Functional Materials in Amperometric Sensing: Polymeric, Inorganic, and Nanocomposite Materials for Modified Electrodes

228 Pages·2014·6.54 MB·English

by  Renato Seeber, Fabio Terzi, Chiara Zanardi (auth.)

Monographs in Electrochemistry
Series Editor: F. Scholz
Renato Seeber
Fabio Terzi
Chiara Zanardi
Functional Materials
in Amperometric
Sensing
Polymeric, Inorganic, and
Nanocomposite Materials for
Modified Electrodes
Functional Materials in Amperometric Sensing
Monographs in Electrochemistry
SeriesEditor:FritzScholz,UniversityofGreifswald,Germany
Surprisingly,alargenumberofimportanttopicsinelectrochemistryisnotcovered
by up-to-date monographs and series on the market, some topics are even not
coveredatall.TheseriesMonographsinElectrochemistryfillsthisgapbypublish-
ingindepthmonographswrittenbyexperiencedanddistinguishedelectrochemists,
covering both theory and applications. The focus is set on existing as well as
emergingmethodsforresearchers,engineers,andpractitionersactiveinthemany
and often interdisciplinary fields, where electrochemistry plays a key role. These
fields will range – among others – from analytical and environmental sciences to
sensors,materialssciencesandbiochemicalresearch.
Moreinformationaboutthisseriesat
http://www.springer.com/series/7386
Renato Seeber • Fabio Terzi • Chiara Zanardi
Functional Materials in
Amperometric Sensing
Polymeric, Inorganic, and Nanocomposite
Materials for Modified Electrodes
RenatoSeeber
FabioTerzi
ChiaraZanardi
DepartmentofChemicalandGeologicalSciences
UniversityofModenaandReggioEmilia
Modena,Italy
ISSN1865-1836 ISSN1865-1844(electronic)
ISBN978-3-662-45102-1 ISBN978-3-662-45103-8(eBook)
DOI10.1007/978-3-662-45103-8
SpringerHeidelbergNewYorkDordrechtLondon
LibraryofCongressControlNumber:2014957538
©Springer-VerlagBerlinHeidelberg2014
Thisworkissubjecttocopyright.AllrightsarereservedbythePublisher,whetherthewholeorpart
of the material is concerned, specifically the rights of translation, reprinting, reuse of illustrations,
recitation,broadcasting,reproductiononmicrofilmsorinanyotherphysicalway,andtransmissionor
informationstorageandretrieval,electronicadaptation,computersoftware,orbysimilarordissimilar
methodologynowknownorhereafterdeveloped.Exemptedfromthislegalreservationarebriefexcerpts
inconnectionwithreviewsorscholarlyanalysisormaterialsuppliedspecificallyforthepurposeofbeing
enteredandexecutedonacomputersystem,forexclusiveusebythepurchaserofthework.Duplication
ofthispublicationorpartsthereofispermittedonlyundertheprovisionsoftheCopyrightLawofthe
Publisher’s location, in its current version, and permission for use must always be obtained from
Springer.PermissionsforusemaybeobtainedthroughRightsLinkattheCopyrightClearanceCenter.
ViolationsareliabletoprosecutionundertherespectiveCopyrightLaw.
The use of general descriptive names, registered names, trademarks, service marks, etc. in this
publicationdoesnotimply,evenintheabsenceofaspecificstatement,thatsuchnamesareexempt
fromtherelevantprotectivelawsandregulationsandthereforefreeforgeneraluse.
While the advice and information in this book are believed to be true and accurate at the date of
publication,neithertheauthorsnortheeditorsnorthepublishercanacceptanylegalresponsibilityfor
anyerrorsoromissionsthatmaybemade.Thepublishermakesnowarranty,expressorimplied,with
respecttothematerialcontainedherein.
