Pressure calibration in high pressure EXAFS experiments

Abstract

To avoid glitches due to Bragg reflection we use boron carbide anvils for our high pressure EXAFS experiments. Since boron carbide precludes the ruby fluorescence pressure calibration we use the EXAFS of selected materials to measure the reduction with pressure of the nearest neighbor distance and infer the pressure from an isothermal equation of state. The requirements for a good pressure calibrant and the difficulties in EXAFS data analysis are discussed. Cu, NaBr and RbCl have successfully been tested as pressure calibrants.     

Sonochemically synthesized core-shell structured Au–Pd nanoparticles supported on γ-Fe2O3 particles

A sample of Au–Pd bimetallic nanoparticles supported on γ-Fe₂O₃ was synthesized in a sonochemically one-pot process. The structural analyses of the synthesized sample were performed by the techniques of X-ray Absorption Fine Structure (XAFS), X-ray Diffraction (XRD), Transmission Electron Microscopy (TEM) and UV–vis spectrometry. Results indicated that the synthesized sample formed a core-shell structure in which a gold core was surrounded by a thin palladium shell. The reaction rate constant for the hydrogenation of cyclohexene of the present sample showed higher value than that of Pd nanoparticles supported on γ-Fe₂O₃ and core-shell structured Au–Pd nanoparticles supported on SiO₂. The present sample is a promising catalyst material which has a high catalytic activity.     

Observation of phase transition of cesium manganese hexacyanoferrates by X-ray absorption spectroscopy

Cesium manganese hexacyanoferrates exhibit an interesting phenomenon of temperature-induced phase transition accompanied by a variation in the magnetic susceptibility. We observed the variation in the electronic state of Mn during the phase transition by using X-ray absorption spectroscopy. The results of the analyses showed that the content ratio of Fe^II-CN-Mn^III and Fe^III-CN-Mn^II systematically varied during the phase transition. However, the ratio of Fe^II-CN-Mn^II remained constant at almost all temperatures. These results suggest that the charge transfer between Fe and Mn ions in the Fe^III-CN-Mn^II or the Fe^II-CN-Mn^III bond produces the phase transition.     

Xas study of actinide solvent extraction compounds. ii: UO(NO)(L) (with L=tri-isobutylphosphate, tri-n-butylphosphate, trimethylphosphate and triphenylphosphate)

In the back-end of the nuclear fuel cycle, liquid–liquid extraction is the selected separation method. For an improved design of new extracting agent, the knowledge of the coordination polyhedra of the metal ions is important. In this paper, we investigated the coordination sphere of a series of uranyl complexes with selected organophosphorus extracting molecules: UO₂(NO₃)₂L₂ (with L=tri-iso-butylphosphate, tri-n-butylphosphate, trimethylphosphate and triphenylphosphate) using X-ray absorption spectroscopy. FEFF7 calculations of the EXAFS spectra corresponding to the model compound UO₂(NO₃)₂(TiBP)₂ (with TiBP=tri-iso-butylphosphate) for which the crystal structure is known led to a multiple scattering approach of the data fitting. EXAFS results show subtle U–O(P) bond distance differences between the different complexes that are discussed in terms of both electronic and steric effects of L. These results are discussed with regards to the extraction ability of L. In the same time, exploratory work has been attempted in order to evaluate U–O–P bond angle variations as a function of L using multiple photon-scattering paths. Satisfactory values have been obtained compared to the crystallographic data.     

Quasi in situ Ni K‐edge EXAFS investigation of the spent NiMo catalyst from ultra‐deep hydrodesulfurization of gas oil in a commercial plant

Ni species on the spent NiMo catalyst from ultra‐deep hydrodesulfurization of gas oil in a commercial plant were studied by Ni K‐edge EXAFS and TEM measurement without contact of the catalysts with air. The Ni–Mo coordination shell related to the Ni–Mo–S phase was observed in the spent catalyst by quasi in situ Ni K‐edge EXAFS measurement with a newly constructed high‐pressure chamber. The coordination number of this shell was almost identical to that obtained by in situ Ni K‐edge EXAFS measurement of the fresh catalyst sulfided at 1.1 MPa. On the other hand, large agglomerates of Ni₃S₂ were observed only in the spent catalyst by quasi in situ TEM/EDX measurement. MoS₂‐like slabs were sintered slightly on the spent catalyst, where they were destacked to form monolayer slabs. These results suggest that the Ni–Mo–S phase is preserved on the spent catalyst and Ni₃S₂ agglomerates are formed by sintering of Ni₃S₂ species originally present on the fresh catalyst.     

EXAFS and XANES Studies on 3d Transition Metal Intercalation Compounds M x TiS2

Abstract

EXAFS and XANES spectra of Ti K-edge have been measured for 3d transition metal intercalation compounds M _x TiS₂ (M = Mn, Fe, Co and Ni; x ≤ 0.33). We have found that the interatomic distance between Ti and the first nearest neighbor S atoms, R(Ti-S), increases with the guest concentration x. The variation in XANES spectra with x reveals the reduction of the valence state of Ti atoms upon intercalation of M. From these results as well as the M K-edge EXAFS data studied previously, we have proposed a simple model on the local structure of M _x TiS₂ to reproduce the observed values of R(Ti-S) by averaging local shift of S atoms caused by intercalation.     

X-ray absorption spectroscopy under high pressures in diamond anvil cells

Abstract

Although potentially extremely important for understanding the high-pressure microscopic behaviour of materials, over the years the area of high-pressure EXAFS in particular using diamond anvil cells has proved to be technically difficult. This has significantly hampered its development. The interference of X-ray dimaction from the diamonds in the diamond anvil cell with the absorption signal has proved to be a challenging problem to tackle, restricting the use of high-pressure EXAFS to energies below about 11 key Below 11 keV however the technique is also limited due to absorption of incident X-rays by the diamonds making it virtually impossible to conduct X-ray absorption experiments below about 9keV In this paper we describe in detail the methodology for scanriirig high-pressure EXAFS in diamond anvil cells and examine the origins of the associated problems and ways of dealing with them. We also demonstrate that it is possible to extend the useful range of studied absorption edges from 7keV up to at least 30keV This brings about new opportunities for high pressure EXAFS using diamond anvil cells.