Sol-gel synthesis of ZnO/rGO thin film for enhanced

photoelectrochemical water splitting

D. Ben Jemia1,2, M. Karyaoui1, M. A. Wederni3, M.V. Martinez-Huerta4, R. Chtourou 1

1
Laboratory of Nanomaterials and Renewable Energy Systems LANSER, Research and Technology
Center of Energy, Borj-Cedria Science and Technology Park, BP 95, 2050 Hammam-Lif, Tunisia.
2
Faculty of Science of Tunis, University of Tunis El Manar, Tunisia.
3
Unité de recherche Matériaux Avancés et Nanotechnologies (URMAN), Institut Supérieur des
Sciences Appliquées et de Technologie de Kasserine, Université de Kairouan, BP 471, Kasserine
1200, Tunisia.
4
lnstitute of Catalysis and Petrochemistry, CSIC, in Madrid, Spain.

Abstract
Today research on PEC systems, mainly consisting of semiconductor materials capable
of converting solar energy into chemical energy through the photoelectrolysis of water have
been developed to solve energy problems and the environmental crisis. The present work
deals with the effect of rGO incorporation on the photoelectrochemical performance of ZnO
based photoanode prepared by two steps sol-gel process. The elaborated thin films were
investigated in detail by several characterization techniques. rGO addition resulted in
amelioration of the crystallinity. Raman studies confirm the successfully chemical reduction
of GO to rGO and the hexagonal phase Wurtzite structure of the thin films. The
morphological studies show the increasing of the rugosity after the addition of rGO.
Transmittance spectra depict a red–shift of the absorption edges with a decrease in the bad
gap for ZnO/rGO thin films. Furthermore, the EIS measurements show a remarkable decrease
in the charge transfer resistance (Rct) from 1001kΩ to 24. 45kΩ.In addition, ZnO/rGO
photoanode was more photoactive than ZnO one. In fact, ZnO/rGO showed remarkably
enhanced current density (0.149mA.cm-2) which is around 3 times higher than that of ZnO
photoanode(0.05mA.cm-2).

Keywords: Zinc oxide, reduced graphene oxide, sol-gel, photoelectrochemical water

splitting.

1
 1. Introduction
In last few decades, researchers shed the light on thin film-based photoelectrochemical
solar cells to reduce the traditional fossil energy. In fact, PEC cells convert solar energy into
storable chemical energy as hydrogen energy via water splitting 1.Since Fujishima and Honda
2
reported water splitting using TiO2 photoanode, several metal oxide semiconductors such as
ZnO, TiO2,SnO2 and SrTiO3 has been intensively studied as photoanodes because of their
wide bang gap, excellent electrochemical stability ,low cost and easy availability3.Compared
to TiO2 photoanode, ZnO is more suitable material due to its higher electron mobility(10-
100times) and a larger exciton binding energy (60 meV)1.
Nevertheless, due to its wide band gap(3.37eV) the photoactivity is observed only
under irradiation with UV light (4% of solar spectra). Furthermore, the easily recombination
of generated excitons resulting a poor photoresponse efficiency. In order to improve the
performance of ZnO based photoanode, many kinds of strategies were used including
elemental doping of metal4,5 and coupling with narrow band gap semiconductors etc.6-8.
Actually, an effective way to raise the photoelectrochemical efficiency of ZnO
photoelectrode is incorporation of electron conducting scaffolds to enhance the charge
separation and transport efficiency. Reduced graphene oxide (rGO) is widely recognized as a
conducting scaffold thanks to its unique properties such as interesting surface area, excellent
mobility of charge carriers with superior electrical and mechanical properties resulting to an
excellent electrons collection and transportation9. There is a scarcity of reports dealing the
synthesis of ZnO/rGO composite photoanode for photoelectrochemical water splitting. Khan
et al.10showed ameliorated PEC hydrogen production for elaborated ZnO NW AS/rGO
heterostructure on FTO substrates using a sonochemical assisted approach. Chandrasekaran et
al.11synthesized triangular shaped on GO which results in the enhancement of PEC activity.
Lin et al.12reported the elaboration of rGO/ZnO nanocomposites through the electrophoresis
technique for PEC water splitting.

