Applied Surface Science 439 (2018) 285–297

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Applied Surface Science

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

Full Length Article

Mn-doping-induced photocatalytic activity enhancement of ZnO

nanorods prepared on glass substrates
Nur Ajrina Putri a, Vivi Fauzia a,⇑, S. Iwan b, Liszulfah Roza c, Akrajas Ali Umar d, Setia Budi e
a
Departemen Fisika, Fakultas MIPA, Universitas Indonesia, Depok 16424, Indonesia
b
Program Studi Fisika, Universitas Negeri Jakarta, Jl. Pemuda No. 10 Rawamangun, Jakarta 13220, Indonesia
c
Jurusan Pendidikan Fisika, Fakultas Keguruan dan Ilmu Pendidikan, Universitas Muhammadiyah Prof. Dr. Hamka, Jakarta Timur, Indonesia
d
Institute of Microengineering and Nanoelectronics (IMEN), Universiti Kebangsaan Malaysia, 43600 UKM Bangi, Selangor, Malaysia
e
Department of Chemistry, Universitas Negeri Jakarta, Jl. Pemuda No. 10 Rawamangun, Jakarta 13220, Indonesia

a r t i c l e i n f o a b s t r a c t

Article history: Mn-doped ZnO nanorods were synthesized on glass substrates via a two-steps process of ultrasonic spray
Received 17 September 2017 pyrolysis and hydrothermal methods with four different concentrations Mn-doping (0, 1, 3, and 7 mol%).
Revised 13 December 2017 Introduction of Mn into ZnO is known could enhance the photocatalytic activity owing to the increase in
Accepted 29 December 2017
the defect sites that effectively suppress the recombination of free electrons and holes. In this study,
Available online 6 January 2018
results show that Mn-doping has effectively modified the nucleations and crystal growth of ZnO, as evi-
denced by the increasing in the diameter, height, and the number of nanorods per unit area, besides
Keywords:
slightly reduced the band gap and increased the oxygen vacancy concentrations in the ZnO lattice.
ZnO nanorods
Hydrothermal
This condition has successfully multiplied the photocatalytic performance of the ZnO nanorods in the
Mn doping degradation of methylene blue (MB) compared to the undoped-ZnO sample where in the typical process
Photocatalytic activity the MB can be degraded approximately 77% within only 35 min under a UV light irradiation.
Methylene blue Ó 2017 Elsevier B.V. All rights reserved.

1. Introduction
ZnO is a wide-bandgap semiconductor (3.37 eV) that has a large
exciton binding energy at room temperature (60 meV) [1]. ZnO has
attracted considerable attention because it is low cost, non-toxic,
environmentally friendly, chemically stable, and its optical and
electrical properties can be tuned via doping [2,3]. ZnO has several
potential applications, such as photocatalysis, light emitting
diodes, solar cells, and sensors [1,4–6]. Photocatalytic reaction is
a reduction–oxidation process that occurs on the surface of the
photocatalyst, which can be used for degrading harmful organic
pollutants, such as textile dyes. Several methods have been pro-
posed to enhance the photocatalytic activity of ZnO. One of these
methods involves doping ZnO with non-metal and metal elements
[7–17]. Doping of transition metal ions, such as Mn, Fe, Co, Ni, and
Cu, into ZnO has been reported to reduce the bandgap energy and
to prevent electron-hole pair recombination through the genera-
tion of new energy states [18–25]. The transition metal Mn is an
interesting material because the radius of Mn2+ is similar to that
of Zn2+, and it can therefore easily replace Zn2+ ions without result-
ing in any significant crystal changes [7]. Many research groups
⇑ Corresponding author.
E-mail address: vivi@sci.ui.ac.id (V. Fauzia).
have reported that the introduction Mn into ZnO could enhance
the photocatalytic activity under UV and visible irradiation and
this is attributed to the increase in the number of defect sites act-
ing as electron traps that effectively suppresses the recombination
of the photogenerated carriers [18,21,26–30]. Very few reports
have observed the effect of Mn dopant on its morphological prop-
erties and photocatalytic activity. Recently, Qun Ma et al. reported
that the incorporation of Mn dopants can greatly affect the trans-
formation of the hierarchical ZnO structure and its photocatalytic
performance [26]. Moreover, Mn-doped ZnO was generally synthe-
sized in the form of powder with macro-scale size [26,28,29,31] or
nanoparticles [18,21,30,32]. The use of ZnO powder as a photocat-
alyst is less effective, because it requires some additional process
such as centrifugation to separate the ZnO powder from the pol-
luted water. Therefore, some researchers have developed ZnO
nanorods grown on substrates to improve the photocatalyst effi-
ciency [33–35].
In this experiment, Mn-doped ZnO nanorods were synthesized
onto glass substrates by using low-cost and simple methods. ZnO
nanorods were strongly bound to the substrates since the growth
process was preceded by a seeding process via the ultrasonic spray
pyrolysis method. Then, ZnO nanorods were grown on ZnO thin
layers by hydrothermal methods. The ZnO photocatalytic activity
was evaluated through photodegradation process of methylene

