Catalysts 09 00856

catalysts
Article
Development of Nickel-BTC-MOF-Derived
Nanocomposites with rGO Towards Electrocatalytic
Oxidation of Methanol and Its Product Analysis
Lubna Yaqoob 1 , Tayyaba Noor 2, *, Naseem Iqbal 3 , Habib Nasir 1 and Neelam Zaman 1
1 School of Natural Sciences (SNS), National University of Sciences and Technology (NUST),
Islamabad 44000, Pakistan; lubnayaqoob96@gmail.com (L.Y.); habibnasir@sns.nust.edu.pk (H.N.);
neelamzaman6650@gmail.com (N.Z.)
2 School of Chemical and Materials Engineering (SCME), National University of Sciences and
Technology (NUST), Islamabad 44000, Pakistan
3 U.S.-Pakistan Centre for Advanced Studies in Energy (USPCAS-E), National University of Sciences and
Technology (NUST), Islamabad 44000, Pakistan; naseem@uspcase.nust.edu.pk
* Correspondence: tayyaba.noor@scme.nust.edu.pk; Tel.: +92-51-9085-5121

Received: 16 September 2019; Accepted: 8 October 2019; Published: 14 October 2019
Abstract: In this study, electrochemical oxidation of methanol to formic acid using the economical
and highly active catalytic Nickel Benzene tricarboxylic acid metal organic framework (Ni-BTC-MOF)
and reduced graphene oxide (rGO) nanocomposites modified glassy carbon electrode GCE in
alkaline media, which was examined via cyclic voltammetry technique. Nickel based MOF and rGO
nanocomposites were prepared by solvothermal approach, followed by morphological and structural
characterization of prepared samples through X-ray diffraction (XRD), scanning electron microscopy
(SEM), Fourier Transform Infrared Spectroscopy (FTIR), and energy dispersive X-ray (EDX) analysis.
The electrochemical testing of synthesized materials represents the effect of the sequential increase in
rGO concentration on electrocatalytic activity. The Ni-BTC/4 wt % rGO composite with a pronounced
current density of 200.22 mA/cm2 at 0.69 V versus Hg/HgO electrode at 50 mV/s was found to be
a potential candidate for methanol oxidation in Direct Methanol Fuel Cell (DMFC) applications.
Product analysis was carried out through Gas Chromatography (GC) and Nuclear Magnetic Resonance
(NMR) spectroscopy, which confirmed the formation of formic acid during the oxidation process,
with approximately 62% yield.
Keywords: MOF/rGO nanocomposites; Ni-BTC; rGO; methanol oxidation; direct methanol fuel cell
1. Introduction
The human appetite for energy is constantly growing and becoming increasingly difficult to
satiate. Currently, the world’s enormous energy demands are mainly met by nonrenewable and
environmentally unfriendly fossil fuels; however, the development of vital energy sources for an
increasingly thriving world to mitigate fossil fuel resource depletion and environmental pollution are
pressing issues for society right now [1,2]. Invention of numerous nonconventional means to bridge
the gap between energy demand and supply is the utmost requirement of the modern era. Fuel cells,
an alternate to fossil fuels, are now emerging as a robust and modest source of renewable energy,
as well as an immaculate, efficient, and benign method for energy conversion [3,4].
To date, a variety of fuel cells are available that are divergent in their operating temperature,
electrical efficiency, power output, and typical applications. Among these different fuel cells, direct
methanol fuel cells (DMFCs) are a remarkable option for portable devices and light duty vehicles
because of their high energy density, inexpensive nature, reduced corrosion, easy handling of liquid
Catalysts 2019, 9, 856; doi:10.3390/catal9100856 www.mdpi.com/journal/catalysts

Catalysts 2019, 9, 856 2 of 21
fuel, and low temperature requirements [5]. A critical approach for aspirational sustainable energy
sources is the fabrication of highly proficient, green, economical catalysts for energy conversion and
storage applications [6]. Electrochemical oxidation of methanol in fuel cell leads to different products;
for instance, CO2 , HCHO, HCOOH, and CO depend on reaction temperature, the reactant’s partial
pressure, and most importantly, the nature of the catalyst [7]. Hydrogen and water are generated as
side products, where hydrogen is further utilized as an energy source for fuel cells. Gaseous products,
such as CO and CO2 , are released to the atmosphere, while formic acid is effectively utilized as a
preservative, antibacterial agent, and for treatment of warts. It is also used in the production of leather,
rubber, and esters, in addition to being used as a solvent in HPLC. Methanol oxidation, an anodic
half-cell reaction of direct methanol fuel cells, is catalyzed by highly efficient Pt catalysts in acidic
media [8,9]. However, formation of poison intermediates, such as HCHO and CO, and their strong
binding with Pt, is responsible for sluggish kinetics. Alkaline electrolytes prove to be better alternatives
in view of their increased current density at particular potentials, their potential shift toward lower
voltage, reduced catalyst loading, strong binding of catalysts to metal sites, as well as the stability of
cheaper non-noble metal catalysts in alkaline media [10–12].
Until now, extensive research work has been done to modify Pt-based catalysts to optimize the
methanol oxidation process. Platinum-based nanorods; nanoflowers; nanocubes; composites of Pt with
metal oxides, such as Fe2 O3 , TiO2 , SnO2 , Cu2 O, ZnO; as well as conductive polymer support-based
Pt catalysts, with enhanced electrical conductivity and reduced charge transfer resistance, have been
extensively studied for methanol oxidation [13–17]. Furthermore, carbon based materials, such as
carbon powder, CNTs, graphene, graphene oxide, and reduced graphene oxide, are potential candidates
for this application because of their increased surface area, high conductivity, thermal stability, reduced
catalytic poisoning, and elevated charge carrier mobility. Among these carbon-based materials,
graphene is the best option because of its large surface area, conductivity, and enhanced electron and
mass transport, while rGO is preferred over GO because of its increased conductivity [18–21].
In recent decades, metal–organic frameworks have moved to the forefront as novel crystalline
materials, extending from one dimensional (1D) to three dimensional (3D). Their huge surface area,
porosity, and stability are effectively utilized for energy conversion, gas separation and storage,
and catalysis, in addition to being used in sensors and for biological applications [22–24]. Limited
applications of MOFs for electrocatalysis, because of their constrained charge transfer and dejected
electrical conductivity, can be overcome by combining them with conductive materials, such as with
CNTs, carbon nanowire, reduced graphene oxide, or graphene, transforming them into potential
candidates for electrochemical processes, such as oxygen reduction reactions (ORR), hydrogen
evolution reactions (HER), oxygen evolution reactions (OER), CO2 reduction, methanol oxidation, and
photocatalysis [25–32]. Furthermore, MOFs and their derived compounds act as efficient catalysts for
evolution reactions during the redox process in fuel cells or water decomposition [33,34].
In this work, we synthesized Ni-BTC-MOF/rGO composites using the solvothermal method
and investigated their electrocatalytic capacity for methanol oxidation in alkaline medium.
The interconversion of Ni in different oxidation states, its resistance toward poisonous intermediates,
and its extraordinary stability make nickel an attractive and appealing candidate for methanol
oxidation [35]. Moreover, the greater surface area, additional stability, and improved electrical
conductivity provided by incorporation of rGO into MOF play important roles in enhancing
the electrocatalytic activity of synthesized materials [36–38]. To the best of our knowledge, the
electrocatalytic response of Ni-BTC-MOF/rGO composites for methanol oxidation, along with
qualitative and quantitative product analysis, has not been reported in literature to date.
2. Results and Discussion

To attain Ni-BTC-MOF/rGO, a solvothermal method was used for the synthesis. In order to
prepare Ni-BTC composites with rGO, a sequence of experiments was performed with varying amounts
of rGO. All these experiments were executed by using 2 g Ni (NO3 )2 ·6H2 O and 1 g of 1,3,5 benzene
solvents C2H5OH and Dimethylformamide (DMF). The homogenous mixture was then transferred to
a 50 mL Teflon-lined autoclave and kept in the oven at 85 °C for 24 h. The prepared solid material
was collected, washed with solvents, and dried at 65 °C for 24 h (see Material and Methods section
for further details). Ni-BTC-MOF and 1–5 wt % rGO composites of MOF were characterized by
employing FTIR,
Catalysts 2019, 9, 856EDX, XRD, and SEM analysis. 3 of 21
The crystalline nature of the synthesized materials revealed through powdered XRD is
illustrated in Figure 1a, where the sharpness of peaks depicts the crystallinity of synthesized
tricarboxlic
materials. acid (linker),
Diffraction with
peaks atan appropriate
23° (004) and amount
17° (002)ofare
rGO added to
ascribed tothe
themixture
crystal of solvents
plane of rGOC2 Hand
5 OH
and Dimethylformamide (DMF). The homogenous mixture was then transferred
partial reduction of the GO peak, which is enhanced in 5 wt%, but these peaks are not highly to a 50 mL Teflon-lined
autoclavein and kept in the oven at 85 ◦ for 24 h. The prepared solid material was collected, washed
significant other composites [39]. ThisCmay be caused by overlapping of significant peaks of metals
◦
atwith
this solvents,
scale becauseand dried at crystalline
of their 65 C for 24 h (seeand
nature, Material
also mayandgive
Methods section for
an indication thatfurther
rGO did details).
not
Ni-BTC-MOF and 1–5 wt % rGO composites of MOF were characterized by employing
interfere in metal–ligand interactions [40]. Peaks at 10° (211), 15° (321), and 24.5° (600) may be caused FTIR, EDX,
byXRD, and SEM
localized metal analysis.
oxides and hydroxide formation [41]. Peaks at 2θ values of 35° (022), 42° (512), and
51° (226) indicate the nature
The crystalline presenceof the synthesized
of nickel materials
[42]. The revealed
XRD pattern forthrough powdered
synthesized samplesXRD is illustrated
is identical to
in Figure
the reported 1a,and
where the sharpness
simulated patternof[43,44].
peaks depicts the crystallinity of synthesized materials. Diffraction
peaks ◦ (004) and 17◦ (002) are ascribed to the crystal plane of rGO and partial reduction of the GO
at 231b
Figure illustrates the XRD pattern of graphene oxide. At the 2 θ value of 10.5° with 0.841 nm
dpeak, which
spacing, is enhanced
a sharp in 5 wt%,
peak proves but theseoxide
the graphene peaksformation.
are not highly
At thesignificant
2 θ value inof other composites
42.2° with d spacing[39].
ofThis may
0.212 nm,beacaused by overlapping
less intense peak appears,of significant
caused bypeaks
the of metals at
presence ofthis scale because
unexfoliated of their crystalline
graphite.
nature, and also may give an indication that rGO did not interfere
Figure 1c illustrates the XRD pattern of reduced graphene oxide. At the 2 θ valuein metal–ligand interactions
of 25.4° with[40].
Peaks at 10 ◦ (211), 15◦ (321), and 24.5◦ (600) may be caused by localized metal oxides and hydroxide
0.4 nm d spacing, the broad peak corresponds to reduced graphene oxide formation. At the 2 θ value
offormation
42.5° with[41]. Peaksofat0.21
d spacing 2θ nm,
values 35◦ (022),
of intense
a less
◦ (512), and 51◦ (226) indicate the presence of
42appears
peak caused by the presence of unexfoliated
nickel [42].
graphite [45]. The XRD pattern for synthesized samples is identical to the reported and simulated
pattern [43,44].
Ni-BTC/5 wt % rGO
Ni-BTC/4 wt % rGO
Ni-BTC/3 wt % rGO
Ni-BTC/2 wt % rGO
Ni-BTC/1 wt % rGO
Ni-BTC
202
002 311
321 004 114

