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Environmentally friendly PtNiCo nanocatalysts

enhanced with multi-walled carbon nanotubes for
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Cite this: Nanoscale Adv., 2024, 6,

5654 sustainable methanol oxidation in an alkaline
medium
Merve Akin,ac Anas El Attar,bd Ramazan Bayat,ac Muhammed Bekmezci, ac

Badr Bouljoihel,b Mama El Rhazib and Fatih Sen *ae

In this study, trimetallic PtNiCo/MWCNT and PtNiCo catalysts were synthesized using a microwave method to
reduce the amount of precious Pt. The prepared catalysts were characterized using XRD, TEM, and EDX
mapping and their electrochemical performances for methanol oxidation were investigated. The results
showed that the MWCNT-supported catalyst showed 2.42 times higher electrochemical activity than the
PtNiCo catalyst with a peak current density of 283.14 mA cm−2 at −0.2 V potential. Moreover, in long-term
stability tests, it exhibited high stability and 4.97 times higher current density at the end of 3600 s. The
Received 1st April 2024
Accepted 26th August 2024
results showed that the MWCNT-supported catalyst offered improved electron transfer, 4.7 times higher
surface area, and resistance to CO poisoning. These performance improvements due to the trimetallic
DOI: 10.1039/d4na00274a
structure are mostly thought to help accelerate the dehydrogenation of methanol. This study contains
rsc.li/nanoscale-advances important findings for future functional catalyst design in the fields of catalysis and energy conversion.

and applications of DMFCs have been increased. The basic

1. Introduction reaction equations of DMFCs are shown below ((1)–(3)).13 As
Today, the increasing energy demand brings along the search seen in the equations, electrochemical reactions of methanol
for alternative sources. At this point, fuel cells as a new- and oxygen take place at the anode and cathode, respectively.
generation green energy have attracted attention as an alter- Further, water and methanol react at the anode, releasing
native that can replace fossil fuel technology. Fuel cells are electrons, protons and CO2. Here, the catalyst accelerates the
devices that convert chemical energy into electrical energy via oxidation of methanol. Thus, it can be said that the efficiency of
electrochemical reaction, and there are different types of fuel catalysts in methanol oxidation is greatly affected.
cells.1–5 In particular, alcohol fuel cells have advantages such as
easier transport, storage, cost-effectiveness and easy production CH3OH + H2O / CO2 + 6H+ + 6e− (anode reaction) (1)
of alcohol, which allow for the expansion fuel cell applications.6 3
O2 þ 6Hþ þ 6e /3H2 O ðcathode reactionÞ (2)
Moreover, alcohol fuel cells have attracted more attention than 2
hydrogen fuel cells owing to their high energy density.7–9 Among
alcohol fuel cells, direct methanol fuel cells (DMFCs) are CH3OH + 32O2 / CO2 + 2H2O (overall reaction) (3)
claimed to be particularly promising for portable devices,
unmanned aerial vehicles and military applications.10 The In DMFC applications, Pt,14,15 Pt group elements (Os,16 Ir,17
increasing use of DMFCs is due to the easy use of methanol, Rh,18 Ru,19,20 and Pd21), Au, and Ag22 elements are frequently
operation at low temperatures, low emission rate and the ability preferred as catalysts.23,24 The high cost of these elements and
to be used in portable systems.11,12 Therefore, the research on problems such as CO poisoning on the Pt surface, particle
aggregation and dissolution, and cell voltage loss due to meth-
a
anol migration are the limitations for commercialization.25,26
Sen Research Group, Department of Biochemistry, Dumlupinar University, Kutahya,
Türkiye. E-mail: fatihsen1980@gmail.com
Since CO has a great affinity for the Pt surface, small amounts of
b
Laboratory of Materials, Membranes, and Environment, Faculty of Science and it can progressively occupy active sites, inhibit the adsorption of
Technology, University Hassan II of Casablanca, Morocco new reactants and eventually poison the Pt catalyst.27 To over-
c
Department of Materials Science & Engineering, Faculty of Engineering, Dumlupinar come these difficulties, signicant efforts have been made to
University, Kutahya, Türkiye explore bimetallic,28,29 trimetallic30,31 or higher metal structures
d
ICGM, University of Montpellier, CNRS, ENSCM, 34095 Montpellier Cedex 5, France using transition metals alloyed with Pt to overcome the CO
e
Incorporated Company, Kutahya Design & Technopole, Calca OSB Neighbourhood,
poisoning effect, reduce Pt loading, and improve MOR
43100 Kutahya, Türkiye

