2628

J. Electrochem. Soc.: E L E C T R O C H E M I C A L S C I E N C E A N D T E C H N O L O G Y

December 1980

Proc. R. Soc. London Ser. A, 256, 81 (1960). 45. O. D. Gonzalez and G. P a r r a v a n o , J. Am. Ceram. Soc., 78, 4533 (1956). 46. G. A. Somorjai, "Principles of Surface Chemistry," P r e n t i c e - H a l l , New J e r s e y (1972). 47. G. R. Bobb and D. M. Mason, Electrochem. Technol., 2, 129 (1964). 48. W. Weppner, Z. Naturforsch., 31a, 1336 (1976). 49. W. Weppner, J. Solid State Chem., 20, 305 (1977). 50. W. Weppner, Electrochim. Acta, 22, 721 (1977). 51. H. H. MSbius and B. Rohland, Rev. Energ. Primaire, 2, 27 (1966). 52. V. N. Chebotin, M. V. Glumov, A. D. Neuimin, and S. F. Pal'guev, Soy. Electrochem., 6, 564 (1970). 53. H. S. Spacil and C. S. Tedmon, Jr., This Journal, 116, 1618, 1627 (1969).

54. D. Yuan a n d F. A. KrSger, ibid., 116, 594 (1969). 55. Y. L. S a n d l e r and D. D. Durigon, J. Phys. Chem.,, 72, 1051 (1968). 56. D. Hoeschen, Thesis, U n i v e r s i t y of G o t t i n g e n (1966). 57. R. E. W. Casselton, Thesis, U n i v e r s i t y of London (1971). 58. P. F a b r y and M. Kleitz, in "Electrode Processes in Solid State Ionics," M. Kleitz and J. Dupuy, Editors, p. 331, D. Reidel Publishing Co., D o r drecht, H o l l a n d (1976). 59. L. Heyne and N. M. Beekmans, Proc. Br. Ceram. Soc., 19, 229 (1971). 60. J. W. Patterson, E. C. Bogren, and R. A. Rapp, This Journal, 114, 752 (1967). 61. L. D. Burke, H. Rickert, and R. Steiner, Z. Phys. Chem., N.F., 74, 146 (1971).

The Activation of Polycrystalline Gold to the Hydrogen Electrode Reaction Promoted with Repetitive Potentiodynamic Perturbations
R. C6rdova 0., M. E. Martins, and A. J. Arvfa ~
Instituto de Investigaciones Fisicoquimicas TeSricas y Aplicadas, DivisiSn Electroqu{mica, Sucursal 4, Casilla de Correo 16, 1900 La Plata, Argentina
ABSTRACT The activation of gold electrodes t o w a r d t h e h y d r o g e n electrode reaction is s t u d i e d using the p o l y c r y s t a l l i n e gold/1M H2SO4 interface at 25~ The electrode activation is p r o m o t e d b y p o t e n t i o d y n a m i c aging in the p o t e n t i a l range w h e r e the O - e l e c t r o s o r p t i o n / O - e l e c t r o d e s o r p t i o n takes place. The activation effect is c o m p a r a b l e to t h a t e a r l i e r described w h e n gold electrodes are cathodized for a r e l a t i v e l y long time in the p o t e n t i a l range of the n e t evolution of hydrogen. The activation effect is r e v e a l e d t h r o u g h the a p p e a r a n c e of a r e m a r k a b l e increase of c u r r e n t associated with the h y d r o g e n ion discharge and an anodic c u r r e n t r e l a t e d to the electrooxidation of hydrogen. F o r the latter, different contributions a r e distinguished, n a m e l y , the m o l e c u l a r H~ diffusion and those r e l a t e d to a d s o r b e d and p r o b a b l y a b s o r b e d hydrogen. The electrochemical characteristics of the gold/1M H2SO4 interface are r e l a t e d to a large e x t e n t to the r e s t r u c t u r i n g of the m e t a l surface. The energetic characteristic of the electrode surface is crucial in electrochemical kinetics. T h e r e are n u m e r o u s e x p e r i m e n t a l p r o c e d u r e s described in the l i t e r a t u r e to activate p a r t i c u l a r m e t a l electrodes such as the a p p l i c a t i o n of certain types of either c u r r e n t or potential pulses, the addition of traces of some p a r t i c u l a r species to the electrolyte solution, the p r o duction of electrodes w i t h a d e t e r m i n e d size of p a r ticles, etc. Sometimes the activation or deactivation of m e t a l electrodes depends to a large e x t e n t on the p r o p e r electrode history. This is the case of the m e c h anism of the h y d r o g e n evolution reaction on gold which is v e r y sensitive to the q u a l i t y of the gold surface (1-3). I n this respect it has b e e n r e c e n t l y shown t h a t the surface s t r u c t u r e of p o l y c r y s t a l l i n e gold electrodes i m m e r s e d in aqueous H2SO~ solutions changed when the electrochemical interface was subjected to several h u n d r e d p o t e n t i o d y n a m i c cycles in the 0-1.9V (NHE) range (4, 5). T h e electrochemical t r e a t m e n t t r a n s f o r m e d the o r i g i n a l l y d i s t u r b e d surface into a s t r u c t u r e d surface w i t h the a p p e a r a n c e of g r a i n b o u n d aries and faceting (4-7) as in the t h e r m a l etching (8). I t is c l e a r l y e l u c i d a t e d t h a t crystal orientation of gold electrodes influences the capacity of the electrical double l a y e r (4, 6, 9, 10). On the other hand, r e p e t i t i v e * Electrochemical Society Active Member. Key words: metals, electrocatalysis, voltammetry. polarization cycles in the --0.8 to 1.2V (vs. SCE) potential range produces a systematic and progressive change of the electrode surface from a (111) to a (110) structure as r e v e a l e d t h r o u g h electron microscopy and electron diffraction and changes the p o t e n tial of zero charge (4). The s t r u c t u r a l surface change is reflected in an increase of electrode activation of gold to the h y d r o g e n electrode reaction (5-7, 11) as c o m p a r e d to the adsorption of h y d r o g e n on nona c t i v a t e d gold (2, 12, 13). Values b e t w e e n 3% a n d 4% of a h y d r o g e n adsorbed m o n o l a y e r have been r e ported. The capacity m a x i m u m at about --0.2V (SCE) found at the (100) gold face, b u t not at the (110) face, was ascribed to h y d r o g e n adsorption (6). It has also been d e m o n s t r a t e d t h a t the surface r e s t r u c t u r i n g requires the electrosorption and electrodesorption of o x y g e n on the m e t a l surface (4, 5, 7, 11), b u t the influence of the p e r t u r b a t i o n v a r i a b l e s on the efficiency of the electrode surface activation concerning the h y d r o g e n electrode reaction is still not comp l e t e l y known. Therefore, in o r d e r to elucidate the p r o b l e m of the gold electrode activation, the t y p e of p e r t u r b a t i o n described in the l i t e r a t u r e to promote the p o t e n t i o d y n a m i c aging of layers of different species electrochemically formed on electrode surface (1416), was s y s t e m a t i c a l l y a p p l i e d to the gold/1M H2SO4 interface. The corresponding results are r e l e v a n t to understand, at least in part, the relationship b e t w e e n

