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: 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 March 1980
8. P e n n t u b e Plastics P r o d u c t Guide, Clifton Heights, 14. B. Miller, This Journal, 117, 491 (1970).
Pa., 19018 (1970). 15. B. Miller and R. E. Visco, ibid., 115, 251 (1966).
9. M. C. H. M c K u b r e and D. D. Macdonald, F i n a l R e - 16. H. Schlichting, " B o u n d a r y L a y e r Theory," M c G r a w
port, U.S. Dept. of E n e r g y Report, Contract Hill, New k o r k (1960).
EM-78-C-01-5159, Feb. 1980. 17. B. Miller, This Journal, 116, 1675 (1969).
10. B. Miller, This Journal, 116, 1117 (1969). 18. J. O'M. Bockris and A. K. N. Reddy, "Modern
11. M. C. H. M c K u b r e a n d D. D. Macdonald, S u b m i t t e d Electrochemistry," Plenum, N e w York (1970).
to This Journal.
12. Y. Beers, "The T h e o r y of Error," A d d i s o n - W e s l e y , 19. D. D. Macdonald, Atomic E n e r g y of Canada L i m -
Reading, Mass. (1962). ited Report 4139 (1972).
13. W. J. A l b e r y and S. Bruckenstein, Trans. Faraday 20. D. D. M a c d o n a l d a n d M. C. H. McKubre, To be
Soc., 62, 1946 (1966). published.
ABSTRACT
E l e c t r o c h e m i c a l responses from the r e d u c t i o n of Ru m (edta) coordinated
to films of high m o l e c u l a r w e i g h t poly ( 4 - v i n y l p y r i d i n e ) on p y r o l y t i c g r a p h i t e
electrodes w e r e s t u d i e d as functions of film thickness, t e m p e r a t u r e , s u p p o r t i n g
e l e c t r o l y t e composition, and solvent. Responses at filmed electrodes f r o m m e t a l
complexes t h a t do not coordinate to the films w e r e also examined. W i t h films
t h i c k e r t h a n ca. 1000A, the c u r r e n t responses a r e l i m i t e d b y the rates of molec-
u l a r motions w i t h i n the films. P e n e t r a t i o n of counterions, s e g m e n t a l motion of
sections of the p o l y m e r chains, and j u x t a p o s i t i o n i n g of pairs of a t t a c h e d m e t a l
complexes to facilitate i n t e r c o m p l e x electron t r a n s f e r w i t h i n the film or com-
binations of the t h r e e a r e suggested as l i k e l y c u r r e n t limiting p r o c e s s e s .
0 ~,
I lo0/zC for R u m ( e d t a ) . W i t h p o l y m e r s of h i g h e r a v e r a g e
m o l e c u l a r w e i g h t t h e e x t e n t of binding of Ru m ( e d t a )
is assumed to reflect a n i n c r e a s e in t h e q u a n t i t y o f
P V P t h a t is p r e s e n t on the g r a p h i t e surface. P V P
samples w i t h a v e r a g e m o l e c u l a r weights in e x c e s s o f
I I i i i i i i i i i i i i 2 X 105 a r e c l e a r l y the most p o t e n t for p r e p a r i n g e l e c -
0.4 0.2 0 -0.2 -0.4 -0.6 -0.8
t r o d e coatings t h a t a c c e p t t h e l a r g e s t q u a n t i t i e s o f
E vs. SSCE, V R u In ( e d t a ) .
Fig. 1. A, voltammogram for the reduction of RutII (edta) at-
F i l m morphology.----Scanning electron m i c r o g r a p h s
tached to o coating of 2.3 X 10 - 7 moles cm - 2 of pyridine as
PVP on a pyrolytic graphite electrode. RuIII (edta) attachment was
of films of P V P on glassy carbon show the p o l y m e r to
that resulting when the PVP-coated electrode was exposed to a 5
be d i s t r i b u t e d s o m e w h a t u n e v e n l y w i t h islands o f
tamale solution of Rum (edta) at pH 3.9 for 15 rain. Supporting
p o l y m e r s u r r o u n d e d b y b a r e o r l i g h t l y covered a r e a s .
