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 x x x ( 2 0 1 7 ) 1 e1 1

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Electroplated Ni-Cu nanocrystalline alloys and

their electrocatalytic activity for hydrogen
generation using alkaline solutions

Mosaad Negem a,*, H. Nady a,b

a
Chemistry Department, Faculty of Science, Fayoum University, Fayoum-Egypt
b
Chemistry Department, Collage of Science & Arts in Qurayat, Aljouf University, Saudi Arabia

article info abstract

Article history: Hydrogen can be significantly considered the sustainable fuel for the energy storage and
Received 27 July 2017 conversion. In this work, we synthesize nanocrystalline Ni-Cu alloys across the range of
Received in revised form compositions and show that Ni-Cu alloys are indeed more active than pure nickel for
20 September 2017 hydrogen evolution reactions. The electroplated Ni-Cu alloy were characterized by scan-
Accepted 25 September 2017 ning electron microscopy (SEM), energy dispersive X-ray spectroscopy (EDX), X-ray
Available online xxx diffraction, XRD, and energy dispersive X-ray, EDX. The HER was studied at electroplated
Ni-Cu alloys in 1.0 M KOH solution at 298 K. The electroplated Ni-Cu alloys were investi-
Keywords: gated by cyclic voltammetry (CV), electrochemical impedance spectroscopy (EIS) and po-
Ni-Cu Alloys larization measurements to determine their electrocatalytic activity for the HER. The use of
EIS the appropriate concentrations of the addition agent simultaneously with the ultrasound
Hydrogen evolution waves during sample preparation was found to produce nanocrystalline Ni-Cu alloys. XRD
Nanocrystalline cathode patterns show that the Ni-Cu alloys possess the face centered cubic structure. The incor-
Ultrasound poration of Cu into the Ni alloys causes surface modification, which catalyzes the hydrogen
Polarization evolution reaction (HER). The electroplated Ni-Cu alloy with z49 at% Cu contents shows
the highest rate of hydrogen evolution. The increase of the Cu content more than z50 at%
was accompanied by a decrease in the rate of HER.
© 2017 Hydrogen Energy Publications LLC. Published by Elsevier Ltd. All rights reserved.

hydrogen with high efficiency using water electrolysis has the

Introduction
The renewable energy such as photovoltaics meets a problem
of storage which urges to find a suitable fuel that can be
transferred and used easily. Hydrogen can be considered the
most convenient contender which is greatest abundant
element on the earth to replace fossil fuel and sustainable to
be used in several applications such as fuel cell to generate
electricity. Therefore, the electrocatalyst which can generate
great interests. The hydrogen evolution reaction is considered
the most important electrochemical reaction which is inves-
tigated during photolytic and electrolytic water electrolysers,
chlor-alkali industry, fuel cells [1e3]. The electrolysis water
which generates hydrogen from alkaline medium is consid-
ered clean and workable techniques. The sustainability of the
electrode materials depends on the energy consumption,
electrocatalytic activity and their stability during electrolysis
process [4]. The electrocatalytic activity of the cathodes can be

* Corresponding author.
E-mail address: mra00@fayoum.edu.eg (M. Negem).
https://doi.org/10.1016/j.ijhydene.2017.09.147
0360-3199/© 2017 Hydrogen Energy Publications LLC. Published by Elsevier Ltd. All rights reserved.