Downloaded on 2013-09-25 to IP 138.251.14.57 address. Redistribution subject to ECS license or copyright; see ecsdl.org/site/terms_use

Vo/. 127, No. 12

ACTIVATION OF POLYCRYSTALLINE

GOLD

2629

t h e electrode surface activation and the surface r e s t r u c t u r i n g p r o v o k e d b y p o t e n t i a l p e r t u r b a t i o n s such as t h e c o m b i n e d c o m p l e x r e p e t i t i v e t r i a n g u l a r p o t e n tial sweeps.

Experimental

to p r e v e n t a n y possible c o n t a m i n a t i o n t h r o u g h the l a b o r a t o r y atmosphere. T h e electronic c i r c u i t r y is the same as e m p l o y e d in previous w o r k s (14, 15).

The e x p e r i m e n t a l p r o c e d u r e was based on t h a t d e scribed in p r e v i o u s w o r k s (14, 15). The w o r k i n g electrode (0.38 cm ~ a p p a r e n t a r e a ) consisted of a p o l y c r y s t a l l i n e spectroscopic q u a l i t y wire (Johnson, M a t t h e y ) m o u n t e d on a Teflon holder. The following electrode p r e t r e a t m e n t s w e r e i n d e p e n d e n t l y applied: (i) The gold electrode was polished w i t h a 300 m e s h A1208 p o w d e r - w a t e r suspension. The electrode was then i m m e r s e d in 1:1 HNO~-H2SO~ m i x t u r e a n d finally r i n s e d for a long time in water. (ii) The gold electrode was d i p p e d w i t h o u t a n y polishing in a 5N HNOa solution. The first p r o c e d u r e gave t h e m o r e r e p r o d u c i b l e results b u t the second one was p a r t i c u l a r l y useful to emphasize the m e m o r y effect of the used electrodes which is d e s c r i b e d f u r t h e r on. The counterelectrode (7 cm 2 a p p a r e n t a r e a ) was m a d e w i t h the same m a t e r i a l a n d a d e q u a t e l y s e p a r a t e d to e l i m i n a t e a n y diffusion of the products f r o m the c o u n t e r e l e c t r o d e section of the cell to the w o r k i n g electrode c o m p a r t ment. A n Hg/Hg2SO4 electrode p r o p e r l y p r o t e c t e d to avoid H g ( I ) diffusion into the electrolysis cell was used. Teflon tubing a n d stopcocks and joints l u b r i c a t e d w i t h the e l e c t r o l y t e solution contained in the cell w e r e employed. The electrode potentials are r e f e r r e d to the r e v e r s i b l e h y d r o g e n electrode ( R H E ) . The e l e c t r o l y t e was 1M H2SO4 solution p r e p a r e d from t r i p l y distilled w a t e r a n d A.R. 98% H2SO4 ( M e r c k ) . The distilled w a t e r was s y s t e m a t i c a l l y tested to satisfy the p u r i t y r e q u i r e m e n t s d e s c r i b e d in the l i t e r a t u r e (17). P l a t i n u m or a n y o t h e r possible elect r o d e c o n t a m i n a n t w e r e c a r e f u l l y avoided. The e x p e r i m e n t s w e r e m a d e w i t h purified gas saturation, e i t h e r N2 or H2, and e m p l o y i n g e i t h e r quiescent or s t i r r e d electrolytes. The t e m p e r a t u r e was fixed at 25~ The activation of gold electrodes to the h y d r o g e n electrode reaction b y means of the p o t e n t i o d y n a m i c aging in the O - e l e c t r o s o r p t i o n / O - e l e c t r o d e s o r p t i o n p o t e n t i a l r a n g e was s t u d i e d b y a p p l y i n g different p o t e n t i a l / t i m e p e r t u r b a t i o n programs. Runs were m a d e covering different switching potentials (Ex,~, Ex,c, a n d E'x,c), p o t e n t i a l sweep rates (v~, Vc, a n d v~) a n d d u r a tions (z) of the i n t e r m e d i a t e p e r t u r b a t i o n . The s u b scripts a, c, and i stand for the positive going (anodic) a n d n e g a t i v e going (cathodic) potential excursions a n d for the i n t e r m e d i a t e r e p e t i t i v e t r i a n g u l a r p o t e n t i a l scan ( R T P S ) , respectively. Both electrode h a n d l i n g and cell a s s e m b l i n g w e r e m a d e t a k i n g precautions

