Full Papers
ChemistrySelect doi.org/10.1002/slct.202000170
z Electro, Physical & Theoretical Chemistry
Enhanced Methanol Electro-Oxidation Activity of Pt/rGO
Electrocatalyst Promoted by NbC/Mo2C Phases
Malaya K. Sahoo and G. Ranga Rao*[a]
Direct methanol fuel cells are attractive power conversion
devices for portable and stationary applications. Many electro-
catalysts have been explored for fuel cell applications but there
is scope to design newer and more efficient electrocatalytic
materials. For this purpose we have synthesized Mo2C and
bimetallic NbC-Mo2C carbide phases by carbothermic reduction
process. The carbide catalysts are characterized by various
analytical techniques. The carbide samples are higly porous
and their surface areas are of the order of 630 m2 g 1. Usually Pt
is the state-of-the-art anode catalyst in direct methanol fuel
cells. Here, Nb-Mo2C and 10 wt% Pt nanoparticles are deposited
on reduced graphene oxide support to obtain Pt/Nb-Mo2C-rGO.
This material shows highest mass activity of 836.4 mA mgPt 1
when compared to 10 wt% Pt/Mo2C-rGO and bare 20 wt% Pt/
rGO catalysts. Notably, electrochemical tests show that the
Introduction
In the modern world, energy conversion and storage processes
are considered important for the energy needs of the growing
population and in this context fuel cells are in the forefront for
supplying electrical energy in clean, silent and efficient
ways.[1–3] Among the six types of fuel cells, direct methanol fuel
cells (DMFCs) have been widely studied as energy converters
using methanol.[4] Methanol has high power density, easy to
store and handle, and soluble in aqueous electrolytes and is
the most reliable source for energy generation.[2,5] The meth-
anol crossover and sluggish kinetic rates of methanol oxidation
reaction (MOR) are the two major barriers for commercial use
of DMFCs.[3] Platinum is the best and most efficient catalyst
used in DMFCs. Eelectro-oxidation of methanol is initiated by
the adsorption of methanol on Pt catalyst surface followed by
the addition of oxygen species leading to the formation of
carbon dioxide as final product. However, the efficiency of Pt
catalyst is severely affected over a period of time since other
intermediate surface species, mainly COads, generated during
the electro-oxidation of methanol block the active sites of Pt.[2,3]
[a] M. K. Sahoo, G. R. Rao
Malaya K. Sahoo and Prof. G. Ranga Rao, Department of Chemistry and
DST-Solar Energy Harnessing Centre (DSEHC), Indian Institute of Technol-
ogy Madras, Chennai 600036, India,
Tel.: + 91 44 2257 4226
Fax: + 91 44 2257 4202
E-mail: grrao@iitm.ac.in
Supporting information for this article is available on the WWW under
https://doi.org/10.1002/slct.202000170
ChemistrySelect 2020, 5, 3805 – 3814
10 wt% Pt/Nb-Mo2C-rGO catalyst exhibits lower onset potential,
large electrochemical surface area, higher activity, and stability
for methanol electro-oxidation in acidic solution compared to
the Pt/Mo2C-rGO and Pt/rGO catalysts. The activty
enhancement is atributed to the defective nature of the
interface between Pt, Nb-Mo2C and rGO. It is found that Nb-
Mo2C not only alleviates CO poisoning of Pt nanoparticles, but
also generates oxygen containing species at lower potentials.
This process helps scavenging the intermediate species such as
COads on Pt surfaces and regenerates the active Pt sites for
routine alcohol oxidation reaction. The chronopotentiometry
and chronoamperometry studies also show that Pt/Nb-Mo2C-
rGO exhibits lower alcohol oxidation overpotential and longer
polarization time/stability compared to Pt/Mo2C-rGO and bare
Pt/rGO catalysts.
The way to overcome this problem is to use bi-functional
systems such as Pt M where M can be another metal, metal
oxides, metal sulphides or metal carbides. These additional
components associated with Pt promote the adsorption of
oxophilic species (-OHads) to scavenge COads on Pt surface.
Further improvement in electro-catalytic performance can be
brought in by controlling the morphology of noble metal
nanostructures and employing newer catalyst support materi-
als. Over decades, carbon materials such as vulcan carbon,
carbon nanotube and reduced graphene oxide have been
widely used as catalyst supports for Pt based nano-materials in
DMFCs. Support materials should have high surface area for
dispersing stable metal nanoparticles and to provide good
conductivity and retaining the structural stability under the
electrochemical operations.[6,7]
Alloying with and/or addition of inexpensive metal compo-
nents to Pt have been considered for resisting the surface
poisoning and oxidizing the undesired intermediate species. It
is believed that the interface between Pt and other inexpensive
metal component provides significant sites for electro-oxida-
tion of methanol.[3] A large number of binary catalytic systems,
Pt Ru, Pt Pd, Pt Rh, Pt Ni, Pt Au, Pt Ag, Pt Cu, and Pt Co
catalysts[8–16] and ternary catalytic systems, Pt Pd-Cu, Pt Pd-Ru,
Pt Ni-Rh, Pt Ru-Co, Pt-Ni P and Pd/PANI/Pd[3,17–22] have been
examined for the oxidation of intermediate COads species. These
multiphase catalytic systems exhibit better catalytic properties
due to modified electronic properties and surface chemistry.
They also promote the bi-functional mechanism for methanol
electro-oxidation. Pt based-metal oxide/metal sulfide catalysts
are being investigated to improve the performance of DMFCs.
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