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Russian Journal of Electrochemistry, Vol. 38, No. 7, 2002, pp. 794–797. Translated from Elektrokhimiya, Vol. 38, No. 7, 2002, pp. 889–893.Original Russian Text Copyright © 2002 by Grinberg, Davydov, Kuznetsov, Petrii, Pleskov, Tsirlina.

Annual meetings of the International Society ofElectrochemistry (ISE) are the most important events inthe world of electrochemistry. The 52nd Meeting,which was held in San Francisco, gathered nearly 2000scientists, of which nine were from Russia. The Meet-ing’s program comprised 17 symposiums and two exhi-bitions: of electrochemical equipment and publicationsby numerous companies and publishers. This was ajoined meeting of ISE and The Electrochemical Society(ECS). Although in the number of participants theMeeting was inferior both to the preceding Meeting inParis in 1997 and to other ECS meetings, still it wasattended by more persons and turned more dramatic inthe number of presentations (1575) than annual ISEmeetings. This is mainly due to its wide scope; indeed,some symposiums were dedicated to problems of solid-state chemistry, traditional for ECS, for example, SixthInternational Symposium on Quantum Confinement;Tenth International Symposium on the Physics andChemistry of Luminescent Materials; Seventh Interna-tional Symposium on Diamond Materials; a Sympo-sium on the Fullerene Nanotechnology; symposiumson thin-film materials, different problems of chemistryand physics of semiconductors and related technolo-gies.

Main electrochemical topics (symposiums) at theMeeting were the following: batteries; fuel cells andconducting polymers; corrosion; electrochemical depo-sition and dissolution; energy and electrochemical pro-cesses for cleaner environment; chemical and biologi-cal sensors and analytical methods; interfacial struc-ture, kinetics, and electrocatalysis; semiconductorelectrochemistry and photoelectrochemistry; and bio-electrochemistry and organic electrochemical reac-tions.

The new ISE award recently established, theFrumkin Memorial Medal, was announced to have beenawarded to Prof. Lev Krishtalik, Principal Researcherof the Frumkin Institute of Electrochemistry, RussianAcademy of Sciences. The Award is to be presented toKrishtalik at the 53rd ISE Meeting in Düsseldorf, 2002.

An important part of the scientific program wasdevoted to processes and phenomena in solids, mainlyin silicon. In his plenary lecture, B. Batlog (US) dis-cussed the transport of charge carriers injected intoorganic crystals by an electric field. In these systems,abnormally high concentrations of charge carriers can

be reached in near-surface layers, which can give rise tosuperconductivity in the materials.

The symposium

Quantum Confinement

demon-strated a steady trend toward miniaturization, in partic-ular, to designing nanosized transistors (G. Timp, US),the more so, one-electron transistors in quantum wires(T. Wang, China). New ideas were highlighted, e.g. useof quantum dynamic memory (S. Bandyopadhyay,US).

Chemical power sources, fuel cells, supercapacitors,and their combinations were among central topics at theMeeting. The attention was focused on lithium batteriesand the electrode materials and electrolytes therefor.The state-of-the-art power sources based on aqueouselectrolytes also were discussed, in particular, thenickel–metal hydride batteries and electrodes therefor.Of cathodic materials for lithium batteries, LiMn

2

O

4

,LiCoO

2

, and their derivatives are most attractive. In thesymposium

Fuel Cells and Conducting Polymers,

thediscussion was centered on the membranes for directmethanol fuel cells, novel membranes for fuel cells,novel types of catalysts, and new ways for synthesizingoptimum catalysts. Molten-carbonate-based fuel cellswere discussed in separate sessions. U. Stimming (Ger-many) analyzed the perspectives for studying fuel cells.Of them, most important are the studies aimed atincreasing the cell power, preventing the noble-metal-based electrocatalysts poisoning with carbon monox-ide, and using nanosized particles in the preparation ofelectrocatalysts enhancing the anodic and cathodicreactions. Preparation of electrocatalysts for methanoloxidation was discussed in several papers. C. Lamy(France) deposited a Pt

0.8

Ru

0.2

alloy on a Vulkan C-72carbon substrate by using galvanostatic cathodicpulses. The alloy appeared very active in the methanoloxidation at 110

°

C. A. Wieckowski (US) used electro-chemical nuclear magnetic resonance spectroscopy(EC-NMR) combined with the potentiodynamic andradio-tracer techniques in his studies of a platinum cat-alyst covered with ruthenium nano-particles. Heshowed that adding ruthenium to a platinum catalystweakened the Pt–CO bond, activated the surface water,and accelerated the surface diffusion of carbon monox-ide toward the Pt/Ru active sites. Of great interest ispaper of T. Duvdevani (Israel) on the hampering ofmethanol crossover in the cathode compartment of afuel cell by replacing Nafion membranes by nanopo-

Joint 52nd Meeting of the International Societyof Electrochemistry and 200th Meeting of The Electrochemical

Society, San Francisco, September 2–10, 2001

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rous proton-conducting membranes and using ethyleneglycol and dimethyl oxalate as new fuels in the direct-oxidation fuel cells. Membranes other than Nafion werealso discussed in the symposium.