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activity.32–35 Within the framework of this approach, platinum– method. In this context, 50 mg MWCNT was added to 20 mL
nickel–cobalt (PtNiCo) alloy has attracted the most attention ethylene glycol and 5 mL 2-propanol mixture and dissolved with
among many trimetallic catalysts due to its high CO tolerance in the help of a sonicator. To the homogenized solution, 10 mM
MOR.29,36 Recently, the use of support materials in catalysts37 has PtCl4, 5 mM NiCl2$6H2O and 5 mM CoCl2$6H2O were added
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also attracted considerable attention, and it can be said that and stirred in a magnetic stirrer for 2 hours. Aer stirring, the
carbon-based materials give quite good results.38,39 In this study, pH of the solution was adjusted to 12 using 1 M NaOH. The
MWCNT, one of the carbon-based materials, was used as mixture was irradiated in a kitchen microwave oven for 90
a support material for the catalyst. MWCNTs have attracted seconds. Aer cooling at room temperature, pH 4 was adjusted
attention due to their high surface area, high electron conduc- using 0.5 M HNO3. Finally, the formed PtNiCo/MWCNT nano-
Open Access Article. Published on 16 September 2024. Downloaded on 11/15/2024 3:27:34 PM.

tivity and superior mechanical strength and their use in fuel cell particles were collected at 4000 rpm and washed several times
catalysts.40 It has also been reported that Pt-based nanomaterials with dH2O–ethanol mixture. Finally, they were dried in an oven
supported with CNT provide higher electrocatalytic activity at 50 °C for 24 hours. The same procedures were repeated for
compared to other carbon derivatives.41,42 In addition, the high the synthesis of MWCNT-free PtNiCo.44
corrosion resistance and enhanced intrinsic catalytic activity of
NiCo alloys have made them a highly effective electrocatalyst.43 2.2. Electrochemical analysis
Thus, PtNiCo/MWCNT particles were synthesized in this study as
a catalyst with high performance and high electron transfer. All electrochemical analyses were carried out with a potentio-
Although platinum has high catalytic activity, it is known to be stat/galvanostat (Gamry Reference 3000). For electrochemical
expensive and prone to poisoning.40 In the scope of this study, the measurements, a classical three-electrode system was used. For
tendency to poisoning and cost were reduced by adding Ni and the modication solution used in the study, 10 mg NP powder,
Co. In addition, the use of NiCo can provide more active area on 500 mL dH2O, 75 mL Naon D-521 and 150 mL DMF were added.
the Pt surface and improve the reaction mechanism. MWCNT The ink was sonicated during 30 minutes in a bath lled with
provides a high surface area and better dispersion of catalyst ice to maintain a low temperature. 10 mL of ink was deposited
nanoparticles. In this context, it can be said that the PtNiCo/ on the glassy carbon surface of the working electrode. The
MWCNT catalyst provides a good synergistic effect and working electrode was dried for 20 min in an oven at 60 °C.
increases the efficiency of methanol oxidation. Then, cycle voltammetry (CV), linear sweep voltammetry (LSV),
In this study, PtNiCo/MWCNT and PtNiCo catalysts were chronoamperometry (CA), and electrochemical impedance
