: This is a critical review of my research on attaching molecules to electrode surfaces. (Author)

Chemically modified electrodes

Polymer films on electrodes: Part II. Film structure and mechanism of electron transfer with electrodeposited poly(vinylferrocene)

Electrocatalysis with ferrocyanide electrostatically trapped in an alkylaminesiloxane polymer film on a Pt electrode

Chemically modified electrodes: Part XXII. Solvent effects on the electrochemistry of thin films of plasma polymerized vinylferrocene

: Vinylferrocene can be polymerized in a radiofrequency Ar plasma to deposit in thin, adherent films on glassy carbon and Pt electrodes. In acetonitrile solvent containing tetraethylammonium perchlorate or tetrafluoroborate electrolyte, these films exhibit electrochemical reactivity qualitatively expectable for polyvinylferrocene films although analytical information of film composition shows some plasma damage and some oxygen incorporation has taken place. The relationship of observed electrochemistry to plasma reaction time and geometry is described. Quantities of electroactive ferrocene in the prepared films range from 0.5 - 300 x 10 to the -10th power mole/sq. cm. The thinner films exhibit non-limiting transport of electrochemical charge, while a thick film gives a diffusion-controlled response. (Author)

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Chemically Modified Electrodes. Radiofrequency Plasma Polymerization Of Vinylferrocene On Glassy Carbon And Platinum Electrodes

The method of glow-discharge polymerisation was applied to deposit highly cross-linked polymer films of 100-1000 A thickness on steel, platinum, and glassy carbon electrodes. These films were characterized by electrical, electrochemical, and optical techniques and found to be stable during electrolysis in liquid solutions of both inert and redox electrolytes. Moreover, interesting correlations between the electrochemical properties of the film-covered electrodes, studied by ac and dc techniques, and the conduction properties of metal-film-metal junctions using the same films, could be established. – Under suitable and well-defined preparation conditions the films possess sufficiently high conductivity that their electrocatalytic properties can be exploited. Insertion of metal clusters or chelate polymers is likely to improve the electrocatalytic activity, and the film electrode systems are thus promising, e. g. in fuel cells and other practical applications.



Mit der Methode der Gasentladungs-Polymerisation wurden auf Metall- und Glaskohlenstoffelektroden quervernetzte Polymerfilme von etwa 100-1000 A Dicke aufgebraucht. Sie waren bei der Elektrolyse in wasrigen Elektrolyten stabil. – Das elektrochemische Verhalten der polymerbedeckten Elektroden wurde mit Wechsel- und Gleichstrommethoden in inerten und Redox-Elektrolyten untersucht. Auserdem wurden die Festkorpereigenschaften der Polymerschichten untersucht und mit den Ergebnissen der elektrochemischen Messungen korreliert. – Die Polymerschichten haben fur die Sauerstoff-Reduktion eine gewisse elektrokatalytische Wirksamkeit. Die katalytische Wirksamkeit last sich wahrscheinlich durch Einbau von Metallen in die Schicht, etwa in Form von Clustern oder Chelat-Polymeren, noch steigern. Damit konnten diese Elektroden auch fur eine praktische Verwendung in Betracht kommen, etwa fur Brennstoffzellen.

J. Ulstrup

Papers

Polymer-Film Covered Electrodes of Stable Electrochemical Performance