The uneveness a p p e a r s to increase w h e n R u IzI (edta)
electrolyte: 0.2M CF~COONa (pH = 2.85). Scan rate: 100 mV
sec - z . B, area under the voltammogram in A obtained by electronic
is coordinated to the polymer. A cross-sectional v i e w
integration of the current as the voltammogram was recorded.
of the l a y e r p r o d u c e d w h e n a m e t h a n o l i c solution con-
Background current and its integral are shown by the dashed lines.
taining 6 X 10 -~ moles c m - 2 of m o n o m e r i c p y r i d i n e
units was a l l o w e d to e v a p o r a t e on a glassy c a r b o n
surface is shown in Fig. 3. The a p p a r e n t thickness o f
p e a k p o t e n t i a l until the r a t e of charge a c c u m u l a t i o n the l a y e r is (8 __. 2) 104A w h i c h corresponds to a n
d e c r e a s e d to b a c k g r o u n d levels. effective density of only ca. 0.08 g / c m - ~ . Since the
To p r o v i d e electrode surfaces containing k n o w n density of b u l k p o l y ( 4 - v i n y l p y r i d i n e ) is 1.1 t h i s
quantities of a t t a c h e d PVP, m e a s u r e d aliquots of a could indicate t h a t the p o l y p y r i d i n e l a y e r is quite p o r -
stock solution of the p o l y m e r in m e t h a n o l w e r e c a r e - ous. However, the a p p a r e n t film thickness o b s e r v e d in
f u l l y t r a n s f e r r e d to the surface of a h o r i z o n t a l l y the SEM m a y not be an a c c u r a t e reflection of t h a t p r e -
m o u n t e d electrode w i t h a m i c r o l i t e r syringe. 1-4 m i c r o - vailing on the electrodes used in the electrochemical
liters of the solution s p r e a d u n i f o r m l y on p y r o l y t i c experiments. F o r example, s e v e r a l of the e x p e r i m e n t s
g r a p h i t e a n d w e l l - p o l i s h e d glassy c a r b o n surfaces to be described in w h a t follows indicate c l e a r l y t h a t
w i t h o u t overflowing, to p r o d u c e a visibly u n i f o r m film PVP films deposited on g r a p h i t e u n d e r some conditions
u p o n e v a p o r a t i o n of the solvent. To i n t r o d u c e Ru m b e h a v e e l e c t r o c h e m i c a l l y as if t h e y p r e s e n t e d ' a dense,
(edta) onto the electrode surfaces the resulting p o l y - i m p e r v i o u s d o m a i n to r e a c t a n t s seeking the electrode
m e r - c o a t e d electrodes w e r e i m m e r s e d in a 5 m m o l e surface. Thus, e x p o s u r e of films deposited f r o m m e t h -
aqueous solution of Ru m (edta) at p H 3.9 for 15 min. anol to the low pressures w i t h i n the SEM m a y cause
A f t e r a t t a c h m e n t of the c o m p l e x b y coordination to a l a r g e expansion of the film as r e s i d u a l t r a p p e d sol-
the p e n d a n t p y r i d i n e ligands in the p o l y m e r coating vent escapes f r o m the film, causing t h e m to a p p e a r less
(9), the electrodes w e r e w a s h e d r e p e a t e d l y w i t h water, dense. F o r this reason we do not r e g a r d the film d e n -
dried, and stored. This p r o c e d u r e is not w e l l calculated sities e s t i m a t e d f r o m SEM m e a s u r e m e n t s as r e p r e s e n -
to ensure a u n i f o r m d i s t r i b u t i o n of coordinated Ru In tative of electrode surfaces t h a t a r e n e v e r exposed to
(edta) t h r o u g h o u t the P V P layer. None of the electro- high vacuum.
chemical e x p e r i m e n t s p e r f o r m e d w i t h these coatings Coatings of PVP on glassy c a r b o n t h a t exceed ca.
of P V P - R u ( e d t a ) gave indications of h i g h l y aniso- 5 10 - s moles cm -2 ( e x p r e s s e d as m o n o m e r i c p y -
tropic film compositions b u t it w o u l d not be s u r p r i s - ridine units) a r e c l e a r l y visible w i t h o u t magnification.
