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Novel Co-MOF/Graphene Oxide Electrocatalyst for Methanol Oxidation

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DOI: 10.1016/j.electacta.2017.09.164

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 Electrochimica Acta 255 (2017) 195–204

Contents lists available at ScienceDirect

Electrochimica Acta
journal homepage: www.elsevier.com/locate/electacta

Research Paper

Novel Co-MOF/Graphene Oxide Electrocatalyst for Methanol Oxidation

Rimsha Meheka , Naseem Iqbalb,* , Tayyaba Noorc , Habib Nasira , Yasir Mehmoodd ,
Safeer Ahmedd
a
School of Natural Sciences (SNS), National University of Sciences and Technology, Islamabad, Pakistan
b
US-Pakistan Centre for Advanced Studies in Energy (USPCAS-E), National University of Sciences and Technology, Islamabad, Pakistan
c
School of Chemical and Materials Engineering (SCME), National University of Sciences and Technology, Islamabad, Pakistan
d
Department of Physical Chemistry, Quaid-i-Azam University, Islamabad, Pakistan

A R T I C L E I N F O A B S T R A C T

Article history:
Received 30 July 2017 In this work the catalytic activity of cobalt based MOF and its composites with graphene oxide (GO)
Received in revised form 26 September 2017 towards electrochemical oxidation of methanol is studied. Co-MOF-71 and its GO composites were
Accepted 27 September 2017 prepared by hydrothermal method and characterized by X-ray diffraction, XPS, scanning electron
Available online 29 September 2017 microscopy and FTIR. XRD patterns revealed incorporation of GO without disturbing the crystal structure.
The synthesized catalysts were tested for their electrocatalytic activity for methanol oxidation reaction
Keywords: (MOR) in alkaline medium. The electrochemical parameters measured with modified GCE represent the
Metal Organic Framework (MOF) effect of graphene oxide on methanol oxidation reaction catalysed by Co-MOF-71. Co-MOF-71/GO
Graphene Oxide (GO)
composite showed excellent peak current density (29.1 mA/cm2) at lower potential (0.1 V) and scan rate
Methanol Oxidation Reaction
of 50 mV/s. The enhanced electrochemical activity and stability is attributed to the synergetic effect of the
Direct Methanol Fuel Cell
MOF and the GO substrate for methanol oxidation.
© 2017 Elsevier Ltd. All rights reserved.

1. Introduction
The furnishing of an unending energy resource to an
increasingly flourishing world after depletion of fossil fuel reserves
and environmental pollution are the most talked about issues
these days [1–3]. An alternative to fossil fuels, fuel cells are the
strongest and modest candidates of renewable energy resources
[4,5]. Among fuel cells, direct methanol fuel cells (DMFCs) are
striking option to power portable electronics and electric vehicles.
The reason is its abundance, inexpensive nature, high volumetric
energy density and easily handling [6]. Methanol is oxidized at
one-half side of the DMFC according to the following reaction [7]:
CH3 OH þ H2 O ! CO2 þ 6Hþ þ 6e Eo ¼ 0:02V
The equilibrium potential lies very close to that of hydrogen
oxidation. However, this reaction is quite slow by several orders of
magnitudes. Total oxidation process involves conversion of
methanol into CO2 or into other oxidized products through
parallel reactions like HCHO, HCOOH that eventually are converted
again into CO2. Both the processes need a suitable catalyst, which
could facilitate these reactions. Pure Pt electrode in acidic medium
being the best catalyst acts as a standard for all the catalysts
studied until now [7].
The electro-oxidation of methanol in acidic media goes through
the formation of catalyst poisoning intermediates like CO, which
strongly bind with Pt and lead to severe limitations in the kinetics
and others features of oxidation. In acidic media, the adsorbed
OHads species from water activation primarily serve only to block/
inhibit the adsorption of methanol and other reaction intermedi-
ates via a well-known site-blocking effect [8]. However, in alkaline
media, the species facilitate the surface binding. Thus, acidic media
is kinetically unfavourable due to weak binding of species on the
active site which leads to its desorption into the bulk electrolyte
and/or catalytic decomposition [9,10]. This clearly demonstrates
that stabilizing the intermediate on the active site is important in
effectively carrying out MOR process, and the higher stability of
intermediate on the active site leads to the so-called kinetic facility
in alkaline media but not in acidic media [10]. Moreover, this
feature is also attributed to the pH dependent adsorption of OHads
species at defect sites. Makovic et al. in 2002, observed a major
potential shift towards lower voltages 0.2–0.3 V in alkaline media
[11]. Therefore, an alternative is to operate it in alkaline electro-

