51

J. Electroanal. Chem., 261 (1989) 51-59 Elsevier Sequoia S.A., Lausanne - Printed in The Netherlands

Microheterogeneous
M.E.G.

catalysis in modified electrodes

Lyons and D.E. McComack

Vnrversity of Dublin, Trinity College, Dublin 2 (Ireland)

Physical Chemistry L&oratory

P.N. Bartlett
Department of

Chemrstry University of Warwick, Coventry, West MidIan& The

CV4 7AL (Great Britain)

(Received 21 July 1988; in revised form 28 October 1988)

ABSTRACT Analytical expressions quantifying the transport and kinetics in conducting polymer modified electrodes containing a homogeneous distribution of spherical microparticulate catalysts are presented. In particular the dependence of the flux on the number of catalytic particles per unit volume, the layer thickness, the substrate concentration, the particle radius and the electrode potential are outlined.

INTRODUCTION

The electrocatalytic activity of polymer modified electrodes has been the subject of considerable study for some time. Most systems utilized to date have required that the electrochemically active centre within the coating exhibit a dual purpose, that of being an efficient electron transfer mediator in addition to displaying good electrocatalytic activity. This dual requirement is too restrictive and a better approach is to utilize an integrated system where the functions of charge transport through the film to the catalytic site and catalytic activity are carried out by different components in the layer. Recent reports in the literature have described modified electrode systems in which the electron conduction and catalytic functions have been provided by different components within the surface deposited coating. In one approach the catalytic centres were incorporated into a conducting polymer matrix [1,2]. In another approach described by Anson et al. [3,4], immobile catalytic molecules and electrochemically reversible inorganic redox couples (the latter acting as electron transfer mediators) were incorporated into an inert polymeric matrix. Provided that good electrical contact is maintained between the catalytic particles and the conducting polymer, it would be expected that the conducting polymer matrix would exhibit a better charge mediating ability than that of an inorganic
0022-0728/89/$03.50 0 1989 Elsevier Sequoia S.A.

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redox couple. Very recently, Holdcroft and Funt [2] examined the electrocatalytic activity of suface deposited polypyrrole layers containing platinum microparticulates with respect to oxygen reduction, and noted that the catalytic current was limited by the rate of oxygen permeation in the film. However, no theoretical model was proposed by these workers. Consequently, the transport and kinetics in these types of integrated modified electrode systems is described in the present communication, and various simple diagnostic parameters are proposed which can be used as an aid towards mechanistic analysis in further experimental studies in this area.
THE MODEL

Macroscopic approach In the following model (outlined in Fig. 1) we assume that the microheterogeneous catalytic particles are dispersed in a uniform manner throughout the conducting polymer film. It is also assumed that the catalytic particles are in intimate electrical contact with the conducting polymer. Furthermore, we assume initially no concentration polarization in the solution and that the substrate concentration s within the layer is given by KS,, where K is the partition coefficient and s, denotes the bulk substrate concentration. Let L denote the layer thickness. Under steady state conditions the diffusion equation takes the form: D, d2s/dx2 - ks = 0 (1)

where k denotes an effective first order rate constant for the substrate product reaction at the surface of the catalytic particle. This equation must be solved subject to the boundary conditions: x=0 x=L ds/dx = 0 s = KS 00 =A exp(x/X,) + B exp( -x/X,) (2) (3)

The diffusion equation admits the general solution: s(x) (4

Oo
0
00

SOLUTION S=Ks,

ELECTRODE

O
0

tiyoo
0 0

I--

CONDUCTING

POLYMER MATRIX

Fig. 1. Model and notation for modified electrode.

53

where X, denotes a kinetic length defined as x, = ( Q/k)2 (5)

The reaction length X, describes the distance that the substrate S will diffuse in the layer before being destroyed by reaction with the catalyst. The boundary conditions are now utilized in order to evaluate the constants A and B. Application of eqn. (2) results in the assignation A = B. Furthermore substitution of the condition outlined in eqn. (3) into eqn. (4) and simplifying, results in an expression for A of the form
A = KsJ2

cosh( L/X,) the substrate concentration

L/X,)}

(6)

Consequently, s(x)

in the layer is given by (7)

= { Ks,/cosh(

{cosh(x/X,)}

The flux j is given by the relation j = D,(ds/dx),,, Differentiation for the flux j = (D,Ks,/X,) (8) of eqn. (7) and utilizing eqn. (8) results in the following expression tanh( L/X,) can be considered. Firstly when L >> X, (9) the flux
(10)

Two rate limiting situations expression reduces to j = D, Ks,/X,

and the overall reaction in the layer is transport controlled. In this case S is consumed in a reaction layer of thickness X, at the surface of the film. Consequently, the flux j is independent of the film thickness. However, if L Ed X,, the flux admits the form: j = D, KS, L/X,,? = Kks, L
(11)

and the overall reaction is kinetically controlled. Now S is consumed by reaction throughout the film and hence increasing the film thickness, L, leads to an increase in the flux, j.
Microscopic approach

