Magnetic properties and structural transitions of fluorite-related rare earth osmates Ln3OsO7 (Ln=Pr, Tb)

International Nuclear Information System (INIS)

Hinatsu, Yukio; Doi, Yoshihiro

2013-01-01

Ternary rare-earth osmates Ln 3 OsO 7 (Ln=Pr, Tb) have been prepared. They crystallize in an ortho-rhombic superstructure of cubic fluorite with space group Cmcm. Both of these compounds undergo a structural phase transition at 130 K (Ln=Pr) and 580 K (Ln=Tb). These compounds show complex magnetic behavior at low temperatures. Pr 3 OsO 7 exhibits magnetic transitions at 8 and 73 K, and Tb 3 OsO 7 magnetically orders at 8 and 60 K. The Os moments become one-dimensionally ordered, and when the temperature is furthermore decreased, it provokes the ordering in the Ln 3+ sublattice that simultaneously becomes three-dimensionally ordered with the Os sublattice. - Graphical abstract: Ternary rare-earth osmates Ln 3 OsO 7 (Ln=Pr, Tb) have been prepared. They crystallize in an orthorhombic superstructure of cubic fluorite with space group Cmcm. Both of these compounds undergo a structural phase transition at 130 K (Ln=Pr) and 580 K (Ln=Tb). These compounds show complex magnetic behavior at low temperatures. Pr 3 OsO 7 exhibits magnetic transitions at 8 and 73 K, and Tb 3 OsO 7 magnetically orders at 8 and 60 K. Highlights: ► Ternary rare-earth osmates Ln 3 OsO 7 (Ln=Pr, Tb) with an ordered defect-fluorite structure have been prepared. ► Both of these compounds undergo a structural phase transition at 130 K (Ln=Pr) and 580 K (Ln=Tb). ► These compounds show complex magnetic behavior at low temperatures due to magnetic ordering of Ln and Os.

Phase transition of the orthorhombic fluorite-related compounds Ln{sub 3}IrO{sub 7} (Ln = Pr, Nd, Sm, Eu)

Energy Technology Data Exchange (ETDEWEB)

Hinatsu, Yukio, E-mail: hinatsu@sci.hokudai.ac.j [Division of Chemistry, Graduate School of Science, Hokkaido University, Sapporo 060-0810 (Japan); Doi, Yoshihiro; Nishimine, Hiroaki; Wakeshima, Makoto [Division of Chemistry, Graduate School of Science, Hokkaido University, Sapporo 060-0810 (Japan); Sato, Mineo [Department of Chemistry and Chemical Engineering, Faculty of Engineering, Niigata University, 8050 Ikarashi 2-nocho, Niigata 950-2181 (Japan)

2009-12-04

Rare earth iridium oxides Ln{sub 3}IrO{sub 7} (Ln = Pr, Nd, Sm, and Eu) were prepared and their structures were determined by X-ray diffraction measurements. At room temperature, Pr{sub 3}IrO{sub 7} crystallized in an orthorhombic superstructure of cubic fluorite with space group Cmcm. The differential thermal analysis (DTA) and specific heat measurements for Ln{sub 3}IrO{sub 7} (Ln = Pr, Nd, Sm, and Eu) showed a phase transition at 262, 342, 420, and 485 K, respectively. At low temperatures, Ln{sub 3}IrO{sub 7} crystallized in a monoclinic structure with the space group P2{sub 1}/n. The transition temperatures increased with decreasing the ionic radius of rare earths, which indicates that the transition is stress-induced and occurs with the lattice contraction on cooling. These results for Ln{sub 3}IrO{sub 7} were compared with the phase transitions observed for Ln{sub 3}MoO{sub 7}, Ln{sub 3}RuO{sub 7}, Ln{sub 3}ReO{sub 7}, and Ln{sub 3}OsO{sub 7}.

Synthesis and electronic properties of LnRhAsO and LnIrAsO compositions

International Nuclear Information System (INIS)

Muir, Sean; Sleight, A.W.; Subramanian, M.A.

