Electrochemical Surface Science: An Atomistic View of Electrochemistry D.M. Kolb Institute of Electrochemistry, University of Ulm, 89069 Ulm, Germany e-mail: [email protected] A long-standing desire in modern electrochemistry has been the understanding of electrochemical processes at an atomistic level. While classical electrochemical techniques have yielded thermodynamic information of utmost importance, it was the lack of structure information, both electronic and geometric, which hampered the development of a truly microscopic picture of metal surfaces in contact with an electrolyte. With the implementation of surface science techniques, such as optical spectroscopies, X-ray diffraction methods or scanning probe microscopies, extremely powerful tools became available to electrochemists, with which they were able to study the structure of electrode surfaces in-situ, i.e., in an electrochemical environment under reaction conditions, and often with atomic-scale resolution. After a brief introduction to some basic considerations, several examples of electrochemical surface science will be given. Ordered adlayers, formed by anions (Fig. 1) or molecules, and potential-induced structure transitions in such adlayers, have been intensively investigated by STM and examples thereof will be given. Metal deposition as a relatively simple, yet technologically very important electrochemical reaction has been investigated in the underpotential and overpotential range. For the latter the great potential of STM for elucidating the nucleation-and-growth behavior during the initial stages of metal deposition is demonstrated (Fig. 2). Marked strain-induced changes in the electrocatalytic properties of metal monolayers pseudomorphically grown on various substrates are briefly discussed. Finally, a new method is shown for the metallization of organic surfaces, demonstrated for Pd layers on aromatic thiol SAMs. Fig. 1: STM image of an ordered adlayer of PdCl 4 2- on Au(110) Fig. 2: Monitoring the growth of a single Cu- cluster on Ag(100)

Electrochemical Surface Science: An Atomistic View of … · 2010-06-01 · Electrochemical Surface Science: An Atomistic View of Electrochemistry D.M. Kolb Institute of Electrochemistry,

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Page 1: Electrochemical Surface Science: An Atomistic View of … · 2010-06-01 · Electrochemical Surface Science: An Atomistic View of Electrochemistry D.M. Kolb Institute of Electrochemistry,

Electrochemical Surface Science: An Atomistic View of Electrochemistry

D.M. Kolb

Institute of Electrochemistry, University of Ulm, 89069 Ulm, Germany e-mail: [email protected]

A long-standing desire in modern electrochemistry has been the understanding of electrochemical processes at an atomistic level. While classical electrochemical techniques have yielded thermodynamic information of utmost importance, it was the lack of structure information, both electronic and geometric, which hampered the development of a truly microscopic picture of metal surfaces in contact with an electrolyte. With the implementation of surface science techniques, such as optical spectroscopies, X-ray diffraction methods or scanning probe microscopies, extremely powerful tools became available to electrochemists, with which they were able to study the structure of electrode surfaces in-situ, i.e., in an electrochemical environment under reaction conditions, and often with atomic-scale resolution. After a brief introduction to some basic considerations, several examples of electrochemical surface science will be given. Ordered adlayers, formed by anions (Fig. 1) or molecules, and potential-induced structure transitions in such adlayers, have been intensively investigated by STM and examples thereof will be given. Metal deposition as a relatively simple, yet technologically very important electrochemical reaction has been investigated in the underpotential and overpotential range. For the latter the great potential of STM for elucidating the nucleation-and-growth behavior during the initial stages of metal deposition is demonstrated (Fig. 2). Marked strain-induced changes in the electrocatalytic properties of metal monolayers pseudomorphically grown on various substrates are briefly discussed. Finally, a new method is shown for the metallization of organic surfaces, demonstrated for Pd layers on aromatic thiol SAMs.

Fig. 1: STM image of an ordered adlayer of PdCl42- on Au(110)

Fig. 2: Monitoring the growth of a single Cu-cluster on Ag(100)