Hydrogen adsorption platinum

Platinum-gold alloys represent an example of group b. The electrochemical properties of these alloys have been studied [93—98] extensively. They can exist [99] as homogeneous alloys or as a mixture of a platinum-rich phase and a gold-rich phase a2. The cold-drawn wires used in these investigations [94—98] were of the latter type. It was demonstrated [96—98] that the electrocatalytic properties of the platinum-rich phase are similar to those of platinum. Hydrogen adsorption [96] and methanol oxidation [97] occur only on this phase. The... 

Adsorption of Reaction Components In many cases, adsorption of a reactant is one of the hrst steps in the electrochemical reaction, and precedes charge transfer and/or other steps of the reaction. In many cases, intermediate reaction products are also adsorbed on the electrode s snrface. Equally, the adsorption of reaction products is possible. The example of the adsorption of molecular hydrogen on platinum had been given earlier. Hydrogen adsorption is possible on the platinum electrode in aqueons solntions even when there is no molecular hydrogen in the initial system at potentials more negative than 0.3 V (RHE), the electrochemical reaction... 

Oxygen adsorption that occurs at platinum at potentials more positive than 0.9 to 1.0 V is irreversible, in contrast to hydrogen adsorption. Oxygen can be removed from the surface by cathodic current, but the curves obtained in the anodic and cathodic scan do not coincide cathodic oxygen desorption occurs within a narrower region of potentials, and these potentials are more negative than the region where the... 

It was quickly seen from studies on platinum single crystals that voltammograms for hydrogen adsorption and desorption differ somewhat among the different faces and between the single-crystal faces and polycrystalline platinum. Despite these differences, though, they have common traits as weU. The areas under these curves,... 

Cyclic voltammetry is perhaps the most important and widely used technique within the field of analytical electrochemistry. With a theoretical standard hydrogen electrode at hand, one of the first interesting and challenging applications may be to try to use it to make theoretical cyclic voltammograms (CVs). In following, we set out to do this by attempting to calculate the CV for hydrogen adsorption on two different facets of platinum the (111) and the (100) facets. 

Biegler T, Rand DAJ, Woods R. 1971. Limiting oxygen coverage on platinized platinum Relevance to determination of teal platinum area by hydrogen adsorption. J Electroanal Chem 29 269-277. 

Cyclic voltammetry studies of single-crystal platinum electrodes in acidic aqueous electrolytes showed that the two characteristic peaks of hydrogen adsorption/desorption on platinum (see Fig. 5.40) correspond in fact to reactions at two different crystal faces the peak at lower potential to Pt(100) and the other one to Pt(lll). 

The second most widely used noble metal for preparation of electrodes is gold. Similar to Pt, the gold electrode, contacted with aqueous electrolyte, is covered in a broad range of anodic potentials with an oxide film. On the other hand, the hydrogen adsorption/desorption peaks are absent on the cyclic voltammogram of a gold electrode in aqueous electrolytes, and the electrocatalytic activity for most charge transfer reactions is considerably lower in comparison with that of platinum. 

Figure 7.9 The mechanism for the hydrogenation of an alkene as catalyzed by finely divided platinum metal (a) hydrogen adsorption (b) adsorption of the alkene (c) and (d), stepwise transfer of both hydrogen atoms to the same face of the alkene (syn addition).

Hydrogen adsorption on platinum electrodes in perchloric acid solutions... 

The cyclic voitammogram for Pt (111) in 5 M sulfuric acid is shown in Fig. 2-21. Compared with that in 0.5 M sulfuric acid (Fig. 2-15), the anodic part of the two split hydrogen adsorption-desorption areas was compressed in the cathodic direction and became two sharp peaks while the cathodic part did not change its shape very much. The asymmetric peak at 700 mV shifted cathodicly and became more symmetric and sharp. The oxidation of platinum shifted about 100 mV in the anodic direction. All these changes could be attributed to the increase in specific adsorption of anions or the decrease of the activity of water as well as the pH change. 

Platinum was deposited on Nafion membrane by the method described earlier. Ibe cyclic voltammogram is shown in Fig. 2-i6 using 3 M H2SO4 as the electrolyte in the solution side of the membrane. The hydrogen adsorption—desorption features are not very well-defined probably because of some impurities. 

Ruthenium was electrochemically deposited on platinum foil at a potential of 50 mV for 10 s. The cyclic voitammogram of this Pt—Ru electrode in 3 M H2SO4 is shown in Fig. 4—2. The voitammogram shows the hydrogen adsorption-desorption features from 50 mV to 200 mV and the oxidation and reduction current over 300 mV. The voltanunogram seemed stable when the upper limit potential was 800 mV. When the upper limit was higher than 800 mV, the voitammogram became slowly like pure... 

Some additives (e.g., tin) decrease the hydrogen adsorptivity of platinum catalysts 74)-. 

The admixture of lead to platinum has a similar effect (Fig. 5). At the same time, the aromatizing activity increases up to about 1 1 Pt Pt atomic ratio 24). With even more lead it scatters aroimd somewhat lower values 66). Electron donation from lead to platinum has been proved by infrared spectroscopy, so one may wonder whether lead is present as metal in the catalyst (75). The additive effect can also be interpreted by its creating hydrogen-deficient surface sites favorable for aromatization. When more lead is present than platinum (i.e., where no more continuous platinum surface is probable), the inverse correlation between hydrogen adsorptivity and activity ceases to exist. 

Fig. 5. Hydrogen adsorptivity (left-hand ordinate, in arbitrary units) and rate of n-heptane aromatization (right-hand ordinate) as a function of relative lead content of a supported platinum catalyst (24).

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