2011-01-01

The synthesis and characterization of the new compositions LnRhAsO (Ln=Ce, Nd) and LnIrAsO (Ln=La, Ce, Nd) are reported. These compounds crystallize in the ZrCuSiAs type structure, isostructural to iron pnictide LnFeAsO materials. Upon substitution of Rh for Fe, both a and c lattice parameters increase relative to 3d transition metal compounds; however, when Ir is substituted for Rh the a-parameter decreases slightly while the c-parameter expands. The decrease in a lattice parameter corresponds to a short metal-metal distance in Ir compounds. CeRhAsO and CeIrAsO compositions show abrupt decreases in resistivity at 7 and 10 K, respectively, coinciding with a small shift in magnetization at the transition temperature. - Graphical abstract: LnIrAsO (Ln=La, Ce, Nd) and LnRhAsO (Ln=Ce, Rh) have been synthesized. These new transition metal oxypnictide compositions are isostructural to LaFeAsO. The 5d Ir compositions demonstrate a shorter metal-metal interaction than the 4d Rh compositions. Highlights: → LnIrAsO (Ln=La, Ce, Nd) and LnRhAsO (Ln=Ce, Nd) have been synthesized. → Ir compositions show a decreased a-parameter and increased c-parameter relative to Rh compositions. → All LnIrAsO and LnRhAsO compositions are metallic while CeIrAsO and CeRhAsO show a sudden drop in resistivity at 10 and 7 K, respectively.

Uranyl and/or rare-earth mellitates in extended organic-inorganic networks: A unique case of hetero-metallic cation-cation interaction with U-VI=O-Ln(III) bonding (Ln = Ce, Nd)

International Nuclear Information System (INIS)

Volkringer, Christophe; Henry, Natacha; Grandjean, Stephane; Loiseau, Thierry

2012-01-01

A series of uranyl and lanthanide (trivalent Ce, Nd) mellitates (mel) has been hydrothermally synthesized in aqueous solvent. Mixtures of these 4f and 5f elements also revealed the formation of a rare case of lanthanide-uranyl coordination polymers. Their structures, determined by XRD single-crystal analysis, exhibit three distinct architectures. The pure lanthanide mellitate Ln 2 (H 2 O) 6 (mel) possesses a 3D framework built up from the connection of isolated LnO 6 (H 2 O) 3 polyhedra (tri-capped trigonal prism) through the mellitate ligand. The structure of the uranyl mellitate (UO 2 ) 3 (H 2 O) 6 - (mel).11.5H 2 O is lamellar and consists of 8-fold coordinated uranium atoms linked to each other through the organic ligand giving rise to the formation of a 2D 3 6 net. The third structural type, (UO 2 ) 2 Ln(OH)(H 2 O) 3 (mel).2.5H 2 O, involves direct oxygen bondings between the lanthanide and uranyl centers, with the isolation of a hetero-metallic dinuclear motif. The 9-fold coordinated Ln cation, LnO 5 (OH)(H 2 O) 3 , is linked to the 7-fold coordinated uranyl (UO 2 )O-4(OH) (pentagonal bipyramid) via one μ 2 -hydroxo group and one μ 2 -oxo group. The latter is shared between the uranyl bonding (U=O = 1.777(4)1.779(6) angstrom) and a long Ln-O bonding (Ce-O = 2.822(4) angstrom; Nd-O = 2.792(6) angstrom). This unusual linkage is a unique illustration of the so-called cation cation interaction associating 4f and 5f metals. The dinuclear motif is then further connected through the mellitate ligand, and this generates organic inorganic layers that are linked to each other via discrete uranyl (UO 2 )O 4 units (square bipyramid), which ensure the three-dimensional cohesion of the structure. The mixed U-Ln carboxylate is thermally decomposed from 260 to 280 degrees C and then transformed into the basic uranium oxide (U 3 O 8 ) together with U-Ln oxide with the fluorite structural type ('(Ln,U)O 2 '). At 1400 degrees C, only fluorite type '(Ln,U)O 2 ' is formed with

