe
Zn0.95Mn0.05O

8
75 4

1.
2=
ln(C0/C)

K
60
46% 3
45 hr.
er
2 8p
=0.
30 hr. K2
1 9 per hr.
15 =0. .7 p
er
K1 0
K 1= .
0 0 K2=0.2 per hr
K1=0.1 per hr.
0 1 2 3 4 0 1 2 3 4
Time of irradiation (in hrs.) Time of Irradiation (in hrs.)
C
Fig. 9. (a) % degradation Vs t (b) ln C0 Vst plot for ZnO, for ZnO, Zn0.98Mn0.02, Zn0.95Mn0.05 Zn0.98Mn0.02, Zn0.95Mn0.05.

0.25g/L 8 ppm
5 5
r.

10 ppm
rh

0.30g/L
12 ppm
pe

r. r.
4 0.35g/L rh 4 rh
.8

pe
=1

pe .7
.3 =1
k

hr.
2

=1
ln(C0/C)

ln(C0/C)

3 3 k1 er
k2 8p
r. k2 =0.
rh
2
hr
.
9 pe 2 hr.
er hr. 0 . hr. per
.0
p
p er k 2= per k 1=
0.6
1 1 . 9
r hr.
k 1= 0.9 r.
1 k1 =0 1 pe
k 1= er h k 2=0
.4
.5 p r.
0
k 1=0 8 per h
0 k 1=0.3
0 1 2 3 4
0 1 2 3 4
Irradiation Time, t (hrs.)
Time of Irradiation ( in hrs.)
C0
Fig. 10. ln Vs t plot for different catalyst loading (initial MB concentra- C0
C
Fig. 11. ln Vs t plot for different initial dye concentration using 0.30 g/L of
tion = 10 ppm, pH-7). C
Zn0.98Mn0.02 (pH = 7).
Comparison of the degradation % of MB dye with photocatalyst
(Zn0.98Mn0.02O) + UV light, MB + UV light, dark with catalyst and Conclusions
dark without catalyst under the optimum condition (10 ppm of MB
solution maintained at pH-10) in a time interval of 2 h is shown in In this study, removal of MB dye is performed using undoped and
Fig. 13. No degradation of the dye was observed for both dark condi- Mn doped ZnO photocatalysts synthesized by wet chemical co-pre-
tions and a slight degradation upto 2% under UV light irradiation cipitation method. It is observed that the degradation activity of ZnO
without catalyst was observed. photocatalyst is enhanced by doping with Mn and 2% Mn-doped ZnO

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