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 3 ( 2 0 1 8 ) 2 1 3 3 3 e2 1 3 4 4

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Influence of Sn content on the electrocatalytic

activity of NiSn alloy nanoparticles-incorporated
carbon nanofibers toward methanol oxidation

Nasser A.M. Barakat a,*, Fahad S. Al-Mubaddel b,

Mohammad Rezual Karim c, Maher Alrashed b, Hak Yong Kim a
a
Chemical Engineering Department, Minia University, El-Minia, Egypt
b
Department of Chemical Engineering, King Saud University, PO Box 800, Riyadh 11421, Saudi Arabia
c
Center for Excellence in Materials Research CEREM, King Saud University, PO Box 800, Riyadh 11421, Saudi Arabia

article info abstract

Article history: Improvement of the electrocatalytic activity of nickel toward methanol oxidation can be
Received 27 May 2018 conducted by exploiting the synergetic influence of a co-catalyst and/or utilizing a proper
Received in revised form support. In this study, utilizing tin as a co-catalyst and supporting on carbon nanofibers are
27 September 2018 proposed to enhance methanol oxidation in the alkaline media. Typically, NiSn nano-
Accepted 30 September 2018 particles alloy-incorporated carbon nanofibers could be prepared by calcination of elec-
Available online 24 October 2018 trospun nanofibers composed of poly (vinyl alcohol), nickel acetate tetrahydrate and tin
chloride under argon atmosphere at a high temperature. The influence of the co-catalyst
Keywords: content and the calcination temperature on the morphology, composition and electro-
NiSn alloy catalytic activity of the proposed nanofibers was investigated. Smooth electrospun nano-
Methanol oxidation fibers can be prepared regardless the tin chloride content up to 35 wt%, and the calcination
Electrospinning process did not distinctly affect the nanofibrous morphology. Mostly, Ni3Sn and Ni3Sn2
Nanofibers nanoparticles-incorporated amorphous carbon nanofibers were obtained at all the utilized
calcination temperatures (700, 850 and 1000
C) and examined SnCl2 contents. However, at
10 wt% SnCl2 content and 850
C calcination temperature, single metallic compound
(Ni3Sn2)-incorporated carbon nanofibers were synthesized. Electrochemical measurements
indicated that the electrocatalytic activity depends strongly on the tin content as well as
the calcination temperature. The nanofibers obtained from electrospun solution contain-
ing 10 wt% SnCl2 and calcined at 850
C showed very good performance compared to the
other formulations. Typically, the corresponding onset potential of the methanol oxidation
reaction using these nanofibers catalyst is 315 mV (vs. Ag/AgCl) while it was 405 mV for the
nanofibers obtained from electrospun solution containing 0, 5, 15, 25 and 35 wt% SnCl2.
Moreover, the best nanofibers reveal the highest current density. Kinetic study indicated
that the corresponding activation energy is 15.6 kJ/mol.
© 2018 Hydrogen Energy Publications LLC. Published by Elsevier Ltd. All rights reserved.