Please cite this article in press as: Negem M, Nady H, Electroplated Ni-Cu nanocrystalline alloys and their electrocatalytic activity for
hydrogen generation using alkaline solutions, International Journal of Hydrogen Energy (2017), https://doi.org/10.1016/
j.ijhydene.2017.09.147
2 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 x x x ( 2 0 1 7 ) 1 e1 1
enhanced by the synergetic combination of electrocatalytic
components and the surface area [5,6]. Ni alloys exhibit
distinguished electrocatalytic activity for the hydrogen evo-
lution reaction and in the various electrochemical processes.
Ni alloys characterize by their chemical stabilities in a strong
alkaline solution, desirable mechanical properties and low
cost. In addition, the enhancement of their electrocatalytic
activity can decrease the consumption of energy [7e9]. Ni
possesses high electrocatalytic activity towards the HER
which can be enhanced by alloying with appropriate metal via
an electrocatalytic synergistic effect well reported in the
literature [10]. The electrocatalytic activity of Ni electrode can
be increased by alloying with transition metal such as Co, Pt,
V, W, Fe, Mo, Zn and Cu by electroplating [11e23]. The elec-
troplating techniques guarantee to form small unit cell
collected in the nanograins structures and the significant
surface area is obtained. The activation energy of the HER can
be changed by the addition of transition metal due to altering
the electrode reaction mechanism [24]. Also, electroplating
has the influence on the chemical and physical properties of
the Ni-based alloys, which can increase the electrocatalytic
activity of the alloys towards the HER. The high electro-
catalytic activity of cathodes towards HER obtained by Ni al-
loys in the alkaline medium leads to the potential application
of these alloys to generate hydrogen in the industry [17].
Moreover, the Ni-Cu alloys show high corrosion resistance
and good stability [21,25]. However, the electroplated Ni-Cu
alloys have no extensive reports to investigate their electro-
catalytic activity toward the HER [13e17]. In this study, the
electroplating of the Ni-Cu alloys is investigated using addi-
tives such as gluconate, cysteine, boric acid under ultra-
sonication conditions using galvanostatic technique. The
electrocatalytic activity of the Ni-Cu alloys cathodes is studied
to generate hydrogen from alkaline medium using cyclic vol-
tammetry, cathodic polarization and electrochemical imped-
ance spectroscopy.
Experimental
Characterization, chemicals and composition of the
electrodes
The electroplating of the Ni-Cu alloys were performed on cop-
per foil of 99.98% purity as cathode and the platinum mesh was
utilizes as anode of 2.4 cm2 area. The Pyrex cylinder cell was
used during the electroplating process and TTI PL310 32V-1A
PSU generates a galvanostatic current. The ultrasonication was
obtained using the ultrasonic bath (Branson 3510, power 100 W,
frequency 42 kHz) and the pH and conductivity-meter of Met-
tler Toledo type was operated to measure the pH and conduc-
tivity of electroplating baths. NiSO4$7H2O, CuSO4$5H2O, H3BO3,
sodium gluconate and cysteine were obtained from Aldrich,
Sigma and Merck, have been dissolved in deionized water as
the chemical bath. The composition of electroplating baths and
conditions for Ni and Ni-Cu coatings were the same as reported
previously [23]. Different current densities, concentration of
brightener (cysteine) and complexing agent (gluconate) were
operated to optimize the electroplating of nanocrystalline Ni,
Cu and Ni-Cu alloys. The suitable electroplating current density
Please cite this article in press as: Negem M, Nady H, Electroplated Ni-Cu nanocrystalline alloys and their electrocatalytic activity for
hydrogen generation using alkaline solutions, International Journal of Hydrogen Energy (2017), https://doi.org/10.1016/
j.ijhydene.2017.09.147
is 2.5 Adm
2 at pH 4 for 1 h and solution temperature is 293 K.
The solution is freshly prepared for every electroplating pro-
cess. Copper oxide layer was removed from the copper foil by
immersion in a (1:1) concentrated nitric acid for 1 min, then
cleaned using deionized water and acetone. The surface
morphology, crystal structure, chemical composition of the
nanocrystalline Ni-Cu alloys were obtained using scanning
electron microscopy, SEM, (JOEL JSM-5300 LV, at 25 kV under
high vacuum), X-ray diffraction (XRD)and energy dispersive X-
ray analysis (EDX) incorporated with SEM, respectively.
Electrochemical measurements
Cyclic voltammetry and the electrochemical impedance
measurements were carried out using Voltalab PGZ 100 “All in
one” potentiostat/galvanostat where Electrochemical
Analyzer under computer control. Moreover, the electro-
chemical cell was used is A double-wall one-compartment cell
with a three electrode configuration. The platinum sheet of
1.5 cm2 surface area was the auxiliary electrode and the
saturated calomel electrode, SCE, (3.0 M KCl) was the refer-
ence electrode. The electrochemical experiments have been
performed using analytical grade reagents and deionized
water. The freshly dissolved KOH of 1.0 M was utilized as the
electrolytes. The potentiodynamic polarization experiments
have been carried out with scan rate of 5 mVs
1 to obtain
quasi-stationary condition. The impedance, Z, and phase
angle, W, have been recorded using the frequency domain
0.1e105 Hz. The superimposed ac-signal was 10 mV peak to
peak and the details of experimental methods have been
described elsewhere [22,23].
Results and discussion
Alloy structure and composition
Different morphological structures of the electroplated Ni-Cu
alloys were obtained using gluconate bath and a current
density of 2.5 Adm
2, and displayed in Fig. 1 which change
from smooth to coral reef-like and granular with the increase
of Cu content. Pure Ni is smooth and lustrous morphology and
the morphological structure of the Ni-19Cu, Ni-26Cu, Ni-
44.5Cu, Ni-49Cu, Ni-59Cu, Ni-86Cuare coral reef-like
morphology as displayed in Fig. 1aef. Ni-94Cu alloy and pure
Cu show spherical and granular structures as shown in Fig. 1g
and h. However, the rough electroplated Ni-Cu alloys were
obtained due to hydrogen evolution reaction on the electro-
catalyst metal presence during the electroplating of the alloys
such as Ni and Cu.
The EDX analysis spectra are merged in Fig. 1 for the
different alloys and the composition is shown in Table 1. The
EDX analysis spectra show that the high purity Ni-Cu alloys
were synthesized and the alloys with different composition of
Ni and Cu are achieved using this bath. Fig. 2 shows that the
XRD patterns were obtained for Ni and Ni-Cu alloys with Cu
content of 1e50% which arranged in face centered cubic
(JCPDS number 351360) and their peaks shifted from that of
Ni-Cu alloys with Cu content more than 50%. The unit cell
parameters of Ni and Ni-Cu alloys with Cu content of 1e50%
 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 x x x ( 2 0 1 7 ) 1 e1 1 3

