i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 2 ( 2 0 1 7 ) 5 2 3 5 e5 2 4 5

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Electrochemical hydrogen storage capacity and

optical properties of NiAl2O4/NiO nanocomposite
synthesized by green method

Tahereh Gholami, Masoud Salavati-Niasari*, Shokufeh Varshoy

Institute of Nano Science and Nano Technology, University of Kashan, Kashan, P.O. Box. 87317, 51167, Islamic
Republic of Iran

article info abstract

Article history: In this work, we successfully prepare NiAl2O4/NiO nanocomposite with thermal decom-
Received 7 September 2016 position method by using green tea extract (GTE) as precipitating agent. The biosynthesized
Received in revised form NiAl2O4/NiO nanocomposite characterize using X-ray energy dispersive spectroscopy
19 October 2016 (EDS), X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FT-IR), scanning
Accepted 22 October 2016 electron microscopy (SEM), N2 adsorption (BET), ultravioletevisible (UVeVis) spectroscopy,
Available online 21 November 2016 and transmission electron microscopy (TEM). Also, we study the electrochemical hydrogen
storage properties of NiAl2O4/NiO nanocomposite porous with different calcination tem-
Keywords: perature. The discharge capacity of samples with calcination temperature 700, 800 and
Nanostructures 900
C are 450, 325 and 800 mAh/g after 15 cycles, respectively.
Green tea extract © 2016 Hydrogen Energy Publications LLC. Published by Elsevier Ltd. All rights reserved.
Hydrogen storage
Discharge capacity
Mesoporous

Compared with the conventional high pressure-low tem-

Introduction
Hydrogen is a carrier of clean energy (nonpolluting nature)
and high energy density, so it's regarded as an ideal and the
environmentally friendly fuel for many energy converters [1].
The development of a cheap, safe and simple storage method
is an imperative condition for the widespread usage of
hydrogen as a popular alternative to fuel oils (diesel, petrol,
etc.), especially for electrical vehicles [2]. Hydrogen is stored in
hydrogen storage materials different ways such as, physical
[3], chemical [4] and electrochemical methods [5].
As compared to conventional low temperatureehigh
pressure hydrogen storage technology, electrochemical
hydrogen storage has been proved as elegant and more effi-
cient at ambient pressure and temperature.
perature hydrogen storage techniques, electrochemical
hydrogen storage in porous materials has been proved as more
efficient at ambient pressure and temperature, as well as the
hydrogen adsorption process occurs directly in electrode ma-
terial during the electrochemical decomposition of an aqueous
solution [6]. One of the most difficult challenges is research for
effective hydrogen-storage materials, this difficulty motivate
scientist to do research on the hydrogen-powered society for
solution to energy problems [7]. To data, many storage media
have been developed to uptake hydrogen such as graphite [8],
metaleorganic frameworks [9], metal alloys, hydride com-
pounds [10] and carbon nanotubes [11]. We are trying to use
new and cheaper materials with high capacity for hydrogen
storage. Metal oxides are interesting, low toxicity, and low cost
energy storage materials for electrochemical capacitor

* Corresponding author. Fax: þ98 31 55913201.