synthesized using the microwave method, which is a fast spectroscopy (EIS) measurements were performed using
method. The obtained catalysts were characterized using XRD, a three-electrode system. Electrochemically active surface area
EDX mapping, and TEM. The obtained catalysts were found to (ECSA) studies were performed in 10 mM [Fe(CN)6]3−/4−
have high chemical stability and large surface area. The electro- medium containing 0.5 M KCl. Alcohol oxidation studies were
oxidation of the electrocatalysts was investigated using cyclic carried out in the potential range from −0.8 V to 0.2 V in 1 M
voltammetry (CV), chronoamperometry (CA), linear sweep vol- KOH solution containing 1 M CH3OH. Scan rate (SR)
tammetry (LSV), CO stripping, and electrochemical impedance measurements were carried out at scan rates of 25 mV s−1,
spectroscopy (EIS) techniques. The results showed that the use 50 mV s−1, 100 mV s−1, 150 mV s−1, and 250 mV s−1 in 1 M KOH
of MWCNT as a support provides higher catalytic activity. The solution containing 1 M CH3OH. Electrochemical impedance
PtNiCo/MWCNT catalyst for direct methanol oxidation studies spectroscopy (EIS) measurements were also performed. EIS
is reported for the rst time in this study. measurements were performed in 1 M KOH solution containing
1 M CH3OH at −0.35 V vs. Ag/AgCl in the frequency range from
10 kHz to 0.01 Hz. CO stripping voltammetry measurements
2. Materials & methods were carried out between −0.2 and 1 V potentials at a scan rate
of 25 mV s−1 aer 15 min CO gas passage in 0.5 M H2SO4
Cobalt(II) chloride hexahydrate (CoCl2$6H2O), nickel(II) chloride
medium.
hexahydrate (NiCl2$6H2O), platinum tetrachloride (PtCl4),
potassium hydroxide (KOH), dimethylformamide (DMF), Naon
D-125, sulphuric acid (H2SO4), sodium hydroxide (NaOH), 3. Results and discussion
ethylene glycol, 2-propanol, MWCNT and nitric acid (HNO3) 3.1. Materials characterization
chemicals were used without any purication process. All
chemicals were purchased from Sigma Aldrich. An X-ray diffrac- In the rst step of the characterization of the electrocatalysts to
tometer (XRD, Rigaku Miniex), scanning electron microscope be used in alcohol studies, XRD was used to determine the
(SEM-EDX mapping) (JEOL JSM-5600LV), and transmission crystal structure of the electrocatalysts. The XRD patterns of
electron microscope (TEM-JEOL 1220) were used in the analyses. PtNiCo and PtNiCo/MWCNT are shown in Fig. 1. PtNiCo
(40.88°, 46.63°, 69.52°, 82.91°) and PtNiCo/MWCNT (40.81°,
46.6°. 68.63°, 82.31°) show the (111), (200), (220), and (311)
2.1. Synthesis of PtNiCo and PtNiCo/MWCNT planes of Pt with the surface-centered cubic (FCC) structure,
electrocatalysts respectively. Moreover, in the PtNiCo/MWCNT XRD diffraction,
PtNiCo and PtNiCo/MWCNT electrocatalysts used in methanol the peak at 26.24° indicates the C (002) plane. When compared
oxidation studies were synthesized using the microwave with the reference code 01-087-0640, it is seen that there are

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The deposition of the particles on the MWCNT surface creates

a large surface area. All images show that the electrocatalyst
samples are well dispersed without agglomeration.47 As clearly
seen in the TEM images, almost spherical metal structures were
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observed on the MWCNT tubes. The particle size obtained

