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I J E N S
Synthesis and characterization of Manganese doped ZnO
nanoparticles

Y. Abdollahi
1
, A. H. Abdullah
1,2
, Z. Zainal
1,2
, N. A. Yusof
2


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
yadollahabdollahi@gmail.com



Abstract: Various levels of manganese (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 the XRD pattern of
samples, there is no signature of impurity peaks,
which could indicate Mn-related secondary
phases. The EDX show the amount of Mn doped
on ZnO is slightly lower than the theoretical value.
The SEM of 1% Mn-doped ZnO illustrated that
morphology is well ordered, has low aggregation,
and homogeneous distribution of particle size.
High aggregation is observed, however, in other
percentages of Mn-doped ZnO. Results of TEM
show that more than 50% of the particles for
undoped and Mn-doped ZnO use between 15 and
35 nm, with 1% Mn doped ZnO having the
highest percentage (77%). The BET shows that
the surface area of synthesized catalyst increases
when the weight ratio of manganese increases up
to 1% Mn, but decreases thereafter. The band gap
of 1% Mn-doped ZnO is 2.2 eV which is smaller
than the undoped ZnO band gap. The results of
characterization show 1% Mn-doped ZnO has the
highest surface area, the lowest particles size and
the lowest agglomerate. Moreover the calculated
band gap of 1% Mn-doped ZnO is lower than
others except 0.5%Mn. Additionally,
photodegradation of cresols under visible light
showed that 1% Mn-doped ZnO had maximum
adsorption and rate of photodegradation. In
conclusion 1% Mn doped ZnO is suitable as the
best photocatalyst to degrade cresols under visible
light irradiation.

Keywords: ZnO; Co-precipitation; Manganese-
doping; Optical properties; Nanoparticles

1. Introduction
ZnO is a II-VI semiconductor with wide direct-
gap (3.37 eV) and exciton binding energy (60 meV)
at room temperature [1]. It is an inexpensive and
environmentally safe host material. Due to its
properties, the interest in ZnO as a photocatalyst has
increased, however it has been mainly used under
ultra violet (UV) irradiation [2-6]. Photocatalytic
reaction is initiated when a photoexcited electron is
promoted from the filled valence band (VB) of a
semiconductor photocatalyst (SC) to the empty
conduction band (CB) as the absorbed photon energy,
h, equals or exceeds the band gap of the
photocatalyst. The hole pair (e
-
-h
+
) is generated at the
surface of the photoexcited photocatalyst as shown
below [7].
Photoexcitation : SC+h e

+h
+
(1)
Adsorbed oxygen: (O
2
)
ads
+e O
2

(2)
Ionization of water : H
2
O OH

+H
+
(3)
Protonation of superoxides : O
2

+H
+
HOO

(4)
HOO

+ e

HO
2

(5)
HOO

+H
+
H
2
O
2
(6)
H
2
O
2
+e
-
OH

+OH

(7)
H
2
O+h
+
H
+
+OH

(8)
Since 46% of solar energy consists of visible light, it
is more economical to use visible light than UV light
in large scale operations. To use visible light, ZnO
however has several drawbacks including the low
surface area or big particles size and an unsuitable
band gap energy (E
g
=3.7 eV). It was observed that
doping with 3d metals reduced the E
g
of
semiconductors by forming interband-gap localized
levels [8]. The charge-transfer transition between the
d-electron of dopant (t
2
g levels) and the CB or VB
was reported [9]. On the other hand, the metal d-
orbitals are mixed with the CB and VB of
semiconductors [10]. This overlap is because wide
VB or CB directly decreases E
g
. Recently, there has
been much attention focused on modifying ZnO by
doping with transition metals such as Ag [11], Ni
[12], Cu [13], Co [14], Cr [15], Ti [16]. These studies
demonstrated that the metals can change E
g
of ZnO
,
and that the dopants can control ZnO grain size. It
demonstrated the presence of the d-electron because
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I J E N S
the t
2g
of manganese (Mn) is very close to the VB
[10, 17]. More recently, synthesis of a Mn-doped
ZnO nano-crystal (not powder) was reported by wet-
chemical techniques [18]. Moreover, ZnO
nanocrystalline powders doped with 1, 3 and 5% Mn
were prepared using a sol-gel process [19].
Unfortunately, up to now the value of the E
g
and
optimum amount of Mn as dopant is not clear.
Additionally, reported results of Mn-doped ZnO
being applied as a photocatalyst are quite different. In
this work, Mn-doped ZnO nano-powder was prepared
with up to 2% Mn by the co-precipitate method. The
samples were characterized to obtain particle size,
surface area and the E
g
. The synthesised Mn-doped
ZnO was applied as photocatalyst to
photodegradation of ortho, meta and para-cresol (o,
m, p-cresol) under visible light irradiation.