To best of our knowledge, the effect of rGO as a front contact on the

photoelectrochemical performance of ZnO/rGO photoanode prepared by sol–gel process has
not been reported earlier.
In this context, this work aims to combine ZnO thin film with rGO sheets using sol -gel
process via two steps spin-coating technique to use it as an efficient photoanode for PEC
water splitting. In addition, the rGO addition influence on structural, morphological, optical
and electrical properties have been investigated.

2
 2. Experimental
2.1 Synthesis of rGO
The rGO powder was obtained in two steps.Firstly,GO was prepared through the
oxidation of graphite using a modified Hummer’s method13.Then, the reduction of GO into
rGO was conducted by a chemical reduction using L-Ascorbic acid as a reducing
agent.Briefly,the graphene oxide powder prepared was dispersed by sonication in distilled
water. Then, 10g of L-Ascorbic acid was dissolved in 100 ml of distilled water, then the
resulting solution was slowly added to the solution of the exfoliated graphite oxide and the
mixture was stirred at 95 °C for 1h. Then, rGO were filtered by cellulose filter paper, and
washed with a 1M hydrochloric acid solution (37%, Merck) and distilled water several times
until pH=7 was achieved. At last, rGO powder was dried overnight at 60°C.
2.2 Synthesis of ZnO and ZnO/rGO thin films.
ZnO thin film was synthesized onto ITO substrates by adopting sol-gel process via the
spin-coating technique. Firstly, the ITO substrates were ultrasonically cleaned for 15 min with
both acetone and iso-propanol, then it was washed with de-ionized water. For the preparation
of solution, zinc acetate dihydrate (Zn (CH3COO)2–2H2 O, 99.9%, Merck) was used as the
precursor solution, absolute ethanol as solvent, and monoethanolamine (NH2CH2CH2–OH,
Sigma Aldrich) as a stabilizer. The solution was prepared by refluxing for 2 h at 60 °C and
then cooled at room temperature for 24 h to ensure obtaining transparent and homogenous
solution. The prepared solution was then growing on ITO glass substrates via spin coating
process. The speed was set at 3000 rpm for deposition time about 30s, then it was dried in the
oven at 300°C for 10 min to tack off the solvents trapped in thin layer structure. The drop and
dry process were repeated 10 times on the same substrate. Finally, the thin film was heated at
550°C for 2h in a programmable furnace.
To obtain ZnO/rGO thin film, at first the rGO solution was prepared by dissolving
20mg of rGO powder in 10mL of ethanol under sonication for 2h in ultrasonic bath. Then, the
solution was deposited by spin coating onto ZnO thin film using a speed at 600 rpm for 1 min.
Finally, to evaporate the solvent the sample was dried at 100°C for 1h in the oven. Figure.1
showed the conditions and synthesis steps of ZnO and ZnO/rGO thin films deposited onto
ITO substrates.

3
 Figure.1 Different synthesis steps of (a) ITO /ZnO and (b) ITO/ZnO/rGO thin films.

2.3 Characterization techniques

In order to investigate the properties of elaborated thin films, several techniques were
used. The crystalline structure and the type of phases were determined using X-ray
diffractometer XRD (BRUKER D8 advance model, CuKα radiation, λ=1.541Å at room
temperature). Raman spectrometer (RENISHAW) was used to record Raman spectra
equipped with a 532nm green laser and 5mw output power.TEM images were analyzed via
the transmission electron microscopy (TEM, HRTEM JEOL2100F) analysis. The topology of
samples was studied via an Asylum MFP3D atomic force microscopy. The transmission
measurements in the UV–Visible domain were performed using A Perkin Elmer Lambda 950
spectrophotometer.
Electrical properties were recorded using electrochemical impedance spectroscopy
(EIS), at open circuit potential with an applied sinusoidal AC perturbation of 10mV in the
frequency domain from 0.1 Hz 100 KHz. ZView2 software was used to determine the fitting
of the collected results from EIS measurements and the equivalent circuit.

