Journal of Rare Earths 38 (2020) 29e38

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Journal of Rare Earths

journal homepage: http://www.journals.elsevier.com/journal-of-rare-earths

Enhanced visible-light photocatalytic activity of samarium-doped zinc

oxide nanostructures
Sukriti a, Prakash Chand a, *, Vishal Singh b
a
Department of Physics, National Institute of Technology, Kurukshetra 136119, India
b
Centre for Materials Science & Engineering, National Institute of Technology, Hamirpur 177005, India

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

Article history: In the present work, we have synthesized samarium doped zinc oxide nanostructures (Zn1exSmxO;
Received 16 October 2018 x ¼ 0.00, 0.02, 0.04 and 0.06) via chemical precipitation method and studied their structural, morpho-
Received in revised form logical, optical and photocatalytic properties. X-ray diffraction (XRD) patterns, PL and Raman spectra
4 February 2019
results indicate that the undoped and Sm-doped ZnO nanostructures are crystallized in a hexagonal
Accepted 15 February 2019
Available online 10 July 2019
wurtzite structure. FESEM images show that the morphology of the sample changes from cubical to
hexagonal nanostructures with increase in Sm3þ doping concentration. The EDX spectra confirm the
incorporation of Sm3þ ion in ZnO. The influence of Sm3þ doping on the structure, morphology, ab-
Keywords:
Photocatalysis
sorption, emission and photocatalytic activity of ZnO nanostructures were investigated systematically.
Sm-doped ZnO The addition of Sm3þ ion leads to a red shift in the optical energy band gap from 3.19 to 2.67 eV and
FESEM hence, increases the visible light absorption ability. The presence of E2 (H) and E1 (LO) modes in micro-
Micro-Raman Raman spectra confirms the crystallinity and defects in the samples. The detailed photocatalytic ex-
UVeVisible spectroscopy periments reveal that Sm-doped ZnO nanostructures show the maximum photodegradation efficiency
Rare earths for Methylene blue (MB) dye for x ¼ 0.04, i.e., 94.94%, under visible light irradiation. The photocatalytic
efficiency improves by 6.98 times when ZnO is doped with rare earth metal ion (Sm3þ) and is a potential
candidate for practical applications. The investigation demonstrates that as-synthesized nano-sized
photocatalysts act as an efficient photocatalyst for the degradation of MB dye.
© 2019 Chinese Society of Rare Earths. Published by Elsevier B.V. All rights reserved.

1. Introduction due to its high photocatalytic activity in the degradation of organic

In recent years, the high secretion of organic pollutants from
different industries such as paint, textile, pesticides, printing,
pharmaceuticals and petroleum has created severe environmental
hazards. These are found to be injurious due to their toxic nature,
non-biodegradability and carcinogenic results on humans and
terrestrial lives.1,2 Accordingly, their removal prior to discharge
from the industries is a primary concern among scientific com-
munity in this field. To overcome this problem, the photocatalytic
reaction has been investigated and twisted to a valuable approach
so as to degrade the organic pollutants in an eco-friendly and
inexpensive way.3,4 A numerous metal oxide semi-conducting
materials such as CuO, ZnO, WO3, TiO2, Bi2O3 and Nb2O5 are the
budding aspirants for the decomposition of the organic
pollutants.5e7 Among them, ZnO is a more appropriate selection
* Corresponding author. Fax: þ91 1744 238050.
E-mail addresses: prakash@nitkkr.ac.in, KK_PC2006@yahoo.com (P. Chand).
pollutants such as pesticides, detergents, dyes and volatile organic
compounds and also due to their long term stability against
corrosion, inert to chemicals, inexpensive and non-toxic in na-
ture.8,9 Zang et al. stated that hydrophobic colloidal ZnO nano-
particles can be used for biological fluorescent imaging along with
the treatment and diagnosis into drug delivery systems.10 Zang
et al. also reported that the fabrication of a high-quality microhole
array and roughened ZnO on the surface of InGaN LEDs improved
the maximum output power to 58.4% by using femtosecond laser.11
Moreover, ZnO is a stable photocatalyst and is susceptible to photo-
corrosion that sustains its reusability. However, the main hindrance
that hampers the efficiency of ZnO is the fast recombination of the
electron-hole pair which is a limiting factor in the photocatalytic
degradation process.12 It is well recognized that the intrinsic charge
carrier recombination and surface charge transfer are related with
the structure and optical properties of photocatalysts.13 Hence,
keeping these issues in mind, metal oxides should be tailored in
such a manner that the separation efficacy of photogenerated
charge carriers could be enhanced to improve the photocatalytic

