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Heat treatment of electrodeposited NiO films for

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improved catalytic water oxidation

Cite this: RSC Adv., 2015, 5, 86713
F. Basharat,a U. A. Rana,*b M. Shahida and M. Serwara

Received 23rd August 2015
Accepted 4th October 2015
DOI: 10.1039/c5ra17041a
www.rsc.org/advances
Recognizing the superior electrocatalytic properties of nickel oxide (NiO), we prepared cathodically
electrodeposited nickel oxide (NiO) on fluorine doped tin oxide (FTO) glass substrates as binder free
electrocatalysts for water oxidation. The electrodeposited nickel oxide film (NiO(ED)) showed remarkable
improvement for electrocatalytic water oxidation after heat treatment. In particular, the NiO(ED)-400
catalyst (electrodeposited nickel oxide film heat treated at 400
C) achieved appreciable current density
 5 mA cm2 for the oxygen evolution reaction (OER) at the overpotential of 0.45 V vs. RHE. These
catalyst films were characterized for structural, morphological, thermal and electrochemical properties,
where the results reveal that the dehydration during heat treatment permanently removes the structural
water with a concomitant amorphous / crystalline transformation in NiO(ED) films, thereby making them
more active catalysts for OER. In parallel investigations, nickel metal was electrodeposited on a stainless
steel (SS) substrate, and was subsequently annealed in hot air to produce NiO(HA) films at different
temperatures. The NiO(HA) films prepared by this method showed relatively high values of Tafel slopes
and corresponding high overpotentials and low currents for OER, when compared to the NiO(ED) films.
Hence, simple heat treatment of the cathodically electrodeposited nickel oxide (NiO(ED)) films showed
remarkable improvements in their catalytic performances for oxygen evolution reaction, thereby making
them efficient electrocatalysts for water oxidation.

large scale applications (for commercial electrolyzers)

Introduction
The economical and sustainable hydrogen production from
water electrolysis has a great signicance in order to shi our
current fossil fuel based economy to a cleaner and renewable
hydrogen energy based economy.1–3 The signicantly high
mass-specic energy density, ability to be formed from renew-
able resources (such as wind or solar powered electrochemical
water splitting) and clean nature make hydrogen the most
promising fuel for the future.4 To achieve this goal, the devel-
opment of low cost and stable electrocatalysts that can carry out
efficient and facile Oxygen Evolution Reaction (OER) in water
splitting hydrogen generators or Polymer Electrolyte Membrane
Fuel Cells (PEMFCs) is highly desired. OER is an important
energy demanding step in water electrolysis/splitting, which
intrinsically in nature not favoured kinetically and requires
efficient catalyst for expediting the reaction.5
The most promising electrocatalysts to date that display
high efficiency for OER at lower overpotentials are Ir6 and Ru7
based materials and Pt group metals.8 However, the signi-
cantly high cost and scarcity of these materials make their
a
School of Chemical and Materials Engineering, National University of Science &
Technology (NUST), H-12, 44000 Islamabad, Pakistan
b
Sustainable Energy Technologies (SET) Centre, College of Engineering, King Saud
University, PO-Box 800, Riyadh 11421, Saudi Arabia. E-mail: urana@ksu.edu.sa
impractical. Moreover, Ru and Ir based catalysts are unstable
in alkaline medium that is used in most of the commercial
water electrolyzer. Recently, new catalysts for OER that are
based on abundant and inexpensive transition metal alterna-
tives such as Mn, Co, Fe and Ni have attracted growing
scientic interest because some of these electrocatalysts
showed signicantly high current densities for OER at rela-
tively low overpotentials.9–12 In particular, nickel oxide (NiO) is
one of the most promising catalyst for water oxidation, and is
one of the most widely used co-catalyst compared to Pt or
RuO2, which has the ability to convert photocatalysts into
more active water splitting catalysts.13 Both Ni and NiO display
facile water oxidation at relatively low overpotential and that is
why the Ni based alloys (such as stainless steel) are commonly
used as anode materials in commercial water electrolyzer
systems. NiO can be synthesized using a variety of techniques
such as thermal decomposition, electron beam evaporation,
electrochemical deposition (both anodic and cathodic),14–16
chemical deposition17 and sol gel technology.18 Among these
methods, electrochemical deposition is a versatile technique,
as it allows control over the thickness of deposited layer simply
by changing either the current or voltage.19 The major advan-
tage of the electrochemical deposition technique is that the
material can be deposited on the desired substrate without the
need of binder.

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Among nickel based materials, nickel oxide (NiO) is
considered to be a promising electrocatalyst for efficient water
electrolysis, however previously NiO has been mostly studied in
the doped form or as mixed oxides for water splitting applica-
tion.20 The typical examples can be seen in the form of iron
doped Ni (NiFe),21 Ni–Cu electrode,22 water oxidizing complex
(WOC) of Ni, Co/Ni mixed oxides23,24 and RuO2/NiO type mixed
oxides.25 There is scarcity of work related to the studies on pure
nickel oxide (NiO) and its application for catalytic water
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oxidation.
The pH is very important parameter for the electrodeposition
of metal and metal oxide. The Pourbaix diagram of nickel
(Fig. 1) shows that the equilibrium composition of different
nickel oxide (NiO) phase varies with change in pH.26
In the present work, we present a facile method to electro-
deposit nickel oxide (NiO) lms on the uorine doped tin oxide
(FTO) glass substrate (these nickel oxide lms are labelled as
NiO(ED), where the subscript “ED” stands for electrodeposited).
Though, the electrodeposition of nickel oxides (NiOx) is re-
ported earlier both by cathodic27,28 and anodic deposition29
techniques, to our knowledge, there is no study reported so far
that explained the effect of heat treatment on the electro-
deposited nickel oxide lms from aqueous media for improved
catalytic performance for water oxidation. Our study reveals that
the electrodeposited NiO(ED) lms from aqueous media likely
incorporate/take up huge amount of bound water that render
the material amorphous in the as-deposited form and thereby
affect their catalytic performances. Heat treatment of these
electrodeposited NiO(ED) lms at temperatures (100, 200, 350
and 400
C) showed remarkable improvements for the catalytic
efficiencies of these lms, making them efficient electro-
catalysts for water oxidation.
