Pretreatment of electrodes

For farther improvement of hydrogen enzyme electrode the commercial carbon filament materials were used as an electrode matrix. Such type of materials are accessible and well characterized, that provides the reproducibility of the results. A procedure for hydrogen enzyme electrode preparation included the pretreatment of electrode support with sulfuric acid followed by enzyme immobilization. This procedure is a critical step, since initially carbon filament material is completely hydrophobic [9]. 

The selective pretreatment of electrodes also has the advantage of preventing the occasional adsorption of other molecules, which is very probable when working with biological materials. 

Pretreatment of electrodes by cychc polarization needs special care because the surface structure depends on the number of cycles and the potential range of polarization. It was shown that during the polarization of Au and Pt electrodes, up to ca. 15V (vs. Normal Hydrogen Electrode) in lAf H2SO4, the quantities of dissolved metals corresponded to the... 

Figure 13.6.1 Cyclic voltammogram for a smooth platinum electrode in 0.5 M H2SO4. Peaks formation of adsorbed hydrogen. Peaks H oxidation of adsorbed hydrogen. Peaks Oq formation of adsorbed oxygen or a platinum oxide layer. Peak Oc reduction of the oxide layer. Point 1 start of bulk hydrogen evolution. Point 2 start of bulk oxygen evolution. The shape, number, and size of the peaks for adsorbed hydrogen depend on the crystal faces of platinum exposed (62), pretreatment of electrode, solution impurities, and supporting electrolyte. See also Figure 13.4.4.

Immobilized Enzymes. The immobilized enzyme electrode is the most common immobilized biopolymer sensor, consisting of a thin layer of enzyme immobilized on the surface of an electrochemical sensor as shown in Figure 6. The enzyme catalyzes a reaction that converts the target substrate into a product that is detected electrochemicaHy. The advantages of immobilized enzyme electrodes include minimal pretreatment of the sample matrix, small sample volume, and the recovery of the enzyme for repeated use (49). Several reviews and books have been pubHshed on immobilized enzyme electrodes (50—52). 

Stationary microwave electrochemical measurements can be performed like stationary photoelectrochemical measurements simultaneously with the dynamic plot of photocurrents as a function of the voltage. The reflected photoinduced microwave power is recorded. A simultaneous plot of both photocurrents and microwave conductivity makes sense because the technique allows, as we will see, the determination of interfacial rate constants, flatband potential measurements, and the determination of a variety of interfacial and solid-state parameters. The accuracy increases when the photocurrent and the microwave conductivity are simultaneously determined for the same system. As in ordinary photoelectrochemistry, many parameters (light intensity, concentration of redox systems, temperature, the rotation speed of an electrode, or the pretreatment of an electrode) may be changed to obtain additional information. 

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. 

The actual values of jo depended slightly on the pretreatment of the solid electrode. Indium-plated platinum electrode. 

The catalytic activity of an electrode is determined not only by the natnre of the electrode metal (its bulk properties) but also by the composition and stmcture of the snr-face on which the electrochemical reaction takes place. These parameters, in tnm, depend on factors such as the method of electrode preparation, the methods of snr-face pretreatment, conditions of storage, and others, all having little effect on the bulk properties. 

The qualitative voltammetric behavior of methanol oxidation on Pt is very similar to that of formic acid. The voltammetry for the oxidation of methanol on Pt single crystals shows a clear hysteresis between the positive- and negative-going scans due to the accumulation of the poisoning intermediate at low potentials and its oxidation above 0.7 V (vs. RHE) [Lamy et al., 1982]. Additionally, the reaction is also very sensitive to the surface stmcture. The order in the activity of the different low index planes of Pt follows the same order than that observed for formic acid. Thus, the Pt(l 11) electrode has the lowest catalytic activity and the smallest hysteresis, indicating that both paths of the reaction are slow, whereas the Pt( 100) electrode displays a much higher catalytic activity and a fast poisoning reaction. As before, the activity of the Pt(l 10) electrode depends on the pretreatment of the surface (Fig. 6.17). 

Before the measurement of HOR activity, a pretreatment of the alloy electrode was carried out by potential sweeps (10 V s ) of 10 cycles between 0.05 and 1.20 V in N2-purged 0.1 M HCIO4. The cyclic voltammograms (CVs) at all the alloys resembled that of pure Pt. As described below, these alloy electrodes were electrochemically stabilized by the pretreatment. Hydrodynamic voltammograms for the HOR were then recorded in the potential range from 0 to 0.20 V with a sweep rate of 10 mV s in 0.1 M HCIO4 saturated with pure H2 or 100 ppm CO/H2 at room temperature. The kinetically controlled current 4 for the HOR at 0.02 V was determined from Levich-Koutecky plots [Bard and Faulkner, 1994]. 

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). 

The study of metal ion/metal(s) interfaces has been limited because of the excessive adsorption of the reactants and impurities at the electrode surface and due to the inseparability of the faradaic and nonfaradaic impedances. For obtaining reproducible results with solid electrodes, the important factors to be considered are the fabrication, the smoothness of the surface (by polishing), and the pretreatment of the electrodes, the treatment of the solution with activated charcoal, the use of an inert atmosphere, and the constancy of the equilibrium potential for the duration of the experiment. It is appropriate to deal with some of these details from a practical point of view. 

The details of the pretreatment of the electrodes and purification of the charcoal and the solution have already been described in an earlier publication43 and review.40... 

Potentiometric measurements with ISEs can be approached by direct potentiometry, standard addition and titrations. The determination of an ionic species by direct potentiometry is rapid and simple since it only requires pretreatment and electrode calibration. Here, the ion-selective and reference electrodes are placed in the sample solution and the change in the cell potential is plotted against the activity of the target ion. This method requires that the matrix of the calibration solutions and sample solutions be well matched so that the only changing parameter allowed is the activity of the target ion. 

In summary, the overall successful effect has been assigned to the fact that any pretreatment of either the electrode surface (use of promoters, use of specific carbon electrodes, with the eventual generation of functional COO groups) or the solutions (addition of multicharged cationic species, proper choice of pH) creates at the bare electroinactive surface more and more specific microscopic active sites able to favour the exchange of electrons with proteins.10 This means that, in the absence of proper pretreatments, the electrode surface does not possess specific sites... 

The changes in reorientation of surface atoms were explained using the dynamic model of the crystal space lattice. It was assumed that during anodic polarization, when the oxidation of adsorbed water is taking place, atoms oscillate mainly in a direction perpendicular to the electrode surface. This process leads to periodic separation of atoms in the first surface layer. Thus, the location of atoms in different orientations is possible. It was stated that various techniques of electrode pretreatment used for... 

Fujishima and coworkers reported a method to electrochemically deposit IrO,. NPs at BDD electrodes [87]. The deposition process was based on preparation of a solution containing hydrolysis products of IrClg and oxalate, followed by anodic electrodeposition of IrO from this solution onto an anodically pretreated BDD electrode. 

However, when the potential of the pretreatment of the GC exceeded -I- 1.75 V (vs SCE) or it was driven longer than 300 s in PBS (pH 5.0), the adsorption of ssDNA at the electrode was found to decrease [46], showing that different conditions for obtained GC(ox) were detrimental for the DNA adsorption and oxidation. A similar negative effect was observed when the adsorption of the DNA was performed on polished GC previously exposed to air for a given time [44]. 

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