Relative intensity (a.u)
211 600 400 022 512 226 517
0 20 40 60 80
Catalysts 2019, 9, x FOR PEER REVIEW 4 of 22
2θ(Degree)
(a)
(b) (c)
Figure 1. X-ray
Figure 1. X-ray diffraction
diffraction (XRD)
(XRD) pattern
pattern of
of (a) Ni-BTC-MOF and
(a) Ni-BTC-MOF and 1–5
1–5 wt
wt % rGO composites
% rGO composites (b)
(b) GO
GO
and
and (c)
(c) rGO.
rGO.
In the FTIR spectrum of GO, strong absorption bands caused by the stretching vibration of
hydroxyl O−H, carbonyl C=O, and carbon to carbon double bond C=C appear at 3200 cm−1, 1722 cm−1,
and 1622 cm−1, respectively, while epoxy and alkoxy groups give stretching vibration peaks at 1220
cm−1 and 1048 cm−1, respectively. Reduction of oxygen-containing functional groups on the surface of
Catalysts 2019, 9, 856 4 of 21
Figure 1b illustrates the XRD pattern of graphene oxide. At the 2 θ value of 10.5◦ with 0.841 nm d
spacing, a sharp peak proves the graphene oxide formation. At the 2 θ value of 42.2◦ with d spacing of
0.212 nm, a less intense peak appears, caused by the presence of unexfoliated graphite.
Figure 1c illustrates the XRD pattern of reduced graphene oxide. At the 2 θ value of 25.4◦ with
0.4 nm d spacing, the broad peak corresponds to reduced graphene oxide formation. At the 2 θ value
of 42.5◦ with d spacing of 0.21 nm, a less intense peak appears caused by the presence of unexfoliated
graphite [45].
In the FTIR spectrum of GO, strong absorption bands caused by the stretching vibration of hydroxyl
O−H, carbonyl C=O, and carbon to carbon double bond C=C appear at 3200 cm−1 , 1722 cm−1 , and
1622 cm−1 , respectively, while epoxy and alkoxy groups give stretching vibration peaks at 1220 cm−1
and 1048 cm−1 , respectively. Reduction of oxygen-containing functional groups on the surface of GO
by hydrazine hydrate is illustrated in the FTIR spectrum of rGO by the disappearance of peaks at
1722 cm−1 and 1220 cm−1 , while the presence of O−H functional groups (O−H) with low intensities
cause a peak at 3247 cm−1 , further confirming sp2 lattice recovery with a peak at 1650 cm−1 [46].
The functional groups’ presence in Ni-BTC-MOF/rGO was verified with the help of FTIR,
as illustrated in Figure 2a.The stretching vibrations of OH groups of physically adsorbed water show a
broad adsorption band in the range of 3600–3000 cm−1 [43,47,48]. The absence of significant peaks in
the region of 1800–1680 cm−1 , as well as deviation of peaks from 1715 to 1608 cm−1 , clearly indicate
complete deprotonation of the COOH group of benzene tricarboxylic acid (BTC) ligands and the
linking of ligands with metals, which is further proved by the metal–ligand peak at 720 cm−1 [44,49].
Furthermore, the distinctive bands of the COOH group caused by asymmetric and symmetric vibrations
appear in the ranges of 1645–1550 cm−1 and 1470–1390 cm−1 , respectively. The C=C stretching vibration
leads to a strong absorption band at 1628 cm−1 in Ni-BTC/5 wt % rGO, and a less intense peak in other
composites (i.e., Ni-BTC/1–4 wt % rGO and pure Ni-BTC). The covalent interactions of an organic
linker strongly alter the extended aromatic character of rGO through conversion of carbon atoms
from sp2 to sp3 hybridization, which results in a decrease of sp2 −C=C bond absorption frequency
(i.e., stretching). However, in this case, the peak intensity of sp2 carbon atoms is increased. These
results clearly reveal the lack of covalent interaction between rGO and Ni-BTC-MOF [50]. A peak
at 1392–1380 cm−1 corresponds to C=O, showing symmetric stretching. The following peaks also
reflect metal deprotonation with ultimate linking of metal with oxygen and successful synthesis of
composites [51,52]. While the peaks at 800 cm−1 caused by C−C stretching vibration and out-of-plane
deformation vibration of the C−H group in the benzene ring are present in all samples, their intensity
is higher in the 5 wt % sample because of its high rGO content [50].
The Raman spectrum of GO illustrated in Figure 3a gives an idea of the existent structural defects
of the graphene layer. Two characteristics bands that appear in the GO spectrum are D and G bands.
The D band displayed at 1352 cm−1 is caused by the stretching vibration of aromatic C=C, while the G
band visible at the 1600 cm−1 position develops because of the transformation of the sp2 hybridized
carbon of the ring system to sp3 hybridized carbon, as well as owing to available oxygen-bearing
functional groups on the surface of GO.
The intensity ratio of D and G bands (0.92), depicting structural defects and disorder, is clear
evidence of oxidation of graphite. On the same grounds, the D band of rGO at 1348 cm−1 and G band
at 1595 cm−1 in (Figure 3b) appear to be caused by structural defects and stretching vibration of sp2
hybridized C=C in aromatic groups, respectively. The ID /IG ratio obtained in this case is 1.42, which
reveals insufficient structural recovery of rGO and existence of sp3 after functionalization [53,54].
The crystal structure and morphology analysis performed through SEM confirm that the hexagonal,
rod-like structures in all synthesized materials (Figure 4a) closely match with reported literature [42].
Moreover, rGO flakes are also clearly visible in prepared composite materials, present between MOF
crystals (Figure 4b–g).
Catalysts 2019, 9, x856
2019, 9, FOR PEER REVIEW 5 of5 22
of 21
Ni-BTC
Ni-BTC/1 wt % rGO
Ni-BTC/2 wt % rGO
Ni-BTC/3 wt % rGO
Ni-BTC/4 wt % rGO
Ni-BTC/5 wt % rGO
Tranmittance (%)
-1
3600-3000cm -1
1628cm
OH 1392-1380cm-1 800cm-1 720cm-1
C=C
C=O C-C Ni-O
4000 3500 3000 2500 2000 1500 1000 500
-1
Wavenumber (cm )
(a)
(b) (c)
Figure2.
Figure 2. FTIR spectrum
spectrum of
of (a)
(a)Nickel
NickelBenzene
Benzenetricarboxylic
tricarboxylicacid (Ni-BTC)
acid MOF
(Ni-BTC) and
MOF 1–51–5
and wt wt
% rGO
% rGO
composites (b) GO and (c) rGO. composites (b) GO and (c) rGO.
The Raman spectrum of GO illustrated in Figure 3a gives an idea of the existent structural defects
of the graphene layer. Two characteristics bands that appear in the GO spectrum are D and G bands.
The D band displayed at 1352 cm−1 is caused by the stretching vibration of aromatic C=C, while the
G band visible at the 1600 cm−1 position develops because of the transformation of the sp2 hybridized
carbon of the ring system to sp3 hybridized carbon, as well as owing to available oxygen-bearing
functional groups on the surface of GO.
The intensity ratio of D and G bands (0.92), depicting structural defects and disorder, is clear
evidence of oxidation of graphite. On the same grounds, the D band of rGO at 1348 cm−1 and G band
at 1595 cm−1 in (Figure 3b) appear to be caused by structural defects and stretching vibration of sp2
hybridized C=C in aromatic groups, respectively. The ID/IG ratio obtained in this case is 1.42, which
reveals insufficient structural recovery of rGO and existence of sp3 after functionalization [53,54].
(a) (b)
Figure
Figure3.3.Raman
RamanIR
IRanalysis
analysisofof(a)
(a)GO
GOand
and(b)
(b)rGO.
rGO.
The crystal structure and morphology analysis performed through SEM confirm that the
hexagonal, rod-like structures in all synthesized materials (Figure 4a) closely match with reported
