International Journal of Basic & Applied Sciences IJBAS-IJENS Vol: 11 No: 04 62

Synthesis and characterization of Manganese doped ZnO

nanoparticles
Y. Abdollahi1, A. H. Abdullah1,2, Z. Zainal1,2, N. A. Yusof2

1
Advanced Materials and Nanotechnology Laboratory, Institute of Advanced Technology Universiti Putra Malaysia,
43400 Serdang, Selangor D.E., Malaysia.
2
Department of Chemistry, Faculty of Science, Universiti Putra Malaysia 43400 UPM Serdang, Selangor, Malaysia
[email protected]

Abstract: Various levels of manganese (Mn)-doped at room temperature [1]. It is an inexpensive and
ZnO were synthesized by precipitation method. environmentally safe host material. Due to its
Characterization was carried out by XRD, TEM, properties, the interest in ZnO as a photocatalyst has
SEM, EDX, BET and the band gap measured by increased, however it has been mainly used under
UV-visible reflectance. In the XRD pattern of ultra violet (UV) irradiation [2-6]. Photocatalytic
samples, there is no signature of impurity peaks, reaction is initiated when a photoexcited electron is
which could indicate Mn-related secondary promoted from the filled valence band (VB) of a
phases. The EDX show the amount of Mn doped semiconductor photocatalyst (SC) to the empty
on ZnO is slightly lower than the theoretical value. conduction band (CB) as the absorbed photon energy,
The SEM of 1% Mn-doped ZnO illustrated that hν, equals or exceeds the band gap of the
morphology is well ordered, has low aggregation, photocatalyst. The hole pair (e--h+) is generated at the
and homogeneous distribution of particle size. surface of the photoexcited photocatalyst as shown
High aggregation is observed, however, in other below [7].
percentages of Mn-doped ZnO. Results of TEM Photoexcitation : SC+hν→ e− +h+ (1)
show that more than 50% of the particles for Adsorbed oxygen: (O2)ads +e→− O2−• (2)
undoped and Mn-doped ZnO use between 15 and Ionization of water : H2O → OH− +H+ (3)
35 nm, with 1% Mn doped ZnO having the Protonation of superoxides : O2−• +H+→ HOO• (4)
highest percentage (77%). The BET shows that HOO• + e− → HO2− (5)
the surface area of synthesized catalyst increases HOO− +H+→ H2O2 (6)
when the weight ratio of manganese increases up H2O2+e-→ OH− +OH• (7)
to 1% Mn, but decreases thereafter. The band gap H2O+h+→H++OH• (8)
of 1% Mn-doped ZnO is 2.2 eV which is smaller Since 46% of solar energy consists of visible light, it
than the undoped ZnO band gap. The results of is more economical to use visible light than UV light
characterization show 1% Mn-doped ZnO has the in large scale operations. To use visible light, ZnO
highest surface area, the lowest particles size and however has several drawbacks including the low
the lowest agglomerate. Moreover the calculated surface area or big particles size and an unsuitable
band gap of 1% Mn-doped ZnO is lower than band gap energy (Eg=3.7 eV). It was observed that
others except 0.5%Mn. Additionally, doping with 3d metals reduced the Eg of
photodegradation of cresols under visible light semiconductors by forming interband-gap localized
showed that 1% Mn-doped ZnO had maximum levels [8]. The charge-transfer transition between the
adsorption and rate of photodegradation. In d-electron of dopant (t2g levels) and the CB or VB
conclusion 1% Mn doped ZnO is suitable as the was reported [9]. On the other hand, the metal d-
best photocatalyst to degrade cresols under visible orbital’s are mixed with the CB and VB of
light irradiation. semiconductors [10]. This overlap is because wide
VB or CB directly decreases Eg. Recently, there has
Keywords: ZnO; Co-precipitation; Manganese- been much attention focused on modifying ZnO by
doping; Optical properties; Nanoparticles doping with transition metals such as Ag [11], Ni
[12], Cu [13], Co [14], Cr [15], Ti [16]. These studies
1. Introduction demonstrated that the metals can change Eg of ZnO,
ZnO is a II-VI semiconductor with wide direct- and that the dopants can control ZnO grain size. It
gap (3.37 eV) and exciton binding energy (60 meV) demonstrated the presence of the d-electron because

