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 ) 9 0 6 e9 1 3

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Preparation of NiO nanofibers by electrospinning

and their application for electro-catalytic oxidation
of ethylene glycol

Sayed Reza Hosseini*, Shahram Ghasemi, Mina Kamali-Rousta,

Seyed Reza Nabavi
Nanochemistry Research Laboratory, Faculty of Chemistry, University of Mazandaran, 47416-95447, Babolsar, Iran

article info abstract

Article history: In this work, nickel oxide nanofibers (NiO-NFs) are produced by electrospinning method
Received 15 July 2016 and calcination in air for 5 h. The thermal gravimetric analysis (TGA), field-emission
Received in revised form scanning electron microscopy (FE-SEM), fourier transform infrared (FT-IR), X-ray diffrac-
11 September 2016 tion (XRD), energy dispersive X-ray spectroscopy (EDS), and electrochemical impedance
Accepted 15 September 2016 spectroscopy (EIS) are used for characterization of the NiO-NFs. The FE-SEM images of the
Available online 7 October 2016 precursor indicate that a large quantity of nanofibers with diameters ranging from 100 to
150 nm with tens of micrometers in length can be acquired. Also, the results show that
Keywords: rough NiO-NFs having large specific surface area are composed of the small nanoparticles.
Electrospinning After calcination, the nanofibers are composed of cubic structure. The EIS study shows that
Nickel oxide nanofibers the value of charge-transfer resistance of the NiO-NFs modified carbon paste electrode
Ethylene glycol (NiO-NFs/CPE) is much smaller than that CPE, indicating a faster electron-transfer process.
Electro-catalysis The NiO-NFs are used as potential catalysts for electro-catalytic oxidation of ethylene
glycol (EG) in 0.2 M NaOH solution. The results demonstrate that the NiO-NFs/CPE reveals
good electro-catalytic activity towards EG oxidation, showing a suitable stability and
robustness.
© 2016 Hydrogen Energy Publications LLC. Published by Elsevier Ltd. All rights reserved.

routes are limited to several microns. The versatile electro-

Introduction
Nowadays, nanostructured materials of mutable morphol-
ogies and aspect ratios especially one-dimensional (1D)
nanostructures such as fibers, wires, rods, tubes, and belts
gained increasing attraction because their electrical properties
depend on directionality [1e5]. Lithographic [6] and wet
chemical techniques [7,8] are suitable methods for the syn-
thesis of 1D nanostructure on a laboratory scale. However,
restricted lengths of the nanostructures concluded these
spinning method is fairly simple and cost-effective technique
for creating 1D nanostructures and it is scalable to yield
nanostructures at an industrial level. The electro-spun nano-
fibers have great porosity and surface-to-volume ratio [9,10]. A
suitable post-electrospinning treatment produces continuous
nanofibers of the matching materials, if the polymer solution
comprises metal ions to form metal oxides [11,12].
Direct alcohol fuel cells (DAFCs), as alternative power
sources; attract significant attentions owing to their portable

* Corresponding author. Fax: þ98 1135302350.

E-mail address: r.hosseini@umz.ac.ir (S.R. Hosseini).
http://dx.doi.org/10.1016/j.ijhydene.2016.09.116
0360-3199/© 2016 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 ) 9 0 6 e9 1 3 907

