G. Vankó

Evolution of Fe species during the synthesis of over-exchanged Fe/ZSM5 obtained by chemical vapor deposition of FeCl3

The evolution of iron in over-exchanged Fe/ZSM5 prepared via chemical vapor deposition of FeCl3 was studied at each stage of the synthesis. Different characterization techniques (EXAFS, HR-XANES, 57 Fe Mossbauer spectroscopy, 27 Al NMR, EELS, HR-TEM, XRD, N2 physisorption, and FTIR spectroscopy) were applied in order to correlate the changes occurring in the local environment of the Fe atoms with migration and aggregation phenomena of iron at micro- and macroscopic scale. Mononuclear isolated Fe-species are formed upon FeCl3 sublimation, which are transformed into binuclear Fe-complexes during washing. During calcination, iron detached from the Bronsted sites migrates to the external surface of the zeolite, finally leading to significant agglomeration. Nevertheless, agglomeration of Fe can be strongly suppressed by adequately tuning the conditions of the calcination.  2002 Elsevier Science (USA). All rights reserved.

Improving the performance of high-resolution X-ray spectrometers with position-sensitive pixel detectors

A dispersion-compensation method to remove the cube-size effect from the resolution function of diced analyzer crystals using a position-sensitive two-dimensional pixel detector is presented. For demonstration, a resolution of 23 meV was achieved with a spectrometer based on a 1 m Rowland circle and a diced Si(555) analyzer crystal in a near-backscattering geometry, with a Bragg angle of 88.5 degrees . In this geometry the spectrometer equipped with a traditional position-insensitive detector provides a resolution of 190 meV. The dispersion-compensation method thus allows a substantial increase in the resolving power without any loss of signal intensity.

Resonant inelastic hard x-ray scattering with diced analyzer crystals and position-sensitive detectors

A novel design of a high-resolution spectrometer is proposed for emission spectroscopy and resonant inelastic hard x-ray scattering applications. The spectrometer is based on a Rowland circle geometry with a diced analyzer crystal and a position-sensitive detector. The individual flat crystallites of the diced analyzer introduce a well-defined linear position-energy relationship within the analyzer focus. This effect can be exploited to measure emission spectra with an unprecedented resolution. For demonstration, a spectrometer was constructed using a diced Si(553) analyzer working at the CuK edge with an intrinsic resolution of 60meV. With the proposed design, spectrometers operating at the K edges of 3d transition metals can have intrinsic resolutions below 100meV even with analyzer crystals not working in Bragg-backscattering conditions.

Organotin(IV) complexes of polyhydroxyalkyl carboxylic acids and some related ligands

A number of dibutyltin(IV) complexes of polyhydroxyalkyl carboxylic acids (O donor atoms) and amino acids (O,N donor atoms) were prepared in the solid state. The binding sites of the ligands were determined by means of FT-IR, Raman and 13C NMR spectroscopy. Partial quadrupole splitting calculations were utilized to determine the coordination geometry around the Sn(IV) centre by means of Mössbauer measurements. The results showed that in the solid state oligomeric complexes are formed, with the -COO- groups as bridges between the organometallic cations. The {Sn} atoms are mostly in trigonal bipyramidal surroundings. The Sn-O and Sn-C bond distances were determined by EXAFS measurements to be 207-234 and 295 pm, respectively. Evaluation of the pH-metric and NMR titration curves in Me2Sn(IV)-D-gluconic acid system revealed that the equilibria in aqueous solution are fairly complicated. In acidic solution, the formation of 1 : 1 and 1 : 2 -COO- coordinated species predominate, but deprotonation of the alcoholic -OH groups also starts at very low pH. In the pH range 5-9, NMR provides experimental evidence of ligand-exchange reactions without pH-metrically detectable proton release. In alkaline solution, further deprotonation processes occur, resulting in either alkoxo or mixed hydroxo complexes. The carboxylate coordination is expected for the amino acid ligands but the shift of the νN-H stretching vibrations in the FT-IR spectra demonstrated that the ammine group also binds to the metal ion in the solid Bu2Sn(IV)complexes.

Zeolite supported Sn-Pt catalysts prepared by surface reactions

Abstract A Pt/H–mordenite (Pt/H–MOR) catalyst has been modified with tin using the controlled surface reaction between tin tetraalklyls and hydrogen adsorbed on platinum. Experimental evidences show that upon modification of Pt/H-MOR catalyst with tin tetraalkyls, the surface chemistry established for Pt/SiO 2 and Pt/Al 2 O 3 cannot be maintained, i.e., the formation of multilayered organometallic complexes (MLOC) is hindered. Consequently, the results indicate that the introduction of tin into platinum is possible if the Sn/Pt s ratio is below 0.5. In this case, zeolite supported alloy type Sn–Pt nanoparticles are formed. At higher Sn/Pt s ratios, in addition to the formation of alloy type Sn–Pt nanoparticles, ionic forms of tin anchored onto the zeolite are also formed. The reaction between tin tetraalkyls and surface OH groups of the zeolite is involved in the formation of ionic forms of tin stabilized on the zeolite surface. Upon applying Mossbauer spectroscopy, different tin containing surface species were identified including two SnPt alloy phases. Tin introduced in this way slightly decreases the H/Pt and CO/Pt ratios measured by chemisorption and changes the activity and selectivity of these catalysts in n -hexane isomerization at 275°C.