* Corresponding author. Chemical Engineering Department, Faculty of Engineering, Minia University, Egypt.
E-mail address: nasbarakat@minia.edu.eg (N.A.M. Barakat).
https://doi.org/10.1016/j.ijhydene.2018.09.196
0360-3199/© 2018 Hydrogen Energy Publications LLC. Published by Elsevier Ltd. All rights reserved.
21334 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 3 ( 2 0 1 8 ) 2 1 3 3 3 e2 1 3 4 4
Introduction
Besides the near expected depletion, environmental degra-
dation is another problem facing the wide utilization of the
fossil fuels. Typically, burning the traditional fossil fuels leads
to create an imbalance in the atmospheric carbon dioxide
levels that is considered the main reason behind the global
warming. Environmentally, hydrogen is the best candidate
due to producing only water as exhaust gas, and nontoxicity
and high combustibility at room temperature and pressure.
However, storage and transportation risks as well as the dif-
ficulties in utilization in the portable devices are the main
dilemma constraining the wide application of the hydrogen.
Accordingly, several compounds have been introduced as
hydrogen storage materials [1e9]. Methanol is the simplest
organic liquid hydrogen storage compound [10]. Besides the
attractive physical and chemical characteristics, methanol
exhibits more efficient storage than the compressed hydrogen
in terms of the weight and volume. Therefore, methanol does
not require the acryogenic container that needs to be main-
tained at very low temperature [10,11]. The low volatility of
this simple alcohol reduces the risk of flash fire and explosion.
Furthermore, the possibility of producing from the biomasses
puts the methanol among the renewable energy sources
[12,13].
Methanol electro oxidation is the simplest methodology to
extract hydrogen from methanol [14]. Economically, the
extraction cost via the electro oxidation process depends on
the applied cell potential as well as the generated current
density. To avoid the high cost of the precious electrodes,
transition metals-based materials were widely investigated as
anodes for the methanol electro oxidation [15]. Due to the
relatively high electrocatalytic activity, nickel is the most
widely investigated anode material for methanol electro
oxidation in the alkaline media [16]. However, the research
efforts are going on to improve both of the onset potential and
the current density. The modification strategies are mainly
based on utilizing a co-catalyst with nickel or immobilizing
the catalyst on proper nanostructural supports. In this regard,
some metals and nonmetals were utilized as co-catalysts
including cobalt [17,18], manganese [19e21], palladium
[22,23], gold [23], copper [24,25] and nitrogen [26,27]. On the
other hand, due to owing a good adsorption capacity, the
carbonaceous nanostructures attract the most attention as
effective supports for the nickel-based electrocatalysts. Car-
bon nanotubes, graphene, graphite and glassy carbon are the
most widely used supports [15,28e30]. Other inorganic sup-
port materials were also investigated including TiO2 nano-
tubes [31] and mesoporous silica [32], however the results are
not good compared to the carbonaceous supports. Due to the
large axial ratio, nanofibrous morphology shows a priority
over the other nanostructures in terms of the low electron
transfer resistance. Typically, the large axial ratio diminishes
the interfacial resistance appeared among the particles of the
other morphologies [33]. Accordingly, carbon nanofibers are
considered a promised carbonaceous support. Several nano-
fibers making techniques were reported, however electro-
spinning is the most widely used process in the research and
industrial levels due to simplicity, high yield, low cost and
applicability for different kinds of materials [18,25,34].
Very recently, NiSn discrete nanoparticles have been re-
ported as a stable electro catalyst for methanol oxidation in
alkaline media [35]. Moreover, these bimetallic nanoparticles
have been immobilized on titanium support to enhance the
electro catalytic activity toward methanol oxidation [36]. In
these reports, the observed onset potentials were relatively
high. Therefore, in this study, synthesis of this promised
bimetallic electro catalyst supported on carbon nanofibers
was targeted to exploit the adsorption capacity and the large
axial ratio of the proposed support. Due to the good solubility,
tin-nickel alloy system has a wide composition range that can
have a distinct influence on the electro catalytic activity.
Therefore, the influence of tin content on the electro catalytic
activity of NiSn alloy nanoparticles-incorporated carbon
nanofibers toward methanol oxidation was investigated.
Moreover, the effect of the calcination temperature on the
electro catalytic performance has been studied. Kinetic
studies were performed to estimate the activation energy of