E-mail address: salavati@kashanu.ac.ir (M. Salavati-Niasari).
http://dx.doi.org/10.1016/j.ijhydene.2016.10.132
0360-3199/© 2016 Hydrogen Energy Publications LLC. Published by Elsevier Ltd. All rights reserved.
5236 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 2 ( 2 0 1 7 ) 5 2 3 5 e5 2 4 5
applications. The NiAl2O4/NiO nanostructures has been used in
different application such as chemical-looping combustor [13],
catalysts [14], pigments [15], anodes for SOFCs [16], refractories
[17] and luminescent materials [18] because of its high thermal
stability and specific catalytic properties [12]. NiAl2O4/NiO
nanostructure have been prepared using different methods,
such as sol gel [19], solid looping reactants of metal oxides [20],
co-precipitation [21] and solidestate reaction [22], etc.
In this work, green synthesis of NiAl2O4/NiO nano-
composite with thermal decomposition method, that is not
harmful to human health and is low cost, has been reported.
This should be mentioned for the first time, the NiAl2O4/NiO
nanocomposite porous has been used for hydrogen storage
that is useful for the environment.
Experimental
Materials and measurements
All chemical reagents in this study were used in analytical
grade and used as received without further purification. XRD
Fig. 1 e Schematic flow chart for the synthesis of NiAl2O4/NiO nanocomposite.
patterns were recorded by a Rigaku D-max C III, X-ray
diffractometer using Ni-filtered Cu Ka radiation. The NiAl2O4/
NiO ratio was determined by X-ray fluorescence measure-
ments (XRF; Supermini, Rigaku Co. Ltd.). SEM images were
obtained using a Philips XL30 ESEM equipped with a field
emission gun and an energy dispersive spectroscopy detec-
tor. Elemental analyses were carried out with Carlo ERBA
Model EA 1108 analyzer. FT-IR spectra were recorded by
using a Shimadzu Varian 4300 FT-IR spectrophotometer
using KBr discs. UVeVis spectroscopy (diffuse reflectance)
carried out with a Shimadzu UV/3101 PC in a range between
200 and 800 nm. GC-2550TG (Teif Gostar Faraz Company,
Iran) were used for all chemical analyses. The EDS analysis
with 20 kV accelerated voltage was done. Bru-
nauereEmmetteTeller (BET) N2 adsorption/desorption anal-
ysis was carried out at 77 K using an automated gas
adsorption analyzer (Tristar 3000, Micromeritics). The pore
size distribution (PSD) was determined from desorption
branch of the isotherm by the Barrett, Joyner and Halenda
(BJH) technique. TEM image was carried out with a Philips
EM208 TEM operating at 200 kV.
 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 2 ( 2 0 1 7 ) 5 2 3 5 e5 2 4 5
Synthesis of NiAl2O4/NiO nanocomposite
All the chemical reagents for nickel aluminate nanostructures
synthesis such as Ni(NO3)2$6H2O, methanol and
Al(NO3)3$9H2O were purchased from Merck and used as
received. In a typical process, a mixed solution of metal ni-
trates was prepared by dissolving Al(NO3)3$9H2O and
Ni(NO3)2$6H2O in water with the molar ratio of Ni2þ/Al3þ ¼ 1:2.
Then, 20 ml green tea extract was added. This mixture was
heated at 80
C for 1 h with continuous stirring so that the ions
react. The obtained solution was evaporated on a hot plate at
120
C for dehydration and continued until powder was ob-
tained. Finally, this powder was calcined in various temper-
atures. Fig. 1 shows schematic for the synthesis of NiAl2O4/
NiO nanocomposite powder.
Electrochemical systems
Chronopotentiometry technique was employed to measure
the hydrogen storage capacity of the electrodes. The charge
and discharge cycles was performed by a three-electrode
system. The CueNiAl2O4/NiO, Ag/AgCl and Pt electrodes are
as the working, reference and counter electrodes, respec-
tively. The electrolyte was 6 M KOH aqueous solution. In this
system, the potential difference was measured between the
Fig. 2 e XRD patterns of NiAl2O4/NiO nanocomposite (a) Ta, (b) Tb, and (c) Tc.
5237
working and the reference electrodes, and a constant current
was applied between the working and counter electrodes. In
order to make an electrode of NiAl2O4/NiO, copper foam of
nano size porosities was used as a substrate for the NiAl2O4/
NiO. The NiAl2O4/NiO was dispersed homogeneously in
ethanol for 20 min. A pure copper plate (with an exposed area
of 1*2 cm2) is coated by a thin layer of NiAl2O4/NiO powder at
100
C without using a binder. In the charging procedure, the
electrolyte dissociates round the cathode (working) electrode
and hydrogen in the solution migrates into it and is absorbed
by the NiAl2O4/NiO. The opposite direction process represents
the discharging reaction; under alkaline circumstance
hydrogen released from NiAl2O4/NiO combine with the hy-
droxyl ion, becoming water in the solution, while discharging
an electron.
Results and discussion
XRD patterns of NiAl2O4/NiO nanocomposite in the presence
of GTE and calcined at 700e900
C for 5 h are shown Fig. 2. GTE
contains ()-epigallocatechin, ()-epicatechin gallate,
()-epigallocatechin gallate and ()-epicatechin and possess
different biological activities [23]. Therefore the polyphenols
groups of GTE acts as a strong precipitating agent. Fig. 2aec
5238 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 2 ( 2 0 1 7 ) 5 2 3 5 e5 2 4 5

