Neutron diffraction studies Raman spectroscopy

The mechanism of the activation of H2O2 by TS-1 and related catalysts has been the subject of much research using spectroscopic and computational techniques. This has centred on the nature of the active site and its mode of reaction with H2O2, solvents and the organic substrates. Work to elucidate the structure of the active site has concentrated on the coordination chemistry of the titanium. X-ray and neutron diffraction studies, coupled with X-ray absorption, infrared and Raman spectroscopies, give evidence that most of the Ti(IV) in calcined TS-1, in the absence of any adsorbate molecules, is in tetrahedral coordination. Upon addition of one molecule of water, one of the Ti-OSi bonds is hydrolysed and the titanium adopts tetrahedral coordination as Ti(0Si)30H. Addition of a further water molecule gives rise to a pentaco-ordinated titanium. ... 

There are several experimental tools available for the determination of the H-H distance and the degree of the H-H bonding interaction. Neutron diffraction studies provide an accurate measure of the H-H distance. The measurement of the spin-lattice proton relaxation time, Ti, for an tf -V 2 complex or the proton-deuteron couphng constant, Jhd. for the corresponding isotopically substituted rf -WT) complex via H nuclear magnetic resonance (NMR) spectroscopy provides a quantitative measure of the H-H distance. The frequency of the v(H-H) stretching band, as determined by Raman or infrared (IR) spectroscopy of / -H2 complexes provides semiquantitative information about the strength of the H-H interaction. 

Nowadays there is a general consensus that the Ti(IV) atoms are incorporated as isolated centers into the framework and are substituting Si atoms in the tetrahedral positions forming [Ti04] units. The model of isomorphous substitution has been put forward on the basis of several independent characterization techniques, namely X-ray [21-23] or neutron [24-26] diffraction studies, IR (Raman) [52-57], UV-Vis [38,54,58], EXAFS, and XANES [52, 58-62] spectroscopies. 

Compared to other biomolecular systems, lipid bilayer membranes and lyotropic lipid mesophases in general have been shown to respond most sensitively to hydrostatic pressure. The methods used in the high pressure studies have mainly included X-ray and neutron diffraction, fluorescence, IR and Raman spectroscopy, light transmission and volumetric measurements. Only a small amount of work has been performed using NMR techniques combined with high-pressure, a field which was pioneered by Jonas and co-workers " although the method is very powerful, non-invasive and allows the study of a series of structural and dynamic properties of the systems in detail and with atomic resolution. 

How can we be sure that the U +(Q2-) complex in a mixed metal oxide is present as the UO octahedron This can be done by studying solid solution series between tungstates (tellurates, etc.) and uranates which are isomorphous and whose crystal structure is known. Illustrative examples are solid solution series with ordered perovskite structure A2BWi aUa 06 and A2BTei-a Ua 06 91). Here A and B are alkahne-earth ions. The hexavalent ions occupy octahedral positions as can be shown by infrared and Raman analysis 92, 93). Usually no accurate determinations of the crystallographic anion parameters are available, because this can only be done by neutron diffraction [see however Ref. (P4)]. Vibrational spectroscopy is then a simple tool to determine the site symmetry of the uranate complex in the lattice, if these groups do not have oxygen ions in common. In the perovskite structure this requirement is fulfilled. 

Other techniques previously described for general investigation of tautomeric equilibria (76AHC(S1)1> involve heats of combustion, relaxation times, polarography, refractive index, molar refractivity, optical rotation, X-ray diffraction, electron diffraction, neutron diffraction, Raman, fluorescence, phosphorescence and photoelectron spectroscopy, and mass spectrometry. The application of several of these techniques to tautomeric studies has been discussed in previous sections. Other results from the more important of these will be referred to later in this section. 

During the last two decades, studies on ion solvation and electrolyte solutions have made remarkable progress by the interplay of experiments and theories. Experimentally, X-ray and neutron diffraction methods and sophisticated EXAFS, IR, Raman, NMR and dielectric relaxation spectroscopies have been used successfully to obtain structural and/or dynamic information about ion-solvent and ion-ion interactions. Theoretically, microscopic or molecular approaches to the study of ion solvation and electrolyte solutions were made by Monte Carlo and molecular dynamics calculations/simulations, as well as by improved statistical mechanics treatments. Some topics that are essential to this book, are included in this chapter. For more details of recent progress, see Ref. [1]. 