the electro oxidation reaction over the optimum nanofibers.
The results indicated that the co-catalyst can enhance both of
the onset potential and current density, however the content
as well as the calcination temperature should be optimized to
get the best performance.
Materials and methods
Materials
Poly (vinyl alcohol) (PVA, Mw.t 89,000; Alfa Aesar, South Korea)
was used to prepare the initial electrospun sol-gel. Nickel (II)
acetate tetrahydrate (NiAc, Ni(CH3COO)2$4H2O Sigma Aldrich)
and tin chloride (SnCl2, Sigma Alrich) were used as metallic
precursors. The aforementioned chemicals were used without
any prior treatment. Deionized water was used as solvent.
Catalyst preparation
First, 10 wt% aqueous solution of PVA was prepared by adding
the polymer granules gradually to the DI water and stirring at
50
C overnight. The metals precursors were dissolved indi-
vidually in the deionized water. NiAc/PVA stock solution was
prepared by mixing 20 wt% NiAc aqueous solution with the
prepared polymer solution with a weigh ration of 1:3. To study
the influence of tin content, a pre-estimated amount of SnCl2
was dissolved in the minimum amount of the DI water and
mixed with 20 g from the NiAc/PVA solution. The final mixtures
were stirred at 50
C for 5 h. Based on the SnCl2 weight ratio
with respect to NiAc, different solutions (5, 10, 15, 25 and 35 wt
%) were prepared. The electrospinning process was carried out
at 20 kV DC potential with a tip-to-collector distance of 15 cm at
room temperature. The collected mats were vacuously dried at
70
C for 24 h. To investigate the influence of the calcination
temperature, the process were carried out under argon atmo-
sphere at different temperatures (700, 850 and 1000
C) with a
heating rate of 2.5 deg/min and holding time of 3 h.
 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 3 ( 2 0 1 8 ) 2 1 3 3 3 e2 1 3 4 4
Characterization
The morphology of the introduced nanofibers was investi-
gated by Scanning Electron Microscope (SEM, JEOL JSM-5900,
Japan) and Field-Emission Scanning Electron Microscope (FE
SEM, JEOL JSM-5900, Japan). The composition of the nanofibers
was studied by X-ray diffraction analysis (XRD, Rigaku, Japan)
with Cu Ka (l ¼ 1.540  A) radiation over Bragg angle ranging
from 20 to 80
. Normal and high resolution images were ob-
tained with transmission electron microscope (TEM, JEOL JEM-
2010, Japan) operated at 200 kV equipped with EDX analysis.
Thermal properties have been studied by thermal gravimetric
analyzer (TGA, Pyris 1, PerkinElmer Inc., USA). The electro-
chemical measurements have been achieved using VersaStat
4 instrument. Ag/AgCl and Pt were utilized as reference and
counter electrode, respectively. On the other hand, the
working electrode was prepared by deposition of the func-
tional material on the surface of a glassy carbon electrode.
Briefly, 2 mg of the function material, 20 mL Nafion solution
(5 wt% in isopropanol) and 400 mL of isopropanol were mixed
and sonicated for 30 min. Later on, 15 mL was deposited on the
surface of the active area of the glassy carbon electrode after
well cleaning and polishing. Accordingly, the mass of the
functional material was 0.073 mg over the active surface of the
glassy carbon electrode. To perform a kinetic study for the
electro oxidation reaction, the electrochemical measurements
have been performed at different temperatures; 12, 25, 35, 45
and 55
C.
Results and discussion
Influence of tin content on the nanofibrous morphology
Overall, the electrospinning process is an efficient polymeric
nanofibers making technique especially from the polymers
own high molecular weight, and suitable electrical conduc-
tivity and viscosity of their solutions. On the other hand,
based on the authors experience and also according to the
Fig. 1 e SEM images for the obtained nanofibers after calcination at 700
C of the electrospun mats containing (A) 5%, (B) 10%,
(C) 15%, (D) 25% and (E) 35% SnCl2.
21335
literature, producing good morphology inorganic nanofibers
mainly depends on the utilized metal precursor. In other
words, the precursors having good tendency for the poly-
condensation process usually reveals very acceptable nano-
fibrous morphology. In details, the polycondensation
characteristic maintains the nanofibrous morphology during
the calcination process, so large axial ratio, beads-free and
smooth nanofibers are usually obtained. Due to presence of
the strongly electronegative oxygen atom which induces
considerable polarity in the dþd-M-O bond, metal alkoxides
possess very high polycondensation tendency that results in
producing very good morphology electrospun nanofibers and,
most importantly, maintaining the good morphology after the
calcination process [34]. Besides, metal acetates have also
revealed an acceptable polycondensation characteristic lead-
ing to producing good morphology nanofibers after the calci-
nation process [37]. Fig. 1 shows SEM images for the obtained