We now consider the pseudo-first-order rate constant k (units s-l) for the substrate reaction at the catalyst particle. In order to examine the latter quantity in detail, it is necessary to adopt a microscopic approach and consider explicitly the spherical geometry of the catalyst particle [5]. Substrate diffusion to the latter is described by the following equation

(12)

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This equation is solved most readily if we set u = sr, where r denotes the radial distance. Once this substitution is effected, the differential equation takes the form

Dd2U=O
dr2
This equation has the solution u=rr+6 which transforms to s=E+S/r

(13)

(14)

(15)

The following boundary conditions pertain. When r = r,, at the surface of the particle, s = s0 and DSds/dr = k,s,. Note that the quantity k, describes a potential dependent rate constant of the form k,=k exp(+@)=kO exp(f&(E-EO)/RT) (16)

In this latter expression, k o and cz are fundamental electrochemical parameters and are termed the standard rate constant and transfer coefficient respectively. The quantity E o is the standard potential which will reflect the thermodynamics of the substrate reaction at the catalytic particles surface. The other symbols have their usual meanings. Also we must define a distance r, which describes a sphere of action of each catalytic particle [5], such that when r = rl, s = s(x). The relation between r, and the number of particles per unit volume N is 4aris/3 = l/N. Application of the boundary conditions results in the assignations E = s(x) + k,s,ri/DSr, (17) (18) at the (19) formally as a second order

6 = - k,s,ri/D, From eqns. (15), (17) and (18) we find that the substrate concentration surface of the spherical catalytic particle is given by sO=s(x)/{l + (&VQ) - (k&/D,ri)}

The substrate/catalyst reaction can be considered reaction with the rate of consumption of S given by ds/dt = -k,s(x)c

(20)

where c denotes the concentration of catalyst particles. Alternatively we can write an expression for the rate of reaction of S which contains the heterogeneous electrochemical rate constant k, explicitly, ds/dt = - k,NAs, (21)

where A denotes the surface area of the spherical particles (i.e. 4vrr:) and N is the number of catalyst particles per unit volume. Comparison of eqns. (20) and (21) shows that the second order rate constant is given by k, = k,NAs,/cs( x) (22)

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We note that the pseudo-first-order rate constant described previously can be related to this latter quantity via the relation k = k,c, provided that the quantity c is a constant, corresponding to a uniform distribution of catalyst particles throughout the film. Consequently, the pseudo-first-order rate constant k is given by k = kENAs,,/.+) We note from eqn. (19) that 1 $j = 1 + (k,r,,/D,) - ( kEr;/Dsrl) (24) in the (23)

Hence, substitution of eqn. (24) into eqn. (23) results, upon inversion, following useful expression for the pseudo-first-order rate constant:

(25)
Since r, x== then the term r,/Dsr, on the r.h.s. of eqn. (25) can be neglected, and r,, consequently the expression for the pseudo-first-order rate constant reduces to 1 -=&($+:I k (26)

It is important to note that macroscopic or planar diffusion effects can be or spherical diffusion effects provided that the separated from microscopic particles are small compared to the film thickness (r. -=s L) and that 4ro -SCX,. This condition is discussed in detail in the appendix.
DISCUSSION

We can now combine eqns. (5), (9) and (26) to obtain a master equation for the flux:

We can identify four limiting cases from this equation. We begin by taking L(4m$N[ Then DsJ$:k,]}2<l

(28)
Equation (28) consists of two components, one involving diffusional substrate transport through the layer and the other involving the electrochemical kinetics at

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the particle/substrate interface. When k, B D,/r,, case I, the reaction particle surface is diffusion controlled and eqn. (28) becomes j, = 4mroNDsKs,L

at the

(29)

On the other hand, if k, -+z D,/r,,, case II, so that the electrode kinetics at the particle surface are rate limiting, then the flux simplifies to: j,, = 4vriNk, Ks, L (30)

Turning to the remaining pair of cases, when L (4m$N( Ds~f~k,)}2 > 1

then eqn. (27) reduces to j = Ks_,D*{ 4nr,iN( Ds~<~k,))12 (31) and D,/r,,. If

Again we identify two cases depending on the relative values of k, k, x=-D,/r,, case III, then eqn. (31) becomes: j,,, = DsKs,(4vrJV)12 and if k, -=c Ds/ro, case IV, then: j,, = Ks,{4?rr~DsNk,}2

(32)

(33)