ing to find t h a t m o r e of the a t t a c h e d complex resided The o r i g i n a l l y b l a c k surface becomes g r a y a n d t h e
n e a r the e l e c t r o l y t e / f i l m interface t h a n the e l e c t r o d e / glassy carbon loses its luster. W h e n Ru m (edta) is
film interface. coordinated to such h e a v y P V P coatings, a distinct
Scanning electron m i c r o g r a p h s w e r e o b t a i n e d w i t h and p e r s i s t e n t golden color develops on t h e e l e c t r o d e
a n ETEC C o r p o r a t i o n A u t o s c a n U-1 ( H a y w a r d , Cali- surface w h e n the R u ( I I I ) is r e d u c e d to R u ( I I ) . T h e
fornia) instrument. Electrodes were coated by the electrode can be cycled r e p e a t e d l y b e t w e e n potentials
p r o c e d u r e j u s t described. Cross-sectional views of that cause r e d u c t i o n a n d o x i d a t i o n of the r u t h e n i u m
coatings a p p l i e d to polished glassy c a r b o n electrodes
w e r e o b t a i n e d b y a p p r o p r i a t e m o u n t i n g of the elec-
t r o d e specimens in t h e microscope. I n this w a y the 4,0 1 I
thickness of the p o l y m e r i c l a y e r s could be estimated. 'E
(D
A v :0.5Vs -I
0.2mA
N-
Z
W
0~
r~
i i i i i i i i 9 i I I i I
light polymer coatings the peak currents are propor- 0 .... L.- [ L I I
tional to the scan rate (Fig. 5) as expected for attached 0.4 f I ' T f I I I l r
A
5
ot 45oc\ /
a
I I I I I I I I I
,; 2'0 0.4 0.2 0 -0.2 -0.4 -0.6
(Time/sec) I/2 E vs. SSCE, V
Fig. 7. Temperature dependence of (A), charge-(time) 1/~ plots and (B), cyclic" voltammograms (sca~n rate: 200 mV s~~ - t ) for Rum
(edta) attached to electrodes coated with 2.3 X 10 - 6 moles cm - 2 of pyridine as PVP. Rum (edta) attachment procedure and supporting
electrolyte as in Fig. 2 except pH was 3.4.
644 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 March 1980
.20
ol
t--
PVP. Supporting electrolytes: Z ~OImA
H20, 0.2M CF.3COONa (pH = LLI
4.2); other solvents, 0.2M rY
NaCIO4. Scan rate: 200 mV rY EtOH
sec -1. RuIn (edta) attachment
procedure as in Fig. 2. A freshly
g ol
coated electrode was used in
each solvent. CH3CN
ol j
DMSO
ot
I I I I I I I 1 I I I I I I I I I I
0.6 0.4 0.2 0 -0.2 -0.4 -0.6 -0.8 -1.0
E vs. SSCE, V
VoI. 127, No. 3 ELECTROCHEMICAL RESPONSES 645
A D
Fig. 12. Steady-state cycllc
voltommograms for 5 mmole
solutions of Fem (edta) or
Ru(NH3)6 8+ at pyrolytic graph-
ite electrodes under following /
conditions: A, D, freshly cleaved
electrode; supporting electrolyte, r-- B Io'lmA
0.2M CF3COONa at pH 5.4 (Fe)
E
or 6.0 (Ru). B, E, coated with
L.L.J ol o,L Jf
4.6 X 10 - ~ moles of pyridine as
PVP; supporting electrolyte as in
A, D. C, F, supporting electrolyte (.~
adjusted to pH 2.2 with /
CFsCOOH. The dashed line in |
curve C is the response at a T o olL_
freshly cleaved electrode a!