nanofibers after calcination of electrospun mats containing 5,
10, 15, 25 and 35 wt% SnCl2 at 700
C. As shown in the figure,
up to 15 wt% SnCl2 (panels A, B and C), good morphology
nanofibers were obtained with small amounts of nano-
particles. However, as shown in Fig. 1D and E, increasing the
amount of the tin precursor led to have more nanoparticles.
Increasing the calcination temperature to 850
C (Fig. 2) did
not affect the overall morphology, however the 10 and 15%
samples produces particles-free nanofibers (Fig. 2B and C). On
the other hand, small-attached nanoparticles can be observed
on the surface of the nanofibers of the other formulations;
Fig. 2A, D and 2E. It is noteworthy mentioning that the sol-gels
having concentrations of SnCl2 more than the used threshold
in this study (35%) could not be electrospun due to the poly-
mer degradation because of the influence of the chlorine ion
on the OH group in the PVA chain.
Increasing the calcination temperature further to 1000
C
did not affect the nanofibrous morphology in general. How-
ever, the nanoparticles appeared with all formulations (data
are not shown). Fig. 3 represents the FE-SEM images for the
10 wt% sample at the utilized three temperatures. As shown,
the best morphology was obtained at 850
C (Fig. 3B) in terms
21336 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 3 ( 2 0 1 8 ) 2 1 3 3 3 e2 1 3 4 4
Fig. 2 e SEM images for the obtained nanofibers after calcination at 850
C of the electrospun mats containing (A) 5%, (B) 10%,
(C) 15%, (D) 25% and (E) 35% SnCl2.
Fig. 3 e FE-SEM images of the nanofibers obtained from calcination of electrospun mats having 10% SnCl2 at (A) 700, (B) 850
and (C) 1000
C.
of smooth nanofibers and absence of the nanoparticles.
Therefore, from the obtained results, it can be concluded that
the best nanofibrous morphology associates with 10 wt%
SnCl2 concentration in the initial electrospun solution and
850
C calcination temperature.
Influence of tin content on the nanofibrous composition
Besides the advantage in maintaining the nanofibrous
morphology during the calcination process, the acetate anion
abnormally decomposes under inert atmosphere to produce
strong reducing gases (hydrogen and carbon). Accordingly,
calcination of metal acetates in the inert atmosphere at high
temperatures results in producing pure metal rather the ex-
pected oxide forms [14,38,39]. As aforementioned in the
introduction section, nickel-tin bimetallic system can form a
wide composition range from the NiSn alloys. X-ray diffraction
analysis is a highly trustable technique to detect the crystal
structure and consequently the composition of the crystalline
materials. Fig. 4 shows the XRD patterns for the nanofibers
obtained from electrospun mats having different contents
from SnCl2 after calcination at 850
C. As shown, the content of
the tin precursor strongly affects the composition of the pro-
duced nanofibers. For instance, for 5 wt% SnCl2 nanofibers, two
forms from nickel-tin alloy systems could be detected. Typi-
cally, appearance the diffraction peaks at 28.6
, 39.3
, 42.5
,
44.8
and 59.3
corresponding to (101), (200), (002), (201) and
(202) crystal plans, respectively indicates formation of Ni3Sn
alloy (JCDPS# 35-1362). Moreover, the diffraction peaks repre-
senting the crystal plans of (101), (002), (102), (110), (201), (112),
(103), (202) and (211) at 2q values of 30.7
, 34.8
, 43.5
, 44.6
,
55.1
, 57.6
, 59.8
, 63.9
, and 73.4
conclude formation of Ni3Sn2
alloy according to the standard JCDPS database (#06-0414). On
the other hand, the nanofibers prepared from the electrospun
solution having 10 wt% SnCl2 compose of a single compound;
Ni3Sn2. It is noteworthy mentioning that, for this sample, all
the appeared peaks in the XRD pattern could be assigned to
Ni3Sn2 which indicates these nanofibers compose of a single
NiSn chemical compound. On the other hand, for the other
formulations, the same mixture obtained in case of the 5 wt%
nanofibers (Ni3Sn and Ni3Sn2) could be also detected as shown
in Fig. 4. Furthermore, the wide peak observed with all for-
mulations at 2q ~25
corresponding to an experimental
d spacing of 3.37  A reveals presence of graphite-like carbon (d
(002), JCPDS; 41-1487). It is worth mentioning that all the
nanofibers obtained at other calcination temperatures having
mixed NiSn alloys structure (data are not shown).
Fig. 5 displays TEM analysis results for the nanofibers
synthesized from an initial electrospun solution containing
10 wt% SnCl2 and calcined at 850
C. As shown in Fig. 5A, the
normal TEM image indicates that the produced nanofibers are
in the form of metallic nanoparticles incorporated in amor-
phous carbon nanofibers. Linear elemental analysis (Fig. 5B)
depicts that nickel and tin have similar distribution along with
 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 3 ( 2 0 1 8 ) 2 1 3 3 3 e2 1 3 4 4 21337