https://doi.org/10.1016/j.apsusc.2017.12.246
0169-4332/Ó 2017 Elsevier B.V. All rights reserved.
286 N.A. Putri et al. / Applied Surface Science 439 (2018) 285–297
blue (MB) under UV radiation. For nanorods on the surface of sub-
strate, it will be easier to observe the morphological changes of
ZnO due to the presence of Mn dopant. Therefore, the analysis of
the enhancement of photocatalytic activity of Mn-doped ZnO not
only based on its microstructural and optical properties as widely
reported previously, but also its morphological properties. This
result directs to an interesting advantage to control the growth
rate and morphological properties of the ZnO nanostructures by
varying the dopant concentration for various application.
2. Experiments
2.1. Materials
Analytical grade zinc acetate dehydrate (C4H6O4Zn
2H2O), zinc
nitrate tetrahydrate (N2O6Zn
4H2O), mangan (II) nitrate tetrahy-
drate (Mn(NO3)2
4H2O), and hexamethylenetetramine (C6H12N4),
purchased from Merck, were used without further purification.
2.2. Synthesis
ZnO nanorods were synthesized directly on the glass substrates
(15 mm  25 mm) using two steps: seeding process via ultrasonic
spray pyrolysis and growth process via hydrothermal methods,
according to a previously reported procedure [11,36,37]. The seed-
ing process began with dissolving 0.2 M zinc acetate dehydrate
into deionized water in room temperature. The seed solution was
then placed into a container in a commercial ultrasonic nebulizer
(1.7 MHz) and then sprayed onto the heated glass substrates at
450 °C for 15 min. The samples were then annealed for 1 h at
450 °C. For the growth solution, equimolar 0.05 M zinc nitrate
tetrahydrate and hexamethylenetetramine were dissolved in
deionized water by stirring for 50 min at room temperature. The
solutions were varied with four different Mn doping concentra-
tions (0, 1, 3, and 7 mol%) by using 0.05 M mangan nitrate tetrahy-
drate solution. Substrates containing the seed layers were then
soaked in 10 ml growth solution and heated in an oven for 6 h at
95 °C.
2.3. Characterization
The surface and cross-section morphologies of the samples
were determined by field emission scanning electron microscopy
(FESEM; JEOL JIB-4610F Multi Beam System) together with energy
dispersive X-ray analysis (EDAX) (Oxford Instruments, UK). The
surface area of ZnO nanorods were calculated manually from
SEM images by multiplying the surface area of a nanorod by the
number of nanorods appears in a surface of substrate. The crystal
structure was characterized by X-ray diffraction (XRD; Rigaku
Smartlab 3 kV). X-ray photoelectron spectroscopy (XPS) measure-
ments were carried out using the Ulvac-PHI Quantera II with Al
Ka X-ray beam at 1486.6 eV. Raman spectra measurements were
carried out using the WITec Raman microscope equipped with a
532-nm laser source. The optical absorption and reflectance spec-
tra were recorded using the Thermo Fisher Scientific GENESYS
10S Ultraviolet–Visible and UV–Vis Diffuse Reflectance U-3900H
Spectrophotometer, respectively. The room temperature photolu-
minescence (PL) spectra were recorded with 325-nm He–Cd laser
excitation using Edinburgh FLS 920. Electrochemical impedance
spectroscopy (EIS) measurement was performed using an electro-
chemical impedance analyzer (EDAQ; ERZ100) embedded to a
potentiostat (EDAQ; 163). Platinum wire was used as the counter
electrode, Ag/AgCl was used as a reference electrode and the ZnO
nanorods on ITO coated glass substrate was used as the working
electrode. All electrodes were soaked in a cell containing an
electrolyte solution of 0.5 M sodium chloride (NaCl). The measure-
ment was performed under UV light (40 W) using a sinusoidal ac
perturbation of 250 mV over the frequency range of 1 Hz–100 kHz.
2.4. Photocatalytic activity measurement
The photocatalytic activity of the Mn-doped ZnO nanorods was
evaluated by the photodegradation of MB dye in an acidic aqueous
condition (pH 5). The ZnO samples were placed in 20 ml of 10 mM
MB solution and irradiated with UV light (40 W). At certain time
intervals, the samples were simply removed from the solution,
and the optical absorption spectra were monitored using a UV–Vis
spectrophotometer at the characteristic absorption peak wave-
length of the MB dye at 596 nm. The reusability performance of
ZnO photocatalyst was also evaluated via the same above proce-
dure in five successive cycles.
3. Results and discussion
3.1. Morphological and structural analysis
Fig. 1 shows FESEM images of the surface morphology of the
ZnO nanorods. All samples show that ZnO generally grows perpen-
dicular to the surface of the glass substrate in the form of hexago-
nal nanorods. In each sample, the diameter of the nanorods varies
and tends to increase with an increase in the Mn concentration.
The diameters of the ZnO nanorods without Mn are in the range
of 100–180 nm, whereas the diameters of the ZnO nanorod with
1 mol% Mn are in the range of 110–250 nm. The samples of 3
and 7 mol% Mn-doped ZnO are not significantly different compared
to the samples of 1 mol% Mn-doped ZnO, but they are character-
ized with dominant nanorods with diameter larger than 200 nm.
Apart from the increasing diameter, the addition of Mn dopant also
increases the number of nanorods per unit area. The number of
pure ZnO nanorods is around 13 lm2, while the number of ZnO
nanorods with 1, 3, and 7 mol% Mn is around 17, 20, and 21
lm2, respectively. The calculated surface area of ZnO nanorods
with 0, 1, 3, and 7 mol% Mn is around 10, 16, 20 and 26 lm2 per
lm2 substrate, respectively.
Moreover, cross-sectional images of the nanorods are shown in
Fig. 2. It can be seen that the average height of the ZnO nanorods
increases with an increase in the Mn concentration. The mean
height of the ZnO nanorods with 0, 1, 3, and 7 mol% Mn is 1.74,
1.83, 2.01, and 2.27 lm, respectively. It is also seen that the diam-
eter of the nanorods increases with the addition of Mn, which is in
accordance with the surface image shown in Fig. 1. The effect of
Mn dopant on the morphology of ZnO has also been reported pre-
viously [7,38]. Panigrahy et al. reported that doping of 5 mol% Mn
increased the diameter of ZnO nanorods from 85 to 150 nm [39]
and 2 at.% Mn increased the diameter range of ZnO nanorods from
120–400 nm to 120–700 nm [40]. These SEM images clearly show
that Mn elements may induce an enhancement of the ZnO crystal
growth, as evidenced by the increase in the diameter, height, and
the number of nanorods per unit area that resulted in the increase
in the ZnO surface area.
As already known that the shape and orientation of ZnO nanos-
tructures fabricated by solution method is strongly correlated with
the degree of supersaturation [41]. It is also believed that in low
supersaturation levels favors crystal growth while in high super-
saturation level favors nucleation [42]. For ZnO hexagonal wurtzite
structure in low supersaturation condition, the nanorods with
(001) plane is the preferential growth due to it has the minimum
surface free energy [43]. Many experimental works found that
the dopants play an important role for controlling degree of
supersaturation [41,44–46]. Based on Sethuraman’s experimental
work, the addition of Mn up to 7% could increases the degree of
 N.A. Putri et al. / Applied Surface Science 439 (2018) 285–297 287