At the symposium

Interfacial Structure, Kinetics,and Electrocatalysis

, O.A. Petrii (Russia) reported onthe new achievements in studying anion electroreduc-tion at high negative electrode charges (close to theactivationless region). A special session was dedicatedto problems in the electrochemical nano-engineering.This topic was covered in papers delivered byTh. Wandlowski (Germany), on the structure of goldsurfaces during their polarization in the presence ofadsorbates; G.A. Tsirlina (Russia), on inorganic spac-ers; W. Plieth, on the stability of nanosize metal clusterson foreign substrates; U. Stimming (Germany), on thereactivity of metallic nanoparticles; B. Pettinger (Ger-many), on the tip-enhanced Raman spectroscopy;N. Tao (US), on the electrochemistry of atomically-thinmetallic wires; and by V. Komanicky and W.R. Fawcett(US), on a novel procedure for fabricating single-crys-tal gold electrodes. B. Sapoval (France) demonstratedthe possibility of transfer from a smooth electrode to a3-D fractal one by changing the frequency of appliedpotential.

Of great interest are studies of electron tunnelingthrough molecular layers. For example, K. Slowinskiand M. Majda (US) presented new data on the tunnel-ing of electrons between two mercury droplets throughadsorbed alkane thiol layers; they showed that the layerdisordering hampered the tunneling.

Interesting data on the behavior of individual facesof single crystals were presented by N. Markovic andPh. Ross (US), R. Adzic (US), V. Macagno (Argentina),E. Lust (Estonia), S.-G. Sun (China), M.S. Zei (Ger-many), J. Feliu (Spain), and others.

S. Sek and R. Bieliewicz (Poland) studied the effectsof hydrogen bonds formed between alkyl chains on theelectron tunneling. Structure transitions in self-assem-bled alkane thiol layers were dealt with in a paper ofM. Schweizer and D. Kolb (Germany). J. Lipkowski(Canada) reviewed data obtained by his group, con-cerning the structure and reactivity of mono- and bilay-ers of amphiphilic neutral and ionic surfactants, as wellas models of biomembranes. By using a complex ofexperimental techniques, the effect of an electric fieldon the stability of mixed bilayers was found.

Interestingly, the adsorbed monolayers can rectifyan electric current, as R.M. Metzger (US) showed. Fur-ther studies can possibly result in designing molecular-electronics devices based on electrochemical systems.

Many papers delivered at the symposium

Bioelec-trochemistry and Organic Electrochemical Reactions

dealt with the electron exchange between electrodesand biological macromolecules. A keynote lecture onthe theory of redox reactions involving electron tunnel-ing was presented by A.M. Kuznetsov (Russia). Thebasic effect discussed in most papers is caused by dif-

ferent orientation of macromolecules and their bondingto electrodes, that is, the factors affecting the distanceof the molecules’ active center from the metal surface.Preparative electrosyntheses of important organic com-pounds were also discussed, e.g. by J. Lessard (Can-ada), who synthesized 5- and 6-nitrobenzofuranes; P.Mussini (Italy), who successfully performed effectiveelectrocatalytical reduction of alkyl halides on silverelectrodes; and V. Grinberg (Russia), who presented hisdata on selective electrode processes involving fluo-roolefins.

Quite unexpectedly, the symposium

Diamond Mate-rials

was completely devoted to the diamond electro-chemistry. This is because the European Conference“Diamond-2001” was held in Budapest concurrentlywith the San Francisco Meeting, and the studies of dia-mond other than electrochemical were presented there.