In parallel developments, we also prepared NiO lms by
annealing (in hot air) the electrodeposited metallic Ni on the
stainless steel substrates (these lms are labelled as NiO(HA),
where the subscript HA stands for hot air annealed). The NiO
lms prepared by both methods were investigated for struc-
tural, morphological and electrochemical properties. Water
Fig. 1Pourbaix diagram calculated for nickel with a concentration of
106 mol L1 corresponding to a concentration of 58 mg L1 nickel.26
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splitting properties of both types of nickel oxides lms ware
studied and Tafel slopes were calculated. The detailed investi-
gations of these catalyst lms involve a range of analytical
techniques including X-ray diffraction (XRD), thermogravi-
metric analysis/differential thermal analysis (TGA/DTA), scan-
ning electron microscopy/energy dispersive X-ray spectroscopy
(SEM/EDX) and electrochemical properties such as Linear
Sweep Voltammetry (LSV). The results from present investiga-
tions indicate that the permanent loss of surface water upon
heat treatment was the key factor for improved catalyst perfor-
mance and enhanced current densities for oxygen evolution
reaction (OER). The comparison of water splitting properties of
these two types of lms was made, which can be useful to design
the best catalyst material for catalytic water oxidation.
Experimental section
Materials
Analytical grade nickel chloride (NiCl2$6H2O), nickel sulphate
(NiSO4$6H2O), ethylenediaminetetraacetic acid (EDTA), potas-
sium chloride (KCl) and potassium hydroxide (KOH) were
purchased from Aldrich and were used as received without any
further purication. Ultra-pure deionized water was used for
making up the electrolyte solution for electrodeposition.
Electrodeposition of nickel oxide (NiO) lms
Scheme 1. Thin lms of nickel oxide (NiO(ED)) were electro-
deposited from an aqueous solution of 0.5 M nickel chloride
containing 0.1 M KCl as supporting electrolyte. In order to
electrodeposit NiO, Pourbaix diagram (Fig. 1) shows that the pH
of electrolyte solution should be $8. Hence, the pH of solution
was maintained at 8 by adding appropriate amount of KOH.
Since, Ni2+ can easily precipitate out as nickel hydroxide at this
pH, approx. 0.4–0.5 M ethylenediaminetetraacetic acid (EDTA)
was used as complexing agent to avoid the hydroxide formation.
Deposition temperature was maintained at 20–30
C. A higher
temperature than this range showed formation of metallic
nickel layer in addition to the NiO. Nickel oxide was electro-
deposited on the uorine doped tin oxide (FTO) glass substrate
having a sheet resistance of 15 U. Prior to deposition, the FTO
glass was ultra-sonicated for 30 min in the dilute solution of
a commercial detergent for degreasing. Aer degreasing, the
FTO glass was thoroughly washed with deionized water and
then ultra-sonicated again in ethanol to remove any residual
detergents le over on the surface of FTO. A graphite rod was
used as counter electrode, while Ag/AgCl (saturated) was used as
reference electrode. The nickel oxide thin lms were electro-
deposited at 25
C for 30 min under galvanostatic conditions
using a current density of 2 mA cm2. The NiO(ED) lms
prepared this way were studied in the as-deposited form and
were heated at 100, 200, 350 and 400
C, which were labelled as
NiO(ED), NiO(ED)-100, NiO(ED)-200, NiO(ED)-350 and NiO(ED)-400
respectively (the subscript ED stands for electrodeposited). All
electrochemical deposition experiments were performed on
Gamry Reference 750 galvanostat/potentiostat system.
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Scheme 2. In the second method, we rst electrodeposited
a thin layer of nickel (metal) on the Stainless Steel (SS)
substrate. In these deposition experiments, SS was used as
a working electrode, Ni rod as counter electrode, while Ag/AgCl
was used as the reference electrode. The bath solution con-
tained 0.5 M NiSO4 and 2 M NaCl. The pH of solution was
maintained at about 4 by adding boric acid (H3BO3). The bath
was operated at 50–60
C under galvanostatic conditions using
a current density of 10 mA cm2. The SS substrate was
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degreased by treating with dilute alkali solution containing
a mixture of NaOH and Na2CO3 and washed thoroughly with hot
deionized water prior to be subjected for deposition. Once the
metallic Ni was electrodeposited, heat treatment was done at
600, 700, 800 and 900
C. In a typical heat treatment method,
the Ni plated SS samples were heated to the desired temperature
at a ramp rate of 10
C min1 aer which the samples were kept
at the aforementioned temperatures for 2 hours in a muffle
furnace under continuous air ow to convert this metallic
nickel into nickel oxide. The nickel oxide lms prepared by hot
air annealing of Ni metal layer were labelled as NiO(HA)-600,
NiO(HA)-700, NiO(HA)-800 and NiO(HA)-900 respectively (the
subscript HA stands for hot air annealed).
Material characterization
The morphology and chemical composition of the nickel oxide
lms were investigated using JEOL JSM-6490A scanning elec-
tron microscope (SEM) that was equipped with energy disper-
sive X-ray analyzer (EDX). The crystal structure was investigated
using STOE q–q X-rays diffractometer within 10–80 (2q degrees)
range using CuKa radiations (wavelength 1.543  A). In order to
obtain the IR spectrum, the scratched powder was mixed with
KBr to prepare pellets. The IR spectrum was recorded in the
spectral range of 400–4000 cm1 using Perkin Elmer spec-
trometer of Spectrum-100 model.
Thermogravimetric analysis (TGA) and differential thermal
analysis (DTA) of the electrodeposited nickel oxide lms
(NiO(ED)) lms were performed on the Perkin Elmer Diamond-II
equipment.
Electrochemical measurements
All electrochemical experiments were performed on VSP Bio-
logic potentiostat/galvanostat 350 system using standard three
electrode conguration. The cyclic voltammetry (CV) experi-
ments for electrodeposition of nickel oxide lms were carried
out on an exposed active surface area (1 cm2) of the FTO
substrate that was used as the working electrode. The platinum
gauze was used as the counter electrode, while saturated silver/
silver chloride (Ag/AgCl) was used as reference electrode.
For catalytic water oxidation on NiO lms, the three elec-
trode system consist of electrodeposited NiO lms on FTO
substrate (NiO(ED) lms) and steel substrates (NiO(HA) lms) as
working electrode, Ti foil as the counter electrode and standard
calomel electrode (SCE) as the reference electrode. The catalytic
water oxidation reactions were carried out in an alkaline solu-
tion of 1 M NaOH. The Linear Scan Voltammetry (LSVs) were
recorded for the oxygen evolution reaction (OER) by scanning
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from 0 to 1 V in oxidation window vs. SCE at a scan rate of 5 mV
s1. The potential axis was rescaled for Reference Hydrogen
Electrode (RHE) using the relation as E (RHE) ¼ E (SCE) +
0.059  pH + 0.241.30 The overpotential (h) is commonly
expressed in terms of oxygen overpotential that was determined
using the relation h (mV) ¼ [E (V) vs. SCE  (1.23  0.059  pH)
+ 0.241]  1000.