* Corresponding author.
E-mail address: naseem@casen.nust.edu.pk (N. Iqbal).

https://doi.org/10.1016/j.electacta.2017.09.164
0013-4686/© 2017 Elsevier Ltd. All rights reserved.
196 R. Mehek et al. / Electrochimica Acta 255 (2017) 195–204
lytes. The vast studies have proved this system to be far superior as
several order of magnitude increases in current occurred at fixed
potential. In addition, the introduction of alkali electrolytes to
DMFC could lead to reduced catalyst loading and use of non-noble
metal catalysts as well [12].
Recently, carbon based electrocatalyst materials for methanol
oxidation in DMFCs have gained great attention [13,14]. Among
these materials graphene-based composites are superior for all
electrochemical energy applications [14]. It answers to one of the
challenges faced by the field of electrochemistry; finding the best
catalyst, which could offer excellent current density at low voltages
and is available at reduced cost. The superiority is due the low cost,
large electrochemically active surface area, mechanical strength,
excellent conductivity and flexibility for further modification
[15,16]. These graphene-based materials enhance the mass
transport of reactants and electron transfer [17]. Moreover, poison
resistance of electrocatalyst can be increased by the presence of
the oxygen-containing groups on the graphene [18]. Major
research work done for methanol oxidation reaction revolves
around modifying Pt based catalysts. Mostly platinum based
catalysts have been decorated with graphene [19,20], graphene
oxide [21] and reduced graphene oxide [22]. Some researchers
have also tested Pt composites with metals and metal oxides like
Ni, NiO, CeO decorated with graphene sheets [23] which resulted
into improved electrical properties.
Over the past decade, immense work has been done in the field
of material sciences with great devotion towards the study of
Metal-Organic Frameworks (MOF) [24]. Their characterization and
physicochemical analysis studies have depicted their large surface
area, high porosity and crystalline nature. MOFs have received
more attention in the field of electrochemistry being capable of
catalysing Oxygen Reduction Reaction (ORR) [25], reduction of
carbon dioxide [26], and photocatalysis [27]. The extensive
development of nanoscience has enabled chemical modifications
in MOFs eventually opening up new routes towards a very new
generation of applications in the field of catalysis. MOFs along with
many nano materials have emerged as a novel catalyst. Nanotubes,
nanocubes, nanowires and graphene, all show remarkable effects
on the fuel cell applications of MOFs [28–30]. MOFs and their nano-
composites have found promising applications in electrochemical
processes like ORR, Hydrogen Evolution Reaction (HER), and
Oxygen Evolution Reaction (OER) [30]. Reduction of oxygen at
cathode is another interesting field of research in electrochemistry
due to its active role in energy conversion in fuel cell. MOFs have an
efficient role in catalysing such a reaction with acceptable current
density [31]. Same goes with hydrogen and oxygen evolution
reactions in which the overall electrochemical process results into
the formation of hydrogen and oxygen species. MOFs and their
derived compounds based catalysts have played crucial role in
catalysing such evolution reactions resulting either from water
splitting [32] or redox process of fuel [30]. One of our interests
among MOFs is cobalt based MOF, also known as Co-MOF-71 [33].
MOF-71 has been successfully tested for its catalytic application to
ORR, HER, and OER with an acceptable current density [30].
Recently, the same material has also been evaluated for its
remarkable thermal and mechanical properties in the form of
composites with mesoporous carbon for applications of waste-
water sensor [34] and other applications [24]. To the best of our
knowledge, the electrochemical activity of any of MOF composite
with GO for methanol oxidation has not been reported yet in the
literature. The enhanced electrochemical activity of the catalyst
material can be attributed to the possible enhancement of surface
area active for the reaction and the improved conductivity
provided by nanomaterials incorporated. Co-MOF/GO composites
combine the uniqueness of the porous Co-BDC framework and
highly conductive GO with improved surface area. GO is the
oxidized form of graphene. Graphene oxidation adds up oxygen
groups over the surface and converts sp2 hybridized carbon into
