Applied Surface Science 439 (2018) 285–297

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Applied Surface Science

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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 have reported that the introduction Mn into ZnO could enhance
the photocatalytic activity under UV and visible irradiation and
ZnO is a wide-bandgap semiconductor (3.37 eV) that has a large this is attributed to the increase in the number of defect sites act-
exciton binding energy at room temperature (60 meV) [1]. ZnO has ing as electron traps that effectively suppresses the recombination
attracted considerable attention because it is low cost, non-toxic, of the photogenerated carriers [18,21,26–30]. Very few reports
environmentally friendly, chemically stable, and its optical and have observed the effect of Mn dopant on its morphological prop-
electrical properties can be tuned via doping [2,3]. ZnO has several erties and photocatalytic activity. Recently, Qun Ma et al. reported
potential applications, such as photocatalysis, light emitting that the incorporation of Mn dopants can greatly affect the trans-
diodes, solar cells, and sensors [1,4–6]. Photocatalytic reaction is formation of the hierarchical ZnO structure and its photocatalytic
a reduction–oxidation process that occurs on the surface of the performance [26]. Moreover, Mn-doped ZnO was generally synthe-
photocatalyst, which can be used for degrading harmful organic sized in the form of powder with macro-scale size [26,28,29,31] or
pollutants, such as textile dyes. Several methods have been pro- nanoparticles [18,21,30,32]. The use of ZnO powder as a photocat-
posed to enhance the photocatalytic activity of ZnO. One of these alyst is less effective, because it requires some additional process
methods involves doping ZnO with non-metal and metal elements such as centrifugation to separate the ZnO powder from the pol-
[7–17]. Doping of transition metal ions, such as Mn, Fe, Co, Ni, and luted water. Therefore, some researchers have developed ZnO
Cu, into ZnO has been reported to reduce the bandgap energy and nanorods grown on substrates to improve the photocatalyst effi-
to prevent electron-hole pair recombination through the genera- ciency [33–35].
tion of new energy states [18–25]. The transition metal Mn is an In this experiment, Mn-doped ZnO nanorods were synthesized
interesting material because the radius of Mn2+ is similar to that onto glass substrates by using low-cost and simple methods. ZnO
of Zn2+, and it can therefore easily replace Zn2+ ions without result- nanorods were strongly bound to the substrates since the growth
ing in any significant crystal changes [7]. Many research groups process was preceded by a seeding process via the ultrasonic spray
pyrolysis method. Then, ZnO nanorods were grown on ZnO thin
⇑ Corresponding author.
layers by hydrothermal methods. The ZnO photocatalytic activity
E-mail address: [email protected] (V. Fauzia).
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- electrolyte solution of 0.5 M sodium chloride (NaCl). The measure-
strate, it will be easier to observe the morphological changes of ment was performed under UV light (40 W) using a sinusoidal ac
ZnO due to the presence of Mn dopant. Therefore, the analysis of perturbation of 250 mV over the frequency range of 1 Hz–100 kHz.
the enhancement of photocatalytic activity of Mn-doped ZnO not
only based on its microstructural and optical properties as widely 2.4. Photocatalytic activity measurement
reported previously, but also its morphological properties. This
result directs to an interesting advantage to control the growth The photocatalytic activity of the Mn-doped ZnO nanorods was
rate and morphological properties of the ZnO nanostructures by evaluated by the photodegradation of MB dye in an acidic aqueous
varying the dopant concentration for various application. 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,
2. Experiments
and the optical absorption spectra were monitored using a UV–Vis
spectrophotometer at the characteristic absorption peak wave-
2.1. Materials
length of the MB dye at 596 nm. The reusability performance of
ZnO photocatalyst was also evaluated via the same above proce-
Analytical grade zinc acetate dehydrate (C4H6O4Zn
2H2O), zinc
dure in five successive cycles.
nitrate tetrahydrate (N2O6Zn
4H2O), mangan (II) nitrate tetrahy-
drate (Mn(NO3)2
4H2O), and hexamethylenetetramine (C6H12N4),
3. Results and discussion
purchased from Merck, were used without further purification.