Fig. 1 e Morphological structure (SEM) of nanocrystalline Ni-Cu alloys produced using the conventional ultrasound waves
for 1 h at 293 K, where: a. Ni-19Cub. Ni-49Cu, c. Ni-86Cu, d. Ni-94Cu and e. pure Cu.

varied between a ¼ 2.033 Angsrom-a ¼ 2.0358 Angsrom.
While, the unit cell of Ni-Cu alloys with Cu content of 51e99%
and pure Cu varied between, a ¼ 2.063 and a ¼ 2.083 Angsrom.
The XRD patterns demonstrated the peaks intensities related
to nano-size grains. The average grain size of the Ni-Cu alloys
was calculated using Debye-Scherer's equation from the XRD
patterns. The grain size of Ni-Cu alloys changes with the Cu
content of 1e50% which varies from 12 nm to 47 nm. Then, the
grain size increases gradually from 50 nm to 90 nm for the Ni-
Cu alloys with the Cu content between 44% and 99.9.

Cyclic voltammetry of coatings

Fig. 3aec displays the cyclic voltammetry measurements for

Table 1 e Chemical compositions of nano-crystalline Ni
and Ni-Cu alloys obtained using conventional ultrasound
waves and additives at 293 K for 1 h from EDX analysis.
coating Ni%
1 99.9
2 81
3 74
4 56
5 51
6 41
7 14
8 6
9 e
Ni, Cu and the different electroplated Ni-Cu alloys in 1.0 M
KOH solution at 298 K. Fig. 3a shows the typical cyclic vol-
tammogram for Ni in the potassium hydroxide solution with
Cu%
starting scan potential of - 1.5 V which located at cathodic
e current for hydrogen evolution reaction. The current density
19
increases slowly with raising of potential due to the active
26
region for Ni dissolution. In alkaline media, the predominant
44
49 soluble nickel species are Ni(OH)þ(aq) or Ni2þ(aq) ions and the Ni
59 dissolution depends on pH which is proposed to a contribu-
86 tion of OH
to the process of the active dissolution [26]. In
94 addition, the total reactions of anodic dissolution are shown
99.9 as in the following Equations (1) and (2):

Please cite this article in press as: Negem M, Nady H, Electroplated Ni-Cu nanocrystalline alloys and their electrocatalytic activity for
hydrogen generation using alkaline solutions, International Journal of Hydrogen Energy (2017), https://doi.org/10.1016/
j.ijhydene.2017.09.147
4 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 x x x ( 2 0 1 7 ) 1 e1 1

Fig. 2 e XRD patterns of nanocrystalline Ni-Cu alloys obtained from gluconate bath using conventional ultrasound waves.

Ni þ OH
/NiðOHÞads þ e (1) NiðOHÞads þ OH
/NiðOHÞ2 þ e (3)

NiðOHÞads /NiðOHÞþ
aq þ e
It was reported that NiO is formed concurrently with
Ni(OH)2 using different pH and potential [27]. Equation (4) is
supposed to accountable for passivation by production of NiO.
(2) NiðOHÞ2 /NiO þ H2 O (4)
Thus, Ni(OH)2 or NiO layer is synthesized during dissolu-
tion of Ni which generates the region of passivation where the
current was stable with the increase of the potential. The

Please cite this article in press as: Negem M, Nady H, Electroplated Ni-Cu nanocrystalline alloys and their electrocatalytic activity for
hydrogen generation using alkaline solutions, International Journal of Hydrogen Energy (2017), https://doi.org/10.1016/
j.ijhydene.2017.09.147
 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 x x x ( 2 0 1 7 ) 1 e1 1
Fig. 3 e Cyclic voltammograms of nano-crystalline
electrodeposited Ni (a), Cu (b) and Ni-Cu alloys in a
stagnant naturally aerated 1 M KOH solution at 25  C and
scan rate of 10 mVs¡1.
reverse scan of the potential has no a cathodic peak related to
the passive layer reduction as a results of both the highly
stable passive layer and the dissolved oxygen reduction and
passive film may continue the hydrogen evolution reaction
potential range [28].
Cyclic voltammogram for electroplated Cu in naturally
aerated 1.0 M KOH medium at 298 K is displayed in Fig. 3b.
Similarly, the scan of potential was started at - 1.5 V which
Please cite this article in press as: Negem M, Nady H, Electroplated Ni-Cu nanocrystalline alloys and their electrocatalytic activity for
hydrogen generation using alkaline solutions, International Journal of Hydrogen Energy (2017), https://doi.org/10.1016/
j.ijhydene.2017.09.147
5
included a significant cathodic current obtained due to
hydrogen evolution. The transition region was obtained
before the active dissolution of copper and this may be due to
the adsorbed species production such as CuðOHÞ
ads at the Cu
surface [27] by the reactions:
Cu þ OH
/CuðOHÞ

