Electrochemical reactions, shape-selective

Mesophase structures self-assembled from surfactants (Figure 8.35) provide another class of useful and versatile templates for generating ID nanostructures in relatively large quantities. It is well known that at critical micellar concentration (CMC) surfactant molecules spontaneously organize into rod-shaped micelles [315c]. These anisotropic structures can be used immediately as soft templates to promote the formation of nanorods when coupled with appropriate chemical or electrochemical reaction. The surfactant needs to be selectively removed to collect the nanorods/nanowires as a relatively pure sample. Based on this principle, nanowires of CuS, CuSe, CdS, CdSe, ZnS and ZnSe have been grown selectively by using surfactants such as Na-AOT or Triton X of known concentrations [238, 246]. 

When both the substance titrated and the titrant undergo electrochemical reactions at the voltage selected, the current wiU decrease (linearly) up to the equivalence point, then increase again with addition of excess titrant, resulting in a V-shaped titration curve. An example of this is the titration of Pb with potassium dichromate in a weakly acidic supporting electrolyte. Dichromate ion is reduced to Cr at the DME with 0 V versus SCE. If —1.0 V is applied to the indicator electrode, both Pb " and Cra07 are reducible, and a V-shaped titration curve will result. If, on the other hand, the applied voltage is —0.2 V, only dichromate ion is reducible, and a reverse L-shaped titration curve results. 

Other properties which have contributed to the attractiveness and versatility of the sol-gel doping approach are the chemical, photochemical and electrochemical inertness as well as the thermal stability of the matrix the ability to induce electrical conductivity16 the richness of ways to modify chemically the matrix and its surface as well as the above-mentioned controllability of matrix structural properties the enhanced stability of the entrapped molecule1,17 the ability of employing the chromatographic properties of the matrix for enhanced selectivity and sensitivity of reactions with the dopant4 the simplicity of the entrapment procedure the ability to obtain the doped sol-gel material in any desired shape (powders, monoliths, films, fibers) and the ability to miniaturize it18,19. 

The choice of an appropriate electrochemical sensor is governed by several requirements (1) the nature of the substrate to be determined (ions or redox species) (2) the shape of the final sensor (microelectrodes) (3) the selectivity, sensitivity, and speed of the measurements and (4) the reliability and stability of the probe. The most frequently used sensors operate under potentiometric or amperometric modes. Amperometric enzyme electrodes, which consume a specific product of the enzymatic reaction, display an expanded linear response... 

The largest exchange current density, j0, of the reaction has to be selected, if possible, since economic limitations are always prevalent in scaled-up engineering. However, with the development of nanodispersed substrates and carbon-supported metal catalysts, this limitation becomes a secondary consideration. At this point, it is important to say that most of the reported values of j usually refer to simple reactions on pure metal substrates using different shapes of electrode designs in a certain and single electrolyte. Thus, the measurement of the real j0 value at select industrial conditions of the electrochemical reactor has to be performed that is, experimental measurements cannot be avoided [4,5]. 

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