sp3 hybridized carbon. Until a certain level of oxidation, the GO is
conductive due to its ability of efficient electron transfer [35]. Here
we report, for the first time Co-MOF-71 and its composite with
graphene oxide (GO) for methanol oxidation reaction (MOR) in
alkaline medium.
2. Experimental
All the chemicals and reagents were bought from Sigma-Aldrich
with best quality assurance and were used without further
processing. Chemicals used were; cobalt nitrate hexahydrate
(CoNO3.6H2O), terephthalic acid (benzene dicarboxylic acid),
triethylamine (TEA), N,N-dimethylformamide (DMF), graphite
powder, sodium nitrate (NaNO3), conc. sulphuric acid (H2SO4),
potassium permanganate (KMnO4), and hydrogen peroxide (H2O2).
2.1. Synthesis of Co-MOF-71
Co-MOF-71 was prepared via hydrothermal method [30]. 1.36 g
of terephthalic acid was dissolved into 300 ml of DMF with
continuous stirring. After some time, few drops of triethylamine
(TEA) were added into the solution. Then, 1.48 g of hydrated cobalt
nitrate was added to the solution. The solution was stirred until all
the solid materials were completely dissolved. The homogenous
solution was poured into Teflon lined autoclave, tightly closed and
put into the oven for 24 hours at 120  C until the magenta coloured
crystals of Co-MOF-71 were formed. The crystals were collected,
washed and dried in oven.
2.2. Synthesis of Graphene Oxide
Graphene oxide was prepared by Hummers’ method [36]. 1 g of
graphite powder and 1 g of sodium nitrate were mixed in 46 ml of
H2SO4. The mixture was stirred in an ice bath for 1 hour using
magnetic stirrer. 8 g of KMnO4 was slowly added keeping the
temperature within 35  5  C in the water bath and were stirred for
another 2 hours. In the thick green paste, 80 ml of water was added
slowly keeping the temperature in the range of 90  5  C. The
solution was diluted by adding more 100 ml of water followed by
the addition of 6 ml of 30% H2O2 which turned the solution to
yellowish brown in colour. The solution was washed several times
with water in centrifuge until the pH of the solution was about
6.5–7. The product was dried under vacuum.
2.3. Synthesis of Co-MOF-71@GO Composites
Two different composites were prepared following the reported
hydrothermal method [30] (Fig. 1). A solution was prepared by
adding 1.36 g of terephthalic acid into DMF with few drops of
triethylamine with continuous stirring. After that, 1.48 g of cobalt
nitrate was added. Stirring was continued until all the solid
material was dissolved. After that 2 wt.% and 5 wt. % of GO was
added into the solution and the whole solution was stirred for half
an hour and then it was sonicated for further homogenous mixing.
After that, the solution was transferred into Teflon lined autoclave,
tightly closed and heated at 120  C for 36 hours. Colour of the
precipitates was according to the amount of GO added. Crystals
were collected, washed and dried under vacuum.
3. Characterization
X-ray powder diffractometer (XRD STOE Germany) connected
with computer interface having Cu Ka at l = 1.5418 Å was used.
XRD of the prepared electro-catalysts was performed at 2u ranging
 R. Mehek et al. / Electrochimica Acta 255 (2017) 195–204
Fig. 1. Sequence of reaction steps in synthesis of Co-MOF-71/GO composites.
from 5–80 and keeping step size at 4 /s. Surface morphologies
were observed through scanning electron microscopy (SEM) using
VEGA3 TESCAN and voltage was kept 20 KV. FTIR was measured
Fig. 2. Powder XRD of Co-MOF-71 (black), GO (red), 2 wt% (blue) and 5 wt% GO-Co-MOF-71 (purple). (For interpretation of the references to colour in this figure legend, the
reader is referred to the web version of this article.)
197
with Bruker ALPHA, Platinum ATR. XPS measurements were
performed using a Scienta-Omicron XPS instrument equipped with
MgK X-ray source (1253.6 eV). The source was operated at 15 KeV,
constant analyser energy (CAE) 100 eV for survey scans and 20 eV
for detailed scans.
4. Electrochemical measurements
The electrochemical measurements were performed using Eco
Chemie Autolab PGSTAT 302 potentiostat/galvanostat (Utrech,
the Netherlands) equipped with GPES software 4.9. In this study,
platinum wire was used as a counter electrode, Ag/AgCl as a
reference electrode and glassy carbon (7.065 mm2) as a working
electrode. Nafion solution 5 wt% was used as an electrolyte to
provide sufficient conductivity and a binding agent while ethanol
was used as a solvent. KOH was used as a supporting electrolyte
