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 ) 1 3 1 9 2 e1 3 1 9 7

Available online at www.sciencedirect.com

ScienceDirect

journal homepage: www.elsevier.com/locate/he

Synthesis of NiPt alloy nanoparticles by galvanic

replacement method for direct ethanol fuel cell

Van Vinh Pham a,*, Van-Thao Ta a, Cho Sunglae b

a
Hanoi National University of Education, Viet Nam
b
The University of Ulsan, South Korea

article info abstract

Article history: The alloy of NiPt nanoparticles was successfully synthesized by galvanic replacement
Received 9 November 2016 method in which Ni nanoparticles used as the templates and H2PtCl6 solution as additional
Received in revised form reagent. The preparation conditions of Ni nanoparticle were optimized. The effect of
28 December 2016 platinum contents on the structure, morphology, magnetic and electrocatalyst of NiPt was
Accepted 16 January 2017 investigated. The phase analysis by XRD showed the presence of Ni and Pt crystalline
Available online 26 April 2017 phases on the alloy. The TEM images indicated that the NiPt nanoparticles had porous
crystalline structure with grain size in the range of 25 nme30 nm. Besides, composition
Keywords: analysis by EDX showed that the ratios of Ni and Pt were changed with a change of the
NiPt alloy nanoparticles amount of H2PtCl6 using for the galvanic reaction. The magnetic properties of NiPt nano-
Electrocatalyst particles change significantly with a change of Pt composition. The NiPt nanoparticles
Galvanic replacement exhibit ferromagnetic behavior depending on the amount of Pt composition. In particular,
Direct ethanol fuel cell saturation magnetization decreases from 6.5 emu/g to 4.0 emu/g with the decrease of Ni:Pt
Ethanol oxidation ratio from 57.0:3.6 to 57.0:8.1 respectively. With lower Ni:Pt ratio (57.0:18.0), the NiPt
nanoparticles exhibits superparamagnetic properties. The magnetic properties were
attributed to the formation of NiPt alloy in which the electrons transfer from Pt atoms to
d band of Ni. The cyclic voltammetry measurement showed that NiPt nanoparticles exhibit
better ethanol oxidation in alkali medium comparing with pure Platinum.
© 2017 Hydrogen Energy Publications LLC. Published by Elsevier Ltd. All rights reserved.

heat-to-mechanical conversion so their efficiency is not

Introduction
In the recent years, with accelerating depletion of fossil fuels
(petroleum, coal, ...), there has been a great deal of interest in
the development of new technologies using alternative energy
sources, including solar, wind, tide or chemical fuel related
energies. Amongst these, the technology related to develop-
ment of fuel cells has been attracted particularly attention
from researchers. Fuel cells (FC) produce electricity by con-
verting chemical energy to electrical energy directly without
affected by limiting efficiency of Carnot cycle. Thus, fuel cell
operation is quiet, high performative and environment
friendly. One of the most attractive fuel cells that have been
studied widely is direct ethanol fuel cell (DEFC) because
ethanol is an excellent electroactive organic fuel which is
possible to provide 12 e
in alkaline ethanol oxidation [1,2].
Moreover, ethanol is non-toxic and easy to be synthesized
from agriculture productions or bioproductions. Up to now,
DEFCs, however, are not yet to be utilized popularly due to
their high cost. The main reason for this is that Pt