2. Experimental

2.1. Materials
Zinc acetate (99%, Merck), Manganese acetate (98%,
Sigma, Alorich), NaOH (99% Merck), H
2
SO
4
(95%-
97%), Ethanol (absolute), o-cresol (99%, Merck), m-
cresol (99%, Merck), p-cresol (99.5%, Fluka),
commercial ZnO (C-ZnO, 99%, Merck), and other
required chemicals are of reagent grade, obtained from
Merck and were used without further purification.

2.2. Preparation
For synthesizing the catalyst, 75mM of ethanolic
Zinc solution was mixed with different
concentrations of an ethanolic manganese solution.
The mixed solutions were heated at 75 C for 45 min
to reduce the amount of the solution and increase the
concentration of the metal ions, after which it was
cooled at room temperature. NaOH solution was then
added to the mixed solution with constant stirring
(150 rpm) until pH 8.3 was reached. The new
colorless solution was kept in a water bath at 67

C
for two hours. It was observed that the solution
started precipitating after one hour in water bath.
After cooling the solution to room temperature for
four hours, the colloidal solution was centrifuged for
20 minutes at 4000 rpm. The resulting precipitate was
washed with ethanol, sonicated (30 min), and
centrifuged (4000 rpm). The above procedure was
repeated five times to remove unreacted ions. The
separated precipitate was dried overnight at 110

C.
The catalysis was ground and then calcined under
compressed air at 650C for 3.5h in the tubular
furnace. Undoped ZnO (U-ZnO) was synthesized
with a similar procedure except for the addition of
manganese acetate

2.3. Characterization
X-ray Diffraction (XRD) analysis of the
photocatalysts for structural characterization was
carried out using a Shimadzu XRD-6000
Diffractometer. Chemical composition and
morphology of the samples was carried out using a
scanning electron microscope (SEM), model Hitachi
S-3400N and Energy Dispersive X-ray (EDX)
thermo electron corporation. The nanostructure and
particle size of the nanocrystals in these samples was
determined from Transmission Electron Microscopy
(TEM) [20] images obtained using a Hitachi H-7100
electron microscope[21]. The Brunauer-Emmett-
Teller (BET) method, using nitrogen adsorption at
liquid nitrogen temperature 77 K, was employed to
measure total surface area of the photocatalysts. This
was done using a Thermo Finnigan Sorptomatic
Instrument model 1900. The optical absorption
spectra were obtained using a Perkin Elmer Lambda
35 UV-Vis-NIR diffuse reflectance spectrometer.
Various concentrations of cresols solutions were
prepared using deionized water. Photodegradation of
cresols was performed in a batch photoreactor,
designed in a column 14.5-cm height with an 11.5-
cm diameter (Fig. not showed). To volatilize
produced gas (may be CO
2
), increase solution
fluidization and access oxygen for eq. (2), air was
blown into the reaction solution by an air pump at a
flow rate of 10m
3
/h. the cooled air into the solution
eliminated the lamps heat effect and kept the
temperature at around 25

C. Magnetic stirring at a
speed of 200 rpm was applied to make the suspension
solution, during the reaction. The photoreactor is
located in an aluminum-sealed tube to enhance the
radiation by reflection. A Philips lamp (23watt) was
used as light source. Throughout the experiment, the
appropriate concentration of cresols solution was
contacted with the correct amount of photocatalyst in
the photoreactor. At specific time intervals, samples
were withdrawn from the bulk solution, and filtered
through 0.2m PTFE filters. The concentration of
cresols was measured using a UV-visible
spectrophotometer (shimadzu, uv-1650pc),

3. Results and discussion

3.1. Phase and Element analysis
The XRD patterns of U-ZnO and Mn-doped ZnO
with different Mn concentration are presented in Fig.
1. The XRD pattern shows only the peaks correspond
to wurtzite crystal structure of ZnO (reference code
01-089-1397). In the XRD pattern of samples, there
is no signature of impurity peaks which might belong
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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I J E N S
atoms are located at substitutional sites for lower
doping concentrations [22].
As observed in Fig. 1, the (101) peak (crystal plate)
of 1% Mn is broader than other peaks, because 1%
Mn photocatalyst has a different crystalline size.
Using the Debye-Scherrer equation [23] and the half-
width of the XRD lines, the average values of
crystalline size of the samples were calculated based
on the 101 crystal plate and are shown in Table 1.
The crystalline size of photocatalyst decreased with
increasing percentage of Mn over 1%. Beyond this,
the crystal size increased again. It may be the doping
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.


