207

.I Electroanal Chem., 250 (1988) 207-211 Elsevier Sequoia S.A., Lausanne - Printed

in The Netherlands

Preliminary note TEMPERATURE DEPENDENCE OF CHARGE TRANSPORT SURFACE DEPOSITED REDOX POLYMER LAYERS PROCESSES IN

M E.G

LYONS

and H.G. FAY

PhJsxal Chemrstry Laboratoty, Unwersrt_vof Dubhn. Trmty College, Dubhn 2 (Ireland) J.G. VOS and A.J. KELLY School of Chemcal Scrences. N.I.H.E., (Received 7th June 1988) Dubhn 9 (Ireland)

The fruitful application of electroactive polymer films in diverse areas such as chemical sensor technology, mediated electrocatalysis, solar energy conversion, electrochromic device technology, macromolecular electronics and advanced battery development is dependent on acquiring a detailed understanding of the mechanisms involved in charge percolation through the polymer layer. It is now established that surface deposited polymer films containing discrete redox sites distributed in a three dimensional manner throughout the layer conduct via an electron hopping process between neighbouring oxidized and reduced sites. The determination of activation parameters for electrochemical reactions in redox polymer layers has not received a great deal of attention to date [l-3]. This is surprising in that activation energy data can yield useful information on the nature of the transport processes involved in charge percolation through these polymer layers. For instance while electron hopping may be a mechanism for electron transport, it is possible that either ion motion, polymer chain motion or electron hopping can constitute the rate determining event for overall charge transport through the layer. The studies presented in the present communication were conducted on thin surface deposited films of the ruthenium containing metallopolymers [Ru(bpy), (PVP)Cl]Cl and [Ru(bpy),(PVP)(MMA)Cl]Cl, where bpy denotes 2,2-bipyridyl, PVP is poly(4-vinyl pyridine) and MMA denotes poly(methylmethacrylate). Details of the synthesis and characterization of these materials have been outlined in a previous communication [4] and the structure of the fundamental repeat unit of the polymer is illustrated in Fig. 1. The redox activity of the material can be attributed to the Ru+/Ru3+ redox process which typically has a formal potential in the region 700-800 mV (vs. Ag/AgCl reference). The exact value of the formal potential observed depends on the nature of the electrolyte and the concentration of redox centres in the layer.
0022-0728/88/$03.50 9 1988 Elsevier Sequoia S.A.

Fig. 1. Schematic

representation

of metallopolymer.

The rate of charge percolation through the redox polymer layer can be quantified in terms of a charge transport diffusion coefficient DCT. In the present work, charge transfer diffusion coefficients were estimated by cyclic voltammetry using a theoretical approach recently proposed by Aoki et al. [5,6]. The relationship between voltammetric peak current i, and sweep rate u can be expressed in the following form provided that electron transfer between the support electrode and the redox centres immediately adjacent is rapid. lP = 0.446nFA{ where W = nFLv/D,, and Y = 0.56W2 + 0.05W (3) RT (21 ID,,/L} W1j2 tanh Y (I)

In these latter expressions n, F, A and I denote the number of electrons transferred in the redox process (unity in the present example), the Faraday constant, the geometric area of the electrode (0.071 cm2) and the surface coverage respectively. Typically. I had values in the region of lo-* mol cmP2 and was estimated from integration of the cyclic voltammogram which is recorded at very low scan rates. The expression outlined in eqn. (1) can be solved numerically for DcT/L2 using the bisection algorithm [7]. The only experimental information required to obtain a numerical estimate of DC-/L2 is I and values for the peak current at each specific sweep rate. The thickness L of the surface deposited layer can be estimated from the equation:

L=rvm
where V, estimated 10e5 cm confirmed denotes the molar volume of the coat. This latter quantity as 1176 cm3 mol-. Layer thickness can be estimated to be of if typical I values are inserted into eqn. (4). This estimate from SEM measurements. Charge transfer diffusion coefficients

(4) has been the order has been typically

209

-255

-285 320

t 31*5 103T-'I K-'

I 370 310 340 103T/K-' 370

Fig. 2. (A) Typical Na>SO,. r = 2. 11 no. 2.1). Electrolyte.

Arrhemus plot for the homopolymer (System no 1) Electrolyte, 0.1 mol dm- IO- mol cm-. (B) Typical Arrhenius plot for the PVP/MMA copolymer (system 0.1 mol dm- HCIO,. I = 2.76 x 10e9 mol cm-.

had values in the range 10--10-2 cm s-, the exact value depending on the nature of the counterion in the electrolyte, the solution pH, and the metal/polymer ratio in the layer. The activation energy E, was subsequently determined by analysis of the voltammetric response as a function of solution temperature and by assuming that the diffusion coefficient varied with temperature via an Arrhenius type relations~p: &r(T) = G?i- exp{ -WRT] (9