Fig. 4 e XRD patterns for the prepared nanofibers at 850
C at different Sn contents.

the selected line, which is further proved in Fig. 5C and D. The
obtained finding confirms formation of NiSn alloys and
simultaneously supports the XRD results.
Thermal analysis
Thermal gravimetric analysis (TGA) can provide useful infor-
mation to study the chemical decomposition carrying out in
the electrospun nanofibers during the calcination process.
Fig. 6 depicts TGA plot for the electrospun nanofibers con-
taining 10 wt% SnCl2 along with the first derivative data. As
shown in the figure, several regions for the weight loss were
translated as peaks in the first derivative curve. The first peak
(at ~ 90
C) matching the slight decrease in the weight at low
temperature can be assigned to losing of the physical moisture.
Later on, the high intensity peak at ~255
C can be assigned to
the carbonization of the used polymer. The used semi-
crystalline polymer (PVA) has high carbon content (ca. 54.5%)
and low cost. However, it is not widely used as a precursor for
carbon nanofibers fabrication due to the decomposition at
temperatures slightly higher than its melting point that leads
to have a low carbonization yield. Enhancing the thermal sta-
bility of the PVA was proposed by several methodologies
including dehydration from 100 to 290
C under tension in a
mixed gas atmosphere [40], pre-oxidation or subsequent
dehydration [41], using iodine which acts as a good stabilizer of
PVA [42] and presence of transition metals (mainly nickel and
cobalt) [43,44]. Accordingly, the detected graphite in both of
XRD and TEM analyses is attributed to the carbonization of
PVA that is catalyzed by the formed metallic nanoparticles.
The remaining peaks represent the decomposition of
nickel acetate to form pristine nickel according the following
equations [32].
Ni(CH3COO)2$4H2O / 0.86Ni(CH3COO)2$ 0.14Ni(OH)2 þ
0.28CH3COOH þ 3.72H2O (1)
0.86 Ni(CH3COO)2$0.14Ni(OH)2 /
NiCO3 þ NiO þ CH3COCH3 þ H2O (2)
NiCO3 / NiO þ CO2 (3)
NiO þ CO / Ni þ CO2 (4)
On the other hand, complete reduction of tin chloride
could be achieved due to formation of the strong reducing
gases (CO and H2) from the decomposition of acetate ion.
Electrochemical measurements
It is known that the catalytic activity toward alcohol oxidation
of nickel-based electrocatalysts is not attributed to the
21338 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 3 ( 2 0 1 8 ) 2 1 3 3 3 e2 1 3 4 4
Fig. 5 e (A) TEM image for the produced 10 wt% Sn nanofiber, (B) linear elemental analysis at a randomly chosen line, and (C)
and (D) nickel and tin distribution along with the selected line.
Fig. 6 e Thermal gravimetric analysis for the 10 wt% SnCl2
nanofibers along with the first derivative data.
electronic structure like the noble metals, but these non-
precious electrocatalysts own the activity due to the possi-
bility of formation of nickel (oxy)hydroxide (NiOOH) active
layer on the surface. This active layer can be generated by
sweeping in an alkaline medium for several cycles [16,45]:
Ni þ 2OH 4 Ni(OH)2 þ 2e (5)
Ni(OH)2 þ OH 4 NiOOH þ H2O þ e (6)
Later on, methanol electro oxidation takes place by suc-
cessive reactions with the active layer [45]. Accordingly, one
important role for the co-catalyst addition is enhancing for-
mation of this layer. Therefore, it was expected that the co-
catalyst content would have a considerable influence on for-
mation of the active layer. For comparison, Sn-free Ni-incor-
porated CNFs were prepared by the same procedure. Fig. 7
displays the 50th cycle from the cyclic voltagmmograms of
the prepared nanofibers activation that was achieved by
sweeping in 1.0 mol/L KOH solution from 0.0 to 1.0 V (vs. Ag/
 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 3 ( 2 0 1 8 ) 2 1 3 3 3 e2 1 3 4 4 21339