Influence of lead oxide addition on LnTiTaO6 (Ln = Ce, Pr and Nd) microwave ceramics

International Nuclear Information System (INIS)

Padma Kumar, H.; Thomas, J.K.; John, Annamma; Solomon, Sam

2011-01-01

The effect of PbO addition on the structural, processing and microwave dielectric properties of LnTiTaO 6 (Ln = Ce, Pr and Nd) ceramics are reported. Conventional solid state ceramic route was used for the preparation of samples. Phase pure LnTiTaO 6 (Ln = Ce, Pr and Nd) ceramics are prepared at a calcination temperature of 1300 deg C. The samples are sintered at optimized temperatures. Addition of PbO reduces the sintering temperature. The crystal structure of the materials was analysed using X-ray diffraction techniques and the surface morphology of the sintered samples was analysed using scanning electron microscopy. The dielectric constant at microwave frequency range decreases for higher PbO addition for all the samples but the quality factor improves on small PbO addition. The thermal stability of resonant frequency was also improved with PbO addition on all the systems. A number of samples with improved microwave dielectric properties were obtained on all the systems suitable for practical applications. (author)

Magnetic properties and structural transitions of fluorite-related rare earth osmates Ln{sub 3}OsO{sub 7} (Ln=Pr, Tb)

Energy Technology Data Exchange (ETDEWEB)

Hinatsu, Yukio, E-mail: hinatsu@sci.hokudai.ac.jp [Division of Chemistry, Graduate School of Science, Hokkaido University, Sapporo 060-0810 (Japan); Doi, Yoshihiro [Division of Chemistry, Graduate School of Science, Hokkaido University, Sapporo 060-0810 (Japan)

2013-02-15

Ternary rare-earth osmates Ln{sub 3}OsO{sub 7} (Ln=Pr, Tb) have been prepared. They crystallize in an ortho-rhombic superstructure of cubic fluorite with space group Cmcm. Both of these compounds undergo a structural phase transition at 130 K (Ln=Pr) and 580 K (Ln=Tb). These compounds show complex magnetic behavior at low temperatures. Pr{sub 3}OsO{sub 7} exhibits magnetic transitions at 8 and 73 K, and Tb{sub 3}OsO{sub 7} magnetically orders at 8 and 60 K. The Os moments become one-dimensionally ordered, and when the temperature is furthermore decreased, it provokes the ordering in the Ln{sup 3+} sublattice that simultaneously becomes three-dimensionally ordered with the Os sublattice. - Graphical abstract: Ternary rare-earth osmates Ln{sub 3}OsO{sub 7} (Ln=Pr, Tb) have been prepared. They crystallize in an orthorhombic superstructure of cubic fluorite with space group Cmcm. Both of these compounds undergo a structural phase transition at 130 K (Ln=Pr) and 580 K (Ln=Tb). These compounds show complex magnetic behavior at low temperatures. Pr{sub 3}OsO{sub 7} exhibits magnetic transitions at 8 and 73 K, and Tb{sub 3}OsO{sub 7} magnetically orders at 8 and 60 K. Highlights: Black-Right-Pointing-Pointer Ternary rare-earth osmates Ln{sub 3}OsO{sub 7} (Ln=Pr, Tb) with an ordered defect-fluorite structure have been prepared. Black-Right-Pointing-Pointer Both of these compounds undergo a structural phase transition at 130 K (Ln=Pr) and 580 K (Ln=Tb). Black-Right-Pointing-Pointer These compounds show complex magnetic behavior at low temperatures due to magnetic ordering of Ln and Os.