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


%Mn
(Theoretical)
%Mn
(EDX)
Crystallite size
(nm)
0 0 51
0.5 0.4 42
1 0.8 13
1.5 1.4 15
2 1.9 30


3.2. Morphology studies
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 SEM image of 1% Mn-doped ZnO illustrates the
morphology is well ordered; a lower aggregation and
better particle size distribution (Fig. 2) than other
percentages of Mn-doped ZnO. TEM were
conducted to investigate the morphology and
particles size of the samples. The TEM morphology
of 1% Mn-doped ZnO confirmed the low aggregation
and better distribution in SEM images (Fig. 3). In
addition, the TEM images showed spherical
nanocrystallites for 1%Mn-doped ZnO (Expanded
part in Fig. 3). The measured particles size of
samples showed (Table 2) more than 50% of
frequency was between 15 and 35 nm while the
highest percentage (77%) belonged to 1% Mn doped
ZnO. This indicates that the addition of Mn may be
control the growth of ZnO grains.



Fig. 2 SEM micrograph for 1% doped ZnO


Table 2 the particles size distribution of the U-ZnO
and Mn-doped ZnO

Particle
size
Frequency (Mn-doped ZnO)

(nm) ZnO 0.5% 1.0% 1.5% 2.0%
15-20 5 8 6 5 3
20-25 9 11 17 10 9
25-30 14 16 29 22 16
30-35 23 24 25 19 27
35-40 26 29 13 25 18
40-45 15 7 7 11 16
45--50 8 3 3 8 11


The surface area (BET) of U-ZnO and Mn doped
ZnO are presented in Fig. 4. As TEM images show,
the photocatalyst particle size decreases with
increasing % of Mn up to 1% Mn. Results of BET
showed the surface area increased when the weight
ratio of Mn increases up to 1% Mn, confirming the
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I J E N S
control of growth of ZnO grains by Mn. However,
the surface area was shown to decrease above 1%
Mn, which confirms the TEM and SEM observations.
Agglomeration is a limiting factor for surface area.
SEM and TEM images showed that with above 1%
Mn, the agglomeration increases, and this may be due
to a decrease in surface area.



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 [(Fh)
1/2
] vs. (eV) are shown by Taucs
plots [24] in Fig. 5. The intersection between the
linear fit and the photon energy axis gives the value
to E
g
. The E
g
of undoped ZnO of 2.75 eV was a little
less than C-ZnOs E
g
. It may be due to a defect in the
synthesised photocatalyst [25]. The E
g
of 0.5% Mn-
doped ZnO is 1.5 eV. It may be due to s-d and p-d
exchange interaction [26-27]. This electron-hole may
improve photodegradation but most of them are
trapped by subsurface recombination [28]. The E
g

of 1% Mn-doped ZnO was 2.2 eV. The d-electron of
Mn (t
2g
level) can easily overlap with the ZnOs
valence band (VB) because t
2g
of Mn is very close to
VB of ZnO [17]. This overlap causes a wide VB and
consequently decreases the E
g
of ZnO photocatalyst
so that the VB electrons can be excited by visible
light irradiation. The E
g
of 1.5% and 2% Mn-doped
ZnO was 2.6 eV, which is higher than the E
g
of 1%
Mn-doped ZnO. Similar behavior was observed for
vanadium doped ZnO, with E
g
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].








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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
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
(1.5g/L)
o-cresol
(mg/L)
m-cresol
(mg/L)
p-cresol
(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
t
2g
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 3040 nm, while C-ZnO particles
size is 400-500 nm and surface area of undoped ZnO
(18.7 m
2
/g) is greater than the surface area of C-ZnO
(3.3 m
2
/g). Improvement of photodegradation
efficiency and rate of reaction may be due to this
surface area difference.

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Fig. 6 Photodegradation of o-cresol by C-ZnO, U-ZnO
and 1%Mn- doped ZnO under visible-light irradiation.
Initial conditions: o-cresol= 35ppm; photocatalyst =
1.5g/L and pH =7.37



Fig. 7 Photodegradation of m-cresol by C-ZnO, U-ZnO
and 1%Mn- doped ZnO under visible-light irradiation.
Initial conditions: m-cresol= 35ppm; photocatalyst =
1.5g/L and pH =7.63


Fig. 8 Photodegradation of p-cresol by C-ZnO, U-
ZnO and 1%Mn- doped ZnO under visible-light
irradiation. Initial conditions: p-cresol= 35ppm;
photocatalyst = 1.5g/L and pH =7.49



Table 4 the rate of photodegradation,
photodegradation% and R
2
of cresols
photodegradation by C-ZnO, U-ZnO and 1%Mn-
doped ZnO under visible irradiation

Cresol Photocatalyst -r (10
-3
) R
2
Remove%
commercial 2 0.99 67
ortho undoped 2.3 0.99 79
1%Mn-doped 2.5 0.98 88

commercial 1.7 0.95 58
meta undoped 2.1 0.99 72
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
photocatalyst. In the XRD pattern of samples, there is
no signature of impurity peaks, which might belong
to Mn-related secondary phases, while the EDX
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
1% Mn-doped ZnO is lower than the others except
0.5% Mn. Additionally, photodegradation of cresols
under visible light showed that 1% Mn doped ZnO
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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