ads (5)
The CuðOHÞ

adsspecies exemplified the adsorbed interme-
diate for active dissolution. In the anodic active region copper
dissolves into the solution as Cuþ ions [29], and the current
density is constantly growing with potential which is ascribed
to the dissolution of the adsorbed layer as the following:
CuðOHÞ



ads þ OH /CuðOHÞ2 ðaqÞ þ e (6)
It is assumed that the reactions 5 and 6 are responsible for
passivation where the Cu2O passive layer is formed and the
anodic peak is obtained at
0.35 V (ai),
2CuðOHÞ

2 ðaqÞ/Cu2 O þ H2 O þ 2OH


(7)
2CuðOHÞ

ads /Cu2 O þ H2 O þ 2e (8)
At potential þ0.19 V, the second anodic peak (aii) was ob-
tained due to converting Cu2O at the external surface of the
oxide film (interface between oxide and solution) to the hy-
drated oxide or Cu(II) oxide [30], consistent with,
Cu2 O þ H2 O/2CuO þ 2Hþ þ 2e (9)
Cu2 O þ 3H2 O/2CuðOHÞ2 þ 2Hþ þ 2e (10)
The two cathodic peaks were obtained at
0.56 V and

0.88 V during cathodic direction. The cathodic peak (cii) is
resulted from the reduction of Cu(OH)2 and the cathodic peak
(ci) is because of the reduction of Cu2O [29]. Moreover, Fig. 3c
shows the cyclic voltammograms for Ni-Cu alloys in 1.0 M
KOH solution. The shapes of voltammograms were recorded
depending on the dominant metal in the alloy. The values of
the dissolution anodic current density decline with the in-
crease of the Ni content in the alloys.
Electrocatalytic activity of the studied electroplated cathodes
towards HER
Polarization measurements
The significant aim of this work is to utilize the electroplated
Ni-Cu alloy for hydrogen evolution reaction. Electrocatalysis
activity of the electroplated Ni-Cu cathodes for hydrogen
evolution reaction was investigated by cathodic polarization
and electrochemical impedance measurements in alkaline
media of 1.0 M KOH. To determine the electrocatalysis activity
of the electroplated Ni-Cu alloys well, we performed the
cathodic polarization measurements to compare between ed.
Ni, bulk Ni, bulk Cu, ed. Cu and Pt cathodes and the electro-
plated Ni-49Cu alloy as shown in Fig. 4a. From Fig. 4a, the
electrocatalytic activity of the electroplated Ni-49Cu alloy is
notably higher than bulk Cu, bulk Ni, or even Pt [31]. The most
important parameter which control the electrocatalytic ac-
tivity of the cathode and the rate of hydrogen evolution is the
hydrogen reduction overpotential. The current density pre-
sented at the same potential is considered a comparison
6 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 x x x ( 2 0 1 7 ) 1 e1 1

parameter for the electrocatalytic activity of the cathodes.
Therefore, Table 2 displays the steady state potential and the
potential of starting hydrogen to evolve for all cathodes under
the identical condition. The electroplating Ni-Cu alloys show
clearly the electrocatalytic activity towards the hydrogen
evolution reaction and possess more positive potential than
that of bulk cathodes (cf. Table 2) for the hydrogen evolution
potential. This is due to small unit cell or nanograins struc-
tures attain huge surface area suitable for hydrogen evolution
reaction which enhances the electrocatalytic activity of the
electroplated Ni-Cu alloys. The low electrocatalytic activity of
bulk cathodes can be ascribed to the smooth surface with
small surface area. In addition, the electrocatalytic activity of
the electroplated Ni-Cu alloys can be attributed to the coral
reef-like morphology which increases surface area and the
higher HER activity of Ni-Cu may be originated owing to syn-
ergistic combination of Ni and Cu. Fig. 4b displays cathodic
polarization curve for the electroplated Ni-Cu alloys as cath-
odes with different Cu content in 1.0 M KOH solution. The
cathodic hydrogen overpotential (Cf. Table 2 and Fig. 4b) is
decreased with the increase of Cu content up to z49%, and
then increases with more content of Cu. Fig. 4b persuades that
the hydrogen evolution reaction obtained by Ni-Cu cathodes
increases with enlarge the Cu content and fast ascending of
current with the applied potential as a results of the evolution
of hydrogen at the cathode. Cathodic polarization data indi-
cated that the developed coatings with high electrocatalytic
activity generate remarkably amount of hydrogen evolution
and the electroplated Ni-49Cu cathode produce high current
density for smallest overpotential.
The electroplated Ni-49Cu cathode possesses more posi-
tive overpotential of hydrogen evolution reaction (Cf, Table 2)
in comparing with the other Ni-Cu alloy and the 49% Cu
content boosts the electrocatalytic activity of the electroplated
Ni-49Cu cathode towards the hydrogen production. It is clear
that the coral reef-like morphology which contains a lot of
valley filled with the electrolyte, containing a massive space of
the internal surface of the Raney nickel, available to electro-
chemical hydrogen gas evolution than smooth surface Raney
nickel layers. Numerous valleys are appropriately short
diffusion paths of dissolved hydrogen, which enables rapid
release of hydrogen gas and precludes unnecessary