literature [42]. Moreover, rGO flakes are also clearly visible in prepared composite materials, present
between MOF crystals (Figure 4b–g).
Catalysts 2019, 9, 856 6 of 21
The elemental analysis using EDX confirmed the presence of carbon, oxygen, as well as Ni in all
prepared samples, without any impurities, as shown in Table 1. Furthermore, the gradual increase
in rGO concentration leading to elevated carbon and oxygen percentages confirms the successful
incorporation of rGO into the MOF structure.
(a) (b)
Table 1. Energy Dispersive X-rays (EDX) analysis of Ni-BTC-MOF and 1–5 wt % rGO composites.
Figure 3. Raman IR analysis of (a) GO and (b) rGO.
Sample Ni-BTC/1 Ni-BTC/2 Ni-BTC/3 Ni-BTC/4 Ni-BTC/5
Ni-BTC
Element wt % rGO wt % rGO wt % rGO wt % rGO wt % rGO
The crystal structure and morphology analysis performed through SEM confirm that the
C wt %rod-like
hexagonal, 35.66
structures 39.66 42.13 materials 45.65
in all synthesized 53.11 match with
(Figure 4a) closely 53.69reported
O wt % 26.89 29.05 36.99 41.88 39.67 41.06
literature [42]. Moreover,
Ni wt % 37.45
rGO flakes
31.29
are also 20.92
clearly visible 12.48
in prepared composite
7.22
materials,
5.25
present
between MOF crystals (Figure 4b–g).
(a) (b)
(c) (d)
Figure 4. Cont.
Catalysts 2019, 9, 856 7 of 21
(d)
(e) (f)
(g)
Figure 4. SEM images
imagesofof(a)
(a)Ni-BTC-MOF,
Ni-BTC-MOF, (b)(b) Ni-BTC/1
Ni-BTC/1 wt wt % rGO,
% rGO, (c) Ni-BTC/2
(c) Ni-BTC/2 wt %wt % rGO,
rGO, (d) Ni-
(d) Ni-BTC/3
BTC/3 wt %(e)
wt % rGO, rGO, (e) Ni-BTC/4
Ni-BTC/4 wt %(f)rGO,
wt % rGO, (f) Ni-BTC/5
Ni-BTC/5 wt %and
wt % rGO, rGO,
(g)and
rGO.(g) rGO.
2.1. Electrochemical
The elemental Measurements
analysis using EDX confirmed the presence of carbon, oxygen, as well as Ni in all
prepared samples, without any impurities,
The electrochemical measurements as pursued
were shown inthrough
Table 1.Potentiostat
Furthermore,(CHtheInstruments
gradual increase in
Inc, CHI
rGO concentration
760, Austin, leading
TX, USA). to the
During elevated carbona and
experiment, oxygen percentages
NaOH-saturated Hg/HgOconfirms
electrodethe
wassuccessful
used as a
incorporation of rGO into the MOF structure.
reference electrode; platinum wire acted as a counter electrode, while a glassy carbon electrode was
selected as the working electrode. Catalyst ink was prepared by mixing 2 mg catalytic material into
Table 1. Energy Dispersive X- rays (EDX) analysis of Ni-BTC-MOF and 1–5 wt % rGO composites.
3 µL of 5 wt% Nafion solution, which has excellent binding properties and electrical conductivity,
along with
Sample97 µL ethanol
Ni- solvent.
Ni-BTC/1 In order to analyze the
Ni-BTC/2 methanol oxidation
Ni-BTC/3 Ni-BTC/4 catalytic activity of
Ni-BTC/5
synthesized
Elementsamples,BTCall electrochemical
wt % rGO measurements
wt % rGO were
wt % performed
rGO % rGO −0.1
wtbetween wtV%andrGO0.7 V at
C wt % 35.66 39.66 42.13 45.65 53.11
different scan rates. At first the data was collected with bare electrodes, and then subsequently with 53.69
O wt %
catalyst-deposited 26.89 Carbon
Glassy 29.05 36.99 electrodes.41.88
electrode (GCE) 39.67
Electrochemical impedance41.06
spectroscopy
Ni wt % 37.45 31.29 20.92 12.48 7.22
(EIS) measurements were performed within a frequency range of 1–1 × 10 Hz and an amplitude 5 5.25
0.005 V in a three-electrode system, while the stability of the catalysts was tested at a peak potential
2.1.
0.69Electrochemical Measurements experiments. Qualitative and quantitative analysis of the product
V with chronoamperometric
was performed through bulk
The electrochemical electrolysis, were
measurements followed by data
pursued acquisition
through via GC and
Potentiostat (CHNMR.
Instruments Inc,
CHI 760, Austin, TX, USA). During the experiment, a NaOH-saturated Hg/HgO electrode was used
2.2.a Preparation
as of Working
reference electrode; Electrodes
platinum wire acted as a counter electrode, while a glassy carbon electrode
was selected
In order as
to the working
formulate electrode.
modified GCE Catalyst ink for
electrodes wasCV,prepared by mixing
Tafel plots, EIS, and2 mg catalytic material
chronoamperometric
into
measurements, catalytic ink was prepared by mixing 2 mg catalyst, 3 µL Nafion, and and
3 µL of 5 wt% Nafion solution, which has excellent binding properties 97 µLelectrical
ethanol.
conductivity, along with 97mixture
Then, 3 µL of homogenous µL ethanol
(1.07solvent.2
mg/cm In order to
catalyst) analyze
was mountedthethrough
methanol oxidation catalytic
micropipette on GCE,
activity of synthesized samples, all electrochemical measurements were performed between −0.1 V
In order to formulate modified GCE electrodes for CV, Tafel plots, EIS, and chronoamperometric
measurements, catalytic ink was prepared by mixing 2 mg catalyst, 3 µL Nafion, and 97 µL ethanol.
Then, 3 µL of homogenous mixture (1.07 mg/cm2 catalyst) was mounted through micropipette on
GCE, followed by drying under an infrared lamp. Complete analysis of synthesized samples was
carried out at different scan rates within a voltage window ranging from −0.1 to 0.7 V.
Catalysts 2019, 9, 856 8 of 21
The catalytic activity tests for MOF and their respective rGO composites were carried out with
an electrochemical workstation (CHI 760E, CH Instruments, Austin, TX, USA) at room temperature
followed
using a by drying three-electrode
standard under an infrared lamp. with
system, Complete
1 M analysis of synthesized
NaOH aqueous samples
solution used was
as a carried out
supporting
atelectrolyte
different scan rates within a voltage window ranging from −0.1 to 0.7 V.
solution. The Hg/HgO electrode and Pt wire were used as reference and counter
The catalytic
electrodes, activity tests
respectively, whilefor MOF
GCE andused
was theirasrespective
a workingrGOelectrode.
composites werevoltammetry
Cyclic carried out with was
an electrochemical
performed workstation
to optimize (CHIamount.
the catalyst 760E, CH Instruments,
Different amountsAustin, TX, USA)
of catalysts at room
ranging temperature
from 0.25 mg to
using
3.5 mg a were
standardloadedthree-electrode
on the surface system,
of GCEwith 1 M cast
by drop NaOH aqueous
method withsolution used
a potential as abetween
sweep supporting−0.1
electrolyte
V and 0.7 solution. The Hg/HgO
V in an alkaline electrode
electrolyte and PtThe
solution. wire were used
current as reference
density increasedand counterin
gradually electrodes,
line with
respectively,
the increase while GCEamount
of catalyst was used as2amg,
until working
whichelectrode.
was foundCyclic voltammetry
to be the was performed
ideal concentration to
for further
optimize
analysis,the catalystinamount.
as shown Figure 5a. Different amounts of catalysts ranging from 0.25 mg to 3.5 mg were
loaded Ononthe
thesame
surface of GCE
grounds, thebyrange
dropbetween
cast method
0.25 Mwith
anda 3.0
potential sweepwas
M methanol tested−0.1
between V and 0.7 V
for optimization,
inwith
an alkaline electrolyte solution. The current density increased gradually
2 M methanol selected for further experimentation, as indicated in Figure 5b. in line with the increase
of catalyst amount until 2 mg, which was found to be the ideal concentration for further analysis,
as shown in Figure 5a.
0.5 mg Ni-BTC 12
15 1.0 mg Ni-BTC (0.25 M) Methanol

