Materials Today: Proceedings 56 (2022) 107–111

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Materials Today: Proceedings

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Graphitic carbon nitride based palladium nanoparticles: A homemade

anode electrode catalyst for efficient direct methanol fuel cells
application
Kirti Mishra a, Vijay Kumar Thakur b,c,d, Samarjeet Singh Siwal a,⇑
a
Department of Chemistry, M.M. Engineering College, Maharishi Markandeshwar (Deemed to be University), Mullana-Ambala, Haryana 133207, India
b
Biorefining and Advanced Materials Research Center, Scotland’s Rural College (SRUC), 10 Kings Buildings, West Mains Road, Edinburgh EH9 3JG, UK
c
Department of Mechanical Engineering, School of Engineering, Shiv Nadar University, Uttar Pradesh 201314, India
d
School of Engineering, University of Petroleum & Energy Studies (UPES), Dehradun, Uttarakhand, India

a r t i c l e i n f o a b s t r a c t

Article history: The composite outline of graphitic carbon nitride (gCN) supported palladium nanoparticle (PdNPs) can
Available online 10 January 2022 act as high catalytic performance for the electro-oxidation of methanol in the presence of alkaline media.
Several characterizations evidence the successful formation of graphitic carbon nitride supported palla-
Keywords: dium nanoparticles (PdNPs-gCN) by spectroscopic and optical techniques. We applied this catalyst as the
Graphitic-carbon nitride electro-oxidation of methanol in the alkaline media shows the better catalytic behavior in methanol fuel
Palladium nanoparticle cells (DMFCs) application. The electrode preparation in the laboratory is a big challenge, especially to
Methanol oxidation
control the thickness and uniformity of the film made by hydraulic press. The catalytic performance of
Cyclic voltammetry
the synthesized material, a comparative study was also executed using gCN system, as reference material,
in support of our proposed material with excellent performances also investigated. The cyclic voltamme-
try of PdNPs-ZnO-gCN for homemade electrodes shows the rise in current density values (0.96 mA/cm2)
with per 500 scans in the presence of 0.5 M methanol and KOH (0.5 M). We went for different techniques,
such as; chronoamperometry and cyclic voltammetry, to check the durability of our synthesized catalyst.
Copyright Ó 2022 Elsevier Ltd. All rights reserved.
Selection and peer-review under responsibility of the scientific committee of the International Confer-
ence on Materials, Machines and Information Technology-2022.

1. Introduction performance of the Palladium nanoparticles (PdNPs) can be

increased by using some support material like carbon nitride
In today’s scenario, much attention is paid to the fuel cell devel- (CN) modified reduced graphene oxide for the methanol as well
opment technologies by various researchers to enhance the use of as formic acid electrooxidation [910]. Further, it was also reported
eco-friendly electric vehicles [1]. Catalyst based on platinum (Pt) that CN and zinc oxide (ZnO) modified CN supported PdNPs were
show better activity for oxidation of methanol (MeOH) [2], but Pt also used to enhance the electrochemical oxidation of methanol
has a very high cost, as well as catalyst poisoning impact, also in which ZnO introduce to observe the effect of oxophilicity [11].
observed in this case, due to the formation of intermediate sub- Some Pd based electrocatalysts like Palladium-cobalt (Pd-Co),
stances which block the catalytic activity of the Pt [3]. To overcome Palladium-copper (Pd-Cu) are also used to electrooxidation of
these obstacles, Pt was alloying with many metals to form a ethanol in which Pd-Co has an activity like Pd catalyst, but Pd-Cu
bimetallic catalyst for electrooxidation of alcohols and used as alloy catalyst shows better performance than Pd [12]. Three-
anode material in energy-producing devices [4–6]. In place of Pt, dimensional graphene supported Pd-Cu catalyst shows good activ-
another noble metal Palladium (Pd), is used as an electrode catalyst ity than commercially used Pd- carbon catalyst for the ethanol’s
with different support materials due to its low cost, availability, electrooxidation in alkaline medium [13–15]. On the other hand,
and greater tolerance to carbon monoxide poisoning with good Pd on three-dimensional porous arrangement shows better cat-
activity as an electrocatalyst [7,8]. It was found that the catalytic alytic activity and constancy for electrooxidation of methanol in
an alkaline medium; porosity increases the electrochemically
⇑ Corresponding author. active surface area [16]. Yuwen et al. show that Pd nanocrystals
E-mail address: [email protected] (S. Singh Siwal). on molybdenum sulphide also act as an electrocatalyst for MeOH

https://doi.org/10.1016/j.matpr.2021.12.342
2214-7853/Copyright Ó 2022 Elsevier Ltd. All rights reserved.
Selection and peer-review under responsibility of the scientific committee of the International Conference on Materials, Machines and Information Technology-2022.
K. Mishra, V. Kumar Thakur and S. Singh Siwal Materials Today: Proceedings 56 (2022) 107–111

