Electrode solution/metal interface

In the next section a brief layout of simulation methods will be given. Then, some basic properties of the models used in computer simulations of electrochemical interfaces on the molecular level will be discussed. In the following three large sections, the vast body of simulation results will be reviewed structure and dynamics of the water/metal interface, structure and dynamics of the electrolyte solution/metal interface, and microscopic models for electrode reactions will be analyzed on the basis of examples taken mostly from my own work. A brief account of work on the adsorption of organic molecules at interfaces and of liquid/liquid interfaces complements the material. In the final section, a brief summary together with perspectives on future work will be given. 

Since specific adsorption is an important phenomenon in electrochemistry, the solution/metal interface has nevertheless been studied in various ways. An ion is considered to be adsorbed specifically in the inner Helmholtz plane when it is partially dehydrated and in direct contact with the metal surface (see, e.g.. Ref. 15). On the other hand, an ion that is adsorbed further away from the electrode with its hydration shell essentially intact is considered to be adsorbed non-specifically in the outer Helmholtz plane . In the classical treatment of contact adsorption, the balance between the energy of hydration of the ion and the strength of the image interactions determines which ions are specifically adsorbed and which ones are not... 

The properties of surfactant molecules properties are (i) their ability to form different aggregate structures (micelles) above die critical micellar concentration (CMC), (ii) their ability to solubilize water-insoluble organic molecules (M) by hydrophobic-hydrophobic interactions, and (iii) their adsorption on electrodes changes the solution-metal interface, which alters redox reactions and produces template effects on the electrode surface (79) (Schem 2). SDS can be used to electropolymerize various thiophene derivatives such as EDOT, BT and MOT in aqueous solution. 

In order to describe the effects of resistance and electrode capacitance in electrochemical cells, it is useful to introduce the concept of the ideal polarizable electrode (IPE). The IPE (Figure 1.6) is one that will not pass any charge across the solution/metal interface when the potential across it is changed. The behavior of the IPE then mimics that of a capacitor in an electrical circuit, with the one difference being that the capacitance of an... 

Dissolution of Semiconductors. The mechanism of dissolution of semiconductors is essentially similar to that of metals, described above. The basic difference in the dissolution behavior of metals and semiconductors lies in the concentration and type of charges responsible for surface reactions. In semiconductors, the concentration of charge carriers is much smaller than in metals because of the predominantly covalent nature of bonding. The electron transfer process may involve either valence band or conduction band electrons at the semiconductor electrode while only conduction band electrons take part at metal electrodes. Furthermore, the kinetics of dissolution of metals is determined by electrochemical reactions occurring in the soiution or at the solution-metal interface, whereas the rate-determining process in the dissolution of semiconductors may also involve phenomena taking place inside the surface. 

The potential of a metallic electrode is determined by the position of a redox reaction at the electrode-solution interface. Three types of metallic electrodes are commonly used in potentiometry, each of which is considered in the following discussion. 

When two conducting phases come into contact with each other, a redistribution of charge occurs as a result of any electron energy level difference between the phases. If the two phases are metals, electrons flow from one metal to the other until the electron levels equiUbrate. When an electrode, ie, electronic conductor, is immersed in an electrolyte, ie, ionic conductor, an electrical double layer forms at the electrode—solution interface resulting from the unequal tendency for distribution of electrical charges in the two phases. Because overall electrical neutrality must be maintained, this separation of charge between the electrode and solution gives rise to a potential difference between the two phases, equal to that needed to ensure equiUbrium. 

Pig. 3. Representation of the electrical double layer at a metal electrode—solution interface for the case where anions occupy the inner Helmholtz plane... 

Figure 17. Energy for the nucleation of a surface film on metal electrode. M, metal OX, oxide film EL, electrolyte solution. Aj is the activation barrier for the formation of an oxide-film nucleus and rj is its critical radius. 7 a is the interfacial tension of the metal-electrolyte interface, a is the interfacial tension of the film-electrolyte interface. (From N. Sato, J. Electro-chem. Soc. 129, 255, 1982, Fig. 5. Reproduced by permission of The Electrochemical Society, Inc.)...