Magnetic properties and structural transitions of fluorite-related rare earth osmates Ln3OsO7 (Ln=Pr, Tb)

Science.gov (United States)

Hinatsu, Yukio; Doi, Yoshihiro

2013-02-01

Ternary rare-earth osmates Ln3OsO7 (Ln=Pr, Tb) have been prepared. They crystallize in an ortho-rhombic superstructure of cubic fluorite with space group Cmcm. Both of these compounds undergo a structural phase transition at 130 K (Ln=Pr) and 580 K (Ln=Tb). These compounds show complex magnetic behavior at low temperatures. Pr3OsO7 exhibits magnetic transitions at 8 and 73 K, and Tb3OsO7 magnetically orders at 8 and 60 K. The Os moments become one-dimensionally ordered, and when the temperature is furthermore decreased, it provokes the ordering in the Ln3+ sublattice that simultaneously becomes three-dimensionally ordered with the Os sublattice.

Magnetic upconverting fluorescent NaGdF4:Ln3+ and iron-oxide@NaGdF4:Ln3+ nanoparticles

Science.gov (United States)

Shrivastava, Navadeep; Rocha, Uéslen; Muraca, Diego; Jacinto, Carlos; Moreno, Sergio; Vargas, J. M.; Sharma, S. K.

2018-05-01

Microwave assisted solvothermal method has been employed to synthesize multifunctional upconverting β-NaGdF4:Ln3+ and magnetic-upconverting Fe3O4/γ-Fe2O3@NaGdF4:Ln3+ (Ln = Yb and Er) nanoparticles. The powder x-ray diffraction data confirms the hexagonal structure of NaGdF4:Ln3+ and high resolution transmission electron microscopy shows the formation of rod shaped NaGdF4:Ln3+ (˜ 20 nm) and ovoid shaped Fe3O4/γ-Fe2O3@NaGdF4:Ln3+ (˜ 15 nm) nanoparticles. The magnetic hysteresis at 300 K for β-NaGdF4:Ln3+ demonstrates paramagnetic features, whereas iron-oxide@β-NaGdF4:Ln3+ exhibits superparamagnetic behavior along with a linear component at large applied field due to paramagnetic NaGdF4 matrix. Both nanoparticle samples provide an excellent green emitting [(2H11/2, 4S3/2)→4I15/2 (˜ 540 nm)] upconversion luminescence emission under excitation at 980 nm. The energy migration between Yb and Er in NaGdF4 matrix has been explored from 300-800 nm. Intensity variation of blue, green and red lines and the observed luminescence quenching due to the presence of Fe3O4/γ-Fe2O3 in the composite has been proposed. These kinds of materials contain magnetic and luminescence characteristics into single nanoparticle open new possibility for bioimaging applications.

Phase transformations during HLnTiO{sub 4} (Ln=La, Nd) thermolysis and photocatalytic activity of obtained compounds

Energy Technology Data Exchange (ETDEWEB)

Silyukov, Oleg I., E-mail: olegsilyukov@yandex.ru; Abdulaeva, Liliia D.; Burovikhina, Alena A.; Rodionov, Ivan A.; Zvereva, Irina A.