3.1. Morphological and structural analysis

2.2. Synthesis
Fig. 1 shows FESEM images of the surface morphology of the
ZnO nanorods were synthesized directly on the glass substrates ZnO nanorods. All samples show that ZnO generally grows perpen-
(15 mm  25 mm) using two steps: seeding process via ultrasonic dicular to the surface of the glass substrate in the form of hexago-
spray pyrolysis and growth process via hydrothermal methods, nal nanorods. In each sample, the diameter of the nanorods varies
according to a previously reported procedure [11,36,37]. The seed- and tends to increase with an increase in the Mn concentration.
ing process began with dissolving 0.2 M zinc acetate dehydrate The diameters of the ZnO nanorods without Mn are in the range
into deionized water in room temperature. The seed solution was of 100–180 nm, whereas the diameters of the ZnO nanorod with
then placed into a container in a commercial ultrasonic nebulizer 1 mol% Mn are in the range of 110–250 nm. The samples of 3
(1.7 MHz) and then sprayed onto the heated glass substrates at and 7 mol% Mn-doped ZnO are not significantly different compared
450 °C for 15 min. The samples were then annealed for 1 h at to the samples of 1 mol% Mn-doped ZnO, but they are character-
450 °C. For the growth solution, equimolar 0.05 M zinc nitrate ized with dominant nanorods with diameter larger than 200 nm.
tetrahydrate and hexamethylenetetramine were dissolved in Apart from the increasing diameter, the addition of Mn dopant also
deionized water by stirring for 50 min at room temperature. The increases the number of nanorods per unit area. The number of
solutions were varied with four different Mn doping concentra- pure ZnO nanorods is around 13 lm2, while the number of ZnO
tions (0, 1, 3, and 7 mol%) by using 0.05 M mangan nitrate tetrahy- nanorods with 1, 3, and 7 mol% Mn is around 17, 20, and 21
drate solution. Substrates containing the seed layers were then lm2, respectively. The calculated surface area of ZnO nanorods
soaked in 10 ml growth solution and heated in an oven for 6 h at with 0, 1, 3, and 7 mol% Mn is around 10, 16, 20 and 26 lm2 per
95 °C. lm2 substrate, respectively.
Moreover, cross-sectional images of the nanorods are shown in
2.3. Characterization Fig. 2. It can be seen that the average height of the ZnO nanorods
increases with an increase in the Mn concentration. The mean
The surface and cross-section morphologies of the samples height of the ZnO nanorods with 0, 1, 3, and 7 mol% Mn is 1.74,
were determined by field emission scanning electron microscopy 1.83, 2.01, and 2.27 lm, respectively. It is also seen that the diam-
(FESEM; JEOL JIB-4610F Multi Beam System) together with energy eter of the nanorods increases with the addition of Mn, which is in
dispersive X-ray analysis (EDAX) (Oxford Instruments, UK). The accordance with the surface image shown in Fig. 1. The effect of
surface area of ZnO nanorods were calculated manually from Mn dopant on the morphology of ZnO has also been reported pre-
SEM images by multiplying the surface area of a nanorod by the viously [7,38]. Panigrahy et al. reported that doping of 5 mol% Mn
number of nanorods appears in a surface of substrate. The crystal increased the diameter of ZnO nanorods from 85 to 150 nm [39]
structure was characterized by X-ray diffraction (XRD; Rigaku and 2 at.% Mn increased the diameter range of ZnO nanorods from
Smartlab 3 kV). X-ray photoelectron spectroscopy (XPS) measure- 120–400 nm to 120–700 nm [40]. These SEM images clearly show
ments were carried out using the Ulvac-PHI Quantera II with Al that Mn elements may induce an enhancement of the ZnO crystal
Ka X-ray beam at 1486.6 eV. Raman spectra measurements were growth, as evidenced by the increase in the diameter, height, and
carried out using the WITec Raman microscope equipped with a the number of nanorods per unit area that resulted in the increase