4
 The photoelectrochemical (PEC) measurements were made using computer-controlled
Autolab potentiostat metrohm AUTOLAB (30PGSTAT). The Ag/AgCl electrode, the Pt plate
electrode, and the sample were utilized as the reference, counter, and working electrodes,
respectively and were submerged in aqueous Na2SO 4 (0.5 M) solution in a quartz electrolytic
cell. A Xenon lamp (CHF-XM-500W) was used as a source of excitation with a 200 mW/cm 2
puissance. The illuminated area of the photoanodes was 1cm2.
3. Results and discussion

3.1 XRD properties

The crystal structure and the phase orientation of the samples were evaluated using X-ray
diffraction spectroscopy. Figure.2 depicts the XRD patterns of ZnO and ZnO/rGO thin films.
The diffraction peaks at around 31.75°,34.38°,36.23°,47.52°,56.73° and 62.88° corresponds to
(100), (002), (101), (102), (110), and (103) planes according to a hexagonal phase Wurtzite
structure of ZnO with polycrystalline natures (JCPDS 036-1451)14.The peak at 34.38° related
to the (002) plane is more intense than the other peaks indicating a favored c-axis orientation
for the crystallites15,16.In XRD of ZnO/rGO, it is predicted that no secondary phase belonging
to rGO was detected which indicates that the amount of deposited sheets of rGO was below
the threshold detection limit of XRD tool 17.After the addition of rGO, the intensity of the
diffraction peak (002) in ZnO/rGO was enhanced which prove that the crystallinity of the thin
films was greatly enhanced18.

ZnO/rGO
* ITO
(002)

ZnO
 ZnO 
Intensity(a.u)

(100)

(101)

(103)
(102)

(110)

* *  *  

10 15 20 25 30 35 40 45 50 55 60 65
2

5
 Figure.2 XRD patterns of ZnO and ZnO/rGO thin films.

3.2 Raman properties

The Raman spectroscopy was used to study the chemical bonding in the ZnO and rGO
layers. Raman spectra of GO,rGO,ZnO and ZnO/rGO were illustrated in Figure.3.The
spectrum of ZnO displayed two strong peaks at 439cm -1 and 101cm-1 which are related to
E2(high) and E2(low) of oxygen atoms and zinc sublattice ,respectively .This are the
characteristic peaks of the hexagonal wurtzite phase ZnO 19.The peaks observed at 205cm-1 ,
335cm-1 ,476cm-1 ,790cm-1 and 1097cm-1 are assigned to 2E2L, E2H-E2L, 2LA, 2A1(TO) and
A1(TO)+E1(TO)+E2L, respectively. In addition, the peaks at 380cm-1 and 580cm-1 are related
to longitudinal and transversal A1 modes ,respectively20.In case of ZnO/rGO thin film, it's
clearly seen lower peaks intensity related to ZnO structure which are due to the interaction
between ZnO and rGO. Moreover, two strong bands at 1344cm -1 (D band) and 1593cm-1(G
band) are shown. The D band refers to some disorder and defects in the graphitic structure
while the G band refers to the in-plane vibration of sp2 carbon type structure21.The successful
chemical reduction of GO to rGO is confirmed by Raman spectroscopy. Indeed, the disorder
degree and average size of the sp2 domains are showed from the ID/IG value. That of rGO
powder (1.02) is enhanced as compared to GO (0.97). In addition, the I D/IG value of ZnO/rGO
(1.07) is larger compared to the values of rGO and GO powders which is due to the increasing
disorder and defects from the interaction with ZnO particles in the composite.

