Catalysis of the rare earth containing mixed oxides Ln(2)CuO(4) in phenol hydroxylation

Mixed oxides Ln(2)CuO(4+/-lambda)(Ln = La, Pr, Nd, Sm, Gd) with K2NiF4 structure were prepared. Their crystal structures were studied with XRD and IR spectra. Meanwhile, the average valence of Cu ions and nonstoichiometric oxygen (lambda) were determined through chemical analyses. Catalysis of the above-mentioned mixed oxides in the phenol hydroxylation was investigated. Results show that the catalysis of these mixed oxides has close relation with their structures and composition. Substitution of A site atom in Ln(2)CuO(4+/-lambda) has a great influence on their catalysis in the phenol hydroxylation.

Luminescence and energy transfer phenomena of several rare earth ions in the CaAl2B2O7

The luminescence properties of Ce3+, Gd3+, and Tb3+ have been investigated in the compound CaAl2B2O7. The single excitation band peaking at about 320 nm and single emission band peaking at about 384 nm for Ce3+, without the characteristic doublet, are attributed to the extensive crystal-field splitting of 4f ground state. The emission of Gd3+ consists of well-known sharp lines and two weak bands around 319.5 and 325 nm. These bands are due to the coupling of Gd3+ with BO33- groups. The green emission of Tb3+ is considerably sensitized by Ce3+. Energy transfer from Ce3+ to Tb3+ in CaAl2B2O7 is efficient. (C) 1997 Elsevier Science Ltd.

Luminescence of Pb2+ and energy transfer from Pb2+ to rare earth ions in silicate oxyapatites

The Pb2+ luminescence in a series of silicate oxyapatites Me(2)(Y, Gd)(8)(SiO4)(6)O-2, Me(4)Y(6)(SiO4)(6)O (Me = Mg: Ca, Sr) is reported and discussed in relation to the crystal structure. The maximum wavelengths of the excitation (S-1(0)-P-3(1)) and emission (P-3(1)-S-1(0)) bands of Pb2+ are independent of the Mc:Y ratio (2:8 or 4:6) but they have lower energies in MgY-oxyapatites than in CaY- and SrY-oxyapatites. The Stokes shift of Pb2+ luminescence amounts to 11 100 to 11 400 cm(-1): which does not depend strongly on the host composition. There exists a mutual energy transfer between Pb2+ and Gd3+ in Sr2Gd8(SiO4)(6)O-2. At last, the dependence of the energy transfer efficiency of Pb2+-Sm3+, Tb3+: Dy3+ in Sr-2(La: Gd)(8)(SiO4)(6)O-2 and Ca-2(Y, Gd)(8)(SiO4)(6)O-2 on their doping concentrations was studied in more detail.

Influence of intraperitoneal injection of rare earth compounds on the activities of antioxidant enzymes and the level of lipid peroxidation in mice livers

Following intraperitoneal injection of lanthanum and terbium chloride and their complexes of diethyltriaminopentagacetic acid (DTPA) to adult mice with a dose of 0.28 mmol/kg body weight/day for three days. The activities of superoxide dismutase (SOD) and glutathione peroxidase (GSH-Px) and the content of lipid end product, malonaldehyde (MDA) in the mice livers have been assayed respectively. The results show that the activity of SOD was increased and the content of MDA was reduced for LaCl3 treated mice and the two targets were not changed for TbCl3, but the activity of GSH-Px was reduced markedly for both LaCl3 and TbCl3 while the above three targets were not changed for La-DTPA and Tb-DTPA complexes.

W-183 NMR characterization of rare earth heteropolymetalates in aqueous solution

W-183 NMR spectra were obtained for [La(AsW11O39)(2)](11-), [La(As2W17O61)(2)](17-), [La(SiW9Mo2O39)(2)](13-), [LaSb9W21O86](16-), [LaAs4W40O140](25-) and alpha-, beta-[(CeO)(3) . (SiW9O34)(2)](14-) complexes, Tungsten NMR studies showed that the C-s symmetry of the square antiprism for [La(ASW(11)O(39))(2)](11-) and [La(As2W17O61)(2)](17-) anions keep constant in aqueous solution; the lanthanide accupied the central S-1 site in [LnSb(9)W(21)O(86)](16-) and [LnAs(4)W(40)O(140)](25-) complexes, respectively, and lanthanide metal cations gave [(CeO)(3) . (SiW9O34)(3)](14-) type of complexes with SiW9O3410-.

Crystal structure dependence of the luminescence of rare earth ions (Ce3+, Tb3+, Sm3+) in Y2SiO5

The luminescence properties of Ce3+, Tb3+, Sm3+ and energy transfer from Ce3+ to Tb3+ were studied in two modifications of Y2SiO5 (low temperature X(1) type and high temperature X(2) type). The Ce3+ cation shows lower emission energy and larger Stokes shift in X(1)-Y2SiO5 than in X(2)-Y2SiO5, and the emission intensities of Ce3+, Tb3+, Sm3+ in the former are weaker than those in the latter. There exists an energy transfer from Ce3+ to Tb3+ in both types of Y2SiO5, and the transfer efficiency in X(2) type is higher than that in X(1) type. All of these results are discussed in relation to the crystal structure of Y2SiO5.

