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Performance of Carbon Nanofiber Supported Pd-Ni Catalysts for Electro-oxidation of Ethanol in Alkaline Medium

Performance of Carbon Nanofiber Supported Pd-Ni Catalysts for Electro-oxidation of Ethanol in Alkaline Medium

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Performance of carbon nanofiber supported Pd-Ni catalysts for electro-oxidation of ethanol in alkaline medium, fuel cells
Performance of carbon nanofiber supported Pd-Ni catalysts for electro-oxidation of ethanol in alkaline medium, fuel cells

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Published by: Maiyalagan Thandavarayan on Aug 05, 2010
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 Journal of Power Sources
195 (2010) 5246–5251
Contents lists available atScienceDirect
Performance of carbon nanofiber supported Pd–Ni catalysts for electro-oxidationof ethanol in alkaline medium
T. Maiyalagan, Keith Scott
School of Chemical Engineering & Advanced Materials, University of Newcastle upon Tyne, Newcastle upon Tyne NE1 7RU, United Kingdom
a r t i c l e i n f o
 Article history:
Received 5 August 2009Received in revised form 18 January 2010Accepted 6 March 2010
Available online 15 March 2010
Ethanol electro-oxidationPd–NiNanostructured materialsElectro-catalystFuel cell
a b s t r a c t
Carbon nanofibers (CNF) supported Pd–Ni nanoparticles have been prepared by chemical reductionwith NaBH
as a reducing agent. The Pd–Ni/CNF catalysts were characterized by X-ray diffraction(XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM) and electrochemi-cal voltammetry analysis. TEM showed that the Pd–Ni particles were quite uniformly distributed on thesurface of the carbon nanofiber with an average particle size of 4.0nm. The electro-catalytic activity of the Pd–Ni/CNF for oxidation of ethanol was examined by cyclic voltammetry (CV). The onset potentialwas 200mV lower and the peak current density four times higher for ethanol oxidation for Pd–Ni/CNFcomparedtothatforPd/C.Theeffectof anincreaseintemperaturefrom20 to60
Chadagreateffect onincreasing the ethanol oxidation activity.
© 2010 Elsevier B.V. All rights reserved.
1. Introduction
Recently there has been increased interest in the developmentofdirectethanolfuelcells(DEFC).Ethanolisaninterestingalterna-tiverenewablefuelwhichhasanenergydensityof8030Whkg
;greater than that of methanol (6100Whkg
), if complete oxida-tion to CO
is attained[1].However, in acidic environments the complete oxidation of ethanol is difficult to achieve and attentionhas been directed to higher pH. The catalysts for ethanol oxidationcan be more active in alkaline medium compared to acid medium[2–5].Ethanolelectro-oxidationbyPt[6–8]inalkalinesolutionhas been reported. However, the high cost and limited supply of Ptconstitute a major limitation to development of DEFC. In order toreduce the cost of catalysts, Pt-free materials such as Pd have beenrecentlystudied[9,10].DatashowthatPdisagoodelectro-catalyst for ethanol oxidation in alkaline media[11].A great deal of interest has recently been focused on materialscheaper than platinum and the use of non-noble transition met-als in alkaline media; in particular the performance of alloys of palladium with non-noble metals for electro-oxidation of ethanol[12].Ethanol electro-oxidation by Ni[13]and Cu–Ni[14]in alka- line solution has been reported. Ni hollow spheres are promisingelectro-catalysts for alcohol oxidation in alkaline media[15].In alkaline solutions nickel can be easily converted to Ni(OH)
Corresponding author. Tel.: +44 191 2225207; fax: +44 191 2225292.