1.5 mg Ni-BTC (0.5 M) Methanol
2.0 mg Ni-BTC 9
(1.0 M) Methanol
12 2.5 mg Ni-BTC (2.0 M) Methanol
C u rre n t d e n s ity (m A /c m 2 )
C urrent den sity(m A /cm 2 )
3.0 mg Ni-BTC (3.0 M) Methanol

without Methanol
9 6
6
3
0
0
-0.2 0.0 0.2 0.4 0.6 0.8

-0.2 0.0 0.2 0.4 0.6 0.8
Voltage (Hg/HgO)
Voltage (Hg/HgO)
(a) (b)
Figure 5.
Figure (a) Effects
5. (a) Effects of
of catalyst
catalyst load
load amount
amountand
and(b)
(b)different
differentmolarities
molaritiesofofmethanol
methanolonon
current density.
current density.
From
On the Figure 6a, it is the
same grounds, clear that between
range the current
0.25density
M and 3.0 shown by Ni-BTC-MOF
M methanol was testedatfor
50optimization,
mV/s is only
27.155 mA/cm 2, while the current densities possessed by 1–4 wt % rGO composites are 86.346
with 2 M methanol selected for further experimentation, as indicated in Figure 5b.
mA/cmFrom2, 112.035 mA/cm2, 125.829 mA/cm2, and 200.22 mA/cm2, respectively; the 5 wt % rGO
Figure 6a, it is clear that the current density shown by Ni-BTC-MOF at 50 mV/s is only
composite
27.155 mA/cm current
2 , whiledensity tendsdensities
the current to be lower. From the
possessed results
by 1–4 it rGO
wt % is clear that incorporation
composites of rGO2is
are 86.346 mA/cm ,
responsible for2 the increase in current
2 density for 42 wt % rGO composites, which
112.035 mA/cm , 125.829 mA/cm , and 200.22 mA/cm , respectively; the 5 wt % rGO composite current then decreases, as
illustrated
density tendsin to
Figure 6b. The
be lower. From main
the reason
results behind this
it is clear is incorporation
that the development of additional
of rGO poresfor
is responsible inthe
the
already developed porous structure of Ni-BTC-MOF, dispersion of MOF nanoparticles
increase in current density for 4 wt % rGO composites, which then decreases, as illustrated in Figure 6b. on the surface
The main reason behind this is the development of additional pores in the already developed porous
structure of Ni-BTC-MOF, dispersion of MOF nanoparticles on the surface of rGO, easy availability
of active sites, and the enhanced surface area of the composites [55–57]. Ni-BTC-MOF/4 wt % rGO
composite is the most efficient catalyst for methanol oxidation, as rGO’s excellent thermal stability,
enhanced electrical conductivity, and tendency to mitigate aggregation provides a huge surface area and
good conductivity by minimizing charge transfer resistance [58]. The Ni-BTC/5 wt % rGO composite
comparatively shows a reduced current density of 60.727 mA/cm2 , as shown in Figure 6b, which could
be caused by accumulation of charges on the rGO surface and blockage of active sites because of
rGO aggregation [41].
Cyclic voltammetry was performed by potential sweep technique between −0.1V and 0.7 V at a
scanning speed of 5–50 mV/s in an alkaline electrolyte to study the effect of scan rate, as demonstrated
in Figure 7. These results reveal that by increasing the scan rate from 5–50 mV/s, the current density
increases in all composites. This behavior can be attributed to the fact that with the increase of scan
rate, more electroactive species reached the electrode surface, leading to high current density [59].
provides a huge surface area and good conductivity by minimizing charge transfer resistance [58].
The Ni-BTC/5 wt % rGO composite comparatively shows a reduced current density of 60.727
mA/cm 2, as shown in Figure 6b, which could be caused by accumulation of charges on the rGO
of rGO, easy availability of active sites, and the enhanced surface area of the composites [55–57]. Ni-
surface
BTC-MOF/4 and blockage
wt % rGO of active sites because
composite of rGO
is the most aggregation
efficient catalyst[41].
for methanol oxidation, as rGO’s
excellent
Catalysts 2019,thermal
stability, enhanced electrical conductivity, and tendency to mitigate aggregation
9, 856 9 of 21
provides a huge surface area and good conductivity by minimizing charge transfer resistance [58].
The Ni-BTC/5 wt % rGO composite comparatively shows a reduced current density of 60.727
200
mA/cm2, as shown without
in Figure
methanol 6b, which could be caused 200
by accumulation of charges on the rGO
Without methanol
175 Ni-BTC Ni-BTC
surface and blockage of active
Ni-BTC/1 wt % rGO sites because of rGO
Current density (mA/cm ) Current density (mA/cm )
aggregation
175 [41]. Ni-BTC/1 wt % rGO
Current density (mA/cm )

150
2
Ni-BTC/2 wt % rGO Ni-BTC/2 wt % rGO
2
150 Ni-BTC/3 wt % rGO
Ni-BTC/3 wt % rGO
Ni-BTC/4 wt % rGO 125
Ni-BTC/5 wt % rGO
100 100
75
200 75
without methanol 200

50 Without methanol
50
175 Ni-BTC Ni-BTC
25

150
2
Ni-BTC/2 wt % rGO Ni-BTC/2 wt % rGO
2
150
0 Ni-BTC/3 wt % rGO
Ni-BTC/3 wt % rGO
0
-0.2 0.0 Ni-BTC/5
0.2 wt % rGO
0.4 0.6 0.8
-0.2 0.0 0.2 0.4 0.6 0.8
100 100
Voltage (Hg/HgO)
Voltage (Hg/HgO)
75 75
50
50
(a) 25
(b)
25
0
Figure6.06.(a)
Figure (a)Comparison
Comparison of of current
current density
density of
of Ni-BTC-MOF
Ni-BTC-MOFand and1–4
1–4wt wt%%rGOrGOcomposites
compositesand
and ofof
(b)
-0.2 0.0 0.2 0.4 0.6 0.8
Ni-BTC-MOF
(b) Ni-BTC-MOF
-0.2 and
0.0 and1–50.2 wt
1–5 wt%% rGO
0.4 rGOcomposites
composites
0.6 0.8 in
in 11 M
M NaOH
NaOH and 2 MM methanol
methanol solution
solution atataascan
scan rate
rate
Voltage (Hg/HgO)
ofof5050mV/s.
mV/s. Voltage (Hg/HgO)
Figure
Cyclic8voltammetry
show the direct (a)
wasrelationship
performed between
by potentialpeaksweep
current density and
technique (b) square
between rootand
−0.1V of scan
0.7 Vrate,
at a
where diffusion
scanning speed coefficient
of 5–50 mV/s is in
proportional
an alkaline to slope of to
electrolyte the straight
study line. of
the effect Therefore,
scan rate,by determining
as demonstrated
Figure 6. (a) Comparison of current density of Ni-BTC-MOF and 1–4 wt % rGO composites and of (b)
the linearity
in Figure 7. of the results
These plot, it reveal
is possible to increasing
that by calculate the thecharge transfer
scan rate coefficient
from 5–50 mV/s, (α), as well density
the current as the
Ni-BTC-MOF and 1–5 wt % rGO composites in 1 M NaOH and 2 M methanol solution at a scan rate
diffusion coefficient (D). The diffusion coefficient is calculated by employing the
increases in all composites. This behavior can be attributed to the fact that with the increase of scanRandles–Sevcik
of 50 mV/s.
equation
rate, more[55], with the area
electroactive (A) ofreached
species the electrode
the electrode in cm2 and
shown surface, the concentration
leading to high current (C)density
of methanol
[59].
shownCyclic
in mole/dm 3 .
voltammetry was performed by potential sweep technique between −0.1V and 0.7 V at a
5
scanning speed of 5–50 mV/s inIpan = alkaline
(2.99 × 10 )1/2study
) n (α nαto
electrolyte ACDthe1/2 1/2
veffect of scan rate, as demonstrated
in Figure 7. These results
For irreversible revealthe
processes, that by increasing
calculated the scan
diffusion rate from
coefficient value 5–50 is mV/s,
(15.35 the current
× 10 −5 cm2density
/s) for
100
increases in30
all composites.
1 wt %, (23.60 × 10 5cm−5 2
mV/sec/s) This behavior can be attributed to
for 2 wt %, (32.74 × 10 cm /s) for 3 wt %,
Ni-BTC
−5 2 the fact that
(84.57
5 mV/sec
with
×%10
Ni-BTC/1 wt rGO
the
−5 cm /s) for 4of
increase
2 wtscan
%,
10 mV/sec Ni-BTC 10 mV/sec Ni-BTC/1 wt % rGO
rate, more
(7.494 × 10 electroactive
−5 25
cm /s) for
2 5 species
wt %,
25 mV/sec Ni-BTC
reached
and (1.643the
× electrode
10 −5 cm 2 surface,
/s) for leading
Ni-BTC-MOF.
75
25 to
mV/sec high
The
Ni-BTC/1wt current
maximum
% rGO density
value [59].
of the
50 mV/sec Ni-BTC 50 mV/sec Ni-BTC/1wt % rGO
Current density (mA/cm 2 )
and the R2 value close to 1 for Ni-BTC 4 wt % rGO composite prove it to be the
2
diffusion coefficient
20
best material,15 following the controlled diffusion process with50 ease, as illustrated in Table 2.
10
25
100
30
5 5 mV/sec Ni-BTC 5 mV/sec Ni-BTC/1 wt % rGO
10 mV/sec Ni-BTC 10 mV/sec Ni-BTC/1 wt % rGO
25
25 mV/sec Ni-BTC 0 25 mV/sec Ni-BTC/1wt % rGO
0 75
50 mV/sec Ni-BTC 50 mV/sec Ni-BTC/1wt % rGO
Current density (mA/cm 2 )
2
20-0.2 0.0 0.2 0.4 0.6 0.8 -0.2 0.0 0.2 0.4 0.6 0.8
Voltage (Hg/HgO) Voltage (Hg/HgO)
50
15
10
25
5 (a) (b)
0
0
-0.2 0.0 0.2 0.4 0.6 0.8 -0.2 0.0 0.2 0.4 0.6 0.8
(a) (b)
Figure 7. Cont.
Catalysts 2019, 9, 856 10 of 21
125 125
5mV/sec Ni-BTC/ 3 wt % rGO
5mV/sec Ni-BTC/ 2 wt % rGO 10mV/sec Ni-BTC/ 3 wt % rGO
100 10mV/sec Ni-BTC/ 2 wt % rGO 100 25mV/sec Ni-BTC/ 3 wt % rGO
Current density (mA/cm 2 ) 25mV/sec Ni-BTC/ 2 wt % rGO 50mV/sec Ni-BTC/ 3 wt % rGO

