Electron spin resonance interface structure

Recent advances in the development of non-invasive, in situ spectroscopic scanned-probe and microscopy techniques have been applied successfully to study mineral particles in aqueous suspension (Hawthorne, 1988 Hochella and White, 1990). In situ spectroscopic methods often utilise molecular probes that have diagnostic properties sensitive to changes in short-range molecular environments. At the particle-solution interface, the molecular environment around a probe species is perturbed, and the diagnostic properties of the probe, which can be either optical or magnetic, then report back on surface molecular structure. Examples of in situ probe approaches that have been used fruitfully include electron spin resonance (ESR) and nuclear magnetic resonance (NMR) spin-probe studies perturbed vibrational probe (Raman and Fourier-transform IR) studies and X-ray absorption (Hawthorne, 1988 Hochella and White, 1990 Charletand Manceau, 1993 Johnston et al., 1993). 

Metal- and proton-exchanged zeolites have been recently attracted much attention because of their selective catalytic activity to efficiently reduce nitrogen monoxide (NO) by hydrocarbon in an 02-rich atmosphere [1]. The formation of nitrogen dioxide (NO2) from NO and O2 has been suggested as an important step in the selective reduction [2, 3] NO2 is one of rare stable paramagnetic gaseous molecules and has been subjected to electron spin resonance (ESR) studies [4-7]. The ESR parameters and their relation/to the electronic structure have been well established [4] and NO2 can be used as a "spin probe" for the study of molecular dynamics at the gas-solid interface by ESR. 

The interfacial aqueous coordination chemistry of natural particles, in particular their surface complexation reactions, owes much of its development to the research of Werner Stumm. Beginning with the tentative interpretation of specific adsorption processes in terms of chemical reactions to form inner-sphere surface complexes, his seminal questions spawned a generation of research on the detection and quantitation of these surface species. The application of noninvasive spectroscopy in this research is exemplified by electron spin resonance and extended X-ray absorption fine structure studies. These studies, in turn, indicate the existence of a rich variety of surface species that transcend the isolated surface complex in both structure and reactivity, thereby stimulating future research in molecular conceptualizations of the particle-water interface. 

Information about fluidity and viscosity of bilayers of artificial and natural membranes has been obtained from electron spin resonance studies in which the mobility of the spin-labelled species along the surface plane of the membrane is determined (17). However, the monolayer of either lipid, protein, or lipid-protein systems at the air-water interface, makes an ideal model because several parameters can be measured simultaneously. Surface tension, surface pressure, surface potential, surface viscosity, surface fluorescence and microviscosities, surface radioactivity, and spectroscopy may be determined on the same film. Moreover, the films can be picked up on grids from which they may be observed by electron microscopy, studied further for composition, and analyzed for structure by x-ray diffraction and spectroscopy. This approach can provide a clear understanding of the function and morphology of the lipid and lipid-protein surfaces of experimental membranes. However, the first objective is to obtain molecular correlations of surface tension, pressure, potential, and viscosity. 

Understanding of the structure of the adsorbed surfactant and polymer layers at a molecular level is helpful for improving various interfacial processes by manipulating the adsorbed layers for optimum configurational characteristics. Until recently, methods of surface characterization were limited to the measurement of macroscopic properties like adsorption density, zeta-potential and wettability. Such studies, while being helpful to provide an insight into the mechanisms, could not yield any direct information on the nanoscopic characteristics of the adsorbed species. Recently, a number of spectroscopic techniques such as fluorescence, electron spin resonance, infrared and Raman have been successfully applied to probe the microstructure of the adsorbed layers of surfactants and polymers at mineral-solution interfaces. 

Several different experimental techniques, such as fluorescence decay, electron spin resonance (ESR) spectroscopy, Raman spectroscopy, nuclear magnetic resonance (NMR) spectroscopy, neutron reflectome-try, calorimetry, Fourier-transform infrared (FT-IR) adsorption spectroscopy, small-angle neutron scattering (SANS), ellipsometry and surface force measurements, have been used to study self-assembled surfactant structures at the solid-liquid interface (11). These measurements, although providing insight into the hemimicellization process, critical aggregation numbers... 

In a carbon-supported metal electrocatalyst, the electronic interaction between metal and carbon support has a significant effect on its electrochemical performance [4], For carbon-supported Pt electrocatalyst, carbon could accelerate the electron transfer at the electrode-electrolyte interface, leading to an accelerated electrode process. Typically, the electrons are transferred from platinum clusters to the oxygen species on the surfece of a carbon support material and the chemical bond formation or the charge transfer process occurs at the contacting phase, which is considered to be beneficial to the enhancement of the catalytic properties in terms of activity and stability of the electrocatalysts. Experimentally, the investigation into the electron interaction between metal catalyst and support materials could be realized by various physical, spectroscopic, and electrochemical approaches. The electron donation behavior of Pt to carbon support materials has been demonstrated by the electron spin resonance (ESR) X-ray photoelectron spectroscopy (XPS) studies, with the conclusion that the electron interaction between Pt and carbon support depends on their Fermi level of electrons. It is considered that the electronic structure change of Pt on carbon support induced by the electron interaction has positive effect toward the enhancement of the catalytic properties and the improvement of the stability of the electrocatalyst system. However, the exact quantitative relationship between electronic interaction of carbon-supported catalyst and its electrocatalytic performance is still not yet fully established [4]. 

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