In situ infrared spectroscopy allows one to obtain stracture-specific information at the electrode-solution interface. It is particularly useful in the study of electrocat-alytic reactions, molecular adsorption, and the adsorption of ions at metal surfaces. 

Interfacial water molecules play important roles in many physical, chemical and biological processes. A molecular-level understanding of the structural arrangement of water molecules at electrode/electrolyte solution interfaces is one of the most important issues in electrochemistry. The presence of oriented water molecules, induced by interactions between water dipoles and electrode and by the strong electric field within the double layer has been proposed [39-41]. It has also been proposed that water molecules are present at electrode surfaces in the form of clusters [42, 43]. Despite the numerous studies on the structure of water at metal electrode surfaces using various techniques such as surface enhanced Raman spectroscopy [44, 45], surface infrared spectroscopy [46, 47[, surface enhanced infrared spectroscopy [7, 8] and X-ray diffraction [48, 49[, the exact nature of the structure of water at an electrode/solution interface is still not fully understood. 

When a liquid-liquid interface is to be investigated using an electrode in the more dense phase, or for studies at the water-air interface, a submarine electrode can be deployed [18,19,34], depicted schematically in Fig. 3(b). In this case, the electrode is inverted in the cell, such that the tip points upwards, and an insulated connection is made through the solution. Metal electrodes down to the nanometer scale can also be fabricated by sealing an etched Pt or Pt-Ir wire in a suitable insulating material, leaving just the etched end exposed [35-37]. 

No investigation of a solid, such as the electrode in its interface with the electrolyte, can be considered complete without information on the physical structure of that solid, i.e. the arrangement of the atoms in the material with respect to each other. STM provides some information of this kind, with respect to the 2-dimensional array of the surface atoms, but what of the 3-dimensional structure of the electrode surface or the structure of a thick layer on an electrode, such as an under-potential deposited (upd) metal At the beginning of this chapter, electrocapillarity was employed to test and prove the theories of the double layer, a role it fulfilled admirably within its limitations as a somewhat indirect probe. The question arises, is it possible to see the double layer, to determine the location of the ions in solution with respect to the electrode, and to probe the double layer as the techniques above have probed adsorption Can the crystal structure of a upd metal layer be determined In essence, a technique is required that is able to investigate long- and short-range order in matter. 

Similar to those observed with the cysteine-modified electrode in Cu, Zn-SOD solution [98], CVs obtained at the MPA-modified Au electrode in phosphate buffer containing Fe-SOD or Mn-SOD at different potential scan rates (v) clearly show that the peak currents obtained for each SOD are linear with v (not v 1/2) over the potential scan range from 10 to 1000 mVs-1. This observation reveals that the electron transfer of the SODs is a surface-confined process and not a diffusion-controlled one. The previously observed cysteine-promoted surface-confined electron transfer process of Cu, Zn-SOD has been primarily elucidated based on the formation of a cysteine-bridged SOD-electrode complex oriented at an electrode-solution interface, which is expected to sufficiently facilitate a direct electron transfer between the metal active site in SOD and Au electrodes. Such a model appears to be also suitable for the SODs (i.e. Cu, Zn-SOD, Fe-SOD, and Mn-SOD) with MPA promoter. The so-called... 

The two reference electrodes and the interface between the two solution are in electronic equilibrium, so that we can express the differences in the inner potential through the differences in the chemical potentials. We denote the chemical potential of the two metal electrodes as hm, those of the two reference systems as / ef and and those of the two redox couples as /u4edox and /ij edox We obtain ... 

The interface is in contact with two bulk phases, the metal electrode (index m ) and the solution (index s). Formally, we consider the metal to be composed of metal atoms M, metal ions Mz+, and electrons e " these particles are present both in the electrode and the interface, but not in the solution. On the other hand, certain cations and anions and neutral species occur both in the solution and the interface. Since the electrode is ideally polarizable, no charged species can pass through the interface. 