Fig. 7 e Cyclic voltammograms (50th cycles) for the activation of the prepared nanofibers at (A) 700
C and (B) 850
C by
sweeping in 1.0 M KOH at scan rate 50 mv/s.

AgCl electrode) at scan rate of 50 mV/s. The observed redox layer. From Fig. 7A, compared to Sn-free nanofibers and other
peaks with all formulations are attributed to Ni(OH)2/NiOOH formulations, the nanofibers prepared from a sol-gel having
transformation (Eq. (6)) [46,47]. Therefore, high current in- 15 wt% SnCl2 possess the best activity toward formation of the
tensity redox peaks refer to intense formation for the active desired layer. On the other hand, increasing the calcination

Fig. 8 e Influence of tin content on the electro catalytic activity of the NiSn nanoparticles-incorporated nanofibers prepared
at 700
C at different methanol concentration. Scan rate 50 mV/s and 15
C.
21340 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 3 ( 2 0 1 8 ) 2 1 3 3 3 e2 1 3 4 4
temperature to 850
C changed the situation to make 10 wt%
SnCl2 content in the electrospun solution is the optimum
value to have a maximum amount from the active species as
shown in Fig. 7B. Another important finding is the sharpness
and closeness of the redox peaks corresponding to the 10 wt%
sample calcined at 850
C compared to all other formulations.
This behavior indicates high reversibility and fast formation
for the sought-after active layer over the surface of these
nanofibers. This characteristic might be attributed to owing a
single NiSn alloy nanoparticles (Ni3Sn2) as it was confirmed in
the XRD results.
Figs. 8 and 9 displays the electro catalytic performance for
the prepared nanofibers at 700 and 850
C, respectively toward
methanol oxidation at different alcohol concentrations. As
shown, the obtained results support the aforementioned hy-
pothesis about the direct relation between the amount of the
formed NiOOH on the catalyst surface and the electrocatalytic
activity. Typically, for the prepared nanofibers at 700
C
(Fig. 8), the nanofibers showed the highest redox peak during
the activation process (15 wt% sample; Fig. 7A) reveal the best
performance as an electro catalyst for methanol oxidation
compared to all other formulations (including Sn-free Ni-
incorporated CNFs) with all methanol concentrations in term
of the current density. However, in term of the onset potential,
Fig. 9 e Influence of tin content on the electro catalytic activity of the NiSn nanoparticles-incorporated nanofibers prepared
at 850
C at different methanol concentration. Scan rate 50 mV/s and 15
C.
addition of Sn did not improve the nanofibers catalytic per-
formance. Instead, compared to the Sn-free nanofibers, a little
undesired shift to the positive direction was observed.
Numerically, the onset potentials for the best sample and Ni-
incorporated CNFs are 405 and 390 mV, respectively.
On the other hand, calcination at 850
C distinctly shows
the advantage of addition of Sn as co-catalyst. As shown in
Fig. 9, a distinguished improvement in the current density and
onset potential compared to the pristine nickel-incorporated
CNFs is associated with the nanofibers prepared from elec-
trospun solution having 10 wt% SnCl2. Typically, addition of
10 wt% SnCl2 and calcination at 850
C led to decrease the
onset potential to 315 mV; this is 80 mV less than Sn-free CNFs
(395 mV) and 110 mV than other formulations (425 mV).
Moreover, the priority of the best nanofibers is gained at all the
investigated methanol concentrations as shown in Fig. 9.
Furthermore, the best sample show the maximum current
density at the methanol oxidation peak compared to all the
remaining nanofibers. Also, presence of the methanol oxida-
tion peak at a smaller applied potential compared to the other
samples is considered a distinct advantage for the 10 wt%
electro catalyst prepared at 850
C.
Although increasing the calcination temperature from
700
C to 850
C resulted in considerable enhancement in the
 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 3 ( 2 0 1 8 ) 2 1 3 3 3 e2 1 3 4 4 21341