because of the histogram was about 8 nm (Fig. 2b). For a tri-
metallic structure, this size was quite good compared to the
literature. However, the SD value increased due to the trime-
tallic structure, suggesting that it is due to metal interactions
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that are not fully understood. Similarly, it was observed that the
MWCNT structure retained its form quite well aer synthesis.
In this case, microwave synthesis is considered to be the main
cause inuencing the formal structure.
In addition, the EDX mapping of the PtNiCo/MWCNT cata-
lyst obtained within the scope of the study was performed and is
shown in Fig. 3. The presence and distribution of Pt, Ni, Co, and
Fig. 1 XRD patterns of the PtNiCo and PtNiCo/MWCNT C in the catalyst obtained here are shown. In the results ob-
electrocatalysts.
tained, it is seen that C is dominant and spread over a large
area. Pt, Ni, Co, and O are also homogeneously distributed on
the surface. EDX mapping shows the presence of elements well
shis in the peaks.12,45 This shi is due to the presence of Ni and
integrated on the MWCNT surface with high surface area and
Co, which are smaller than Pt, indicating that the synthesis was
high potential for catalytic activity.
completed and the PtNiCo alloy was realized.46 In addition,
To assess the impact of adding MWCNTs on the electro-
according to the XRD data, the diffraction peaks of Ni and Co
chemical characteristics of the modied PtNiCo, an electro-
cause signicant changes in the peak intensities due to partial
chemical characterization was carried out. Therefore, the CVs
intersections. When the XRD peaks taken with and without
PtNiCo and PtNiCo/MWCNTs were recorded in 0.5 M KCl
support are examined, it is seen that the support in the catalyst
solution containing 10 mM of [Fe(CN)6]3−/4−, as shown in Fig. 4.
creates some differences in the diffraction peaks. At this point,
As can be seen, the PtNiCo present a current density value of
it can be said that the support provides an increase in the peak
about 1.73 mA cm−2 with a peak-to-peak separation (DEp) of
current densities, increases the degree of crystallinity and the
about 0.181 V. Aer the introduction of MWCNT, we noticed
narrower peaks give an idea that the crystal defects are reduced.
that the value of current density of PtNiCo/MWCNT increased to
The fact that no shi is observed for the peak indicates that the
4.58 mA cm−2 with a decrease in the DEp value (0.12 V). This
crystal structure of PtNiCo has not changed.
result supports the assertion made by many researchers that the
Aer investigating the crystal structure, the morphological
presence of MWCNT enhanced the electronic transfer at the
properties were determined using low magnication TEM. As
electrode surface.48,49
seen in Fig. 2, PtNiCo nanoparticles were uniformly distributed.

Fig. 2 TEM images of the PtNiCo/MWCNT nanostructure synthesized using the microwave method. (a) Image obtained at 100 nm magnifi-
cation. (b) Image obtained at 50 nm magnification and particle size histogram.

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Fig. 3 EDX mapping and elemental plot of PtNiCo/MWCNTs at 2 mm magnification.

The electrochemical parameters of PtNiCo and PtNiCo/ area of PtNiCo (0.0694 cm−2). This result conrms that the
MWCNT are presented in Table 1. introduction of MWCNT enhances the electroactive surface of
The electrochemically active surface area (ECSA) of PtNiCo the electrocatalyst, which lead to the improvement of their
and PtNiCo/MWCNT was calculated using the Randles–Sevcik electrocatalytic activities.
equation (eqn (4))50

Ipa = (2.69 × 105)n3/2AECSAD1/2Cn1/2 (4) 3.2. Electrochemical studies

The primary goal is the oxidation of methanol in an alkaline
where C is the solution concentration (mol cm−3), n is the solution; thus, cyclic voltammetry was used to examine how
number of electrons transferred (n = 1), AECSA is the ECSA (cm2), PtNiCo and PtNiCo/MWCNT react to the electrooxidation of
n is the potential scan rate (V s−1), Ipa is the anodic current (A), methanol in a solution with 1 M methanol and 1 M KOH. The
and D is the diffusion coefficient (cm2 s−1). cyclic voltammograms performed at various electrocatalysts are
The electroactive surface area of PtNiCo/MWCNT is 0.329 displayed in Fig. 5a and the results are shown in the bar graph
cm2, which is 4.7 times higher than the electroactive surface in Fig. 5b. As can be seen in Fig. 5a, PtNiCo/MWCNT showed

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As can be seen, the value of current density increased with