Each of these four cases corresponds to a different physical situation. In case I the film is much thinner than the kinetic layer, X,, so the substrate penetrates throughout the film. Hence increasing the film thickness, L, leads to an increase in the flux, j. The reaction on the catalyst particles in this case is very fast and is limited by spherical diffusion within the film to each particle. Note that k, does not occur in the expression for j, and hence the flux is independent of the electrode potential. In case II, the substrate still penetrates throughout the film, but now the reaction at the catalyst particle surface is rate limiting and thus k, occurs in our expression for the flux. Since k, is potential dependent (eqn. 16) the flux will depend on the electrode potential for this case. We now turn to cases III and IV. In this regime, the film is sufficiently reactive that the substrate is consumed in a reaction layer of thickness X, at the film surface. For case III, the reaction on the catalyst particles is diffusion controlled and so the thickness of this reaction layer is determined by the diffusion to the particles. In case IV, the reaction at the surface of the particles is kinetically controlled and hence the reaction layer thickness depends upon k,, and hence on the electrode potential. The interaction between these four cases is shown in the case diagram outlined in Fig. 2. Also illustrated in this diagram are the concentration profiles for the substrate in the layer for each of the limiting cases. Inspection of the expressions for the flux in each of the four cases, eqns. (29), (30) (32) and (33) shows that for each

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j = ksr,Nk,Ks,L

L,N
Fig. 2. Case diagram illustrating various rate limiting situations. D and K denote diffusion and kinetic control respectively.

TABLE

M~han~stic indicators for microheterogeneous catalysis in modified electrodes Case Reaction order w.r.t.
L

'0
1 2 0.5 1.0

c (or N)

k, 0 1 0 0.5

1 2 3 4

1 1 1 1

1 1 0 0

1 1 0.5 0.5

case there is a unique set of dependences of the flux on the experimental parameters s m, L, ro, and the electrode potential (expressed through the electrochemical rate Iv, constant kE). These are given in Table 1. It is clear that on the basis of these dependences, it should be possible to identify the particular case clearly.

ACKNOWLEDGEMENTS

The support of the Trinity Trust, the Science Faculty, Trinity College Dublin, and the Commission of the European Communities Stimulation Action Program (Grant Number 86300283FRBPUJUl) is gratefully acknowledged. D.E.McC. acknowledges receipt of a Trinity College postgraduate award.

58 APPENDIX

In this appendix we consider the conditions under which it is valid to treat the macroscopic, planar diffusion of the reactant S independently of the microscopic, spherical diffusion to the catalyst particles. In Fig. 3, a single catalyst particle of radius r, and its sphere of action of radius ri is outlined. Firstly, for cases I and II, the concentration of substrate S in the film is uniform, and the particles see the same concentration of S in all directions. Under these circumstances we can clearly separate the planar and spherical components. In cases III and IV, the concentration of S varies through the film. Now our treatment is most likely to break down when the reaction of S at the catalyst particle surface is diffusion controlled (case III). Under these conditions the particle perturbs the concentration of S over a distance r, from its surface [5]. Our approximation is therefore valid provided the concentration of S does not vary significantly over a distance 4r, corresponding to the difference between the front face of the catalyst particle, and the back face. Thus our approximation is valid provided that: 4r,(ds/dx) +z s(x) (Al) where the quantity 4r,(ds/dx) is the change in concentration between the front and back of the particle. Now differentiation of eqn. (7) yields that: ds -= dx KS m X, {taiMx/Xk))

so substituting from eqns. (7) and (A2) in (Al) and simplifying, we find that: $
k

sinh( x/Xk) +Z cosh( x/&)

(A31

Fig. 3. Schematic representation of a single catalytic particle of radius r,, and its sphere of action of radius r,.

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Rearranging
4r, -=x X,

and noting that 1 tanh(x/&)

< 1, we obtain:
(Ad)

Substituting for X, from eqns. (5) and (26): (A51 Now the particles only perturb the concentration of S significantly when r,/D, l/k,. Under these circumstances eqn. (A5) becomes: 4r, < {1/4mrON}2 But we recall that: l/N = 4rrr:/3 Hence 3.3r, << r
(48) z+

tA6)

(A7)

Thus, our approximation is valid up to quite high catalyst loadings where 3% of the film by volume is made up of catalyst particles. This is the worst case where the reaction is diffusion limited at the particle surface (case III).
REFERENCES 1 2 3 4 5 R.A. Bull, F.R. Fan and A.J. Bard, J. Electrochem. Sot., 130 (1983) 1636. S. Holdcroft and B.L. Funt, J. Electroanal. Chem., 240 (1988) 89. D.A. Buttry and F.C. Anson, J. Am. Chem. Sot.. 106 (1984) 59. H. Liu and F.C. Anson, J. Electroanal. Chem., 158 (1983) 181. W.J. Albery and P.N. Bartlett, J. Electroanal. Chem., 131 (1982) 137.