Platinum electrode structure

The presence of o-qulnone surface waves seems, at the present time, to be coincidental to activation particularly In the case of ascorbic acid oxidation. On the other hand. Its presence may serve as a criterion of cleanliness and activation. Thus, the surface waves at 0.250 and 0.190 are Indicators or signatures for active GCE electrodes and should be used as diagnostic for a clean GCE surface as Is the hydrogen fine structure for platinum (31). It Is unfortunate that the o-qulnone peaks do not appear to be proportional to the surface area as Is the platinum fine structure. 

A prepassivated platinum electrode and an electrode of the metal of interest have been used to follow the development of a biofilm to determine its effects on the corrosion behavior of structural materials. The time dependence of the open circuit potential of several stainless steels... 

We have also discussed two applications of the extended ab initio atomistic thermodynamics approach. The first example is the potential-induced lifting of Au(lOO) surface reconstmction, where we have focused on the electronic effects arising from the potential-dependent surface excess charge. We have found that these are already sufficient to cause lifting of the Au(lOO) surface reconstruction, but contributions from specific electrolyte ion adsorption might also play a role. With the second example, the electro-oxidation of a platinum electrode, we have discussed a system where specific adsorption on the surface changes the surface structure and composition as the electrode potential is varied. 

In order to assess the role of the platinum surface structure and of CO surface mobility on the oxidation kinetics of adsorbed CO, we carried out chronoamperometry experiments on a series of stepped platinum electrodes of [n(l 11) x (110)] orientation [Lebedeva et al., 2002c]. If the (110) steps act as active sites for CO oxidation because they adsorb OH at a lower potential than the (111) terrace sites, one would expect that for sufficiently wide terraces and sufficiently slow CO diffusion, the chronoamperometric transient would display a CottreU-hke tailing for longer times owing to slow diffusion of CO from the terrace to the active step site. The mathematical treatment supporting this conclusion was given in Koper et al. [2002]. 

The potential of the stripping peak, and hence the activity of the electrode for CO oxidation, also depends on the platinum surface structure in general and on the step density in particular. Based on the chronoamperometry experiments described in Section 6.2.1.1, one would expect the stripping peak to shift to lower potential with increasing step density. That this is indeed the case is shown in Fig. 6.6. Again, this... 

Wang H, Baltruschat H. 2007. DEMS study on methanol oxidation at poly- and monocrystalline platinum electrodes The effect of anion, temperature, surface structure, Ru adatom, and potential. J Phys Chem C 111 7038-7048. 

Clavilier J, Feliu JM, Aldaz A. 1988. An irreversible structure sensitive adsorption step in bismuth underpotential deposition at platinum electrodes. J Electroanal Chem 243 419-433. 

Beden B, Juanto S, Leger JM, Lamy C. 1987. Infrared spectroscopy of the methanol adsorbates at a platinum electrode Part III. Structural effects and behaviour of the polycrystalline surface. J Electroanal Chem 238 323-331. 

The electrochemical oxidation of polyhydric alcohols, viz. ethylene glycol, glycerol, meso-erythritol, xilitol, on a platinum electrode show high reactivity in alkaline solutions of KOH and K2C03 [53]. This electro-oxidation shows structural effects, Pt(lll) being the most active orientation. This results from different adsorption interactions of glycerol with the crystal planes [59]. 

Figure 10 Cyclic voltammograms recorded at a platinum electrode in a CH2CI2 solution of [(rf-CriH6)Cr(CO)3], Supporting electrolytes (a) [NBU4] [PF6] (b) [NBu4][C104]. Scan rate 0.2 V s. (c) Molecular structure of [fr,6-C6H6)Cr(CO)3]...

As mentioned above, contradicting results were produced between smooth and dispersed platinum electrodes. It is no doubt that the surface structures play an important role in the reaction mechanism and catal rtic... 

Another approach has been developed to fabricate electrodes with loading as low as 0.1 mg Pt/cm (32). The electrode structure was improved by increasing the contact area between the electrolyte and the platinum clusters. The advantages of this approach are that a thinner catalyst layer of 2 to 3 microns and a uniform mix of catalyst and ionomer are produced. For example, a cell with a Pt loading of 0.17 to 0.13 mg/cm has been fabricated. The cell generated 3 A/cm at > 0.4V on pressurized O2 and 0.65 V at 1 A/cm on pressurized air (32,... 

Sometimes, semiconductivity depends on the type of a structural phase that arises from synthesis. Thus, in the case of (TCNQ) Cu the semiconducting phase is thermodynamically disfavored. To prepare this semiconductor, Harris et al. (2005) proposed to perform the reduction of TCNQ in acetonitrile at glass-carbon, gold, or platinum electrode in the presence of Cu. This allows the electrocrystallization of sparingly soluble TCNQCu semiconducting phase to occur by a nucleation... 

Platinum electrodes are widely used as an inert electrode in redox reactions because the metal is most stable in aqueous and nonaqueous solutions in the absence of complexing agents, as well as because of its electrocatalytic activity. The inertness of the metal does not mean that no surface layers are formed. The true doublelayer (ideal polarized electrode) behavior is limited to ca. 200-300 mV potential interval depending on the crystal structure and the actual state of the metal surface, while at low and high potentials, hydrogen and oxygen adsorption (oxide formation) respectively, occur. 

Effect of Adsorption and Surface Structure on the Voltammetric Behavior of Platinum Electrodes... 

A fast repetitive triangular potential sweep (lO" V s between 0.05 and 1.5 V for 2 h) was applied to platinized platinum electrode [217]. This treatment resulted in a considerable decrease in the real surface area and in the formation of a (lOO)-type preferentially oriented surface structure. 

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