the increase in the scan rate value for both the electrocatalysts.
This result indicates that a diffusion-controlled system was
reached for both catalysts and the mass transfer was success-
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fully achieved.52,53
In order to conrm that the introduction of MWCNT
increases the stability of the electrocatalysts, the chro-
noamperometric technique was performed in a solution con-
taining 1 M KOH in the presence of 1 M CH3OH at −0.35 V vs.
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Ag/AgCl for 3600 s. Fig. 6a shows the obtained results for both
the electrocatalysts. Both electrocatalysts exhibit a reduction in
the current density from their peak values in the rst few
seconds, as can be seen. The adsorption of incomplete oxida-
tion products onto the electrocatalyst surfaces may be the cause
of this decline.54,55 It should be noted that the PtNiCo/MWCNT
electrocatalyst reached a value of 18.71 mA cm−2 at 3600 s,
which is 4.97 times higher than the value obtained by PtNiCo
Fig. 4 Cyclic voltammograms for PtNiCo/MWCNTs and PtNiCo in (3.76 mA cm−2). The presence of MWCNT led to the availability
10 mM [Fe(CN)6]3−/4− and 0.5 M KCl at 50 mV s−1. of a higher number of active sites on the surface of PtNiCo/
MWCNT, which is the main reason behind this behavior.56,57
The electrochemical impedance spectroscopy (EIS) tech-
a value of 283.14 mA cm−2, which is 2.42 times higher than that nique of PtNiCo/MWCNT and PtNiCo was performed in order to
of PtNiCo (116.77 mA cm−2). The increased in the current prove the role of MWCNT for the enhancement of the electro-
density value of PtNiCo/MWCNT compared to PtNiCo is related catalytic activity of the electrocatalyst. Fig. 6b shows the ob-
to the presence of MWCNT, which led to a high adsorption tained results of both the electrocatalysts. As mentioned in the
capability of methanol on the surface due to their high surface literature, a small semicircle in the impedance graphs seen in
area. Also, the presence of MWCNT increases the catalytic the gure gives information about faster mass transfer.58 The
performance of the PtNiCo electrocatalyst toward methanol PtNiCo/MWCNT presents a smaller semicircular diameter Rct
oxidation reaction (MOR). (10 U) compared to PtNiCo (Rct = 35 U). This decrease in the Rct
Another key parameter is the amount of (If/Ib), where If is the value aer introducing MWCNT clearly demonstrates the ease
forward peak current density and Ib is the backward peak of charge transfer at the surface of PtNiCo/MWCNT. This result
current density.51 A high value of If/Ib generally means that the is in agreement with the LSV results and showed that the faster
poisoning of the electrode by the intermediate species is avoi- reaction allowed the reaction to start at an earlier potential. The
ded. Table 2 summarizes the obtained results. equivalent circuit compatible with the results is presented in
A value of (If/Ib) of 3.64 and 5.09 was obtained on PtNiCo/ the inset of Fig. 6b. In these circuits, Rs is the solution resis-
MWCNT and PtNiCo. The results shown suggest that tance, CPE is the constant phase element corresponding to the
throughout the methanol oxidation process, fewer species of double layer capacitance and Rct is the charge transfer resis-
intermediates were adsorbed on the catalyst. Also, these results tance associated with the oxidation of methanol.
gave an idea about CO poisoning in the structure.50 The ob- The cyclic voltammetry technique with a high number of
tained results conclude that both catalysts have very high CO cycles is an important experiment to study the long-term
tolerance. In addition, the LSV results obtained within the scope stability of electrocatalysts towards methanol oxidation. Fig.
of the study (Fig. 5c and d) showed that the oxidation reaction of 6c and d show the obtained results of PtNiCo/MWCNT and
the PtNiCo/MWCNT structure started 1.2 times earlier than that PtNiCo aer cycling in methanol solution under 200 cycles.
of the PtNiCo catalyst. This result conrmed that the addition of Both electrocatalysts present a decrease in the current density
MWCNT to the structure contributed to the formation of an easy value with the increase in the cycle number. A loss of 35% of its
and earlier oxidation reaction in the electrocatalyst surface initial current aer 200 cycles was recorded for PtNiCo/
compared to PtNiCo. MWCNT, which is 1.85 higher than that of PtNiCo (65%). This
The scan rate experiments were also carried out for both result indicates that the presence of MWCNT increases the
electrocatalysts. Fig. 5e, f, g and h regroup the obtained results stability of the electrocatalyst and avoids the poisoning of the
at PtNiCo/MWCNT and PtNiCo, respectively.

