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Fig. 5.40 Cyclic voltammogram of a bright platinum electrode in 0.5 M H2SO4. Geometrical area of the electrode 1.25 x 10~3cm2, periodical triangular potential sweep (dE/dt = 30 V s"1), temperature 20 C, the solution was bubbled with argon. (By courtesy of J. Weber)

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Even in monophasic systems, polymer properties can be bene cial to photoresponses and can level up the effects beyond the association dissociation occurring at the molecular scale. Intrapolymer associations of colloid nanoparticles (e.g., micelles or proteins) most typically exhibit multipoint attachments, that is, several azobenzene groups would simultaneously attach onto the same particle. Chemical equilibrium requires that the energy of transfer of azobenzene from water into their binding sites balances the conformation energy of the chain segments forming loops on the particle (Fig. 7.5a). In addition, if a necklace of bound colloid particles is formed, an additional intrachain particle particle interaction may also contribute to the association energy. Finally, at concentration above C* for the polymer, the association may transiently cross-link the chains and markedly modify the dynamic and mechanical properties. Altogether, these contributions to association result in complex responses to photovariations of the af nity for azobenzene. This section presents the essential features of such

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17

then the picture changes quite markedly. The shape of the voltammetric curve is also affected strongly by the procedure of annealing the electrode prior to the experiment. There are also very marked differences between the first voltammetric curve and the curve obtained after repeated pulsing. All these features are typical for electrocatalytic phenomena. It was demonstrated by R. Parsons and H. Gerischer that the adsorption energy of the hydrogen atom determines not only the rate of the Volmer reaction (5.7.1) but also the relative rates of all three reactions (5.7.1) to (5.7.3). The relative rates of these three reactions decide over the mechanism of the overall process of evolution or ionization of hydrogen and decide between possible rate-determining steps at electrodes from different materials. The effect of adsorption on the electroreduction of hydrogen ions, i.e. the Volmer reaction, is strongly affected by the potential difference in the diffuse electrical layer (Eq. 5.3.20). In the presence of iodide ions, the overpotential at a mercury electrode decreases, although the adsorption of iodide is minimal in the potential region corresponding to hydrogen evolution. The adsorption of iodide

Bound nanoparticle (protein, micelle, vesicle, etc) (b)

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Fig. 5.41 A single-crystal sphere of platinum (magnification 100x). It is prepared from a Pt wire by annealing in an oxygen-hydrogen flame or by electric current and by subsequent etching. The sphere is then cut parallel to the face with a required Miller index to obtain a single-crystal electrode. (By courtesy of E. Budevski)

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Figure 7.5. Schematic drawing of the light-responsive association between a exible polymer and nanoparticles. See color insert.

retards the electrode process at other electrodes with large hydrogen overpotentials, such as the lead electrode. Hydrogen is evolved from water molecules in alkaline media at mercury and some other electrodes. As the adsorption energy increases, the rate of the Volmer reaction can increase until equilibrium is attained and the rate of the process is determined by either the Tafel or the Heyrovsky reaction. However, it is more probable for kinetic reasons that the Tafel reaction will occur at electrodes that form a moderately strong bond with adsorbed hydrogen (e.g. at platinum electrodes, at least in some cases). Electrodes that adsorb hydrogen strongly such as tungsten electrodes, are in practice completely covered with adsorbed hydrogen over a wide range of electrode potentials.

complexes in dilute and semidilute solutions, with emphasis on the origin of ampli cation of the responses to light.

The Tafel reaction would require breaking the adsorption bonds to two hydrogen atoms strongly bound to the electrode, while the Heyrovsky reaction requires breaking only one such bond; this reaction then determines the rate of the electrode process. The isotope effect (i.e. the difference in the rates of evolution of hydrogen from H2O and D2O) on hydrogen evolution is very important for theoretical and practical reasons. The electrolysis of a mixture of H2O and D2O is characterized, like in other separation methods, by a separation factor

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