https://doi.org/10.1016/j.jre.2019.02.009
1002-0721/© 2019 Chinese Society of Rare Earths. Published by Elsevier B.V. All rights reserved.
30 Sukriti et al. / Journal of Rare Earths 38 (2020) 29e38

performance. Doping rare earths (RE) ions is an effective way to


improve the photocatalytic properties of metal oxide semi- ZnðOHÞ2
4 / ZnO þ 2OH (3)
conductor materials. Further, rare earth ions are well identified for
their skill to trap the electrons, which can efficiently setback
recombination rate of photogenerated electron-hole pairs and
2.2.2. Sm-doped ZnO nanostructures
eliminate the organic pollutants in wastewater.14e16 In addition to
Sm-doped nanostructures (Zn1exSmxO; x ¼ 0.00, 0.02, 0.04 and
this, RE metals have superior thermal constancy, owing to their 4f
0.06), i.e., Z2, Z4 and Z6, were prepared by the same method as
electron and multi-electron array. As a result, the amalgamation of
mentioned above. The zinc acetate dihydrate and samarium nitrate
the RE ions into ZnO crystalline matrices could afford a prospective
hexahydrate were dissolved in ethanol separately in the particular
way to restrain the combination of photo hole and photo electron
stoichiometric ratio. Both the solutions were then mixed to obtain
pairs and to broaden the light adsorption of the semiconductor, and
homogeneity. Then, 1 mol/L NaOH was added to obtain the Sm3þ-
consequently to enhance the visible light photocatalytic activity. To
ZnO precipitates. The precipitates were subsequently washed and
the best of our knowledge, only a very few studies have been re-
filtered and washed several times with ethanol and DI water. Then,
ported on the comparison of photocatalytic degradation of organic
the precipitates were dried at 80  C in an oven followed by grinding
pollutants by the ZnO nanostructures doped with RE metal. The
to get a fine powder. The synthesis procedure is also shown in Fig. 1.
endeavor of the present study is to analyze the physical parameters
and photocatalytic activity of Sm-doped ZnO at different doping
concentrations of Sm3þ in the degradation MB dye. 2.3. Material characterization
In the current work, we present a chemical precipitation tech-
nique to synthesize the Sm-doped ZnO nanostructures with The XRD analysis of the synthesized samples was carried out
different doping concentrations. The impacts of Sm3þ doping with a Rigaku Miniflex II Diffractometer for the identification of
concentration on the structural, morphological, optical and pho- phase and structure with a Cu Ka radiation source (l ¼ 0.1542 nm)
tocatalytic properties for degradation of the MB dye were investi- at an operating voltage of 30 kV and current 15 mA. The XRD
gated in details. spectrum was observed within the scanning range of 20 to 80
with a rate of 2 ( )/min. The morphology of the nanoparticles was

2. Experimental

2.1. Chemicals

For the synthesis of samarium doped nanostructures, the

chemicals used, i.e., zinc acetate dihydrate (Zn(CH3COO)2$2H2O),
samarium nitrate hexahydrate (Sm(NO3)3$6H2O), sodium hydrox-
ide pellets (NaOH), ethanol, de-ionized (DI) water and MB dye were
purchased from Sigma Aldrich. All the chemicals used were of
analytical grade and used without further purification.

