Electrodes multilayer-coated

Attaching the catalyst molecules to the electrode surface presents an obvious advantage for synthetic and sensor applications. Catalysis can then be viewed as a supported molecular catalysis. It is the object of the next section. A distinction is made between monolayer and multilayer coatings. In the former, only chemical catalysis may take place, whereas both types of catalysis are possible with multilayer coatings, thanks to their three-dimensional structure. Besides substrate transport in the bathing solution, the catalytic responses are then under the control of three main phenomena electron hopping conduction, substrate diffusion, and catalytic reaction. While several systems have been described in which electron transport and catalysis are carried out by the same redox centers, particularly interesting systems are those in which these two functions are completed by two different molecular systems. 

Redox and Chemical Catalysis at Monolayer and Multilayer Coated Electrodes... 

Electron transport in electrode coatings containing redox centers is a necessary ingredient of their functioning as a catalytic device. They indeed serve as an electron shuttle between the electrode and the catalyst present inside the film. As discussed in the next section, the same molecule may play the role of catalyst and of electron carrier, since as shown earlier, redox catalysis is possible in these multilayered coatings. They may also be different, as exemplified is Section 4.3.6. 

In zone R, all three phenomena that take place in the film are fast compared to the diffusion of the substrate from the bulk of the solution to the film-solution interface. The concentrations of both Q and A are constant through the film. The RDEV response is similar to that of a monolayer coating (Section 4.3.2), except that more catalytic material is present on the surface of the electrode (it is multiplied by the number of layers in the multilayered coating). A linear Koutecky-Levich plot is obtained from the intercept, from which the kinetics of the catalytic reaction can be characterized. 

Immobilizing the catalyst on the electrode surface is useful for both synthetic and sensors applications. Monomolecular coatings do not allow redox catalysis, but multilayered coatings do. The catalytic responses are then functions of three main factors in addition to transport of the reactant from the bulk of the solution to the film surface transport of electrons through the film, transport of the reactant in the reverse direction, and catalytic reaction. The interplay of these factors is described with the help of characteristic currents and kinetic zone diagrams. In several systems the mediator plays the role of an electron shuttle and of a catalyst. More interesting are the systems in which the two roles are assigned to two different molecules chosen to fulfill these two different functions, as illustrated by a typical experimental example. 

Still with an enzyme monolayer, the synthesis and current responses of a system that involves simultaneous attachment of the cosubstrate to the electrode coating are then described. The next step consists in constructing a multilayered coating constituted by successive layers of enzyme built thanks to antigen-antibody interactions. Sensing the diffusion of the cosubstrate through the film thus constructed provides evidence for spatial order and an estimate of the distances between layers. 

Figure 7. Amperometric response of glucose sensors prepared using LB film-coated electrodes. ( ) multilayer GOx (o) monolayer GOx sensors.

Phillips (19) formed a reference electrode by coating a noble metal with a Langmuir-Blodgett multilayer of calcium palmitate and used it to detect the presence of a polar vapor in dry atmospheres by its adsorption on an uncoated metal electrode. Water vapor and oxygen were carefully excluded from the surrounding atmosphere, since either gas penetrated the multilayer coating on the reference electrode. This report describes the preparation, properties, and several applications of a more general and useful type of reference electrode. 

A pH sensor, based on a.c. conductivity measurements of a thin polymer film, has been developed. The sensor consists of a planar interdigitated electrode array coated with a polypyrrole multilayer, built-up using the Langmuir-Blodgett technique. Impedance spectroscopy has been used to investigate the complex admittance of the device when exposed to aqueous solutions of different pH. The experimental data have been fitted to the theoretical response of an equivalent electrical network of capacitors and resistors. A response over the pH range 3.5 to 8 has been measured. 

From the fitting, this has a value of 36 pF (slightly greater than obtained with the uncoated electrode). Rppy represents the in-plane resistance of the polypyrrole-palmitic acid film, which from the curve fitting is found to be 3030 Q. The capacitance of the polypyrrole multilayer coated interdigitated electrodes measured in vacuum was only a few pF has been ignored in the model. 

The LB technique is amenable to the fabrication of ECDs as demonstrated by the report of a thin-film display based on bis(phthalocyaninato)praseodymium(III).75 The electrochromic electrode in the display was fabricated by deposition of multilayers (10-20 layers, r+00-200 A) of the complex onto ITO-coated glass (7 x4cm2) slides. The display exhibited blue-green-yellow-red polyelectrochromicity over a potential range of —2 to +2V. After 105 cycles no significant... 

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