oxidation in alkaline medium with excellent performance than 15 min with stirring, resulting in the reduction of substance. The
commercially available Pd- C catalyst [17]. reacting mixture is now filtered, and the obtained residue was
In this recent study, we demonstrate the synthesis of gCN based washed several times with DI water to get solid powdered gCN.
palladium NPs [18] as a catalyst on the homemade electrode for ZnO approximate 10 wt% doped gCN was prepared using Zinc
efficient direct methanol fuel cell application, in which both ZnO nitrate (Zn (NO3)2) and urea as precursors with solid-state pathway
and PdNPs are doped with gCN with improved properties. Various at 550◦C temperature. PdNPs (5 wt%) [11] incorporated with gCN
characterization techniques show the doping of ZnO and PdNPs on (PdNPs-gCN) was synthesized for this gCN powder with DI water
the gCN support. We found that doped catalyst has a better impact was mixed and allowed to stand for 6 h, and 10–2 M potassium
on methanol oxidation by using the homemade electrode. tetrachloropalladate (II) (K2 [PdCl4]) was applied as palladium pre-
cursor and allowed to react for two hours. Now 10–3 M NaBH4 was
2. Experiments added to the reaction mixture one stroke and allowed to react for
15 min at room temperature, known as single-step borohydride
2.1. Materials reduction method. As a result, Pd (II) was reduced to Pd (0) and
we got PdNPs. PdNPs-ZnO incorporated gCN (PdNPs-ZnO-gCN)
All the materials like chemicals as well as solvents used in this was synthesized by using solid-state route using K2 [PdCl4], Zn
work were of analytical grade. (NO3)2 and urea as precursors. The doping of various particles
was confirmed by using various characterization techniques.
2.2. Electrode preparation
3. Results and discussion
To prepare an electrode for further utilization, a glass tube of
10 mm diameter is taken by removing its rubber, and its tip was 3.1. Microscopic and optical characterization
cut with a sharp instrument and made into a glass tube. After that,
we took a copper (Cu) wire and cleaned it with sandpaper to The schematic diagram of the study is shown in Scheme 1. Fig. 1
remove deposited impurities or substances like the oxide layer. (a) transmission electron microscopy (TEM) shows the thin film-
Inserted this Cu-wire into the glass tube and folded it, making a like morphology with the smooth surface of gCN (graphitic carbon
coil according to the diameter of the glass tube and fixed it with nitride) of diameter 200 nm. Fig. 1(b) TEM image of PdNPs-ZnO
the tube walls by using conducting glue; this surface area is used compounds incorporated in gCN. The much dense nanoparticle of
as the active surface area of homemade electrode for the deposi- Pd and ZnO diameter 50 nm (some 8.89 nm or 14.12 nm). Decreas-
tion of synthesized catalyst. Prepared catalyst fixed on this area ing the size enhances the surface area that increases the catalytic
in pellet form by using carbon black as fixing material. activity of composite material PdNPS-ZnO-gCN for oxidation of
MeOH, increasing the value of current density while lowering the
2.3. Catalyst’s preparation potential value.
The prepared substance’s phase purity, i.e., PdNPs-ZnO-gCN,
In this study, we prepare gCN, ZnO-gCN, PdNPs- gCN and was analysed using X-ray Diffraction analysis (XRD), as shown in
PdNPs-ZnO-gCN for the electrooxidation of methanol for fuel cell Fig. 2. The most intense peak observed at around 37◦ is confirmed
application. In this experiment, CN was prepared using the previ- the formation of PdNPs. Additionally, it is also confirmed the for-
ous technique as explained by Nandi et al. [19]. The gCN was syn- mation of ZnO and gCN. The amorphous nature of the gCN provides
thesized using urea (H2N-CO-NH2) as a precursor. This urea is a large surface area to the PdNPs-ZnO for better catalytic perfor-
calcinated then mixed with deionized water (DI water) for 6 h by mance. The Fourier Transform Infrared spectra (FTIR) was per-
continuous stirring at room temperature. After this, a stroke of formed to know the effect of PdNPs doping on gCN and ZnO-gCN.
10–3 M sodium borohydride (NaBH4) was added and allowed for The above Fig. 3 shows the FT-IR spectra of PdNPs-gCN (black col-

Scheme 1. Schematic representation of the proposed study.

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K. Mishra, V. Kumar Thakur and S. Singh Siwal Materials Today: Proceedings 56 (2022) 107–111

Fig. 3. FTIR spectra of PdNPs-gCN (black curve) and PdNPs-ZnO-gCN (red curve).
(For interpretation of the references to colour in this figure legend, the reader is
referred to the web version of this article.)

Fig. 1. TEM image of (a) gCN and (b) PdNPd-ZnO-gCN.

