EXAFS coordination numbers

The EXAFS coordination numbers for MgO powder-supported clusters formed by decarbonylation of [Os5C(CO)i4] agree with those of OS5C chosen in oiu investigation, but the Os-Os bond distances are calculated to be about SOSO pm shorter than the values measured by EXAFS spectroscopy. For such... 

Solid state NMR is a relatively recent spectroscopic technique that can be used to uniquely identify and quantitate crystalline phases in bulk materials and at surfaces and interfaces. While NMR resembles X-ray diffraction in this capacity, it has the additional advantage of being element-selective and inherently quantitative. Since the signal observed is a direct reflection of the local environment of the element under smdy, NMR can also provide structural insights on a molecularlevel. Thus, information about coordination numbers, local symmetry, and internuclear bond distances is readily available. This feature is particularly usefrd in the structural analysis of highly disordered, amorphous, and compositionally complex systems, where diffraction techniques and other spectroscopies (IR, Raman, EXAFS) often fail. 

The X-ray absorption fine structure (XAFS) methods (EXAFS and X-ray absorption near-edge structure (XANES)) are suitable techniques for determination of the local structure of metal complexes. Of these methods, the former provides structural information relating to the radial distribution of atom pairs in systems studied the number of neighboring atoms (coordination number) around a central atom in the first, second, and sometimes third coordination spheres the... 

Table 1 Coordination number (N) and bond distance (R) of cluster core of crystalline A determined by XRD [3] and EXAFS data of PtRu/MgO prepared from cluster A and acac precursors after ligand removal...

The EXAFS results suggested that the iridium-rhodium clusters dispersed on alumina differed in size and/or shape from those dispersed on silica, based on the result that the total coordination nunbers of the iridium and rhodium atoms in the clusters were very different (7 and 5 in the alumina supported clusters vs. 11 and 10 in the silica supported clusters). These coordination numbers suggested that the clusters dispersed on alumina were smaller or that they were present in the form of thin rafts or patches on the support. The possibility of a "raft-like" structure in the case of the alumina supported clusters suggests an interaction between the metal clusters and the support which is much more pronounced for alumina than for silica. If the clusters on the alumina were present as rafts with a thickness of one atomic layer, one could have a situation in which the rhodium concentration at the perimeter of the raft was greater... 

The extended fine structure (EXAFS) was used to determine bond distances, coordination number and disorder. The near edge (XANES) was used as an Indication of electronic state. Significant results Include, 1) a reversible change of shape of clean supported metal clusters as a function of temperature, 2) supported Pt clusters have more disorder or strain compared to the bulk metal, and 3) a clear determination of the bonds between the catalytic metal atoms and the oxygen atoms of the support. 

Figure 2. Fhase adjusted Fourier transforms of Ft metal, 1% Ft/ Cabosil catalyst in H2 and 0.5% Ft/Cabosil catalyst in H2, all at 90 K. All are plotted to the same scale to emphasize the diminished magnitude because of the smaller average coordination numbers in the catalysts. The INSET shows the Ft-0 peak area retransformed with the appropriate Ft-0 phase shift. The artifact at low R is due to the EXAFS extraction procedure.

If a vacant site is occupied by another Nb atom, such that it is a dimer, new catalysts may be designed. The Nb dimer catalyst(2) was prepared by reaction of [Nb(ri -C5H5)H-p-(T, Ti -CsH4)]2 with a Si02 at 313 K, followed by treatment with 02 at 773 K. A proposed structure(2) was characterized by EXAFS, x-ray absorption near-edge structure(XANES), FT-IR, UV-vis, and XPS, which shows Nb-Nb (coordination number 0.9) and Nb-Si(2.3)... 

After treatment at 373 K in helium flow, the coordination numbers of Mo-0, Mo-S and Mo-Mo were not largely different from those in the cluster 1 and the distances of Mo-0, Mo-S and Mo-Mo were hardly changed. After treatment at 573 K in He flow, however, the color of NaY changed from brown to black and the curve fitting results of the EXAFS data exhibited lower coordination numbers of all interactions than those of the cluster 1. The decrease in the coordination number seems to be not due to the decrease in sulfur amount in the catalyst but to the disordering of each interaction since the S/Mo ratio hardly decreased after thermal treatment. These results show that the structure of the cluster 1 loaded on NaY was maintained at 373 K, but lost at 573 K. 