Fig. 1. Surface morphology of Mn-doped ZnO nanorods.

Fig. 2. Cross-sectional images of Mn-doped ZnO nanorods.

supersaturation but still in the low to intermediate level [44]. This
condition may be favorable for both crystal growth and nucleation.
Hence, the addition of Mn up to 7 mol% in this experiment, the
degree of supersaturation may increases up to intermediate level.
The increase of Mn dopant stimulates the new nucleation and fas-
ter crystal growth simultaneously. During 6 h growth process, the
new nucleation is occurred on the ZnO seed layer, while the existed
ZnO with a preferentially on c- axis are kept growing at a faster
rate. Then, the condensed phase of ZnO nanorods with high aspect
ratio perpendicular to the glass substrate is obtained and finally
the denser and larger diameter of ZnO NR arrays are achieved as
the increase of Mn dopant.
288 N.A. Putri et al. / Applied Surface Science 439 (2018) 285–297
Fig. 3a–c shows the EDAX spectra of Mn-doped ZnO nanorods.
The elements of Zn, O, Si and Mn are present in all samples, where
Si comes from the glass substrate. The chemical compositions are
measured and it is indicated that the dominant elements are Zn
(86.3–86.5 wt%) and O (13.1–13.5 wt%). Mangan (Mn) is detected
in each sample with very small concentration (0.0–0.1% wt%)
hence it cannot show the Mn concentration in ZnO when the
amount of Mn was changed during synthesize. But from the
elemental map on the right of each figure, it appears that Mn
element is uniformly distributed throughout the surface of ZnO
nanorods.
XRD patterns of the ZnO standard and Mn-doped ZnO nanorods
are shown in Fig. 4. Based on the reference ICDD 98-005-7478, the
XRD patterns show that all samples are composed of ZnO with
wurtzite hexagonal structure. All the diffraction peaks at angles
2h = 31.7, 34.4, 36.2, 47.5, 62.8, and 67.8 correspond to the
Fig. 3. EDAX spectra and elemental maps of Mn-doped ZnO nanorods.
reflection from the (1 0 0), (0 0 2), (1 0 1), (1 0 2), (1 0 3), and (1 1 2)
crystal planes. There are no peaks associated with the Mn-related
secondary phases or impurities. The peak intensities of those
nanorods are almost similar for all variants of Mn concentrations,
which indicates that an increase in the doping concentration does
not alter the preferred crystal orientation of the nanorods arrays.
Fig. 4 shows that the highest diffraction peak of all samples is
the (0 0 2) crystal plane, which indicates that the preferred orien-
tation of the ZnO nanorods is perpendicular to the substrate. This
confirms the morphological images as shown in Fig. 1. Therefore,
the preferred orientation is measured qualitatively by the texture
coefficient (TC) parameter using the following equation [47]:
IðhklÞ =I0ðhklÞ
TC ðhklÞ ¼
hP I i
1 ðhklÞ
N N I0ðhklÞ
 N.A. Putri et al. / Applied Surface Science 439 (2018) 285–297 289

Fig. 4. XRD spectra of Mn-doped ZnO nanorods.
where I(h k l) and I0(h k l) represent the measured relative intensity
and the standard intensity of plane (h k l)), and N represents the
number of peaks. Table 1 shows the TC values of ZnO nanorods with
0, 1, 3, and 7 mol% Mn along six different diffraction planes. All sam-
ples have the highest TC value for the (0 0 2) plane, suggesting that
all the samples have c-axis preferred orientation, as shown in Fig. 1.
The preferred orientation (0 0 2) plane in the XRD patterns was
then used as a data source for calculating the lattice parameters, d-
spacing, crystallite size, and FWHM, as shown in Table 2. In gen-
