EXAFS Study on the Coordination Chemistry of the Solvated Copper(II) Ion in a Series of Oxygen Donor Solvents

The structures of the solvated copper(II) ion in water and nine organic oxygen donor solvents with similar electron-pair donor ability, but with different space-demanding properties at coordination, have been studied by EXAFS. N,N'-Dimethylpropyleneurea and N,N,N',N'-tetramethylurea are sufficiently space demanding at coordination to make the axial positions not accessible, resulting in square-planar copper(II) solvate complexes with an intense green color. The mean Cu-O bond distances in these two solvate complexes are 1.939(3) and 1.935(3) angstrom, respectively. The best fits of the remaining solvates, which are light blue in different hues, are obtained with a Jahn-Teller distorted-octahedral model consisting of four strongly bound solvent molecules in the equatorial positions at 1.96(2) angstrom and two in the axial positions but with different Cu-O-ax bond distances: ca. 2.15 and 2.32 angstrom. This is in agreement with observations in solid-state structures of compounds containing hexaaquacopper(II) complexes crystallizing in noncentrosymmetric space groups and all reported crystal structures containing a [Cu(H2O)(5)(O-ligand)] complex with Jahn-Teller distortion. Such a structure is in agreement with previous EPR and EXAFS studies proving the hydrated copper(II) ion to be a noncentrosymmetric complex in aqueous solution. The refinements of the EXAFS data of the solids [Cu(H2O)(6)](ClO4)(2), [Cu(H2O)(6)] (BrO3)(2), [Cu(H2O)(6)]SiF6, Cu(NO3)(2)center dot 2.5H(2)O, and CuSO4 center dot 5H(2)O gave Cu-O bond distances significantly different from those reported in the crystallographic studies but similar to the configuration and bond distances in the hydrated copper(II) ion in aqueous solution. This may depend on whether the orientation of the axial positions is random in one or three dimensions, giving a mean structure of the solid with symmetry higher than that of the individual complexes. This study presents the very first experimental data from the new X-ray absorption spectroscopy beamline Balder at the MAX IV synchrotron radiation facility in Lund, Sweden, as well as the utilized properties of the beamline

Low Temperature Anharmonicity and Superconductivity in Cuprates

Temperature-dependent X-ray absorption spectra of the hole-doped $La_{2−x}Sr_{x} CuO_{4}$ and electron-doped $Nd_{2−x} Ce _{x} CuO_{4−\delta}$ high-temperature superconductors were investigated above the Cu K absorption edge. We observed strong anharmonicity in the superconductive $CuO_{2}$ plane. For x=0.15 it was shown that part of oxygen ions oscillate in a double-well potential and their vibrations are correlated with the local electron (hole) pair transfer. We suppose that at a low temperature the phase coherence of the local pair movement is determined by the peculiarities of the perovskite-like structure which includes the stiff $CuO_{n}$ (n = 4,6) complexes combined by collective rotational and breathing modes

Pd/H-Beta catalysts: Characterization and reactivity in piperonyl alcohol selective oxidation

Pd/H-Beta catalysts with different silica-to-alumina ratio prepared by an impregnation method have been studied by XANES/EXAFS, IR, XRD and TEM. It was shown that palladium in calcined Pd/H-Beta samples exists as palladium oxide that can be easily reduced to Pd metal. The catalysts were tested in selective oxidation of piperonyl alcohol to piperonylaldehyde at 80 °C. The Pd/H-Beta zeolite catalysts with the lowest silica-to-alumina ratio possess the highest catalytic activity in benzylic alcohol oxidation reaction

Supported palladium nanoparticles on hybrid mesoporous silica: Structure/activity-relationship in the aerobic alcohol oxidation using supercritical carbon dioxide

The preparation, characterization, and catalytic properties of Pd nanoparticles supported on mesoporous organic–inorganic hybrid materials are described for continuous-flow aerobic oxidation of alcohols using supercritical carbon dioxide (scCO2) as a mobile phase. The nanoparticles were generated “bottom-up” from molecular precursors that were precoordinated to the support through suitable anchor units. The most active material allows high single-pass conversions in scCO2 at temperatures as low as 60 °C. This high activity may be associated with the presence of small primary crystallites (approx. 2 nm) that conglomerate to ensembles about 25 nm in size, leading to a larger number of high-indexed planes in small volume units. These findings may provide useful guidelines for further catalyst design on the nanoscale for green oxidation methods

Exciton interaction with Ce³⁺ and Ce⁴⁺ ions in (LuGd)₃(Ga,Al)₅O₁₂ ceramics

Scintillators based on Ce-doped garnets are regularly co-doped with Mg2+ or Ca2+ to form Ce ions in 4+ state and reduce undesired afterglow. However overly high Ce4+ concentration leads to poor light yield performance. In order to understand the reason for variation in luminescence efficiency of Ce3+- and Ce4+-doped garnets we investigate the differences in energy conversion processes in complex LuGd2Ga3Al2O12:Ce3+/Ce4+ ceramics by means of VUV synchrotron irradiation. At first we have established via transmission spectroscopy and X-ray absorption spectroscopy that LuGd2Ga3Al2O12:Ce, Mg sample contains cerium in the 4+ state only. Then we show with VUV spectroscopy efficient interaction of excitons with Gd3+ and Ce3+, and lack of exciton absorption edge in LuGd2Ga3Al2O12:Ce4+ excitation spectrum. Instead, Ce4+ exhibits charge-transfer absorption band in the range of exciton emission. We suggest that when Ce4+ concentration becomes too high, the exciton → Gd3+ → Ce3+ energy transfer path is hindered. It leads to high intensity of Gd3+ luminescence in Lu1Gd2Ga3Al2O12:Ce, Mg ceramics, but lowered Ce3+ X-ray excited luminescence. Fine balance between 3+ and 4+ Ce concentrations is necessary to achieve the best performance of garnet scintillators.RST/Luminescence Material