Results Quiescent N~-seturated electrolyte.--The E/I

files resulting at 0.2 V/see w i t h i n Ex~ = 1.67V a n d Ex,c : --0.2V, o b t a i n e d w i t h a n d w i t h o u t the p o t e n t i o d y n a m i c aging b e t w e e n Ex,a a n d E'x,r are c o m p a r a t i v e l y depicted in Fig. 1. The p o t e n t i o d y n a m i c aging at 0.2 V/sec was confined to a p o t e n t i a l r a n g e (Ex,a = 1.67V and E'x,r ---- 1.26V), w h e r e about o n e - h a l f of the O-containing l a y e r was i n v o l v e d in each elect r o d e s o r p t i o n / e l e c t r o s o r p t i o n cycle. The p o t e n t i a l sweep r u n i m m e d i a t e l y a f t e r the i n t e r m e d i a t e R T P S b e t w e e n Ex,a = 1.67V a n d Ex,e : --0.2V distinguishes the following features, as c o m p a r e d to the stabilized RTPS: (i) %'he shift of the O - e l e c t r o d e s o r p t i o n c u r rent p e a k t o w a r d m o r e negative potentials and its simultaneous slight increase in charge. The cathodic c u r r e n t p e a k becomes m o r e s y m m e t r i c and t h i n n e r t h a n the corresponding c u r r e n t p e a k r e c o r d e d in t h e stabilized RTPS. (ii) A r e m a r k a b l e increase of the h y d r o g e n evolution current. (iii) A net anodic c u r r e n t in the 0.1-0.4V p o t e n t i a l r a n g e w h i c h is a t t r i b u t e d to the h y d r o g e n e l e c t r o o x i d a t i o n (1, 5, 11). The p o t e n t i a l of the a n o d i c c u r r e n t p e a k r e c o r d e d d u r i n g the positive going potential sweep is located in the 0.1200.165V range. The charge QH,a r e l a t e d to the h y d r o g e n e l e c t r o o x i d a t i o n u n d e r fixed values of Ex,a, EX,c, a n d E'x,c depends on the t i m e T and on the f r e q u e n c y of the i n t e r m e d i a t e RTPS (Fig. 2). The m a x i m a l Q~,a v a l u e is o b t a i n e d at ca, 2 V/sec. W i t h i n the E'X,c r a n g e indicated in the figure and w i t h i n the 0-30 m i n range, QH,a increases with ~. The QH,a value recorded d u r i n g the negative going potential sweep, r e v e a l s a composite c u r r e n t p e a k involving at least two contributions. The m o r e positive contribution is in the 0.3-0.5V range, while the m o r e negative one is in the 0.15-0.17V range. The potentials of the anodic c u r r e n t p e a k d u r ing successive potentials sweeps are r e p r o d u c i b l e w i t h in _10 mV. The QH,a v a l u e depends s t r o n g l y on E'x,r a n d corr e s p o n d i n g l y on the percentage of the O - c o n t a i n i n g species being r e m o v e d d u r i n g the i n t e r m e d i a t e R T P S (Fig. 3). The m a x i m a l Qs,a value results at ca. 80% of the electrosorbed o x y g e n involved in the i n t e r m e d i a t e RTPS. This p e r c e n t a g e is r e f e r r e d to the charge of the O - e l e c t r o d e s o r p t i o n c u r r e n t p e a k in the stabilized E l i profile. The gold electrode, which b e came a c t i v a t e d t o w a r d t h e h y d r o g e n electrode r e a c -

pro-

(a)

c 0I]
I..-

"~,...... / , "
1~0

(1I)

O.li I \ A a AA f--E~.a ,(11)

\/~ V
~'i-\"/"-" E~,c

13
(b) ()
0 ~

!"
i

V___.
Time

2.0

Fig. 1. Potentiodynamic E/I profile resultlng from the potential/time perturbation program |ndlcat.~d in the figure. N2saturation. (a) (I) Stabilized RTPS E/I profile before the electrode activation. (ll) r First E/I display after the intermediate potentiodynamic perturbation. va = ve -" vi = 0.2 V/sec. (b) Positive potential going scans at va = 0.2 V/sec after the intermediate perturbation during different T. 1, 10 rain; 2, 20 rain; 3, 30 rain.

1.3

0.9

0.5

0.1
Potential/(V)

2630

J. Electrochem. Soc.: E L E C T R O C H E M I C A L S C I E N C E A N D T E C H N O L O G Y
10 20 30

December 1980

Time/(min)
A

~ , 0.15

0.3 % r

'E
Fig. 2. Dependence of QH.a on vi and on T. N2-saturation. Ex,a -" 1.7V; EX,~ : --0.05V; E'x,e ---- 1.09V; and V a - - ve -" v~ "- 0.2 V/sec. F: 0.10 -~ z" C~ 005

02 c~ C~ 0.1
:E

12

16

Potential tion, p r o g r e s s i v e l y deactivates w i t h a f u r t h e r p o t e n tial cycling b e t w e e n E;~,a and Ex,c. The r a t e of decrease of the electrode activation can be followed t h r o u g h the change of the r e l a t i v e charge (QH,a)n/(QH,a)I (Fig. 4) w h e r e (QH,a)n is the h y d r o gen e l e c t r o o x i d a t i o n charge a f t e r the n t h RTPS b e t w e e n Ex,a and Ex,c and (QH,~)I refers to the same charge for the first p o t e n t i a l sweep i m m e d i a t e l y after the i n t e r m e d i a t e R T P S c a r r i e d out b e t w e e n Ex,a and E'x,e. The charge r e l a t e d to h y d r o g e n e l e c t r o o x i d a t i o n decreases m o r e r a p i d l y w h e n E~,,a becomes more n e g a tive t h a n the potential which corresponds to the O-electrosorption. This r e s u l t reveals the influence of the O-electrosorption on the activation for the h y d r o g e n electrode reaction. F o r a constant set of p e r t u r b a t i o n conditions the charges QH,a and QH,c recorded d u r i n g the t r i a n g u l a r potential sweep r u n i m m e d i a t e l y a f t e r the electrode activation increase as Ex,c becomes m o r e negative, but for a fixed Ex,~, QH,a is l a r g e r t h a n QH,c (Table I). T h e r e is, however, an o p t i m a l Ex,c value (Ex,c ---- --0.05V for Va ---- vo -- 0.2 V/sec and vi -- 2 V / s e c ) at which QH,c p r a c t i c a l l y compensates QH,a. On the other hand, u n d e r the same p o t e n t i o d y n a m i c aging conditions in the O-electrosorption region, QH,a decays according to a r a t e l a w of the form QH,~ ~ t x (Fig. 5) w h e r e the e x p o n e n t x depends on the switching potentials of the t r i a n g u l a r p o t e n t i a l p e r t u r b a t i o n following the i n t e r m e d i a t e RTPS. A n a l o g o u s l y QH.~ also decreases w i t h ~p, the t i m e at which the electrode J . i . i ' B1

Sweep

Rate/(Vsec -1)

(~8

-~-=~0.4 t
.~_E~,~ ......... ,;._~_~

~ " ~ r ~

{21

0.0| n~ ~'c 0

, 2

Time ,~
4

I 6

I 8

n u m b e r of cycles Fig. 4. Relative change of QH,a as a function of the number of RTPS operating after the potentiodynamic aging. N2-saturation. Ex,a = 1.7V; Ex,~ = --0.05V; E'x,c = 1.09V; ~ = 30 min; va = vc = 0.2 V/sec. v1 : 2 v/sec. Curve 1, without covering the O-electrosorption potential range during the potential cycling. Curve 2, the O-electrosorption potential range is covered.

is held at E~,c after its p o t e n t i o d y n a m i c activation. The decay of QH,a fits a reasonable l i n e a r QH,a Vs. log Tp plot (Fig. 6).