Fig. 4 e (a) Polarization curves of the bulk Cu, bulk Ni, electrodeposited Ni, electrodeposited Cu, Ni-49Cu and Pt in stagnant
naturally aerated 1 M KOH solutions at 25  C.(b)- Cathodic current potential curves of nano-crystalline electrodeposited Cu
and Ni-Cu coatings in 1 M KOH solution at 25  C.

Please cite this article in press as: Negem M, Nady H, Electroplated Ni-Cu nanocrystalline alloys and their electrocatalytic activity for
hydrogen generation using alkaline solutions, International Journal of Hydrogen Energy (2017), https://doi.org/10.1016/
j.ijhydene.2017.09.147
 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 x x x ( 2 0 1 7 ) 1 e1 1
Table 2 e The steady state potential, hydrogen evolution potential and the cathodic hydrogen overpotential determined
from cathodic current epotential curves for the different investigated materials and Pt in stagnant naturally aerated 1.0 M
KOH at 25  C.
Materials Ess/mV E Hydrogen evolution/mV
Ni bulk
275
1380
Ni deposited
335
1326
Cu deposited
260
1260
Ni-94Cu
295
1243
Ni-86Cu
190
1145
Ni-59Cu
280
1226
Ni-49Cu
290
1108
Ni-27Cu
255
1131
Ni-19Cu
245
1197
Pt
235
1220
accumulation of hydrogen gas and concentration polarization
in these valleys [32]. These valleys increase the surface area
lowering the overpotential for hydrogen evolution reaction
and the surface area increases progressively with Cu content
up to 49% Cu and the most suitable cathode for hydrogen
evolution is the electroplated Ni-49Cu alloy. The activity to-
wards hydrogen evolution reaction is influenced by synergetic
effect between the physical and chemical properties of the
electroplated Ni-Cu cathodes. Besides, electroplated Ni-Cu
cathodes attain differences in the electrocatalytic activities
mainly because of changes in their chemical composition
where the electrocatalytic activity was at the highest value for
the Ni-Cu electrode containing only 49% Cu. Tafel slope values
have been measured by linear least square fitting of the linear
part of the semi logarithmic steady-state Tafel plots. The Tafel
slope values obtained for the different testes electrodes in the
HER are close to 120 mV dec
1. These values are in line with
the one reported for Ni metallic electrodes [14] indicating that
the rate determining step for the HER is the proton discharge
electrosorption (Volmer reaction: H2O þ e
þ M 4 M-
Hads þ OH
) [19].
Electrochemical impedance spectroscopy, EIS
EIS measurements were performed on a computer-controlled
combination potentiostat/galvanostat/frequency response
analyzer using Volta lab 10 potentiostat (Radiometer PGZ100)
controlled by Tacussel corrosion analysis software model
(Volta master 4). EIS analysis were carried out using diverse
cathodic potentials varied from
1250 mV to 1500 mV to
investigate the electrocatalytic activity of the electroplated
cathodes in 1.0 M KOH. Nyquist plots are displayed in Fig. 5 for
different cathodes of electroplated Ni-27Cu, Ni-49Cu and Ni-
59Cu alloys at 1300 mV overpotential which includes signifi-
cant evolution rate of hydrogen. The model of the simple
Randle's circuit was used to fit the EIS data as shown in inset of
Fig. 5a and b presents the EIS spectra for Ni-49Cu at
1300 mV
and show that a very good agreement between the experi-
mental (symbols) and simulated (lines) data was obtained
when the equivalent circuit shown in inset of Fig. 5a. The
solution resistance, Rs, is located in series with combination of
parallel including double layer capacitance, Cdl, and the
charge transfer resistance, Rct which is appropriate model to
interpret the impedance records during evolution of
hydrogen. Fig. 5 shows that the different radius of the faintly
Please cite this article in press as: Negem M, Nady H, Electroplated Ni-Cu nanocrystalline alloys and their electrocatalytic activity for
hydrogen generation using alkaline solutions, International Journal of Hydrogen Energy (2017), https://doi.org/10.1016/
j.ijhydene.2017.09.147
7
Cathodic hydrogen overpotential/mV