532-nm laser source. The optical absorption and reflectance spec- in the ZnO surface area.
tra were recorded using the Thermo Fisher Scientific GENESYS As already known that the shape and orientation of ZnO nanos-
10S Ultraviolet–Visible and UV–Vis Diffuse Reflectance U-3900H tructures fabricated by solution method is strongly correlated with
Spectrophotometer, respectively. The room temperature photolu- the degree of supersaturation [41]. It is also believed that in low
minescence (PL) spectra were recorded with 325-nm He–Cd laser supersaturation levels favors crystal growth while in high super-
excitation using Edinburgh FLS 920. Electrochemical impedance saturation level favors nucleation [42]. For ZnO hexagonal wurtzite
spectroscopy (EIS) measurement was performed using an electro- structure in low supersaturation condition, the nanorods with
chemical impedance analyzer (EDAQ; ERZ100) embedded to a (001) plane is the preferential growth due to it has the minimum
potentiostat (EDAQ; 163). Platinum wire was used as the counter surface free energy [43]. Many experimental works found that
electrode, Ag/AgCl was used as a reference electrode and the ZnO the dopants play an important role for controlling degree of
nanorods on ITO coated glass substrate was used as the working supersaturation [41,44–46]. Based on Sethuraman’s experimental
electrode. All electrodes were soaked in a cell containing an 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 new nucleation is occurred on the ZnO seed layer, while the existed
condition may be favorable for both crystal growth and nucleation. ZnO with a preferentially on c- axis are kept growing at a faster
Hence, the addition of Mn up to 7 mol% in this experiment, the rate. Then, the condensed phase of ZnO nanorods with high aspect
degree of supersaturation may increases up to intermediate level. ratio perpendicular to the glass substrate is obtained and finally
The increase of Mn dopant stimulates the new nucleation and fas- the denser and larger diameter of ZnO NR arrays are achieved as
ter crystal growth simultaneously. During 6 h growth process, the 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. reflection from the (1 0 0), (0 0 2), (1 0 1), (1 0 2), (1 0 3), and (1 1 2)
The elements of Zn, O, Si and Mn are present in all samples, where crystal planes. There are no peaks associated with the Mn-related
Si comes from the glass substrate. The chemical compositions are secondary phases or impurities. The peak intensities of those
measured and it is indicated that the dominant elements are Zn nanorods are almost similar for all variants of Mn concentrations,
(86.3–86.5 wt%) and O (13.1–13.5 wt%). Mangan (Mn) is detected which indicates that an increase in the doping concentration does
in each sample with very small concentration (0.0–0.1% wt%) not alter the preferred crystal orientation of the nanorods arrays.
hence it cannot show the Mn concentration in ZnO when the Fig. 4 shows that the highest diffraction peak of all samples is
amount of Mn was changed during synthesize. But from the the (0 0 2) crystal plane, which indicates that the preferred orien-
elemental map on the right of each figure, it appears that Mn tation of the ZnO nanorods is perpendicular to the substrate. This
element is uniformly distributed throughout the surface of ZnO confirms the morphological images as shown in Fig. 1. Therefore,
nanorods. the preferred orientation is measured qualitatively by the texture
XRD patterns of the ZnO standard and Mn-doped ZnO nanorods coefficient (TC) parameter using the following equation [47]:
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 IðhklÞ =I0ðhklÞ
TC ðhklÞ ¼
hP I i
wurtzite hexagonal structure. All the diffraction peaks at angles 1 ðhklÞ
N N I0ðhklÞ
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.