(115

E O (D
0.10 cs cY

) 35

0,0. E

Quiescent H~-saturated solution.--In the H2-satur a t e d electrolyte the increase of QH,a is a l r e a d y o b served for E~,c = 0.0V, a potential at which no m a c r o scopic H2 gas evolution is p r o d u c e d (Fig. 7a and 7b). The electrode subjected to the p o t e n t i o d y n a m i c aging in the O - e l e c t r o s o r p t i o n / O - e l e c t r o d e s o r p t i o n potential range exhibits an anodic c u r r e n t contribution in the n e g a t i v e potential going sweep before r e a c h i n g Ex,c, w i t h two anodic c u r r e n t peaks at 0.39 and a t 0.19V, respectively. The r e t u r n i n g positive going sweep e x hibits a single anodic c u r r e n t peak. D u r i n g the t r i a n g u l a r potential cycling as Qs,a decays, a g r a d u a l shift of the anodic c u r r e n t p e a k potential t o w a r d m o r e negative potentials is observed. The heights of the anodic c u r r e n t p e a k decrease, p a r t i c u l a r l y the one
Table I. Influence of E~,c on the charges related to the hydrogen electrode reaction

0'6

,.2
E~,c/(V)
Ex, c / ( V ) --0.20 -- 0.15 -- 0.05 -- 0.05 - 0.05 -- 0.05 ( m C x c m -2) 0.58 0.46 0.37 0.33 0.17 0.40

Qma/

( m C e m -~) 9.97 2.96 0.40 0.53 0.20 0.46

Qmo/

Q~,a/Qmc
0.06 0.16 0.94 0.63 0.84 0.86

Fig. 3. Dependence of QH,a on E'x,c. N2-saturation. E~,a ~i.67V; Ex,e ~ --0.05V; va = vc = 0.2 V/s~c; vi ~ 2 V/see; = 30 rain. For each experimental point the percentage of the O-~lectrodesorptlon at E%e in the first intermediate negative potential going sweep is indicated.

Vol. 127, No. 12

ACTIVATION OF POLYCRYSTALLINE

GOLD

2631

2
E...~uI 0.2 _

.-:, __~._., ~;:

/f~', ~" E:"c -'-u

(a)

--Time

E~

~--4~

Time

2
2.1

o
0 . 1

(b) [c) ~ D

(QH)q,MQH2)

2)

1.9

(1)
. . . . . .

--~

aE_
d3

E),a

' 08

i 03

' -02

' O.g

d3

' -02

{3,8 '

-{:L2 '

~/ x, --~ 1.0

Time, 1.5

2.0 tog (t/sec )

Fig. 5. Log-log plot for the Q~,a decay. N2-saturation. The time counting starts immediately after "~ = 30 min. Ex,a ~ 1.7V; Ex,c --0.05V; E'x,o = 1.09V; va = Ve = 0.2 V/sec; vi = 2 V/see. Curve 1, the O-electrosorption potential range is covered, Ex,a 1.7V. Curve 2, without covering the O-electrosorption potentiol range during the potential cycling.

located on the m o r e positive p o t e n t i a l side. A similar q u a l i t a t i v e Eli response results w h e n the electrode is held at Ex.c = 0.0V d u r i n g ~p = 30 min (Fig. 7c) a l t h o u g h the charge is s m a l l e r t h a n that o b s e r v e d u n d e r the p o t e n t i o d y n a m i c aging. The gold electrode activation in the H2-saturated e l e c t r o l y t e is g r e a t e r t h a n that observed in the N2saturated electrolyte under comparable perturbation conditions.

Potentiatl(V) Fig. 7. Comparative E/I displays obtained after the electrode activation process with the potential/time perturbation programs indicated in the figure. H2-saturation. Ex,a = 1.7V; Ex,e = 0.0V; E'x~c = |.09V; Va - - vc - - 0.2 V/see; vi = 2 V/see; 1; = "cp = 30 min. (a) The triangular potential sweep after the potentiodynamic aging initiates toward positive potentials. The dashed lines correspond to the estimated contributions of H-adatoms and H2 in the E/I profile during the negative potential going half-cycle. Still solution. (b) The same as (a) but with solution stirring. (c) Comparative successive Eli displays (curves 1, 2 and 3) run with the electrode activated by holding the potential at Ex,r during ~p. With solution stirring.

InJ~uence of the solution stirring.--The influence of s t i r r i n g is d e t e r m i n e d u n d e r p r e s e t potential p e r t u r b a tion conditions. Thus, either for H2- or for N2-satur a t e d s t i r r e d solution, the h y d r o g e n - e l e c t r o o x i d a t i o n c u r r e n t g r a d u a l l y decreases w h e n Ex.c is b e t w e e n 0.0 a n d --0.2V a n d it increases again if the potential cycling continues and the s t i r r i n g is i n t e r r u p t e d . U n d e r the same p o t e n t i a l p e r t u r b a t i o n conditions a r e m a r k a b l e decrease of QH,a due to s t i r r i n g is

noticed in the E/I d i s p l a y r u n i m m e d i a t e l y a f t e r the p o t e n t i o d y n a m i c activation of the gold electrode. This effect, however, is significantly less in the negative going p o t e n t i a l excursion t h a n in the p r e c e d i n g positive going potential scan (Fig:. 7a a n d 7b). W h e n the gold electrode activation is p r o d u c e d b y cathodization at Ex, c = --0.2V, the solution s t i r r i n g produces a net decrease of the electrode activation. The decrease continues during the r e p e t i t i v e p o t e n t i a l cycling, especially w h e n E~,a is m o r e negative t h a n the O - e l e c t r o s o r p t i o n / O - e l e c t r o d e s o r p t i o n p o t e n t i a l range. W h e n Ex,a exceeds this v a l u e the Eli d i s p l a y r e c o r d e d d u r i n g the n e g a t i v e going p o t e n t i a l scan t h e n exhibits the anodic doublet p r e v i o u s l y r e p o r t e d (Fig. 7).

a2 ,

oz. ,

0.6 ~

0.8 ,

1,o ,

I.~

Iog(~plmin) 1;4

u (3 -r or o.~
0.2
i i I ]

Fig. 6. Decoy of QI-I,a as a function of Tp. N2-saturotion. Ex,a 1.7V; Ex,c ---- --O.2V; E'x,c ---- ].09V; T ----- 30 rain; va ---- vc 0.2 V/see; vi = 2 V/sec.

