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A Wide Variety of Electrochemistry As Irresistible Attraction

ou bien

Le charme discret de l'électrochimie dans sa diversité

Nice, September 29, 2010

Oleg A. Petrii

Award lecture

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Experimental verification of the charge transfer theories

Electrocatalysis

Surface thermodynamics of the perfectly polarizable electrode

Electrochemical material science

My Variety of Electrochemistry

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Tatyana A. Kryukova

Nina V. Fedorovich

T.A.Kryukova,

Peroxodisulfate reduction at thedropping mercury electrode andthe effect of the electric field ofthe electrode surface on the proceeding of electrochemicalreaction

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[Fe(CN)6]3- S2O82- [PtCl4]2-

Various supporting electrolyteconcentrations, mM

10

1

510

100

1 10

1000

Typical effect of cation nature(decrease: Cs…Li)

and corresponding CTP

Galina M. Florianovich

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A.N.Frumkin and A.D.Obrucheva

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R. Kh. BurshteinM. I. Temkin

Grahame’s visit to Moscow, 1956

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Karpov Institute (Moscow), 1935

A.N.BakhN.A.Bakh

Frederic and Iren Jolio-Curie

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I thank Prof. Cl.Bues-Hermann for her kind help.

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Reactant charge

Supporting ion charge

Corresponds to constantelectrode charge, if it is high enough

First published in: A.N.Frumkin, O.A.Petrii, Doklady AN SSSR, 1962, v.147, p.418.

Next step: O.A.Petrii, B.B.Damaskin, Elektrokhimiya, 1974, v.10, p.756.

Later (for ion pairing complications): G.A.Tsirlina, O.A.Petrii, Russ. J.Electrochem., 2003, v.39, p. 323-327 and Refs therein

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Corrected Tafel Plots: logI - ψ’ vs. E –ψ‘

peroxodisulfate

hexacyanoferrate

JACS, 1961, v.83, 3396-4000

Original idea:

Li

LiNa

KCsKCs

Cations effect is still a challenge

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H2PtCl6

K2PtCl4

On the mechanism of electrochemical reduction of platinum halogenide complexesat the dropping mercury electrode, Zh. Fiz. Khimii, 1961, v.35, 1270-1277.

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15

10

5

0

–5

–10

–15

–20

lg (arbitrary units)i

–2,0 –1,5 –1,0 –0,5 0 0,5 1,0E E – , Vq=0

Frumkin

LDKMarcus

n

Experimental data forK Fe(CN) on Hg 3 6

[ ]( ) ( )RT

FCkRTFn

j si

//

lnln ψϕαψ −−=+

}kT/)z,(Eexp{)z()(f)(dzd]C[Fj aeFDz

ef

min

εΔκεερεπ

ω−⎟⎟

⎠

⎞⎜⎜⎝

⎛= ∫ ∫

+∞

∞−

∞

2),( zEa εΔ tottotifi E/)EF(W 42εΔ −++=

Frumkin:

Levich-Dogonadze-Kuznetsov (LDK):

Hexacyanoferrate reduction – activationless process

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J. Heyrowsky and A.N. Frumkin in Prague, 1964

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Peroxodisulphate reduction affectedby tetrabutyl ammonium cation

Current-time curves of anions reduction on the dropping electrode

Various types ofoscillations observedfor cation-affectedreduction of anions

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O.A.Petrii,Doklady AN SSSR,160(1965)871-874

On the activity of electrolytic mixed platinum-rutheniumdeposits in methanol electrooxidation reaction

Recommended by Academician A.N.Frumkin, August 6, 1964

H2PtCl6 + K2Ru(NO)Cl5, 5-10-23-30-100 wt.% Ru; Pt foil supportFurther studies:

1964-1970, with participation of V.EntinaO.A.Petrii, V.E.Kazarinov, Elektrokhimiya 1(1965)1389106Ru radiotracer technique: K2

106Ru(NO)Cl5, galvanostatic

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Pt/Pt

Raney Pt-Ru,5; 10; 20 wt.%

Electrodeposited Pt-Ru(10 wt.% Ru)

Entina, Petrii, Zhitnev,Elektrokhimiya 3(1967)344

Steady-state data for sol-gel Pt-Ru catalyst, fromJ.Y.Kim, Z.G.Yang, C.-C.Chang, Y.I.Valdez, S.R.Narayanan, P.N.Kumta, J.Electrochem. Soc. 150(2003)A1421

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nitrite

nitrate

Electrocatalytic reduction of inorganic anions on Pt metals

Peroxodisulfateon Pt(111)

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Picasso portrait: manual to study the electrode kinetics

1965

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Surface thermodynamics of the perfectly polarizable electrode