applications [13,14]. Among numerous types of alcohols, electrode (CPE) with NiO-NFs was performed according to our
ethylene glycol (EG) is one of the most promising candidates previous work [47] with some modification. Briefly, a combi-
as it can be produce straightly from biomass [15]. The EG is nation of NiO-NFs, graphite powder and paraffin oil in a ratio
mostly prepared from heterogeneous hydrogenation of cel- of 20:56:24 (w/w %) was blended until a homogeneously
lulose derivatives [16]. This diol has great water solubility, low wetted paste was achieved. The NiO-NFs/CPE was further
flammability and little volatility [17]. Moreover, EG has larger electrochemically conditioned by potential cycling between
theoretical energy density (7.56 kWh L1) and higher boiling 0.1 and 0.7 V in 0.2 M NaOH solution at y ¼ 50 mV s1 for 100
point (198  C) than methanol [18]. Pt-based catalysts were cycles. TGA (STA504, BAHR Co., Germany) was performed on a
widely applied in DAFCs [19e26]. Also, Pd-based catalysts are thermo-analyzer in temperature ranging from 25  C to 600  C
known as suitable alternatives to Pt-based catalysts due to with a heating rate of 10  C min1 in air. Electrospinning was
their good electro-catalytic properties [27e36]. Although the carried out in a home-made setup (Fanavaran Nanomeghyas
noble metals exhibit high electro-catalytic activities towards Co., Iran) with a motor-controlled rotating drum as a collector.
electro-oxidation of EG, the electrode surfaces are simply The materials, solution preparation, electrospinning process,
fouled by chemisorbed intermediates. Furthermore, high cost construction of the NiO-NFs/CPE and instrumental were
and low abundance of the electrode materials may restrict described in Supplementary information.
their marketable applications.
Discovering novel anode catalysts is extremely desire
which indicates increasing benefits in the progress of noble Results and discussion
metals-free catalysts in current years. Also, it should be noted
that oxidation of the EG in alkaline media is much easier than Physical characterization
acidic solutions [37,38]. Besides the precious metals, in
particular Ni which is less costly and more plentiful on earth Morphological features of the as-fabricated samples are
than Pt and Pd, has been noted to be extremely active in analyzed through FE-SEM. Fig. 1 shows FE-SEM image of the
alkaline media. In contrast to Ni, which is unstable and simply electro-spun PVA/Ni(OAc)2 nanofibers, indicating a large
oxidized in air and solution, its oxide (or hydroxide) is fairly quantity of nanofibers with diameters ranging from 100 to
stable [39e41]. Previously, NiO nanofibers were obtained by 150 nm. The electro-spun nanofibers have approximately
calcining the electro-spun composite fibers of poly (styrene- uniform surfaces, thickness and bead-free structures. This
co-acrylonitrile) and nickel (II) acetate tetra hydrate. The figure evidently reveals the morphology of the NFs which are
electro-spun NiO nanofiber webs were used for thermistor randomly orientate due to bending instability associated with
applications [42]. Till now, there have been some reports on a spinning jet.
the application of Ni oxide modified electrodes for EG electro- The PVA/Ni(OAc)2 nanofibers obtained by electrospinning
oxidation. Although Ni oxide-based electrodes were used in should be calcined because large amounts of organic poly-
the EG oxidation, their application is extremely limited to mer and solvent are contained in these fibers. The corre-
some conducting polymers which were made in presence of sponding thermal behavior of the PVA/Ni(OAc)2 fibers is
sodium dodecyl sulfate; such as poly (o-aminophenol) [43], shown in Fig. 2A. When the temperature exceeds at about
poly (4-aminoacetanilide) [44], poly (N,N-dimethyl aniline) [45] 500  C, no more weight loss occurs, indicating whole removal
and poly (m-toluidine)/Triton X-100 film [46].
Recently, we have introduced an electro-spun CuO
nanoparticles/CPE and its application for hydrazine hydrate
electro-oxidation [47]. The polyvinyl alcohol/copper acetate
(PVA/Cu(OAc)2) nanofibers with diameter ranging from 200
to 300 nm were obtained and after calcination, the fibers
didn't remain as continuous structures and altered to CuO
nanoparticles. In present work, PVA/Ni(OAc)2 composite
nanofibers were formulated by electrospinning process and
the nickel oxides nanofibers (NiO-NFs) were achieved by
following thermal treatment procedure. As far as we know,
application of the electro-spun NiO-NFs for electro-catalysis
of EG oxidation has been not reported. Encouraged by the
great length-to-diameter ratio and high surface-to-volume
ratio of 1D nanostructure which is satisfied by electro-
spinning technique, the electro-catalytic properties of the
prepared NiO-NFs/CPE towards EG oxidation were tested in
alkaline medium.