ZnO/rGO D band
G band
rGO powder
GO powder
ZnO
Intensity(a.u)

-1
-1 439cm
101cm -1 -1
-1 335cm-1 476cm-1 790cm 1097cm
205cm
-1 -1
380cm 580cm

200 400 600 800 1000 1200 1400 1600 1800

-1
Raman shift(cm )

6
 Figure.3 Raman spectra of GO and rGO powders, ZnO and ZnO/rGO thin films.

3.3 Surface morphology properties

The surface morphology and microstructures of the prepared samples are analyzed by
transmission electron microscopy (TEM). Figure.4 shows the typical TEM images of ZnO
and ZnO/rGO thin films. In the case of ZnO (Figure.4a), it can be seen some hexagonal
shaped grains. From the TEM image of ZnO/rGO(Figure.4b), it is clearly seen that the rGO
nanosheets are successfully deposited onto the ZnO nanoparticles which might be due to the
Vander-Waals interactions by offering attractive forces between ZnO nanoparticles and rGO
through the interactions with the oxygen component of rGO sheets 22.This electrical
connection between ZnO and rGO facilitates the charge transfer process during the interfacial
interactions.

(a) rGO (b)

ZnO

Figure.4 TEM images of (a)ZnO and (b) ZnO/rGO thin films.

To complement the results of TEM, the morphology is further investigated by using

atomic force microscopy (AFM). Figure.5 shows 3D AFM micrographs of the synthesized
ZnO and ZnO/rGO thin films scanned over an area of 10 × 10 μm2.The roughness value
(RMS) of ZnO is 35. 24nm.For ZnO/rGO thin film, the root mean square roughness becomes
more rougher than that of ZnO and was found to increase from 35.24nm to 50.55nm.

7
 (a) (b)

Figure.5 AFM micrographs of ZnO and ZnO/rGO thin films.

3.4 Optical properties

The UV–Vis transmittance spectra of ZnO and ZnO/rGO thin films at room temperature
in the 300-800 nm domain are shown in Figure.6(a). From this figure, it can be seen that ZnO
thin film exhibits high light transmittance (90%) in the visible domain due to its large band
gap. In the case of ZnO/rGO thin film, the addition of rGO slightly reduces the intensity of the
transmittance (from 90% to 60%). Moreover, it can be seen that a slight red shift toward
higher wavelength which may be due to the Zn-O-C bond formation in the interface of rGO
and ZnO which cause the decrease in the band gap value. This behavior was interpreted by
Mina Ghorbani et al 1. as the unpaired π electrons on rGO might bond with the free electrons
on the surface of Zn2+ in order to form Zn-O-C bonding.

The optical band gap of the samples was calculated from the transmittance spectra
using the Tauc formula combined with the Lambert–Beer law 23:

1
α = ln ¿ Eq.1
d
αhν=k ¿ Eq.2

where α is the absorption coefficient, d is the thickness of the thin film, T is the Transmittance
k is constant, h is the Planck’s constant, ν is the photon frequency, Eg is the optical band gap
and n is the 1/2 for direct band.

8
 Figure.6(b) shows the evolution of (h)2 vs. (h) for the synthesized samples. The
linear extrapolation at the absorption edge to (h)2 = 0 gives an estimate band gap energy. It
could be seen that the band gap decreases from 3.265eV for ZnO thin film to 3.220eV for
ZnO/rGO thin film due to the interfacial interaction between ZnO and rGO 24. Similar results
were seen in previous works 1,19,25.

9
 100

80
(a)

Transmittance(%) 60

40 ZnO
ZnO/rGO
20

0
300 400 500 600 700 800
Wavelength(nm)

1000
(b)
Eg=3,265eV
800 ZnO
ZnO/rGO Eg=3,220eV
-1 2
)

600
2 (eV.cm

400
( h )

200

0
3,05 3,10 3,15 3,20 3,25 3,30 3,35
h (eV)

Figure.6 (a) Transmittance spectra and (b) Tauc plots of ZnO and ZnO/rGO thin films.