* Corresponding author. Faculty of Physics, Hanoi National University of Education, 136 Xuan Thuy, Cau Giay, Hanoi, Viet Nam.
E-mail address: vinhpv@hnue.edu.vn (V.V. Pham).
http://dx.doi.org/10.1016/j.ijhydene.2017.01.236
0360-3199/© 2017 Hydrogen Energy Publications LLC. Published by Elsevier Ltd. All rights reserved.
 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 ) 1 3 1 9 2 e1 3 1 9 7
nanoparticles have widely been used as electrocatalysts for
ethanol oxidation in DEFCs [3]. This electrocatalyst is not only
expensive but also poisoned by strongly adsorbed CO in-
termediates during ORR [4]. To find solutions for these issues,
current tendency is towards searching new materials or the
materials with unique structures in order to reduce the
amount of Pt used and improve the efficiency of the FCs.
Recent studies showed that hollow structures exhibited great
enhancement of the catalytic activity over the solid nano-
catalysts, and thus cut down the costs of the fuel cells.
Indeed, because of the lower densities and higher specific
surface areas compared with that of solid ones, hollow
nanostructures exhibited steadily improved catalytic perfor-
mance [5e9]. Besides, control shape and size of nanoparticles
are also studied for this purpose [10] e.g. N.V. Long et al. [11,12]
have demonstrated that sharp polyhedral Pt exhibited better
electrocatalyst activity. However, such approaches are limited
by not solving the carbonaceous poison problem. Alloyed
nano-catalysts exhibited significantly enhanced electro-
catalytic activity and durability over the pure Pt nano-
catalysts, and thereby reduce the costs of the catalysts
[5,13]. According to this trend, the Pt-based alloy materials,
combining of Pt and a much cheaper metal such as, Fe, Co, Ni
or Cu nowadays, have been also studied widely [6,7]. Among
them, NiPt exhibits the noble properties which can be utilized
for electrochemical activities. Theoretical and experimental
studies revealed that NiePt catalysts with Pt-rich surfaces and
Ni-rich subsurfaces are very active towards the ORR [8,14e16].
Indeed, in alkaline media, the formation of nickel hydroxide
such as NiOH, Ni(OH)2 and NiOOH [9] during ORR can remove
the carbonaceous intermediate. Moreover, charges transfer
from Ni to Pt modified the electronic structure of Pt, resulting
in weakened CO adsorption on NiPt binary clusters [17].
Therefore, this study is focused on the synthesis and
evaluation electrocatalyst ability of the porous NiPt alloy
nanoparticles for ethanol oxidation reaction (EOR). The main
purpose of the study is to improve the electrocatalytic activity
of Pt-based catalyst as well as reduce the Pt content used for
the production of ethanol fuel cells.
Experimental
Alloy of NiPt nanoparticles were synthesized by galvanic
replacement method using Ni nanoparticles as the templates.
The experimental process is described as following:
Preparation of Ni nanoparticles
0.9 g Ni(NO3)2$6H2O (Sigma Aldrich, USA: Purification of
99.999%) was dissolved in 50 ml polyvinyl pyrrolidone (PVP-
Sigma Aldrich, USA: Purification of 99.999%) solution. The
concentrations of PVP were varied in tern 0.3, 0.5, 07 M in order
to determine the effect of PVP on the structure of Ni nano-
particles. The solutions were bubbled for 60 min by pure ni-
trogen gas to remove the oxygen remain. After that, 0.4 g ml
NaBH4 (BDH, UK: Purification of 98%) dissolved in 2 ml DI
water was dropped slowly in the solution. NaBH4 reduced
Ni(NO3)2$6H2O to form Ni nanoparticles due to following
chemical reaction:
13193
2þ
þ 4BH

2Ni 4 þ 12H2 O/2Ni þ 14H2 þ 4BðOHÞ3 (1)
The black solution containing Ni nanoparticles and un-
wanted materials that produced during the reaction were
separated by a centrifuge to collect Ni nanoparticles. The
materials thus obtained were washed in DI water many times.
Amount of them was kept at room temperature and the others
were annealed in hydrogen gas at 250  C, 300  C and 400  C to
purge and to study their crystallization process.
Preparation of NiPt nanoparticles
Selected Ni nanoparticles gained after washing were quickly
redispersed in PVP solution 7 M. The solution containing Ni
nanoparticles then separated equally in three parts. Different
amount of H2PtCl6 (Alpha Aesar; Purification of 99.99%) solu-
tion 0.5 M was in tern dropped slowly in each part solution.
Galvanic replacement reaction is described by equation:
2Ni þ H2 PtCl6 ¼ Pt þ 2NiCl2 þ 2HCl (2)
After 2 h reaction, the productions were purged and
centrifugally collected. The collected particles were dried and
annealed in hydrogen gas at 300  C for 60 min.
Physical properties analysis
The crystalline phases were determined by an X-ray diffrac-
tometer (Bruker, D8 Advance). The morphologies and chemi-
cal compositions were characterized by scanning electron
microscopy (SEM, HitachiS-4800) with an energy dispersive X-
ray spectroscope (EDS), and transmission electron microscopy
(TEM). Magnetic properties were studied by a vibrating sample
magnetometer (VSM, Lakeshore 7400).
Preparation of electrode for cyclic voltammetry
measurement
0.05 g of material had been ultrasonically mixed with 30 ml
nafion® 5% (Alpha Aesar) until it started to condense. The
working electrodes were prepared by stuffing the mixed ma-
terial to a plastic tube (diameter of 0.2 mm) with a graphite
electrode inside. Cyclic voltammetry were preformed at room
temperature by an instrument using a three-electrode (Met-
rohm, 797 VA Computrace) in 1 M KOH þ 2 M ethanol solution.
The measurements were carried out at the potential sweep
rate of 50 mVs
1 in the range from
0.8v to 0.6v for the alloy of
NiPt nanoparticles and
0.4v to 0.8v for the Ni nanoparticles.
The test solutions were purged with high-purity nitrogen gas
before measurement.
Results and discussions
Ni nanoparticles synthesized by a reduction method using the
strong reductant of NaBH4 were used as the templates to
prepare NiPt nanoparticle. To obtain fine NiPt nanoparticles,
the templates should be pure and possible to disperse in PVP
solution. However, unwanted elements such as nickel oxide
and nickel hydroxide are able to be created during
13194 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 ) 1 3 1 9 2 e1 3 1 9 7