electro catalytic activity of the introduced NiSn-incorporated
carbon nanofibers, more increase in the sintering tempera-
ture showed a negative influence as shown in Fig. 10. This
figure depicts the electro catalytic activities for 10 wt% SnCl2
prepared at 700, 850 and 1000
C at various methanol con-
centrations. Typically, the nanofibers obtained at a
calcination temperature of 1000
C reveals the lowest perfor-
mance at all methanol concentration. It is known that the
calcination temperature has a considerable impact of the de-
gree of crystallinity of the metal nanostructure. Accordingly, it
can be claimed that the crystallinity degree obtained at 850
C
reveals the best electronic structure for catalyzing the

Fig. 10 e Influence of the calcination temperature on the electro catalytic activity of the prepared Ni/Sn carbon nanofibers at
different methanol concentration, scan rate 50 mV/s at 15
C.

Fig. 11 e Kinetic study for the electro oxidation of methanol over the prepared Ni/Sn CNFs containing 10 wt% Sn calcined at
700
C. (A) Influence of reaction temperature on the amount the reacted methanol oxidation over the Sn/Ni (10 wt%)
nanofibers calcined at 700
C. (B) Arrhenius equation plot.
21342 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 3 ( 2 0 1 8 ) 2 1 3 3 3 e2 1 3 4 4

methanol electro oxidation reaction. Overall, studying the
influence of tin content and the preparing temperature indi-
cated that the optimum SnCl2 content in the electrospun so-
lution is 10 wt% with respect to NiAc, and 850
C is a highly
recommended calcination temperature.
From the kinetic point of view, most of the heterogeneous
electro catalytic reactions can be represented by the zero-
order rate of reaction model. This hypothesis was confirmed
in the present study as showing in the obtained results (Figs.
8e10). Typically, almost no influence for the methanol con-
centration on the generated current density was observed
which concludes that the reaction is a zero-order one.
Furthermore, it is known that the main function of the cata-
lyst is decreasing the activation energy. Therefore, the acti-
vation energy for the methanol oxidation over the introduced
nanofibers was estimated. The activation energy was deter-
mined by performing the electro oxidation process at various
temperatures, and then Arrhenius equation could be applied.
Overall, based on the performed electrochemical mea-
surements, it safe to claim that addition of tin can distinctly
improve the electrocatalytic activity of nickel/CNFs composite
toward methanol oxidation when the co-catalyst content and
the calcination temperature are optimized.
Fig. 13 displays the effect of the scan rate on the electro-
chemical oxidation of methanol over the surface of the pro-
posed electrode; 10 wt% Sn. As shown in the figure, the current
density at the oxidation peak slightly increases with
increasing the scan rate. This finding indicates that the mass
transfer operation is the rate controlling step.
Overall, according to the obtained results, the proposed
NiSn-incorporated carbon nanofibers can be exploited
commercially in the electro extraction of hydrogen from
methanol. The suggested nanofibers can distinctly decrease
the required electrolysis energy which is highly desirable.
Moreover, the observed high stability in the alkaline media
adds another important economic aspect.

