Plasma-polymerized vinylferrocene

Daum, P, Lenhard, J.R., Rolison, D., and Murray, R.W. 1980. Diffusional charge transport through ultrathin films of radiofrequency plasma polymerized vinylferrocene at low temperature. Journal of the American Chemical Society 102,4649 653. 

Fig. 5.3 Comparison of experimental data obtained for plasma-polymerized vinylferrocene (solid circles) and the theoretical calculation (open circles) according to (5.39). (Reproduced from [14] with the permission of Elsevier)...

Daum R. andMurray R. W. (1981), Charge-transfer diffusion rates and activity relationships during oxidation and reduction of plasma-polymerized vinylferrocene films , J. Phys. Cfera., 85, 389-96. 

Plasma-polymerized vinylferrocene was one of the first electrode coatings developed [576,577]. Using a radiotracer method, the uptake/release of coimterions into similar electrode coatings upon oxidation/reduction could be investigated [527]. Recently, two charge transport mechanisms were found in thin ferrocene-containing composite films (electron hopping and bounded diffusion) [578]. 

Electropolyraerization is useful and has been successfully applied to 4-vinylpyridine complexes and to 4-methyl-4 -vinyl-2,2 -bipyridyl.52 Vinylferrocene (vide infra) has been polymerized on to platinum, glassy carbon and titanium dioxide electrodes by introduction to a radiofrequency argon plasma discharge. Electropolymerization and plasma polymerization are likely to be of value to produce copolymers on electrode surfaces. 

Prospects for efficient electrocatalysis are the strongest driving force behind the development of modified electrodes. Ascorbic acid is often used to test new catalytic systems because of its overpotential, amenability to electrocatalysis, and biological importance. Plasma polymerized poly(vinylferrocene) (49) and pentachloroiridate bound to protonated plasma polymerized poly(vinylpyridine) ( ) were each shown to serve as electrocatalysts for oxidation of ascorbic acid. Several other examples of electrocatalysis are described in later sections, but these are only a small sample of work going on in this field. 

J. Nowak, F. A. Schultz, M. Umana, R. Lam, and R. W. Murray, Chemically modified electrodes. XX. Radiofrequency plasma polymerization of vinylferrocene on glassy carbon and platinum electrodes, Anal.Chem., 52 315 (1980). 

Plasma polymerization of vinylferrocene on Pt or Ti/TiOj has been described The composition of the films obtained depends on the reaction conditions employed. Cg gOj Fe, CjjH 2.602 > lo ii i, Fe [ideal composition [CjoHjjFe)]. In general, the degradation of ferrocene sites in the film is minimized by increasing the rate of deposition The thickness of the films is 0.1 pm. 

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