synthesizing process. The purification can be controlled by the

Table 1 e The composition analysis of Ni nanoparticles
heat treatment in hydrogen gas or varying the legend con-
synthesized with different PVP concentrations.
tents. The heat process always accompany with the crystal-
PVP concentrations Ni at% O at% Totals %
line growing resulting in the extended crystals size. Besides,
water content in the materials diminishes whereby the par- 0.3 M 74.27 25.73 100.00
ticles become inert and not to redisperse in the solution. In 0.5 M 75.06 24.94 100.00
0.7 M 97.02 2.98 100.00

Fig. 2 e XRD diffractogram of Ni particles annealing in

hydrogen environment with different temperatures: (a)
room temperature; (b) 250  C; (c) 300  C; (d) 400  C.

this study, the different concentration of PVP was used to

determine the optimum condition to prepare the templates.
Fig. 1 is FE-SEM images of Ni nanoparticles synthesized with
PVP concentration of 3 M, 5 M and 7 M. Although PVP con-
centration was not significant effect on the morphology and
the particle size, this influenced on concentration of oxygen in
the samples. The composition analysis (in Table 1) showed
that Ni nanoparticles synthesized with PVP solution 7 M
exhibited lest oxygen. Therefore, this concentration was used
for further studies.
The XRD patterns in Fig. 2 show the influence of annealing
temperatures on crystalline structure of Ni nanoparticles. No
XRD peaks are found for the samples prepared without
annealing. This means that the nanoparticles after centrifugal
collection were formed in amorphous phase. The XRD pat-
terns of Ni nanoparticles after annealing show the presence of
peaks corresponding to face centered cubic structure of Ni
crystal and the intensity of the peaks increase with an in-
crease of the annealing temperatures. This result is used as a
reference data for heating treatment of NiPt in further studies.