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 International Journal of Basic & Applied Sciences IJBAS-IJENS Vol: 11 No: 04 63

the t2g of manganese (Mn) is very close to the VB 2.3. Characterization

[10, 17]. More recently, synthesis of a Mn-doped X-ray Diffraction (XRD) analysis of the
ZnO nano-crystal (not powder) was reported by wet- photocatalysts for structural characterization was
chemical techniques [18]. Moreover, ZnO carried out using a Shimadzu XRD-6000
nanocrystalline powders doped with 1, 3 and 5% Mn Diffractometer. Chemical composition and
were prepared using a sol-gel process [19]. morphology of the samples was carried out using a
Unfortunately, up to now the value of the Eg and scanning electron microscope (SEM), model Hitachi
optimum amount of Mn as dopant is not clear. S-3400N and Energy Dispersive X-ray (EDX)
Additionally, reported results of Mn-doped ZnO thermo electron corporation. The nanostructure and
being applied as a photocatalyst are quite different. In particle size of the nanocrystals in these samples was
this work, Mn-doped ZnO nano-powder was prepared determined from Transmission Electron Microscopy
with up to 2% Mn by the co-precipitate method. The (TEM) [20] images obtained using a Hitachi H-7100
samples were characterized to obtain particle size, electron microscope[21]. The Brunauer-Emmett-
surface area and the Eg. The synthesised Mn-doped Teller (BET) method, using nitrogen adsorption at
ZnO was applied as photocatalyst to liquid nitrogen temperature 77 K, was employed to
photodegradation of ortho, meta and para-cresol (o, measure total surface area of the photocatalysts. This
m, p-cresol) under visible light irradiation. was done using a Thermo Finnigan Sorptomatic
Instrument model 1900. The optical absorption
2. Experimental spectra were obtained using a Perkin Elmer Lambda
35 UV-Vis-NIR diffuse reflectance spectrometer.
2.1. Materials Various concentrations of cresols solutions were
Zinc acetate (99%, Merck), Manganese acetate (98%, prepared using deionized water. Photodegradation of
Sigma, Alorich), NaOH (99% Merck),  H2SO4 (95%- cresols was performed in a batch photoreactor,
97%),  Ethanol (absolute), o-cresol (99%, Merck), m- designed in a column 14.5-cm height with an 11.5-
cresol (99%, Merck), p-cresol (99.5%, Fluka), cm diameter (Fig. not showed). To volatilize
commercial ZnO (C-ZnO, 99%, Merck), and other produced gas (may be CO2), increase solution
required chemicals are of reagent grade, obtained from fluidization and access oxygen for eq. (2), air was
Merck and were used without further purification. blown into the reaction solution by an air pump at a
flow rate of 10m3/h. the cooled air into the solution
2.2. Preparation eliminated the lamp’s heat effect and kept the
For synthesizing the catalyst, 75mM of ethanolic temperature at around 25 ºC. Magnetic stirring at a
Zinc solution was mixed with different speed of 200 rpm was applied to make the suspension
concentrations of an ethanolic manganese solution. solution, during the reaction. The photoreactor is
The mixed solutions were heated at 75 ◦C for 45 min located in an aluminum-sealed tube to enhance the
to reduce the amount of the solution and increase the radiation by reflection. A Philips lamp (23watt) was
concentration of the metal ions, after which it was used as light source. Throughout the experiment, the
cooled at room temperature. NaOH solution was then appropriate concentration of cresols solution was
added to the mixed solution with constant stirring contacted with the correct amount of photocatalyst in
(150 rpm) until pH 8.3 was reached. The new the photoreactor. At specific time intervals, samples
colorless solution was kept in a water bath at 67 ◦C were withdrawn from the bulk solution, and filtered
for two hours. It was observed that the solution through 0.2μm PTFE filters. The concentration of
started precipitating after one hour in water bath. cresols was measured using a UV-visible
After cooling the solution to room temperature for spectrophotometer (shimadzu, uv-1650pc),
four hours, the colloidal solution was centrifuged for
20 minutes at 4000 rpm. The resulting precipitate was 3. Results and discussion
washed with ethanol, sonicated (30 min), and
centrifuged (4000 rpm). The above procedure was 3.1. Phase and Element analysis
repeated five times to remove unreacted ions. The The XRD patterns of U-ZnO and Mn-doped ZnO
separated precipitate was dried overnight at 110◦C. with different Mn concentration are presented in Fig.
The catalysis was ground and then calcined under 1. The XRD pattern shows only the peaks correspond
compressed air at 650ºC for 3.5h in the tubular to wurtzite crystal structure of ZnO (reference code
furnace. Undoped ZnO (U-ZnO) was synthesized 01-089-1397). In the XRD pattern of samples, there
with a similar procedure except for the addition of is no signature of impurity peaks which might belong
manganese acetate to Mn-related secondary phases. However, EDX
analysis confirmed the presence of Mn in the samples
(Table 1). One reason is that the majority of Mn