2015-03-15

Layered HLnTiO{sub 4} (Ln=La, Nd) compounds belonging to Ruddlesden–Popper phases were found to form partially hydrated compounds Ln{sub 2}Ti{sub 2}O{sub 7}·xH{sub 2}O during thermal dehydration as well as defect oxides Ln{sub 2}□Ti{sub 2}O{sub 7} as final products. Further heating of metastable defect Ln{sub 2}□Ti{sub 2}O{sub 7} substances leads to the formation of pyrochlore-type oxides Ln{sub 2}Ti{sub 2}O{sub 7} {sub (p)}, with subsequent transformation under higher temperatures to stable layered 110-type perovskites Ln{sub 2}Ti{sub 2}O{sub 7}. The occurring structure transformations lead to an increase of photocatalytic activity in the order of HLnTiO{sub 4}<Ln{sub 2}Ti{sub 2}O{sub 7}·yH{sub 2}O{sub 2}□Ti{sub 2}O{sub 7}<Ln{sub 2}Ti{sub 2}O{sub 7} {sub (p)}<Ln{sub 2}Ti{sub 2}O{sub 7} in the reaction of hydrogen evolution from aqueous isopropanol solution. - Graphical abstract: Layered HLnTiO{sub 4} (Ln=La, Nd) compounds form partially hydrated Ln{sub 2}Ti{sub 2}O{sub 7}·xH{sub 2}O compounds during thermal dehydration, further heating results to the formation to defect oxides Ln{sub 2}□Ti{sub 2}O{sub 7}, pyrochlor-type oxides Ln{sub 2}Ti{sub 2}O{sub 7} {sub (p)}, with subsequent transformation to layered 110-type perovskites Ln{sub 2}Ti{sub 2}O{sub 7}. Structure transformations lead to an increase of photocatalytic activity in the order of HLnTiO{sub 4}<Ln{sub 2}Ti{sub 2}O{sub 7}·yH{sub 2}O{sub 2}□Ti{sub 2}O{sub 7}<Ln{sub 2}Ti{sub 2}O{sub 7} {sub (p)}<Ln{sub 2}Ti{sub 2}O{sub 7}. - Highlights: • We studied dehydration and further thermolysis of HLnTiO{sub 4} (Ln=La, Nd) compounds. • XRD, STA and solid state IR studies were carried out. • A new series of metastable Ln{sub 2}Ti{sub 2}O{sub 7}·yH{sub 2}O compounds was obtained. • We examined the photocatalytic activity of all obtained compounds. The hydrogen evolution rate increased in the course of the structure changes during thermolysis.

Ln28Ti2O7 (Ln = La, Nd, Sm, Gd): a novel series of defective Ruddlesden–Popper phases formed by topotactic dehydration of HLnTiO4

OpenAIRE

Thangadurai, V; Subbanna, GN; Gopalakrishnan, J

1998-01-01

Topotactic dehydration of HLnTiO4 (Ln = La, Nd, Sm or Gd) around 480–500 °C yields a new series of metastable layered perovskite oxides, Ln28Ti2O7, that possess a defective Sr3Ti2O7 structure, where the cubooctahedral sites within the double-perovskite layers are most likely vacant.

Structures, magnetic, and thermal properties of Ln3MoO7 (Ln=La, Pr, Nd, Sm, and Eu)

International Nuclear Information System (INIS)

Nishimine, Hiroaki; Wakeshima, Makoto; Hinatsu, Yukio

2005-01-01

Ternary lanthanide-molybdenum oxides Ln 3 MoO 7 (Ln=La, Pr, Nd, Sm, Eu) have been prepared. Their structures were determined by X-ray diffraction measurements. They crystallize in a superstructure of cubic fluorite and the space group is P2 1 2 1 2 1 . The Mo ion is octahedrally coordinated by six oxygens and the slightly distorted octahedra share corners forming a zig-zag chain parallel to the b-axis. These compounds have been characterized by magnetic susceptibility and specific heat measurements. The La 3 MoO 7 shows complex magnetic behavior at 150 and 380K. Below these temperatures, there is a large difference in the temperature-dependence of the magnetic susceptibility measured under zero-field-cooled condition and under field-cooled condition. The Nd 3 MoO 7 show a clear antiferromagnetic transition at 2.5K. From the susceptibility measurements, both Pr 3 MoO 7 and Sm 3 MoO 7 show the existence of magnetic anomaly at 8.0 and 2.5K, respectively. The results of the specific heat measurements also show anomalies at the corresponding magnetic transition temperatures. The differential scanning calorimetry measurements indicate that two phase-transitions occur for any Ln 3 MoO 7 compound in the temperature range between 370 and 710K

Borate electrolyte additives for high voltage lithium nickel manganese oxide electrode: A comparative study

International Nuclear Information System (INIS)

Chen, Zhiting; Wang, Cun; Xing, Lidan; Wang, Xianshu; Tu, Wenqiang; Zhu, Yunmin; Li, Weishan