Table 2 e Atomic ratio of Ni:Pt nanoparticles synthesized

with different amount of H2PtCl6.
Sample name Ni:Pt ratios
(a) 57.0:3.6
Fig. 1 e FE-SEM images of nickel particles with different (b) 57.0:8.1
(c) 57.0:18.0
PVP concentration (a) 3 M; (b) 5 M; (c) 7 M.
 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 ) 1 3 1 9 2 e1 3 1 9 7
Fig. 3 e XRD diffractogram of NiPt nanoparticles with
different Ni:Pt ratios: (a) 57.0:3.6; (b) 57.0:8.1 and (c)
57.0:18.0.
Fig. 4 e Hysteresis loop of Ni and NiPt nanoparticles with
different Ni:Pt ratios: (a) pure Ni; (b) 57.0:3.6; (c) 57.0:8.1 and
(d) 57.0:18.0.
The compositional analysis (EDX) was used to determine
the atomic ratios of Ni:Pt in the NiPt alloy nanoparticles
after annealing at 300  C in hydrogen gas. The ratio de-
creases with the increase of the amount of H2PtCl6 (Table 2).
Fig. 5 e TEM images of NiPt nanoparticles with different Ni:Pt ratios: (a) 57.0:3.6; (b) 57.0:8.1 and (c) 57.0:18.0.
13195
Only a few percent of remaining oxygen found confirmed
the purification of the nanoparticles. The crystal analysis
was characterized by X-ray powder diffraction method. The
XRD pattern in Fig. 3 shows that two crystal phases corre-
sponding to Pt and Ni crystals presented for the sample with
Ni:Pt ratio of 57.0:3.6. Further increase of Pt contents, the
XRD peaks of Ni were disappeared while the intensity of Pt
peaks increased and shifted toward the high 2q angle. In
general, the peak shift toward the higher angle is believed to
originate from the incorporation of Ni into Pt lattice or
substitution of Ni to Pt in the Pt lattice due to smaller Ni
atom comparing to Pt atom. Beside, theoretical study of NiPt
alloy shows that the separation between the majority spin
s- and d-band centers of Pt atoms caused by interaction
between Ni and Pt lowered the S potential leading to a
reduce of the lattice [18,19]. According to Bragg's Law, the
reduced lattice shifted the XRD peaks toward higher 2q
angle. This confirmed that the nanoparticles were formed as
NiPt alloy. The supposition agrees with argument of and
some others authors [20,21].
Fig. 4 shows the hysteresis loops of the Ni and NiPt nano-
particle measured at 300 K. Ni and NiPt nanoparticles with low
Pt contents exhibited ferromagnetic behaviors. The magneti-
zations decreased with the increase of Pt contents. With
higher Pt content (curve (d)), NiPt nanoparticles showed
superparamagnetic behavior.
Theoretical studies [22] showed that NiPt alloy exhibits
ferromagnetic behavior and magnetic properties were strong
influence by contributions of Pt atoms occupied the surface of
Ni particles and Pt changes d band structure of Ni resulting in
the changes of magnetic properties. In detail, the decrease of
magnetization was attributed to the transfer of electrons from
Pt to Ni d band resulting in the decrease of the number of non-
paired electrons [23]. On the other hand, platinum is a para-
magnetic material and Nickel is a ferromagnetic material but
no paramagnetic phase of Pt is observed in the hysteresis loop.
This reconfirms that Pt incorporated with Ni to form NiPt
alloy.
Fig. 5 is TEM images of NiPt nanoparticles with different
Ni:Pt ratios. Most of the nanoparticles had polyhedron shapes
with the sizes ranging from 20 to 30 nm. The polyhedron
shapes revealed the crystalline structure of the nanoparticles.
It is interesting to find that a part of nanoparticles were
formed as the hollow shapes for the samples with Ni:Pt ratio
of 57.0:18.0 (Fig. 5c).
The cyclic voltammetry measurement was used to deter-
mine the ethanol oxidation activity of the materials in 1.0 M
13196 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 ) 1 3 1 9 2 e1 3 1 9 7
KOH and 2.0 M ethanol. The measurement was first carried
out with Ni nanoparticles and then with NiPt nanoparticles.
Fig. 6 shows the cyclic voltammogram (CV) of the Ni
nanoparticles. The present peak at the applied voltage of
0.37 V was attributed to the oxidation of Ni(II) to Ni(III) due to
changing of Ni(OH)2 to NiOOH [24]. The oxidation reaction
process is described as following equations [9]:
Ni þ OH
/Ni
OHads þ e

Ni
OHads þ OH
/NiðOHÞ2 þ e

NiðOHÞ2 /NiOOH
The peaks that relate with the oxidation of Ni(0) to Ni(I) did
not present in the range of measurement because of its
occurrence at low negative potential (about
0.8 V [1]).
Fig. 7 (a) is the CV of pure Pt wire. A current peak in forward
sweep (If) is the result of ethanol oxidation reaction and the
current peak in backward sweep (Ib) is related with the
carbonaceous intermediate in which the oxidation of COads is
not complete oxidized in anodic sweep [1].
Fig. 7 (b, c and d) show the CV of NiPt nanoparticles with
different Ni:Pt ratio. The first peak (marked by “I”) is related to
ethanol oxidation due to equation:
C2 H5 OH þ 12OH
/2CO2 þ 9H2 O þ 12e

