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Power Ultrasound in
Electrochemistry
i
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Power Ultrasound in
Electrochemistry
From Versatile Laboratory Tool
to Engineering Solution
Edited by
BRUNO G. POLLET
The University of Birmingham
Edgbaston, United Kingdom
A John Wiley & Sons, Ltd., Publication
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Thiseditionfirstpublished2012
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LibraryofCongressCataloging-in-PublicationData
Powerultrasoundinelectrochemistry:fromversatilelaboratorytooltoengineeringsolutionsonoelectrochemistry/editedby
BrunoG.Pollet.
p.cm.
Includesbibliographicalreferencesandindex.
ISBN978-0-470-97424-7(cloth)
1.Sonochemistry. 2.Sonicwaves–Industrialapplications. 3.Electrochemistry. I.Pollet,BrunoG.
QD801.P692012
541(cid:2).370284–dc23
2011043940
AcataloguerecordforthisbookisavailablefromtheBritishLibrary.
HBISBN:9780470974247
Setin10/12ptTimesbyAptaraInc.,NewDelhi,India.
iv
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Idedicatethisbookto:
AwonderfulManandabrilliant Scientist–
ProfessorJohnPhilLorimer
and
Mesparentsetmapetitesoeurquej’aime e´norme´ment
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Contents
Foreword xiii
AbouttheEditor xv
ListofContributors xvii
Acknowledgements xix
IntroductiontoElectrochemistry 1
BrunoG.PolletandOliverJ.Curnick
I.1 Introduction 1
I.2 PrinciplesofElectrochemistry 1
I.3 Electron-TransferKinetics 2
I.4 DeterminationofOverpotentials 10
I.4.1 DecompositionVoltages 10
I.4.2 DischargePotentials 10
I.5 ElectroanalyticalTechniques 11
I.5.1 Voltammetry 11
I.5.2 Amperometry 17
References 20
1 AnIntroductiontoSonoelectrochemistry 21
TimothyJ.MasonandVero´nicaSa´ezBernal
1.1 IntroductiontoUltrasoundandSonochemistry 21
1.2 ApplicationsofPowerUltrasoundthroughDirectVibrations 23
1.2.1 Welding 23
1.3 ApplicationsofPowerUltrasoundthroughCavitation 25
1.3.1 HomogeneousReactions 26
1.3.2 HeterogeneousReactionsInvolvingaSolid/LiquidInterface 26
1.3.3 HeterogeneousLiquid/LiquidReactions 27
1.4 Electrochemistry 27
1.5 Sonoelectrochemistry–TheApplicationofUltrasound
inElectrochemistry 28
1.5.1 UltrasonicFactorsthatInfluenceSonoelectrochemistry 29
1.6 ExamplesoftheEffectofUltrasoundonElectrochemicalProcesses
underMassTransportConditions 32
1.7 ExperimentalMethodsforSonoelectrochemistry 34
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viii Contents
1.7.1 CellConstruction 34
1.7.2 StabilityoftheElectrodesUnderSonication 36
1.7.3 SomeApplicationsofSonoelectrochemistry 38
References 40
2 TheUseofElectrochemistryasaTooltoInvestigateCavitation
BubbleDynamics 45
PeterR.Birkin
2.1 Introduction 45
2.2 AnOverviewofBubbleBehaviour 46
2.3 MassTransferEffectsofCavitation 48
2.4 IsolatingSingleMechanismsforMassTransferEnhancement 48
2.5 ElectrochemistryNexttoaTetheredPermanentGasBubble 51
2.6 MassTransferfromForcedPermanentGasBubbleOscillation 55
2.7 MassTransferEffectsfromSingleInertialCavitationBubbles 62
2.8 InvestigatingNon-inertialCavitationUnderanUltrasonicHorn 65
2.9 MeasuringIndividualErosionEventsfromInertialCavitation 67
2.10 Conclusions 73
Acknowledgements 73
References 73
3 Sonoelectroanalysis:AnOverview 79
JonathanP.Metters,JaanusKruusmaandCraigE.Banks
3.1 Introduction 79
3.2 AnalysisofPesticides 87
3.3 QuantifyingNitrite 87
3.4 Biogeochemistry 88
3.5 QuantifyingMetalin‘LifeorDeath’Situations 89
3.6 AnalysisofTraceMetalsinClinicalSamples 90
3.7 BiphasicSonoelectroanalysis 92
3.8 ApplyingUltrasoundintotheField:TheSonotrode 93
3.9 Conclusions 93
References 94
4 SonoelectrochemistryinEnvironmentalApplications 101
PedroL.BoneteFerra´ndez,Mar´ıaDeseadaEsclapez,Vero´nicaSa´ezBernal
andJose´ Gonza´lez-Garc´ıa
4.1 Introduction 101
4.2 SonoelectrochemicalDegradationofPersistentOrganicPollutants 102
4.2.1 SonoelectrochemicalApplications 102
4.2.2 HybridSonoelectrochemicalTechniquesApplications 115