10
 3.5 EIS analysis

Electrochemical impedance spectroscopy is a prominent method exploited for the

investigation of the charge-transfer mechanism and the capacitive behavior across an
electrolyte/electrode interfacial system 26. Figure.7 shows the Nyquist and bode phase angle
plots for an AC frequency varying from 0.1Hz to 100 KHz. As can be seen in Figure.7(a), the
Nyquist plots of ZnO and ZnO/rGO electrodes depict only one semicircle curve which is
characteristic of the electron transfer process at the contact interface between electrode and
electrolyte solution. Moreover, a remarkable decrease in the diameter of the semicircle is
observed for ZnO/rGO electrode as compared with ZnO electrode which indicates that the
incorporation of rGO improved the transport of interfacial electron27,28.An equivalent circuit
(Randles equivalent circuit) as a model of the experimental impedance results is used to
clarify this behavior using the Zview2. The equivalence fitted model circuit for ZnO and
ZnO/rGO electrodes are shown in the inset of Figure.7(a). The associated equivalent circuit
consists of two series connected combinations; the first is the ohmic resistance of the
electrolyte (Rs) and the second is a connection in parallel of a combination of a charge transfer
resistance (Rct) and a constant phase element (CPE). The capacitive elements are replaced by a
constant phase element (CPE) because the noted depression in the center of the semicircles
below the real axis proves the non-Debye nature of the studied samples29. The constant phase
element is typically defined by an admittance Y(CPE) through the following equation30:

Y ( CPE ) =A 0 ¿ Eq.3

with A =A0 cos (α π/2) and B = A0 sin (α π/2), where A0 and α are temperature dependent but
frequency independent parameters. A0 determines the magnitude of the occurred dispersion,
and 0 ˂ α ˂1 (for an ideal capacitor α =1 and for an ideal resistor α = 0).

11
 It’s clearly seen, a close agreement between the experimental and fitted data (solid black
line) with an estimated standard deviation of the parameters less than 6%. The estimated
values of Rs, Rct and CPE are presented in Table.1, in which we observed that the charge
transfer resistance (Rct) and constant phase element (CPE) are changed after adding rGO
sheets which confirms the clear decrease in the diameter of the semi-circle constituting the
Nyquist diagrams. Rct decreased from 1001 kΩ to 24.45 kΩ and conversely, CPE increased
from 552µF to 658µF. The obtained results are coherent with the previous works 27,31.

Figure.7(b) shows the bode diagram, in which the attitude of electron transfer can be
observed through phase angle versus. log frequency plots. It’s clearly seen in the selected
frequency range, the appearance of a single phase angle peak which had a high magnitude
value at the frequency range of 0.1-10 Hz.This graphical variation showed a capacitive
behavior in this corresponding range.Indeed,it’s noted that for an ideal capacitive electrode,
the phase angle at the low frequency region is closer to 90°, whereas, it shifts towards 45° in
the case of pseudo-capacitance electrode32.In this case, we found that , the phase angle value
decrease from 82° to 73° which implying the combined contribution of ideal capacitance and
pseudo-capacitance. Bhavana Rikhari et al.33 related the decrease in the magnitude of Bode
phase angle to the improvement of ionic conductivity between electrolyte and electrode
interface .Moreover, the charge transfer process at the platinum counter electrode /electrolyte
interface could be seen through the small sloping on the high frequency range27.

Electrodes RS(Ω) Rct (kΩ) CPE(µF) α

ZnO 98.57 1001 552 0.951
ZnO/rGO 165.2 24.45 658 0.819

Table.1 Equivalent circuit parameters for ZnO and ZnO/rGO electrodes.

12
 4
2,8x10
ZnO
2,4x10
4 (a) ZnO/rGO
FIT
4
2,0x10

4
- Z " ( )

1,6x10

4
1,2x10

3
8,0x10

3
4,0x10

0,0
0,0 3
3,0x10 6,0x10
3 3
9,0x10 1,2x10
4

Z'()

90
ZnO
80
(b) ZnO/rGO
70
60
-phase(°)

50
40

30

20
10

0
-1 0 1 2 3 4 5
10 10 10 10 10 10 10
logf(Hz)

13
 Figure.7 (a) Nyquist plots, the inset shows the electrical equivalent circuit. The solid lines are
calculated using values in Table.1, and (b) phase impedance curves of synthesized samples.