Printedonacid-freepaper
SpringerispartofSpringerScience+BusinessMedia(www.springer.com)
Preface of the Editor
In modern interfacial electrochemistry, one can find two opposite directions of
research: one focused on the most well-defined and clean interfaces (e.g., single
crystal metal surfaces), and another in which attempts are made to construct the
most complicated architectures at the interfaces. In some cases, these are also
highly defined (e.g., in cases of self-assembled monolayers), but in other cases
they may lack a high order, or we do not yet know the order, but these interfaces
WORK as desired for certain applications. The immense variety of modified
electrode surfaces is difficult to survey, and anybody entering into research and
development of electrochemical sensors will greatly appreciate the competent
advice available from a monograph such as this, written by highly experienced
scientists. Renato Seeber, the senior author, and his colleagues Fabio Terzi and
Chiara Zanardi from the University of Modena and Reggio Emilia, Italy, have
focussed their book on amperometric sensors. Although amperometric sensing of
the endpoint of a titration was first described in 1897 in a PhD thesis by Ernst
Salomon[1–3],astudentofWaltherNernstinGo¨ttingen,progresswasratherslow
inthefirsthalfofthetwentiethcentury,andamperometricsensorsremainedmainly
confinedtoindicatingtitrationendpoints.Amperometrictitrationswereintensively
developed by Songina et al. [4] in the former USSR; unfortunately, this detailed
Russian work [5] has never been translated to English. Clark filed a patent
for his famous oxygen sensorin1959 andpublishedit in1962[6, 7].Thesecond
half of the last century saw a burst of innovations, especially in the area
of biochemical sensors, most prominently the glucose sensor [8]. Now, electro-
chemists (and chemists using electrochemical measuring techniques) have no
hesitation in putting whatever they believe could be useful on electrode surfaces
to achieve their goals. This experimental entrepreneurship is a challenge for
many scientists who try to understand how these systems work. The present
monograph is an important step towards a systematic view of complex sensors
v
vi PrefaceoftheEditor
for amperometric measurements. The authors have avoided aspiring to complete
literature coverage, but instead present a selection of instructive examples in the
frameworkofasystematicclassification.
Greifswald,Germany FritzScholz
August2014
References
1. Scholz F (2012) Salomon, Ernst. In: Bard AJ, Inzelt G, Scholz F (eds) Electrochemical
dictionary,2ndedn.Springer,Berlin,p817
2.SalomonE(1897)TheoriedesReststromes,denmanbeipolarisiertenElektrodenbeobachtet.
PhDthesis,Engelman,Leipzig
3.SalomonE(1897)ZPhysChem24:55.
4.ScholzF(2013)JSolidStateElectrochem17:1493
5.SonginaOA(1957)Amperometricheskoye(polyarometricheskoye)titrovanievmineral’nogo
syr’ya, 3rd edn. Gosgeoltekhizdat, Moskva. Songina OA, Zakharov VA (1969) Amperome-
tricheskoyetitrovanie.Khimiya,Moskva
6.ClarkLC(1959)USPatent2,913,386
7.ClarlLC,LyonsC(1962)AnnNYAcadSci102:29.