eral, the lattice parameter, volume, and d-spacing are similar,
and this is probably because the Mn2+ radius is similar to the
Zn2+ radius so it easily substitutes Zn2+ without any significant
crystal changes [7,39,48]. The crystalline size was calculated from
the full-width at half-maximum (FWHM) by using the Debye–
Scherrer formula [49]:
0:9k
D¼
B cos h
where D is the crystallite size, k is the X-ray wavelength in Ang-
strom, h is the Bragg angle, and B is the FWHM. The addition of
Mn increases the crystalline size significantly from 18.7 to 46.5
nm. This increase, as in the case of the other previous results, is
generally due to the ionic radius of Zn2+ (0.74 Å) being smaller than
that of Mn2+ (0.80 Å) [26,48,50–52], while some reports state that
Mn doping decreases the crystallite size of ZnO [28,53]. Further-
more, the position of (0 0 2) peaks shift toward the lower and higher
angle that strongly indicated that the Mn2+ ions successfully substi-
tute the Zn2+ ions in the ZnO host structure [53–57].
XPS measurements were performed to identify the chemical
states of the constituent elements and oxygen vacancies in the
ZnO nanorods. Fig. 5 shows the XPS spectra of the undoped and
Mn-doped ZnO (7 mol% Mn) nanorods with an emphasis on the
peaks associated with Zn 2p, Mn 2p, and O 1s. As shown in
Fig. 5a and b, the spectra for Zn 2p3/2 and Zn 2p1/2 of the ZnO
and Mn-doped ZnO samples exhibit symmetric single peaks. The
binding energy of Zn 2p3/2 and Zn 2p1/2 of the pure ZnO is located
at 1021.1 eV and 1044.2 eV, respectively, which correspond to
ZnAO bonds in the ZnO lattice [18]. These two strong peaks indi-
cate that Zn2+ is dominant in the ZnO structure [39,54]. The inten-
sity of both peaks increased with the addition of Mn; this indicates
that more Zn2+ ions are detected in the ZnO surface. This may be
related to an increase in the surface area of ZnO nanorods, as
shown in Figs. 1 and 2, which results in more ZnAO bonds being
recorded by the XPS instrument. The binding energy of Zn2+ in
Mn-doped ZnO also slightly shifts to 1021.5 eV and 1044.7 eV,
which indicates that there is a partial substitution of Zn2+ by
Mn2+ and that the Zn–Mn bonding structure is formed [51].
Fig. 5c shows that XPS spectra of O 1s could be decomposed into
three peaks, namely lattice oxygen of ZnO with a binding energy of
529.95 eV, and the CO/C@O bond at 531.13 eV, indicating the pres-
ence of oxygen vacancies, and at energy 532.52 eV, representing
the existence of hydroxyl (COOH) bonds [31,51,58,59]. These
hydroxyl bonds tend to stick to the empty space in the ZnO lattice
[60,61]. Some authors reported that these hydroxyl bonds are
related to the ZnO surface ability to absorb OHA groups and oxy-
gen vacancies, which is useful for photocatalytic activity [51].
Meanwhile, Fig. 5d shows that the O 1s spectra of Mn-doped ZnO
contain a new peak of MnO with the binding energy of 529.74 eV
and that there is a shift peak of ZnO from 529.95 eV to
530.26 eV. This indicates that Mn element has been bound with
the ZnO structure.
Fig. 5e shows that the XPS spectra of the Mn binding energy in
the Mn-doped ZnO sample. There are two peaks of Mn 2p3/2 and
Mn 2p1/2 with the binding energies of 640.7 eV and 655.8 eV,
respectively. This indicates that Mn2+ ions are present predomi-
nantly in ZnO [62]. In addition, the Mn 2p1/2 peak intensity is
higher than the Mn 2p3/2 peak intensity, which is different from
previous result that the Mn 2p3/2 peak has a higher intensity than
that of the others [58]. The reason for this is not clearly understood