E-mail addresses:
maiyalagan@gmail.com(T. Maiyalagan),K.Scott@ncl.ac.uk(K. Scott).
the Ni
redox centers show high catalytic activity towardsthe oxidation of some small organic compounds.In addition to development of efficient electro-catalysts forethanol oxidation research has considered the role and use of alternative catalysts supports. Graphite nanofiber (GNF)[16],car- bon nanotubes (CNT)[17–20],carbon nanohorns[21]and carbon nanocoils[22]provide alternate candidates of carbon support for fuel cell applications. Due to the high electric conductivity andstructural properties, carbon nanofibers have been considered aspromisingcatalystsupportmaterialsinfuelcellelectrodes[23,24].In this work, synthesis of Pd–Ni/CNF based catalysts areexplored for possible use in DEFC in view of the good electro-catalytic activity of Pd and the ability of Ni to adsorb OH
ions inthe form of Ni(OH)
[25].The presence of Ni species is expected toassist in the electro-oxidation of poisonous reaction intermediatesadsorbed on the active Pd sites. Additionally, the use of Ni enablesa reduction in catalyst cost[34].
2. Experimental
 2.1. Materials
Allthechemicalsusedwereanalyticalgrade.Vapor-growncar-bon nanofibers were purchased from Pyrograf Products Inc. (OH,USA. Products PR24-LHT). Extensive characterization of represen-tative commercially available Pyrograf carbon nanofiber has beenreported[26,27].Palladium chloride and nickel chloride hydrate were procured from Sigma–Aldrich and used as received. Ethanoland KOH were obtained from Fischer chemicals. 20%Pd/C carbon
0378-7753/$ – see front matter
© 2010 Elsevier B.V. All rights reserved.
T. Maiyalagan, K. Scott / Journal of Power Sources
195 (2010) 5246–5251
blackwaspurchasedfrom(E-TEK,USA);Nafion5wt.%solutionwasobtained from Sigma–Aldrich and was used as received.
 2.2. Preparation of 20% Pd–Ni (3:1)/CNF catalyst 
undermagneticstirringfor24h[28].Theoxidizedfiberswerethen repeatedlywashedwithdistilledwatertoremoveresidualacidandevaporated to dryness.The required amount of PdCl
and NiCl
O, were added to10ml of water and 60mg functionalized CNF were mixed by mag-neticstirringfor3htoachieve20%Pdloading.Excess,diluteNaBH
solution was added to the solution to reduce the Pd and Ni speciesto form electro-catalyst. After that electro-catalyst was repeatedlywashed with distilled water to remove residual salts, centrifugedand dried at 70
C. The catalyst obtained is the Pd–Ni/CNF catalystwith 20wt.% Pd and the atomic ratio of Pd:Ni=3:1.
 2.3. Catalyst characterization
Scanning electron microscopy (SEM) and energy dispersive X-ray(EDX)measurementswerecarriedoutusingaJEOLJSM-5300LVscanning electron microscope with a ROUTEC UHV Dewar Detec-tor at an acceleration voltage of 25kV. Powder X-ray diffractionwas recorded on a PAN analytical X’Pert Pro MPD diffractome-ter using CuK
radiation. For transmission electron microscopicstudies, catalysts dispersed in ethanol were placed on the coppergridandtheimageswereobtainedusingPhillipsCM100transmis-sion electron microscope, operating at an accelerating voltage of 100keV.
 2.4. Electrochemical measurements
Glassy carbon (GC) (BAS) electrode (0.07cm
) was polished toa mirror finish with 0.05
m alumina suspensions before eachexperiment and served as substrate for the working electrode. Theworking electrodes were fabricated by coating catalyst ink onto aglassycarbonelectrode.Thecatalystsinkwaspreparedbydispers-ing35mgofthecatalystin0.8cm
of5wt.%Nafionsolutionandultrasonicatedfor20min.Nafionwasusedsimplyasabinder.Aknownamountofsuspensionwasaddedto the glassy carbon (GC) electrode and slowly dried in air. Theloading of the noble metal catalyst was 0.3mgcm
. A solution of 1.0moldm
(M) ethanol in 1M KOH was used to study ethanoloxidation activity.Electrochemical measurements were collected using a com-puter controlled Gill AC potentiostat (ACM Instruments Ltd.,Cumbria,UK).Allexperimentswerecarriedoutinathree-electrodeglass cell, incorporating the glassy carbon working electrode,a mercury–mercury oxide reference electrode and a platinummesh (25mm
25mm) counter electrode. All the electrochemi-cal experiments were carried out at room temperature in 1M KOHelectrolyte. The electrolyte solution was purged with high puritynitrogen for 30min prior to a series of voltammetric experiments.The catalytic performance was observed in 1moldm
KOH solu-tion,1MethanolatpH14.Currentdensitieswerecalculatedbased
Fig. 1.