displays XRD patterns of samples TaeTc, respectively. When
the sample Ta calcined at 700
C the NiAl2O4 and NiO diffrac-
tion peaks overlap together and broad peaks were recognized.
With increasing temperature from 700 to 800, or 900
C,
NiAl2O4 and NiO peaks were separately appeared. With
increasing temperature from 800 to 900
C, NiAl2O4 crystals
are grown more than NiO crystals and the NiAl2O4 peaks
higher than the NiO peaks. All peaks can be well assigned the
cubic phase NiAl2O4 (JCPDS card No 01-1299 for Tb sample,
JCPDS card No 10-0339 for Tc sample) and rhombohedral
phase NiO (JCPDS card No 22-1189). The average diameter (D)
of the crystallite has been estimated from the DebyeeScherrer
formula which illustrated in Eq. (1).
D ¼ Kl/Bcosq
The Tb sample was including separate nanoparticles and
aggregate. When the calcination temperature increased to
900
C for Tc sample, the particles size and morphology of are
uniform. The average size is about 30e80 nm (Fig. 4c). Also, Tc
sample SEM is includes number plates. Each image shows two
different magnifications of product.
To inspect the optical absorption properties of NiAl2O4/NiO
nanocomposite, the UVeVis study was done witch is shown in
Fig. 5a. The UVeVis spectra of the NiAl2O4/NiO nanocomposite
was dispersed homogeneously in absolute ethanol. The strong
absorption peak is observed about 280e300 nm and 380 nm
that related to charge transfer and ded transitions
(3A2g / 1T1g), respectively [29]. According to the absorption
data, the band gap was estimated by Tauc's formula which
(1) illustrated in Eq. (2).

where, K (usually takes a value of about 0.9) is the so-called

a ¼ a0 (hg  Eg)n/hg (2)
shape factor. Ө, b, and l are, the diffraction angle, the X-ray
full width at half maximum height (FWHM) of the diffraction
where hg, a, a0 and Eg are the photon energy, the absorption
peak, and the wavelength of incident X-rays (1.5406
A for Cu
coefficient, the constants and the optical band gap of the
Ka), respectively [24]. The estimated crystallite size (according material, respectively. The value of n is depend on of the
to XRD information) in the temperature range 700e900
C are electronic transition (any value between ½ and 3) [30]. The
shown in Table 1. Also to study the relative phase of NiAl2O4 to NiAl2O4/NiO nanocomposite have direct band gap and the
NiO in the nanocomposite sample Tc used XRF analysis that value n is 2 [31].
ratio NiAl2O4:NiO is 75.25:23.98 w/w%. In the next step, as shown in Fig. 5b the energy gap of the
Fig. 3a show the FT-IR spectrum of NiAl2O4/NiO nano- Ta, Tb and Tc samples have been calculated by extrapolating
composite to study the functional group of organic molecules. the linear portion of the plot of (ahg)2 against hg to the energy
The absorption band from 3000 to 3600 cm1 and weak peak
1620 to 1640 cm1 are due to the OeH bond-stretching vibra-
tional and HeOeH bending vibration of the adsorbed water
molecule, respectively. The weak peaks 1028 to 1116 cm1 in
the three Ta, Tb and Tc samples corresponding to AleOH
bending mode [25]. The absorption bands 500e900 cm1 are
due to the stretching vibration of MeO, AleO and MeOeAl
bonds [26]. The NieO stretching is observed at rang
500e570 cm1 and bands around 500e570 cm1 and
720e764 cm1 which indicate that the product is spinel [27].
It is observed that, intensity and location peaks are
changing small amount with increasing calcination temper-
ature. The purity of the NiAl2O4/NiO nanocomposite was
confirmed by EDS spectrum. Fig. 3b shows EDS analysis of
NiAl2O4/NiO (sample Tc in Table 1). EDS showed the presence
of Ni, Al and O in sample Tc.
To study the effect of calcination temperature on mor-
phologies and size of NiAl2O4/NiO products, three different
calcination temperatures were selected. Fig. 4a shows SEM
image of Ta sample that composed of particle with average
20e50 nm, and very uniform and free aggregate. It is observed
in Fig. 4b that by increasing calcination temperature, particles
size decreased but by decreasing of the grain size because of
increasing grain surface charge, agglomeration increased [28].