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 International Journal of Basic & Applied Sciences IJBAS-IJENS Vol: 11 No: 04 64

atoms are located at substitutional sites for lower conducted to investigate the morphology and
doping concentrations [22]. particles size of the samples. The TEM morphology
As observed in Fig. 1, the (101) peak (crystal plate) of 1% Mn-doped ZnO confirmed the low aggregation
of 1% Mn is broader than other peaks, because 1% and better distribution in SEM images (Fig. 3). In
Mn photocatalyst has a different crystalline size. addition, the TEM images showed spherical
Using the Debye-Scherrer equation [23] and the half- nanocrystallites for 1%Mn-doped ZnO (Expanded
width of the XRD lines, the average values of part in Fig. 3). The measured particles size of
crystalline size of the samples were calculated based samples showed (Table 2) more than 50% of
on the 101 crystal plate and are shown in Table 1. frequency was between 15 and 35 nm while the
The crystalline size of photocatalyst decreased with highest percentage (77%) belonged to 1% Mn doped
increasing percentage of Mn over 1%. Beyond this, ZnO. This indicates that the addition of Mn may be
the crystal size increased again. It may be the doping control the growth of ZnO grains.
of Mn in ZnO can control crystal size, as observed
for other transition metals such as Co [14], Cr [15].

Fig. 1 X-ray diffraction patterns of the undoped

powders (a) undoped ZnO, and (b) 0.5%, (c) 1 %, (d)
1.5%, (e) 2 % Mn-doped ZnO after heat treatment. Fig. 2 SEM micrograph for 1% doped ZnO

Table 1 XRD data, Mn determined by EDX and Table 2 the particles size distribution of the U-ZnO
particles size of U-ZnO and Mn doped ZnO and Mn-doped ZnO

Particle Frequency (Mn-doped ZnO)

%Mn %Mn Crystallite size size
(Theoretical) (EDX) (nm) (nm) ZnO 0.5% 1.0% 1.5% 2.0%
0 0 51 15-20 5 8 6 5 3
0.5 0.4 42 20-25 9 11 17 10 9
1 0.8 13 25-30 14 16 29 22 16
1.5 1.4 15 30-35 23 24 25 19 27
2 1.9 30 35-40 26 29 13 25 18
40-45 15 7 7 11 16

3.2. Morphology studies 45--50 8 3 3 8 11

The influence of different percentages of Mn on the
surface morphologies of photocatalysts (0-2% Mn-
doped ZnO) was studied by SEM (Fig. not show). The surface area (BET) of U-ZnO and Mn doped
The SEM image of 1% Mn-doped ZnO illustrates the ZnO are presented in Fig. 4. As TEM images show,
morphology is well ordered; a lower aggregation and the photocatalyst particle size decreases with
better particle size distribution (Fig. 2) than other increasing % of Mn up to 1% Mn. Results of BET
percentages of Mn-doped ZnO. TEM were showed the surface area increased when the weight
ratio of Mn increases up to 1% Mn, confirming the