SEM images of (a) Pd/C, (b) Pd–Ni/CNF and (c) EDX spectra of Pd–Ni/CNF catalysts.
T. Maiyalagan, K. Scott / Journal of Power Sources
195 (2010) 5246–5251
on the geometric area of the electrode. Triply distilled water wasused throughout for the preparation of solutions.
3. Results and discussion
ThemicrographofthePd/CandPd–Ni/CNFelectrodeshavebeeninvestigatedbySEM(Fig.1)andtheEDXspectrumforPd–Ni/CNFis presented inFig. 1crespectively. The agglomerated globular mor- phology of Pd/C resulted in rough surface with larger particles.The surface morphology of Pd–Ni/CNF catalysts was found to beuniformandtubularwallsaresufficientlydecoratedwithnanopar-ticles. EDX analysis confirmed the presence of Pd and Ni in thePd–Ni/CNF catalyst. According to the EDX measurements (Fig. 1c), Pd–Ni/CNFcatalystpreparedinthisworkcontained20.1wt.%ofPdwith a Pd/Ni atomic ratio of 3:1.0–1.1, which agrees well with thestoichiometric ratio of 3:1 used in the starting mixture.Fig. 2shows the XRD profiles of the Pd/C (curve a) andPd–Ni/CNFs(curveb)catalysts.XRDpatternsrevealthebulkstruc-tureofthecatalystanditssupport.Itcanbeseenthatthefirstpeaklocated at a 2
value of about 26
is referred to carbon (002). Theotherfourpeaksarecharacteristicoffacecenteredcubic(fcc)crys-talline Pd (JCPDS, Card No. 05-0681), corresponding to the planes(111), (200), (220) and (311) at 2
values of about, 47
, 68
. The nickel particles are air-sensitive, both in the stable sus-pension and in the solid state. The presence of the oxide phaseNiO (reflections (200) and (220)) can be observed on the electrondiffraction pattern[29].The average particle sizes of the catalyst were calculated from Pd (220) peak by the Scherrer formula[30]:
(Å )
is a coefficient (0.9),
the wavelength of X-ray used(1.54056Å),
the full-width half maximum and
is the angle atposition of peak maximum.The mean particle size obtained from the XRD patterns were2.9nm for Pd/C and 2.5nm for Pd–Ni/CNF. Typical TEM images of the Pd/C and Pd–Ni/CNF catalysts (Fig. 3)show an average par- ticle size of 4.8 and 4.0nm for Pd/C and Pd–Ni/CNF respectively.Thus, the values of the mean particle size obtained from XRD areslightlylowerthanthatobtainedfromTEManalysis.AlthoughsomeagglomerationofPdnanoparticlesoccurredontheVulcansupport,itcanbeseenfromtheTEMimagethatPdparticlesdispersionwas
Fig. 2.
XRD patterns of (a) Pd/C and (b) Pd–Ni/CNF catalysts.
Fig. 3.
TEM images of (a) Pd/C and (b and c) Pd–Ni/CNF catalysts.
reasonably uniform on the outer walls of the CNFs. Consideringthat Pd nanoparticles strongly interact with oxygen atoms, it canbe suggested that Pd nucleation centers occur in the proximity of oxygenated defects created during the treatment. Therefore, theimproved metal nanoparticle dispersion for the nitric acid-treated

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