2
50mV/sec Ni-BTC/ 2 wt % rGO
75 75
50
50
25
25
0
0
-0.2 0.0 0.2 0.4 0.6 0.8 -0.2 0.0 0.2 0.4 0.6 0.8
(c) (d)
200 75
5mV/sec Ni-BTC/ 4wt% rGO
175 10mV/sec Ni-BTC/ 4wt% rGO 5 mV/sec Ni-BTC/5wt% rGO
25mV/sec Ni-BTC/ 4wt % rGO 10 mV/sec Ni-BTC/5wt% rGO
150 50mV/sec Ni-BTC/ 4wt % rGO 25mV/sec Ni-BTC/5wt% rGO
C urre n t d e nsity(m A /cm 2 )
50mV/sec Ni-BTC/5wt% rGO

50
2
125
100
75 25
50
25
0
0
-0.2 0.0 0.2 0.4 0.6 0.8
-0.2 0.0 0.2 0.4 0.6 0.8
Voltage (Hg/HgO)
Voltage (Hg/HgO)
(e) (f)
Figure
Figure 7. 7. Comparison
Comparison of of effect
effect of scan
of scan raterate
on on current
current density
density of Ni-BTC-MOF,
of (a) (a) Ni-BTC-MOF, (b) 1wt
(b) 1wt %,2 (c)
%, (c) wt 2%,wt
(d)%,3wt
(d)%,3wt
(e)%,4 wt(e)%,
4 and
wt %,(f)and
5 wt(f)
% 5rGO/Ni-BTC
wt % rGO/Ni-BTC composites
composites in 1 M
in 1 M NaOH NaOH
and and 2 M solution
2 M methanol methanol
atsolution
a scan rateat aofscan
5–50rate of 5–50 mV/s.
mV/s.
Figure 8 show the 200

direct relationship between peak current density and square root of scan rate,
Y=16.0045x+88.4493
Ni BTC
where diffusion coefficient is proportional
Ni BTC 1 wt % rGO to slope of the straight line.
Ni BTC 2 wt % rGO
Therefore,
R =0.9983 by determining the 2
180
linearity of the plot, it is possible NitoBTCcalculate
Ni BTC 3 wt % rGO
4 wt % rGO
the charge transfer coefficient (α), as well as the diffusion
160 Ni BTC 5 wt % rGO
coefficient (D). The diffusion coefficient is calculated by employing the Randles–Sevcik equation [55],
Current density(mA/cm )
2
with the area (A) of 140 the electrode shown in cm2 and the concentration (C) of methanol shown in
Y=8.2514x+66.7668
2
R =0.9698
mole/dm . 3 120
Y=9.8397x+43.0860
2
100 R =0.9807
Ip = (2.99 × 105) n (α nα)1/2ACD1/2v1/2
Y=5.1932x+47.7531
80 2
R =0.9980
For irreversible processes, the calculated diffusion coefficient value is (15.35 × 10−5 cm2/s) for 1
wt %, (23.60 × 10−5 cm602/s) for 2 wt %, (32.74 × 10−5 cm2/s) for 3 wt %,Y=6.0166x+17.5228
(84.57 × 10−5 cm2/s) for 4 wt %,
R =0.9918
2
(7.494 × 10−5 cm2/s) for405 wt %, and (1.643 × 10−5 cm2/s) for Ni-BTC-MOF. The maximum value of the
Y=3.1316x+5.8282
diffusion coefficient and
20 the R2 value close to 1 for Ni-BTC 4 wt % rGO composite prove it to be the
R =0.9925
2
best material, following the controlled diffusion process with ease, as illustrated in Table 2.
2 3 4 5 6 7
1/2
(Scan rate) (mV/sec)
Figure 8. A plot of the linear relationship between peak current density and square root of scan rate in
Figure 8. A plot of the linear relationship between peak current density and square root of scan rate
1 M NaOH and 2 M methanol solution.
in 1 M NaOH and 2 M methanol solution.
Table 2. Value of R2 and diffusion coefficient of Ni-BTC-MOF and 1–5 wt % rGO composites for
comparison at 50mV/s.
Catalyst R2 Diffusion Co-Efficient (cm2/s)

Ni-BTC 0.99256 1.643 × 10−5
Ni-BTC/1 wt % rGO 0.98716 15.35 × 10−5
Catalysts 2019, 9, 856 11 of 21
Table 2. Value of R2 and diffusion coefficient of Ni-BTC-MOF and 1–5 wt % rGO composites for
comparison at 50 mV/s.
Catalyst R2 Diffusion Co-Efficient (cm2 /s)

Ni-BTC 0.99256 1.643 × 10−5
Ni-BTC/1 wt % rGO 0.98716 15.35 × 10−5
Ni-BTC/2 wt % rGO 0.99269 23.60 × 10−5
Ni-BTC/3 wt % rGO 0.98708 32.74 × 10−5
Ni-BTC/4 wt % rGO 0.99833 84.57 × 10−5
Ni-BTC/5 wt % rGO 0.99184 7.494 × 10−5
The electrochemical impedance spectroscopy (EIS) is another excellent technique for investigating
the catalytic activity of synthesized materials [60]. Electrochemical impedance is measured by using
the potentiostatic mode in the same three-electrode system in 1 M NaOH and 2 M methanol solution
with reformed GCE in the frequency range of 1–105 Hz, with amplitude of 0.005 V and a peak potential
of 0.69 V. In electrochemical studies, two significant factors to be considered are (a) solution resistance
and (b) resistance between the reference and working electrode. Figure 9 represents the nyquist plots
of all electrocatalysts, showing a distinct frequency dependent semicircle impedance curve in the high
frequency region and a straight line with a slope of 45◦ in the low frequency region, expressing Warburg
diffusion impedance. The semicircle in the high frequency region is also related to the partial oxidation
of methanol to aldehyde and acid [61]. The charge transfer resistance at the electrode–electrolyte
interface or the blocking properties of the rough electrode responsible for the faradic process of the ionic
exchange is determined by the diameter of the semicircle. The small diameter of the semicircle indicates
low charge transfer resistance (Rct ), and amplified reaction kinetics give an idea of the remarkable
interfacial structural change, which most probably results from the high electrical conductivity of the
rGO framework [62–65]. Among different rGO composites, the most efficient is Ni-BTC/4 wt % rGO
composite, which has a minimum resistance toward electron and ion transfer, low activation energy,
maximum approach of reactants toward active sites, and fast reaction kinetics.
Ni-BTC
Nii-BTC /1 wt % rGO
Ni-BTC / 2 wt % rGO
4 Ni-BTC / 3 wt % rGO
1.2x10 Ni-BTC / 4 wt % rGO
1 Ni-BTC / 5 wt % rGO
Bare 8.0x10
4
1.0x10 rGO
1
3
8.0x10 6.0x10
3
6.0x10
Z (Ohm)
Z /ohm
1
4.0x10
"
3
4.0x10
''
1
2.0x10
3
2.0x10
0.0 0.0
0.0 3
2.0x10 4.0x10
3 3
6.0x10
3
8.0x10
4
1.0x10 0.0 5.0x10
1 2
1.0x10
2
1.5x10
'
Z (Ohm) Z'/ohm
(a) (b)
Figure
Figure9.9.EIS
EIScomparison
comparisonofof(a)
(a)bare
baresolution
solutionand
andrGO,
rGO,and
andofof(b)
(b)Ni-BTC-MOF
Ni-BTC-MOFand
and1–5
1–5wt
wt%%rGO
rGO
composites in 1 M NaOH and 2 M methanol solution at peak potential 0.69
composites in 1 M NaOH and 2 M methanol solution at peak potential 0.69 V. V.
Table
Table33 shows
shows aa comparison
comparisonof
of RRssand
andRRctct, ,and
andthe
thecapacitance
capacitanceofofNi-BTC-MOF
Ni-BTC-MOFand
and1–5
1–5wt
wt%%
rGO
rGOcomposites.
composites.
Table 3. Electrochemical parameters from EIS data of Ni-BTC and Ni-BTC/1–5 wt % rGO composites
in 1 M NaOH and 2M methanol solution.
Sr.No Sample Resistance (Rs) Ohm Resistance (Rct) Ohm Capacitance (C) Farad
1 Ni-BTC 1.340 158.00 6.209e−6
2 Ni-BTC/1 wt % rGO 0.624 112.90 8.316e−6
3 Ni-BTC/2 wt % rGO 0.663 28.23 1.444e−5
4 Ni-BTC/3 wt % rGO 0.464 19.12 1.229e−5
5 Ni-BTC/4 wt % rGO 0.328 18.12 9.156e−6
6 Ni-BTC/5 wt % rGO 0.496 102.00 4.728e−6
Catalysts 2019, 9, 856 12 of 21
Table 3. Electrochemical parameters from EIS data of Ni-BTC and Ni-BTC/1–5 wt % rGO composites in
1 M NaOH and 2 M methanol solution.
Resistance (Rs ) Resistance Capacitance