and the second peak agrees with the oxidation of Ni(II) to
Ni(III) as showing in Fig. 6.
The ethanol oxidation peak (I) increases with the increase
of Pt content. The increase of the peak is believed to the
contribution of Pt in NiPt alloy and the removal of the carbo-
naceous adsorption. Indeed, platinum, an active metal for Ce
C bond activation has been known as an excellent electro-
catalyst material for ethanol oxidation. Therefore, increasing
amount of Pt improves its ability to activate the CeC bond
resulting in increasing the oxidation reactions. In addition, the
present of NiOOH is expected to remove the carbonaceous
intermediates according to reaction:
Fig. 6 e The cyclic voltammogram of the Ni nanoparticles
in KOH 1 M þ C2H5OH 2 M.
(3)
(4)
(5)
Fig. 7 e The cyclic voltammogram of the NiPt nanoparticles
with different Ni:Pt ratios: (a) pure Pt wire; (b) 57.0:3.6; (c)
57.0:8.1 and (d) 57.0:18.0 in KOH 1 M þ C2H5OH 2 M.
2OH
PtðCOÞads ƒ!Pt þ CO3 2
þ 2Hþ (7)
It is possible to see that in the backward sweep (Fig. 7bed),
(6) the oxidation peak of COads did not appear clearly like it did for
pure Pt wire (Fig. 7a). This is an experimental evidence of NiPt
alloy to demonstrate the removal of the carbonaceous
adsorption.
Besides carbonaceous removal, the improvement of the
electrocatalyst should be concerned with the contribution of
weakening PteCO bonding. Pt atoms adsorb CO by receiving
the electrons from the 5s orbit of CO molecules and trans-
ferring electrons from their d band to the 2p* antibonding
orbit of CO molecules [25]. The PteCO bonding will be weak-
ened when Pt alloys with Ni because Pt atoms have to donate
electrons to Ni atoms instead of to CO molecules. Thus, it
limited the electrode poisoning effect.
Conclusions
The alloy of NiPt nanoparticles were successfully synthesized
by galvanic replacement method using Ni nanoparticles as the
templates. The presence of the peaks of Ni and Pt in XRD
pattern as well as polyhedron shapes in TEM demonstrated
that NiPt alloys had crystalline structure with the particle
sizes ranging from 25 nm to 30 nm. NiPt nanoparticles
exhibited ferromagnetic behavior with the Ni:Pt ratio lesser
than 57.0:18.0 and became superparamagnetic for further in-
crease of Pt contents. The XRD peaks of Pt shift toward high 2q
angle and the magnetic properties of NiPt nanoparticles
revealed the formation of NiPt alloy. The result indicated that
the electrocatalytic activities for ethanol oxidation reactions
of NiPt nanoparticles were better than that of pure platinum.
The electrocatalytic activities for ethanol oxidation of NiPt
increased with increasing of Pt content. The improvements of
the electrocatalytic activities were the results of the formation
of NiPt alloy due to the weakening of PteCO bonding and the
removal of carbonaceous intermediate.
 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 ) 1 3 1 9 2 e1 3 1 9 7
Acknowledgement
This research is funded by Vietnam National Foundation for
Science and Technology Development (NAFOSTED) under
grant number of 103.02-2013.50.
references
[1] Soundararajan D, Park JH, Kim KH, Ko JM. PteNi alloy
nanoparticles supported on CNF as catalyst for direct ethanol
fuel cells. Curr Appl Phys 2012;12:854e9.
[2] Wang Y, Zou S, Cai W-B. Recent advances on electro-
oxidation of ethanol on Pt- and Pd-Based catalysts: from
reaction mechanisms to catalytic materials. Catalysts
2015;5:1507e34.
[3] Akhairi MAF, Kamarudin SK. Catalysts in direct ethanol fuel
cell (DEFC): an overview. Int J Hydrogen Energy
2016;41:4214e28.
[4] Huang W, Wang H, Zhou J, Wang J, Duchesne PN, Muir D,
et al. Highly active and durable methanol oxidation
electrocatalyst based on the synergy of platinumenickel
hydroxideegraphene. Nat Commun 2015;6:1e8.