3.6 Photoelectrochemical performance

In order to study the effect of rGO incorporation on the photoelectrochemical properties

of ZnO thin film, photocurrent density–potential (J–V) curves of ZnO and ZnO/rGO films in
the dark and under xenon lamp illumination in 0.5 M aqueous Na2SO4 solution(pH=7) were
recorded. The applied potential was between -0.4 and 0.2V vs Ag/AgCl.As seen in Figure.8,
in the dark condition the current density is negligible for ZnO and ZnO/rGO electrodes. After
the illumination of the junction, an anodic photocurrent density appears for the electrodes
which confirmed the n type of semiconductors. Moreover, it’s clearly seen an enhancement in
the photocurrent density for ZnO/rGO photoanode as compared to ZnO one. The
enhancement in the photocurrent density after the addition of rGO is in general related to its
unique two-dimensional π−¿conjugation structure which contributed to a rapid transport of
photo-induced charge carriers from ZnO into rGO sheets through percolation mechanism34.
From Figure.8, we deduced the photoelectrochemical output parameters (VOC, JSC) after
illumination. These parameters are gathered in Table.2. The fill factor (FF) and the efficiency
(η) were determined using the following equations23,35:

I max V max
FF= Eq.4
I SC V OC

V OC I SC FF
η= ∗100 Eq.5
P

with Imax and Vmax are the maximum current and voltage respectively, Isc is the short
circuit current, Voc is the open circuit potential which are extracted from the (J-V) curves and
P is the input light intensity.

From Table .2, we observed that the values of the PEC parameters are enhanced after
the incorporation of rGO in the ZnO photoanode.

14
 Electrodes Jsc (mA/cm2) Voc(v) FF η(%)
ZnO 0.032 0.37 0.72 0.0043
ZnO/rGO 0.075 0.33 0.94 0.012

Table.2 PEC parameters of synthesized photoanodes.

0,14

0,12
ZnO(dark)
Current density(mA/cm2)

ZnO/rGO(dark) 0,10
ZnO(illum)
ZnO/rGO(illum) 0,08

0,06

0,04

0,02

0,00
-0,4 -0,3 -0,2 -0,1 0,0 0,1 0,2
-0,02
Applied potential(V)

Figure.8 Photocurrent density(J-V) of ZnO and ZnO/rGO thin films in the dark and under
illumination.

To further explore the photoelectrochemical properties of the synthesized electrodes, a

performing potentiostatic measurements (current density vs time, (J-t)) were carried out using
ON/OFF cycles for a total duration of 300s.From Figure.9, it’s clearly seen the stability of all
electrodes and denote that the excitons were immediately generated then separated in the ZnO
thin films. Moreover, we observed that the photocurrent density generated by ZnO/rGO
photoanode achieved 0.149 mA.cm-2. This value is three times greater than that measured for

15
pure ZnO (0.05mA.cm-2).Our results are compared to those reported by Swe Jyan Teh et al.27
who found that ZnO/ rGO photoanode with rGO as front contact has a current density greater
than that of ZnO photoanode.

0,20
ZnO
ZnO/rGO
0,16
Current density (mA/cm 2)

0,12

0,08

0,04

0,00
50 100 150 200 250 300
t(s)

Figure.9 Photocurrent density (J-t) of ZnO and ZnO/rGO thin films.

4. Conclusion

In summary, ZnO/rGO thin films were successfully synthesized using sol-gel process
via two steps spin-coating technique. The effect of rGO incorporation on structural,
morphological, optical and electrical properties were studied. Infact, the addition of rGO
improves the crystallinity of the thin films. Besides, for ZnO/rGO thin film the optical
measurements reveal a positive contribution of rGO sheets to expose a red–shift of the
absorption edges onto the visible domain with a narrower band gap compared to the ZnO thin
films. The EIS measurements show that the rGO addition reduce the charge transfer resistance
(Rct) from 1001kΩ to 24. 45kΩ.Moreover, the PEC performance of ZnO/rGO photoanode is
three times greater than that of ZnO thin films which is due to the improvement charge
separation and photogenerated electron transportation properties. This work paved the way
the industrial application of ZnO/rGO thin films to convert solar energy into storable chemical
energy (hydrogen and Oxygen energy).

16
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