Composites electrochemistry

Investigations of multicentre electrochemical metalloprotein function including metalloenzyme function have also been brought to a level, where both direct and catalytic modes, and elements of molecular mechanisms can be addressed. The latter are, however, entangled by features such as composite electrochemistry, extremely complicated molecular interaction patterns when more than two metallic redox centres are involved, fragile surface enzyme preparations, and lack of structural surface characterization of the adsorbed metalloenzymes. In this respect, two-centre metalloproteins constitute interesting promising intermediates where the coop-erativity between the metallic redox centres can be accurately addressed with molecular resolution within reach. 

Kitani, A., et al. 1999. Electrochemical behaviors of polyaniline/poly(an0ine-2,5-disulfonic acid) composites. Electrochemistry 67 1262. 

The presence of polymer, solvent, and ionic components in conducting polymers reminds one of the composition of the materials chosen by nature to produce muscles, neurons, and skin in living creatures. We will describe here some devices ready for commercial applications, such as artificial muscles, smart windows, or smart membranes other industrial products such as polymeric batteries or smart mirrors and processes and devices under development, such as biocompatible nervous system interfaces, smart membranes, and electron-ion transducers, all of them based on the electrochemical behavior of electrodes that are three dimensional at the molecular level. During the discussion we will emphasize the analogies between these electrochemical systems and analogous biological systems. Our aim is to introduce an electrochemistry for conducting polymers, and by extension, for any electrodic process where the structure of the electrode is taken into account. 

It must be emphasized that Equations (5.24) and (5.25) stem from the definitions of Fermi level, work function and Volta potential and are generally valid for any electrochemical cell, solid state or aqueous. We can now compare these equations with the corresponding experimental equations (5.18) and (5.19) found to hold, under rather broad temperature, gaseous composition and overpotential conditions (Figs. 5.8 to 5.16), in solid state electrochemistry ... 

Skotheim et al. [286, 357, 362] have performed in situ electrochemistry and XPS measurements using a solid polymer electrolyte (based on poly (ethylene oxide) (PEO) [363]), which provides a large window of electrochemical stability and overcomes many of the problems associated with UHV electrochemistrty. The use of PEO as an electrolyte has also been investigated by Prosperi et al. [364] who found slow diffusion of the dopant at room temperature as would be expected, and Watanabe et al. have also produced polypyrrole/solid polymer electrolyte composites [365], The electrochemistry of chemically prepared polypyrrole powders has also been investigated using carbon paste electrodes [356, 366] with similar results to those found for electrochemically-prepared material. 

Y.J. Hu, N.F. Hu, and Y.H. Zeng, Electrochemistry and electrocatalysis with myoglobin in biomembrane-like surfactant-polymer 2C 2N+PA composite films. Talanta 50, 1183-1195 (2000). 

Y.H. Wu and S.S. Hu, Direct electrochemistry of glucose oxidase in a colloid Au-dihexadecylphos-phate composite film and its application to develop a glucose biosensor. Bioelectrochemistry. Available online 6 May (2006). 

Despic, A. R. and Jovic, V. D., Electrochemical Deposition and Dissolution of Alloys and Metal Composites - Fundamental Aspects, in Modern Aspects of Electrochemistry, R. E. White, J. O. M. Bockris, and B. E. Conway, Editors. 1995, Plenum Press New York, p. 143. 

Calculation of the internal cell potential is a very complicated matter because the electrochemistry of all of the species within the protocell would have to be balanced subject to their composition quotient Q, after which the standard free energy would have to be established from tabulations. The transport of Na+ would also change this balance, along with the ionic strength of the solution and the stability of the proteins or prebiotic molecules within the protocell. Such non-equilibrium thermodynamics forms the basis of the protocell metabolism. The construction... 

If a solution forms part of an electrochemical cell, the potential of the cell, the current flowing through it and its resistance are all determined by the chemical composition of the solution. Quantitative and qualitative information can thus be obtained by measuring one or more of these electrical properties under controlled conditions. Direct measurements can be made in which sample solutions are compared with standards alternatively, the changes in an electrical property during the course of a titration can be followed to enable the equivalence point to be detected. Before considering the individual electrochemical techniques, some fundamental aspects of electrochemistry will be summarized in this section. 

As pointed out above the comparison between both sets of results relies upon the physical equivalence of the two measureable quantities work function (surface science) and electrode potential (electrochemistry) 111. This equivalence has been realized in electrochemistry some time ago and has been exploited to analyze measured values of the potential of zero charge 111 and of work function changes upon emersion of electrodes at fixed potential 181. In the simulation experiments the approach is quite similar in that one prepares a well-defined composition of the synthetic electrochemical adsorbate layer and then obtains the electrostatic potential drop across it by a work function measurement. 

The methodology of surface electrochemistry is at present sufficiently broad to perform molecular-level research as required by the standards of modern surface science (1). While ultra-high vacuum electron, atom, and ion spectroscopies connect electrochemistry and the state-of-the-art gas-phase surface science most directly (1-11), their application is appropriate for systems which can be transferred from solution to the vacuum environment without desorption or rearrangement. That this usually occurs has been verified by several groups (see ref. 11 for the recent discussion of this issue). However, for the characterization of weakly interacting interfacial species, the vacuum methods may not be able to provide information directly relevant to the surface composition of electrodes in contact with the electrolyte phase. In such a case, in situ methods are preferred. Such techniques are also unique for the nonelectro-chemical characterization of interfacial kinetics and for the measurements of surface concentrations of reagents involved in... 

All the discussions of electrochemistry so far in this chapter concern current - the flow of charged electrons. We call this branch of electrochemistry dynamic, implying that compositions change in response to the flow of electrons. Much of the time, however, we wish to perform electrochemical experiments at equilibrium. 

---