Among basic studies, we find the paper of S. Eaton,Yu.V. Pleskov, Yu.E. Evstefeeva,

et al

. (US, Russia)where the electrochemical behavior of n-type diamondwas studied for the first time. Until recently, no appro-priate donor dopant has existed, which would impartroom-temperature conduction to diamond; therefore,electrochemical studies were performed entirely withboron-doped p-type diamond. Two years ago T. Ando(Japan) reported sulfur as a shallow donor in diamond;however, this report was disproved by R. Kalish(Israel), who showed the Ando’s films to be p-conduct-ing, due to the boron impurity (probably, the residue ofprevious syntheses in the same reactor). This discrep-ancy between the results of two groups was reconciledin the electrochemical investigation. The sulfur impu-rity turned to impart n-conductance to diamond,indeed: this was proved by the sign of the slope ofMott–Schottky plots, as well as the photopotential andthermoelectromotive-force sign. Importantly, boronshould also be added to the source gas, to make the sul-fur doping effective (probably, volatile sulfur–boroncompounds are adsorbed on the diamond surface, andthus sulfur easier builds itself into the growing diamondcrystal lattice). However, the B : S ratio in the sourcegas should not exceed some critical value, otherwisethe excessive boron overcompensates sulfur, which wasprobably the case in the Ando and Kalish works.

Yu.V. Pleskov (Russia) showed the differencebetween the impedance and the kinetic characteristicsof individual faces of diamond single crystals to be pri-marily associated with different acceptor concentra-tions in them, due to different ability of the faces to trapboron during the synthesis of diamond.

The composition of diamond film surface properand its effect on the electrode properties, was dealt within several papers. According to M. Alexander (UK),oxygen chemisorption on moderately boron-doped dia-mond reveals its semiconductor nature, whereasadsorption of hydrogen imparts a metal-like behavior todiamond. J. Foord (UK) described various methods ofthe modification of diamond electrode surfaces (depo-

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GRINBERG

et al

.

sition of noble metals, electrooxidation and electrore-duction, passivation) and their effects on the electro-chemical reactions involving organic dyes, contami-nants, etc.

Of great interest are spectroelectrochemical studies,in which diamond films were used as electrodes trans-parent in IR and visible light. H. Martin (US) usedspectra of multiple inner total reflection of IR light fordetermining the coverage of diamond surface byadsorbed oxygen during anodic polarization; J. Zak(Poland) studied the kinetics of the K

3

Fe(CN)

6

oxida-tion at diamond anodes by recording absorption spectrafor a near-electrode layer of solution.

Diamond electrodes are very effective in the anodicoxidation (destruction) of organic contaminants, e.g.phenol (W. O’Grady, US), pentachlorophenol(L. Avaca, Brazil), 1,4-difluorobenzene (F. Okino,Japan). And yet, electrocatalytical activity of diamondleaves much to be desired. Therefore, attempts weremade to deposit catalysts on diamond surfaces. I. Duo(Switzerland) coated diamond electrodes with IrO

2

film(IrO

2

is a well-known catalyst for anodic reactions).The diamond substrate is superior to metal (Ti, Ta, etc.)substrates in that no metal impurities are transferred toIrO

2

during its deposition, which could deteriorate itselectrocatalytic activity. J. Wang (US) developed amethod of attaching platinum clusters to diamond elec-trode surfaces.

Among the applied studies, we address A. Fujish-ima’s (Japan) paper first. He reviewed the electroana-lytical applications of diamond electrodes, referring tonumerous examples of detecting important biologicalobjects used in medical diagnostics: uric acid (in bloodand urine), caffeine, theophylline, etc. In some cases,electrode surfaces were modified by nanosized parti-cles of Ni, Cu, and other metals, e.g. for assaying glu-cose.

W. Haenni (Switzerland) suggested to disinfectwater in swimming pools by active chlorine producedby oxidation, at diamond anodes, of chlorides presentin water (either natural or added on purpose). Electro-chemical generation of active chlorine is much moreeffective in disinfecting than the traditional chemicalprocedure (by adding hypochlorite).

The two aforementioned papers are supplementedby papers presented by German and Swiss researchersat the symposium

Energy and Electrochemical Pro-cesses for Cleaner Environment.

In these studies, per-formed in close cooperation with industry companies,electrodes DiaChem® were applied. The electrodeswere fabricated by depositing diamond heavily-dopedwith boron onto grids, plates, or cylinders made of met-als (Nb, Ti, Ta, etc.), ceramics, graphite, and othermaterials. They have a surface area of up to 0.5 m

2

. Theelectrodes are used in purifying industrial waste waterfrom organic contaminants in automobile manufacture(M. Fryda, Germany); from CN

–

, in electroplating(T. Matthée, Germany); and in synthesis of ozone and

peroxodisulfate (W. Haenni, Switzerland). S.-G. Park(Korea) suggested using the anodic ozone in homewashing machines.