[5] Zhou X-W, Zhang R-H, Zhou Z-Y, Sun S-G. Preparation of
PtNi hollow nanospheres for the electrocatalytic oxidation of
methanol. J Power Sources 2011;196:5844e8.
[6] Stamenkovic VR, Fowler B, Mun BS, Wang G, Ross PN,
Lucas CA, et al. Improved oxygen reduction activity on
Pt3Ni(111) via increased surface site availability. Science
2007;315:493e7.
[7] Stamenkovic VR, Mun BS, Arenz M, Mayrhofer KJ, Lucas CA,
Wang G, et al. Trends in electrocatalysis on extended and
nanoscale Pt-bimetallic alloy surfaces. Nat Mater
2007;6:241e7.
[8] Hoover RR, Tolmachev YV. Electrochemical properties of Pt
coatings on Ni prepared by atomic layer deposition. J
Electrochem Soc 2009;156:A37e43.
[9] Mukherjee P, Bagchi J, Dutta S, Bhattacharya SK. The nickel
supported platinum catalyst for anodic oxidation of ethanol
in alkaline medium. Appl Catal A General 2015;506:220e7.
[10] Peng Z, Yang H. Designer platinum nanoparticles: control of
shape, composition in alloy, nanostructure and
electrocatalytic property. Nano Today 2009;4:143e64.
[11] Long NV, Ohtaki M, Nogami M, Hien TD. Effects of heat
treatment and poly(vinylpyrrolidone) (PVP) polymer on
electrocatalytic activity of polyhedral Pt nanoparticles
towards their methanol oxidation. Colloid Polym Sci
2011;289:1373e86.
13197
[12] Long NV, Ohtaki M, Uchida M, Jalem R, Hirata H, Chien ND,
et al. Synthesis and characterization of polyhedral Pt
nanoparticles: their catalytic property, surface attachment,
self-aggregation and assembly. J Colloid Interface Sci
2011;359:339e50.
[13] Long NV, Yang Y, Thi CM, Minh NV, Cao Y, Nogami M. The
development of mixture, alloy, and core-shell
nanocatalysts with nanomaterial supports for energy
conversion in low-temperature fuel cells. Nano Energy
2013;2:636e76.
[14] Menning CA, Hwu HH, Chen JG. Experimental and theoretical
investigation of the stability of Pt
3d
Pt(111) bimetallic
surfaces under oxygen environment. J Phys Chem B
2006;110:15471e7.
[15] Radillo-Diaz A, Coronado Y, Perez LA, Garzon IL. Structural
and electronic properties of PtPd and PtNi nanoalloys. Eur
Phys J D 2009;52:127e30.
[16] Yang Z, Zhang Y, Wang J, Ma S. First-principles study on the
Ni@Pt12 Ih coreeshell nanoparticles: a good catalyst for
oxygen reduction reaction. Phys Lett A 2011;375:3142e8.
[17] Jiang Q, Jiang L, Hou H, Qi J, Wang S, Sun G. Promoting effect
of Ni in PtNi bimetallic electrocatalysts for the methanol
oxidation reaction in alkaline media: experimental and
density functional theory studies. J Phys Chem C
2010;114:19714e22.
[18] Singh PP. Relativity and magnetism in NiePd and NiePt
alloys. J Magn Magn Mater 2003;261:347e52.
[19] Singh PP, Gonis A, Turchi PEA. Toward a unified approach to
the study of metallic alloys: application to the phase stability
of Ni-Pt. Phys Rev Lett 1993;71:1605.
[20] Park K-W, Choi J-H, Kwon B-K, Lee S-A, Sung Y-E. Chemical
and electronic effects of Ni in Pt/Ni and Pt/Ru/Ni alloy
nanoparticles in methanol electrooxidation. J Phys Chem B
2002;106:1869e77.
[21] Jiang S, Ma Y, Tao H, Jian G, Wang X, Fan Y, et al. Highly
dispersed PteNi nanoparticles on nitrogen-doped carbon
nanotubes for application in direct methanol fuel cells. J
Nanosci Nanotechnol 2010;10:3895e900.
[22] Wang L, Yang Y, Wang N, Huang S. Theoretical
investigation of structural, electronic and magnetic
properties for PtnNi55-n (n ¼ 0e55) nanoparticles. Comput
Mater Sci 2016;117:15e23.
[23] Benguedouar Y, Keghouche N, Belloni J. Structural and
magnetic properties of NiePt nanoalloys supported on silica.
Mater Sci Eng B 2012;177:27e33.
[24] Riyanto, Othman MR, Salimon J. Analysis of ethanol using
copper and nickel sheet electrodes by cyclic voltammetry.
Malays J Anal Sci 2007;11:379e87.
[25] Blyholder G. Molecular orbital view of chemisorbed carbon
monoxide. J Phys Chem 1964;68:2772e7.