while methanol was being used as a fuel. The electrochemical
properties of the synthesized material were tested using cyclic
voltammetry (CV) in 1 M KOH and 3 M methanol solution. MOR
was performed in three electrode system using glassy carbon
electrode (GCE) as working electrode. The system was first run
with bare GCE (without any material deposition) and later on
with modified GCE. The electrochemical impedance spectroscopy
was done using the same three electrode system of methanol
with bare and modified GCE under potentiostatic mode. The
frequency range was set to be 10 to 40 kHz with amplitude at
50 mVs1 scan rate.
4.1. Preparation of working electrode- modified GCE
For CV and EIS measurements, 2 mg of material (Co-MOF-71,
2 wt% GO/Co-MOF-71 and 5 wt% GO/Co-MOF-71), 20 mL Nafion
(5 wt%) and 100 mL of ethanol were mixed to make catalyst ink
[37]. The mixture was thoroughly mixed and 15 ml of the catalyst
ink was deposited onto a GCE with micro pipette. The modified
GCE was then dried at room temperature before electrochemical
measurements. All the materials were tested with different
concentrations at scan rate 50 mVs1 and at different scan rate
at optimum concentration of 2 mg.
198 R. Mehek et al. / Electrochimica Acta 255 (2017) 195–204
5. Results and Discussion
Co-MOF-71 and its composites with 2 and 5 wt% GO were
characterized by SEM, XRD, FTIR and XPS. The crystalline structure
of samples was determined with powder XRD (Fig. 2). Since in our
materials Co-MOF-71 represents the major component, one would
expect a predominance of Co-MOF-71 structure features on the
X-ray diffraction patterns of the composites.
The 2u values show cubic phases of Co-MOF-71 which was
intact in the presence of GO. 2u values at 28 , 34 and at 53 oo
indicates the presence of cobalt species while that at 11 evidently
represents the presence of GO. The relative intensity of 2u value at
11 in both the composites clearly shows the increase in GO
concentration. Thus, Co-MOF-71 was successfully incorporated
within the layers of GO without any significant modification in
crystal structure. It should only happen when during Co-MOF-71
synthesis in the presence of GO does not hinder the formation of
linkages between the Co and organic linker. The major diffraction
pattern of Co-MOF-71 is preserved in our composites and this
pattern is in agreement with those previously reported for
Co-MOF-71 [38,39].
Fig. 3. SEM images of a. Co-MOF, b. 2 wt% GO-Co-MOF-71, c. 5 wt% GO-Co-MOF-71, and d. GO.
The morphology and structure of synthesized material was
investigated using scanning electron microscopy (SEM) (Fig. 3).
The images clearly show the embedded Co-MOF-71 cubes within
the layers of GO [30] while the elemental composition in EDX
results show the accuracy of the chemical composition in all the
three manufactured catalysts (Table 1).
The functional groups present in Co-MOF-71 and the composite
were characterized by FTIR. (Fig. 4). The sharp band at around
1590 cm1 indicates the presence of carbonyl group in all the three
catalysts. The shift of the C¼O stretch for Co-MOF-71/GO
composites as compared to the corresponding band for Co-MOF-
71 is due to the Co:O coordination. So, IR absorptions of the
materials also illustrate the successful synthesis of composites.
X-ray photoelectron spectroscopic (XPS) measurements were
conducted to investigate the chemical state of the metal in
catalytic materials. Fig. 5 shows the XPS spectrum with character-
istic peaks of Co+2 without any change in all the samples. The
positions of binding energy peaks and satellite peaks is accordance
with the reported XPS spectra for Co-MOF-71 [40]. This confirms
that the Co+2 oxidation state remains intact with addition of GO in
composites.
 R. Mehek et al. / Electrochimica Acta 255 (2017) 195–204
Table 1
EDX; Elemental composition of Co-MOF-71, 2 wt. % GO/Co-MOF-71 and 5 wt. % GO/Co-MOF-71.
Element/Sample Co-MOF-71
C wt % 40.53
O wt % 44.83
Co wt % 14.63
Fig. 4. FTIR of Co-MOF-71 and its composites with 2 and 5 wt. % GO.
Electro-catalytic activity of Co-MOF-71/GO composites for
methanol oxidation was investigated by CV measurements
(Fig. 6) by running a potentiostatic scan of the bare and modified
glassy carbon electrode (GCE) in 3 M methanol. The results show an
increased overall peak current density with respective increase in
concentration of GO. This means that the GO has provided the
catalyst with larger surface area and enhanced conductivity.The
sample with higher concentration of GO (5 wt. %) has improved