In addition to crystalline diamond, the electrochem-ical behavior of amorphous diamond-like carbon (inparticular, doped with N or Pt) was discussed byB. Miller (US) and Yu.V. Pleskov (Russia).

Symposium

Corrosion

was held as two concurrentsessions; it was devoted to the following topics: passiv-ity; film destruction and pitting; local corrosion;adsorption, inhibition, and formation of films; protec-tion with polymer films; high-temperature corrosion;safety of materials and electronic devices; and atmo-spheric corrosion. The symposium comprised 178 oraland poster presentations, with a separate sessiondevoted to papers of researchers winning ISE and ECSawards: N. Sato (Japan) “Surface Oxides in MetallicCorrosion” (ECS Palladium Medal); D.D. Macdonald(US) “Theory of the Transpassive State” (ECSH.H. Uhlig Prize); E. Akiyama (Japan) “Enhancementof Corrosion Resistance of Amorphous AluminumAlloys by Alloying Additions” (ISE Hans-Jürgen-Engell Prize); S.F. Nitodas (Greece) “Chemical VaporDeposition of Silica, Alumina, and Aluminosilicatesfrom Mixtures of Aluminum Trichloride, Chlorosilane,Carbon Dioxide, and Hydrogen” (ISE Moris CohenAward).

Symposium

Electrochemical Deposition and Disso-lution

was opened with the Pergamon ElectrochimicaActa Gold Medal address of A.J. Arvia (Argentina)“Microscopic Studies of Molecular Adsorption onSolid Metal Electrode Surfaces”. Of the 144 oral andposter presentations, a great majority dealt with the fol-lowing topics: the adsorption and initial stages of elec-trocrystallization; electrochemical deposition of semi-conductor, magnetic metal, or oxide films; preparationof polymer–metal, metal–ceramics, and organic–ceramics deposits; plating of multilayered metal coat-ings in a pulsed mode; effects of organic additives andcomplexing agents on the plating process and proper-ties of deposited metals and alloys; electroless (chemi-cal) deposition of metal and alloy films; studies of thestructure and properties (protective, magnetic, etc.) ofcoatings; metal plating on non-traditional substrates(e.g., a nanostructured Ni–W film for catalyst prepara-tion; a porous anodic oxide film on Al); manufacturingof diverse metallic structures by template-based plat-ing; local electrochemical deposition and etching ofmetals; behavior of anodes in galvanic baths; photo-electrochemical etching of semiconductors; and elec-trochemical size-machining of metals. The Russiangroup of electrochemists was represented by A.D. Da-vydov’s paper “Effect of Natural Convection on theAnodic Dissolution of Metals.”

At a very representative symposium

Chemical andBiological Sensors and Analytical Methods

, the follow-ing problems were discussed: amperometric and poten-tiometric sensors; EQCM-based sensors; biological

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sensors with different detecting techniques; environ-mentally-oriented sensors; specialized sensory sys-tems, in particular, those using scanning electrochemi-cal microscopy and microflow devices; optical sensors.A.A. Karyakin (Russia) presented a paper “PrussianBlue and Its Analogues for Designing Chemical andBiological Sensors.”

Administrative problems were discussed during theISE General Assembly. Among new initiatives of ISE,we call first and foremost: opening an ISE on-line site;establishing, beginning with 2003, additional springmeetings (the first spring meeting will be held at Ali-kante, Spain); and free access to the “ElectrochimicaActa” site for each ISE member. However, the latter ini-tiative requires that the membership fee be almost dou-bled, and the idea was opposed by the Russian (andmany other) representatives. All these topics were dis-cussed lively by National Secretaries and DivisionOfficers during their sessions preceding the General

Assembly. We note that the Russian group is the solegroup that increased its membership during 2000/2001;in all other countries, practically no new membersentered ISE. This rise is undoubtedly due to the freeadmission announced at the Warsaw ISE Meeting andthe Moscow Frumkin Symposium; and the increasingmembership fees may start the reverse process. Wehope, however, that the negotiations with the ExecutiveCommittee, started in San Francisco, will successivelyretain the membership fee at the present level.

The group of Russian researchers attended the SanFrancisco Meeting owing to financial assistance of theRussian Foundation for Basic Research and the Meet-ing Organizers.

V. A. Grinberg, A. D. Davydov, A. M. Kuznetsov,O. A. Petrii, Yu. V. Pleskov, and G. A. Tsirlina