Transition
metal carbides have received significant attention for
oxygen reduction reaction (ORR) applications primarily owing to their
good conductivity. However, cobalt carbide based catalysts (CoC
x
) are difficult to prepare, owing to the
preferential formation of metallic cobalt and cobalt oxide instead.
Also, cobalt carbide nanoparticles rapidly coarsen and undergo grain
growth. This is a problem as it results in low current density and
poor active site exposures. In this study, carbon-supported CoC
x
(C@CoC
x
) is
successfully synthesized using the solid–solid separation synthesis
method. The limitations identified to be associated with cobalt carbide
nanoparticle based electrocatalysts are overcome. Here, the synthetic
approach ensures good distribution and protection of CoC
x
on in situ generated carbon nanotubes. This results
in robust activities with an appreciable onset potential of ∼0.92
V, a half-wave potential of ∼0.8 V, and a durability of ∼100%
(tested on ∼22 h continuous operation runs). In alkaline medium,
C@CoC
x
compares favorably with commercial
platinum dispersed on carbon (20 wt % Pt/C) and shows a higher current
density of ∼300 μA/cm2 at an electrode potential
of 0.6 V. All of these indicate that there is a synergistic charge
transfer between CoC
x
and an in situ generated
carbon nanotube. This is due to intimate contact that exists between
the two phases; it is in fact responsible for superior methanol tolerance
observed, making it a good candidate for direct methanol fuel cells.