Time/(min) -~

Memory eJ~ect.--Gold electrodes, whieh w e r e r e p e t i t i v e l y activated t h r o u g h p o t e n t i o d y n a m i c aging followed b y storing for a long p e r i o d of time in a 5N HNO3 solution, e x h i b i t a r e s i d u a l activation w h e n t h e y w e r e cycled b y a t r i a n g u l a r p o t e n t i a l signal in quiescent, H2-saturated 1M H2SO4 solution b e t w e e n Ex,c -- --0.2V and Ex.a -~- 1.3V. U n d e r these conditions, the positive going p o t e n t i a l excursion shows an anodic c u r r e n t p e a k r e l a t e d to h y d r o g e n electrooxidation. The n e g a t i v e going p o t e n t i a l excursion after a p r o gressive increase of Ex.a r e p e a t s the complex m u l t i p l e E/I d i s p l a y p r e v i o u s l y described. The stable R T P S E/I profile is a t t a i n e d after about 10-15 cycles. The effect can be r e v e r s e d s i m p l y b y changing Ex,a to m o r e negative potentials. Thus, the stable RTPS Eli profile of the a c t i v a t e d electrode (Fig. 8a) changes to t h a t shown in Fig. 8b w h e n Ex.a decreases to 0.6V. Now the charge involved in the successive Eli profile in both directions decreases, as i n d i c a t e d b y the arrows, to a t t a i n the n e w stable R T P S Eli profile shown in Fig. 8c (dashed line). U n d e r these circumstances, an increase of Ex,a to 1.TV, the E l i profile first shows an increase of the c u r r e n t peaks up to a m a x i m a l v a l u e and a f t e r w a r d a slight decrease to a t t a i n a g a i n the stable profile depicted in Fig. 8d (dashed line). Finally,

2632

J. Electrochem. Soc.: E L E C T R O C H E M I C A L S C I E N C E A N D T E C H N O L O G Y

December I980

1.0

(a)

0.5 0.0

--i

(b)
0.5

/,,',,

(d)

"~'

\?

&O -0.5

L
I t r

1,0

05

0.0

1i]

0.5

&O

Potential/(V)
Fig. 8. Potentiodynamic E/I displays (Ex,c = --0.16V; va ----vc = 0.2 V/sec; ~ = rp = 20 min; H:2-saturation) run according to the following sequence. (a) E/I profile run immediately after the potentiodynamic activation. (b) Stabilized Eli profile from (a) (dashed trace) and successive E/I displays after fixing E~,a = 0.6V (full traces). (c) Stabilized E/I profile from (b) (dashed trace) and successive E/I displays after fixing Ex,a ---- 1.7V (full traces). (d) Stabilized E/I profile from (c) (dashed line) and successive E/I displays after fixing E~,a = 0.6V (full traces).

a decrease of Ek,a from 1.7V back to 0.6V produces again a decrease of the electrode activation. The m e m o r y effect disappears or it is a p p r e c i a b l y a t t e n u a t e d after m e c h a n i c a l l y polishing the electrode w i t h a water-A1208 suspension.

Discussion
The g o l d / a q u e o u s acid interface can be a c t i v a t e d for the e l e c t r o o x i d a t i o n of h y d r o g e n u n d e r either potentiostatic cathodization or after p o t e n t i o d y n a m i c a g ing in the O-electrosorption potential range. In the f o r m e r case, the effect depends on Ex.c and on ~p (3-5) while in the l a t t e r it is influenced b y E;~,a, E'Mc, v, and the f r e q u e n c y of the r e p e t i t i v e t r i a n g u l a r pot e n t i a l p e r t u r b a t i o n b e t w e e n E'x.r and Ex~a. The values of Ex,a and E'x,c d e t e r m i n e the a m o u n t of electrosorbed o x y g e n which is a l t e r n a t i v e l y e l e c t r o f o r m e d and elect r o r e d u c e d d u r i n g the i n t e r m e d i a t e RTPS. The m a x i m u m effect corresponds to a charge which is about 80% of the O - m o n o l a y e r charge on gold. A l t h o u g h both activation p r o c e d u r e s give c o m p a r a b l e results, the activation of the h y d r o g e n electrooxidation on gold p r o d u c e d t h r o u g h t h e p o t e n t i o d y n a m i c aging is a l r e a d y noticed b y holding the potential of the electrode at E ~ 0V. The activation of the gold electrode t o w a r d the h y d r o g e n electrode r e a c t i o n implies both an increase of the overall cathodic c u r r e n t r e l a t e d to the evolution of h y d r o g e n and the a p p e a r a n c e of two anodic c u r r e n t p e a k s associated w i t h the electrooxidation of h y d r o g e n on gold. The possibility that the cathodic c u r r e n t increase is due to the increase of the electrode r o u g h ness is, in principle, d i s r e g a r d e d because the charge r e l a t e d to the O - e l e c t r o d e s o r p t i o n before and after the electrode activation remains p r a c t i c a l l y the same. The two anodic c u r r e n t peaks present a different response to the solution stirring. Thus, the height of the m a i n anodic p e a k located at m o r e negative

