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Surface Reactions of Hot Electrons at Metal—Liquid Interfaces

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Solid—Liquid Interfaces

Part of the book series: Topics in Applied Physics ((TAP,volume 85))

Abstract

Surface reactions especially with hot charge carriers (related to photoelectronchemistry) are investigated at noble metal—liquid interfaces. The hot charge carriers are produced in Metal—Insulator—Metal (MIM) junctions. The top metal is a thin (d = 20 nm) silver or gold film. The hot carriers are injected by a tunnel voltage into the film which simultaneously acts as a working electrode in a normal electrochemical circuit.

The light emission of the tunnel junction drastically increases when changing the electrode potential from E = E pzc to E = E pzc-0.3V. A corresponding effect was found in ultra-high vacuum conditions, when the top electrode of a MIM was charged negatively by evaporation of 0.6 nm potassium. The results are discussed in terms of light emission caused by direct excitation of surface plasmon polaritons at the noble metal—liquid interface.

The injected hot electrons can change the kinetics of faradaic reactions at the surface. As an example the hydrogen evolution reaction was found to lose its over potential at silver—neutral electrolyte interfaces by the injection of hot electrons. The results are discussed in terms of an overlap of the hot electron wavefunction with the wavefunction of the water OH-groups in the inner Helmholtz layer.

The tunnel current at constant tunnel voltage was found to increase, when surface defects are applied to a smooth silver top electrode by the deposition of submonolayers of silver at potentials E = E pzc+0.8V. A model is presented, which explains the tunnel process as a coherent eigenstate of the hot electron on both sides of the insulator. The tunnel current increase due to the addition of surface defects can be motivated by an enhanced dephasing of the hot electron wave function at the silver—electrolyte interface.

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  1. Lehrstuhl für Oberflächenwissenschaft (IPkM), Heinrich-Heine-Universität Düsseldorf, 40225, Düsseldorf, Germany

    Detlef Diesing, Guido Kritzler & Andreas Otto

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  1. Detlef Diesing
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  2. Guido Kritzler
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  1. Institut für Physikalische Chemie, Universität Bonn, Wegelerstr. 12, 53115, Bonn, Germany

    Klaus Wandelt

  2. School of PSET, Murdoch University, South Sreet, Murdoch, 6150, WA, Australia

    Stephe Thurgate

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Diesing, D., Kritzler, G., Otto, A. (2003). Surface Reactions of Hot Electrons at Metal—Liquid Interfaces. In: Wandelt, K., Thurgate, S. (eds) Solid—Liquid Interfaces. Topics in Applied Physics, vol 85. Springer, Berlin, Heidelberg. https://doi.org/10.1007/3-540-44817-9_12

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