Oxide-solution interfaces, theoretical

Ellipsometry at noble metal electrode/sohitiOTi interfaces has been used to test theoretically predicted microscopic parameters of the interface. Investigated systems include numerous oxide layer systems [5-10], metal deposition processes, adsorption processes [11], and polymer films on electrodes [12-14]. Submonolayer sensitivity has been claimed. Expansion and contraction of polyaniline films was monitored with ellipsometry by Kim et al. [15]. Film thickness as a function of state of oxidation of redox active polyelectrolyte layers has been measured with ellipsometry [16]. The deposition and electroreduction of Mn02 films has been studied [17] below a thickness of 150 nm, the anodically formed film behaved like an isotropic single layer with optical constants independent of thickness. Beyond this limit, anisotropic film properties had to be assumed. Reduction was accompanied by a thickness increase it started at the oxide/solution interface. 

The metal oxide/electrolyte solution interface is one of the most well-known systems existing in our environment. The coadsorption of inorganic and organic compounds has been studied from both theoretical and practical points of view. 

In electrochemistry an electrode is an electronic conductor in contact with an ionic conductor. The electronic conductor can be a metal, or a semiconductor, or a mixed electronic and ionic conductor. The ionic conductor is usually an electrolyte solution however, solid electrolytes and ionic melts can be used as well. The term electrode is also used in a technical sense, meaning the electronic conductor only. If not specified otherwise, this meaning of the term electrode is the subject of the present chapter. In the simplest case the electrode is a metallic conductor immersed in an electrolyte solution. At the surface of the electrode, dissolved electroactive ions change their charges by exchanging one or more electrons with the conductor. In this electrochemical reaction both the reduced and oxidized ions remain in solution, while the conductor is chemically inert and serves only as a source and sink of electrons. The technical term electrode usually also includes all mechanical parts supporting the conductor (e.g., a rotating disk electrode or a static mercury drop electrode). Furthermore, it includes all chemical and physical modifications of the conductor, or its surface (e.g., a mercury film electrode, an enzyme electrode, and a carbon paste electrode). However, this term does not cover the electrolyte solution and the ionic part of a double layer at the electrode/solution interface. Ion-selective electrodes, which are used in potentiometry, will not be considered in this chapter. Theoretical and practical aspects of electrodes are covered in various books and reviews [1-9]. 

However, the last few years have also seen a growing awareness of the problems inherent in using the semiconductor-electrolyte interface as a means of solar-energy conversion. Very long-term stability may not be possible in aqueous electrolytes and no oxide material has been identified that has properties suitable for use as a photoanode in a photoelectrolysis cell. Highly efficient photovoltaic cells are known, both in aqueous and non-aqueous solutions, but it is far from clear that the additional engineering complexity, over and above that required for the dry p-n junction photovoltaic device, will ever allow the "wet photovoltaic cells to be competitive. These, and other problems, have led to something of a pause in the flood of papers on semiconductor electrochemistry in the last two years and the current review is therefore timely. I have tried to indicate what is, and is not, known at present and where future lines of development may lie. Individual semiconductors are not treated in detail, but it is hoped that most of the theoretical strands apparent in the last few years are discussed. 

The intent of this chapter is to present a brief review of simple, fundamental physicochemical principles and experimental results which are necessary to understand both the mechanism of adsorption of ionic surfactants from aqueous solutions on oxide surfaces and the action of some simple, fundamental applications. It does not enter into details in the theoretical consideration, nor does it attempt to explain complex industrial uses. Both problems have been thoroughly treated in several review articles and monographs [e.g., 1-10]. Here emphasis is placed on the contribution the adsorption calorimetry makes to the improvement of current understanding of the interactions of ionic surfactants at the mineral-water interface. All experimental data, used for the illustrative purposes throughout this chapter, were obtained at the Laboratoire des Agregats Moleculaire et Materiaux Inorganiques. 

FIG. 4 SECM current-distance curves for a 12.5-/xm-radius Pt tip UME in benzene solution approaching the water/benzene interface. Benzene contained 0.5 mM ZnPor and 0.25 M THAC104. The aqueous phase contained 0.1 M NaCl, 0.01 M NaC104 and (curve 2) 50, (curve 3) 5, (curve 4) 0.5, or (curve 5) 0 mM Ru(CN)7,. Curve 1 is the theoretical curve for a diffusion-controlled process obtained using Eq. (6). The tip potential was held at 0.95 V vs. Ag/AgCl, corresponding to the plateau current of first oxidation of ZnPor. The tip was scanned at 0.5 gm/s. Circles are experimental data and lines represent theoretical fit obtained from Eqs. (4) and (5). (From Ref. 25.)... 

Oxidation-reduction processes involving the Fe -Fe couple have been intensively studied, and the elementary electron exchange, taking place either in solution or at an electrode interface, has served for a long time as a test case for theoretical interpretations of electron transfer kinetics. For reactions involving ground-state ions, the mechanisms of the reactions are now well understood for the homogeneous systems, for example, electron transfer can occur, as demonstrated by Taube, via either a simple outer-sphere electron... 

Numerous studies have attempted to elucidate the role of Mo in the passivity of stainless steel. It has been proposed from XPS studies that Mo forms a solid solution with CrOOH with the result tiiat Mo is inhibited from dissolving trans-passively [9]. Others have proposed that active sites are rapidly covered with molybdenum oxyhydroxide or molybdate salts, thereby inhibiting localized corrosion [10]. Yet another study proposed that molybdate is formed by oxidation of an Mo dissolution product [11]. The oxyanion is then precipitated preferentially at active sites, where repassivation follows. It has also been proposed that in an oxide lattice dominated by three-valent species of Cr and Fe, ferrous ions will be accompanied by point defects. These defects are conjectured to be canceled by the presence of four- and six-valent Mo species [1]. Hence, the more defect-free film will be less able to be penetrated by aggressive anions. A theoretical study proposed a solute vacancy interaction model in which Mo " is assumed to interact electrostatically with oppositely charged cation vacancies [ 12]. As a consequence, the cation vacancy flux is gradually reduced in the passive film from the solution side to the metal-film interface, thus hindering vacancy condensation at the metal-oxide interface, which the authors postulate acts as a precursor for localized film breakdown [12]. 

Polymers can adsorb spontaneously from solution on to surfaces if the interaction between the polymer and the surface is more favorable than that of the solvent with the surface. For example, a polymer like poly(ethylene oxide) (PEO) is soluble in water but will adsorb on various hydrophobic surfaces and on the water/air interface. This is the case of equilibrium adsorption where the concentration of the polymer monomers increases close to the surface with respect to their concentration in the bulk solution. We discuss this phenomenon at length both on the level of a single polymer chain (valid only for extremely dilute polymer solutions), see Section II, and for polymers adsorbing from (semidilute) solutions, see Section III. In Fig. 2a we schematically show the volume fraction profile (p(z) of monomers as a function of the distance z from the adsorbing substrate. In the bulk, i.e., far away from the substrate surface, the volume fraction of the monomers is (p], whereas, at the surface, the corresponding value is (p > (p]. The theoretical models address questions in relation to the polymer conformations at the interface, the local concentration of polymer in the vicinity of the surface, and the total amount of adsorbing polymer chains. In turn, the knowledge of the polymer interfacial behavior is used to calcu-... 

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