Oxides aqueous surface chemistry

Parks, G. A. (1967), "Aqueous Surface Chemistry of Oxides and Complex Oxide Minerals Isoelectric Point and Zero Point of Charge," in Equilibrium Concepts in Natural Water Systems, Advances in Chemistry Series, No. 67, American Chemical Society, Washington, DC. 

Aqueous Surface Chemistry of Oxides and Complex Oxide Minerals... 

Parks, G.A. 1967. Aqueous surface chemistry of oxides and complex oxide minerals Isoelectric point and zero point of charge, p. 121-160. In R.F. Gould (ed.) Equilibrium concepts in natural water systems. Vol. 67. Advances in Chemistry Series, ACS, Washington, DC. 

In the present study the surface chemistry of birnessite and of birnessite following the interaction with aqueous solutions of cobalt(II) and cobalt(III) amine complexes as a function of pH has been investigated using two surface sensitive spectroscopic techniques. X-ray photoelectron spectroscopy (XPS) and secondary ion mass spectrometry (SIMS). The significant contribution that such an investigation can provide rests in the information obtained regarding the chemical nature of the neat metal oxide and of the metal oxide/metal ion adsorbate surfaces, within about the top 50 of the material surface. The chemical... 

Preparation of non-aqueous dispersions of colloidal silver by phase transfer has been described [51] and advantage has been taken to form monodisperse, 7.0-nm-diameter silver particles by simultaneously reducing Ag+ and partially oxidizing Agn particles (radiolytic push-pull reduction method) [52]. The surface chemistry of nanosized silver particles has continued to receive attention [53, 54],... 

Macroscopic experiments allow determination of the capacitances, potentials, and binding constants by fitting titration data to a particular model of the surface complexation reaction [105,106,110-121] however, this approach does not allow direct microscopic determination of the inter-layer spacing or the dielectric constant in the inter-layer region. While discrimination between inner-sphere and outer-sphere sorption complexes may be presumed from macroscopic experiments [122,123], direct determination of the structure and nature of surface complexes and the structure of the diffuse layer is not possible by these methods alone [40,124]. Nor is it clear that ideas from the chemistry of isolated species in solution (e.g., outer-vs. inner-sphere complexes) are directly transferable to the surface layer or if additional short- to mid-range structural ordering is important. Instead, in situ (in the presence of bulk water) molecular-scale probes such as X-ray absorption fine structure spectroscopy (XAFS) and X-ray standing wave (XSW) methods are needed to provide this information (see Section 3.4). To date, however, there have been very few molecular-scale experimental studies of the EDL at the metal oxide-aqueous solution interface (see, e.g., [125,126]). 

The majority of studies on surface chemistry of ion-bombarded samples are concerned with the oxidation arid corrosion of materials. One part of the experiments covers the corrosion and oxidation in gaseous atmosphere such as air or oxygen at normal or high temperatures. The other, smaller, part deals with aqueous corrosion, in particular with the dissolution of metals and the formation of passivating layers in aqueous solutions. The interest in this subject found its expression in two conferences in 1975 and in 1978 ... 

In order to understand the surface chemistry at a solid oxide/water interface, high-temperature electrokinetic studies should be carried out. Recently, micro-electrophoretic studies of the ZrC>2- and TiC>2-water suspensions to 200 °C showed that such measurements are possible, but substantial effort will be needed to extend these measurements to a temperature range above 300 °C. In addition, a possibility to study nanoparticulate aqueous suspensions at high temperatures would be very beneficial. 

The phenomena presented in this book were discussed in many reviews. For example, Schwarz [13] discussed methods used to characterize the acid base properties of catalysts. The review on sorption on solid - aqueous solution interface by Parks [14] includes also principles of surface science. The book Environmental Chemistry of Aluminum edited by Sposito reviews the solution and surface chemistry of aluminum compounds. Chapter 3 [15] provides thermochemical data for aluminum compounds. Chapter 5 [16] lists the points of zero charge of aluminum oxides, oxohydroxides and hydroxides with many references on adsorption of metal cations and various anions on these materials. Unlike the present book, which is confined to sorption from solution at room temperature, publications on coprecipitation and adsorption from gas phase or at elevated temperatures are also cited there. Brown et al. [17] reviewed on dry and wet surface chemistry of metal oxides. Stumm [18] reviewed sorption of ions on iron and aluminum oxides. The review by Schindler and Stumm [19] is devoted to surface charging and specific adsorption on oxides. Schindler [19] published a review on similar topic in German. Many other reviews related to specific topics are cited in respective chapters. 

Catalytic Oxidation of Fe(II) in Aqueous Media A detailed study of this reaction was carried out recently, where the influence of the AC surface chemistry was assessed [211]. Two situations were considered ... 

The second major aspect of the surface chemistry of chromia-alumina that has to be considered is the acidic nature of its surface. The exact chemical nature of the acid sites of solid oxide catalysts such as alumina or silica-alumina has been a subject of considerable research and speculation for a number of years, yet despite these efforts a fully satisfactory chemical description of catalyst acidity has not been obtained. Nevertheless, in the case of chromia-alumina, there is good evidence for the existence of acid sites of one kind or another on the surface. Voltz and Weller (29), for example, studied the chemisorption of quinoline on chromia-alumina, with and without potassium promotion, and at the same time measured their titrable acidities in aqueous suspensions. Both methods indicated that chromia-alumina was acidic, and that the addition of potassium decreased the acidity. This observation was supported by the fact that the double bond isomerization of 1-pentene, normally an acid-catalyzed reaction, proceeded quite readily over pure chromia-alumina, but less readily over a chromia-alumina treated with potassium. 

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