Ea=
k ¼ A0 e RT (7)

which can be simplify as

Ea
lnðkÞ ¼ lnðA0 Þ  (8)
RT
where k is the reaction constant (mol/s, equals the rate of re-
action numerically), A0 is constant, Ea is the apparent activation
energy (J/mol), T is the temperature (K) and R is the universal gas
constant (8.314 J/K.mol). Fig. 11A represents the change in the
reacted methanol with time at different reaction temperatures;
12, 25, 35, 45 and 55
C. From the obtained data, Arrhenius plot
could be graphed (Fig. 11B). It is noteworthy mentioning that
the data points fit the linear model accurately as the corre-
sponding R2 value was close to unity (0.9637). Accordingly, the
activation energy could be estimated as 15.53 kJ/mol at meth-
anol concentration of 2.0 M for the 10 wt% sample calcined at
700
C. It is noteworthy mentioning that the obtained value of
Fig. 12 e Multistep chronoapmerometry analysis for 10 wt
the activation energy is lower than the reported in literature for
% nanofibers calcined at 700
C using 1.0 M methanol
methanol oxidation in the alkaline media. Few reports have
solution at 12
C.
been introduced and studied the activation energy of methanol
oxidation in the alkaline media. For instance, Volfkovich et al.
performed a study of the electro oxidation of methanol at a
smooth Pt electrode in alkaline media [48]. The values obtained
in 0.05 M alcohol concentration and 1.0 M KOH ranged from 54.4
to 62.8 kJ/mol. While, compared to this study, several higher
activation energy values have been introduced for oxidation
process in the acid media [49].
Stability is another important parameter should be inves-
tigated for the transition metals electro catalysts. Chro-
noamperometry is a widely used and trustable technique for
checking the stability of the electro catalysts. Fig. 12 displays
the multistep chronoamperometry measurement for the
10 wt% SnCl2 nanofibers calcined at 700
C using 1.0 M
methanol solution. As shown in the figure, a good stability for
the synthesized nanofibers can be concluded. Mostly, the alloy
structure reveals high resistance toward the chemical corro-
sion which can be suggested as an acceptable reason for the
observed high stability. It is noteworthy mentioning that
switching the applied voltage off for 10 s before every incre- Fig. 13 e Influence of scan rate on the electrochemical
ment did not affect the electrode stability as it can be activity of the NiSn-incorporated CNFs (10 wt%) at 1.0 M
concluded from the figure. methanol solution and 12
C.
 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 3 ( 2 0 1 8 ) 2 1 3 3 3 e2 1 3 4 4
Conclusion
NiSn nanoparticles-incorporated carbon nanofibers can be
prepared by electrospinning of a sol-gel composed of poly
(vinyl alcohol), nickel acetate tetrahydrate and tin chloride.
However, increasing the tin chloride content more than 35 wt
% with respect to nickel acetate leads to degrade the polymer
which makes the electrospinning process very difficult. The
calcination temperature does not have a strong impact on the
nanofibrous morphology. However, the electrocatalytic ac-
tivity toward methanol oxidation depends on the tin content
as well as the calcination temperature. To get high perfor-
mance as an anode material in the methanol oxidation pro-
cess, the tin chloride content in the electrospun solution has
to be 10 wt% compared to nickel acetate and the electrospun
nanofiber mats have to be sintered at 850
C. Overall, the study
opens a new avenue for tin to be exploited as an effective co-
catalyst to enhance the electrocatalytic activity of nickel
based materials toward alcohols oxidation.
Acknowledgement
The authors would like to extend their thanks to The Dean-
ship of Scientific Research King Saud University, Riyadh, Saudi
Arabia for their support of this work through the group RG-
1439-042.
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