2.2. Synthesis method

2.2.1. Undoped ZnO nanostructures

The nanostructures were synthesized by chemical precipitation
method. Firstly, the zinc acetate dihydrate and sodium hydroxide
were taken as precursors for the preparation of ZnO nano-
structures. 13.23 g of zinc acetate dihydrate was dissolved in 60 mL
of ethanol at room temperature. 1 mol/L solution of NaOH was
made separately in a different beaker in 40 mL DI. The latter was
added to the former solution dropwise until a milky white solution
was obtained that shows the formation of ZnO precipitates. The
solution was stirred for 2 h at 60  C on a magnetic stirrer to assure
homogeneity. The obtained solution was set aside overnight so that
the precipitates settle down. Then, the precipitates were filtered
and washed several times with ethanol and DI water to remove any
impurities present beside ZnO. Further, the precipitates were dried
at 80  C in an oven and annealed in a muffle furnace at 300  C. The
obtained nanostructures were ground using a pestle mortar to get a
fine powder.
The reaction involving the growth mechanism of undoped ZnO
nanostructures is shown as follows17:

ZnðACÞ2 þ 2NaOH/ZnðOHÞ2 ðYÞ þ 2CH3 COONa (1)

ZnðOHÞ2 þ 2H2 O/ZnðOHÞ2

4 (2)
Fig. 1. Schematic flowchart for the synthesis of Zn1exSmxO (x ¼ 0.00, 0.02, 0.04 and
0.06) nanostructures.
 Sukriti et al. / Journal of Rare Earths 38 (2020) 29e38 31

probed using a field emission scanning electron microscope

(FESEM; FEG-Quanta-450, FEI). The elemental analysis of the as-
prepared samples was performed using an energy dispersive X-
ray (EDX) spectroscopy. The UV-Visible spectra were investigated
using a Camspec spectrometer (model-M550) within the range of
190e1100 nm at room temperature. The samples were analyzed by
dispersing in ethanol using an ultrasonicator at 20  C. The resulting
solution was then placed in quartz cuvette having 1 cm path length
and then the spectrum was obtained. Raman spectra (InVia;
Renishaw) of undoped and Sm-doped ZnO were recorded with Arþ
ion laser beam of 50 mW power having excitation wavelength of
514 nm. Photoluminescence measurements were carried out using
a Shimadzu Spectro fluorophotometer (Japan) (model- RF-5301PC)
at room temperature using a Xe lamp as an irradiation source at an
excitation wavelength of lex ¼ 345 nm.

2.4. Photocatalytic measurements

The photocatalytic activities of undoped and Sm-doped nano-

structures (Zn1exSmxO; x ¼ 0.00, 0.02, 0.04 and 0.06), i.e., Z0, Z2, Z4
and Z6, were recorded using a photocatalytic reactor. The synthe-
sized samples were used as photocatalysts to check the degradation
Fig. 2. Room temperature XRD patterns of undoped ZnO and Sm-doped ZnO nano-
of MB dye under visible light irradiation. In photocatalytic reactor, structures (Zn1exSmxO) with different concentrations (x ¼ 0.00, 0.02, 0.04 and 0.06).
the photo degradation of dye was conducted by making use of an
efficient photocatalyst. The samples to be analyzed were immersed
in a photocatalytic reactor which is equipped with the quartz
47.37, 56.41, 62.85 , 66.38 , 67.91, 69.11, 72.38 and 77.03 in
double jacket tube, a water circulating unit, a magnetic stirrer and
planes (100), (002), (101), (102), (110), (103), (200), (112), (201),
an opening to air supply. In the reactor, a 300 W visible lamp was
(004) and (202) can be ascribed to the hexagonal wurtzite structure
placed in the centre of the quartz double jacket tube with the
of the samples. No extra peak is found for all the samples indicating
continuous water circulation in the outer tube. The continuous cold
the absence of any amorphous content in the synthesized samples.
water circulation was provided from circulating unit in order to
Fig. 3 shows the magnified XRD patterns of the three most intense
prevent the heating up of the lamp. The temperature PID controller
peaks ((100), (002) and (101)) of the Sm-doped ZnO samples. There
helped in keeping a continuous check on the temperature. There is
is a slight shift in the peaks towards the lower angles with the in-
a timer so that we can analyze the effect of radiation on the samples
crease in dopant concentration. The average crystallite size (D) is
in a given time interval. A fixed amount of photocatalyst was taken
found using Debye-Scherrer's formula which is as follows19: D ¼ kl/
and dispersed in dye solution for a fixed interval of time in order to
observe the photo degradation efficiency. The photocatalytic ac-
bhklcosq; where k is shape factor ¼ 0.89, l wavelength of the inci-
dent X-rays radiation ¼ 0.1542 nm, bhkl Full width at half maximum
tivities of obtained undoped and doped ZnO nanostructures were
(FWHM), and q Bragg's angle in radians. The strain (ε) can be
evaluated by checking the degradation of aqueous solution of MB
dye under visible radiation. The initial concentration and volume of
dye were 20 ppm and 100 mL and, the concentration of photo-
catalyst was 2 g/L, respectively. The solution was magnetically
stirred for 15 min in the dark and then, the photocatalyst was added
to it. Subsequently, the solution was stirred for 30 min further to
establish absorption/desorption equilibrium between MB dye and
photocatalyst. Then, 3 mL aliquot of the degraded solution was
collected in certain intervals and the absorption spectrum was
studied using a Camspec M550 UV-visible spectrometer. The pho-
todegradation efficiency (h) of MB was studied by the following
equation18: h ¼ (1eC/C0)  100%; where, C0 is the initial absorption
peak intensity of MB dye and C is the absorption peak intensity after
the desired irradiation time interval, respectively.