Sr.No Sample
Ohm (Rct ) Ohm (C) Farad
1 Ni-BTC 1.340 158.00 6.209e−6
2 Ni-BTC/1 wt % rGO 0.624 112.90 8.316e−6
3 Ni-BTC/2 wt % rGO 0.663 28.23 1.444e−5
4 Ni-BTC/3 wt % rGO 0.464 19.12 1.229e−5
5 Ni-BTC/4 wt % rGO 0.328 18.12 9.156e−6
6 Ni-BTC/5 wt % rGO 0.496 102.00 4.728e−6
The Tafel plot helps in understanding the kinetics and reaction mechanism of the catalytic process
by relating the overpotential with the natural logarithm (ln) of current density. Overpotential is
the potential exceeding the required potential for a reaction to be carried out. Among synthesized
samples, the maximum current density is retained by the Ni-BTC/4 wt % rGO composite at a specific
overpotential, which might be caused by the availability of reaction sites for reactants after rGO
incorporation, as shown in Figure 10. The Tafel slope, representative of kinetic behavior, is calculated
with the following equation [61]:
η = A + b log i
0.22 Ni-BTC
Ni-BTC/1 wt % rGO
Ni-BTC/2 wt % rGO
0.20 Ni-BTC/3 wt % rGO
Ni-BTC/4 wt % rGO
Over potential (V)
Ni-BTC/5 wt % rGO
0.18
0.16
0.14
0.12
0.10
-3 -2 -1 0 1 2 3 4 5
2
ln j(mA/cm )
Figure 10. Tafel plot of Ni-BTC-MOF and 1–5 wt % rGO composites in 1 M NaOH and 2 M methanol
solution at 50 mV/s.
The Tafel slope of Ni-BTC-MOF and 1–4 wt % rGO composites at low overpotential (0.14 V) is in
Table 4. Comparison of resistance and Tafel slope of Ni-BTC and 1–5 wt % rGO composites at 50
the order of 59.75, 33.69, 29.58, 28.10, and 27.89 mV/dec, respectively. After this, the Ni-BTC-MOF/5
mV/s.
wt % rGO composite shows a comparatively higher Tafel slope, while at high overpotential, the Tafel
Catalyst
slope is in the following sequence: 78.79, 36.48,R34.60,
ct (Ohm) 32.57,Tafel SlopemV/dec
and 29.30 (mV/dec) for Ni-BTC-MOF and
Ni-BTC
1–4 wt % rGO composites, respectively; followed158 59.65 in Tafel slope for 5 wt %
by subsequent increase
rGO composite to 44.41 Ni-BTC/1 wt % rGOthe charge
mV/dec. Moreover, 112 transfer resistance
33.69 Rct is lower for 4wt% which
Ni-BTC/2oxidation
show best activity for methanol wt % rGOfollowed 28.23by 3wt%,2wt%, 29.58
1wt% and 5wt% rGO/Ni-BTC
Ni-BTC/3
MOF as illustrated in Table 4. Thewt Tafel
% rGO plot is19.12
basically divided 28.10
into two regions: low and high
potential regions; whereNi-BTC/4 wtmechanism,
the reaction % rGO 18.12
or 27.89
at the least rate determining step, is quite different
Ni-BTC/5 wt %
and conveys different information. InrGO 102
the low potential 75.47
range, methanol dehydrogenation is the
main process, while oxidative removal of CO occurs in the high potential range. The low Tafel slope
The relativewt stability
of Ni-BTC-MOF/4 of synthesized
% rGO composite of 27.89electrocatalytic
mV/dec reflects materials was ofanalyzed
faster removal hydrogenthrough
from
chronoamperometric measurements by employing a three-electrode system
methanol and instant CO removal in low and high potential ranges, respectively [66–69]. in 1 M NaOH and 2M
methanol solution at a fixed potential of 0.69 V, as shown in Figure 11. These curve stability values
do not illustrate the initial drop with 100% accuracy because of the adsorption of reaction
intermediates, such as CO, COOH, and CHO, on the catalyst surface. After this, the relative stability
reaches a steady state until 3600 s [70,71]. After the deployment of the set potential (i.e., 0.69 V for
3600 s), the highest stability is shown for Ni-BTC/4 wt % rGO, reaching up to 83%, which is possibly
because of the 2D structure of rGO leading to high specific surface area, minimal charge transfer
resistance, and tolerance to poisonous intermediates [69]. This is followed by Ni-BTC/3 wt % rGO at
ln j(mA/cm )
CatalystsTable
2019, 9,4.856
Comparison of resistance and Tafel slope of Ni-BTC and 1–5 wt % rGO composites at1350of 21
mV/s.
Table 4. Comparison of resistance and Tafel slope
Catalyst Rct of Ni-BTC Tafel
(Ohm) and 1–5Slope
wt % rGO composites at 50 mV/s.
(mV/dec)
Ni-BTC
Catalyst 158
Rct (Ohm) 59.65(mV/dec)
Tafel Slope
Ni-BTC/1 wt % rGO 112 33.69
Ni-BTC 158 59.65
Ni-BTC/2
Ni-BTC/1 wt %wt
rGO% rGO 28.23
112 29.58
33.69
Ni-BTC/3 wt
Ni-BTC/2 wt % rGO% rGO 19.12
28.23 28.10
29.58
Ni-BTC/4
Ni-BTC/3 wt %wt
rGO% rGO 19.1218.12 27.89
28.10
Ni-BTC/4 wt % rGO
Ni-BTC/5 wt % rGO 18.12
102 27.89
75.47
Ni-BTC/5 wt % rGO 102 75.47
The relative stability of synthesized electrocatalytic materials was analyzed through

The relative stability measurements
chronoamperometric of synthesized electrocatalytic
by employing materials was analyzed
a three-electrode through
system inchronoamperometric
1 M NaOH and 2 M
measurements by employing
methanol solution at a fixedapotential
three-electrode system
of 0.69 V, in 1 M
as shown inNaOH
Figure and 2 M methanol
11. These solution
curve stability at
values
a fixed potential of 0.69 V, as shown in Figure 11. These curve stability
do not illustrate the initial drop with 100% accuracy because of the adsorption of reactionvalues do not illustrate the
initial drop withsuch
intermediates, 100% asaccuracy
CO, COOH, because of theon
and CHO, adsorption
the catalyst ofsurface.
reactionAfter
intermediates, such as
this, the relative CO,
stability
COOH,
reachesand CHO, on
a steady theuntil
state catalyst
3600surface. After
s [70,71]. Afterthis,
thethe relative stability
deployment of the reaches a steady
set potential (i.e.,state
0.69until
V for
3600 s [70,71]. After the deployment of the set potential (i.e., 0.69 V for 3600 s),
3600 s), the highest stability is shown for Ni-BTC/4 wt % rGO, reaching up to 83%, which is possibly the highest stability
is because
shown forof Ni-BTC/4 wt % rGO,
the 2D structure reaching
of rGO up to
leading to 83%,
high which
specific is surface
possiblyarea,
because of thecharge
minimal 2D structure
transfer
ofresistance,
rGO leadingandto high specific
tolerance surface intermediates
to poisonous area, minimal[69]. charge
Thistransfer resistance,
is followed and tolerance
by Ni-BTC/3 wt % rGO toat
poisonous intermediates
80%, Ni-BTC/2 wt % rGO [69].
at This
78%,isNi-BTC/1
followedwt by% Ni-BTC/3
rGO at 74%, wt %Ni-BTC/5
rGO at 80%,wt % Ni-BTC/2 wt % rGO
rGO at 74.5%, and atNi-
78%,
BTCNi-BTC/1
at 73%. wt % rGO at 74%,
Ni-BTC-MOF Ni-BTC/5
shows a fastwtdecline,
% rGO in at 74.5%,
contrast andtoNi-BTC at 73%. Ni-BTC-MOF
other catalysts (i.e., 1–5wt %
shows a fast decline,
composites), in contrast
and then shows to other catalysts
a sluggish decline (i.e.,
over1–5time
wt % composites),
until and thenat
reaching stability shows
3600 as.sluggish
decline over time until reaching stability at 3600 s.
105
Ni-BTC
100 Ni-BTC/1wt% rGO
Ni-BTC/2wt% rGO
95 Ni-BTC/3wt% rGO
Relative stability (%)
Ni-BTC/4wt% rGO
90 Ni-BTC/5wt% rGO
85
80
75
70
0 500 1000 1500 2000 2500 3000 3500 4000
Time (s)
Figure 11. Chronoamperometry curves of Ni-BTC-MOF and 1–5 wt % rGO composites in 1 M NaOH
and 2 M methanol solution at 0.69 V.
Ni-BTC-MOF/1–4 wt % rGO composites improved the electrocatalytic activity results because of

the synergistic effects of rGO sheets and Ni-BTC-MOF. In the literature, subsequent elementary steps
are proposed to take place during the reaction, which includes adsorption and dehydrogenation of
methanol into intermediates. The overall reactions in the process are represented in Scheme 1.
Bulk Electrolysis and Product Analysis

Electrocatalytic oxidation of methanol into CO2 can generate the maximum amount of electricity
in direct methanol fuel cells, but high overpotential (0.45 V) is responsible for sluggish kinetics, even
when using state-of-the-art Pt catalysts, because of poisoning of catalysts by intermediates in the
oxidation process, such as CH, CH3 , and COOH [72,73]. In this work, product identification and
quantification of Ni-BTC/4 wt % rGO composite’s catalyzed methanol oxidation process was carried
out by bulk electrolysis on a glassy carbon plate in 2 M methanol solution containing 1 M NaOH as
a supporting electrolyte, as illustrated in Figure 12. At the start of the experiment, N2 was purged
for 45 min to remove oxygen, after which the potential was fixed at 0.69 V for the oxidation process.
Catalysts 2019, 9, 856 14 of 21
Initially, the sharp decline in current density is because of the double layer charging process, but later on
the constant current density (i.e., 199.6 mA/cm2 ) during bulk electrolysis for 1.5 h reflects the catalyst’s
stability under catalytic turnover conditions [74]. The electrolytic product was collected after a 52.7 ◦ C
charge had been passed and was further analyzed by 1 H NMR spectroscopy technique. Figure 13
symbolizes the NMR spectra of blank and Ni-BTC/4 wt % rGO composite, whereas Figure 14 represents
the NMR spectra of reference electrolyte. The NMR spectra of Ni-BTC/ 4 wt% rGO composite after
bulk electrolysis is shown in Figure 15. The possible products during bulk electrolysis are as follow:
+ −
CH3 OH → H2 CO + 2H + 2e (1)
Figure 11. Chronoamperometry curves of Ni-BTC-MOF and 1–5 wt % rGO composites in 1M NaOH
and 2 M methanol solution H
at 0.69
CO V.+ 2 CH OH → CH (OCH ) + H O (2)
2 3 2 3 2 2
+ −
Ni-BTC-MOF/1–4 wt % rGO 3 OH + H2 Oimproved
CHcomposites → HCOOH the+electrocatalytic
4 H + 4e (3)
activity results because of
the synergistic effects of rGO sheets and Ni-BTC-MOF. In the literature, subsequent elementary steps
HCOOH + CH3 OH → HCOOCH3 + H2 O (4)
are proposed to take place during the reaction, which includes adsorption and dehydrogenation of
methanol into intermediates. TheCH + H2 O →in
3 OH reactions
overall CO
the 6H+ + are
2 +process 6e− represented in Scheme 1. (5)

