Encyclopedia of Electrochemistry, Electrochemical by Allen J. Bard, Martin Stratmann, Digby Macdonald, Patrik

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

This 11-volume encyclopedia offers either a simple creation to all issues regarding smooth electrochemistry in addition to a accomplished review of the topic. Unrivalled in its breadth and intensity, this commonplace reference has been created and written via popular scientists, overlaying every thing from primary learn to parts of software.

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05 30 j [mA cm−2] permits estimation of the tpb length via Eq. (18) once the gas-exposed electrode surface area NG is known. 05 M H2 SO4 solution showing the principle of the method to integrate the electric charge for the hydrogen desorption. 05 V s−1 . (b) Cyclic voltammogram of Pt/Vulcan dispersed electrode with a loading of 28 µg Pt cm−2 . The gray rectangle is the estimated double-layer charge and the Vulcan capacitance used to correct the charge due to the hydrogen adsorption–desorption. 02 V s−1 .

02 V s−1 . (Reprinted with permission from Ref. 9, Copyright 2003 by John Wiley & Sons Ltd). Fig. 5 M H2 SO4 , dashed lines after CO removal. (a) Pt and (b) Ru. Immersion and adsorption at 250 mV, sweep rate: 20 mV s−1 . (Reprinted with permission from Refs 45, 46, Copyright 1994 by the American Chemical Society). Fig. 1 Overpotentials and the Butler–Volmer Equation The concept and theory of overpotential is of central importance in understanding electrocatalysis [47–55]. Operationally, the measured overpotential η of a working electrode (W), is the deviation of its potential from its opencircuit (I = 0) value and can be considered to be the sum of three terms, that is: ηW = ηac,W + ηconc,W + ηohmic,W (19) where ηac,W , ηconc,W , and ηohmic,W are the activation overpotential, the concentration (diffusion or mass transport) overpotential, and the ohmic overpotential respectively.

The observed changes in intensity are due to changes in the orientation of the water molecules at the interface. At the pzc, the water molecules are nearly parallel to the surface and change from oxygen-up to oxygen-down in going from negative to positive charges. The structure at positive potentials is interpreted to be icelike as in Fig. 7. 8 V owing to perchlorate anion adsorption. Another example of the abrupt change in interfacial water structure near the pzc is presented in Fig. 10 which shows the potential dependence of the in-bending mode of water adsorbed at a Pt(111) electrode.

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