Table Of ContentFritz Scholz · Uwe Schröder
Rubin Gulaboski
Antonio Doménech-Carbó
Electrochemistry
of Immobilized
Particles and
Droplets
Experiments with Three-Phase Electrodes
2nd Edition
Electrochemistry of Immobilized Particles
and Droplets
ThiSisaFMBlankPage
Fritz Scholz (cid:129) Uwe Schro¨der (cid:129) Rubin Gulaboski (cid:129)
Antonio Dome´nech-Carbo´
Electrochemistry
of Immobilized Particles
and Droplets
Experiments with Three-Phase Electrodes
2nd Edition
FritzScholz UweSchro¨der
InstituteofBiochemistry Inst.ofEnvironm.andSustain.Chemistry
UniversityofGreifswald TechnicalUniversityBraunschweig
Greifswald,Germany Braunschweig,Germany
RubinGulaboski AntonioDome´nech-Carbo´
FacultyofMedicalSciences Dept.ofAnalyticalChemistry
GoceDelcevUniversity UniversityofValencia
Stip,Macedonia Burjassot,Spain
ISBN978-3-319-10842-1 ISBN978-3-319-10843-8(eBook)
DOI10.1007/978-3-319-10843-8
SpringerChamHeidelbergNewYorkDordrechtLondon
LibraryofCongressControlNumber:2014953771
©SpringerInternationalPublishingSwitzerland2015
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)
Foreword to the First Edition
Fundamental Electrode Kinetics is represented by treatments of reactions such as
O +4H++4e(cid:1)Æ2H O,stillimportantinthetheoryofelectrocatalysis.Asforthe
2 2
cutting edge in electrochemistry is concerned, that is now far away into areas of
complexity. In this fascinating book, Professor Scholz and his colleagues have
writtenacademicallyaboutagroupofphenomenaborderingonpracticalreality.
The material in the book develops out from a vast change which came to
electrochemistry in the 1960s when it was realized that metals were not the only
materialswhichcouldactaselectrodes:germaniumandsiliconwerethefirsttobe
examined, but the leading principle which allowed such developments was the
many orders of magnitude change in conductivity which is brought about by
impuritiesnaturallypresentoradded.
ProfessorScholz’booktakesacertaingroupofmetallicandnonmetallicmate-
rials—immobilized particles and droplets—and presents their electrochemistry.
Much of this detailed work involves three-phase boundary and many fuel cell-
oriented electrochemists will be familiar with something similar arising in the
theoryofsometypesofporouselectrodes.
The treatments in this book are certainly modern—to make sure of this, the
authors have a preliminary chapter in which they compress a description of work
before about 1990, dealing, e.g., with colloids and sandwich electrodes. Then
comes Chapter 2 in which three-phase electrodes are met. After that comes a
solid chapter on the experimental methods of the field: for example, how does
one immobilize small particles for measurement or attach droplets? Chapter 4 is
called Hyphenated Techniques and it brings out the applications to the field of
spectroelectrochemistry. Chapter 5 concerns immobilized particles and here we
realizethefullcomplexityofthesystemstreated,e.g.,voltammogramsareshown
ofsystemscontainingseveralphases;andrelevantdataontheelectrochemistryof
minerals is described. The theory of such systems is presented with impressive
clarityanddetail.
v
vi ForewordtotheFirstEdition
The last chapter (6) is about droplets and the electrochemistry of compounds
dissolvedthereinandincludesaproperlymoderndiscussionoftheelectrochemistry
ofliquid–liquidinterfaces.
Treatments of the thermodynamics of these systems is fully described, but the
kinetic treatments are less than full because of the interplay of resistance effects,
concentrationoverpotential,andthebasicelectrontransferkinetics whichisposi-
tion dependent. There is good opportunity for impedance spectroscopy in these
systems. Descriptions of many electrochemical events seldom met elsewhere is
given,e.g.,iontransferfromwatertonitrobenzene,atom-forcemicroscopytostudy
immobilized silver nanocrystals and their oxidation, which proceeds via an
oversaturatedsilverhalidesolution.
