X-ray absorption fine structure spectroscopy XAFS

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]). 

Extended X-ray absorption fine structure (EXAFS) spectrum Part of an X-ray absorption spectrum that is used to identify the coordination of atoms, estimate bond lengths, and determine the adsorption complexes on the surfaces of adsorbents. EXAFS spectra may provide useful information on the speciation (valence state), surface complexes, and the coordination of arsenic on adsorbents (e.g. (Randall, Sherman and Ragnarsdottir, 2001 Ladeira, et al. (2001) Teixeira and Ciminelli (2005) Kober, et al. (2005)) (compare with X-ray absorption spectroscopy (XAS), X-ray absorption near edge structure (XANES) spectra, and X-ray absorption fine structure spectroscopy (XAFS)). 

Chloride complexation studies of the actinide ions An3+, An4+, An02, and AnO + (An = U, Np, Pu) were reported in several comprehensive reviews [293-295], More recent investigations on aqua and chloro complexes of U02+, NpOz+, Np4+, Pu3+, etc., by x-ray absorption fine structure spectroscopy (XAFS) were reported [296,297]. In particular, it was established for U(IV) and Th(IV) aqua ions and fluoride complexes that both M(IV) aqua ions are 10-coordinate with M — O bond distances for U(IV) and Th(IV) of 2.42 0.01 A and 2.45 0.01 A, respectively [297], Physical and chemical studies of uranium aqueous complexes are reported [298,299a], A series of articles is dedicated to specific sequestering agents for the actinides [299b-e],... 

In addition to the structure in the dehydrated state, the structure of supported vanadia catalysts under redox reaction conditions is directly related to the catalytic performance. Vanadia catalysts are usually reduced to some extent during a redox reaction, and the reduced vanadia species have been proposed as the active sites [4, 19-24]. Therefore, information on the valence state and molecular structure of the reduced vanadia catalysts is of great interest. A number of techniques have been applied to investigate the reduction of supported vanadia catalysts, such as temperature programmed reduction (TPR) [25-27], X-ray photoelectron spectroscopy (XPS) [21], electron spin resonance (ESR) [22], UV-Vis diffuse reflectance spectroscopy (UV-Vis DRS) [18, 28-32], X-ray absorption fine structure spectroscopy (XAFS) [11] and Raman spectroscopy [5, 26, 33-41]. Most of these techniques give information only on the oxidation state of vanadium species. Although Raman spectroscopy is a powerful tool for characterization of the molecular structure of supported vanadia [4, 29, 42], it has been very difficult to detect reduced supported... 

A unique capability of the synchrotron X-ray microprobe is microbeam applications of X-ray absorption fine structure spectroscopy (XAFS) for the determination of chemical speciation. Thus, not only can one obtain the concentration of a trace element but also its oxidation state, coordination number, and the identity of nearest neighbors. 

In the applications of X-ray absorption spectrometry (XAS, also called X-ray absorption fine structure spectroscopy, XAFS) the energy dependence of the inner shell photoelectric cross is exploited to increase specificity of measurements or to obtain information on the chemical environment (speciation analysis). 

In addition to TEM, XRD, and XPS characterizations, a detailed X-ray absorption fine structure spectroscopy (XAFS) analysis of the atomic-scale coordination structures was carried out, revealing increased heteroatomic coordination with improved alloying structures for the catalyst treated at the elevated temperatures. By comparing the results for the same PtNiFe/C catalyst treated at 400 and 800 C from fitting using either PtNi or PtFe model, we found that the fitted parameters for Pt neighbors including coordination number (CN), bond... 

EXAFS is part of the field of X-ray absorption spectroscopy (XAS), in which a number of acronyms abound. An X-ray absorption spectrum contains EXAFS data as well as the X-ray absorption near-edge structure, XANES (alternatively called the near-edge X-ray absorption fine structure, NEXAFS). The combination of XANES (NEXAFS) and EXAFS is commonly referred to as X-ray absorption fine structure, or XAFS. In applications of EXAFS to surface science, the acronym SEXAFS, for surface-EXAFS, is used. The principles and analysis of EXAFS and SEXAFS are the same. See the article following this one for a discussion of SEXAFS and NEXAFS. 

HexOMe, methyl glycoside Hex-onic, aldohexonic acid hmba, 2-hydroxy-2-methylbutanoate2 HYSCORE, hyperfine sublevel correlation spectroscopy mod. ampl., modulation amphtude polyGalA, galacturonan Qa, quinic acid XAFS, X-ray absorption fine structure spectroscopy... 

Conradson SD (1998) Application of X-ray absorption fine structure spectroscopy to materials and environmental science. Appl Spectrosc 52 252A-279A Conradson SD, Clark DL, Neu MP, Runde W, Tait CD (2000) Characterizing the plutonium aquo ions by XAFS spectroscopy. Los Alamos Science 26 (Vol. 2) 418-421 Conradson SD, Mahamid IA, Clark DL, Hess NJ, Hudson EA, Neu MP, Palmer PD, Runde WH, Tait CD... 

Lindau I, Spicer WE (1980) Photoemission as a tool to study solids and surfaces. In Winick H, Doniach S (eds) Synchrotron Radiation Research, Plenum Press, New York, p 159-221 Lindqvist-Reis P, Lamble K, Pattanaik S, Persson I, Sandstrocni. M (2000) Hydration of the yttrium(III) ion in aqueous solution. An X-ray diffraction and XAFS structural study. J Phys Chem 104 402-408 Lindqvist-Reis P, Munoz-Paez A, Diaz-Moreno S, Pattanaik S, Persson I, Sandstroem M (1998) The structure of the hydrated gallium(III), indium(HI), and chromium(III) ions in aqueous solution. A large angle X-ray scattering and EXAFS study. Inorg Chem 37 6675-6683 Liu C, Frenkel AI, Vairavamurthy A, Huang PM (2001) Sorption of cadmium on humic acid Mechanistic and kinetic studies with atomic force microscopy and X-ray absorption fine structure spectroscopy. Canadian J Soil Sci 81 (3, Spec. Issue) 337-348... 