B.J.H. methods) (iii) the average diameter (T.E.M.) and/or the dispersion (chemisorption of probe molecule) of the metallic particle. EXAFS will also provide average coordination numbers, which decrease sharply as the particle size decreases. 

For example, clusters identified by IR spectra and extraction as Ir4(CO)i2 on y-Al203 were found by EXAFS spectroscopy to have an Ir-Ir coordination number of nearly 3, consistent with the tetrahedral structure of the metal frame EXAFS spectroscopy produces the equivalent result for sohd Ir4(CO)i2 [27]. EXAFS spectroscopy is the most appropriate method for determination of framework structures of supported clusters, but it is limited by the errors to clusters with at most about six metal atoms. Thus, it has been used to determine frameworks that are triangular (EXAFS first-shell metal-metal coordination number of 2), tetrahedral (EXAFS first-shell metal-metal coordination number of 3), and octahedral (EXAFS first-shell metal-metal... 

Local surface structure and coordination numbers of neighbouring atoms can be extracted from the analysis of extended X-ray absorption fine structures (EXAFS). The essential feature of the method22 is the excitation of a core-hole by monoenergetic photons modulation of the absorption cross-section with energy above the excitation threshold provides information on the distances between neighbouring atoms. A more surface-sensitive version (SEXAFS) monitors the photoemitted or Auger electrons, where the electron escape depth is small ( 1 nm) and discriminates in favour of surface atoms over those within the bulk solid. Model compounds, where bond distances and atomic environments are known, are required as standards. 

Table 8.53 shows the main features of XAS. The advantages of EXAFS over diffraction methods are that the technique does not depend on long-range order, hence it can always be used to study local environments in amorphous (and crystalline) solids and liquids it is atom specific and can be sensitive to low concentrations of the target atom (about 100 ppm). XAS provides information on interatomic distances, coordination numbers, atom types and structural disorder and oxidation state by inference. Accuracy is 1-2% for interatomic distances, and 10-25 % for coordination numbers. 

EXAFS has been used to determine the second hydration shell of zinc in aqueous solution. Aqueous solutions of zinc nitrate over a range of concentrations were examined and a Zn—O distance of 2.05 A for the first shell of the six-coordinate zinc center found, which is unaffected by concentration. The second hydration shell shows a Zn—O distance which has no systematic trend but an average distance of 4.1 A. The coordination number for the second shell is 11.6 1.6 with unusual behavior for the most concentrated 2.7 M solution, which has a decrease in coordination number to 6.8 1.5 340... 

If the identity of the backscatterer is known, then the interest is in determining the number of near neighbors. In this case, one needs to compare the amplitude of the EXAFS of the material of interest (unknown) to that for a compound of known coordination number and structure. However, unlike transferability of phase, which is generally regarded as an excellent approximation, the transferability of amplitude is not. This is because there are many factors that affect the amplitude and, except for the case of model compounds of very similar structures, these will not necessarily (and often will not) be the same. As a result, determination of coordination numbers (near neighbors) is usually no better than 20%. 

Another noteworthy example is x-ray absorption fine structure (EXAFS). EXAFS data contain information on such parameters as coordination number, bond distances, and mean-square displacements for atoms that comprise the first few coordination spheres surrounding an absorbing element of interest. This information is extracted from the EXAFS oscillations, previously isolated from the background and atomic portion of the absorption, using nonlinear least-square fit procedures. It is important in such analyses to compare metrical parameters obtained from experiments on model or reference compounds to those for samples of unknown structure, in order to avoid ambiguity in the interpretation of results and to establish error limits. 

The EXAFS, which occurs at higher energies above the edge, is due to the interference between the outgoing and the backscattered photoelectron waves (10-14). EXAFS provides information about the local structure of the x-ray absorbing atom. Typically, nearest neighbor bond lengths and coordination numbers can be determined to 0.02 A (1%) and one atom in four (25%) (4 ). The accuracy of these determinations is somewhat worse for outer-shell atoms, for disordered systems, or for systems with asymmetric distributions of atoms within a shell (15,16). 

Coordination Number (N) and Interatomic Distance (R) of Co-O and Co-Co Shells Calculated from Co K-edge EXAFS Spectra of Calcined Catalysts, and Polycrystalline Co304 and a-Co2Si04 (Figure 6.10)... 

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