Table 1
Texture coefficient.

Doping concentrations Crystal Plane

100 002 101 102 103 112
Mn 0% 0.22 2.47 0.37 1.38 1.07 0.48
Mn 1% 0.28 2.53 0.54 1.05 0.83 0.78
Mn 3% 0.43 2.60 0.60 0.96 0.79 0.63
Mn 7% 0.24 1.99 0.46 1.56 1.08 0.68

Table 2
XRD data of Mn-doped ZnO nanorods in (0 0 2) crystal plane.

Doping Concentrations 2h Volume (Å3) a = b (Å) c (Å) dhkl Crystallite size (nm) FWHM
Mn 0% 34.407 47.680 3.252 5.205 2.604 18.7 0.371
Mn 1% 34.410 47.660 3.251 5.205 2.604 43.1 0.296
Mn 3% 34.412 47.631 3.251 5.203 2.604 41.0 0.296
Mn 7% 34.386 47.679 3.253 5.203 2.606 46.5 0.293
290 N.A. Putri et al. / Applied Surface Science 439 (2018) 285–297

yet, and hence, further analysis is required to identify the existence
of other Mn ions with different electron valence conditions.
Fig. 6 shows the room temperature Raman spectra of the
undoped and 7 mol% Mn-doped ZnO nanorods. The spectra
reveal five modes of ZnO at 97, 330, 378, 437, and
575 cm1, corresponding to E2(low), E2(high)  E2(low), A1(TO),
E2(high), and A1(low), respectively [39,57,58]. The E2(low)
mode involving a Zn sub-lattice motion [63]. E2(high) 
E2(low) is a second order mode of multi-phonon processes
[63]. The high intensity of the E2(high) mode indicates that
all samples have good wurtzite hexagonal structure of ZnO
[58,64]. The higher intensity of E2(high) in Mn-doped ZnO
reveals that the Mn atom does not deform the crystal lattice
of ZnO and even increases the crystallite sizes of ZnO, as
shown in the XRD spectra. The A1(low) peak relates to crystal
defects, especially the oxygen vacancies [57,58,65]. The inten-
sity of the A1(low) mode also increases with the addition of
Mn into ZnO, indicating that Mn doping increases the number
of oxygen vacancies, which will be confirmed in the following
photoluminescence measurement results.

Fig. 5. XPS spectra of Mn-doped ZnO nanorods.