3. Results and discussion

3.1. Powder XRD analysis

Fig. 2 depicts the X-ray diffraction patterns of undoped and Sm-

doped nanostructures (Zn1exSmxO; x ¼ 0.00, 0.02, 0.04 and 0.06),
i.e., Z0, Z2, Z4 and Z6. These patterns were examined to study the
crystallographic properties of the synthesized samples such as
average crystallite size, lattice parameters, strain, crystal orienta-
tion, phase, nature of the sample. The diffraction peaks obtained for
synthesized samples are in good agreement with JCPDS Card No 80- Fig. 3. XRD patterns of the three most intense peaks ((100), (002) and (101)) of the
0075. The peaks of Zn0.98Sm0.02O located at 31.78 , 34.31, 36.25 , Sm-doped ZnO samples showing shifting of the centre of diffraction.
32 Sukriti et al. / Journal of Rare Earths 38 (2020) 29e38
calculated using: ε ¼ bhkl/4tanq. The average crystallite size of
synthesized nanostructures is estimated to be 33.7, 31.3, 27.1 and
29.5 nm for Z0, Z2, Z4 and Z6, respectively. There is a decrease in
the average crystallite size with increase in the concentration of
doping due to increase in FWHM up to Z4. There is a shift in the
diffraction pattern with change in doping concentration indicating
the incorporation of Sm3þ ions in the ZnO lattice.20 This is due to
the mismatch of the ionic radii of zinc ions (~74 pm) and samarium
ions (~96 pm).21 Moreover, the incorporation of rare earth ion in
ZnO lattice also indicates the decrease in the value of average
crystallite size as they inhibit the further growth of the crystal and
reduces the rate of nucleation.22 This increases the strain in the
structure due to the larger size of the Sm3þ ion. The lattice pa-
rameters and volume of unit cellpffiffiffi were calculated using the
following
pffiffiffi formulae
23,24
: a ¼ b ¼ l/ 3 sinq100, c ¼ l/sinq002 and
V ¼ ( 3/2)a2c. The variation of lattice parameters and unit cell
volume of synthesized nanostructures is reported in. The change in
lattice parameters indicates the presence of strain in the crystal
lattice which can be seen in.
3.2. FESEM and EDX analysis
Fig. 4 shows the FESEM images of undoped and Sm-doped
nanostructures (Zn1exSmxO; x ¼ 0.00, 0.02, 0.04 and 0.06). There
is an alteration in the morphology of the nanostructures with in-
crease in doping concentration. As the concentration of dopant
increases, the morphology of the sample changes from cubical to
rod-like that further leads to the formation of hexagonal nano-
structures. With change in crystallite size at higher concentrations,
the change in morphology takes place along with the agglomera-
tion. The agglomeration increases with increase in the
Fig. 4. FESEM images of Zn1exSmxO nanostructures. (a) Z0; (b) Z2; (c) Z4; (d) Z6.
concentration of doping element because the uniformity inside the
crystal is disturbed.25 This may be due to the formation of
SmeOeSm on the surface of the synthesized doped samples, which
hinders the growth of crystalline samples.26 The elemental
composition of synthesized samples was done through energy
dispersive X-ray (EDX) spectroscopy. Fig. 5(a,b) show the results of
EDX spectra for undoped and Zn0.94Sm0.06O nanostructures.
Fig. 5(a) displays the peaks corresponding to the elements Zn and O
confirming the phase purity while Fig. 5(b) concludes that there is
an addition of Sm element along with Zn and O on the surface. This
indicates that samarium ion was successfully incorporated in ZnO
crystal structure.
3.3. UVevisible study
UVeVisible spectroscopy is a technique to study the energy
band gap of the materials. There is strong absorption in UV region
because ZnO acts as a UV blocking material. Fig. 6 depicts the Tauc
plot of the undoped and rare earth ion, i.e., Sm-doped ZnO nano-
structures (Zn1exSmxO; x ¼ 0.00, 0.02, 0.04 and 0.06). The inset
curve gives the absorption spectrum for the synthesized samples
for the wavelength range of 300e600 nm. The energy band gap was
evaluated from Tauc plot by extrapolation of the linear part of
(ahn)2 vs curve, according to the following equation27:
(ahn)2 ¼ A(hneEg); where, a is an optical absorption coefficient, hv
energy of the incident photon in eV, A a constant that depends upon
the effective mass of charge carriers present in conduction and
valence band, Eg energy band gap in eV. The estimated band gap
values are shown in Table 1. The optical band gap reduces from 3.19
to 2.67 eV for samples Z0 to Z4 and after that it again increases for
sample Z6. A slight red shift has been observed with increase in the