Ideal polarizable interfaces are critical for the interpretation of electrochemical kinetic data. Ideality has been approached for certain metal electrode-solution interfaces, such as mercury-water, allowing for the collection of data that can be subjected to rigorous theoretical analysis. 

Herein, criteria are developed for ideal polarizable semiconductor electrode-solution interfaces. A variety of experimental studies involving metal dichalcogenide-solution interfaces are discussed within the context of these criteria. These interfaces approach ideality in most respects and are well suited for fundamental studies involving electron transfer to solution species or adsorbed dyes. 

The authors propose that a major difficulty in interpreting kinetic current flow at the semiconductor-solution interface lies in the inability of experimentalists to prepare interfaces with ideal and measurable properties. In support of this hypothesis, the importance of ideal interfacial properties to metal electrode kinetic studies is briefly reviewed and a set of criteria for ideality of semiconductor-solution interfaces is developed. Finally, the use of semiconducting metal dichalcogenide electrodes as ideal interfaces for subsequent kinetic studies is explored. 

L/evelopment of sophisticated surface analytical techniques over the past two decades has revived interest in the study of phenomena that occur at the electrode-solution interface. As a consequence of this renewed activity, electrochemical surface science is experiencing a rapid growth in empirical information. The symposium on which this book was based brought together established and up-and-coming researchers from the three interrelated disciplines of electrochemistry, surface science, and metal-cluster chemistry to help provide a better focus on the current status and future directions of research in electrochemistry. The symposium was part of the continuing series on Photochemical and Electrochemical Surface Science sponsored by the Division of Colloid and Surface Chemistry of the American Chemical Society. 

Valuable information can be obtained from thermal desorption spectra (TDS) spectra, despite the fact that electrochemists are somewhat cautious about the relevance of ultrahigh vacuum data to the solution situation, and the solid/liquid interface in particular. Their objections arise from the fact that properties of the double layer depend on the interaction of the electrode with ions in the solution. Experiments in which the electrode, after having been in contact with the solution, is evacuated and further investigated under high vacuum conditions, can hardly reflect the real situation at the metal/solution interface. However, the TDS spectra can provide valuable information about the energy of water adsorption on metals and its dependence on the surface structure. At low temperatures of 100 to 200 K, frozen molecules of water are fixed at the metal. This case is quite different from the adsorption at the electrode/solution interface, which usually involves a dynamic equilibrium with molecules in the bulk. 

Fig. 4-11. Energy diagram for electron transfer from a standard gaseous electron across a solution/vacuum interface, through an electrolyte solution, and across a metal/solution interface into a metal electrode = real potential of electrons e,s) in electrolyte...

For a metal electrode at which a metal ion transfer reaction Mf = Mfi, is in equilibrium, as shown in Fig. 4-19, the metal ion level aM (M/s/v) in the electrode equals the hydrated metal ion level aM-(s/v) in the aqueous solution and the energy for the metal ion transfer across the electrode/solution interface equals zero (ciii-(M ) = 0). As shown in Fig. 4-20, then, we obtain Eqn. 4-22 ... 

On the mixed electrode of metallic iron immersed in acidic solutions, the anodic and cathodic charge transfer reactions (the anodic transfer of iron ions and the cathodic transfer of electrons) proceed across the electrode interface, at which the anodic ciurent (the positive charge current) is exactly balanced with the cathodic current (the negative charge current) producing thereby zero net current. 

Electrodic reactions that underlie the processes of metal deposition, etc., cannot be understood without knowing the potential difference at the electrode/solution interface and how it varies with distance from the electrode. The ions from the solution must be electrically energized to cross the interphase region and deposit on the metal. This electrical energy must be picked up from the field at the interface, which itself depends upon the double-layer structure. Thus, control over metal deposition processes can be improved by an increased understanding of double layers at metal/solutioii interfaces. 

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