1105

991

1000

948

955

946

818

876

952

985
depressed capacitive semicircle shape is obtained by electro-
plated Ni-27Cu, Ni-49Cu and Ni-59Cu cathodes. The charge
transfer process is considered predominantly to control the
hydrogen evolution reaction which is assured by the uni-loop
of Nyquist plots. The values of impedance measured for the
electroplated Ni-27Cu and Ni-59Cu are higher than that ob-
tained by the electroplated Ni-49Cu cathode which advocates
the different activity of electroplated cathodes towards the
hydrogen evolution reaction. In absence of response related to
hydrogen adsorption, the simple model is utilized to explain
the response of the HER on relatively smooth surfaces [33],
porous surfaces with narrow or wide cylindrical pores [34].
The pores of surface (inhomogeneity of the catalyst surface)
relate to the physical, chemical or geometrical in-
homogeneities [33]. Only depends on the intrinsic catalytic
activity of metals. Furthermore, synergistic combination of Ni
and Cu improves the HER kinetic and the porous structure of
the surface. The fitted parameters of the impedance data are
listed in Table 3 which displays clearly how the charge
transfer resistance for the hydrogen evolution on the elec-
troplated Ni-49Cu cathode is lower than that obtained for the
Ni-27Cu and Ni-59Cu electrodes. This can be attributed to the
morphology and composition of the electroplated layers. It
can be seen that the electroplated Ni-49Cu alloy is most effi-
cient electrocatalysts for the HER.
The high corrosion resistance of the electrocatalyst coating
is significantly essential to improve the sustainability leading
to low costs of maintenance and operating during electro-
catalysis processes. Fig. 6 exhibits EIS data for different Ni-Cu
cathodes recorded in 1.0 M KOH at open circuit potential for
the investigation of the corrosion resistance during the elec-
trolysis as shown in the form of Nyquist and Bode plots. The
phase angle curves contain obviously two maxima and this
indicates that two times constant are obtained for all elec-
troplated Ni-Cu cathodes. The diameter of semicircle of the
Ni-49Cu alloy is larger comparing to that obtained by other
electroplated Ni-Cu alloys in 1 M KOH solution. Therefore, the
Ni-49Cu attains the highest corrosion resistance which is due
to the copper content. The copper content in the Ni-Cu alloys
has an important role by lessening the corrosion rate in
alkaline solution. Moreover, the larger maximum phase angle
is displayed by the electroplated Ni-49Cu alloy while the other
electroplated Ni-Cu alloys shows smaller maximum phase
angle than the electroplated Ni-49Cu alloy as shown in Fig. 6c.
8 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 x x x ( 2 0 1 7 ) 1 e1 1
Fig. 5 e a) Nyquist plots of Ni-27Cu (), Ni-49Cu (:::)
and Ni-59Cu (---) electrodes at ¡1.3 V potential in 1 M
KOH at 25  C.(Inset) Equivalent circuit used for fitting of the
experimental impedance. Rs ¼ solution resistance,
Cdl ¼ double layer capacitance and Rct ¼ charge transfer
resistance. Fig. 5b Nyquist complex plane plots recorded
for Ni-49Cu electrode at ¡1.3 V potential in 1 M KOH at
25  C. Symbols are experimental and solid lines are
modeled data.
In fact, these results confirm that the electroplated Ni-49Cu
alloy possesses the highest barrier property because of the
stability and surface coverage of this coating. The EIS data
reveal that the electroplated Ni-49Cu alloy has the best
corrosion protection performance. The experimental imped-
ance results were fitted to theoretical data according to the
equivalent circuit model presented in Fig. 6d. This model
consists of a capacitor representing the double layer capaci-
tance, Cdl, in parallel to a resistor representing the charge
Table 3 e Equivalent circuit parameters obtained by
fitting the experimental impedance data recorded at
¡1.3 V on nano-crystalline electrodeposited Ni-59Cu, Ni-
49Cu and Ni-27Cu coatings in stagnant naturally aerated
1 M KOH at a 25  C, according to the equivalent circuit of
Fig. 6 (inset).
Alloys Rs/U Rct/U cm2 Cdl/mF cm
2
Ni-59Cu 2.5 3.6 3.5
Ni-49Cu 2.5 2.5 8.1
Ni-27Cu 2.7 3.1 2.6
Please cite this article in press as: Negem M, Nady H, Electroplated Ni-Cu nanocrystalline alloys and their electrocatalytic activity for
hydrogen generation using alkaline solutions, International Journal of Hydrogen Energy (2017), https://doi.org/10.1016/
j.ijhydene.2017.09.147
transfer resistance, Rct. This combination is in parallel to
another combination representing the coating capacitance,
Ccoat, and coating resistance, Rcoat. The two combinations are
in series to a resistor representing the solution resistance, Rs.
The high-frequency time constant reflects the characteristics
of the coatings resistance, and the low-frequency time con-
stant is characteristic for the charge-transfer resistance.
During immersion of electroplated Ni-Cu alloys in the elec-
trolyte, the corrosion initiates rapidly at the pores located in
the coatings which causes localized galvanic cells dominating
the galvanic corrosion process. The two electrochemical in-
terfaces can be included which are electrolyte/coating and
electrolyte/substrate. Table 4 presents calculated data of
fitting parameters for EIS measurements where Rp for elec-
troplated Ni-49Cu alloy is higher than other alloys and Ni-
49Cu alloy possesses higher corrosion protection. This con-
firms that the composition of oxi/hydroxide layer which is
formed on the surface of electroplated Ni-Cu alloys attains
different structure depending on Ni/Cu ratio. The Niþ/Ni2þ
incorporate into the unit cell of the barrier Cu2O layer. The
Cu2O layer is a p-type semiconductors where the mobile


