Post on 08-Mar-2020
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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