 Sukriti et al. / Journal of Rare Earths 38 (2020) 29e38
Fig. 5. EDX analysis of undoped ZnO (Z0) (a) and Zn0.94Sm0.06O (Z6) (b)
nanostructures.
doping content of Sm3þ ion in ZnO. This decrease in energy band
gap is attributed to the transfer of charge between dopant 4f level
electrons and the ZnO conduction or valence band, leading to the
narrower band gap.28 This shows that the Sm-doped ZnO absorbs
UV as well as visible light.29 Hence, it could be a promising material
for the photodegradation process as it enhances the absorption of
light in visible region.
Fig. 6. Tauc plot [(ahv)2 vs hv] for undoped ZnO and Sm-doped ZnO nanostructures.
Inset curve shows the UVeVisible spectra for undoped ZnO and Sm-ZnO
nanostructures.
33
3.4. Micro-Raman spectroscopy
Micro-Raman spectroscopic technique provides useful infor-
mation about the concentration, stress, crystallinity and molecular
structure of the synthesized samples. Fig. 7 depicts micro-spectra of
undoped and samarium doped ZnO nanoparticles at different
doping concentrations (Z0, Z2, Z4 and Z6) at room temperature
with visible excitation. It is widely known that ZnO has wurtzite
structure belonging to the space group C 46v.30 The group theory
predicts that the optical modes of vibration at G point of Brillouin
zone are represented as31: G ¼ 1A1þ2B1þ1E1þ2E2; where, A1, E1
and E2 are Raman active modes while B1 is Raman and infrared
inactive mode only. A1 and E1 modes are further split into trans-
verse (TO) and longitudinal optical (LO) phonon components with
infrared being active in these polar modes while two E2 modes
being non-polar.32 The strong peak observed around 437 cme1 is
assigned to the E2 (H) which is a characteristic Raman active mode
for the wurtzite hexagonal phase of ZnO. This peak representing
second-order Raman scattering that originates from non-polar
optical phonons of E2 (H) mode is associated with vibration of
oxygen atoms.33 All the samples show that this peak is due to the
Zn and O sub-lattices, respectively.34 There is a suppressed peak at
575 cme1 indicating the E1 (LO) mode which is associated with the
impurities and formation of defects.35 The high intensity of E2 (H)
and low intensity of E1 (LO) mode validate the crystallinity of the
sample possessing the wurtzite phase. In addition, a peak occurs
around 336 cme1 corresponding to the multi-phonon scattering
process and (E2H e E2L) mode of vibration.36 There is a variation in
intensity with change in doping concentration of Sm ion that ul-
timately results in enhancement in defect formation in the pre-
pared samples.
3.5. Photoluminescence study
The PL spectrum of synthesized samples investigates the im-
purities present, ability of charge trapping and photo-degradation
efficiency of synthesized photocatalysts. The two distinct emis-
sion bands in UV as well as visible region in the spectrum are ex-
pected. Fig. 8 shows the variation in the PL intensity of the undoped
and Sm-doped ZnO nanostructures with wavelength of incident
photon. The peaks around 390 nm are observed due to the
recombination of free excitons corresponding to the near band
edge emission in ZnO.37 The emission in blue region occurs in the
region around 450e490 nm with the highest intensity at 470 nm.38
The peaks in blue region originate due to the transition of electrons
from donor level of V (Oþ) to the valence band.39 With the intro-
duction of dopant ion, i.e., Sm3þ in ZnO, perturbation takes place
inside the energy levels of host crystal and some new energy levels
are also created.40 This leads to the generation of charge imbalance
and trapping centers within the system that trigger cross-
relaxation and non-radiative transitions resulting in quenching of
the signal.41 This resulted in creation of more number of vacancies
and defects in the synthesized samples. The intensity of PL emis-
sion signal is observed to be highest in case of Z4 nanostructures.
The variation in emission intensity can also be ascribed to the
variation in crystallite size with increase in dopant concentration.42
3.6. Photocatalytic mechanism of MB dye
The photocatalytic activity has been observed by determining the
change in absorption spectra of the samples as a function of wave-
length at regular time intervals. Fig. 9(aed) show the change in
absorbance of MB dye with wavelength in 60 min in presence of
undoped and Sm-doped ZnO nanostructures as photocatalysts. The
maximum absorption peak of MB dye is observed at 664 nm which
34 Sukriti et al. / Journal of Rare Earths 38 (2020) 29e38