electrocatalytical activity towards MOR with peak current density
of 29.1 mAcm1 at 0.1 V and scan rate of 50 mV/s Fig. 6(c). The data
presented in Table 2 shows the catalyst with 5 wt. % GO has better
electrochemical response for MOR than that with 2 wt. % which
suggests that the GO concentration has impact on conductivity and
activity for redox reaction. This feature is very important for
electrochemical applications of fuel cell. From Table 2, it can also be
perceived that the overall efficiency of the Co-MOF-71/GO
catalysts is quite close to that of Pt/rGO [41] and Pt/Co [42]. The
CoMOF-71 shows high peak current density at very low peak
potential of 0.1 V as compared to reported peak potential of 0.7 V
[41] and 0.5 V [42]. The peak current density for methanol
oxidation is 10.4 mAcm2 in case of Co-MOF-71 modified
electrode. With addition of GO the peak current density increases
to 17.6 mAcm2 for 2 wt% GO/Co-MOF-71. Best results were
obtained with 5 wt% GO/Co-MOF-71 which exhibited peak current
density of 29.1 mAcm2 at peak potential 0.10 volts and scan rate of
50 mVs1. This improved current density of 5 wt% GO composite
suggests smaller activation energy is required for oxidation of
methanol.
199
2 Wt. % GO/Co-MOF-71 5 Wt. % GO/Co-MOF-71
36.06 56.14
45.88 25.83
18.06 18.03
The enhanced electrochemical activity is due to synergic effect
of Co-MOF-71 and GO in the composite. The presence of cobalt in
its framework with terephthalic acid introduces pores into the
structure which are good for surface enhancement and charge
transfer properties of the catalyst. Also the incorporation of GO
enhances pores in the structure and conductivity. Manipulation at
the nano-scale provides enhanced surface area with better surface
properties like diffusion dominated enhanced charge transfer rate.
The overall electrocatalytic performance of the sample is improved
providing more protons at more negative potential [43].
Moreover, the concentration vs. current density plot for
Co-MOF-71 at 50mVs1 is also obtained Fig. 6(b) which shows
that increasing the concentration of Co-MOF-71 also enhances the
activity. This is due to the fact that increasing the concentration of
catalyst decreases the overall activation energy of the system. Fig. 6
shows that as we increased the concentration of Co-MOF-71 from
1.5-3.0 mg, the current density also increased. The catalyst in
concentration 1.5 mg, 2.0 mg and 2.5 mg gave a high peak current
density at peak potential ranging from 0.0 V to 0.1 V, but the
catalyst with 3.0 g concentration showed peak current density at
higher peak potential about 0.2 V. This is attributed to the
cluttering of catalyst with increasing concentration which results
in the charge transfer at higher voltage.
The peak current densities of the voltammograms are linearly
proportional to sweep rates. Fig. 7 represents the effect of scan rate
(mVs1) i.e., 50 mVs-1, 100 mVs1, 150 mVs1 and 200 mVs1 over
peak current density. At faster scan rates, two peaks i.e. forward
and backward are more prominent. Reason lies in the fact that the
200 R. Mehek et al. / Electrochimica Acta 255 (2017) 195–204
Fig. 5. XPS peaks showing Co 2p spectra of (a) Co-MOF-71 and its composites with
(b) 2 wt. % GO and (c) 5 wt. % GO.
faster scan rate doesn’t allow the components of reactions to be
oxidized or reduced into products which are not electro-active
[44]. Thus, only electro-active products are formed giving off
overall higher current density. By comparing the results, the trend
Fig. 6. Cyclicvoltammogram of bare GCE, Co-MOF-71 in various concentrations and
its composites with 2 wt. % GO and 5 wt. % GO in 1 M KOH and 3 M methanol at
50 mVs1.
can be observed that by increasing the scan rate with both the
composites, current density increased accordingly. The peak
current densities are linearly increasing with increase in the
sweep rates from 50 to 200 mVs1 as per expectations. Such a
response is attributed to the fact that electrochemical activity of
the redox couple over the surface is enhanced with the speed of
reaction.
Fig. 8 shows a linear relationship between peak current
densities and square root of scan rates for both the catalysts.
The linear plot has a slop proportional to the D1/2. Transfer
coefficient a and diffusion coefficient (D) can be determined by
measuring this linearity and also the rate constant of charge
transfer between surface deposited layer and the electrode used
[45].
 R. Mehek et al. / Electrochimica Acta 255 (2017) 195–204 201