Results and discussion
Electrodeposition of nickel oxide (NiO) lms
Cyclic voltammetry (CV) was performed to cathodically elec-
trodeposit nickel oxide (NiO) thin lms onto the surface of FTO
glass (Fig. 2). The pH of the bath solution (0.5 M nickel chloride
containing 0.1 M KCl as supporting electrolyte in water) was
maintained at 8 by adding appropriate amount of KOH. Since,
Ni2+ can easily precipitate out as nickel hydroxide at this pH,
EDTA (0.4–0.5 M) was used as complexing agent to avoid the
precipitation.
The cyclic voltammogram (CV) traces were recorded within
the range of +0.3 to 0.8 V vs. Ag/AgCl(saturated) at the scan rate of
50 mV s1. In the cathodic scan, the rst reduction peak
observed at an onset of ca. 0.24 V can be attributed to the
electrochemical reduction of (Ni2+ / Ni).31 The second reduc-
tion phenomenon observed at around 0.3 V corresponds to
the electrochemical reduction of water to hydroxide, which
subsequently formed nickel hydroxide Ni(OH)2 (as per eqn (1))
and nally end up in the formation of nickel oxide (NiO) (as per
eqn (2)).31 The nal reduction phenomenon observed at above
0.5 V onwards can be attributed to the electrochemical
reduction of water at the surface of NiO(ED) thin lm.
NiCl2$6H2O + H2O / Ni(OH)2 + 2HCl + 5H2O (1)
Ni(OH)2 / NiO + H2O (2)
From Fig. 2, we can see that the oxidation of metallic nickel
layer (Ni / Ni2+) could give rise to a peak during the anodic
scan at about 0.2 V,28 where a metallic Ni layer was initially
Fig. 2 The cyclic voltammogram of the complexed nickel solution
(0.5 M NiCl2$6H2O + 0.1 M KCl + 0.4 M EDTA) on FTO glass.
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deposited during the cathodic scan (Ni2+ / Ni). A. C. Sonavane
and co-workers have reported the Ni2+ / Ni reduction during
the cathodic electrodeposition of nickel oxide on FTO glass.31
However, the authors found large reduction currents for this
phenomenon, which caused signicant amount of metallic
nickel deposited onto the surface of FTO substrate. In our study,
we found that when the amount of EDTA (complexing agent)
was kept less than 0.3 M against 0.5 M NiCl2$6H2O solution,
a thick layer of metallic nickel was deposited along with nickel
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oxide. Hence, we used 0.4–0.5 M EDTA for complexing the Ni2+
ions in the bath solution (0.5 M nickel chloride containing 0.1
M KCl as supporting electrolyte in water) that was used for
electrodeposition. In contrast to the previous report on NiO
deposition,31 we found that using large amount of EDTA helped
to reduce the deposition of metallic nickel layer, which was
evidenced from the small reduction currents for Ni2+ / Ni
phenomenon in the CV diagram (Fig. 2). Hence, by using the
high concentration of nickel solution (0.5 M NiCl2$6H2O) and
high concentration of complexing agent (0.4–0.5 M EDTA),
there was still a large amount of Ni2+ ions, which were com-
plexed by OH ions produced during the subsequent reduction
phenomenon. There were few more observations for the
presence of Ni2+ ions aer the rst reduction phenomenon of
Ni2+ / Ni;
(1) The colour of Ni-EDTA complexed solution didn't fade
aer the rst reduction (Ni2+ / Ni) and remained deep blue,
indicating the complex solution of Ni2+ with EDTA.
(2) There was no distinct fading of the blue coloured Ni-
EDTA complex solution even aer continuous 30 min galvano-
static electrodeposition.
Structural characterization
The structural analysis of both types of nickel oxide lms
(NiO(ED)) and (NiO(HA)) were carried out by X-ray diffraction
(XRD) technique. Fig. 3 shows the XRD patterns of FTO glass,
electrodeposited (NiO(ED)) and heat treated (NiO(ED)-100,
Fig. 3 X-rays diffraction (XRD) patterns recorded for electrodeposited
NiO films on the FTO substrate viz. NiO(ED), NiO(ED)-100, NiO(ED)-200,
NiO(ED)-350 and NiO(ED)-400.
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NiO(ED)-200, NiO(ED)-350 and NiO(ED)-400) lms. The corre-
sponding planes (hkl) and observed d-values conrm the pres-
ence of crystalline nickel oxide for samples that were annealed
at 350
C and above this temperature. Similar XRD patterns
were reported earlier for nickel oxides.32,33 The peaks obtained
cantered around (ca.) 37
2q (111), 43
2q (200), and 62.8
2q
(220) conrms the cubic NiO (ICSD#01-073-1523), which agrees
well with the standard values.34 No X-rays diffraction (XRD)
peaks corresponding to NiO were observed in the as-deposited
lms neither in the lms heated at 100
C and 200
C. These
results show that the freshly electrodeposited lms were
amorphous in nature and crystallinity was achieved in the lms
that were annealed at temperatures $ 350
C. The supporting
electrolyte (KCl) peaks were denoted by oval in Fig. 3. Later on,
the TGA/DTA data conrm the amorphous / crystalline tran-
sition in the NiO(ED) lms that occurs at temperatures $ 350
C.
The electrodeposited NiO(ED) lms and the lms that were
subjected to heat treatment at 100
C and 200
C are deemed to
be amorphous in nature and the presence of bound water might
stop the nickel oxide phase to achieve the true crystalline phases
in the as-deposited thin lms (NiO(ED)) or in the lms that were
heat treated at 100
C (NiO(ED)-100) and 200
C (NiO(ED)-200).34
In a visual examination, the electrodeposited NiO(ED) lms
were green in colour and a colour change from green to black
was observed when NiO(ED) lms were heat treated at the
temperatures  350
C and 400
C. This black colour is attrib-
uted to the non-stoichiometric NiO (indicating that the Ni : O
ratio deviates from 1 : 1).35 Typically, the stoichiometrically
correct NiO is green in colour (Ni : O ratio of 1 : 1) as was
observed in the electrodeposited NiO(ED) lms, while the colour
change from green to black in NiO(ED)-400 indicate towards the
development of non-stoichiometric NiO aer heat treatment at
this temperature.