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 International Journal of Basic & Applied Sciences IJBAS-IJENS Vol: 11 No: 04 65

control of growth of ZnO grains by Mn. However, less than C-ZnO’s Eg. It may be due to a defect in the
the surface area was shown to decrease above 1% synthesised photocatalyst [25]. The Eg of 0.5% Mn-
Mn, which confirms the TEM and SEM observations. doped ZnO is 1.5 eV. It may be due to s-d and p-d
Agglomeration is a limiting factor for surface area. exchange interaction [26-27]. This electron-hole may
SEM and TEM images showed that with above 1% improve photodegradation but most of them are
Mn, the agglomeration increases, and this may be due trapped by sub–surface recombination [28]. The Eg
to a decrease in surface area. of 1% Mn-doped ZnO was 2.2 eV. The d-electron of
Mn (t2g level) can easily overlap with the ZnO’s
valence band (VB) because t2g of Mn is very close to
VB of ZnO [17]. This overlap causes a wide VB and
consequently decreases the Eg of ZnO photocatalyst
so that the VB electrons can be excited by visible
light irradiation. The Eg of 1.5% and 2% Mn-doped
ZnO was 2.6 eV, which is higher than the Eg of 1%
Mn-doped ZnO. Similar behavior was observed for
vanadium doped ZnO, with Eg higher with an
increased vanadium concentration [29]. This might
be due to the influence of numerous factors such as
structural parameters, carrier concentrations and the
presence of defects such as oxygen vacancies, which
may lead to the Burstein Moss shift [30].

Fig. 3 TEM images of the 1% Mn doped ZnO

nanoparticles

Fig. 4 Effect of doping level on the specific surface

area (BET) of the undoped ZnO and various percent
of Mn doped ZnO

3.3. Band gap measurement

The diffuse reflectance (R%) spectra of the samples
(0-2% Mn-doped ZnO catalysts) after Kubelka-Munk
treatment [(Fhν)1/2] vs. һν (eV) are shown by Tauc’s
plots [24] in Fig. 5. The intersection between the
linear fit and the photon energy axis gives the value
to Eg. The Eg of undoped ZnO of 2.75 eV was a little

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 International Journal of Basic & Applied Sciences IJBAS-IJENS Vol: 11 No: 04 66

C-ZnO and synthesised photocatalyst (0-2% Mn

doped ZnO). Whereas the activity of photocatalyst
seriously depends on the adsorption of an amount of
removable pollutants over photocatalysis [31-32], the
amount of adsorbed cresols on the C-ZnO, U-ZnO
and Mn-doped ZnO is tabulated in Table 3. Results
show the adsorption on the C-ZnO ≤ U-ZnO ≤ 0.5%
Mn ≤ 1% Mn doped ZnO. However the adsorption is
decreased above 1% Mn. As observed, the adsorption
of cresols on 1% Mn-doped ZnO is the highest. It
may be due to the 1% Mn doped ZnO having the
highest BET surface area as previously discussed.

Table 3 Amount of adsorbed cresols on catalyst

during reaction time; initial condition: cresols
concentration = 35 ppm, photocatalyst = 1.5g/L and
natural pH

Photocatalyst o-cresol m-cresol p-cresol

(1.5g/L) (mg/L) (mg/L) (mg/L)
C-ZnO 1.8 1.2 1.8
U-ZnO 2.8 2.3 2.9
0.5% Mn- 3.6 2.8 3.7
1.0% Mn- 4.3 3.3 4.6
1.5% Mn- 3.4 2.6 3.4
2.0% Mn- 2.9 2.4 3.0