cation vacancy is VCu ðoxÞ which is the charge carrier [35]. Ni
ions from the alloys diffuse into the Cu2O barrier layer and
Niþ/Ni2þ reacts by solid state reaction with VCu

ðoxÞ producing
complexes depending on the solute vacancy interaction
model (SVIM) [36] as shown the following Equations (12) and
(13):
CuCu ðoxÞ/Cuþ ðaqÞ þ VCu


ðoxÞ (12)


NiNi ðmÞ þ 2VCu ðoxÞ/½NiCui ð2VCu  þ 2e (13)
þ 2þ
Where CuCu (ox) is the Cu /Cu in a unit cell site of the


oxide layer, VCu ðoxÞ is the negative charged cation vacancy.
NiNi (m) is the Ni atom in the unit cell of alloy, and [NiCu(VCu)2]
is the neutral complex. Formation of the complex decreases
the free ions and ascends the electronic conductivity of the
barrier layer that leads to the increase of the corrosion resis-
tance of the oxide layer at the surface of the electroplated Ni-
Cu alloys.
From the impedance data, it is clear that the electroplated
Ni-49Cu alloy obtains the highest complexation of mobile
copper cation vacancies, is more stable against corrosion, and
is stable enough to be applied for hydrogen evolution. The
passive film disappears up under cathodic polarization and
the simple model can be applied [31]. The total impedance, Z,
recorded under polarization is lower than that measured
under open circuit potential using the same concentration
which is due to the surface activation of the electroplated Ni-
Cu alloys by reduction of the hydrogen and passive oxide
layer. The highest value of the Rct (i.e. largest semicircle) was
obtained for the electroplated Ni-Cu alloys with low and high
Cu content, and Rct decreases as the Cu content reaches about
50 at%. This behavior is due to the surface roughness [37],
hydride formation [38] and the absorption of hydrogen.
Fig. 7 displays the EIS spectra measured to explain the ef-
a fect of cathodic polarization on the behavior of the electro-
0.99 plated Ni-49Cu alloy which were operated in stagnant
0.99 naturally aerated 1.0 M KOH at different cathodic potentials. It
0.94 is obvious that one-time constant response is obtained at all
 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 x x x ( 2 0 1 7 ) 1 e1 1 9

Fig. 6 e Nyquist (a) and Bode plots (b&c) of electrodeposited Ni-Cu alloys at the open circuit potential in 1 M KOH solutions at
25  C.(d) Equivalent circuit used for fitting of the experimental impedance. Rs ¼ solution resistance, Cdl ¼ double layer
capacitance, Rct ¼ charge transfer resistance, Cp ¼ passive film capacitance and Rf ¼ passive film resistance.