potentials decreases s t r o n g l y b y s t i r r i n g the solution, as one should e x p e c t for a diffusion-controlled r e d o x reaction. This c u r r e n t p e a k should be r e l a t e d to the electrooxidation of m o l e c u l a r hydrogen, s u p e r s a t u r a t ing the diffusion l a y e r (18, 19). This local s u p e r s a t u r a t i o n is o n l y o b s e r v e d w i t h p r e v i o u s l y activated gold electrodes. The l a r g e s t degree of H2 s u p e r s a t u r a tion at the electrode surface is achieved t h r o u g h the cathodic potentiostatie activation a n d it depends both on the potential a p p l i e d to the i n t e r f a c e and on the time ~p. The corresponding c u r r e n t p e a k potential is displaced t o w a r d the positive p o t e n t i a l side from the H2/H+ e q u i l i b r i u m p o t e n t i a l due to the i r r e v e r s i b i l i t y of the r e d o x reaction. Most of the E/I profile r e c o r d e d d u r i n g the positive going p o t e n t i a l scan a f t e r cathodic potentiostatic activation can be r e p r o d u c e d using the equation of a r e d o x process (20) w i t h the exchange c u r r e n t density, ~ ~ 10 . 5 A / e r a 2 (2) and the estim a t e d h y d r o g e n s u p e r s a t u r a t i o n 10 -1 m o l e / l i t e r (19). The s m a l l e r anodic c u r r e n t p e a k at ca. 0.3V a p p e a r s as i n d e p e n d e n t of the s t i r r i n g of the solution. The E/I profile also indicates a possible t h i r d anodie c u r r e n t contribution at ca. 0.2V although it is m o s t l y o v e r l a p p e d b y the m a i n diffusion-controlled c u r r e n t p e a k a l r e a d y discussed. The charge of the anodie c u r r e n t p e a k at ca. 0.3V as e s t i m a t e d from the n e g a t i v e p o t e n tial going E/I display, is a l w a y s less t h a n the charge e x p e c t e d for the H - a d a t o m m o n o l a y e r (210 ~C/em2 for p o l y e r y s t a l l i n e p l a t i n u m ) (21). This charge c a n be associated w i t h the presence of H - a d a t o m s whose surface concentration should d e p e n d on a v a i l a b l e active m e t a l sites p r o m o t e d on the surface b y the p o t e n t i o d y n a m i c aging in the O-electrosorption potential range. The gold electrode activation process for the h y d r o gen electrode reaction can be i n t e r p r e t e d on the basis of the data r e p o r t e d for the dependence of the h y d r o gen overvoltage with the t y p e of gold electrode used (2). The h y d r o g e n overvoltage o b t a i n e d w i t h smooth gold electrodes a r e similar and r a t h e r high. T h e y agree w i t h calculation for EAu-H ~ 46 kcal (22, 23). F o r a smooth gold electrode, the cathodic Tafel slope is ca. 0.1 V / d e c a d e o r slightly higher and some evidence has been obtained for a l o w e r slope at l o w e r overvoltages (24, 25). Otherwise, for electrolytic gold deposits, s m a l l e r overvoltages and lower Tafel slopes a r e r e p o r t e d (24-26) especially for electrodes s u b jected to anodic-cathodic activations (1,. 27). These results m a k e it difficult to d r a w definite conclusions r e g a r d i n g the m e c h a n i s m of the reaction u n d e r stat i o n a r y conditions. But t h e y correlate w i t h the p r e s e n t data if one admits that the r e s t r u c t u r i n g of gold electrode surfaces, which was d e m o n s t r a t e d t h r o u g h optical methods (4-8), plays a significant role in defining their degree of activation. To develop a q u a l i t a t i v e f o r m a l i s m of the reactions at the gold electrode, let us first consider that it consists of a clean gold surface s t r u c t u r e which r e mains p r a c t i c a l l y u n a l t e r e d d u r i n g the potential p e r t u r b a t i o n and that no H~ is dissolved into the electrolyte. Because of the ( H ) A u bond e n e r g y value, the h y d r o g e n a d a t o m concentration on the m e t a l is p r o b a b l y v e r y low. Therefore, the following reaction steps of the electrochemical process can be proposed +e A u -b ( H + ) s ----A u Jr ( H + ) e ---- A u ( H ) a d = A u -t- 1~H2

[1]
w h e r e s, e, and ad denote the b u l k of the solution, electrode surface, and a d s o r b e d species, respectively. The reaction sequence [1] has been considered to i n t e r p r e t e a r l i e r e x p e r i m e n t a l results w i t h the a s s u m p tion that the concentration of adsorbed H is negligible and the a d s o r b e d species is w r i t t e n as a postulated reaction i n t e r m e d i a t e (22). The r a t e - d e t e r m i n i n g step u n d e r s t a t i o n a r y conditions has been assigned to the

Vol. I27, No. 12

ACTIVATION OF POLYCRYSTALLINE

GOLD

2633

discharge plus H - d e s o r p t i o n step. However, it is claimed t h a t a fraction of the h y d r o g e n atoms electroc h e m i c a l l y p r o d u c e d can p e n e t r a t e into the metal t h r o u g h a slow diffusion process. The diffusion coefficient of h y d r o g e n in gold is estimated, at 25~ equal to 4 10 -12 cm2/sec (5). Then, this means t h a t reaction sequence [1] should be w r i t t e n as follows Au + (H+)s = Au + (H+). Au+ ~H, [2a]

+e
-- A U (H)aa

A u (H) ab

[2b]

w h e r e ab stands for the a b s o r b e d hydrogen. The e l e c t r o o x i d a t i o n of a b s o r b e d h y d r o g e n w o u l d occur t h r o u g h a reaction w h i c h m a y be either u n d e r a c t i v a tion or diffusion control. The p a r t i c i p a t i o n of sorbed h y d r o g e n in the electrochemical process is a p p r e c i a b l y influenced b y the O - e l e c t r o s o r p t i o n / O - e l e c t r o d e s o r p t i o n processes occurr i n g at m o r e positive potentials. These processes m o d i f y the c r y s t a l l o g r a p h i c o r d e r at the first l a y e r s of the m e t a l lattice (7, 14). T h r o u g h the m o b i l i t y of m e t a l atoms out of the lattice assisted b y t h e i r r e a r r a n g e m e n t d u r i n g the O - e l e c t r o d e s o r p t i o n stage and b y the a n i s o t r o p y of the surface e n e r g y due to the i n c o m p l e t e r e m o v a l of the O-containing l a y e r (7). These changes in the m e t a l lattice should d e p e n d b o t h on the f r e q u e n c y (~) and d u r a t i o n (~) of the i n t e r m e d i a t e R T P S and attains a m a x i m a l v a l u e for a p a r t i c u l a r set of p e r t u r b a t i o n v a r i a b l e s as shown in Fig. 2 a n d 3. The p r e c e d e n t discussion and the a l r e a d y r e p o r t e d d a t a on the O - e l e c t r o s o r p t i o n / O - e l e c t r o d e s o r p t i o n on gold (28) suggest t h a t the o v e r a l l processes occurring in the Ex,a-E~.c p o t e n t i a l r a n g e o n the a c t i v a t e d gold electrode u n d e r p o t e n t i o d y n a m i c conditions can be ascribed b y the following reactions A u ~ H20 : - A u ( O H ) ad ~ ( H + ) e -~- e Au(OH)ad = Au*(O) + (H+)e+ e [3] [4] [5]

ka
Au* (O) --> A u ( O )