Ox R edne ⎯⎯→+ ←⎯⎯

ReOx ddE d dμ μ= −Nernst Equation

Re Reox Ox d d i ii

d d d dσ μ μ μ= −Γ −Γ − Γ∑Gibbs Equation

Ox

Re

When ,

d i ii

constd dE d

μ

σ μ

=

= Γ − Γ∑RedWhen ,

Ox i ii

constd dE d

μ

σ μ

=

= −Γ − Γ∑

( ) Re,Ox i

dE μ μσ∂ = Γ∂ ( )

Re ,d iOxE μ μ

σ∂ = −Γ∂

Two Lippman Equations:

Re Re , d d ox OxA Aε εΓ = − + Γ = +

Total charges:

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Hydrogen electrode (platinized platinum)

H H HA HA CA CAd d d dσ μ μ μ= −Γ −Γ −Γ

,

,

,

CAH

H CA

CAH

H

rr

HH

r

EE

E

μ μ

μ

μ μ

μ

+

+

+

+

Γ

∂Γ⎛ ⎞⎜ ⎟∂⎝ ⎠⎛ ⎞∂ =⎜ ⎟∂ ∂Γ⎛ ⎞⎝ ⎠ ⎜ ⎟∂⎝ ⎠

,H CA

rdl total

H

EC Cμ

μ +Γ

⎛ ⎞∂= ⎜ ⎟∂⎝ ⎠

Isoelectric shift

Total capacity

Double layer capacity

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Experimental techniques to verify surface thermodynamics concept

t – the quantities related to the total electrode charge

f – related to free electrode charge

Still possible to apply only to the electrodes of high true surface area

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1 1 2 2d d dσ μ μ= −Γ −ΓCoadsorption

1 2

1 2

2 1μ μμ μ

∂Γ ∂Γ⎛ ⎞ ⎛ ⎞=⎜ ⎟ ⎜ ⎟∂ ∂⎝ ⎠ ⎝ ⎠

B.B.Damaskin, O.A.Petrii, V.E.Kazarinov,Elektrokhimiya, 1972, v.8, p.1373.

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Free electrode charge: pH dependence

Hydrogen region,

0H

A + = ( )0

2.3 1

1r

H

H E

RTEpH F

Aε +=

∂ = −∂ ∂Γ⎛ ⎞− ⎜ ⎟∂⎝ ⎠0OHOxygen region, A − =

( )0

2.3 1

1r

r

OH

H E OH

H E

RT AEpH F Aε +

+

=

⎛ ⎞∂∂ = − ⎜ ⎟∂ ∂Γ ⎛ ⎞∂⎝ ⎠ + ⎜ ⎟∂Γ⎝ ⎠0HIf A = or 0OHA =

( )0

0EpH ε =

∂ =∂

Doklady AN SSSR, 1975, v.222, 1159; 1976, v.226, 117

pH

RhPt

Chloridesolutions

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Partial charge transfer Ox R edne ⎯⎯→+ ←⎯⎯

1Ox Adn e ⎯⎯→+ ←⎯⎯2Ad R edn e ⎯⎯→+ ←⎯⎯

Re1

d

En

Σ

∂Γ⎛ ⎞= ⎜ ⎟∂Γ⎝ ⎠

2Ox

En

Σ

∂Γ⎛ ⎞= ⎜ ⎟∂Γ⎝ ⎠

ReOx dΣΓ = Γ + Γ

Na+ adsorption on Pt/Pt

sulphatechloride

bromide

iodide

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1974: Edward Kennedy visit to USSR

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The intersect of 3D electrocapillary curve

Charging curves of the 2nd kind

iodide

bromide

sulfate, cloride

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Electrochim. Acta, 1987, v.32, 37 and 649

Tungsten and chromium carbides:

Electrochemical material science

High temperature oxide superconductors

Rechargeable oxides (a brief review):

Electrochim. Acta, 1996, v.41, 2307

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Electrochemical material sciencePt-ZrO2: spillover

O. A. Petrii, S. Ya. Vasina, Yu. D. Seropegin, Russ. J. Electrochem. 1995, v.31, 1274

CeNi3 – CeCo3 system:

O. A. Petrii, I. V. Kovrigina, S. Ya. Vasina, Mater. Chem. Phys. 1989, v.22, 51

For review, see

Yu. M. Vol’fkovich, O. A. Petrii, A. A. Zaitsev, I.V. Kovrigina, Vestn. Mosk. Univ. Ser. 2, 1988, No29, 173

301974, Horiuti and Frumkin

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Alma-Ata, 1975

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Roger Parsons

Jean Clavilier

Lev Krishtalik

Sergio Trasatti

Boris Damaskin

Oleg Petrii

Electrochemistry on three foundations

«diffusion» «double layer»«electron transfer»

Material science

1999

2009

Bio

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Home-made movie, 1965