4.3 RecoveryofMetalsandTreatmentofToxicInorganicCompounds 121
4.4 DisinfectionofWaterbyHypochloriteGeneration 129
4.5 SoilRemediation 130
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Contents ix
4.6 Conclusions 134
ListofSymbolsandAbbreviations 134
References 135
5 OrganicSonoelectrosynthesis 141
DavidJ.Walton
5.1 Introduction 141
5.2 Scale-UpConsiderations 142
5.3 EarlyHistoryofOrganicSonoelectrochemistry 143
5.4 ElectroorganicSyntheses 144
5.4.1 Electroreductions 144
5.4.2 Organochalcogenides 149
5.4.3 SyntheticElectrooxidations 151
5.4.4 SonoelectrochemicallyProducedElectrodeCoatings:
DesirableandUndesirable 157
5.5 OtherSystems 161
5.5.1 Hydrodynamics 161
5.5.2 Low-temperatureEffects 162
5.6 Conclusions 163
Acknowledgements 163
References 163
6 Sonoelectrodeposition:TheUseofUltrasoundinMetallic
CoatingsDeposition 169
Jean-YvesHihn,FrancisTouyeras,Marie-LaureDoche,
Ce´dricCostaandBrunoG.Pollet
6.1 IntroductiontoMetalPlating 169
6.1.1 WhytheNeedtoCoverSurfaceswithMetals? 169
6.1.2 ProcessandTechnologyofPlating 170
6.2 TheUseofUltrasoundinSurfaceTreatment 170
6.2.1 UltrasoundintheCleaningStepforSurfaceTreatment
Processes 170
6.3 UltrasoundandPlating:WhyStudyPlatingunderSonication? 172
6.4 ElectrodepositionAssistedbyUltrasound 173
6.4.1 TheElectrodepositionProcess 173
6.4.2 UltrasonicEffectsonElectrodepositedCoatingProperties 175
6.4.3 MicroscopicEffectsofUltrasoundonElectrodeposited
MetalCoatings 179
6.4.4 TheInfluenceofAcousticEnergyDistributiononCoatings 182
6.4.5 InfluenceofUltrasoundonCopperElectrodepositionin
UnconventionalSolvents 187
6.4.6 IncorporationofParticlesAssistedbyUltrasound 195
6.5 ElectrolessCoatingAssistedbyUltrasound 198
6.5.1 TheElectrolessProcess 198
6.5.2 UltrasoundEffectsuponElectrolessCoatingProperties 198
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x Contents
6.5.3 CopperCoatingonNon-conductiveSubstratesunder
Insonation 201
References 209
7 InfluenceofUltrasoundonCorrosionKineticsanditsApplication
toCorrosionTests 215
Marie-LaureDocheandJean-YvesHihn
7.1 IntroductiontoMetalCorrosion 215
7.1.1 WhatExactlyisCorrosion? 215
7.1.2 WhyDoMetalsCorrode? 215
7.1.3 ThePricetoPay:theEconomicalImpactofCorrosion 216
7.1.4 CorrosionControlTechnology:theNeedforReliable
CorrosionTests 217
7.1.5 WhyStudyCorrosionUnderSonication? 219
7.1.6 CorrosionandCorrosion-CavitationMechanisms 220
7.1.7 CorrosionRate 221
7.1.8 ElectrochemicalStudyofCorrosionReactions 222
7.1.9 FormsofCorrosion 223
7.1.10 Cavitation-Corrosion 223
7.2 InfluenceofUltrasoundontheCorrosionMechanismsofMetals 231
7.2.1 InfluenceofUltrasoundonGeneralCorrosion 232
7.2.2 InfluenceofUltrasoundonPassivityofMetals 240
7.3 UltrasoundasaTooltoDevelopAcceleratedCorrosionTesting 242
7.3.1 AtmosphericCorrosionofZincPlatedSteel 242
7.3.2 AcceleratedCorrosionTestforStainlessSteelUsed
inExhaustSystems 243
7.3.3 AcceleratedCorrosionTestforEvaluatingOilfield
CorrosionInhibitors 243
7.3.4 AcceleratedCorrosionTestforSurgicalImplantMaterials
inBodyFluids 244
References 244
8 Sonoelectropolymerisation 249
FabriceLallemand,Jean-YvesHihn,MahitoAtobeandAbdeslamEtTaouil
8.1 IntroductiontoElectropolymerisation 249
8.2 InnovativeProcessesforElectrodeActivation 251
8.3 SolubilisationofMonomerswithUltrasound 256
8.4 ChemicalPolymerisation 257
8.5 ElectropolymerisationunderUltrasonicIrradiation 259
8.6 EffectsofUltrasoundonFilmProperties 262
8.6.1 Mass-TransferEffect 262
8.6.2 MorphologyEffect 264
8.6.3 DopingEffect 272
8.6.4 EffectonLocalControlofSurfaces 276
References 278
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Contents xi
9 SonoelectrochemicalProductionofNanomaterials 283
JonathanP.MettersandCraigE.Banks
9.1 Introduction 283
9.2 ExperimentalConfigurations 286
9.3 PureMetals 287
9.3.1 Cobalt,IronandNickel 287
9.3.2 Silver 287
9.3.3 Copper 288
9.3.4 Magnesium 288
9.3.5 Aluminium 289
9.3.6 LeadandCadmium 290
9.3.7 CoreShellNanoparticles 290