Table 1 e Preparation conditions for the synthesis of NiO/

NiAl2O4 nanocomposite.
Sample Calcination Crystal size
abbreviation temperature (
C) (XRD)/nm
Ta 700 15.29
Tb 800 24.17 Fig. 3 e (a) FT-IR spectra and (b) EDS pattern of NiAl2O4/NiO
Tc 900 19.75
nanocomposite.
 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 2 ( 2 0 1 7 ) 5 2 3 5 e5 2 4 5 5239

Fig. 4 e SEM images of NiAl2O4/NiO nanocomposite obtained with different calcination temperature (a) Ta, (b) Tb, and (c) Tc.

axis. Fig. 7 shows the optical band gaps for direct transitions.
T (Ta, Tb, Tc) þ nH2O þ ne 4 (T þ nH) þ nOH (3)
The optical band gaps calculated 3.5, 3.25 and 3 eV for the Ta,
Tb and Tc, respectively. The amount impurities, type of elec-
tronic transition, crystal size and variations in the stoichi- Cu(OH)2 þ OH 4 CuOOH þ H2O þ e (4)
ometry are the reasons for different in optical band gap values
[32]. Here, it was observed that increasing calcination tem-
perature resulted in a shift of optical band gap to lower values. nCu(OH)2 þ T 4 nCuOOH þ (T þ nH) (5)
The hydrogen storage capacity has been tested in 6 M KOH
aqueous medium which the summary of electrochemical re- From left to right, the charging process of the samples
action process in samples electrode is the following equations: electrode (cathode) shown in Eq. (3) which the electrolyte
5240 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 2 ( 2 0 1 7 ) 5 2 3 5 e5 2 4 5

Fig. 7 e Discharge curves of Ta sample electrode at a

current of 1 mA.

Fig. 5 e (a) UVeVis absorption spectrum and (b) optical

direct band gap of NiAl2O4/NiO nanocomposite.

dissociates around the working electrode (cathode) and

hydrogen in the solution migrates to the cathode and is
absorbed by the samples. The hydrogen atoms come out of the
working electrode under alkaline circumstance and become
water again then freeing an electron in opposite direction. Eq.
(4) from left to right shows charging process of the counter
electrode (anode) which the activated material is oxidized and
produces an electron. The reverse reaction indicates the Fig. 8 e Discharge curves of Tb sample electrode at a
discharge process during which the anode material attains an current of 1 mA.
electron and is deoxidized. Eq. (5) shows the total reaction

Fig. 6 e Diagram of copper foam discharge capacity in Fig. 9 e Discharge curves of Tc sample electrode at a current
absence of NiAl2O4/NiO nanocomposite. of 1 mA.
 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 2 ( 2 0 1 7 ) 5 2 3 5 e5 2 4 5 5241

Fig. 12 e (a) Pore size distribution and (b) N2 desorption/

desorption isotherms of Tc sample.

process of charging and discharging. The larger the polariza-

Fig. 10 e (a) Comparison between the discharges curves in
tion of the samples electrode, the bigger the ability of
15 cycles and (b) cycling performance of Ta, Tb and Tc
hydrogen adsorption and oxidation of the cathode makes
samples at a current of 1 mA.
better performance of Ta, Tb and Tc in charging and