Intermediate valence behaviour under pressure: how precisely can we probe it by means of resonant inelastic x-ray emission?

Rare earths and their compounds show many interesting physical phenomena caused by the complex electronic structure related to f electrons. External pressure can affect the hybridization between 5d band electrons and the more atomic-like 4f ones, giving rise to intermediate valence behaviour. Resonant x-ray emission spectroscopy (RXES) has been shown to be a very effective tool for probing the mixed valence ground state under pressure. A RXES experiment detects the x-ray emission that follows decay into a resonantly created core hole. Being a photon- in-photon-out spectroscopic technique, it is not hindered by the presence of the pressure cell. In the case of rare earths we chose to detect the 3d-2p x-ray emission following a 2p-5d resonant excitation process. The divalent and trivalent components of the ground state are separately enhanced because they resonate at different incident photon energies. Very good precision in the determination of even small changes of valence is reached. We will present experimental results on ytterbium compounds (YbAl2 and YbS), as well as recent data on the valence state of SmS in the gold phase, that have allowed us to unveil the progressive valence change towards the completion of trivalency. The spectral changes and the way to extract the valence from measured spectra will be discussed.

Hard x-ray spectroscopy in Na x Co O 2 and superconducting Na x Co O 2 ∙ y H 2 O : Bulk Co electronic properties

The electronic properties of Co in bulk Na0.7CoO2 and the superconducting hydrated compound Na0.35CoO2 - y H2O have been investigated by x-ray absorption spectroscopy (XAS) and resonant inelastic x-ray scattering (RIXS) using hard x-rays. The XAS spectra at the Co K-edge were measured in both compounds with two different polarization directions. The changes in the XAS spectra upon hydration and their polarization dependence are well accounted for by linear muffin- tin orbital calculations in the local density approximation. The underlying electronic structure indicates the strong hybridization between the Co 3d and O 2p states in both compounds, while the electron localization is enhanced in the hydrated compound due to the increase of the Co-Co interplanar distance. The Co K pre-edge further highlights the splitting of the d band as a result of the crystal field effect and demonstrates the Co valency increase when Na0.7CoO2 is hydrated. The RIXS spectra measured at the Co K-edge show an energy loss feature around 10 eV in both compounds in fair agreement with the calculated dynamical structure factor. The RIXS feature is associated to a damped plasmon excitation.

Switching reciprocity on and off in a magneto-optical x-ray scattering experiment using nuclear resonance of α-(57)Fe foils.

Reciprocity is when the scattering amplitude of wave propagation satisfies a symmetry property, connecting a scattering process with an appropriate reversed one. We report on an experiment using nuclear resonance scattering of synchrotron radiation, which demonstrates that magneto-optical materials do not necessarily violate reciprocity. The setting enables us to switch easily between reciprocity and its violation. In the latter case, the exhibited reciprocity violation is orders of magnitude larger than achieved by previous wave scattering experiments.

Nuclear Inelastic Scattering of Synchrotron Radiation on Solutions of 57Fe Complexes

Nuclear inelastic resonant scattering of synchrotron radiation was applied to the study solutions of 57Fe complexes. In order to reveal different inelastic contributions solutions of two different 57Fe complexes of different molecular dimensions with solvents of substantially different viscosities were studied. We argue that the only former experiment available in the literature overestimates the role of the diffusivity in affecting the spectrum. The first direct observation of an intramolecular vibrational transition assisting the nuclear resonance absorption in a liquid is reported.

Zero Sound Mode in Normal Liquid {sup 3}He

Inelastic x-ray scattering has been utilized to study the elementary excitations of normal liquid 3He at the temperature T=1.10+/-0.05 K and saturated vapor pressure in the wave vector range 0.15<or=Q<or=3.15 A(-10. The present data provide direct information on the zero-sound mode in the mesoscopic wave vector range where it was expected to decay into particle-hole excitations. The obtained results show no evidence of such a decay: the zero-sound mode remains well defined in the whole explored wave number range, thus witnessing a continuous transition of the atom dynamics from the collective to the single particle regime similarly to what is usually found in simple liquids.