9.3.8 Gold 292
9.3.9 Tungsten 295
9.4 AlloyNanoparticles 295
9.5 PolymerNanoparticles 296
9.6 Conclusions 296
References 296
10 SonochemistryandSonoelectrochemistryinHydrogenandFuel
CellTechnologies 301
BrunoG.Pollet
10.1 Introduction 301
10.2 SonoelectrochemicalProductionofHydrogen 303
10.3 SonochemicalProductionofNobleMetalsandFuelCell
Electrocatalysts 305
10.3.1 SonochemicalMono-MetallicSyntheses 306
10.3.2 SonochemicalBi-MetallicSyntheses 309
10.3.3 SonochemicalPerovskiteOxidesSyntheses 311
10.4 SonoelectrochemicalProductionofNobleMetalsandFuelCell
Electrocatalysts 311
10.4.1 EffectofSurfactantsandPolymers 315
10.4.2 EffectofAqueousSolutions 317
10.5 SonochemicalandSonoelectrochemicalPreparationofFuel
CellElectrodes 318
10.6 IndustrialApplicationsoftheUseofUltrasoundfortheFabrication
ofFuelCellMaterials 319
10.7 Conclusions 320
Acknowledgement 321
ListofAbbreviations 321
References 322
Appendix:SonochemicalEffectsonElectrodeKinetics 327
Index 335
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Foreword
When I think back to my first excursions into the world of ultrasound and its effects on
chemicalreactionsittakesmebackto1975whenIobtainedmyfirstpermanentacademic
postasanorganicchemistataninstitutionthatwasthencalledLanchesterPolytechnicbut
laterbecameCoventryUniversity.ThedepartmentIjoinedwasChemistryandMetallurgy,
reflectingtheappliednatureofsciencecoursesatthattime.OnedayIwaswalkingthrough
ametallurgylaboratoryandsawanultrasonicbathbeingusedtocleanmetalsamples.The
processintriguedmeforIcouldseethattheultrasonicbathwasproducingalargeamountof
energyasevidencedbythedisturbanceofthewaterwithwhichitwasfilled.Itoccurredto
methatthiswasperhapsaformofenergywhichmightbeemployedtoinfluencechemical
reactivity using as an example a simple solvolysis reaction. However, the initial results
were puzzling but I was sharing an office with a physical chemist, the late Phil Lorimer,
butneitherofushadheardofusingultrasoundasasourceofenergytopromotechemical
reactivity.Togetherwepursuedthisnewsubjectandmetmanyproblemsinconvincingthe
UKsciencefraternitythatwewere‘ontosomethingbig’.Weproducedourfirstpaperin
1980asaChemicalCommunication,inwhichwereportedasmall(twofold)enhancement
inthehydrolysisrateof2-chloro-2-methylpropane.By1986theideaofusingultrasound
toinfluencereactionshadgreatlyexpandedworldwideandwewereinvolvedinorganising
thefirsteverinternationalconferenceonsonochemistryatWarwickUniversity.
Sowheredoeselectrochemistryfitintothedevelopmentofsonochemistry?PhilLorimer
was originally an electrochemist and so had an interest in all things that might influence
electrochemical processes. Together with another colleague, David Walton, we began to
apply ultrasound to electrochemistry in the late 1980s and discovered that it could, for
example,modifytheelectrochemicaloxidationmechanismofcyclohexanecarboxylate.In
1990 we published a review using the term ‘Sonoelectrochemistry’ for the first time in a
peer-reviewedjournal.Thisreviewforcedustolookattheliteraturesurroundingtheuses
of ultrasound in electrochemistry and brought to light a number of research publications
thathadnotpreviouslybeendrawntogether.Othersourceshavebeenunearthedsincethen,
including the pioneering work of Young and Kersten in 1936 on the effects of ultrasonic
radiation on electrodeposits. This was perhaps the first observation of improvements in
hardness and brightness induced by ultrasound. Walker reinvestigated and advanced the
workinthe1970sandin1993wroteacomprehensivereviewofhisandotherworkentitled
‘UltrasonicAgitationinMetalFinishing’.Itissurprisingtomethattheveryearlyworkon
sonoelectrochemistryhasnotbeencitedextensively.Thisisthecasewiththe1953paper
of Yeager and Hovorka entitled ‘Ultrasonic Waves and Electrochemistry’. It provided a
surveyoftheelectrochemicalapplicationsofultrasonicwavesthatwerediscussedinterms
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