Table 6.3 provides a summary of the different microscopic techniques that have been applied to hydrate studies and the type of information that can be obtained from these tools. The following discussion provides a brief overview of the application of diffraction and spectroscopy to study hydrate structure and dynamics, and formation/decomposition kinetics. For information on the principles and theory of these techniques, the reader is referred to the following texts on x-ray diffraction (Hammond, 2001), neutron scattering (Higgins and Benoit, 1996), NMR spectroscopy (Abragam, 1961 Schmidt-Rohr and Spiess, 1994), and Raman spectroscopy (Lewis and Edwards, 2001). 

Now that the range of likely shapes has been defined by experiments on related molecules and by energy calculations, we focus on the details of specific structures that have been observed for real, crystalline cellulose molecules, primarily by x-ray, neutron, and electron diffraction studies. A number of landmark concepts have been established with electron microscopy, as well. Infrared (IR), Raman, and nuclear magnetic resonance (NMR) spectroscopy have all also been important in the quest for understanding cellulose structure. Such data, while so far not able to provide complete definitive structures themselves, constitutes additional criteria that any proposed structure must be able to explain. In addition, unlike crystallography, the resolution of spectroscopic methods is not directly affected by the dimensions of the... 

The active site on the surface of selective propylene anmioxidation catalyst contains three critical functionalities associated with the specific metal components of the catalyst (37—39) an CC-H abstraction component such as Bi3+, Sb3+, or Te4+ an olefin chemisorption and oxygen or nitrogen insertion component such as Mo6+ or Sb5+ and a redox couple such as Fe2+/Fe3+ or Ce3+/ Ce4+ to enhance transfer of lattice oxygen between the bulk and surface of the catalyst. The surface and solid-state mechanisms of propylene ammoxidation catalysis have been determined using Raman spectroscopy (40,41), neutron diffraction (42—44), x-ray absorption spectroscopy (45,46), x-ray diffraction (47—49), pulse kinetic studies (36), and probe molecule investigations (50). 

New techniques such as laser Raman spectrophotometry, NMR spectroscopy and X-ray and neutron diffraction methods, as well as EXAFS and XANES spectroscopy, provide us tools to observe solution phenomena from the microscopic point of view on the bases of structural chemistry and reaction dynamics. Thus, structural and dynamic studies of solutions have been developed as new streams of solution chemistry. 

NMR success motivated other spectroscopic studies to measure the hydrate phase directly. This work represented an experimental departure, because previously only the fluid phases (vapor and liquid(s)) were measured, and any experimental error was incorporated in the solid-phase model of van der Waals and Platteeuw, However, with modem solid-phase measurements, the errors in the van der Waals and Platteeuw model could be clarified and corrected. Raman spectroscopy and diffraction (X-ray and neutron, supplemented by Rietveld analysis ) have been successful the first method to measure the relative occupation of single guest cages, and the second to extend the work to hydrate isothermal, adiabatic, and isobaric compressibilities. As shown in Section 4, these measurements combine with spectroscopic hydrate phase measurements to enable improvements of the model. 

Direct methods for studying the structure of molten salts are X-ray and neutron diffraction analyses, infrared and Raman spectroscopy, NMR (nuclear magnetic resonance) measurement, and also very recently, XAFS (X-ray Absorption Fine Structure) measurement in melts, were developed. Fiowever, the most frequently used direct methods are X-ray and XAFS measurements, Raman spectroscopy, and NMR measurements. Therefore these three methods of direct investigation will be briefly described here. 

The most important experimental techniques in this field are structural analyses by both X-ray and neutron diffraction methods, and infrared and Raman spectroscopic measurements. Less frequently used techniques are nuclear magnetic resonance, both broad band NMR spectroscopy and magic angle spinning methods (MAS), nuclear quadrupole resonance (NQR), inelastic and quasielastic neutron scattering, conductivity and permittivity measurements as well as thermal analyses such as difference thermal analysis (DTA), differential scanning calorimetry (DSC), and thermogravimetry (TG and DTG) for phase transition studies. 

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