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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
applications. The NiAl2O4/NiO nanostructures has been used in patterns were recorded by a Rigaku D-max C III, X-ray
different application such as chemical-looping combustor [13], diffractometer using Ni-filtered Cu Ka radiation. The NiAl2O4/
catalysts [14], pigments [15], anodes for SOFCs [16], refractories NiO ratio was determined by X-ray fluorescence measure-
[17] and luminescent materials [18] because of its high thermal ments (XRF; Supermini, Rigaku Co. Ltd.). SEM images were
stability and specific catalytic properties [12]. NiAl2O4/NiO obtained using a Philips XL30 ESEM equipped with a field
nanostructure have been prepared using different methods, emission gun and an energy dispersive spectroscopy detec-
such as sol gel [19], solid looping reactants of metal oxides [20], tor. Elemental analyses were carried out with Carlo ERBA
co-precipitation [21] and solidestate reaction [22], etc. Model EA 1108 analyzer. FT-IR spectra were recorded by
In this work, green synthesis of NiAl2O4/NiO nano- using a Shimadzu Varian 4300 FT-IR spectrophotometer
composite with thermal decomposition method, that is not using KBr discs. UVeVis spectroscopy (diffuse reflectance)
harmful to human health and is low cost, has been reported. carried out with a Shimadzu UV/3101 PC in a range between
This should be mentioned for the first time, the NiAl2O4/NiO 200 and 800 nm. GC-2550TG (Teif Gostar Faraz Company,
nanocomposite porous has been used for hydrogen storage Iran) were used for all chemical analyses. The EDS analysis
that is useful for the environment. 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
Experimental adsorption analyzer (Tristar 3000, Micromeritics). The pore
size distribution (PSD) was determined from desorption
Materials and measurements branch of the isotherm by the Barrett, Joyner and Halenda
(BJH) technique. TEM image was carried out with a Philips
All chemical reagents in this study were used in analytical
EM208 TEM operating at 200 kV.
grade and used as received without further purification. XRD
Synthesis of NiAl2O4/NiO nanocomposite working and the reference electrodes, and a constant current
was applied between the working and counter electrodes. In
All the chemical reagents for nickel aluminate nanostructures order to make an electrode of NiAl2O4/NiO, copper foam of
synthesis such as Ni(NO3)2$6H2O, methanol and nano size porosities was used as a substrate for the NiAl2O4/
Al(NO3)3$9H2O were purchased from Merck and used as NiO. The NiAl2O4/NiO was dispersed homogeneously in
received. In a typical process, a mixed solution of metal ni- ethanol for 20 min. A pure copper plate (with an exposed area
trates was prepared by dissolving Al(NO3)3$9H2O and of 1*2 cm2) is coated by a thin layer of NiAl2O4/NiO powder at
Ni(NO3)2$6H2O in water with the molar ratio of Ni2þ/Al3þ ¼ 1:2. 100 C without using a binder. In the charging procedure, the
Then, 20 ml green tea extract was added. This mixture was electrolyte dissociates round the cathode (working) electrode
heated at 80 C for 1 h with continuous stirring so that the ions and hydrogen in the solution migrates into it and is absorbed
react. The obtained solution was evaporated on a hot plate at by the NiAl2O4/NiO. The opposite direction process represents
120 C for dehydration and continued until powder was ob- the discharging reaction; under alkaline circumstance
tained. Finally, this powder was calcined in various temper- hydrogen released from NiAl2O4/NiO combine with the hy-
atures. Fig. 1 shows schematic for the synthesis of NiAl2O4/ droxyl ion, becoming water in the solution, while discharging
NiO nanocomposite powder. an electron.
Electrochemical systems
Results and discussion
Chronopotentiometry technique was employed to measure
the hydrogen storage capacity of the electrodes. The charge XRD patterns of NiAl2O4/NiO nanocomposite in the presence
and discharge cycles was performed by a three-electrode of GTE and calcined at 700e900 C for 5 h are shown Fig. 2. GTE
system. The CueNiAl2O4/NiO, Ag/AgCl and Pt electrodes are contains ()-epigallocatechin, ()-epicatechin gallate,
as the working, reference and counter electrodes, respec- ()-epigallocatechin gallate and ()-epicatechin and possess
tively. The electrolyte was 6 M KOH aqueous solution. In this different biological activities [23]. Therefore the polyphenols
system, the potential difference was measured between the groups of GTE acts as a strong precipitating agent. Fig. 2aec
Fig. 2 e XRD patterns of NiAl2O4/NiO nanocomposite (a) Ta, (b) Tb, and (c) Tc.