d e p e n d on the values of ka, k6, kT, and the c h a r a c t e r istics of the p e r t u r b a t i o n p r o g r a m a p p l i e d to the electrode. The H2-discharge r e a c t i o n occurring on A u a n d Au* a r e e x p l a i n e d b y steps [8] a n d [9], respectively. The Au* sites a r e those which e x h i b i t t o w a r d the h y d r o g e n a d a t o m s a r e a c t i v i t y h i g h e r t h a n the A u sites. Reactions [8a] a n d [8b] should be r e sponsible for the changes p r o d u c e d in the p o t e n t i o d y n a m i c E l i d i s p l a y a f t e r the p o t e n t i o d y n a m i c aging. W h e n the e l e c t r o l y t e l a y e r a d j a c e n t to the electrode is s a t u r a t e d w i t h H2, the H2 e l e c t r o o x i d a t i o n should p r e f e r e n t i a l l y occur at the Au* sites (reaction [10]). The presence of the Au* sites should favor the e x i s tence of h y d r o g e n a d a t o m s e i t h e r e l e c t r o c h e m i c a l l y f o r m e d as w e l l as p r o d u c e d f r o m the dissociation of m o l e c u l a r hydrogen. Then, the surface concentration of H - a d a t o m s should d e p e n d on the surface c o n c e n t r a tion of Au* sites. The p o t e n t i a l of the corresponding e l e c t r o o x i d a t i o n c u r r e n t p e a k indicates a slight i n crease in the a v e r a g e Au* (H) bond e n e r g y as comp a r e d to t h a t of the A u (H) bond. U n d e r these c i r c u m stances the b e h a v i o r of the a c t i v a t e d gold electrode w i t h respect to the h y d r o g e n electrode reaction a p proaches t h a t of the p l a t i n u m electrode. The o v e r a l l processes r e p r e s e n t e d b y reactions [3]-[10] u n d e r p o t e n t i o d y n a m i c conditions i m p l y either the M - O and M - M or the M - H a n d M - M bonds changing s i m u l taneously. The effect of the activation process depends on the time spent to achieve it. Thus, w h e n the activation process operates d u r i n g a short time the electrode activation decays l i n e a r l y w i t h the l o g a r i t h m of time (Fig. 5 a n d 6), a relationship c o m m o n l y o b t a i n e d in electrodesorption of different species f r o m solids (29). This suggests t h a t the activation effect is p r e d o m i n a n t l y associated w i t h the first layers of the m e t a l lattice. On the other hand, w h e n the t i m e of the activation process is sufficiently large, the electrode acquires an activation m e m o r y w i t h respect to the h y d r o g e n electrode reaction which can be i n t e r p r e t e d as a d e e p e r and longer lasting change of the electrode surface s t r u c t u r e resulting f r o m the processes t a k i n g place over the O - e l e c t r o s o r p t i o n / O - e l e c t r o d e s o r p t i o n potential range. This effect is p r o b a b l y assisted b y

k6
A u * ( O ) -]- ( H + ) e + e_._~ A u * ( O H ) a d - ~ ( H + ) e W e_.~ A u * - ~ H 2 0 4 k7 $ $ A u ( O ) + ( H + ) e - ] - e ~ - ~ A u ( O H ) a a + ( H + ) e + e --* AU + H 2 0 ~ A u * (H) ab Au* + ( H + ) e + e = Au* ( H ) ~ + Au* Au + ( H + ) e W e ----A u ( H ) a d = J/2H2 ~- A u
(H)ab

[6] [7]

[8a] [8b] [9] [10a] [10b]

2Au* -t- H2 = 2Au* (H) ad~,~ Au*"~:Au* -t- H + -F e $ Au

the possible a c c u m u l a t i o n of a d s o r b e d o x y g e n in the m e t a l as was suggested e a r l i e r to e x p l a i n the disc r e p a n c y o b s e r v e d b e t w e e n the complex evolution of the optical p r o p e r t i e s of the m e t a l associated w i t h r e s t r u c t u r i n g of its surface and the p r e d i c t i o n of the simple faceting m o d e l (30). The resulting effects can be r e l a t e d to the p e n e t r a t i o n of h y d r o g e n into the metal.

Acknowledgment

Reactions [3] to [5] e x p l a i n the m a i n processes i n v o l v e d in the p o t e n t i o d y n a m i c O - e l e c t r o s o r p t i o n / O - e l e c t r o d e s o r p t i o n on gold (28). Reactions [3] and [4] a r e the initial steps r e l a t e d to the O - e l e c t r o s o r p t i o n occurring on the n o n a c t i v a t e d gold electrode. Reaction [5] represents the aging of the O - e l e c t r o s o r b e d species, ka is the corresponding r a t e constant. This reaction plays an i m p o r t a n t role d u r i n g the p o t e n t i o d y n a m i c aging covering the potential range of the O - e l e c t r o s o r p t i o n / O - e l e c t r o d e s o r p t i o n processes. Reactions [3] to [5] i m p l y at least t h e occurrence of two different surface sites, d e n o t e d as A u and Au*. Then, the Oelectrodesorption m a y occur t h r o u g h the series of reactions [6] and [7] which also i m p l y possible deactivation processes of the Au* species (dashed a r r o w s ) . The r e l a t i v e surface concentration of A u a n d Au*

I N I F T A is sponsored b y the Consejo Nacional de Investigaciones Cientificas y Tdcnicas, The U n i v e r sidad Nacional de La Plata, and the Comisi6n de Investigaciones Cientificas (Provincia de Buenos A i r e s ) . This w o r k was p a r t i a l l y s u p p o r t e d b y the Regional P r o g r a m for the Scientific and Technological D e v e l o p m e n t of the Organization of t h e A m e r i c a n States. M a n u s c r i p t s u b m i t t e d M a y 16, 1979; revised m a n u script received Feb. 19, 1980. A n y discussion of this p a p e r will a p p e a r in a Discussion Section to be p u b l i s h e d in the J u n e 1981 JOURNAL. A l l discussions for the J u n e 1981 Discussion Section should be s u b m i t t e d b y Feb. 1, 1981. Publication costs of this article w e r e assisted by the Instituto de Investigaciones Fisicoquimicas Tedricas y Applicadas.

2634

J. EZectrochem. Soc,: E L E C T R O C H E M I C A L S C I E N C E A N D T E C H N O L O G Y

December 1980

REFERENCES 1. G. Gruneberg, Electrochim. Acta, 10, 339 (1965). 2. A. T. K u h n and M. Byrne, ibid., 16, 39 (1971). 3. G. Picq and P. Vennereau, J. Electroanal. Chem. Interracial Electrochem., 96, 131 (1979). 4. J. Lecoeur, C. Sella, J. C. Martin, L. Tertian, a n d J. Deschamps, C. R. Acad. Sci. Paris, Set. C,

281, 71 (1975).

