December 16, 2011
2011 American Chemical Society
J. Phys. Chem. C
2012, 116, 2630
Highly Stable Pt
Ru Nanoparticles Supported on Three-DimensionalCubic Ordered Mesoporous Carbon (Pt
Ru/CMK-8) as PromisingElectrocatalysts for Methanol Oxidation
T. Maiyalagan,* Taiwo O. Alaje, and Keith Scott
School of Chemical Engineering and Advanced Materials, University of Newcastle Upontyne, NE1 7RU, United Kingdom
Energy, its widespread distribution, availability, and a
ord-ability has come to the foreground in developmental issues worldwide as a result of the challenges confronting the use of fossil fuels, namely, their rapid depletion and increasing environ-mental pollution.
The fuel cell, a fuel conversion technology,is widely touted as having the potential to address these.
Thedirect methanol fuel cell operated with the electrochemical oxida-tionofmethanolasfuelattheanodeandthereductionofoxygenatthecathodestandsoutamongothersbecauseofitshighconversione
ciency, low pollution, low weight, and high power density.
Methanol also o
ers the advantage of easy storage, refuelling, andtransportation when compared with hydrogen
oxygen fuel cell.
However, one of the major challenges facing the marketcompetitiveness of direct methanol fuel cells is the cost of thecatalyst, mainly the platinum
ruthenium bimetallic alloy, whichhas been discovered to be the most appropriate among otheroptions.
This catalyst is very often dispersed on a conven-tionalcarbonsupport,whichin
orts are being channelledtoward obtaining a support material that simultaneously optimizesthe catalyst dispersion, loading, and electrocatalytic e
ciency. An ideal support-catalyst assembly should ensure facilemolecular transport of reactants and products, have goodelectronic conductivity, and possess high surface reactivity;these would enhance the molecular conversion.
A highly ordered mesoporous carbon (HOMC) with tunable poresizes, high surface area, large pore volume, and more narrow pore size distribution lends itself to the foregoing merits.
In general, ordered mesoporous carbons, especially CMK-3,have been used extensively as supports for direct methanolfuel cell catalysts.
CMK-8 mesoporous carbons are unique because of their 3-Dcubic
mesostructure, which consists of two interpenetratingcontinuous networks of chiral channels.
This is a replica of the mesoporous silica (KIT-6) hard template that follows theG-surface.
Hence their structure is also referred to as bicontin-uous gyroidal.Merits of CMK-8 like other HOMC include extremely highsurfacearea,well-de
exibleframework composition, and intrinsic conductivity.
Com-pared with other HOMCs like CMK-3, the unique highly branched intertwined 3-D channel network (nanoscale level)of CMK-8 is likely to provide more accessible entrances andchannelsaswellasserveasahighlyopenedporoushostwitheasy and direct access for guest species, this would result in a higherloading of electroactive species and also facilitate inclusion or dif-fusion throughout the pore channels without pore blockage.
Another advantage of CMK-8 over other HOMCs is that itpossesses a higher
symmetry that leads to a relatively isotropic graphitized structure with a higher conductivity; thisenhances heterogeneous electron transfer more e
In this study, we seek to exploit the aforementioned structuralcharacteristics of CMK-8. By varying the mole ratio of startingreactants, two di
erent types of highly ordered mesoporous silicaKIT-6weresynthesizedandusedashardtemplateforsynthesizing
October 26, 2011
December 11, 2011
The cost of the catalysts used in the direct methanol fuel cellposes a challenge to its widespread use as an energy e
cient and environmentfriendly fuel conversion technology. In this study, two types of highly orderedmesoporous carbon CMK-8 (I and II) with high surface area and 3-D bicontinuous interpenetrating channels were synthesized and deposited withPt
Ru nanoparticles using the sodium borohydride reduction method. Theelectrocatalytic capabilities for methanol oxidation were investigated usingcyclic voltammetry and chronoamperometry, and the results were compared with that of Pt
Ru deposited on Vulcan XC-72 using the same prepara-tion method as well as with commercial Pt
Ru/C (E-TEK) catalyst. Pt
Ru/CMK-8-I synthesized by the method developed in this work revealed anoutstanding speci
c mass activity (487.9 mA/mg) and superior stability compared with the other supports, thus substantiating its potential to reducethe costs of DMFC catalysts.