Table 1
Variation of various lattice parameters such as lattice constants, volume of unit cell, strain, average crystallite size and energy gap of Zn1exSmxO (x ¼ 0.00, 0.02, 0.04 and 0.06)
nanostructures.

Samples Average crystallite size D (nm) Lattice constants (nm) Volume of the unit cell V (nm)3 Strain Energy band gap Eg (eV)

a¼b c

Z0 ~33.7 0.3255 0.5220 4.8895 0.0032 3.19

Z2 ~31.3 0.3264 0.5234 4.8289 0.0034 2.84
Z4 ~27.1 0.33275 0.5248 4.8745 0.0039 2.67
Z6 ~29.5 0.269 0.5237 4.7465 0.0037 2.74

Fig. 7. Raman spectra for Zn1exSmxO (x ¼ 0.00, 0.02, 0.04 and 0.06) nanostructures.
Inset curve shows the magnified Raman spectra for undoped ZnO and Zn0.98Sm0.02O
nanostructures (Z0 and Z2).

diminishes gradually under the effect of visible light. As no new peak

has been observed during the analysis of the samples, hence, the
Fig. 8. PL spectra of Zn1exSmxO (x ¼ 0.00, 0.02, 0.04 and 0.06) nanostructures.
degradation has been successful. The photodegradation efficiency
was calculated using C/C0 where C denotes the absorption of the dye
after the desired irradiation time interval and C0 denotes the initial $OOH þ Hþ þ e
CB /H2 O2 (8)
absorption of the dye. The photodegradation efficiency (PDE) for
undoped and Sm-doped ZnO photocatalyst after 60 min is shown in

