Preparing the Electrode Surface

In order to reduce the chance for the misinterpretation of a SERS result, it is important to prepare the electrode surface properly. For example, after roughening the surface, one may conduct an electrochemical cleaning procedure to remove... 

Electrochemical polymeriza tion of heterocycles is useful in the preparation of conducting composite materials. One technique employed involves the electro-polymerization of pyrrole into a swollen polymer previously deposited on the electrode surface (148—153). This method allows variation of the physical properties of the material by control of the amount of conducting polymer incorporated into the matrix film. If the matrix polymer is an ionomer such as Nation (154—158) it contributes the dopant ion for the oxidized conducting polymer and acts as an effective medium for ion transport during electrochemical switching of the material. 

The differential capacitance method cannot be used for reactive metals, such as transition metals in aqueous solutions, on which the formation of a surface oxide occurs over a wide potential re ion. An immersion method was thus developed by Jakuszewski et al. 3 With this technique the current transient during the first contact of a freshly prepared electrode surface with the electrolyte is measured for various immersion potentials. The electrode surface must be absolutely clean and discharged prior to immersion.182-18 A modification of this method has been described by Sokolowski et al. The values of obtained by this method have been found to be in reasonable agreement with those obtained by other methods, although for reactive metals this may not be a sufficient condition for reliability. 

Hence, it is important to remember that the products, reaction mechanism and the rate of the process may depend on the history and pretreatment of the electrode and that, indeed, the activity of the electrode may change during the timescale of a preparative electrolysis. Certainly, the mechanism and products may depend on the solution conditions and the electrode potential, purely because of the effect of these parameters on the state of the electrode surface. 

Electropolymerization is also an attractive method for the preparation of modified electrodes. In this case it is necessary that the forming film is conductive or permeable for supporting electrolyte and substrates. Film formation of nonelectroactive polymers can proceed until diffusion of electroactive species to the electrode surface becomes negligible. Thus, a variety of nonconducting thin films have been obtained by electrochemical oxidation of aromatic phenols and amines Some of these polymers have ligand properties and can be made electroactive by subsequent inincorporation of transition metal ions... 

A series of Be-Pt intermetallic compounds arc prepared during the electrodeposition of Be on Pt from a solution of BeCl2 in an equimol NaCl-KCl mixture at 710°C. X-Ray diffraction of the electrode surface shows the presence of BePt, BcjPt. Electrolytic methods are also used to extract single crystals of Be,V from alloys prepared by arc melting Be and the transition metal in the proportion 15 1. 

A third way to increase both the active surface area and the number of oxygenated species at the electrode surface is to prepare alloy particles or deposits and then to dissolve the non-noble metal component. This technique, which is similar to that used to prepare Raney-type catalysts, yields very high surface area electrodes and hence some improvements in the electrocatalytic activities compared with those of pure platinum. However, it is always difficult to be sure whether the mechanism of enhancment of the activities is due to this effect or the possible presence of remaining traces of the dissolved metal. Results with PtyCr and PtSFe were encouraging, although the effect of iron is still under discussion. From studies in a recent work on the behavior of R-Fe particles for methanol electrooxidation, it was concluded that the electrocatalytic effect is due to the Fe alloyed to platinum. ... 

Most of the studies have involved the alloying of a second metal to platinum. The second metal was generally chosen because of its ability to increase the concentration of oxygenated species on the electrode surface, but also for its corrosion resistance. Even if some discrepancies exist in the literature, R-Ru is now widely accepted as the most interesting one, and hence our analysis will focus on this alloy in the next subsection. Other alloys such as R-lr, R-Os, or R-Re have also been reported to be good candidates, and R-Mo under specific conditions of preparation was claimed to have the desired properties. The Pt-Sn alloy is still a subject... 