Scheme 1. Stepwise Mechanism of methanol oxidation to formic acid.
Scheme 1. Stepwise Mechanism of methanol oxidation to formic acid.
Bulk Electrolysis and Product Analysis

1699
Electrocatalytic oxidation of methanol into CO2wtcan

Ni-BTC/4 generate
% rGOBulk the maximum amount of electricity
electrolysis
Current density(mA/cm )
1415
2
in direct methanol fuel cells, but high overpotential (0.45 V) is responsible for sluggish kinetics, even
when using state-of-the-art Pt catalysts, 1132 because of poisoning of catalysts by intermediates in the
oxidation process, such as CH, CH 849
3, and COOH [72,73]. In this work, product identification and
quantification of Ni-BTC/4 wt % rGO composite’s catalyzed methanol oxidation process was carried
566
out by bulk electrolysis on a glassy carbon plate in 2 M methanol solution containing 1 M NaOH as
a supporting electrolyte, as illustrated 283 in Figure 12. At the start of the experiment, N2 was purged for
45 min to remove oxygen, after which the potential was fixed at 0.69 V for the oxidation process.
0
Initially, the sharp decline in current density 0 is because
1000 2000 of the
3000 double
4000 5000 layer6000 charging process, but later
on the constant current density (i.e., 199.6 mA/cm Time(Sec)

2) during bulk electrolysis for 1.5 h reflects the
catalyst’s
Figurestability
12. Bulkunder catalytic
electrolysis turnover
of Ni-BTC/4 wt %conditions
rGO composites [74].inThe1 Melectrolytic
NaOH and 2 product
M methanolwas collected
solution
Figure
after aat52.7 °C 12. Bulkhad
charge electrolysis
been of Ni-BTC/4
passed and was wtfurther
% rGOanalyzed
composites by in
1H1NMR M NaOH and 2 M methanol
spectroscopy technique.
peak potential of 0.69 V.
Figure 13 solution at peakthe
symbolizes potential
NMRofspectra
0.69 V.of blank and Ni-BTC/4 wt % rGO composite, whereas Figure
According
14 represents thetoNMRthe above
spectraequations,
of reference methanol
electrolyte. oxidation
The NMR generatesspectra formaldehyde
of Ni-BTC/ 4and wt%formic
rGO
composite According
acid, which may
after tocondense
bulk the abovewith
electrolysis equations,
methanol
is shown methanol
in Figure oxidation
to produce
15. methyl
The possiblegenerates
formate
productsformaldehyde
and and formic acid,
dimethoxymethane,
during bulk electrolysis
which may[75].
respectively condense
Detectionwithofmethanol
gaseous to produce
products methyl
such as CO formate and dimethoxymethane, respectively
are as follow: 2 was carried out by an Agilent 7820 A gas
[75]. Detection system
chromatography of gaseous products
equipped with an such
Agilentas CO HP-5 2 was carried out by an Agilent 7820 A gas
column, with dimensions of 30 m × 0.32 µm.
CH 3OH → H2CO + 2H+ + 2e− (1)µm.
chromatography system equipped with
The result was identical to CO2 being sucked from the airan Agilent HP-5 column, with dimensions
and injected into the of
GC 30instrument,
m × 0.32
The result
clarifying thatwas
COidentical toHCO2CO 2 being
+ 2 CHsucked
3OH → from CH2 (OCH the air 3)2 and
+ H2O injected into of
theliquid
GC instrument,
(2)
2 is not a final product during analysis. Qualitative analysis products
clarifying that CO 2 is not a final product during analysis. Qualitative analysis1 of liquid products such
such as formaldehyde and formic acid was undertaken with a Bruker
H2O → HCOOH − DRX400 H NMR spectrometer.
as formaldehyde and formic CH acid3OH was+undertaken with a+Bruker
4 H+ + 4e DRX400 1H NMR spectrometer. (3)The
final product of bulk electrolysis HCOOH of catalytic
+ CH3OH → HCOOCH
material under experimental
3 + H2O conditions was found(4) to be
formic acid, with 60.26% yield calculated through a faradic+ efficiency formula.
CH3OH + H2O → CO2 + 6H + 6e− (5)
F.E = n × N × F/Q × 100
where N is the number of electrons involved in the oxidation process; n is the number of moles in the
According to the above equations, methanol oxidation generates formaldehyde and formic acid,
which may condense with methanol to produce methyl formate and dimethoxymethane, respectively
[75]. Detection of gaseous products such as CO2 was carried out by an Agilent 7820 A gas
chromatography system equipped with an Agilent HP-5 column, with dimensions of 30 m × 0.32 µm.
The result
Catalysts 2019,was
9, 856identical to CO2 being sucked from the air and injected into the GC instrument,
15 of 21
clarifying that CO2 is not a final product during analysis. Qualitative analysis of liquid products such
as formaldehyde and formic acid was undertaken with a Bruker DRX400 1H NMR spectrometer. The
The final product of bulk electrolysis of catalytic material under experimental conditions was found to
final product of bulk electrolysis of catalytic material under experimental conditions was found to be
be formic acid, with 60.26% yield calculated through a faradic efficiency formula.
formic acid, with 60.26% yield calculated through a faradic efficiency formula.
F.E==nn×× N
F.E N×× F/Q ×× 100
100
where
where NN is
isthe
thenumber
numberofofelectrons
electronsinvolved
involvedinin
the oxidation
the oxidationprocess; n isnthe
process; number
is the of moles
number in the
of moles in
product;
the product; Q is the total charge pass during bulk electrolysis; and F is Faraday’s constant. The side
Q is the total charge pass during bulk electrolysis; and F is Faraday’s constant. The side
products would be
products would be water
water and
and O
O2 produced
produced during
during the
the parallel
parallel water
water oxidation
oxidation process.
process.
2

NMR spectra
Figure 13. NMR
Figure spectra of
of blank
blank and
and Ni-BTC/4
Ni-BTC/4 wt % rGO composite.
Figure 14. NMR spectra of reference electrolyte.

Figure 14.NMR
Figure14. NMRspectra
spectraof
ofreference
referenceelectrolyte.
electrolyte.
Figure 15. NMR spectra of Ni-BTC/4 wt % rGO composite after bulk electrolysis.
Figure 15. NMR spectra of Ni-BTC/4 wt % rGO composite after bulk electrolysis.
Table
Table 55 below
below shows
shows aa comparison
comparison of of synthesized
synthesized MOFs
MOFs and
and their
their composites
composites with
with the reported
the reported
Table
materials 5 below
utilized shows
for a comparison
methanol oxidation.of synthesized
The MOFs
Ni-BTC/4 wt and
% rGOtheir composites
composite with
shows
materials utilized for methanol oxidation. The Ni-BTC/4 wt % rGO composite shows comparable the reported
comparable
materials
catalytic utilized
activity to for
the methanol
Pt-Ni oxidation.
catalyst for The
methanol Ni-BTC/4
oxidationwt % rGO
reaction composite
(MOR) and shows
better comparable
performance
catalytic activity to the Pt-Ni catalyst for methanol oxidation reaction (MOR) and better performance
catalytic
than
than otheractivity
other reported
reportedto materials.
the Pt-Ni catalyst
materials. This
This is for methanol
is because
because of theoxidation
of the synergic reaction
synergic effect
effect of (MOR) and better
of Ni-BTC-MOF
Ni-BTC-MOF withperformance
with rGO.
rGO.
than other reported materials. This is because of the synergic effect of Ni-BTC-MOF with rGO.
Table 5. Comparison of catalytic activity of synthesized samples with reported materials.
Peak
Methanol Catalyst Scan Anodic
Peak
Current Resistance
Catalytic Materials Methanol
Concentration Catalyst
Amount Scan Potential
Rate Anodic Ref.
Current
Density Resistance
(Ohm)
Catalytic Materials Concentration
(M) Amount
(mg/cm 2) Rate
(mV/s) Potential
(V) Ref.
Density
(mA/cm 2) (Ohm)
(M) (mg/cm2) (mV/s) (V)
Catalysts 2019, 9, 856 16 of 21
Methanol Catalyst Peak Current