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 Tb sample was including separate nanoparticles and
the sample Ta calcined at 700 C the NiAl2O4 and NiO diffrac- aggregate. When the calcination temperature increased to
tion peaks overlap together and broad peaks were recognized. 900 C for Tc sample, the particles size and morphology of are
With increasing temperature from 700 to 800, or 900 C, uniform. The average size is about 30e80 nm (Fig. 4c). Also, Tc
NiAl2O4 and NiO peaks were separately appeared. With sample SEM is includes number plates. Each image shows two
increasing temperature from 800 to 900 C, NiAl2O4 crystals different magnifications of product.
are grown more than NiO crystals and the NiAl2O4 peaks To inspect the optical absorption properties of NiAl2O4/NiO
higher than the NiO peaks. All peaks can be well assigned the nanocomposite, the UVeVis study was done witch is shown in
cubic phase NiAl2O4 (JCPDS card No 01-1299 for Tb sample, Fig. 5a. The UVeVis spectra of the NiAl2O4/NiO nanocomposite
JCPDS card No 10-0339 for Tc sample) and rhombohedral was dispersed homogeneously in absolute ethanol. The strong
phase NiO (JCPDS card No 22-1189). The average diameter (D) absorption peak is observed about 280e300 nm and 380 nm
of the crystallite has been estimated from the DebyeeScherrer that related to charge transfer and ded transitions
formula which illustrated in Eq. (1). (3A2g / 1T1g), respectively [29]. According to the absorption
data, the band gap was estimated by Tauc's formula which
D ¼ Kl/Bcosq (1) illustrated in Eq. (2).
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. 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. 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- Fig. 10a shows a comparison between the discharge curves
nism for electrochemical hydrogen storage in samples in 15 cycle of Ta, Tb and Tc sample. The discharge plateau with
electrode. the increase in cycle number for Tc sample is much longer
Fig. 6 shows hydrogen storage capacity curve of copper than the other samples. We clearly observed that discharge
foam without presence NiAl2O4/NiO nanocomposite, that is capacity of Tc sample is greater than the Ta, Tb sample. The
less than 1 mAh/g. Fig. 7 shows the discharge capacity curves discharge capacity of Ta, Tb and Tc sample are 450, 325 and
Ta samples electrode after 15 cycles under 1mA current. This 800 mAh/g after 15 cycles, respectively (Fig. 10b). The porosity
curve shows the increased discharge capacity of CueNiAl2O4/ and presence of various hydrogen adsorption sites in the
NiO in the alkaline medium is due presence NiAl2O4/NiO cathode electrode can be the major reasons increasing
nanocomposite. As one can see, the discharge profile of the Ta discharge capacity [25]. We used of XRD analysis to confirm
sample electrode in the five looks different from first cycles, the electrochemical storage mechanism of CueNiAl2O4/NiO.
which discharge capacity increased with repeating the cycles. Fig. 11a shows XRD pattern Cu foam (without sample). All
The discharge capacity increased from 35 mAh/g in one cycle diffraction peaks can be well indexed to the Cu foam. The XRD
to 450 mAh/g after 15 cycles, corresponding to z1.59 wt%. pattern of CueNiAl2O4/NiO after 15 chargeedischarge cycles
With increased calcination for Tb sample, the discharge ca- shown in Fig. 11b. The all diffractions peaks can be indexed to
pacity changed to 60 mAh/g for one cycle (Fig. 8). The NiAl2O4/NiO and Cu(OH)2 (JCPDS 42-0746). In the Fig. 11b, a
discharge capacity reached to 325 mAh/g after 15 cycles (cor- number of XRD line of Cu(OH)2 can be seen which support the
responds to z1.15 wt%). The plateau of discharge potential for electrochemical hydrogen storage mechanism. Also shows
Tb sample electrode reached 0.1 mV. Fig. 9 shows the that water is decomposed and hydrogen is adsorbed into the
discharge curve of Tc sample electrode for 15 cycles. This NiAl2O4/NiO, physically due to the XRD pattern of NiAl2O4/NiO
curve shows the increased discharge capacity of Tc sample in Fig. 2c is different from NiAl2O4/NiO XRD pattern after 15
form 300 mAh/g to constant and stabilized 800 mAh/g amount chargeedischarges cycles in Fig. 11b.
after 15 cycles. The discharge curves of Tc sample are very The pore size distributions of Tc sample are shown in
close together and overlap, which shows the Tc sample, is Fig. 12a and calculated by BarretteJoynereHalenda (BJH)
more stable than the Ta, Tb sample. Also, creates new sites for technique of the N2 isotherm. As can be seen, the Tc sample
hydrogen absorption and desorption in work electrodes as contains meso- and macrospores and displays a broad pore
time goes makes step diagram. size distribution. The total pore volume (p/po) and mean pore
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]
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(M¼Mo, Ti) nanotubes. Front Chem China 2006;3:260e3. [37] Hu W-K, Noreus D. Alpha nickel hydroxides as lightweight
[36] Zhao X, Ding Y, Ma L, Wang L, Yang M, Shen X. nickel electrode materials for alkaline rechargeable cells.
Electrochemical properties of MmNi3.8Co0.75Mn0.4Al0.2 Chem Mater 2003;15:974e8.