Table 1 The value of anodic and cathodic peaks for PtNiCo and PtNiCo/MWCNTs

Electrode Ipa (mA cm−2) Ipc (mA cm−2) Ea (V) Ec (V) DEp (V)

PtNiCo 1.73 −3.3 0.26 0.079 0.181

PtNiCo/MWCNT 4.58 −6.67 0.24 0.124 0.116

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Fig. 5 (a) CV curves for PtNiCo and PtNiCo/MWCNTs in 1 M KOH solution containing 1 M CH3OH. (b) Bar graph representation of CV oxidation
peaks. (c) LSV curves for PtNiCo and PtNiCo/MWCNT. (d) Bar graph representation of onset potentials. (e) Scan rate CV curves for PtNiCo/
MWCNTs. (f) Current densities obtained versus the square root of the scan rate for PtNiCo/MWCNTs. (g) Scan rate CV curves for PtNiCo. (h)
Current densities obtained versus the square root of the scan rate for PtNiCo.

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Table 2 If and Ib values obtained from CV results

Electrocatalysts If Ib If/Ib

PtNiCo/MWCNT 283.14 77.68 3.64

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PtNiCo 116.77 22.94 5.09

surface of PtNiCo/MWCNT by the intermediate species during

the MOR.
Finally, the behavior of both electrocatalysts in the presence
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of CO was electrochemically studied. CO stripping voltammetry

measurements were carried out between potentials of −0.2 V vs.
Ag/AgCl and 1 V vs. Ag/AgCl at a scan rate of 25 mV s−1 aer
15 min CO gas evolution in 0.5 M H2SO4 medium. Fig. 7 shows
the CV curves of PtNiCo and PtNiCo/MWCNT in 0.5 M H2SO4
saturated with CO.
From the results obtained, it is seen that the PtNiCo/ Fig. 7 CO stripping curves for PtNiCo and PtNiCo/MWCNTs in 0.5 M
MWCNT electrocatalyst presents the lowest value of the CO H2SO4.
onset potential (0.27 V) and CO oxidation peak (0.47 V)
compared to PtNiCo (CO onset potential is 0.41 V and the CO
oxidation peak is 0.51 V). These results could be explained by In Table 3, the electrocatalytic performance of PtNiCo and
the presence of MWCNT, which makes the PtNiCo/MWCNT PtNiCo/MWCNT materials is compared to that of previously re-
electrocatalyst more tolerant to CO compared to the PtNiCo ported materials in the literature. This comparison shows that the
electrocatalyst.22,59,60 trimetallic structures provide higher electrocatalytic activity

Fig. 6 (a) Chronoamperometric curves for PtNiCo and PtNiCo/MWCNTs in 1 M KOH solution containing 1 M CH3OH. (b) Nyquist plots for PtNiCo
and PtNiCo/MWCNTs in 1 M KOH solution containing 1 M CH3OH at −0.3 V. (c and d) Long term durability test for PtNiCo/MWCNTs, and PtNiCo.

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Table 3 Comparison of the MOR activity for the obtained catalysts with literature studies

Scan rate mV Current density

Electrocatalyst Applied solution s−1 (mA cm−2) Reference
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Pt1Fe2@NC/MWCNT 0.1 M HClO4 + 0.05 M CH3OH 50 18.19 61

Pt–Pd/RGO/GCE 0.5 M H2SO4, 0.5 M CH3OH 50 4.29 62
PtCo@AC–VC 1 M KOH + 1 M CH3OH 50 73 44
PtNi/rGO 1 M KOH + 1 M CH3OH 50 12.18  0.36 63
PtCo 1 M KOH + 1 M CH3OH 50 23.59 25
PtNiCo 1 M KOH + 1 M CH3OH 50 116.77 This work
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PtNiCo/MWCNT 1 M KOH + 1 M CH3OH 50 283.14 This work

compared to PtCo. It is also seen that the PtNiCo catalyst shows Acknowledgements
a very good synergistic effect. It can also be said that the carbon
used as a support affects the electrocatalytic activity considerably. R. Bayat is supported by the Council of Higher Education
The results show that the PtNiCo/MWCNT catalyst provides (CoHE) with 100/2000 PhD Scholarship and TUBITAK 2211-
signicantly higher electrocatalytic activity compared to other C. M. Bekmezci is supported by the TUBITAK 2211-C. The
electrocatalysts. These results conrm that our electrocatalysts authors also would like to thank to DPU-BAP (2016-75; 2017-40
could be considered as a good electrocatalyst for MOR in an and 2018-29)
alkaline medium.

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