 N.A. Putri et al. / Applied Surface Science 439 (2018) 285–297
Fig. 6. Raman spectra of Mn-doped ZnO nanorods.
3.2. Optical properties
Fig. 7a shows the optical absorbance spectra of ZnO nanorods
with different Mn doping concentrations. All samples show a
strong absorption in the ultraviolet region and weak absorption
for the visible light. ZnO nanorods exhibit a sharp absorption edge
at a wavelength around 380 nm, which correlates with the value of
the ZnO bandgap. In addition, an increase in the Mn concentration
causes a wider absorbance in the visible region, as has also been
reported in previous works [31,66]. The increase in Mn doping
from 0 to 7 mol% shifts the shoulder peak from a wavelength of
430–520 nm. The increased absorbance in the visible region may
be caused by the increase in the crystal defects in the forbidden
bandgap [31]. The increase in the Mn concentrations lead to an
increase in the crystal defects, especially oxygen vacancies, as
shown in the XPS spectra and the A1(low) mode in the Raman spec-
tra results.
In order to obtain the energy gap, UV–vis diffuse-reflectance
spectra were recorded at room temperature, as shown in Fig. 8.
There is a significant increase in intensity at 370–390 nm, which
correlated with the absorption edge in the absorbance spectrum.
Fig. 7. UV–vis absorbance spectra of Mn-doped ZnO nanorods.
291
The bandgap energy is calculated from the reflectance data using
the Kubelka–Munk equation [38]:
ð1  RÞ2
FðRÞ ¼
2R
where R is the reflectance and FðRÞ is equal to the absorption coef-
ficient a in the Tauc equation:
ðFðRÞhv Þ ¼ Aðhv  Eg Þ
2
where h is the Planck constant, v is frequency, and Eg is the bandgap
energy.
Bandgap energy is determined using the Tauc plot by extrapo-
lating the linear part of the plot when FðRÞ ¼ 0 or at the intersec-
tion of the linear slope with the energy axis, as shown in Fig. 9.
By using this method, it is found that the optical bandgap of
undoped ZnO is 3.286 eV and those of the 1, 3, and 7 mol% Mn-
doped ZnO are 3.286 eV, 3.283 eV, and 3.251 eV, respectively. It
is clearly seen that the optical bandgap of ZnO decreases with
the increase in the Mn doping concentration. The narrowing of
the bandgap energy of Mn-doped ZnO nanorods was attributed
to the increase in the sp-d exchange interaction between the d
electrons of Mn with the s and p electrons of the host ZnO that
forms the new energy level [38,53,67,68]. Other authors have also
mentioned that the bandgap decrease can be caused by the pres-
ence of crystal defects, such as oxygen vacancies [30,69].
As already indicated by XPS result that Mn2+ ions are present
predominantly in ZnO, these dopant ions may occupy the new
localized electronic states within the band gap near the conduction
band of undoped ZnO promoting the narrower band gap [70].
Moreover, these dopant ions could serve as both electron and hole
shallow traps and loss its spin energy significantly due to the
change in electronic states from half-filled high spin to low spin
that are highly unstable. The trapped electron/hole will be trans-
ferred to adsorbed oxygen, water molecules or hydroxyl groups
to return its spin energy so that the recombination rate of
electron-hole pairs could be suppressed [70,71].
Mn2þ þ e ! Mnþ

Mnþ + O2 ! Mn 2þ
+ O 2
þ
Mn2þ þ h ! Mn3þ
Mn 3þ
+ OH  ! Mn 2þ
+ OH 
Fig. 8. Reflectance spectra of Mn-doped ZnO nanorods.
292 N.A. Putri et al. / Applied Surface Science 439 (2018) 285–297

Fig. 9. Bandgap energy of Mn-doped ZnO nanorods.

The room temperature PL spectra of undoped and Mn-doped
ZnO nanorods are shown in Fig. 4.10. There are five prominent
emission peaks at 397, 413, 450–475, 545–560, and 619 nm,
while emissions in the range of 430–450 nm are believed to
come from the glass substrate [72]. The addition of Mn ele-
ments generally increases the emission intensity of all peaks,
especially in the visible region. The UV emission (397 nm) orig-
inates from the near band edge emission, which is due to the
exciton recombination of the valence and the conduction bands
of ZnO [73]. The emissions in the visible region are related to
the native defects of ZnO, such as such as oxygen and zinc
vacancies, interstitial Zn, interstitial O, Zn anti-site (zinc at oxy-
gen site), and O anti-site (oxygen at zinc site) [66]. The violet
emission (413 nm) is related to the Zn vacancy [74]. The blue