 N.A. Putri et al. / Applied Surface Science 439 (2018) 285–297 289

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
Fig. 4. XRD spectra of Mn-doped ZnO nanorods. 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].
where I(h k l) and I0(h k l) represent the measured relative intensity
Fig. 5c shows that XPS spectra of O 1s could be decomposed into
and the standard intensity of plane (h k l)), and N represents the
three peaks, namely lattice oxygen of ZnO with a binding energy of
number of peaks. Table 1 shows the TC values of ZnO nanorods with
529.95 eV, and the CO/C@O bond at 531.13 eV, indicating the pres-
0, 1, 3, and 7 mol% Mn along six different diffraction planes. All sam-
ence of oxygen vacancies, and at energy 532.52 eV, representing
ples have the highest TC value for the (0 0 2) plane, suggesting that
the existence of hydroxyl (COOH) bonds [31,51,58,59]. These
all the samples have c-axis preferred orientation, as shown in Fig. 1.
hydroxyl bonds tend to stick to the empty space in the ZnO lattice
The preferred orientation (0 0 2) plane in the XRD patterns was
[60,61]. Some authors reported that these hydroxyl bonds are
then used as a data source for calculating the lattice parameters, d-
related to the ZnO surface ability to absorb OHA groups and oxy-
spacing, crystallite size, and FWHM, as shown in Table 2. In gen-
gen vacancies, which is useful for photocatalytic activity [51].
eral, the lattice parameter, volume, and d-spacing are similar,
Meanwhile, Fig. 5d shows that the O 1s spectra of Mn-doped ZnO
and this is probably because the Mn2+ radius is similar to the
contain a new peak of MnO with the binding energy of 529.74 eV
Zn2+ radius so it easily substitutes Zn2+ without any significant
and that there is a shift peak of ZnO from 529.95 eV to
crystal changes [7,39,48]. The crystalline size was calculated from
530.26 eV. This indicates that Mn element has been bound with
the full-width at half-maximum (FWHM) by using the Debye–
the ZnO structure.
Scherrer formula [49]:
Fig. 5e shows that the XPS spectra of the Mn binding energy in
0:9k the Mn-doped ZnO sample. There are two peaks of Mn 2p3/2 and
D¼ Mn 2p1/2 with the binding energies of 640.7 eV and 655.8 eV,
B cos h
respectively. This indicates that Mn2+ ions are present predomi-
where D is the crystallite size, k is the X-ray wavelength in Ang- nantly in ZnO [62]. In addition, the Mn 2p1/2 peak intensity is
strom, h is the Bragg angle, and B is the FWHM. The addition of higher than the Mn 2p3/2 peak intensity, which is different from
Mn increases the crystalline size significantly from 18.7 to 46.5 previous result that the Mn 2p3/2 peak has a higher intensity than
nm. This increase, as in the case of the other previous results, is 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 all samples have good wurtzite hexagonal structure of ZnO
of other Mn ions with different electron valence conditions. [58,64]. The higher intensity of E2(high) in Mn-doped ZnO
Fig. 6 shows the room temperature Raman spectra of the reveals that the Mn atom does not deform the crystal lattice
undoped and 7 mol% Mn-doped ZnO nanorods. The spectra of ZnO and even increases the crystallite sizes of ZnO, as
reveal five modes of ZnO at 97, 330, 378, 437, and shown in the XRD spectra. The A1(low) peak relates to crystal
575 cm1, corresponding to E2(low), E2(high)  E2(low), A1(TO), defects, especially the oxygen vacancies [57,58,65]. The inten-
E2(high), and A1(low), respectively [39,57,58]. The E2(low) sity of the A1(low) mode also increases with the addition of
mode involving a Zn sub-lattice motion [63]. E2(high)  Mn into ZnO, indicating that Mn doping increases the number
E2(low) is a second order mode of multi-phonon processes of oxygen vacancies, which will be confirmed in the following
[63]. The high intensity of the E2(high) mode indicates that photoluminescence measurement results.

