Table Of ContentScanning Electrochemical
Microscopy
Second Edition
Scanning Electrochemical
Microscopy
Second Edition
edited by
Allen J. Bard
Michael V. Mirkin
Boca Raton London New York
CRC Press is an imprint of the
Taylor & Francis Group, an informa business
CRC Press
Taylor & Francis Group
6000 Broken Sound Parkway NW, Suite 300
Boca Raton, FL 33487-2742
© 2012 by Taylor & Francis Group, LLC
CRC Press is an imprint of Taylor & Francis Group, an Informa business
No claim to original U.S. Government works
Version Date: 20120215
International Standard Book Number-13: 978-1-4398-3113-7 (eBook - PDF)
This book contains information obtained from authentic and highly regarded sources. Reasonable efforts have been
made to publish reliable data and information, but the author and publisher cannot assume responsibility for the valid-
ity of all materials or the consequences of their use. The authors and publishers have attempted to trace the copyright
holders of all material reproduced in this publication and apologize to copyright holders if permission to publish in this
form has not been obtained. If any copyright material has not been acknowledged please write and let us know so we may
rectify in any future reprint.
Except as permitted under U.S. Copyright Law, no part of this book may be reprinted, reproduced, transmitted, or uti-
lized in any form by any electronic, mechanical, or other means, now known or hereafter invented, including photocopy-
ing, microfilming, and recording, or in any information storage or retrieval system, without written permission from the
publishers.
For permission to photocopy or use material electronically from this work, please access www.copyright.com (http://
www.copyright.com/) or contact the Copyright Clearance Center, Inc. (CCC), 222 Rosewood Drive, Danvers, MA 01923,
978-750-8400. CCC is a not-for-profit organization that provides licenses and registration for a variety of users. For
organizations that have been granted a photocopy license by the CCC, a separate system of payment has been arranged.
Trademark Notice: Product or corporate names may be trademarks or registered trademarks, and are used only for
identification and explanation without intent to infringe.
Visit the Taylor & Francis Web site at
http://www.taylorandfrancis.com
and the CRC Press Web site at
http://www.crcpress.com
Contents
Preface..............................................................................................................................................vii
Contributors.......................................................................................................................................ix
Chapter 1 Introduction.and.Principles...........................................................................................1
Allen J. Bard
Chapter 2 Instrumentation...........................................................................................................15
Fu-Ren F. Fan, Allen J. Bard, and Peixin He
Chapter 3 Preparation.of.Tips.for.Scanning.Electrochemical.Microscopy.................................25
Fu-Ren F. Fan and Christophe Demaille
Chapter 4 Scanning.Electrochemical.Microscopic.Imaging.......................................................53
Fu-Ren F. Fan
Chapter 5 Theory.........................................................................................................................75
Michael V. Mirkin and Yixian Wang
Chapter 6 Heterogeneous.Electron.Transfer.Reactions.............................................................127
Shigeru Amemiya
Chapter 7 Visualizing.and.Quantifying.Homogeneous.Chemical.Reactions.
in.Electrochemical.Processes....................................................................................157
Patrick R. Unwin
Chapter 8 Charge.Transfer.Processes.at.the.Liquid–Liquid.Interface.......................................191
Michael V. Mirkin and Michael Tsionsky
Chapter 9 Imaging.Molecular.Transport.across.Membranes....................................................233
Henry S. White and Frederic Kanoufi
Chapter 10 Potentiometric.Probes...............................................................................................275
Guy Denuault, Geza Nagy, and Klara Toth
Chapter 11 Biotechnological.Applications..................................................................................317
Benjamin R. Horrocks and Gunther Wittstock
v
vi Contents
Chapter 12 Scanning.Electrochemical.Microscopy.of.Living.Cells...........................................379
Janine Mauzeroll and Steen B. Schougaard
Chapter 13 Localized.Flux.Measurements.and.Kinetic.Imaging.at.Interfaces...........................417
Patrick R. Unwin and Julie V. Macpherson
Chapter 14 Applications.of.Scanning.Electrochemical.Microscopy.in.Corrosion.Research......451
Dennis E. Tallman and Mark B. Jensen
Chapter 15 Micro-.and.Nanopatterning.Using.Scanning.Electrochemical.Microscopy.............489
Daniel Mandler
Chapter 16 Application.to.Electrocatalysis.and.Photocatalysis.and.Surface.Interrogation........525
Joaquín Rodríguez López, Cynthia G. Zoski, and Allen J. Bard
Chapter 17 Hybrid.Scanning.Electrochemical.Techniques:.Methods.and.Applications.............569
Julie V. Macpherson and Christophe Demaille
Chapter 18 Additional.Recent.Applications.and.Prospects.........................................................635
Allen J. Bard, Fernando Cortés Salazar, and Hubert H. Girault
Preface
During.the.10.years.that.have.passed.since.the.publication.of.the.first.edition.of.this.book,.scanning.
