By Allen J. Bard, Martin Stratmann, Digby Macdonald, Patrik Schmuki

This 11-volume encyclopedia presents either a simple advent to all subject matters regarding smooth electrochemistry in addition to a accomplished evaluation of the topic. Unrivalled in its breadth and intensity, this regular reference has been created and written by way of well known scientists, masking every thing from basic study to components of program.

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The first method leads to the total catalyst surface area, whereas the second leads to the specific (active metal) surface area. , Pt) surface area. In situ techniques are based primarily on the determination of the charge stored in the H adsorption region of the CV of the electrocatalyst (Fig. 21). As shown in this figure, the double-layer charge must be subtracted for a reliable measurement. The currently recommended normalization value, based on a 1:1 H to Pt chemisorption is 210 µC cm−2 , which roughly corresponds to the surface density of Pt(111) [38].

One may distinguish three different cases: the surface at the pzc; the surface at a potential more positive than the pzc, thus having a positive charge; and the surface at more negative potentials than the pzc, thus having a negative charge. Owing to the strong dipole moment of water and the high electric fields present at the interface, one expects that the structure of the water–metal interface in the region close to the metal will exhibit significant differences between these three cases. Indeed, this is the case as shown in Fig.

It can be shown [23, 56] that I0 ∼ [θO (1 − θO )]1/2 (28) or, equivalently, 1/4 1/2 I0 ∼ KO pO2 /(1 + KO pO2 ) (29) which satisfactorily explains the observed maxima and the fact that I0 is proportional 1/4 −1/4 to pO2 for low pO2 and to pO2 for high pO2 [23, 56]. According to this model, the I0 maxima correspond to θO = 1/2. It has been found, however, that for low T and high pO2 the situation becomes more complicated owing to the formation of surface Pt oxide PtO2 [23]. When other gases are present in the gas phase in addition to O2 , then I0 can be affected in two different ways: first, because θO may be affected because of a catalytic reaction and/or because of competitive chemisorption.

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