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

 N.A. Putri et al. / Applied Surface Science 439 (2018) 285–297 291

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
Fig. 6. Raman spectra of Mn-doped ZnO nanorods.
the bandgap energy of Mn-doped ZnO nanorods was attributed
to the increase in the sp-d exchange interaction between the d
3.2. Optical properties 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
Fig. 7a shows the optical absorbance spectra of ZnO nanorods mentioned that the bandgap decrease can be caused by the pres-
with different Mn doping concentrations. All samples show a ence of crystal defects, such as oxygen vacancies [30,69].
strong absorption in the ultraviolet region and weak absorption As already indicated by XPS result that Mn2+ ions are present
for the visible light. ZnO nanorods exhibit a sharp absorption edge predominantly in ZnO, these dopant ions may occupy the new
at a wavelength around 380 nm, which correlates with the value of localized electronic states within the band gap near the conduction
the ZnO bandgap. In addition, an increase in the Mn concentration band of undoped ZnO promoting the narrower band gap [70].
causes a wider absorbance in the visible region, as has also been Moreover, these dopant ions could serve as both electron and hole
reported in previous works [31,66]. The increase in Mn doping shallow traps and loss its spin energy significantly due to the
from 0 to 7 mol% shifts the shoulder peak from a wavelength of change in electronic states from half-filled high spin to low spin
430–520 nm. The increased absorbance in the visible region may that are highly unstable. The trapped electron/hole will be trans-
be caused by the increase in the crystal defects in the forbidden ferred to adsorbed oxygen, water molecules or hydroxyl groups
bandgap [31]. The increase in the Mn concentrations lead to an to return its spin energy so that the recombination rate of
increase in the crystal defects, especially oxygen vacancies, as electron-hole pairs could be suppressed [70,71].
shown in the XPS spectra and the A1(low) mode in the Raman spec-
Mn2þ þ e ! Mnþ
tra results.
In order to obtain the energy gap, UV–vis diffuse-reflectance 
Mnþ + O2 ! Mn 2þ
+ O 2
spectra were recorded at room temperature, as shown in Fig. 8.
There is a significant increase in intensity at 370–390 nm, which þ
correlated with the absorption edge in the absorbance spectrum. Mn2þ þ h ! Mn3þ

Mn 3þ
+ OH  ! Mn 2þ
+ OH 

Fig. 7. UV–vis absorbance spectra of Mn-doped ZnO nanorods. 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 inates from the near band edge emission, which is due to the
ZnO nanorods are shown in Fig. 4.10. There are five prominent exciton recombination of the valence and the conduction bands
emission peaks at 397, 413, 450–475, 545–560, and 619 nm, of ZnO [73]. The emissions in the visible region are related to
while emissions in the range of 430–450 nm are believed to the native defects of ZnO, such as such as oxygen and zinc
come from the glass substrate [72]. The addition of Mn ele- vacancies, interstitial Zn, interstitial O, Zn anti-site (zinc at oxy-
ments generally increases the emission intensity of all peaks, gen site), and O anti-site (oxygen at zinc site) [66]. The violet
especially in the visible region. The UV emission (397 nm) orig- 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 3.3. Photoelectrochemical properties
green emissions (545–560 nm) is related to the oxygen vacancy,
while the orange emissions (619 nm) is from the oxygen inter- The electrochemical impedance measurement was performed
stitial [76,77]. ZnO nanorods with 7 mol% Mn have the highest for completing the information about the interface charge separa-
PL intensity in the visible region, indicating that they have tion and charge transfer efficiency of ZnO photocatalysts. Fig. 11
more crystal defects, either Zn vacancies, Zn interstitial, oxygen shows a Nyquist plot between a real impedance (Z0 ) and imaginary
vacancies, or oxygen interstitial. These results are in accordance impedance (Z00 ) for Mn-doped ZnO nanorods. The interface layer
with the increase in the intensity of the A1(low) mode in the resistance at the electrode’s surface is reflected by the radius of
Raman spectra and the absorbance in the visible region, as the arc [78]. The lower efficiency of charge transfer, the bigger
shown in Figs. 7 and 10. 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) 285–297 295

Fig. 15. FESEM images of recycled Mn-doped ZnO nanorods.

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