electrochemical.microscopy.(SECM).has.evolved.substantially..The.number.of.publications.in.this.
field.has.greatly.increased,.and.their.focus.has.changed.from.proof-of-concept.experiments.to.real-
world.applications..SECM.has.been.employed.as.an.electrochemical.tool.to.study.heterogeneous.
and.homogeneous.reactions,.for.high-resolution.imaging.of.various.substrates,.including.biological.
cells,.and.for.microfabrication..This.technique.is.now.used.by.a.number.of.research.groups.in.many.
different.countries..We.think.the.time.has.come.for.a.new.edition.of.this.book.that.will.provide.
up-to-date.comprehensive.reviews.of.different.aspects.of.SECM.
All.chapters.in.this.edition.are.either.new.or.thoroughly.updated..Chapters.1.through.5.contain.
experimental.and.theoretical.background,.which.is.essential.for.everyone.working.in.this.field..
Chapter.1.covers.the.principles.of.SECM.measurements,.Chapter.2.deals.with.instrumentation,.
Chapter.3.describes.the.preparation.of.SECM.probes,.Chapter.4.covers.imaging.methodologies,.
and.Chapter.5.deals.with.theory..Other.chapters.are.dedicated.to.specific.applications.and.are.
self-contained..Although.some.knowledge.of.electrochemistry.and.physical.chemistry.is.assumed,.
the.key.ideas.discussed.are.at.a.level.suitable.for.beginning.graduate.students.
SECM.has.proved.useful.for.a.broad.range.of.interdisciplinary.research..Various.applications.
discussed.in.this.book.range.from.studies.of.biological.systems.to.sensors.to.probing.reactions.
at.the.liquid–liquid.interface..Although.we.did.not.intend.to.present.even.a.brief.survey.of.these.
diverse.areas.of.research,.each.chapter.provides.sufficient.details.to.allow.a.specialist.to.evaluate.
the.applicability.of.SECM.for.solving.a.specific.problem..We.hope.it.will.be.useful.to.all.interested.
in.learning.about.this.technique.and.applying.it.
Four.new.chapters.in.this.book.describe.recent.advances.of.SECM.in.several.areas.of.current.
interest,.i.e.,.studies.of.single.biological.cells.(Chapter.12),.corrosion.(Chapter.14),.electrocatalysis.
(Chapter.16),.and.hybrid.techniques.(Chapter.17)..Another.major.development.covered.throughout.
the.book.is.the.ongoing.shift.from.micrometer-scale.experiments.to.the.nanoscale..Recent.meth-
odological.advances.have.greatly.increased.the.capacity.of.SECM.to.characterize.interfaces.at.the.
nanoscale.and.to.obtain.molecular-level.chemical.information..To.keep.this.new.edition.to.a.man-
ageable.size,.it.was.felt.necessary.to.omit.some.material.from.the.first.edition.(e.g.,.in.Chapter.2)..
Interested.readers.should.still.be.able.to.access.this.material.from.the.first.edition.of.this.book.
In.closing,.we.thank.our.students,.coworkers,.and.colleagues.who.have.done.so.much.to.develop.
SECM..The.future.for.this.technique,.which.is.unique.among.scanning.probe.methods.in.its.quan-
titative.rigor.and.in.its.ability.to.study.with.ease.samples.in.liquid.environments,.continues.to.be.a.
bright.one.
Allen J. Bard
Michael V. Mirkin
vii