pH 2.2. The response fol
Ru(NH3)6 8+ showed no signifi-
cant pH dependence. Scan rate:
200 mV sec -z. I I I I I I I I I I I I I I I I I I I ! I I I I I I
0.4 0.2 0 -0.2 -0.4 -0.6 0.4 0.2 0 -0,2 -0.4 -0.6
E vs. SSCE, V
blocking l a y e r into one at w h i c h the F e ( C N ) e ~ - / 4 - charge t r a n s f e r m a y be possible b y suitable m a n i p u l a -
r e d o x r e a c t i o n can proceed. The cyclic v o l t a m m o g r a m tion of mass t r a n s f e r and charge t r a n s f e r rates a n d we
obtained at a n u n c o a t e d electrode (curve A) is a n - have such e x p e r i m e n t s u n d e r w a y . However, it m a y b e
nihilated b y the presence of an u n p r o t o n a t e d P V P w o r t h emphasizing two points in conclusion. (i) T h e
coating (curve B) b u t it reappears, in a s l i g h t l y dis- presence of electroactive r e d o x centers w i t h i n p o l y m e r
torted form, w h e n Ru m (edta) [a monoanion at p H films is no assurance t h a t the films will s u p p o r t charge
5.4 (17)] is coordinated to the p o l y m e r (curve C). In t r a n s f e r either to the a t t a c h e d r e d o x centers or to r e -
this case the d e n s i t y of b o u n d (anionic) charge is not actants dissolved in solution: P V P coatings containing
as high as t h a t resulting f r o m p r o t o n a t i o n of the p o l y - l a r g e quantities of coordinated Ru m (edta) n e v e r t h e -
m e r at low p H b u t the r e s t o r e d response is almost as less b e h a v e as insulating layers in certain nonaqueous
g r e a t as that o b t a i n e d at the uncoated electrode. The solvents (Fig. 10). (ii) Charge t r a n s f e r b e t w e e n dis-
coated electrode can also be u n b l o c k e d b y protonation, solved reactants and electrode surfaces covered w i t h
as in Fig. 12. thick (1-10 #m) P V P films can occur r a p i d l y even w h e n
The response o b s e r v e d for the F e (CN) 88-/4- couple the films do not have r e d o x centers a t t a c h e d to them:
in curve C of Fig. 13 can be u n d e r s t o o d s i m p l y in t e r m s p r o t o n a t i o n converts an insulating P V P film to one t h a t
of an increase in the p o r o s i t y of the film w h i c h allows does not i m p e d e the r e d u c t i o n of dissolved r e a c t a n t s
the r e a c t a n t to pass into the film m u c h m o r e r e a d i l y (Fig. 12).
t h a n was true u n d e r the conditions of curve B. H o w - Acknowledgments
ever, a second possible origin of the increased film The assistance of Prof. J. P. Revel a n d P a t Cohen in
conductance in this case (as contrasted w i t h curves C obtaining electron m i c r o g r a p h s is a c k n o w l e d g e d g r a t e -
and F in Fig. 12) is the transmission of electrons fully. Drs. A l a n R e m b a u m and Roger W i l l i a m s k i n d l y
t h r o u g h the film via the a t t a c h e d Ru m (edta) centers. p r o v i d e d the samples of f r a c t i o n a t e d P V P t h a t w e r e
That is, electron t r a n s f e r f r o m the g r a p h i t e to the used to o b t a i n the d a t a for Fig. 2. S e v e r a l p e r c e p t i v e
F e ( C N ) 8 8 - / 4 - couple m a y be m e d i a t e d b y electron comments and criticisms b y the r e v i e w e r s of a n e a r l i e r
t r a n s f e r among the a n c h o r e d r e d o x centers in the film. version of this m a n u s c r i p t h e l p e d us to f o r m u l a t e our
Distinguishing b e t w e e n these two m e c h a n i s m s of speculations m o r e clearly.
This w o r k was s u p p o r t e d b y the National Science
F o u n d a t i o n a n d the U.S. A r m y Research Office.
ABSTRACT
C u r r e n t - p o t e n t i a l (i-E) curves for the electrochromic process at WO8 e l e c -
t r o d e s w e r e c a l c u l a t e d w i t h a digital simulation m o d e l which assigns the r a t e
of charge t r a n s f e r at the o x i d e / s o l u t i o n interface and the r a t e of diffusion of
h y d r o g e n into the b u l k of the film as m a j o r variables. The s i m u l a t e d i-E curves
a g r e e d well w i t h e x p e r i m e n t a l ones for different types of WO3 films and p r e -
dicted the o b s e r v e d d e p e n d e n c y of c u r r e n t on scan rate. The simulation r e -
q u i r e d k n o w l e d g e of the form of the electrochemical isotherm, which was o b -
t a i n e d e x p e r i m e n t a l l y , and a d j u s t m e n t of a charge t r a n s f e r r a t e constant, kf,
and the h y d r o g e n a t o m diffusion coefficient w i t h i n the film, Dm The best fit
was obtained w i t h kf ~- 9 10 -~ sec -1 ( m o l e / c m ~ ) - 2 a n d DH : 1 X 10 -9 to
2 X 10 - l ~ cm2/sec for the WO~ films p r e p a r e d by v a c u u m e v a p o r a t i o n and
kf -- 7.2 sec -1 ( m o l e / c m 3 ) - 2 and DH = 5 X 10 - s cm2/sec for WOz anodic
films. S i m u l a t e d p o t e n t i a l step results, w h i c h a r e s i m i l a r to the e x p e r i m e n t a l
curves at longer times b u t show some d i s c r e p a n c y in the short t i m e region,
a n d concentration profiles a r e also reported.