Fig. 4(a) displays the XRD patterns of electrodeposited nickel
metal (Ni) and the nickel oxide lms formed by the heat treat-
ment of the electrodeposited nickel metal at 600, 700 and 800
C.
The Fig. 4(b) shows the XRD pattern of nickel oxide formed by the
same method at 900
C. The XRD peaks ca. 37
, 43
and 62.8
2q
exhibit the presence of cubic nickel oxide (ICSD#01-073-1523)
phase along with the peaks due to the metallic fcc nickel
(ICSD#01-070-1849) just above 44
, 51.8
and 76.3
2q due to
(111), (200) and (220) lattice planes respectively.36
The electrodeposited nickel (metal) layer had a silvery lustre.
Heat treatment at 600
C and 700
C changed the appearance of
the metallic Ni to light green (suggesting the formation of NiO).
Upon further heat treatment of this lm till 800
C caused
a colour change from green to black, which was due to the
formation of composite electrode (nickel oxide and iron oxide)
as shown in the XRD pattern of the NiO(HA)-800 in Fig. 4(a). The
XRD peaks generated due to the formation of iron oxides
(ICSD#01-089-0598) in NiO(HA)-800 sample is represented by
oval shape in Fig. 4(a). At temperature as high as 900
C, the
reaction between electroplated nickel and underneath iron
from stainless steel caused the formation of nickel ferrite, as
can be seen from the XRD pattern of NiO(HA)-900 (Fig. 4(b))
(ICSD#067846). While heating the NiO lms from 600
C to
800
C, an increase in the peak intensity corresponding to
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Fig. 4 (a). XRD patterns recorded for electrodeposited metallic Ni,
NiO(HA)-600, NiO(HA)-700 and NiO(HA)-800, (b) XRD pattern of elec-
trodeposited NiO(HA)-900.
nickel oxide lms, while a concomitant decrease in the peak
intensity for metallic nickel can also be seen at the same time. It
was also observed that the electrodeposited metallic Ni layer on
mild steel substrate does not change to nickel oxide, if heated
below 600
C. The XRD analysis shows only peaks from metallic
Ni for the samples heated below 600
C. Therefore, 600
C is the
minimum temperature required to convert the electroplated
metallic nickel into nickel oxide (NiO).
Thermal analysis
Fig. 5 shows the TGA and DTA traces of the electrodeposited
nickel oxide (NiO(ED)) lm. The TGA curve (blue) shows that
below 400
C, the weight loss (%) occurred in two major steps.
The rst weight loss step in TGA (spanned from 60
C to 200
C)
can be correlated to the rst endothermic peak on DTA, which
indicate towards the removal of structural water present in the
as-deposited lms of NiO(ED). A study by Zhou, Macfarlane and
co-workers showed that the heat treatment of manganese oxide
(MnOx) lms electrodeposited from aqueous electrolytes show
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Fig. 5 TGA and DTA traces of the electrodeposited nickel oxide
(NiO(ED)) film. The NiO(ED) films was scratched from the FTO substrate,
and was loaded into the aluminium pan that was hermetically sealed
prior to run TGA/DTA experiment.
remarkable improvement in catalytic water oxidation, primarily
due to the loss of structural water.37 A few other metal oxides
also showed similar effects of heat treatment as reported
earlier.38 Fig. 5 shows that the wt loss (%) due to the removal of
bound water was around 13% upto 200
C. Earlier, it has been
reported that a characteristics wt loss due to the removal of
water from electrodeposited nickel hydroxide (Ni(OH)2) occurs
around 250–350
C that accompanies endothermic peak.38
However, in our work, the second weight loss peak on TGA trace
started above 350
C, and was accompanied by the corre-
sponding exothermic peak in DTA curve. This wt loss peak in
TGA along with the exothermic peak in DTA can be attributed to
the removal of water from nickel oxide (NiO(ED)) with
a concomitant phase transformation, as was observed in the
case of amorphous / crystalline transition of CeOx.39 The TGA/
DTA results therefore suggest the likely presence of amorphous
nickel oxide along with the bound water in the electrodeposited
(NiO(ED)) lm, while the presence of amorphous (Ni(OH)2)
cannot be excluded just on the basis of these TGA/DTA results.
In the next section, FTIR results throw more light on the pres-
ence of both nickel oxide (NiO) and nickel hydroxide (Ni(OH)2)
in addition to bound water in these electrodeposited (NiO(ED))
catalyst lms.
FTIR analysis
Fig. 6 shows the FTIR spectra of electrodeposited nickel oxide
(NiO(ED)) and heat treated lms (NiO(ED)-100, NiO(ED)-200,
NiO(ED)-350 and NiO(ED)-400) within the frequency range of 400–
4000 cm1. We can see that the NiO(ED) lm didn't show sharp
intense bands compared to NiO(ED)-100, NiO(ED)-200, which
could be due to the presence of bulk water that was randomly
distributed in the freshly electrodeposited nickel oxide (NiO(ED))
lm. The only IR peaks that were fairly observable in the NiO(ED)
lm (3435 and 1594 cm1) were mainly from the water mole-
cules. At this point, it is important to correlate the behaviour of
the electrodeposited NiO(ED) lm with the heat treated lms in
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Fig. 6 FTIR spectra of NiO(ED), NiO(ED)-100, NiO(ED)-200 and NiO(ED)-
350 and NiO(ED)-400 recorded over the frequency range of 400–
4000 cm1.
the light of various techniques used in this study. The thermal
studies using TGA/DTA (Fig. 5) suggest that the NiO(ED) lm
contained the maximum amount of water compared to the heat
treated lms, while the morphology studies using SEM (Fig. 7)
shows no clear morphology for this lm. These observations on
the (NiO(ED)) were nally reected by poor catalytic performance
of this lm, where the Linear Sweep Voltammetry (LSV) plot
(Fig. 9(a)) shows the lowest current densities for water oxidation
achieved by this lm. In contrast, the FTIR spectra of NiO(ED)-
Fig. 7 SEM images of electrodeposited nickel oxide (NiO(ED)) and the
heat treated nickel oxide films (NiO(ED)-100, NiO(ED)-200, NiO(ED)-350
and NiO(ED)-400).
