•  
  •  
 

Abstract

The nature of formic acid adsorbates formed on porous platinum electrode has been studied by in situ infrared reflectance spectroscopic (FTIR) and differential electrochemical mass spectroscopic (DEMS) techniques. By carefully avoiding the contamination of the environment( i.e ., air) voltammetric experiments show that the oxidation of formic acid adsorbates depends on both adsorption potential and adsorption time. The online DEMS results show furthermore that the number of electrons necessary for the formation of one molecule of CO 2 from adsorbed formic acid is independent of the adsorption potential. Its value of 2.2 demonstrates that the composition of formic acid adsorbates is a mixture of CO and COH, but not CO or COH alone. The existence of these two species has been clearly proved by in situ FTIR experiments on electrodeposited platinum with a roughness factor of 11. The bands at 1 262 cm -1 , 1 840 cm -1 , and in the frequency range of 2 048 to 2 060 cm -1 are due to the surface adsorbed COH, bridge and linearly bound CO ad , respectively. In addition, the interaction between formic acid adsorbates and CO has been investigated by using DEMS via isotopic labelled 13 C formic acid as a probe as well. These experiments show that the surface species previously fromed from CO and formic acid cannot be exchanged by formic acid in solution. whereas about 75 percent of the firstly formed formic acid adsorbates can be replaced by bulk CO.

Publication Date

1997-02-28

Online Available Date

1997-02-28

Revised Date

1997-02-28

Received Date

1997-02-28

References

1XiaXH,IwasitaT,GeFYetal.Structuralefectsandreactivityinmethanoloxidationonpolycrys-talineandsinglecrystalplatinum.Electrochim.Acta,1996,41:7112CaponA,ParsonsR.Theoxidationofformicacidatnoblemetalelectrodes;PartⅢIntermediatesandmechanismonplatinumelectrodes.J.Electroanal.Chem.,1972,45:2053IwasitaT,XiaXH,HerreroE.EarlystagesduringtheoxidationofHCOOHonsinglcrystalPtelec-trodesascharacterizedbyinfraredspectroscopy.Langmiur,1996,12:42604LamyC,LegerJM,ClavilierJetal.StructuralefectsinElectrocatalysis:AcomparativestudyoftheoxidationofCO,HCOOHandCH3OHonsinglePtelectrode.J.Electroanal.Chem.,1983,150:715BagotzkyVS,VassilievYuB,KhazovaOA.Generizedschemeofchemisorption,electrooxidationandelectroreductionofsimpleorganiccompoundsonplatinumgroupmetals.J.Electroanal.Chem.,1977,81:2296BreiterMV.Adsorptionoforganicspeciesonplatinummetalelectrodes.InModernAspectsofElectro-chemistry(EditedbyBockrisJOMandConwayBE).Princeton,NJ:PlenumPress,1975,10:1787WilsauJ,HeitbaumJ.AnalysisofadsorbedintermediatesanddeterminationofsurfacepotentialshiftsbyDEMS.Electrochim.Acta.,1986,31:9438WieckowskiA,SobkowskiJ.Comparativestudyofadsorptionandoxidationofformicacidandmethanolonplatinizedelectrodesinacidicsolution.J.Electroanal.Chem.,1975,63:3659KutschkerA,VielstichW.ZumMechanismusderElektrochemischenAmeisensaueroxidationinsaurenLeitelektrolyten.Electrochim.Acta,1963,8:98510Angerstein-KozlowskaH,McdougalD,ConwayBE.Originofactivationofacetonitrileandmercuryinelectrocatalyticoxidation.J.Electrochem.Soc.,1973,120:75611(a)BedenB,LamyC,BewickAetal.Electrosorptionofmethanolonaplatinum—IRspectroscopicevi-denceforadsorbedCOspecies.J.Electroanl.Chem.,1981,121:343;(b)BewickA,KunimatsuK,BedenBetal.32ndISEMeeting,Dubrovnik,Ext.Abstr.Sept.1981,A28,Vol.4:9212ParsonsR,VandernootT.Theoxidationofsmalorganicmolecules;Asurveyofrecentfuelcelrelatedresearch.J.Electroanal.Chem.,1988,257:913WilsauJ.WolterO,HeitbaumJ.Onthenatureoftheadsorptionduringmethanoloxidationatplat-inum.J.Electroanal.Chem.,1985,185:16314AnastasijevicNA,BaltruschatH,HeitbaumJ.DEMSasatoolfortheinvestigationofdynamicprocess-es:galvanostaticformicacidoxidationonaPtelectrode.J.Electroanal.Chem.,1989,272:8915ChristensenPA,HamnettA,WeeksSA.InsituIRstudyofadsorptionandoxidationofmethanolonplatinumandplatinizedglassycarbonelectrodes.J.Electroanal.Chem.,1988,250:12716XiaXH,VielstichW.EnhancedoxidationofcarbonmonoxideonplatinuminHClO4viainteractionwithacetonitrile.Electrochim.Acta,1994,39:1317Bitins-CataneoB,CataneoE,Ko¨nigshovenPetal.Newdevelopmentsinelectrochemicalmassspec-troscopy.ElectroanalyticalChemistry(EditedbyBardAJ).NewYork:MarcelDekker,1991,17:18118SunSG,ClavilierJ.ThemechanismofelectrocatalyticoxidationofformicacidonPt(100)andPt(111)insulphuricacidsolution:anEMIRSsutdy.J.Electroanal.Chem.,1988,240:14719IwasitaT.ProgressinthestudyofmechanoloxidationbyInsitu,Exsitu,andonlinemethods.Ad-vancesElectrochemicalScienceandEngineering,Eds.GerischerH,TobiasCW,VCHWeinheim1990,1:12720LeungLam-WingH,WeaverMicheaelJ.AdsorptionandElectrooxidationofsomesimpleorganicmoleculesonRhodium(111)asprobedbyreal-timeFTIRspectroscopy:comparisonswithplatinum(111).J.Phys.Chem.,1989,93:721821IwasitaT,VogelU.InteractionofmethanolandCOadsorbateonplatinumwithCH3OHandCOinso-lution.Electrochim.Acta,1988,33:557

Share

COinS
 
 

To view the content in your browser, please download Adobe Reader or, alternately,
you may Download the file to your hard drive.

NOTE: The latest versions of Adobe Reader do not support viewing PDF files within Firefox on Mac OS and if you are using a modern (Intel) Mac, there is no official plugin for viewing PDF files within the browser window.