Fig. 10. The maximum value of PDE is found to be 94.94% in case of H2 O2 þ e $
CB / OH þ OH ðFormation of hydroxyl radicalÞ (9)
Zn0.96Sm0.04O under visible light irradiation. This can be explained on
the mechanism of advanced oxidation process (AOP). It involves the hþ þ $
VB þ H2 O/H þ OH ðHole trapÞ (10)
use of hydroxyl radical for the removal of organic contaminants from
the water as it is one of the strongest oxidant that can treat the
wastewater.43 When the aqueous solution of photocatalyst is irradi- hþ  $
VB þ OH / OH ðFormation of hydroxyl radicalÞ (11)
ated with visible light, electrons and holes are generated in con-
duction and valence band of ZnO, respectively. The mechanism of MB dye þ OH$ /CO2 ð[Þ þ H2 O ðMineralization of MB dyeÞ
photocatalysis follows the steps as mentioned below 22:
(12)
ZnO þ hvðvisibleÞ/e
CB þ hþ
VB ðGeneration of charge carriersÞ Fig. 11 shows the mechanism taking place during the photo-
(4) catalysis of MB dye while using Sm-doped ZnO as photocatalyst.
The electrons in conduction band react with the rare earth ion
(Sm3þ) because it is a strong Lewis acid that has partially filled 4f
Sm3þ þ e
CB /Sm
2þ
ðElectron trapÞ (5) orbital which can trap the electron and inhibit the recombination of
charge carriers further.44 This leads to the formation of unstable
Sm2þ þ O2 /Sm3þ þ O$
2 (6) Sm2þ ions that has the tendency to transfer the electron to oxygen
molecules to form active superoxide radical which on protonation
gives $OOH radical. This $OOH radical gets converted into active
O$ þ $
2 þ H / OOH (7)
$OH radical. The standard potential of $OH radical varies from 2.8 to
1.55 V for pH 0 to 14 with respect to the normal hydrogen electrode
 Sukriti et al. / Journal of Rare Earths 38 (2020) 29e38 35

Fig. 9. Absorption spectra for degradation of MB dye using (a) undoped ZnO (Z0) (b) Zn0.98Sm0.02O (Z2), (c) Zn0.96Sm0.04O (Z4) and (d) Zn0.94Sm0.06O (Z6) nanostructures as
photocatalysts for 60 min.

(NHE).45 The standard potential for H2O2 varies from 1.78 to 0.85
while for superoxide radical (Oe 2 ) is 2.4.
46
The higher oxidation
potential for $OH states that it is highly reactive radical amongst
others leading to the decomposition of hazardous pollutants into
inorganic compounds. Simultaneously, holes in the valence band
react with the H2O molecules adsorbed on the surface and form
$OH radical. Oxygen and water molecules act as scavengers in order
to trap electrons and holes to form hydroxyl radicals that further
react with dye molecule and favor the mineralization into
degradable products.47 The doping of samarium in ZnO improves

Fig. 10. Variation of Photodegradation Efficiency (PDE) with time in minutes for the
undoped and Sm-doped ZnO nanostructures (Zn1exSmxO) with different concentra- Fig. 11. Mechanism of photocatalytic degradation of Methylene Blue (MB) dye using
tions (x ¼ 0.00, 0.02, 0.04 and 0.06). Sm-doped ZnO as photocatalyst.
36 Sukriti et al. / Journal of Rare Earths 38 (2020) 29e38

Table 2
Photocatalytic degradation of previously reported studies using samarium doped ZnO as photocatalysts.

Photocatalyst Concentration of Amount of pH Light Dye Degradation Ref.

dye (mg/L) Photocatalyst (g/L) efficiency (%)
20
Sm/ZnO 50 1 6 Sunlight 2-CP 99%
100 1 70% (1.5 h)
150 1 64%
22
Sm/ZnO (1%, 3%, 5%) 5 1 e UV MG 63.53% in 80 min (for 3% Sm-ZnO)
47
Sm/ZnO 20 e 5.2 Visible Phenol 95.9% in 300 min
53
ZnOeAg-Sm 10 1 e UV MB 94%
54
Sm/TiO2 (Pure, 0.5%, 1%, 2%) 100 1 8 UV ARS 93% in 2 h for 1% Sm/TiO2
55
Sm/TiO2 (Pure and 0.75%) e 1 e UV RhB 95.76% in 120 min
Sm-ZnO (x ¼ 0.00,0.02, 0.04,0.06) 20 2 12 Visible MB 94.94% in 60 min (for x ¼ 0.04) Present study

the efficiency to segregate charge carriers and hence, increases the
photodegradation efficiency of MB dye. The intensity of the ab-
sorption peak decreases with increase in irradiation time due to
variation in number of photo generated charge carriers. The PDE is
in the same order as that of PL intensity. The PL intensity corre-
sponds to the amount of vacancies and defects present in the
sample. More is the content; stronger will be the PL emission.48
These vacancies and defects act as trapping centers for photo-
induced electrons to inhibit the recombination of charge car-
riers.49 Additionally, the reduction in energy gap also enhances the
photocatalytic efficiency. The decrease in the crystallite size can
also be related to the separation of photogenerated charge car-
riers.50 The present study shows the enhancement in the photo-
degradation efficiency of photocatalyst in comparison to the
previously reported results as summarized in Table 2.
The variation between degradation ratios (C/C0) of MB dye and
time for Z0, Z2, Z4 and Z6 was investigated and is represented by
Fig. 12(a). Fig. 12(b) shows the least fit curve of logarithmic ratio of
concentrations with time for the as-synthesized samples with
different molar concentrations of samarium ion in ZnO. The straight
line curve indicates that the rate of photo-degradation of MB dye
obeys pseudo first-order kinetics as stated by Langmuir-Hinshel