8.WollenbergerU(2012)Glucosesensor.In:BardAJ,InzeltG,ScholzF(eds)Electrochemical
dictionary,2ndedn.Springer,Berlin,p423
Contents
1 ImportanceofModifiedElectrodesinAmperometricSensing. . . . . . 1
1.1 FromaLookattheHistoricalBackgroundtoConsiderationsfor
EffectivePerspectives. . .. . . . . . .. . . . . . .. . . . . . .. . . . . . .. . 3
1.2 AdvantagesSoughtwithRespecttoBareElectrodes. . . . . . . . . . 8
1.3 GeneralOverviewoftheModifyingMaterials. . . . . . . . . . . . . . . 14
1.4 AmperometricSensingforSpecificandAspecificAnalyses. . . . . 19
References. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 20
2 IntrinsicallyConductingPolymers. . . . . . . . . . . . . . . . . . . . . . . . . . . 23
2.1 SynthesisandDepositionofICPsontoElectrodeSurfaces. . . . . . 25
2.2 PolymerDopingandDe-Doping. . . . . . . . . . . . . . . . . . . . . . . . . 28
2.3 PrincipalICPsDerivativesUsedinElectroanalysis. . . . . . . . . . . 32
2.3.1 Polypyrrole. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 32
2.3.2 Polyaniline. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 33
2.3.3 Polythiophene. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 34
2.3.4 Polyphenazines,Polyphenothiazines,and
Polyphenoxazines. . . . . . . . . . . . . . . . . . . . . . . . . . . . . 35
2.4 ApplicationsofICPsinElectroanalysis. . . . . . . . . . . . . . . . . . . . 35
2.4.1 DirectDetectionofOrganicSpecies. . . . . . . . . . . . . . . . 35
2.4.2 MolecularlyImprintedPolymers. . . . . . . . . . . . . . . . . . 40
2.4.3 DetectionofMetalIons. . . . . . . . . . . . . . . . . . . . . . . . . 41
2.4.4 ElectronicTongues. . . . . . . . . . . . . . . . . . . . . . . . . . . . 45
2.4.5 EnzymaticBiosensors. . . . . . . . . . . . . . . . . . . . . . . . . . 46
2.4.6 Genosensors. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 51
References. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 52
3 RedoxPolymersandMetallopolymers. . . . . . . . . . . . . . . . . . . . . . . . 59
3.1 MainCharacteristicsofRedoxPolymers. . . . . . . . . . . . . . . . . . . 59
3.2 PreparationofElectrodeModifiedbyRPs. . . . . . . . . . . . . . . . . . 62
3.3 WhyModificationswithRPs?. . . . . . . . . . . . . . . . . . . . . . . . . . . 63
vii
viii Contents
3.4 RPsinApplicationsorSuitableforApplications:
MuchtoDoinElectroanalysis. . . . . . . . . . . . . . . . . . . . . . . . . . 64
3.5 DifferentSpeciesforDifferentRoles:RP-BasedComposites. . . . 66
3.6 PrussianBlueandAnalogousTransitionMetal
Hexacyanoferrates. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 67
3.7 FromPureRedoxtoRedox-ElectronicConductioninthe
SameMolecule:TheMetallopolymers. . . . . . . . . . . . . . . . . . . . . 71
3.8 RepresentativeMetallopolymers. . . . . . . . . . . . . . . . . . . . . . . . . 80
3.8.1 Metallocenes. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 82
3.8.2 BipyridineandTerpyridineLigands. . . . . . . . . . . . . . . . 84
3.8.3 PhenanthrolineLigand. . . . . . . . . . . . . . . . . . . . . . . . . . 87
3.8.4 SchiffBaseLigands. . . . . . . . . . . . . . . . . . . . . . . . . . . . 88
3.8.5 PorphyrinRings. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 90
3.8.6 PhthalocyanineRing. . . . . . . . . . . . . . . . . . . . . . . . . . . 92
3.8.7 CyclamCycle. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 92
3.8.8 Sulphur-BasedLigands. . . . . . . . . . . . . . . . . . . . . . . . . 93
3.8.9 PhosphineLigands. .. . . . . . . .. . . . . . . .. . . . . . . .. . . 93
References. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 94
4 IonExchangePolymers. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 99
4.1 PolymersforIonExchangeVoltammetry. . . . . . . . . . . . . . . . . . 99
4.2 PolymersforInclusionofRedoxMediators. . . . . . . . . . . . . . . . . 101
4.3 PolymersforGasSensors. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 102
4.4 OtherApplicationsofIon-ExchangePolymers. . . . . . . . . . . . . . . 103
References. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 104
5 Monolayers. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 105
5.1 AnchoringMonolayerstoSubstrate. . . . . . . . . . . . . . . . . . . . . . . 106
5.2 CommonSubstratesforPreparationofMonolayers. . . . . . . . . . . 110
