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The potential of zero charge (pzc) is a fundamental property of the metal–electrolyte interface, and its knowledge is important for a detailed understanding of double-layer phenomena, electrochemical kinetics and the adsorption behaviour of charged and neutral species [1,2]. The pzc is commonly defined as the potential, at which the electrode surface has no excess charge; for solid surfaces its value can in many cases be obtained from double-layer capacity measurements in dilute solutions, where a pronounced minimum appears at the pzc (Gouy–Chapman minimum) [3]. This has been demonstrated very nicely by the Meudon group for the three low-index faces of gold and silver single crystals [4,5]. This technique, however, cannot be usually employed for the more reactive metals, such as transition metals, because of the formation of adlayers or surface oxides over a wide potential range. A typical example is Pt(1 1 1), where the Gouy–Chapman minimum is conspicuously absent [6], and the pzc still a matter of considerable controversy [7–10]. Due to our continued interest in the electrocatalytic properties of Pd single crystal surfaces and epitaxially grown Pd overlayers on gold substrates [11,12], we performed capacitance measurements for a full interface characterisation. Unlike for Pt(1 1 1), a clear Gouy– Chapman minimum was readily observed for Pd(1 1 1), which allowed the determination of the pzc in a rather direct and unambiguous manner. The corresponding values for a massive Pd(1 1 1) single crystal electrode and for thin Pd(1 1 1) overlayers of various thicknesses on Au(1 1 1) in NaF solutions are shown and discussed as follows. [ Last edited by xuweipotato on 2010-3-2 at 12:12 ] |
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