The book gives strong attention to quartz crystal microbalance, able to record
changesofnanograms.Impressivesensitivityof10(cid:1)3Kisexhibitedbyequipment
usedtodetermineentropy changesinhexacyanoferrates. Thedescriptiongivenin
Chapter 4 of the thermodynamics of minerals is impressive—and will find appli-
cation,e.g.,inrechargeableMnO cells.Descriptionsofthepenetrationofparticles
2
byredoxreactionsthroughmicrocrystalstypifysomeofthematerial.
I read this book with increasing pleasure. It is certainly specialized, but in my
opinionitssignificanceisgreatlyincreasedbythefactthatitclearlyrepresentsan
attempt by these German colleagues to gather descriptions of work closely
approaching that of real systems—and for that they should be greatly thanked,
andtheirbookwidelydistributed.
Gainesville,FL JohnO’M.Bockris
Preface to the Second Edition
The Firstedition of this book has been published in 2005. Now, 9 years later, the
number of publications in the field of immobilized particles and droplets has
increased by more than one third, and the authors felt the need to present these
newdevelopments.TheauthorsofthepreviouseditionareverygladthatProfessor
Antonio Dome´nech-Carbo´ (University of Valencia, Spain) was so kind to join as
coauthor. He has very extensively contributed to the further development of
electrochemical techniques based on solid particles immobilized on electrode
surfacesand has indeed opened new horizons.Most ofthe new text inthe second
edition has been written by him, so that finally it can be said that all 4 coauthors
haveequallycontributedtothesecondedition.
Theentire secondedition hasbeenthoroughly revised,updated, and corrected.
The book is now organized in such way that each chapter is self-consistent with
respect tothe references. The Backmatter again contains a complete bibliography
ofallpaperswhichhavebeenpublishedinthistopic.Ofcourse,onlythosepapers
have been included where an immobilization of particles was made with the
deliberategoaltostudythepropertiesoftheimmobilizedsolidparticles.
Greifswald,Germany FritzScholz
September2014
vii
ThiSisaFMBlankPage
Preface to the First Edition
Electrochemistry provides a range of powerful techniques, which can be used to
study liquid electrolyte solutions, solid electrolytes, metal and semiconductor
electrodes, as well as mixed ion and electron conductors. The most important
questionindecidingontheapplicabilityofelectrochemicaltechniqueshasalways
beenonthehowofmakinganelectrodeorasolutionofacompoundtobestudied.
Thishassetthemostseriouslimitationstogeneralapplications.Animportantstep
forwardintheapplicabilityofelectrochemistryhasbeenachievedbyshowingthat
amechanicalimmobilizationofparticlesontothesurfaceofinertelectrodesallows
electrochemicalmeasurementsonanycompoundormaterial,provideditdoesnot
dissolveintheelectrolytesolution.Organicliquidsandsolutions immisciblewith
aqueouselectrolytesolutionscanbeimmobilizedonelectrodesurfacesintheform
ofdroplets.Theelectrochemistrypresentedinthismonographisverydiversewhile
thereisonecommonfeature:allelectrodeswithimmobilizedelectroactiveparticles
and droplets are characterized by electron transfer and an ion transfer occurring
simultaneously at one and the same electrode. As a result, the model of a three-
phaseelectrodewillbetheguidingprinciplethroughouttheentirebook.
Thismonographsummarizesthecontentofmorethan300publicationslistedat
the end of the book in a bibliography. They are referenced as, e.g., “B 235.”
Additionalreferencesthatdonotbelongtothebibliographyarecitedasfootnotes
ontherespectivepages.
The book introduces the experimental basis and theoretical foundations of the
electrochemistryofimmobilizedparticlesanddroplets.Theauthorsareawarethat
variousresultsandtheoreticalconsiderationsfromotherfieldsofelectrochemistry
woulddeservetobementionedaswell;however,thescopeofthisbooklimitssuch
detail.
The mechanical immobilization of particles and droplets on electrode surfaces
hasprovedtobeusefulforsolvingbothfundamentalandappliedissues:quantita-
tive analysis of alloys, qualitative detection of alloy phases, study of the
ix