It was found that the intensity of Co2ps/2 decreased significantly (by a factor of 2.5), supporting the concept of Co dissolution from the alloy and formation of the Pt skin layer on the electrode surface during electrochemical stabilization. As shown in Fig. 10.4b, a clear CL shift was stUl observed in the Pt4/7/2 spectmm for the stabilized Pt-Co, in spite of the dissolution of Co, although the CL shift after stabilization was slightly smaller (0.15 eV) than in the as-prepared alloy (0.19 eV). Thus, we... 

A qualitatively new approach to the surface pretreatment of solid electrodes is their chemical modification, which means a controlled attachment of suitable redox-active molecules to the electrode surface. The anchored surface molecules act as charge mediators between the elctrode and a substance in the electrolyte. A great effort in this respect was triggered in 1975 when Miller et al. attached the optically active methylester of phenylalanine by covalent bonding to a carbon electrode via the surface oxygen functionalities (cf. Fig. 5.27). Thus prepared, so-called chiral electrode showed stereospecific reduction of 4-acetylpyridine and ethylph-enylglyoxylate (but the product actually contained only a slight excess of one enantiomer). 

Finally, we can also find in the literature arrangements where the working electrode is also the emitter part of the transducer, normally named as sonotrode [22] or sonoelectrode [41]. Some authors have used only the main emitter surface as electrode [42], see Fig. 4.2b, and other authors have used the fully surface tip as working electrode [43], see Fig. 4.2c. In theory, this arrangement assures that all the specific effects derived from the ultrasound field propagation are directly focused on the surface electrode. Not only the shorted-lived bubbles non-uniformly collapse on the electrode surface but also the electrode surface itself oscillates. This provides additional effects which have been specifically used in the nanoparticles preparation. 

Techniques for attaching such ruthenium electrocatalysts to the electrode surface, and thereby realizing some of the advantages of the modified electrode devices, have been developed.512-521 The electrocatalytic activity of these films have been evaluated and some preparative scale experiments performed. The modified electrodes are active and selective catalysts for oxidation of alcohols.5 6-521 However, the kinetics of the catalysis is markedly slower with films compared to bulk solution. This is a consequence of the slowness of the access to highest oxidation states of the complex and of the chemical reactions coupled with the electron transfer in films. In compensation, the stability of catalysts is dramatically improved in films, especially with complexes sensitive to bpy ligand loss like [Ru(bpy)2(0)2]2 + 51, 519 521... 

As referred to previously, if the active site of a biocatalyst is close enough to the electrode surface, direct electron transfer to/from an electrode can result. It has been shown in recent years that direct electron transfer from the GOx active site is possible using appropriate electrode preparation procedures. These preparation procedures usually aim to provide nano-structured features on the electrode surface that can penetrate sufficiently the GOx active site to allow for direct electron transfer. The direct electron... 

Negatively charged species such as carboxylic acid group in acid-treated CNTs can attract positively charged enzymes from solution as long as the pH value of the enzyme solution is controlled to be lower than the iso-electric point of the enzyme thus, multilayer films of the enzyme can be formed by the layer-by-layer technique. For example, five layers of GOx can be immobilized on the electrode surface by alternatively dipping a poly(diallyldimethylammonium chloride (PDDA))-functionalized GC into a CNT solution and a GOx solution (pH 3.8). Figure 15.15 illustrates the preparation process for the formation of a multilayer film of GOx on the electrode. 

CNTs offer an exciting possibility for developing ultrasensitive electrochemical biosensors because of their unique electrical properties and biocompatible nanostructures. Luong et al. have fabricated a glucose biosensor based on the immobilization of GOx on CNTs solubilized in 3-aminopropyltriethoxysilane (APTES). The as-prepared CNT-based biosensor using a carbon fiber has achieved a picoamperometric response current with the response time of less than 5 s and a detection limit of 5-10 pM [109], When Nation is used to solubilize CNTs and combine with platinum nanoparticles, it displays strong interactions with Pt nanoparticles to form a network that connects Pt nanoparticles to the electrode surface. The Pt-CNT nanohybrid-based glucose biosensor... 

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