Experimental

Ni(CH3COO)2$H2O (>99%, Riedel-deHaen) and EG (>99%,

Merck) were used as received. Modification of carbon paste Fig. 1 e FE-SEM image of the PVA/Ni(OAc)2 nanofibers.
908 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 ) 9 0 6 e9 1 3
Fig. 2 e (A) TGA of the PVA/Ni(OAc)2 nanofibers. (B) FT-IR
spectrum of the NiO-NFs.
of the organic species. After 600  C, there is no change in
weight loss, indicating the creation of pure inorganic oxides.
Therefore, calcination temperature at about 600  C is
employed. The FT-IR spectrum of the NiO-NFs is taken in a
region between 4000 and 400 cm1 by using KBr pellet tech-
nique (Fig. 2B). The absence of characteristics peaks of PVA
[48] and presence of only NieO (metal-oxygen covalent bond)
stretching vibration peak at about 455 cm1 reveal the
complete elimination of polymeric template and formation
of uncontaminated metal oxides. The broad peak at about
3427 cm1 is attributed to the symmetric stretching vibration
of OH groups (water absorbed by the fibers sample or KBr).
The peaks corresponding to the adsorbed gases such as
dioxygen (1135 and 1460 cm1) and carbon dioxide
(1658 cm1) are also observed in the spectrum.
The surface of nanofibers turns rough during calcination
and PVA template vanishes after thermal treatment. Fig. 3
shows the FE-SEM image of NiO-NFs. It is observed that the
surface of nanofibers are been rough and they are composed
Fig. 3 e (A) FE-SEM image and (B) EDS of the NiO-NFs.
of closely packed nanoparticles as primary building blocks.
After calcination treatment, the resultant NiO-NFs inherits
the 1D shape from the precursor fibers and diameters of the
NFs become non-uniform. However, the surface are much
rougher which are derived from decomposition of the
organic components such as PVA, acetate groups and the
crystallization of the PVA/Ni(OAc)2 precursors. The EDS
spectrum of NiO-NFs shows the peaks corresponding to
86.2 wt % Ni and 13.8 wt % O elements. The presence of Ni
and O peaks and absence of C peak in the spectrum can be
pointed to removal of the organic components and forma-
tion of pure NiO.
Powder XRD pattern of the NiO-NFs is displayed in Fig. 4.
The shrill peaks in the pattern reveals the crystalline char-
acteristic of the NiO-NFs. The complete elimination of
organic materials and the simultaneous conversion to NiO
take place at calcination temperature. All the diffraction
peaks can be assigned to cubic structural of NiO. The peaks at
2q positions about 37.2, 43.3, 62.7, 75.3 and 79.4 correspond
to 111, 200, 220, 311 and 222 reflections of cubic NiO phase,
respectively. Absence of any other peaks in the XRD pattern
implies the NiO-NFs have good phase purity. Lack of broad
 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 ) 9 0 6 e9 1 3 909

Fig. 4 e XRD pattern of the electrospun NiO-NFs.

peaks around at 2q ¼ 20 confirms that the semi-crystalline

PVA template [49] thoroughly is decomposed. Moreover, Fig. 5 e EIS obtained at open circuit potential for CPE (a) and
average crystallite size of the NiO-NFs according to Debye- NiO-NFs/CPE (b) in 1.0 mM Fe(CN)3¡/4¡
6 þ 0.1 M KCl
Scherer's equation [50] is evaluated at about 60 nm from (200) solution.
reflection peak.

EIS study an electro-catalytic activity (an increment in the anodic peak

current followed a decrease in cathodic peak current (com-
A typical impedance spectrum (Nyquist plot) involves a parison of curves c and d)). This behavior is typical of that
semicircle quota at higher frequencies (limited electron- assumed for mediated oxidation of EG as previously was re-
transfer process) and a linear part at lower frequency (diffu- ported in literature [43e46]:
sion-limited process). Diameter of the semicircle equals the
electron-transfer resistance which controls the electron
transfer kinetics of the redox probe at the interface. Thus, the
resistance describes the interface properties. Nyquist plots for
the CPE (a) and NiO-NFs/CPE (b) acquired in the presence of
1.0 mM [Fe(CN)6]3/4 (1:1) þ 0.1 M KCl solution at open circuit
condition are presented in Fig. 5. It can be observed from this
figure that with introduction of the NiO-NFs into the CPE (plot
b), semicircle part is almost eliminated due to significant
decrease in the charge transfer resistance and its diagram is
comprised of only a linear part. It means that the electron
transfer resistance becomes unimportant in relation to War-
burg impedance. The reason may be featured to nanometer
sizes of the materials which bring in great surface areas and
active sites.