Table 2
Comparison of voltage, current and current densities with reported catalyst materials.

Catalyst Material Scan Rate (mVs1) E vs. Ag/AgCl (V) Peak Current Density (mAcm2) Impedance Z” (Ohms) Reference
Pt/rGO 50 0.70 32.01 [41]
Pt/Co 50 0.50 38.51 [42]
Co-MOF-71 50 0.75 10.4 3.0  102 This work
2 wt. % GO/Co-MOF-71 50 0.10 17.6 2.0  102 This work
5 wt. % GO/Co-MOF-71 50 0.10 29.1 1.5  102 This work

Fig. 8. Plots of Anodic and Cathodic Peak Current Densities vs. Square Root of Scan
Rate.

Fig. 7. Effect of Scan Rate on Current Density. Cyclic voltammograms, 50, 100, 150,
200 mVs1 for 2 and 5 wt% Co-MOF-71.

Here, we determine diffusion constant (D) via Randles Sevcik

equation; [46–49]
 
nFvD 1=2
ip ¼ 0:4463nFAC
RT
The value of diffusion coefficient for the catalyst materials
calculated as 1.41 105 cm2s1 for 2 wt. % GO/Co-MOF-71 and
2.77  105 cm2s1 for 5 wt. % GO/Co-MOF-71. The results show
that the system runs on the diffusion controlled mechanism.
The evaluation of cyclic voltammograms for the corresponding
values of current, voltage and current density can be summarized
in Table 2. The corresponding values from some previous work
[41,42] are added for comparative purpose.
Fig. 9 shows the Tafel plots based on polarization curves in the
linear area of the cyclic voltammogram. Tafel plots are a fine way to
evaluate the activity of MOR [30,50]. Tafel plots illustrate the
electrochemical kinetics by comparing overpotential and current
density. It depicts how much overpotential has to be increased to
Fig. 9. Tafel plots. Low frequency curves at linear part of cyclic voltammogram.
increase the reaction kinetics. Pt (commercial) being the best
material until now shows these curves at or near 0.0 V [24] but
other materials in this run show curves at higher voltage. In our
study, 5 wt% GO/Co-MOF-71 composite shows a curve at lower
overpotential.
The improved value for overpotential suggests this composite
to be electrocatalytically more active, requiring less activation
energy in the presence of GO. According to Volmer equation,
formed ions are captured within the pores on the surface of
catalyst material [51]. With the incorporation of GO, more surface
enhancement is provided in the form of pores which can capture
202 R. Mehek et al. / Electrochimica Acta 255 (2017) 195–204
more ions at lower potentials, thus leading to increased kinetics
with decreased activation energy.
The electrochemical impedance spectroscopy (EIS) is another
excellent technique to represent the activity of modified electrode
[52]. In EIS electrochemical impedance is measured using
potentiostatic mode in the same three electrode system in 1 M
KOH and 3 M Methanol with bare and modified GCE (Fig. 10).
Solution resistance is a major factor in electrochemical studies. The
Fig. 10. EIS plot of (a) Bare GCE, (b) Co-MOF-71 in various concentrations and (c)
composites of Co-MOF-71 with 2 wt. % GO and 5 wt. % GO in 1 M KOH and 3 M
methanol at 50 mVs1 at potentiostatic mode, 40–100 kHz frequency range, 15 mV
amplitude.
resistance between reference and working electrode must be
considered wile calculating electrochemical impedance of a circuit.
The Nyquist plots given in Fig. 10 shows that as the amount of
Co-MOF increase the charge transfer resistance decreases system-
atically which is a clear indication of facilitation of charge transfer
for the catalytic conversion of methanol. The same has been
concluded from voltammetry studies as conferred above. Further,
when the GO was incorporated into the MOF material, the response
was even better as shown in Fig. 10 (c). The impedance results
complements the voltammetric findings.
The improved electrocatalytic activity of the above-mentioned
material can be understood based on the synergistic behaviour of
Co-BDC framework and GO sheets. The overall process of methanol
oxidation undergoes following some necessary elementary steps
like methanol adsorption, methanol dehydrogenation into inter-