5.2.1 SubstratePreparation. . . . . . . . . . . . . . . . . . . . . . . . . . . 112
5.2.2 ArrangementoftheHeadGroupsontheSubstrate
Surface. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 112
5.2.3 AdsorptionSitesfortheHeadGroups. . . . . . . . . . . . . . . 113
5.3 Spacers. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 116
5.4 StabilityoftheMonolayers. . . . . . . . . . . . . . . . . . . . . . . . . . . . . 117
5.5 ReactivityoftheMonolayers. . . . . . . . . . . . . . . . . . . . . . . . . . . 118
5.6 MixedMonolayers. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 120
5.7 MonolayersBasedonOligomersandPolymers. . . . . . . . . . . . . . 121
5.8 ElectrochemistryofMonolayers. . . . . . . . . . . . . . . . . . . . . . . . . 123
5.9 AnalyticalApplications. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 127
References. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 134
6 NanosizedMaterials. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 139
6.1 ClassificationofNanosizedMaterials. . . . . . . . . . . . . . . . . . . . . 140
6.2 SynthesisTechniques. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 142
6.3 StabilityinSolution. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 145
Contents ix
6.4 SynthesisofNanostructureswithinTemplates. . . . . . . . . . . . . . . 147
6.5 SynthesisofPolymericNanostructures. . . . . . . . . . . . . . . . . . . . 151
6.6 SynthesisofMetalNano-ObjectsthroughChemicalReduction
ofMetalSalts. . .. . . . . .. . . . . .. . . . .. . . . . .. . . . .. . . . . .. . 154
6.6.1 Brust’sMethod. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 154
6.6.2 Turkevich’sMethod. . . .. . . . . . .. . . . . . . .. . . . . . .. . 156
6.7 ReactivityoftheEncapsulatingAgent. . . . . . . . . . . . . . . . . . . . . 157
6.8 MulticomponentMaterials. . . . . . . . . . . . . . . . . . . . . . . . . . . . . 158
6.9 GraftingNanosizedMaterialsontoaSubstrate. . . . . . . . . . . . . . . 160
6.9.1 GraftingofPre-formedNano-Objectsthrough
Monolayers. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 163
6.9.2 GraftingPre-formedNano-ObjectsintheForm
ofHybridMaterial. . . . . . . . . . . . . . . . . . . . . . . . . . . . . 164
6.9.3 SimultaneousSynthesisandDepositionof
Nano-Objects. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 164
6.10 ElectroanalyticalApplications. . . . . . . . . . . . . . . . . . . . . . . . . . . 167
6.10.1 NanosizedMaterialsinElectrocatalyticReactions. . . . . . 167
6.10.2 NanosizedMaterialsinStrippingVoltammetric
Techniques. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 169
6.10.3 NanosizedMaterialsinBio-CatalyticSensors. . . . . . . . . 171
6.10.4 NanosizedMaterialsinAffinityBiosensors. . . . . . . . . . . 172
6.11 FinalRemarks. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 174
References. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 175
7 Silica-BasedMaterialsandDerivatives. . . . . . . . . . . . . . . . . . . . . . . . 183
7.1 Clays. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 184
7.1.1 GeneralAspects. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 184
7.1.2 ElectrochemicalBehaviorofClay-Modified
Electrodes. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 187
7.1.3 DepositionofClaysontheElectrodeSurfaces. . . . . . . . 191
7.1.4 ApplicationofClaysinElectroanalysis. . . . . . . . . . . . . . 192
7.2 Zeolites. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 199
7.2.1 GeneralAspects. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 199
7.2.2 ElectrochemicalBehaviorofZeolite-Modified
Electrodes. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 200
7.2.3 DepositionofZeoliteontoElectrodeSurface. . . . . . . . . 202
7.2.4 AnalyticalApplications. . . . . . . . . . . . . . . . . . . . . . . . . 203
7.3 AdditionalSilica-BasedMaterials. . . . . . . . . . . . . . . . . . . . . . . . 208
7.3.1 SilicaGel. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 209
7.3.2 Sol-Gel. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 210
References. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 215
AbouttheAuthors. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 221
AbouttheEditor. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 223