Electro-catalytic oxidation of EG

As is well-known, EG does not suffer oxidation prior to

discharge of supporting electrolyte at the CPE in NaOH solu-
tion in potential range between 0.1 and 0.7 V due to large over-
potential (comparison of curves a and b). Therefore, CPE has
no catalytic activity, hence its surface is modified with suit-
able nano-scale catalysts (i.e., NiO-NFs). The electro-catalytic Fig. 6 e Electrochemical response of the CPE in 0.2 M NaOH
activity of the NiO-NFs/CPE for EG oxidation is examined by solution at y ¼ 20 mV s¡1 (a) in the absence and (b)
cyclic voltammetry (CV) in 0.2 M NaOH solution containing presence of 30 mM EG. CVs of the NiO-NFs/CPE; (c) in the
30 mM EG at y ¼ 20 mV s1 (Fig. 6). The NiO-NFs/CPE exhibits absence and (d) presence of EG at the same conditions.
910 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 ) 9 0 6 e9 1 3

It was generally agreed that nickel oxides in an alkaline

media catalyze the EG oxidation through an overall eight
electron process for creating oxalate anions as final product:

C2 H6 O2 þ 10OH /C2 O4 2 þ 8H2 O þ 8e (3)

It should be mentioned that reliable comparison between

Ni-based catalysts reported in literature and our electro-spun
NiO-NFs is difficult. That is due to different factors such as
concentration of supporting electrolyte, potential scan rate,
and EG concentration which affect activity of the electro-
catalysts towards EG oxidation. However, we have tried to
prepare a rough comparison between the our electrochemical
data with some previous researches for Ni modified electrodes
(Table 1). In comparison with previous works, it seems that
NiO-NFs/CPE can acts as a comparable catalyst in the EG
oxidation and shows a good performance. Among nano-sized
ceramic architectures, nanofibers due to their high aspect
ratios are more attractive over their nano-particulate coun-
terparts. The technique used for preparation of the NiO-NFs is
simple and environmental friendly. Furthermore, it has eco-
nomic cost and is scalable at industrial levels. The catalyst
layer (polymer þ nickel prepared in the previous works) was
deposited as a thin film on the electrode surface (surface
modification); meanwhile the NiO-NFs/CPE is centered based
on bulk modification (a rapid method for generating a
renewable and reproducible surface). Also, the materials
chosen to be catalyst in previously published works, are
formed from many materials which leads to many variables
that are difficult to control and consequently to obtain
reproducible results in electro-catalytic oxidation of EG in
NaOH solution. However, the proposed electro-catalyst needs
to further improvements in the catalytic activity and stability
to realize the practical applications.

Effects of EG concentration and potential sweep rates

Fig. 7A discloses the effect of EG concentration on the NiO-

Fig. 7 e (A) Electrochemical responses of the NiO-NFs/CPE
NFs/CPE in 0.2 M NaOH solution. As can be seen, EG oxida-
in 0.2 M NaOH solution with different EG concentrations at
tion can be catalyzed at the modified electrode surface. In
y ¼ 20 mV s¡1. (a) 0, (b) 10, (c) 15, (d) 25, (e) 30, (f) 40, (g) 60,
addition, the anodic peak current density (jp) rises with
(h) 85 and (i) 115 mM. Inset of plots: jp as a function of EG
increasing concentration up to 55 mM. While the EG concen-
concentration. (B) CVs of the NiO-NFs/CPE in 30 mM
tration exceeds from this limit, no more significant current
EG þ 0.2 M NaOH solution at different potential scan rates:
increasing occurs. Also, the CVs are recorded at different po-
(a) 5, (b) 10, (c) 20, (d) 30, (e) 50, (f) 80, (g) 100, (h) 200, (i) 400,
tential scan rates in 0.2 M NaOH solution containing 30 mM EG
(j) 600 and (k) 800 mV s¡1. Inset of plot: jp vs. y1/2.

