Electrochemical Surface Science

Abstract

The last 30 years have seen remarkable changes in interfacial electrochemistry, particularly in the kind of questions that were addressed in electrochemical studies. Ever since classical surface science, traditionally performed under ultrahigh vacuum conditions, has succeeded in describing surfaces and surface reactions on a molecular level, electrochemists longed for a microscopic understanding of the solid/electrolyte interface and, at the same time, searched widely for new experimental ways to reach that goal. Herein, studies are described concerning the structure and the dynamics of bare and adsorbate‐covered electrode surfaces and of metal deposition as a simple, yet important, electrochemical process. In all these cases, the scanning tunneling microscope plays a pivotal role emphasizing the surface‐science approach to the problems.

Electrochemically controlled self-assembled monolayers characterized with molecular and sub-molecular resolution

“…78,79 In such configuration, both the STM substrate and tip are fully controlled by the electrochemical potential versus a common reference electrode. Using in situ STM, reconstruction of metallic electrode surfaces at the solid/liquid interfaces under electrochemical potential control, 80 metal deposition, [81][82][83] anion adsorption 25,84,85 and organic molecule adsorption 82 have been characterized at atomic or/and molecular level. In situ STM has even been employed for nanofabrication of metallic nanoclusters or pits with precise positioning and designed patterns on the well defined surfaces.…”

“…An obstacle arises in the form of the tip coating materials. Well-developed tip coating materials for aqueous solution such as nail polish 82 or Apiezon wax 83 do not withstand organic solvents. This obstacle can, however, perhaps be classified as a ''technicality'', and suitable other tip coating materials such as polyethylene are well on the road to being tested and generally introduced.…”

Multidimensional electrochemical imaging in materials science

“…1a) and found applications in catalysis research [7], for electrodeposition studies of metals and conductive polymers [8], for investigation of morphology changes resulting from electrochemical treatment [9], and for corrosion studies [9,10]. Practical details of how to perform EC-STM are extensively described in the literature, to which the reader is referred [4,[10][11][12][13][14][15][16].…”

Phase Transitions Involving Dissociated States of Water at the Electrochemical Ni(111)/H2O Interface

“…An understanding of the atomic structure of water at the electrochemical interface is therefore critical to the rational design of electrocatalysts, corrosion resistant alloys, and biomimetic scaffolds between biological substrates and metal surfaces. Whereas experimental techniques, such as surface enhanced Raman spectroscopy, in situ electron microscopy and crystal rod truncation techniques are now beginning to capture some of the chemical changes occurring at the electrochemical interface 1,2 , there is still a significant demand for theoretical insight. The recently developed abilities to directly observe potentialdependent interfacial phenomena such as changes in molecular structure 3,4 , chemisorption 5,6 , water activation 7 and surface reconstruction 8 require the development of competitive theoretical models that can incorporate electrochemical surface phenomena into an overall predictive and interpretive framework.…”

“…V NHE = V abs -(4.6 ± 0.2) V [1] In the absence of a sufficient model for the surrounding solvent and counter-charge, however, electrochemical potentials derived using reaction-core cluster models for the electrochemical interface are weak approximations. Such systems can not be readily tuned for varying surface charge densities/applied electrochemical potentials, except by the location of distant ions with known ionization potentials/electron affinities (an approach also adopted by Crispin et al 13 ).…”