Photodegradation of cresols by using C-ZnO, U-ZnO

and 1%Mn-doped ZnO were plotted against
irradiation time (Fig. 6-8). As Table 4 shows, the
photoreaction rates and the photodegradation
efficiency were 1%Mn-doped > U-ZnO > C-ZnO.
This can be attributed to the characteristics of the
photocatalyst, with a decrease in particle size,
agglomeration size and increase in surface area of 1%
Mn. Another reason could be related to overlap of the
t2g of Mn with the VB of ZnO [17]. On the other hand
%photodegradation by the synthesised ZnO is a little
better than C-ZnO. Average particles size of
synthesised ZnO is 30–40 nm, while C-ZnO particles
size is 400-500 nm and surface area of undoped ZnO
(18.7 m2/g) is greater than the surface area of C-ZnO
(3.3 m2/g). Improvement of photodegradation
efficiency and rate of reaction may be due to this
surface area difference.

Fig. 5 Kubelka-Munk transformed reflectance spectra

of undoped and Mn-doped ZnO

3.4. Photodegradation studies

In order to determine the optimum amount of Mn
doped for a photocatalyst, photodegradation of
cresols was studied under visible-light irradiation by

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 International Journal of Basic & Applied Sciences IJBAS-IJENS Vol: 11 No: 04 67

Table 4 the rate of photodegradation,

photodegradation% and R2 of cresols
photodegradation by C-ZnO, U-ZnO and 1%Mn-
doped ZnO under visible irradiation

Cresol Photocatalyst -r (10-3) R2 Remove%

commercial 2 0.99 67
ortho undoped 2.3 0.99 79
1%Mn-doped 2.5 0.98 88

Fig. 6 Photodegradation of o-cresol by C-ZnO, U-ZnO commercial 1.7 0.95 58

and 1%Mn- doped ZnO under visible-light irradiation.
Initial conditions: o-cresol= 35ppm; photocatalyst = meta undoped 2.1 0.99 72
1.5g/L and pH =7.37 1%Mn-doped 2.2 0.98 78

commercial 2.1 0.99 72

para undoped 2.4 0.97 81
1%Mn-doped 2.5 0.98 89

4. Conclusion
Various levels of Mn-doped ZnO were synthesized
by precipitation method. Characterization was carried
out by XRD, TEM, SEM, EDX, BET, and the band
gap measured by UV-visible reflectance. In order to
evaluate the synthesised photocatalyst, cresol
photodegradation was studied under visible-light
irradiation with C-ZnO and synthesised
Fig. 7 Photodegradation of m-cresol by C-ZnO, U-ZnO photocatalyst. In the XRD pattern of samples, there is
and 1%Mn- doped ZnO under visible-light irradiation. no signature of impurity peaks, which might belong
Initial conditions: m-cresol= 35ppm; photocatalyst = to Mn-related secondary phases, while the EDX
1.5g/L and pH =7.63 confirmed the amount of Mn doped on ZnO which
was very close to the theoretical value. The SEM of
1% Mn-doped ZnO illustrated the morphology is well
ordered, has low aggregation, and has a
homogeneous distribution of particle size. Results of
TEM showed that more than 77% of the 1% Mn
doped ZnO particles were between 15-35 nm. The
BET show that the surface area of the 1% Mn doped
ZnO was the highest. The band gap of 1% Mn-doped
ZnO is 2.2 eV which is smaller than U-ZnO band
gap. The characterization of photocatalyst indicated
that 1% Mn-doped ZnO in comparison with U-ZnO,
0.5%, 1.5% and 2% Mn-doped ZnO has a higher
surface area, lower particle size and lower
agglomerate. Moreover, the calculated band gap of
Fig. 8 Photodegradation of p-cresol by C-ZnO, U- 1% Mn-doped ZnO is lower than the others except
ZnO and 1%Mn- doped ZnO under visible-light 0.5% Mn. Additionally, photodegradation of cresols
irradiation. Initial conditions: p-cresol= 35ppm; under visible light showed that 1% Mn doped ZnO
photocatalyst = 1.5g/L and pH =7.49 had maximum adsorption and rate of
photodegradation. In conclusion, 1% Mn-doped ZnO
is suitable as the best photocatalyst for removing
cresols.

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