Fig. 4. Electrochemical impedance spectroscopy (EIS) (a) gCN, (b) ZnO-gCN, (c)
PdNPs-gCN, (d) PdNPs-ZnO-gCN.

Fig. 4 (a) gCN, (b) ZnO-gCN, (c) PdNPs-gCN, (d) PdNPs-ZnO-gCN

modified homemade electrode were plotted and measured
between frequency range 3MHZ to 10HZ in 0.5 M KOH. The plots
show that the value of charge transfer resistance decreases with
doping, and the current value increases.
The material gCN analysed as a composite toward the oxidation
of MeOH and was observed by CV technique. We also analysed the
activity of the bare gCN electrode in the absence of MeOH and in
Fig. 2. XRD pattern of PdNPs-ZnO-gCN.
the presence of methanol (0.5 M) in 0.5 M KOH solution. In Fig. 5
(a) two CV curves, black and red, are obtained for bare gCN and
gCN in the presence of methanol, respectively. The current density
our) and PdNPs-ZnO-gCN (red colour), which indicate the con- (CD) value, as obtained from voltammogram curves for bare and
densed heterocyclic aromatic ring carbon–nitrogen. gCN with MeOH, has shown that the red curve highly improves
current density. In the absence of MeOH bare gCN electrode, a
maximum CD of 0.02 mA/cm2 at 0.2 V, but in the presence of
3.2. Electrochemical studies 0.5 M methanol, the CD value increases up to 0.098 mA/cm2. The
CV graph consists of two clear peaks at the forward as well as
EIS is one of the preeminent methods to know the electrochem- reverse scan. The peak of the forward scan is recognized as the oxi-
ical behaviour of different materials. The Nyquist plot of above dation of intermediate products, mainly carbon monoxide [20].
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K. Mishra, V. Kumar Thakur and S. Singh Siwal Materials Today: Proceedings 56 (2022) 107–111

The composite substances ZnO-gCN has been tested as an elec-

trode catalyst for the MeOH oxidation and recorded by CV tech-
niques. In the Fig. 5 (b) shown graph obtained in 0.5 M KOH
shows the value of current density. The peak obtained in the for-
ward scan shows the oxidation of 0.5 M methanol; on the other
hand, the peak obtained in the backwards scan shows the oxida-
tion of carbon monoxide, which is an intermediate product in the
presence of ZnO-gCN material a catalyst. The progressive enhance-
ment in the CD value had been noted while the scan repeated with
a decrease in value of the potential peak. The MeOH oxidation peak
shows the decrease in potential from 0.1 V to 0.1 V with the
increase in CD value from 0.17 mA/cm2 to 0.20 mA/cm2.
The material PdNPs-gCN (palladium nanoparticles-graphitic
carbon nitrides) has been evaluated as an electrode catalyst for
MeOH oxidation and recorded by cyclic CV techniques. Fig. 6 (a)
shown graph obtained in 0.5 M KOH shows the value of current
density. The peak obtained in the forward scan shows the oxida-
tion of 0.5 M methanol; on the other hand, the peak obtained in
the backward scan shows the oxidation of carbon monoxide, an
intermediate product in the presence of PdNPs-gCN material as a
catalyst. The progressively rise in CD value is noted while scans
are repeated with a decrease in peak potential value. The methanol
oxidation peak shows the decrease in potential from 0.1 V to
0.1 V with the rise in CD from 0.65 mA/cm2 to 0.81 mA/cm2.

Fig. 6. (a) CV of PdNPs -gCN for homemade electrode shows the rise in the CD
values with per 500 scans in presence of 0.5 M methanol and KOH (0.5 M). (b) The
cyclic voltammetry of PdNPs-ZnO-gCN for homemade electrodes shows the rise in
current density values (0.96 mA/cm2) with per 500 scans in the presence of 0.5 M
methanol and KOH (0.5 M).

Fig. 7. Chronoamperometric profiles for 0.5 M KOH oxidation with 0.5 M CH3OH on
the different electrode, (a) gCN, (b) ZnO-gCN, (c) PdNPs-gCN, and (d) PdNPs-ZnO-
gCN.

Fig. 5. (a) Cyclic voltagram (CV), current density (mAcm 2) as a function of

potential bare gCN and gCN with methanol. (b) CV of ZnO-gCN for homemade The composite material PdNPs- ZnO-gCN has been analysed as
electrode represents the enhancement in CD values for every 500 scans in the
an electrode catalyst for the MeOH oxidation and recorded by CV
presence of 0.5 M methanol and KOH (0.5 M).

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K. Mishra, V. Kumar Thakur and S. Singh Siwal Materials Today: Proceedings 56 (2022) 107–111

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The authors acknowledge the support from Department of of methanol, Int. J. Hydrogen Energy 42 (37) (2017) 23599–23605.
Chemistry and Research & development Cell of Maharishi Markan-
deshwar (Deemed to be University), Mullana, Ambala, Haryana,
India.

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