LUMINESCENCE AND ENERGY-TRANSFER OF RARE-EARTH-METAL IONS IN MG2Y8(SIO4)(6)O-2

The photoluminescence of Ce3+, Tb3+ and Sm3+, and energy transfer from Ce3+ to Tb3+, Dy3+ and Sm3+ in Mg2Y8(SiOd(4))(6)O-2 are reported and discussed. The Ce3+ ion shows blue luminescence under UV excitation, and occupies simultaneously the 4f site and 6h site in the host lattice. The optimum concentrations for the D-5(3) and D-5(4) emissions of Tb3+ and the (4)G(5/2) emission of Sm3+ are determined to be 0.04, 0.20 and 0.10 mol in every mol of Mg2Y8(SiO4)(6)O-2, respectively. The critical distances responsible for the cross-relaxation between the D-5(3)-D-5(4) and F-7(6)-F-7(0) transitions of Tb3+ and between the (4)G(5/2)-F-4(9/2) and H-6(5/2)-F-4(9/2) transitions of Sm3+ are estimated to be 1.43 and 1.06 nm, respectively. Both Tb3+ and Dy3+ can be sensitized by Ce3+, but Ce3+ and Sm3+ quench each other.

Preparation and properties of rare earth hydroxides and oxides ultrafine powders in alcohol

A series of rare earth hydroxides and oxides ultrafine powders have been prepared by precipitation method using alcohol as dispersive and protective reagent. It was first to find that the crystallite size of cubic rare earth oxides had Lanthanide shrinking effect,but average crystal lattice distortion rate possessed lanthanide swelling effect;the change of diffraction intensity with atomic number presented an inverted W type, and double peaks structure was formed.

LUMINESCENCE AND ENERGY MIGRATION IN THE OXYAPATITE CA2GD8(SIO4)6O2 DOPED WITH SEVERAL RARE-EARTH AND MERCURY-LIKE IONS

Energy transfer phenomena have been observed by activating the oxyapatite host-lattice Ca2Gd8(SiO4)6O2 with Eu3+, Tb3+, Dy3+, Sm3+. This is based on the energy migration in the Gd3+ sublattice and trapping by the activators. The trapping efficiency for G

PHOTOELECTRON-SPECTRA OF VARIOUS CORE LEVELS IN SOME RARE-EARTH N-ACETYLVALINE BIOINORGANIC COMPLEXES

X-ray photoelectron spectra of some bioinorganic complexes of La, Pr, Nd, Sm, and Gd with N-acetylvaline have-been measured. The complex formation does not give any detectable influence on the binding energy of the N 1s peak in the amino group, but has some appreciable effect on the binding energy of the C 1s peak and the O 1s peak in the carboxyl and carbonyl group of the biological ligand. The spin-orbit splitting between the 3d5/2 and 3d3/2 core level of the rare earth ion in these bioinorganic complexes also becomes slightly larger than that of the free rare earth atom due to the effect of the crystal field from the biological ligands.

DETERMINATION OF TRACE AMOUNT OF 14 RARE-EARTH IMPURITIES IN HIGH-PURITY YTTRIUM-OXIDE WITH ICP-AES

A method of analysis of high purity yttrium oxide with ICP-AES was described with emphasis on the study of Y_2O_3 matrix effects. The results showed that the line intensities of ana]ytes decreased with the increase of Y_2O_3 concentration in solution because of following factors. (1) The presence of matrix resulted in the decrease of the amount of analytes reaching ICP. (2) Matrix Y_2O_3 entering the plasma decreased the excitation temperature of the plasma and depressed the ionization of analytes in the pl...

Geochemistry of rare earth elements in cobalt-rich crusts from the Mid-Pacific M seamount

Rare earth elements (RFEs) and major elements of 25 cobalt-rich crusts obtained from different depths of Mid-Pacific M seamount were analyzed using inductively coupled plasma-atomic emission spectrometer and gravimetric method. The results showed that they were hydrogenous crusts with average Sigma REE content of 2084.69 mu g/g and the light REE (LREE)/heavy REE (HREE) ratio of 4.84. The shale-normalized PEE patterns showed positive Ce anomalies. The total content of strictly trivalent REEs increased with water depth. The Ce content and LREE/HREE ratios in Fe-Mn crusts above 2000 in were lower than those below 2000 m. The change in RE E with water depth could be explained by two processes: adsorptive scavenging by setting matters and behaviors of REE in seawater. However, the Ce abundance took no obvious correlation with water depth reflects the constant Ce flux. The Cc in crusts existed mainly as Ce(IV), implying that the oxidative-enriching process was controlled by kinetic factors.

Rare earth elements in bottom sediments of major rivers around the Yellow Sea: implications for sediment provenance

Rare earth elements (REEs) of 91 fine-grained bottom sediment samples from five major rivers in Korea (the Han, Keum, and Yeongsan) and China (the Changjiang and Huanghe) were studied to investigate their potential as source indicator for Yellow Sea shelf sediments, this being the first synthetic report on REE trends for bottom sediments of these rivers. The results show distinct differences in REE contents and their upper continental crust (UCC)-normalized patterns: compared to heavy rare earth elements (HREEs), light rare earth elements (LREEs) are highly enriched in Korean river sediments, in contrast to Chinese river sediments that have a characteristic positive Eu anomaly. This phenomenon is observed also in primary source rocks within the river catchments. This suggests that source rock composition is the primary control on the REE signatures of these river sediments, due largely to variations in the levels of chlorite and monazite, which are more abundant in Korean bottom river sediments. Systematic variations in I LREE pound/I HREE pound ratios, and in (La/Yb)-(Gd/Yb)(UCC) but also (La/Lu)-(La/Y)(UCC) and (La/Y)-(Gd/Lu)(UCC) relations have the greatest discriminatory power. These findings are consistent with, but considerably expand on the limited datasets available to date for suspended sediments. Evidently, the REE fingerprints of these river sediments can serve as a useful diagnostic tool for tracing the provenance of sediments in the Yellow Sea, and for reconstructing their dispersal patterns and the circulation system of the modern shelf, as well as the paleoenvironmental record of this and adjoining marginal seas.