Fig. 10. Photoluminescence spectra of Mn-doped ZnO nanorods. Fig. 11. Nyquist plots of Mn-doped ZnO nanorods.
 N.A. Putri et al. / Applied Surface Science 439 (2018) 285–297 293

emission (450–475 nm) is caused by the Zn interstitial [75]. The
green emissions (545–560 nm) is related to the oxygen vacancy,
while the orange emissions (619 nm) is from the oxygen inter-
stitial [76,77]. ZnO nanorods with 7 mol% Mn have the highest
PL intensity in the visible region, indicating that they have
more crystal defects, either Zn vacancies, Zn interstitial, oxygen
vacancies, or oxygen interstitial. These results are in accordance
with the increase in the intensity of the A1(low) mode in the
Raman spectra and the absorbance in the visible region, as
shown in Figs. 7 and 10.
3.3. Photoelectrochemical properties
The electrochemical impedance measurement was performed
for completing the information about the interface charge separa-
tion and charge transfer efficiency of ZnO photocatalysts. Fig. 11
shows a Nyquist plot between a real impedance (Z0 ) and imaginary
impedance (Z00 ) for Mn-doped ZnO nanorods. The interface layer
resistance at the electrode’s surface is reflected by the radius of
the arc [78]. The lower efficiency of charge transfer, the bigger
arc radius [78]. Fig. 11 shows that the ZnO nanorods with higher

Fig. 12. Absorbance spectra of methylene blue.

294 N.A. Putri et al. / Applied Surface Science 439 (2018) 285–297

content of Mn reveals the arc with smaller diameter. This result

shows that the interface layer resistances decrease as the more
addition Mn on ZnO nanorods, indicating the higher efficiency of
interfacial charge carrier’s separation and charge transfer on the
surface of ZnO. This agrees with optical characterization results
that higher concentration Mn in ZnO nanorods could produce
higher free charge carriers that accelerates charge transfer and
decreases the resistance. It is beneficial for enhancement of photo-
catalytic activity of ZnO nanorods.

3.4. Photocatalytic activity

Photocatalytic activity of a catalyst is determined by its ability

to create photogenerated electron-hole pairs [79]. Fig. 12 shows
the absorption spectra of the MB solution with and without ZnO
photocatalysts under UV irradiation for different durations of time
until 38 min. It can be seen that MB is degraded for all kind of ZnO
samples. The mechanism underlying the photocatalytic degrada- Fig. 13. Photocatalytic degradation kinetics under UV light by Mn-doped ZnO
nanorods.
tion of MB solution can be understood as follows. When ZnO sam-
ples are irradiated by UV, the electrons excite from the valence
band to the conduction band forming free electrons and holes. valence band to conduction band. Third, the Mn elements may also
These electron–hole pairs will react with the oxygen and water induce the increase of number of oxygen vacancies, as indicated by
to produce (O 
2 ) and ( OH) free radicals. These highly reactive spe- the decrease in the lattice constants, the increase in the A1(low)
cies are strong oxidizing agent that can react with MB dye and peak in the Raman spectra, and the visible light emission. These
break its chemical bond structure resulting colorless form crystal defects are also well known to inhibit the recombination
[63,80]. The MB degradation process by ZnO photocatalyst can be process of electrons and free holes because Mn2+ ions can act as
seen in the following reaction [7,33,63]: electron traps or intermediate steps [7,18,48,52,81]. Donkova
ZnO þ hv ! e ðCBÞ þ h ðVBÞ
þ et al. reported that these doping ions would shift the Fermi level
up to the bottom edge of the conduction band, which would
e  + O2 !  O2 
increase the adsorption ability to the oxygen [29]. This synergetic
effect actually depends on the Mn content in the ZnO because
some reports indicate the opposite effect if the Mn content is not
h þ
+ OH  !  OH
optimum [26,28,32,52].
The intensity of PL in all wavelength range may proportional to
hþ + H 2 O !  hþ + 
OH the photocatalytic activity. The higher PL intensity, the higher pho-
tocatalytic activity. It can be explained that in photoluminescence

OH + MB ! degradation product process, photogenerated electrons could recombine with holes and
defects so those PL signals occur. Meanwhile, during the photocat-