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100, NiO(ED)-200 show several intensive bands at different
frequencies viz. 453, 663, 1111, 1404, 1594 and 3435 cm1. The
broad peak observed at 3435 cm1 in the FTIR spectra of these
lms can be attributed to the stretching vibration of the
hydrogen bonded water, while the intense peak at 1594 cm1
corresponds to the bending vibration of water in these lms.
The high intensity of the –OH group peaks in NiO(ED)-100,
NiO(ED)-200 lms suggest that the heat treatment improved the
hydrogen bonding networks in these lms. It seems that the le
over water in these lms adopted some order, which could be
more likely the water of crystallisation. Another important peak
in these lms around 453 cm1 can be assigned to the
stretching vibration of nickel to oxygen bond,40 which could be
due to either nickel hydroxide or nickel oxide phases. The
hydroxide phase (Ni(OH)2) was also conrmed by the peak at
667 cm1.41 Other IR peaks conrm the presence of chloride
and hydroxyl ions present in these lms.
As a matter of fact, the FTIR spectrum didn't give enough
information on how much nickel hydroxide was converted to
nickel oxide with the increase in annealing temperature from
100
C to 400
C. Fig. 6 shows that there was no observable
difference in the FTIR spectra of NiO(ED)-350 and NiO(ED)-400
catalyst lms, beside the fact that the amorphous / crystalline
phase transition occur at temperatures $ 350
C. The FTIR peak
for nickel to oxygen bond, which appeared at 453 cm1 in
NiO(ED)-100 and NiO(ED)-200 samples couldn't be observed in
NiO(ED)-350 and NiO(ED)-400 lms. However, the XRD analysis
(Fig. 3) described above clearly indicates the emergence of NiO
(111) and NiO (200) phases in the NiO(ED)-350 and NiO(ED)-400
catalyst lms. We can also see that the IR spectra for NiO(ED)-350
and NiO(ED)-400 exhibited relatively low intensity for –OH
groups stretching and bending vibration (3435 cm1 and 1594
cm1), which can be explained by the loss of water (as shows by
TGA analysis (Fig. 5)) and transformation of Ni(OH)2 to NiO as
shown by XRD studies (Fig. 3).
In summary, the IR spectra reveal that the NiO(ED), NiO(ED)-100
and NiO(ED)-200 contain signicant amount of water compared to
NiO(ED)-350 and NiO(ED)-400 samples. The improved hydrogen
bonding network in NiO(ED)-100 and NiO(ED)-200 lms by heat
treatment indicate that the remaining water has adopted some
order, more likely in the form of water of crystallization. In short,
the FTIR study could only help to differentiate the amount and
nature of water in these lms. This technique was not found
enough sensitive to clearly identify the presence of amorphous
and crystalline phases in these catalyst lms.
Microstructure of NiO lms
Fig. 7 shows the scanning electron microscopy (SEM) images of
the thin lms of electrodeposited nickel oxide (NiO(ED)) and
heat treated nickel oxide lms viz. NiO(ED)-100, NiO(ED)-200 and
NiO(ED)-350 and NiO(ED)-400. We can see that the NiO(ED) lm
couldn't achieve a clear morphology, probably due to the pres-
ence of large quantity of bound water in this material. However,
the cracks can be seen in this lm, as the NiO(ED) was dried
before taking the SEM images. This cracked nature of the
NiO(ED) lm is attributed to the contraction upon drying due to
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the tensile stress. Earlier, it has been reported that the lms
with thickness above 0.2 micron usually show cracked struc-
ture.42 Similar observation was reported earlier for electro-
chemically deposited thin lms of zirconia43 and molybdenum
oxide that were electrodeposited under galvanostatic condi-
tions.44 A granular and dense morphology was observed for
heat-treated thin lms. The NiO(ED)-100 lm exhibited a loose
morphology with granular shaped nickel oxide particles. This
kind of loose structure provides high surface area for catalytic
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water splitting.45 Agglomeration of particles was observed for
the lms of NiO(ED)-200 and NiO(ED)-350. This agglomeration
became further dense upon heat treatment of these nickel oxide
lms. The NiO(ED)-400 lm contains bulk of crystalline nickel
oxide comparing to other lms thereby showing somewhat
different morphology.
For the nickel oxide (NiO(HA)) lms that were prepared via
high temperature annealing of electroplated nickel metal, clear
morphological changes were observed upon annealing from
600
C to 900
C (Fig. 8). The changes in morphology were
probably due to the different phases present in the lms, which
have their origin in different annealing temperatures. The pres-
ence of other phases in NiO(HA)-800 and NiO(HA)-900 was also
indicated by the XRD patterns of these lms (Fig. 4(a) and (b)).
Further conrmation for the presence of metallic nickel in
the NiO(HA)-600, NiO(HA)-700 and NiO(HA)-800 is evident from the
EDX analysis of these nickel oxide lms, while the presence of
iron oxide in addition to nickel oxide was also conrmed by the
EDX analysis of NiO(HA)-800 and NiO(HA)-900 lms. The EDX
analysis supported the XRD results in identifying the presence
of other impurities in these NiO(HA) lms.
Electrochemical analysis
The catalytic activities of the electrodeposited NiO(ED) lms
were examined by linear scan voltammetry (LSV) in 1 M
NaOH(aq.) at the scan rate of 5 mV s1. Fig. 9 shows that the thin
Fig. 8 SEM images of NiO(HA)-600, NiO(HA)-700, NiO(HA)-800 and
NiO(HA)-900 films prepared by hot air annealing of electrodeposited
nickel film on stainless steel substrate.
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RSC Advances
lm of NiO(ED)-400 catalyst (prepared by the heat treatment of
electrodeposited NiO(ED) lms at 400
C) achieved appreciable
current density  5 mA cm2 at the overpotential of 0.45 V vs.
RHE for water oxidation. On the other hand, the as-deposited
NiO(ED) lm could generate only small currents. We can
expect this kind of behaviour, since the as-deposited NiO(ED)
lm was highly amorphous with signicant amount of bound
water in it. In contrast to the as deposited lm, the heat treated
nickel oxide lms viz. NiO(ED)-100 and NiO(ED)-200 lms showed
improvements in currents densities for water oxidation (Fig. 9).