Fig. 11 e (a) XRD pattern of Cu foam and (b) XRD pattern of CueNiAl2O4/NiO after 15 chargeedischarge cycles.
5242 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 2 ( 2 0 1 7 ) 5 2 3 5 e5 2 4 5
discharging [33]. The mainly physical adsorption is mecha-
nism for electrochemical hydrogen storage in samples
electrode.
Fig. 6 shows hydrogen storage capacity curve of copper
foam without presence NiAl2O4/NiO nanocomposite, that is
less than 1 mAh/g. Fig. 7 shows the discharge capacity curves
Ta samples electrode after 15 cycles under 1mA current. This
curve shows the increased discharge capacity of CueNiAl2O4/
NiO in the alkaline medium is due presence NiAl2O4/NiO
nanocomposite. As one can see, the discharge profile of the Ta
sample electrode in the five looks different from first cycles,
which discharge capacity increased with repeating the cycles.
The discharge capacity increased from 35 mAh/g in one cycle
to 450 mAh/g after 15 cycles, corresponding to z1.59 wt%.
With increased calcination for Tb sample, the discharge ca-
pacity changed to 60 mAh/g for one cycle (Fig. 8). The
discharge capacity reached to 325 mAh/g after 15 cycles (cor-
responds to z1.15 wt%). The plateau of discharge potential for
Tb sample electrode reached 0.1 mV. Fig. 9 shows the
discharge curve of Tc sample electrode for 15 cycles. This
curve shows the increased discharge capacity of Tc sample
form 300 mAh/g to constant and stabilized 800 mAh/g amount
after 15 cycles. The discharge curves of Tc sample are very
close together and overlap, which shows the Tc sample, is
more stable than the Ta, Tb sample. Also, creates new sites for
hydrogen absorption and desorption in work electrodes as
time goes makes step diagram.
Fig. 13 e (a, b) TEM image at different scales of Tc sample.
Fig. 10a shows a comparison between the discharge curves
in 15 cycle of Ta, Tb and Tc sample. The discharge plateau with
the increase in cycle number for Tc sample is much longer
than the other samples. We clearly observed that discharge
capacity of Tc sample is greater than the Ta, Tb sample. The
discharge capacity of Ta, Tb and Tc sample are 450, 325 and
800 mAh/g after 15 cycles, respectively (Fig. 10b). The porosity
and presence of various hydrogen adsorption sites in the
cathode electrode can be the major reasons increasing
discharge capacity [25]. We used of XRD analysis to confirm
the electrochemical storage mechanism of CueNiAl2O4/NiO.
Fig. 11a shows XRD pattern Cu foam (without sample). All
diffraction peaks can be well indexed to the Cu foam. The XRD
pattern of CueNiAl2O4/NiO after 15 chargeedischarge cycles
shown in Fig. 11b. The all diffractions peaks can be indexed to
NiAl2O4/NiO and Cu(OH)2 (JCPDS 42-0746). In the Fig. 11b, a
number of XRD line of Cu(OH)2 can be seen which support the
electrochemical hydrogen storage mechanism. Also shows
that water is decomposed and hydrogen is adsorbed into the
NiAl2O4/NiO, physically due to the XRD pattern of NiAl2O4/NiO
in Fig. 2c is different from NiAl2O4/NiO XRD pattern after 15
chargeedischarges cycles in Fig. 11b.
The pore size distributions of Tc sample are shown in
Fig. 12a and calculated by BarretteJoynereHalenda (BJH)
technique of the N2 isotherm. As can be seen, the Tc sample
contains meso- and macrospores and displays a broad pore
size distribution. The total pore volume (p/po) and mean pore
 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 2 ( 2 0 1 7 ) 5 2 3 5 e5 2 4 5 5243

Table 2 e Compare hydrogen storage capacity between NiAl2O4/NiO with other materials.
Material Discharage capacity (mAh/g) Morphology TEM References
MoS2 262 Nanotube [35]

Mg64Pd3Co33 624 Particle [34]

Multi-wall carbon nanotubes 741.1 Nanotube [1]

MmNi3.8Co0.75Mn0.4Al0.2 337.5 [36]

Nickel hydroxide 350 e e [37]

NiAl2O4/NiO 800 Particle/plate This paper

diameter for Tc sample calculated 0.1292 cm3 g1and

14.895 nm, respectively. Also, the BET analysis showed
34.706 m2 g1 specific surface areas.
Fig. 12b shows the N2 adsorption/desorption profile of Tc
sample. Using the IUPAC classification, the Tc sample is a
type III isotherm with a large type H3 hysteresis loop. This
kind of hysteresis is typically found on solids involving of
aggregates or agglomerates of particles forming slit shaped
pores, with a non-uniform size and/or shape. Fig. 4c shown
SEM image of Tc sample that includes agglomerated particles
and plates.
The morphology and structure of NiAl2O4/NiO nano-
composite prepared with green tea extract was illustrated by
TEM images which are from different parts of Tc sample.
Fig. 13a shows the TEM image of sample Tc which contains
ultrafine particles and together has created porosity. Fig. 13b is
confirmed for plates in Tc sample which observed in Fig. 4c
SEM image and is consistent with BET analysis.
Conclusions
In summary, NiAl2O4/NiO was synthesized via simple thermal
decomposition by using green tea extract. The effects of
calcination temperature on the hydrogen storage capacity,
morphology and band gap were investigated. It was shown
that hydrogen storage capacity increased from 450 to
800 mAh/g with increasing calcination temperature. Dis-
charging capacity of different nanostructures reported in
Table 2. In this paper, hydrogen storage capacity of NiAl2O4/
NiO nanocomposite reported for the first time that in com-
parison to other materials with structures different, shown in
Table 2, this material has a high hydrogen storage capacity.
The NiAl2O4/NiO can become one of the ideal materials for
electrochemical hydrogen storage. It also helps prevent envi-
ronmental pollution with synthesis of NiAl2O4/NiO nano-
composite by using green method.
5244 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 2 ( 2 0 1 7 ) 5 2 3 5 e5 2 4 5
Acknowledgments
The authors are grateful to University of Kashan for support-
ing this work by Grant No. (159271/375).
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