potentials for electroplated Ni-49Cu alloy and the EIS data are leading to the increase of current density i.e. an increase in the
fitted to theoretical model as the equivalent circuit model rate of hydrogen evolution. The diameter of the semicircles
showed in Fig. 5 (inset). Table 5 present the Rct for the Ni-49Cu decreases with the cathodic overpotential as shown in Fig. 7,
alloy calculated at various potentials which decreased as the indicating that the two semicircles are due to the electrode
cathodic potential moved to more negative which means the kinetics [39,40].
increase of hydrogen evolution rate enhanced the electro- Moreover, as the overpotential increases, the decrease of
catalytic activity of the cathode material. As the Rct decreases semicircle obtained in the impedance plots is due to the
adsorption process facilitated and the charge transfer process
dominates the impedance response as the potential increases.
Rct presents the information about the rate of the electro-
Table 4 e Equivalent circuit parameters obtained by
chemical reaction such as hydrogen evolution reaction where
fitting the experimental EIS recorded at the open circuit
the smallest value of the Rct produces highest rate of the
potential on the investigated electrodeposited coatings in
stagnant naturally aerated 1 M KOH at a 25  C, according hydrogen evolution reaction. The Rct which is the ideal case
to the equivalent circuit of Fig. 7d. can be defined as semicircle diameter according to impedance
Alloys Rs/U Rct/U Cdl/mF a1 Rp/U Cp/mF a2 data [41]. It is known that the more negative value of the
cm2 cm
2 cm2 cm
2 cathodic potential leads to decrease the calculated Cdl values
which can be explained by blocking the electrode surface by
Cu 3.0 7.1 446.6 0.99 136.1 11.7 0.99
Ni-94Cu 2.9 27.1 293.8 0.99 177.3 1.7 1.0
adsorbed hydrogen [42,43]. Besides, the hydrogen gas bubbles
Ni-86Cu 3.2 15.1 843.6 0.99 103.1 12.3 0.98 trap the active surface because of the excess hydrogen evo-
Ni-59Cu 3.2 27.1 926.4 0.96 104.2 15.3 0.99 lution at more negative potentials. The interfacial capacity
Ni-49Cu 2.4 161.9 621.2 0.98 499.1 3.19 0.99 has been obtained by all electroplated Ni-Cu cathodes which
Ni-27Cu 3.1 113.3 443.5 0.99 205.4 3.1 0.99 is regular for double layer capacitance. The value of capaci-
Ni-24Cu 3.5 129.2 123.1 0.96 217.3 1.8 0.98
tance was recorded for electroplated Ni-49Cu alloy is greatly

Please cite this article in press as: Negem M, Nady H, Electroplated Ni-Cu nanocrystalline alloys and their electrocatalytic activity for
hydrogen generation using alkaline solutions, International Journal of Hydrogen Energy (2017), https://doi.org/10.1016/
j.ijhydene.2017.09.147
10 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 x x x ( 2 0 1 7 ) 1 e1 1
Fig. 7 e Nyquist plots of electrodeposited nano-crystalline
Ni-49Cu electrode at different applied potential in 1 M KOH
at 25  C.
Table 5 e Equivalent circuit parameters obtained by
fitting EIS experimental spectra recorded at various
potential on Ni-49Cu alloy coating in 1.0 M KOH at 25  C,
according to the equivalent circuit of Fig. 6 (inset).
E/mV Rs/U Rct/U cm2 Cdl/mF cm
2

1250 2.2 5.8

1300 2.5 2.5

1400 2.8 1.1

1500 3.1 0.6
higher than that for other Ni-Cu alloys which can be ascribed
for surface roughness, formation of hydrides and hydrogen
absorption [39].
Conclusion
Nanocrystalline Ni-Cu alloys were electroplated on copper
substrates and characterized. The prepared electroplated Ni-
Cu alloys were used as cathodes for hydrogen evolution. The
prepared cathodes have remarkably high catalytic activity for
the HER. The increase of the hydrogen activity was related to
the Cu content and increasing the electrocatalytic active sur-
face area. The rate of hydrogen production increases as the
atomic ratio of Cu in the electrodeposit increases up to z50 at
%. The electroplated Ni-Cu alloy with about 49 at% Cu exhibit
the highest electrocatalytic activity for the HER and produce
the highest rate of hydrogen evolution with lower hydrogen
overpotential. In addition, the Polarization and impedance
results have shown that the hydrogen evolution occurs at
lower overpotential on Ni-49Cu compared to the well-known
electrocatalyst for hydrogen evolution, namely Pt. The in-
crease of Cu content more than 50 at% leads to a decrease in
the rate of hydrogen production, which means that the Ni-
49Cu alloy is the best alloy for the hydrogen production in
1 M KOH solutions. Ni-49Cu alloy can be considered as a
Please cite this article in press as: Negem M, Nady H, Electroplated Ni-Cu nanocrystalline alloys and their electrocatalytic activity for
hydrogen generation using alkaline solutions, International Journal of Hydrogen Energy (2017), https://doi.org/10.1016/
j.ijhydene.2017.09.147
promising cathode for the hydrogen evolution reaction and
can be applied as cathode in industrial water electrolyzer.
Acknowledgement
The authors are grateful for Prof. M. El-Rabiei, Chemistry
Department, Faculty of Science, Fayoum University, for his
help in the Electrochemical measurements.
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