It is interesting to note that the XRD patterns of these lms
(Fig. 3) didn't show any peaks that indicate the presence of
crystalline nickel oxide. However, if we consult the TGA/DTA
results, we can see that these lms did loose water upon heat-
ing. Hence, regardless of the fact that NiO(ED)-100 and NiO(ED)-
200 lms didn't exhibit any improvement in the crystallinity
(based on XRD results), the improved current densities
observed for these lms indicate that the removal of water by
heat treatment had a positive effect on the catalytic perfor-
mances of these electrocatalyst NiO(ED) lms. Previously, D. R.
MacFarlane and co-workers reported similar observations of
improved catalytic performances for manganese oxides lms
(MnOx)46 aer heat treatment. Nevertheless, crystallinity always
is not a direct indicative of the better catalytic performance. In
past, catalytic activity of cobalt oxides (CoOx) lms was found to
decrease with increase in crystallinity of the material.45 Fig. 9(a)
also shows that the NiO(ED)-100 and NiO(ED)-200 achieved less
current densities for OER than NiO(ED)-350 and NiO(ED)-400
beside the fact that the value of Tafel slopes for NiO(ED)-100 was
96 mV per decade and for NiO(ED)-200 was 135.7, which were
lower than 210 mV per decade for NiO(ED)-350 and 136.4 mV per
decade for NiO(ED)-400. In principle, a lowering in the Tafel
slope value is an indicative of the better catalytic activity of any
catalyst materials. Though, the NiO(ED)-100 and NiO(ED)-200
showed relatively low values of Tafel slope, the occurrence of
water in these catalyst lms (shown by TGA/DTA) might be
responsible for their loose amorphous structure and such
materials oen undergo mechanical degradation, when elec-
trochemical reactions take place at the catalyst surface. Method
of preparation and durability of material are also found to affect
the electrochemical properties of many water oxidation
catalysts.8
Fig. 9 (a) Linear Sweep Voltammetry (LSV) and (b) Tafel plots of
electrochemically as-deposited and heat treated nickel oxide (NiO(ED))
films in 1 M NaOH at the scan rate of 5 mV s1. The subscript “ED”
stands for electrodeposited samples.
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The materials prepared at high temperatures usually posses
better crystallinity, less defective structure and corresponding
higher catalytic activity compared to the amorphous ones that
are oen obtained at low temperature.8,47,48 Fig. 9(b) shows that
the NiO(ED)-400 lm prepared at temperature above amorphous
/ crystalline phase transition exhibited a Tafel slope value 
136.7 mV per decade. This value of Tafel slope was close to that
for NiO(ED)-200 and even higher than that for as synthesized
NiO(ED) lm. A close inspection of Fig. 9(a) shows that the onset
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value for OER was lowest in the case of NiO(ED)-400 and the
same material achieved the highest current density for OER
among all other samples. It seems that the crystalline NiO(ED)-
400 lm exhibits the best catalytic performance among all other
electrodeposited nickel oxide lms.
A closer look at the LSVs of these NiO(ED) lms in Fig. 9(a), we
can see a small oxidation phenomenon at or just above 1.4 V vs.
RHE. Previously, the water oxidation studies of nickel oxide
lms suggest that this phenomenon corresponds to the oxida-
tion of Ni2+ to Ni3+ in alkaline media and can be indicated by the
following equation.31
NiO + xOH1 / NiOOH + xe1
By observing the physical appearance of the electrodeposited
nickel oxide lms, we found that the NiO(ED)-100 and NiO(ED)-
200 lms were light green in colour initially, which later con-
verted to brownish grey, when these electrodes were subjected
to water oxidation in 1 M NaOH(aq.) solution. Previously, it is
reported that this brownish grey colour is due to the formation
of nickel oxy hydroxide (NiOOH),31 which is a highly conductive
material and contains signicantly high number of active sites
for OER.49–51 In contrast to as-deposited NiO(ED), NiO(ED)-100
and NiO(ED)-200 lms, the NiO(ED)-350 and NiO(ED)-400 were
already dark grey in colour and hence no clear change in colour
was observed during OER; the high current density achieved by
these high temperature NiO lms can therefore be attributed to
the water removal and high crystallinity of these catalyst
materials. In addition, the possible formation of NiOOH during
water electrolysis and its contribution towards OER can't be
ignored for NiO(ED)-350 and NiO(ED)-400 lms. Further studies
are required to investigate the current generated due to the
oxidation of Ni2+ to Ni3+ with the possible formation of NiOOH
and its contribution in the OER for these NiO electrocatalysts
lms.
Revisiting the LSVs in Fig. 9(a), the second onset of potential
above 1.6 V vs. RHE can be assigned to the OER, which agreed
well with the previously reported values for OER using NiO
electrocatalysts lms.52 Here, we can see that the NiO(ED)-400
catalyst (prepared by the heat treatment of as-deposited NiO(ED)
lms at 400
C) achieved appreciable current density  5 mA
cm2 at the overpotential of 0.45 V vs. RHE for OER.
In parallel investigations, we also studied the electro-
chemical behaviour of as deposited Ni (metal) and nickel
oxide (NiO) lms, where the NiO lms were formed by the
oxidation of initially deposited Ni layer on stainless steel (SS)
substrate. Fig. 10(a) shows the LSVs and Fig. 10(b) shows the
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Paper
Fig. 10 (a) Linear Sweep Voltammetry (LSV) and (b) Tafel plots of pure
nickel (Ni) and nickel oxide (NiO(HA)) films in 1 M NaOH(aq.) at the scan
rate of 5 mV s1. The subscript “HA” stands for hot air annealed
samples.
corresponding Tafel plots of electroplated nickel (Ni) metal and
nickel oxide lms prepared by the heat treatment of electrode
plated metallic Ni layer at 600, 700, 800 and 900
C. Fig. 10(a)
shows that the electrode with metallic Ni layer achieved the
highest current density with lowest overpotential for OER,
which could be due to the excellent corrosion resistance prop-
erties of Ni metal itself in alkaline media. We can also see that
the nickel oxides viz. NiO(HA)-600, NiO(HA)-700, NiO(HA)-800 and
NiO(HA)-900 display low current density values for OER
compared to the metallic Ni. Among these nickel oxide based
electrocatalysts lms, the NiO(HA)-900 exhibited the highest
value of overpotential and lowest current density, which could
be due to the presence of signicant amount of iron oxide in
NiO(HA)-900 sample.