O2  + MB ! degradation product alytic reaction, holes and defects could become the trap centers of
photogenerated electrons hence the recombination could be effec-
The photocatalytic efficiency for the MB degradation was deter- tively inhibited [82]. This is not contrary to the usual belief that a
mined by using the following equation [63]: higher PL intensity indicates a higher recombination rate, since the
A0  At luminescence intensity is also influenced by non-radiative recom-
g¼  100% bination which do not affect the total recombination of charged
A0
carriers [24]. The above results demonstrate that the introduction
where A0 is the original MB absorbance intensity value at 596 nm, Mn into the ZnO up to 7 mol% linearly escalate the surface area of
and At is the MB absorbance intensity value after the photodegrada-
tion at certain times. The results in Fig. 13 indicate that the degra-
dation rates for the ZnO nanorods photocatalyst with 0, 1, 3, and 7
mol% Mn are 15.25%, 67.13%, 70.43%, and 76.75%, respectively. It is
also seen that MB without the photocatalyst is slightly degraded
with UV irradiation as a reference. It is clearly shown that the pho-
todegradation rate of MB with the Mn-doped ZnO is faster than that
with pure ZnO.
This improvement can be attributed to three factors. First, Mn
elements may induce an enhancement of ZnO surface area, as evi-
denced by the increase in the diameter, height, and the number of
nanorods per unit area, as shown in the SEM images. Meanwhile,
the ZnO wurtzite structure is well-preserved, even the crystallites
size are increased, as indicated by the XRD spectra and the
enhanced intensity of XPS Zn2p and O1s and Raman spectra at
437 cm1. This morphological effect considerably increases the
surface area of the ZnO and hence the generation of free electrons
and holes for photodegradation of MB dye molecules are enhanced
[7,32,81]. Second, Mn elements may lead the narrowing of band
gap that is favorable for photoexcitation of more electrons from Fig. 14. Photocatalytic activity of recycled Mn-doped ZnO nanorods.
 N.A. Putri et al. / Applied Surface Science 439 (2018) 285–297
Fig. 15. FESEM images of recycled Mn-doped ZnO nanorods.
ZnO to increase the adsorption of pollutant supporting charges
transfer with lower recombination rate and thereby enhances the
photocatalytic activity.
In order to evaluate the reusability of ZnO nanorods photocata-
lysts, the degradation efficiency of methylene blue under UV radi-
ation in five successive cycles is shown in Fig. 14. After recycling
four times over 150 min reaction, all samples show a slightly
decrement of degradation efficiency from 68–77% to 70–63%. In
the fifth cycle, there is a very different result; the degradation effi-
ciency of undoped ZnO was significantly dropped to 44%, while all
Mn-doped ZnO samples only slightly decreased down to 61–66%.
This reduction can be attributed to the saturation level of pollutant
adsorption on photocatalyst during the successive cycles. This
clearly indicates that the synthesized Mn-doped ZnO nanorods
on glass substrate are reusable and more stable hence it is a
promising reusable material for photocatalytic degradation.
After recycling five times, the morphology of undoped ZnO and
7 mol% Mn-doped ZnO were observed as shown in Fig. 15. Gener-
ally, the FESEM images show there is no significant effect of recy-
cling process on the morphology of ZnO nanorods, but the
nanorods appear to be more swelling that may be due to the
adsorption of water-based methylene blue into the ZnO structures.
4. Conclusions
Mn-doped ZnO nanorods were successfully synthesized on
glass substrates by ultrasonic spray pyrolysis and hydrothermal
methods. The incorporation of Mn into ZnO leads to the improve-
ment of the photodegradation rate of methylene blue under UV
light. The key role of the Mn element may be it could stimulates
the new nucleation and faster crystal growth simultaneously hence
the denser and larger diameter of ZnO NR arrays were achieved.
Finally, the surface area of ZnO NR arrays is improved significantly
and generates more free electrons and holes for degradation of MB
dye molecules. Narrowing band gap and the enhancement of oxy-
gen vacancy concentrations also play a significant role in inhibiting
the recombination of free electron and holes by trapping the
excited electrons. Furthermore, the reusability evaluation results
shows that the Mn-doped ZnO nanorods photocatalyst could be
easily reused and more stable for practical environmental safety
application of photocatalyst.
Acknowledgments
This research was financially supported by Hibah Publikasi
International Terindeks untuk Tugas Akhir Mahasiswa (PITTA)
2017 Universitas Indonesia No. 694/UN2.R31/HKP.05.00/2017
and FRGS Grant No. FRGS/1/2016/STG02/UKM/02/2 from the Min-
istry of Higher Education, Malaysia.
295
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