New PDF release: Encyclopedia of Electrochemistry, Electrochemical

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

This 11-volume encyclopedia presents either a simple creation to all issues regarding smooth electrochemistry in addition to a finished review of the topic. Unrivalled in its breadth and intensity, this typical reference has been created and written through popular scientists, protecting every little thing from basic study to components of software.

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The second treats the surface as a slab in which a certain ensemble of atoms is repeated periodically [85–88]. 5 Cu(111) Pd/Ru(0001) Cu/Pt(111) −1 An important result recently obtained by Hammer and Norskov using extensive DFT/GGA calculation is that energies of adsorption of molecules, such as CO (Fig. 29), can be related in a linear fashion to the energy of the center of the d band, εd , relative to the Fermi level of the metal (Fig. 30) [87]. The closer the center of the d band relative to the Fermi level of the metal, the stronger the binding propensity with molecules, such as CO, where enhanced electron backdonation leads to stronger binding to the surface.

The I0 dependence on gaseous composition is usually complex. It has therefore 49 50 2 Electrocatalysis been shown [23, 56] that I0 goes through a maximum with increasing pO2 at any fixed temperature for Pt|ZrO2 (Y2 O3 ) catalyst films. These results can be described adequately on the basis of Langmuir-type adsorption of oxygen at the tpb, that is, θO = 1/2 1/2 KO pO2 /(1 + KO pO2 ) (27) where θO is the oxygen coverage. 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].

Reprinted with permission from Ref. 23, Copyright 2003 by Kluwer/Plenum Publisher). Fig. 5 Normalization of Active Surface For the quantitative comparison of different electrocatalysts, it is necessary to know their true active surface area. The experimental techniques which allow for the determination of the true surface area of an electrocatalyst can be divided into ex situ and in situ techniques. In the first group belong the techniques which are also used in heterogeneous catalysis for determining the surface area of catalysts.

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