where D& is a pre-exponential factor and E, denotes the activation energy for charge percolation. Typical Arrhenius plots recorded for the homopolymer (Ru/VP ratio 1: 5) and for one of the PVP/MMA copolymer systems (VP/MMA ratio 1 : 1 and Ru/VP ratio 1: 7.43) are outlined in Fig. 2. It is obvious from these results that the Arrhenius plot obtained for the homopolymer (Fig. 2A) differs considerably from that obtained for the copolymer (Fig. 2B). In the former a simple well defined linear plot is obtained which on analysis yields an activation energy of 40 kJ mol-. This latter value is characteristic of counter ion motion through the polymer [8]. A more complicated and novel temperature dependence is observed for the copolymer however. Two distinct linear regions are observed. Firstly at high temperature a rather large activation energy of ca. 140 kJ mol-i is obtained, the latter being possibly attributed to the movement of the polymer sidechains containing the redox centres. At lower temperatures an activation energy of ca. 40 kJ mol- (analogous to that observed for the homopolymer) is obtained, which again can be attributed to counter ion movement. The transition between these two regions can be described as a polymer swelling temperature. Activation energies were determined as a function of electrolyte composition, solution pH and nature of the polymer back-

210 TABLE Activation Electrolyte 1 parameters lOV/ mol cm-

Ed/

kJ mol-

AH*/ kJ mol-

AS/ J mol-

Km

AG/ kJ mold

Po!vmer svstem No. 1 (VP : MMA ratlo 1: 0, Ru 0 1 M HCIO, 0.21 43 0.7 M HCI 15 36 0.1 M Na,SO, 0.21 36 0 05 M H,SO, 3.0 32 Polvmer system No. 2.1 (VP.MMA 0.1 M HCIO, 2.76 ratto I 40 139

: VP ratio 1. 5)
40 33 34 30 -71 -152 - 101 -79 61 79 64 53

: I, Ru: VP ratlo I .7.43)

37 137 -117 219 72 71

Polvmer system No. 2.2 (VP. MMA ratto I : 3.2, Ru. VP ratlo I. 3.36) 137.5 0.05 M H,SO, 6.8 140

234

68

bone. The results of the latter series of experiments are outlined in Table slope behaviour was only observed for the copolymer. The activation entropy AS* can be evaluated from the Eyring equation: DCF;. es{ k,T/h} = exp[ ASS/R]

1. Dual

(6)

where 6 denotes the distance between adjacent ruthenium centers, e is the base of the natural logarithm and k,, h denote the Boltzmann constant and Planck constant respectively. The activation enthalpy AH* can be evaluated directly from the activation energy using the relation AH=E,-RT (7)

The quantity S is difficult to determine accurately but to a good approximation can be assigned the value of 2.5 nm. A careful inspection of the data outlined in Table 1 results in the assignment of a rather large negative activation entropy for charge transport within the layer. The latter is observed over the entire temperature region investigated for the homopolymer films but is observed only at low temperatures for the copolymer samples. Similar large negative entropy valus have been reported by Murray et al. [l] for diffusional charge transport through very thin films of radiofrequency plasma polymerized vinylferrocene deposited on platinum electrode surfaces. In this latter work activation energies and activation enthalpies in the region of 16 kJ mall and -133 J mol- K- were obtained. In the present work rather positive entropy values are obtained for the copolymer at more elevated temperatures. These observations can be rationalised as follows. The fundamental charge transport process between adjacent ruthenium centres requires an ordering deformation of polymer chains in a localized volume element or activation zone around the redox active sites between which charge transfer occurs. Furthermore transport of charge compensating counterions and solvent molecules requires a certain degree of

211

expansion of the polymeric lattice which by necessity will result in a decrease in chain mobility and by implication an increase in the degree of order of the system. In contrast the rather large positive activation entropies observed for copolymer films at more elevated temperatures can be ascribed to the disordering effects caused by substantial polymer side chain motions. It is possible to speculate that the copolymer backbone is somewhat more flexible than that of the homopolymer [9]. Further work has to be performed before the latter proposal can be confirmed however.
ACKNOWLEDGEMENTS

The support of the National Board for Science and Technology (Grant Number St/Eng/084/86) and the Trinity Trust is gratefully acknowledged. The authors also thank Johnson-Matthey Chemicals Ltd. for the generous loan of ruthenium trichloride.
REFERENCES 1 2 3 4 5 6 7 P. Daum, J.R. Lenbard, D. Rolison and R.W. Murray, J. Am. Chem. Sot., 102 (1980) 4649. N. Oyama, T. Ohsaka and T. Ushirogouchi, J. Phys. Chem., 88 (1984) 5274. T. Oh&a, H. Yamamoto and N. Oyama, J. Phys. Chem., 91 (1987) 3775. J.M. Clear, J.M. Kelly, C.M. OConnell and J.G. Vos, J. Chem. Res., (1981) (M) 3039. K. Aoki, K. Tokuda and H. Matsuda, J. Electroanal. Chem., 146 (1983) 417. K. Aoki. K. Tokuda and H. Matsuda, J. Electroanal. Chem., 160 (1984) 33. W.H. Press. B.P. Flannery, S.A. Teukolsky and W.T. Vetterling, Numerical Recepies: The Art of Scientific Computing, Cambridge University Press, London. 1986, Ch. 9. 8 W.J. Albery, M.G. Boutelle, P.J. Colby and A.R. Hillman, J. Electroanal. Chem., 133 (1982) 135. 9 R.T. Batley, A.M. North and R.A. Pethrick, Molecular Motion in High Polymers, Clarendon Press, Oxford, 1981, Ch. 10, p. 322.