Scan Rate Anodic Resistance
Catalytic Materials Concentration Amount Density Ref.
(mV/s) Potential (V) (Ohm)
(M) (mg/cm2 ) (mA/cm2 )
Pt-Ni 1 20 50 1.44 vs. RHE 265.6 - [9]
Ru@Pt/MWCNT 2 4 50 1.81 vs. RHE 182.4 606 [29]
NiCo2 O4 -rGO 0.5 - 50 1.26 vs. RHE 48.0 1000 [52]
Nanoporous Pt/Al
2 - 100 0.8 vs. RHE 6.0 - [76]
thin films
Ni-BTC 2 1.07 50 1.66 vs. RHE 27.155 158 This work
Ni-BTC/1 wt % rGO 2 1.07 50 1.66 vs. RHE 86.346 112 This work
Ni-BTC/2 wt % rGO 2 1.07 50 1.66 vs. RHE 112.04 28.23 This work
Ni-BTC/5 wt % rGO 2 1.07 50 1.66 vs. RHE 60.72 102 This work
3. Material and Methods
3.1. Materials
All chemicals and reagents employed for synthesis of required materials were of analytical grade
and utilized without any need for further purification. Chemicals utilized for synthesis, namely Ni
(NO3 )2 .6H2 O, Trimesic acid (1, 3, 5 benzene tricarboxlic acid), NaNO3 , KMnO4 , H2 O2 , and graphite
powder, were purchase from Sigma Aldrich (St. Louis, MO, USA). Ethanol, DMF, H2 SO4 , hydrazine
hydrate, and deionized water were bought from Merck (Kenilworth, NJ, USA).
3.2. Instrumentation
The crystal structure and phase purity of synthesized samples was confirmed using an X-ray
powder diffractometer (STOE, Darmstadt, Germany) equipped with Cu Kα radiation of λ = 1.54060 Å,
within the 2 θ range of 5–80◦ , at operational conditions of 20 kV and 5 mA, and with a step size of 4◦ /s.
The shape and morphology was analyzed by scanning electron microscopy (VEGA3, TESCAN, Brno,
Czech Republic).
The composition was confirmed via energy dispersive X-ray spectroscopy (Oxford Instruments,
Abingdon, UK). Metal–ligand coordination was studied by using Spectrum 100 FTIR spectrophotometer
(PerkinElmer, Waltham, MA, USA), at a wavenumber range of 500–4000 cm−1 .
3.3. Synthesis of Ni-BTC-MOF

Ni-BTC-MOF was synthesized through the reported solvothermal method [77]. Here, 2 g Ni
(NO3 )2 .6H2 O was dissolved in 17 mL H2 O and 1 g of 1,3,5 benzene tricarboxlic acid was added to 34 mL
of a mixture of C2 H5 OH and DMF solvents (1:1), followed by slow addition of the linker solution to the
metal salt solution with continuous stirring for 1 h. The homogenous mixture was then transferred to a
50 mL Teflon-lined autoclave and kept in an oven at 85 ◦ C for 24 h. After completion of the reaction,
the autoclave was slowly cooled down to room temperature, the solid material was collected through
filtration, followed by washing with solvents three times, and vacuum drying at 65 ◦ C for 24 h.
3.4. Synthesis of GO and rGO

Synthesis of GO was carried out via Hummers’ method [34]. Graphite powder and sodium nitrate
(2:1) were first dissolved in 46 mL sulfuric acid through magnetic stirring for 1 h in an ice bath at a
temperature of 5 ◦ C. Later on, 7 g potassium permanganate (KMnO4 ) was gradually added at the
same condition, followed by 6 h continuous stirring at 35 ◦ C. Then, 80 mL deionized (DI) water was
slowly added to the brown paste in such a way that the temperature was not allowed to rise above
60 ◦ C. Moreover, dilution was achieved through addition of 200 mL DI water, and finally the reaction
was stopped after addition of 10 mL 30% H2 O2 . The reaction mixture was repeatedly washed with
Catalysts 2019, 9, 856 17 of 21
diluted HCl and DI water through centrifugation to ensure aa pH of 6–7. Sonication was done to
obtain exfoliated GO, and the product was then vacuum dried at 45 ◦ C for 24 h.
In order to prepare rGO, 100 mg GO was dissolved in 100 mL DI water and sonicated for 2 h to
obtain a homogenous mixture. Hydrazine hydrate (1 mL) was then added to the reaction mixture and
refluxed for 24 h at 100 ◦ C. Hydrophobic rGO appeared on the surface after completion of the reaction.
The porous, blackish product was filtered and washed with DI water and ethanol, followed by vacuum
drying at 45 ◦ C [33].
3.5. Synthesis of Ni-BTC-MOF/rGO Composites

A series of rGO composites of Ni-BTC-MOF were synthesized using the abovementioned procedure.
A linker solution prepared in DMF and ethanol was slowly added to the metal salt aqueous solution
and stirred
aqueous for 1 h.and
solution Subsequently, anSubsequently,
stirred for 1 h. appropriate amount of rGO was
an appropriate amountadded to the
of rGO MOF
was addedsolution,
to the
followed by 2 h sonication to acquire a homogenous mixture. After this, the reaction
MOF solution, followed by 2 h sonication to acquire a homogenous mixture. After this, the reaction mixture was
poured into a Teflon-lined autoclave and kept in an oven for 24 h at 85 ◦ C. the obtained solid product
mixture was poured into a Teflon-lined autoclave and kept in an oven for 24 h at 85 °C. the obtained
was
solidthen repeatedly
product was thenwashed with washed
repeatedly a mixture of asolvents
with mixture and dried in
of solvents a vacuum
and 65 ◦ C for
dried in aatvacuum 24 °C
at 65 h.
The layout of synthesis scheme is given in Figure 16.
for 24 h. The layout of synthesis scheme is given in Figure 16.
Figure 16. Synthetic procedure of Ni-BTC-MOF and 1–5 wt % rGO composites.

Figure 16. Synthetic procedure of Ni-BTC-MOF and 1–5 wt % rGO composites.
4. Conclusions
4. Conclusions
Ni-BTC-MOF and its 1–5 wt % rGO composites synthesized by the solvothermal method were
Ni-BTC-MOF
analyzed and oxidation
for methanol its 1–5 wt in % alkaline
rGO composites
media. Thesynthesized
as-preparedby the solvothermal
samples exhibitedmethod were
remarkable
analyzed for methanol oxidation in alkaline media. The as-prepared samples exhibited
potential for formic acid production during this oxidation process, particularly the Ni-BTC 4 wt % remarkable
potential
rGO for formic
composite showsacid production
highest activity.during this oxidation
The loading amount ofprocess, particularly
the highly the Ni-BTC
efficient Ni-BTC/4 wt %4 wt
rGO%
rGO composite
composite shows
was four timeshighest
less thanactivity. The loadingPtamount
the state-of-the-art of the
metal, with highlydensity
a current efficientofNi-BTC/4 wt %
200.22 mA/cm 2
rGO composite was four times less than the state-of-the-art Pt metal, with a current
at a peak potential of 0.69 V versus Hg/HgO. It also possessed a low Tafel slope (27.89 mV/dec) and density of 200.22
mA/cm2 resistance
minimal at a peak(18.12
potential
Ohm), of making
0.69 V itversus Hg/HgO.
an efficient It also
alternate possessed materials
to expensive a low Tafelthatslope (27.89
are utilized
mV/dec) and minimal resistance (18.12 Ohm), making it an efficient
for selective oxidation of methanol to formic acid in direct methanol fuel cells. alternate to expensive materials
that are utilized for selective oxidation of methanol to formic acid in direct methanol fuel cells.
Author Contributions: Conceptualization, L.Y. and T.N.; data curation, methodology, and investigation, L.Y.
and N.Z.; supervision T.N., H.N., and N.I.; original draft preparation, L.Y.; writing—reviews and editing, all
authors.
Funding: Financial support received from Higher Education Commission (HEC) Pakistan under its National
Catalysts 2019, 9, 856 18 of 21
Author Contributions: Conceptualization, L.Y. and T.N.; data curation, methodology, and investigation, L.Y. and
N.Z.; supervision T.N., H.N., and N.I.; original draft preparation, L.Y.; writing—reviews and editing, all authors.
Funding: Financial support received from Higher Education Commission (HEC) Pakistan under its National
Research Program for Universities (NRPU), project no. 6013, is greatly acknowledged.
Acknowledgments: The author would like to acknowledge the School of Chemical and Material Engineering
(SCME), School of Natural Sciences (SNS), and U.S.–Pakistan School for Advance Studies in Energy (USPCAS-E)
at NUST for providing the lab facilities.
Conflicts of Interest: The authors declare no conflict of interest.
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catalysts

Catalysts 2019, 9, 856; doi:10.3390/catal9100856 www.mdpi.com/journal/catalysts

2. Results and Discussion

321 004 114

211 600 400 022 512 226 517

15 1.0 mg Ni-BTC (0.25 M) Methanol

3.0 mg Ni-BTC (3.0 M) Methanol

-0.2 0.0 0.2 0.4 0.6 0.8

Current density (mA/cm )

Ni-BTC/2 wt % rGO Ni-BTC/2 wt % rGO

without methanol 200

Current density (mA/cm )

Ni-BTC/2 wt % rGO Ni-BTC/2 wt % rGO

Current density (mA/cm )

50mV/sec Ni-BTC/5wt% rGO

Figure 8 show the 200

Catalyst R2 Diffusion Co-Efficient (cm2/s)

Catalyst R2 Diffusion Co-Efficient (cm2 /s)

Resistance (Rs ) Resistance Capacitance

The relative stability of synthesized electrocatalytic materials was analyzed through

Ni-BTC-MOF/1–4 wt % rGO composites improved the electrocatalytic activity results because of

Bulk Electrolysis and Product Analysis

Catalysts 2019, 9, x FOR PEER REVIEW 15 of 22

Bulk Electrolysis and Product Analysis

Electrocatalytic oxidation of methanol into CO2wtcan

on the constant current density (i.e., 199.6 mA/cm Time(Sec)

Catalysts 2019, 9, x FOR PEER REVIEW 16 of 22

Figure 14. NMR spectra of reference electrolyte.

Table 5. Comparison of catalytic activity of synthesized samples with reported materials.

Methanol Catalyst Peak Current

3. Material and Methods

3.3. Synthesis of Ni-BTC-MOF

3.4. Synthesis of GO and rGO

3.5. Synthesis of Ni-BTC-MOF/rGO Composites

Figure 16. Synthetic procedure of Ni-BTC-MOF and 1–5 wt % rGO composites.

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