5. F. Chao and M. Costa, ibid., 284, 603 (1977); ibid., 284, 639 (1977); ibid., 284, 763 (19.77). 6. G. M. S c h m i d and N. H a c k e r m a n , This Journal, 110, 243 (1962). 7. F. Chao, M. Costa, a n d A. Tadjeddine, Surl. Sci., 46, 265 (1974). 8. J. B~nard, Werks. Korr., 21, 107 (1970). 9. C. N g u y e n Van Huong, C. Hinnen, J. Lecoeur, and R. Parsons, J. Electroanal. Chem. Inter]acial EIectrochem., 92, 239 (1978). 10. C. Hinnen, C. N g u y e n Van Huong, A. Rousseau, and J. P. Dalbera, ibid., 95, 131 (1979). 11. R. C6rdova, M. E. Martins, and A. J. Arvia, Electrochim. Acta, 24, 469 (1979). 12. M. Breiter, C. A. Knorr, and V. Volkl, Bet. Bunsenges. Phys. Chem., 59, 681 (1955). 13. F. G. Will and C. A. Knorr, ibid., 62, 378 (1960). 14. N. R. de Tacconi, J. O. Zerbino, M. E. Folquer, and A. J. Arvia, J. Electroanal. Chem. Inter~acial EIectrochem., 85, 213 (1977). 15. M. E. Folquer, J. O. Zerbino, N. R. de Tacconi, and A. J. Arvia, This Journal, 126, 592 (1979). 16. A. J. Arvia, Israel J. Chem., 18, 89 (1979).

17. B. E. Conway, H. A n g e r s t e i n - K o z l o w s k a , E. E. Criddle, and W. B. A. Sharp, Anal. Chem., 45, 1331 (1973). 18. S. Shibata, Bull. Chem. Soc. Jpn., 33, 1635 (1960). 19. S. Shibata, ibid., 36, 53 (1963). 20. R. S. Nicholson a n d L Shain, Anal. Chem., 36, 706 (1964). 21. D. A. J. Rand and R. Woods, J. Electroanal. Chem. Interracial Electrochem., 31, 29 (1971). 22. L. I. Krishtalik, "Advances in E l e c t r o c h e m i s t r y and Electrochemical Engineering," Vol. VII, P. D e l a h a y and C. W. Tobias, Editors, W i l e y - I n t e r science (1970). 23. D. O. H a y w o r d and B. M. W. Trapnell, "Chemisorption," Butterworths, London (1964). 24. M. Breiter, H. K a m m e r m a i e r , and C. A. Knorr, Z. Elektrochem., 60, 119 (1956); ibid., 60, 454 (1956). 25. N. Pentland, J. O'M. Bockris, and E. Sheldon, This Journal, 104, 182 (1957). 26. J. O'M. Bockris and R. Parsons, Trans. Faraday Soc., 44, 860 (1948). 27. S. S c h u l d i n e r and J. P. Hoare, J. Phys. Chem., 61, 705 (1957). 28. C. M. Ferro, A. J. Calandra, and A. J. Arvia, J. Electroanal. Chem., Interracial Electrochem., 59, 239 (1975) ; ibid., 65, 963 (1975). 29. A. W. Adamson, "Physical C h e m i s t r y of Surfaces," Interscience Publishers, N e w Y o r k (1960). 30. F. Chao, M. Costa, and A. Tadjeddine, Bull. Soc. Chim. Ft., 7, 2465 (1971).

Electrochemical Reactions at Multiple Interfaces

The Nickel Hydroxide Electrode Formed by Precipitation on a Platinum Surface
M. E. Folquer, J. R. Vilche,* and A. J. Arvia*
Instituto de Investigaciones Fisicoquimicas Te6ricas y Aplicadas, DivisiSn Electroquimica, Sucursal 4, Casilla de Correo 16, 1900 La Plata, Argentina
ABSTRACT The f o r m a t i o n of a m u l t i p l e interface consisting of a p l a t i n u m - b a s e electrode covered b y a chemically p r o d u c e d Ni (OH)2 l a y e r is i n v e s t i g a t e d in a l k a line electrolytes. The p o t e n t i o d y n a m i c response of the m u l t i p l e interface is r e l a t i v e l y complex b u t can be i n t e r p r e t e d as the sum of two m a i n c o n t r i b u tions, namely, the processes r e l a t e d to the electrosorption and e l e c t r o d e s o r p tion of h y d r o g e n a n d o x y g e n on p l a t i n u m and the conjugate r e d o x processes r e l a t e d to the nickel h y d r o x i d e electrode. The m u t u a l i n t e r f e r e n c e of the o x y g e n electrosorption and electrodesorption reactions w i t h those of the nickel h y d r o x i d e electrode is i n f e r r e d from the change of the aging characteristics of the o x y g e n electrodesorption process. The o v e r a l l electrochemical reaction is i n t e r p r e t e d t h r o u g h a reaction m o d e l involving two limiting planes dividing the electrochemical interface in two m a i n regions associated w i t h the two processes r e f e r r e d to above. In a r e c e n t p u b l i c a t i o n the concept of the m u l t i p l e electrochemical interface was a p p l i e d to e x p l a i n the p o t e n t i o d y n a m i c b e h a v i o r of i r i d i u m in different acid electrolytes (1, 2). A m u l t i p l e electrochemical interface involves at least t h r e e different phases, namely, the base metal, the conducting or semiconducting film which covers the base m e t a l either p a r t i a l l y or totally, and the electrolyte. The cations or atoms of the m e t a l in the film f o r m i n g chemical species are different from those of the base m e t a l electrode. Various electrochemical processes t a k e place at the m u l t i p l e e l e c t r o chemical interface. The sites of each reaction w i t h i n such an interface are differently located so t h a t a reaction plane p r o p e r to each reaction can be as* Electrochemical Society Active Member. Key words: metals, potential, voltammetry. signed. During the electrochemical reaction the different planes move at r a t e s w h i c h d e p e n d on the characteristics of the reactions, w h e t h e r t h e y r e f e r to a corrosion of the base metal, a m o n o l a y e r formation, a t h i c k e n i n g of the anodic film, or a proton t r a n s f e r process occurring t h r o u g h the film. The reaction model, which p r o v e d useful for i n t e r p r e t i n g the a b o v e m e n t i o n e d reaction, m a y have a m o r e g e n e r a l a p p l i c a tion. In this sense, it is interesting to test it t h r o u g h coupling the characteristics of both the nickel h y d r o x i d e electrode and the p l a t i n u m / a l k a l i n e solution interface and f u r t h e r to a t t e m p t to elucidate some of the questions r e g a r d i n g the kinetics of the f o r m e r p r o cess. Recent studies on the nickel hydroxide electrode have shown t h a t the overall electrochemical reaction