Fig. 12. (a) Photocatalytic degradation kinetics of undoped and Sm-doped ZnO nanostructures (Zn1exSmxO) with different concentrations (x ¼ 0.00, 0.02, 0.04 and 0.06). (b) Plot for
ln (C//C0) with time in minutes for the undoped and Sm-doped ZnO nanostructures. (c) Comparison between the rate constants for undoped and Sm-doped ZnO nanostructures.
 Sukriti et al. / Journal of Rare Earths 38 (2020) 29e38
Model51; where C is the absorption peak intensity at the desired
irradiation time interval, C0 the initial absorption intensity of MB
dye, k the rate constant and t irradiation time. The data obtained
from graph was used to obtain pertinent kinetic parameters, such
as the rate constant (k) and the correlation coefficient (R).52 The
values of R2 obtained from the plot are 0.9819, 0.95084, 0.91187 and
0.98857 for Z0, Z2, Z4 and, Z6, respectively. The kinetic rate con-
stant attained from the slope of Fig. 12(b) is 0.0068, 0.02396,
0.04747 and 0.02139 for Z0, Z2, Z4 and, Z6, respectively. It can be
noted that the degradation rate constant increases in the same
order as that of the photodegradation efficiency. It can be
concluded from Fig. 12(c) that the ratio of degradation rate constant
between Z4 and Z0 is approximately 6.98, hence, the photocatalytic
activity is improved by 6.98 times when x ¼ 0.04 for Zn1exSmxO.
This delays the rate of recombination of photogenerated charge
carriers, thereby, enhancing the photocatalytic efficiency with an
appropriate amount of dopant, i.e., Sm3þ in ZnO.
4. Conclusions
In summary, Zn1exSmxO (x ¼ 0.00, 0.02, 0.04 and 0.06) nano-
structures were successfully synthesized via chemical precipitation
method and chemical precipitation method. XRD analysis reveals
that the synthesized nanostructures exhibit crystalline nature with
a wurtzite hexagonal structure. The PL and Raman spectra also
confirm the wurtzite structure of synthesized samples. FESEM
images illustrate that the morphology of the as-synthesized sample
alters from cubical to hexagonal nanostructures with increasing
Sm3þ doping concentration. The EDX pattern shows the presence of
successful insertion of rare earth ion (Sm3þ) in the crystal structure.
The impact of Sm3þ doping on the structure, morphology, absorp-
tion, emission and photocatalytic activity of ZnO nanostructures
was investigated systematically. The red shift observed in the ab-
sorption spectra leads to increment in the utilization of visible light.
The increase in PL intensity with change in dopant concentration
also affects the recombination rate of photogenerated charge car-
riers. It results in greater separation rate of electronehole pairs of
Sm-doped ZnO as compared to undoped ZnO. The photocatalytic
efficiency for the degradation of MB dye is the highest for
Zn0.96Sm0.04O under visible light irradiation. The enhanced pho-
tocatalytic activity might be due to the increase in the content of
defects and vacancies and decrease in crystallite size. The photo
degradation kinetics reveal that the rate constant of Zn0.96Sm0.04O
increases by 6.98 times to that of undoped ZnO. Therefore, it has
been accomplished that as-synthesized Sm-doped ZnO nano-
structures have a significant influence of doping for the enhanced
photocatalytic activity and act as a potential photocatalysts for
green environment.
Acknowledgments
The authors would like to acknowledge the technical support
provided by the Department of Material Science & Engineering, NIT
Hamirpur for FESEM and Raman measurements. The authors are
also grateful to the Director, NIT Kurukshetra for providing the fa-
cilities in Physics Department.
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