G. Bunker, Introduction to XAFS A Practical Guide to X-ray Absorption Fine Structure Spectroscopy, Cambridge University Press, Cambridge, UK (2010). 

For bulk structural detemiination (see chapter B 1.9). the main teclmique used has been x-ray diffraction (XRD). Several other teclmiques are also available for more specialized applications, including electron diffraction (ED) for thin film structures and gas-phase molecules neutron diffraction (ND) and nuclear magnetic resonance (NMR) for magnetic studies (see chapter B1.12 and chapter B1.13) x-ray absorption fine structure (XAFS) for local structures in small or unstable samples and other spectroscopies to examine local structures in molecules. Electron microscopy also plays an important role, primarily tlirough unaging (see chapter B1.17). 

XAFS V, Proceeding of the Fifth International Conference on X-ray Absorption Fine Structure. (J. M. de Leon, E. A. Stern, D. E. Sayers, Y. Ma, and J. J. Rehr, eds.) North-Holland, Amsterdam, 1989. Also in Physica B. 158, 1989. Report of the International Workshop on Standards and Criteria in X-ray Absorption Spectroscopy (pp. 701-722) is essential reading. 

Groothaert et al., using operando UV-vis spectroscopy combined with online GC analysis [176] and operando X-ray absorption fine structure (XAFS) [177], presented the first experimental evidence for the formation of the bis( x-oxo)dicopper core in Cu-ZSM-5 and for its key role of intermediate in the sustained high activity of Cu-ZSM-5 in the direct decomposition of NO into N2 and 02. In particular, monitoring the catalytic conversion of NO and N20 above 673 K, they found that the bis( x-oxo)dicopper core is formed by the O abstraction of the intermediate N20 (Figure 4.14). Subsequently,... 

The most prevalent technique exploiting synchrotron radiation is X-ray absorption spectroscopy (XAS, also called X-ray absorption fine structure, XAFS). Two related types of experiments are conducted X-ray absorption near-edge spectroscopy (XANES), which probes the initial absorption edge and related nearby structure, and... 

Temperature-programmed reduction combined with x-ray absorption fine-structure (XAFS) spectroscopy provided clear evidence that the doping of Fischer-Tropsch synthesis catalysts with Cu and alkali (e.g., K) promotes the carburization rate relative to the undoped catalyst. Since XAFS provides information about the local atomic environment, it can be a powerful tool to aid in catalyst characterization. While XAFS should probably not be used exclusively to characterize the types of iron carbide present in catalysts, it may be, as this example shows, a useful complement to verify results from Mossbauer spectroscopy and other temperature-programmed methods. The EXAFS results suggest that either the Hagg or s-carbides were formed during the reduction process over the cementite form. There appears to be a correlation between the a-value of the product distribution and the carburization rate. 

The aim of this work was to apply combined temperature-programmed reduction (TPR)/x-ray absorption fine-structure (XAFS) spectroscopy to provide clear evidence regarding the manner in which common promoters (e.g., Cu and alkali, like K) operate during the activation of iron-based Fischer-Tropsch synthesis catalysts. In addition, it was of interest to compare results obtained by EXAFS with earlier ones obtained by Mossbauer spectroscopy to shed light on the possible types of iron carbides formed. To that end, model spectra were generated based on the existing crystallography literature for four carbide compounds of... 

The pHPZC of ferric hydroxide surfaces is about 8 [127], so aqueous Pb2+ should be electrostatically repelled from these surfaces at pH values less than 8. However, as seen in Figure 7.6(a), the Pb2+ present in this aqueous solution is sorbed essentially completely to ferric hydroxide surfaces at pH 6. This behavior suggests that Pb2+ forms direct chemical bonds to these surfaces in order to overcome the repulsive electrostatic forces below the pHpzc of ferric hydroxide. This conclusion based on macroscopic uptake data has been confirmed by direct spectroscopic observation using X-ray absorption fine structure (XAFS) spectroscopy under in situ conditions (i.e., with aqueous solution in contact with a-FeOOH surfaces at ambient temperature and pressure) [133,134]. These studies showed that the aquated Pb(II) ion forms dominantly inner-sphere, bidentate complexes on a-FeOOH surfaces. 

Many important heterogeneous catalytic reactions occur at the interface between a solid catalyst and liquid or liquid-gas reactants. Notwithstanding the importance of solid-catalyzed reactions in the presence of liquid reactants, relatively little attention has been paid to spectroscopic methods that allow researchers to follow the processes occurring at the solid-liquid interface during reaction. This lack can be explained in part by the fact that there are only a few techniques that give access to information about solid-liquid interfaces, the most prominent of them being attenuated total reflection infrared spectroscopy (ATR-IR) and X-ray absorption fine structure (XAFS) spectroscopy. 

In recent years, it has been realized that techniques based on X-ray absorption provide important additional possibilities for catalyst characterization. Techniques such as X-ray absorption fine structure (XAFS) spectroscopy have had a significant impact on catalyst research. For example, the application of these techniques has for the first time allowed structural descriptions of many catalysts which, because of the presence of microcrystalline structures (nanophase particles) or amorphous phases, cannot be elucidated by XRD. 

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