mediates, and oxidation of these intermediates eventually into
CO2. The process of adsorption occurs into the voids of Co-MOF-71,
which is further enhanced by the presence of GO. Moreover, the
pores of metal organic framework also adsorb water molecules
which facilitates the oxidation of intermediates to CO2. Increased
surface area of GO and porosity of the metal frameworks play an
important role in facilitating the methanol adsorption and
subsequent oxidation by providing an extended active surface
area [21,19].
The overall process can be summarized as the following
proposed mechanism;
Co  BDC þ CH3 OH ! Co  BDC  ðCH3 OHÞads
Co  BDC  ðCH3 OHÞads ! Co  BDC  ðCH2 OHÞads þ Hþ þ e
Co  BDC  ðCH2 OHÞads ! Co  BDC  ðCHOHÞads þ Hþ þ e
Co  BDC  ðCHOHÞads ! Co  BDC  ðCOHÞads þ Hþ þ e
Co  BDC  ðCOHÞads ! Co  BDC  ðCOÞads þ Hþ þ e
Co  BDC þ H2 O ! Co  BDC  ðH2 OÞads
Co  BDC  ðH2 OÞads ! Co  BDC  ðOHÞads þ Hþ þ e
Co  BDC  ðCOHÞads þ Co  BDC  ðH2 OÞads
! Co  BDC þ CO2 þ 3Hþ þ 3e
Co  BDC  ðH2 OÞads þ Co  BDC  ðCOÞads
! Co  BDC þ CO2 þ 2Hþ þ 2e
Co  BDC  ðOHÞads þ Co  BDC  ðCOÞads
! Co  BDC þ CO2 þ Hþ þ e
To investigate the stability of electrocatalyst, current-time (i-t)
chronoamperometry was performed at a constant voltage of 0.1 V
in 1 M KOH and 3 M methanol solution within the same three
electrode system. Fig. 11 shows the chronoamperometric curves
for all the three catalysts. These curves show that composites of Co-
MOF-71 with GO have retained more stable current over time i.e.
 R. Mehek et al. / Electrochimica Acta 255 (2017) 195–204
Fig. 11. Chronoamperometric curves of Co-MOF-71, 2 wt. % GO/Co-MOF-71 and
5 wt. % GO/Co-MOF-71 in 3 M methanol and 1 M KOH at 50 mVs1 and 0.1 V fixed
potential.
62% for 5 wt. GO/Co-MOF-71 composite and 38% for 2 wt. % GO-Co-
MOF-71. Although for the composite with 5 wt. % GO the current
remain stable for about 600 seconds but later on it drops to certain
level and then gets constant again. The corresponding current-
time profile of 5 wt. % GO composite exhibits nearly no further
decrease in current after 38% loss. While the current loss in Co-
MOF-71 and its composite with 2 wt. % GO was 86% and 62%
respectively. This enhanced stability for 5 wt. % GO composites
might be due to the enhanced proton conduction and more feasible
electron conduction on the surface of GO sheets. This implies that
increasing the concentration of GO also increases the stability and
durability of the catalyst with higher electrical activity towards
methanol oxidation reaction. The results are quite encouraging and
are indicative of some treatment of the material to improve the
stability further.
6. Conclusions
The Co-MOF-71 and its GO incorporated composites were
synthesized by an economic and environmentally friendly
hydrothermal method. Our work demonstrates that the synthe-
sized catalysts possess a great potential for their applications in
direct methanol fuel cell. The materials were tested to demonstrate
their catalytic activity towards methanol oxidation reaction. The
5 wt. % GO-Co-MOF-71 composite showed best results with
highest current density of 29.1 mAcm1 at low potential of 0.1 V,
exhibiting low impedance of 1.5  102 ohms, low over-potential
values and high stability with only 38% current loss over 3600 sec.
The Co-MOF-71/GO composite having non-noble metal makes it an
inexpensive, but a potential candidate in the field of electro-
catalysts to compete with Pt for methanol oxidation reaction. The
remarkable property with acceptably high current density and low
cost makes it a promising alternative to the expensive electro-
catalyst in various fuel cell applications.
Acknowledgements
This work is supported by School of Natural Sciences (SNS), and
US-Pakistan Centre for Advanced Studies in Energy (USPCAS-E) at
National University of Sciences and Technology (NUST), and
Laboratory of Electrochemistry and Photovoltaic at Quaid-i-Azam
University (QAU), Pakistan.
203
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