In contrast, NiO(HA)-600 showed lowest overpotential among
other oxides, while NiO(HA)-800 displayed the lowest Tafel slope
value. It was worth noticeable that the NiO(HA)-800, which con-
tained nickel oxide as the major fraction (as indicated by XRD
analysis) still showed high overpotential and low current
density for OER (Fig. 10(a)). If we compare these results with
NiO(HA)-900, it can be concluded that the inclusion of iron oxide
has a negative impact on the electrocatalytic properties of these
NiO based catalyst lms for OER. As the concentration of iron
oxide increases (such as in NiO(HA)-900), the overpotential for
OER also increases accordingly. These results also indicate that
the iron oxide phases formed in this way are poor catalyst
materials compared to the pure nickel oxides phases for oxygen
evolution reaction (OER).
Another important observation in the LSVs of the metallic
nickel and the nickel oxides (prepared by oxidation of Ni) shown
in Fig. 10(a) is a single oxidation phenomenon, which is more
likely the OER. The rst oxidation phenomenon observed in the
nickel oxide lms (NiO(ED), NiO(ED)-100, NiO(ED)-200, NiO(ED)-
350 and NiO(ED)-400) that corresponds to the oxidation of Ni2+ to
Ni3+ in alkaline media was not observed in the LSVs of metallic
nickel (Ni) and the nickel oxide lms (NiO(HA)-600, NiO(HA)-700,
NiO(HA)-800 and NiO(HA)-900). To our understanding, the
absence of rst oxidation phenomenon in the later cases
suggests that the nickel oxides prepared by the heat treatment
of metallic nickel is not pure in nature but a mixture of pure
metal and metal oxides. The oxidation of Ni2+ to Ni3+ and the
concomitant formation of nickel oxy hydroxide (NiOOH), which
was found to accelerate the oxygen evolution reaction (OER) in
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Paper
case of pure nickel oxides (formed by Scheme 1) seem to be
absent in these NiO(HA) lms (formed by Scheme 2). A plausible
explanation for the absence of this oxidation process is that the
water oxidation at metallic nickel dominates the other electro-
chemical phenomena (water oxidation at nickel oxide surface),
which can be evidenced from the fact that all electrocatalysts
lms prepared by Ni oxidation (NiO(HA)-600, NiO(HA)-700,
NiO(HA)-8000 and NiO(HA)-900) formed from the oxidation of
metallic nickel layer followed the same trend as shown by
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metallic nickel lm itself (Fig. 10(a)). Since, metallic nickel was
present in almost all these nickel oxide lms, the dominant
process of OER at the metallic nickel might inhibit the oxida-
tion of Ni2+ to Ni3+ in the nickel oxide fraction of these lms.
Conclusions
Herein, we prepared nickel oxide (NiO(ED)) lms on the FTO
substrate by cathodic electrodeposition in aqueous electrolyte
media. The NiO(ED) lms aer facile heat treatment showed
signicant improvements for catalytic water oxidation. In
particular, the NiO(ED)-400 lm achieved appreciable current
density  5 mA cm2 for oxygen evolution reaction (OER) at the
overpotential of 0.45 V vs. RHE. The electrocatalyst lms
NiO(ED)-100 and NiO(ED)-200 contain signicant quantity of
nickel hydroxide and therefore showed poor catalytic activities
for water oxidation. In contrast, the NiO(ED)-350 and NiO(ED)-400
lms, which contained more nickel oxide fraction compared to
the hydroxide phase exhibited improved catalytic performances
for OER. The detailed investigations of the physiochemical and
electrochemical properties of these electrodeposited and heat
treated nickel oxide lms reveal that the heat treatment
primarily caused the permanent loss of structural water along
with amorphous / crystalline transformation in these NiO(ED)
lms, especially when heated at temperatures $ 350
C. In
parallel development, we also prepared the NiO(HA) lms by rst
electroplating metallic nickel layer on a stainless-steel
substrate, followed by the annealing of electroplated Ni layer
in hot air. The results reveal that the NiO(HA) lms formed by
this method were impure in nature and consist of a mixture of
Ni metal and mixed metal oxides. The NiO(HA) lms formed this
way showed higher overpotentials, indicating poor catalytic
performances of these catalyst lms for water oxidation.
Acknowledgements
U. A. Rana would like to extend his sincere appreciation to the
Deanship of Scientic Research at the King Saud University for
its funding of this research through the Prolic Research
Group, Project No. PRG-1436-18.
References
1 T. Abbasi and S. A. Abbasi, Renewable Sustainable Energy Rev.,
2011, 15, 3034–3040.
2 S. U. M. Khan, M. Al-Shahry and W. B. Ingler, Science, 2002,
297, 2243–2245.
This journal is © The Royal Society of Chemistry 2015
View Article Online
RSC Advances
3 V. Artero, M. Chavarot-Kerlidou and M. Fontecave, Angew.
Chem., Int. Ed., 2011, 50, 7238–7266.
4 P. Zegers, J. Power Sources, 2006, 154, 497–502.
5 H. Dau, C. Limberg, T. Reier, M. Risch, S. Roggan and
P. Strasser, ChemCatChem, 2010, 2, 724–761.
6 F. A. Frame, T. K. Townsend, R. L. Chamousis, E. M. Sabio,
T. Dittrich, N. D. Browning and F. E. Osterloh, J. Am. Chem.
Soc., 2011, 133, 7264–7267.
7 A. Mills, P. A. Duckmanton and J. Reglinski, Chem. Commun.,
2010, 46, 2397–2398.
8 A. Izgorodin, O. Winther-Jensen and D. R. MacFarlane, Aust.
J. Chem., 2012, 65, 638–642.
9 F. Zhou, A. Izgorodin, R. K. Hocking, L. Spiccia and
D. R. MacFarlane, Adv. Energy Mater., 2012, 2, 1013–1021.
10 M. Nakayama, A. Tanaka, Y. Sato, T. Tonosaki and K. Ogura,
Langmuir, 2005, 21, 5907–5913.
11 G. F. Swiegers, D. R. MacFarlane, D. L. Officer, A. Ballantyne,
D. Boskovic, J. Chen, G. C. Dismukes, G. P. Gardner,
R. K. Hocking, P. F. Smith, L. Spiccia, P. Wagner,
G. G. Wallace, B. Winther-Jensen and O. Winther-Jensen,
Aust. J. Chem., 2012, 65, 577–582.
12 P. Du and R. Eisenberg, Energy Environ. Sci., 2012, 5, 6012–
6021.