Table 1 e Comparison of the electrochemical data of some modified CPEs in the electro-catalytic oxidation of EG in NaOH
solution at y ¼ 20 mV s¡1.
Modifier NaOH con./mol L1 EG con./mol L1 Ep/V jp/mA cm2 Reference
Ni/SDS-POAP 0.1 0.28 0.80 11.1 [43]
Ni/SDS-PPAA 0.1 0.25 0.70 5.9 [44]
Ni/SDS-PDMAN 1.0 0.20 0.85 83.1 [45]
Ni/TX-100-PMT 0.1 0.06 0.67 10.5 [46]
NiO-NFs 0.2 0.03 0.63 10.1 This work
 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 ) 9 0 6 e9 1 3 911

Fig. 8 e Iet transient of the NiO-NFs/CPE for 30 mM EG oxidation in 0.2 M NaOH at 0.63 V vs. AgjAgCljKCl (3 M). (B) CVs of the
NiO-NFs/CPE in 0.2 M NaOH solution in the presence of 30 mM EG at y ¼ 20 mV s¡1; 1st (a) and 100th CV (b). (C) CVs of the
NiO-NFs/CPE; 1st day (a) and 21st day (b). Other conditions are the same of part B.

(Fig. 7B). It can be seen that a linear relationship is obtained (Fig. 8C). The electrode response retains 97% and 95% of its
when jp values are plotted against to the square root of po- initial response, respectively.
tential scan rates (y1/2). This behavior displays that the electro-
oxidation of EG is a diffusion controlled process.

Conclusion

Stability of the NiO-NFs/CPE The PVA/Ni(OAc)2 nanofibers were successfully prepared

Practically, long-term stability of the electrode is very impor-
tant. Chronoamperometry method is usually applied for study
of activity and stability. A chronoamperogram with a large
time window for the modified electrode is obtained at 0.63 V in
presence of 0.03 M EG in 0.2 M NaOH solution (Fig. 8A). As can
be seen, the decrease in current is relatively slow and, when
the time is above 100 s, the current reaches a relatively stable
value, which is still about 60% of the initial current. It is
obvious that the NiO-NFs/CPE exhibits a high stability toward
EG oxidation. The long-term stability of the NiO-NFs/CPE is
confirmed by measuring its response for EG oxidation after
100 CVs in the presence of 0.03 M EG þ 0.2 M NaOH (Fig. 8B)
and 3 weeks of storage in laboratory atmosphere condition
without occurrence of beads and defects by electrospinning
process and the NiO-NFs were obtained after calcination.
Structures and morphology of the materials were character-
ized by TGA, FE-SEM, FT-IR, XRD and EDS analysis. The FE-
SEM images showed that NiO-NFs were formed by calcina-
tion in air for 5 h. Moreover, after calcination at about 600  C,
polymeric template of the NFs thoroughly was decomposed
and their surface turned into harsh. The XRD pattern of the
calcined sample showed that the precursor converted into
pure NiO cubic structure. The result of EIS showed that the
charge transfer resistance was decreased, when the carbon
paste was spiked with NiO-NFs. The electro-catalytic perfor-
mance of the low cost and renewable bulk modified elec-
trode (i.e. electro-spun NiO-NFs/CPE) for EG oxidation was
912 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 ) 9 0 6 e9 1 3
investigated in the electro-catalysis of EG oxidation in alkaline
solution. The modified electrode exhibited good electro-
catalytic activity towards EG oxidation, demonstrating a
reasonable stability and durability.
Appendix A. Supplementary data
Supplementary data related to this article can be found at
http://dx.doi.org/10.1016/j.ijhydene.2016.09.116.
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