13 F. E. Osterloh, Chem. Mater., 2007, 20, 35–54.
14 E. Azaceta, S. Chavhan, P. Rossi, M. Paderi, S. Fantini,
M. Ungureanu, O. Miguel, H.-J. Grande and R. Tena-Zaera,
Electrochim. Acta, 2012, 71, 39–43.
15 M. Wu, Y. Huang, C. Yang and J. Jow, Int. J. Hydrogen Energy,
2007, 32, 4153–4159.
16 F. Vera, R. Schrebler, E. Muñoz, C. Suarez, P. Cury,
H. Gómez, R. Córdova, R. E. Marotti and E. A. Dalchiele,
Thin Solid Films, 2005, 490, 182–188.
17 X. Hou, J. Williams and K.-L. Choy, Thin Solid Films, 2006,
495, 262–265.
18 R. Cerc Korosec and P. Bukovec, Acta Chim. Slov., 2006, 53,
136–147.
19 A. El-Shaer, A. R. Abdelwahed, A. Tawk, M. Mossad and
D. Hemada, International Journal of Emerging Technology
and Advanced Engineering, 2014, 4, 595–602.
20 G. Wu, N. Li, D.-R. Zhou, K. Mitsuo and B.-Q. Xu, J. Solid
State Chem., 2004, 177, 3682–3692.
21 M. Gong and H. Dai, Nano Res., 2015, 8, 23–39.
22 A. K. M. Fazle Kibria and S. A. Tarafdar, Int. J. Hydrogen
Energy, 2002, 27, 879–884.
23 G. Wu, N. Li, D.-R. Zhou, K. Mitsuo and B.-Q. Xu, J. Solid
State Chem., 2004, 177, 3682–3692.
24 E. B. Castro and C. A. Gervasi, Int. J. Hydrogen Energy, 2000,
25, 1163–1170.
25 I. J. Godwin, R. L. Doyle and M. E. G. Lyons, J. Electrochem.
Soc., 2014, 161, F906–F917.
26 P. Moller, J. B. Rasumussen, S. Kohler and L. P. Nielsen,
NASF, 2013, 78, 15–24.
27 E. Azaceta, N. T. Tuyen, D. F. Pickup, C. Rogero, J. E. Ortega,
O. Miguel, H.-J. Grande and R. Tena-Zaera, Electrochim. Acta,
2013, 96, 261–267.
28 A. C. Sonavane, A. I. Inamdar, P. S. Shinde, H. P. Deshmukh,
R. S. Patil and P. S. Patil, J. Alloys Compd., 2010, 489, 667–673.
RSC Adv., 2015, 5, 86713–86722 | 86721

RSC Advances
29 A. Singh, S. L. Y. Chang, R. K. Hocking, U. Bach and
L. Spiccia, Catal. Sci. Technol., 2013, 3, 1725–1732.
30 Y. Zhao, R. Nakamura, K. Kamiya, S. Nakanishi and
K. Hashimoto, Nat. Commun., 2013, 4, 1–7.
31 A. C. Sonavane, A. I. Inamdar, P. S. Shinde, H. P. Deshmukh,
R. S. Patil and P. S. Patil, J. Alloys Compd., 2010, 489, 667–673.
32 Y. Sato, M. Ando and K. Murai, Solid State Ionics, 1998, 113,
443–447.
33 S. Z. F. Rodzi and Y. Mohd, in Humanities, Science and
Published on 06 October 2015. Downloaded by SUNGSIL UNIVERSITY on 10/5/2018 9:44:08 AM.
Engineering Research (SHUSER), 2012 IEEE Symposium,
2012, pp. 531–535.
34 K.-W. Nam and K.-B. Kim, J. Electrochem. Soc., 2002, 149,
A346–A354.
35 D. Mohammadyani, S. A. Hosseini and S. K. Sadrnezhaad,
Int. J. Mod. Phys.: Conf. Ser., 2012, 05, 270–276.
36 K. J. A. raj and B. Visnathan, Indian J. Chem., Sect. A: Inorg.,
Bio-inorg., Phys., Theor. Anal. Chem., 2011, 50, 176–179.
37 F. Zhou, A. Izgorodin, R. K. Hocking, V. Armel, L. Spiccia and
D. R. MacFarlane, ChemSusChem, 2013, 6, 643–651.
38 H.-Y. Wu and H.-W. Wangint, J. Electrochem. Sci. Eng., 2012,
7, 4405–4417.
39 M. L. Dos Santos, R. C. Lima, C. S. Riccardi, R. L. Tranquilin,
P. R. Bueno, J. A. Varela and E. Longo, Mater. Lett., 2008, 62,
4509–4511.
86722 | RSC Adv., 2015, 5, 86713–86722
View Article Online
Paper
40 S. Mochizuki, Phys. Status Solidi B, 1984, 126, 105–114.
41 A. Šurca, B. Orel and B. Pihlar, J. Solid State Electrochem.,
1998, 2, 38–49.
42 I. Zhitomirsky and A. Petric, Mater. Lett., 2000, 46, 1–6.
43 X. Pang, I. Zhitomirsky and M. Niewczas, Surf. Coat. Technol.,
2005, 195, 138–146.
44 R. S. Patil, M. D. Uplane and P. S. Patil, Appl. Surf. Sci., 2006,
252, 8050–8056.
45 B. H. R. Suryanto, X. Lu, H. M. Chan and C. Zhao, RSC Adv.,
2013, 3, 20936.
46 F. Zhou, A. Izgorodin, R. K. Hocking, V. Armel, L. Spiccia and
D. R. Macfarlane, ChemSusChem, 2013, 6, 643–651.
47 S. Trassati, Electrochim. Acta, 1984, 29, 1503.
48 B. S. Yeo and A. T. Bell, J. Am. Chem. Soc., 2011, 133, 5587–
5593.
49 M. E. G. Lyons and M. P. Brandon, Int. J. Electrochem. Sci.,
2008, 3, 1386–1424.
50 J. McBreen, in Handbook of Battery Materials, Wiley-VCH
Verlag GmbH, 2007, pp. 135–151.
51 P. W. T. Lu and S. Srinivasan, J. Electrochem. Soc., 1978, 125,
1416.
52 I. M. Sadiek, A. M. Mohammad, M. E. E. Shakre, M. S. E.-D.
M. Ismail Awad and E. El-Anadouli, Int. J. Electrochem. Sci.,
2012, 7, 3350–3361.
This journal is © The Royal Society of Chemistry 2015