2017-01-01

Highlights: •TMB and TEB effective improve the cyclic stability of LNMO at high voltage. •The performance of LNMO with TMB-containing electrolyte is superior to that of TEB. •LNMO shows catalytic effect on the oxidation reaction of TEB. •The film generated in TMB shows better ability on suppressing LNMO shedding than TEB. -- Abstract: Trimethyl borate (TMB) and triethyl borate (TEB) are used as film-forming electrolyte additives for high voltage Lithium nickel manganese oxide (LNMO) cathode. DFT calculation and initial charge curve of LNMO reveal that the oxidation activity of TEB is higher than that of TMB. Addition of 2% TMB and 2% TEB effectively improve the capacity retention of high voltage LNMO from 23.4% to 85.3% and 72.6% after 600 cycles, respectively. The film generated in TMB-containing electrolyte shows better ability on suppressing the LNMO shedding in comparison with that of TEB, resulting in higher capacity retention of LNMO in TMB-containing electrolyte at high voltage. The superior performance of LNMO with TMB-containing electrolyte should be ascribed to its less intense film-forming reaction which generates a denser protective surface film on LNMO surface. However, why LNMO shows catalyzation effect on TEB oxidation but not on TMB is unclear, which needs further intensive investigation.

Thermochemistry of rare earth doped uranium oxides LnxU1-xO2-0.5x+y (Ln = La, Y, Nd)

Science.gov (United States)

Zhang, Lei; Navrotsky, Alexandra

2015-10-01

Lanthanum, yttrium, and neodymium doped uranium dioxide samples in the fluorite structure have been synthesized, characterized in terms of metal ratio and oxygen content, and their enthalpies of formation measured by high temperature oxide melt solution calorimetry. For oxides doped with 10-50 mol % rare earth (Ln) cations, the formation enthalpies from constituent oxides (LnO1.5, UO2 and UO3 in a reaction not involving oxidation or reduction) become increasingly exothermic with increasing rare earth content, while showing no significant dependence on the varying uranium oxidation state. The oxidation enthalpy of LnxU1-xO2-0.5x+y is similar to that of UO2 to UO3 for all three rare earth doped systems. Though this may suggest that the oxidized uranium in these systems is energetically similar to that in the hexavalent state, thermochemical data alone can not constrain whether the uranium is present as U5+, U6+, or a mixture of oxidation states. The formation enthalpies from elements calculated from the calorimetric data are generally consistent with those from free energy measurements.

New family of lanthanide-based inorganic-organic hybrid frameworks: Ln2(OH)4[O3S(CH2)nSO3]·2H2O (Ln = La, Ce, Pr, Nd, Sm; n = 3, 4) and their derivatives.

Science.gov (United States)

Liang, Jianbo; Ma, Renzhi; Ebina, Yasuo; Geng, Fengxia; Sasaki, Takayoshi

2013-02-18

We report the synthesis and structure characterization of a new family of lanthanide-based inorganic-organic hybrid frameworks, Ln(2)(OH)(4)[O(3)S(CH(2))(n)SO(3)]·2H(2)O (Ln = La, Ce, Pr, Nd, Sm; n = 3, 4), and their oxide derivatives. Highly crystallized samples were synthesized by homogeneous precipitation of Ln(3+) ions from a solution containing α,ω-organodisulfonate salts promoted by slow hydrolysis of hexamethylenetetramine. The crystal structure solved from powder X-ray diffraction data revealed that this material comprises two-dimensional cationic lanthanide hydroxide {[Ln(OH)(2)(H(2)O)](+)}(∞) layers, which are cross-linked by α,ω-organodisulfonate ligands into a three-dimensional pillared framework. This hybrid framework can be regarded as a derivative of UCl(3)-type Ln(OH)(3) involving penetration of organic chains into two {LnO(9)} polyhedra. Substitutional modification of the lanthanide coordination promotes a 2D arrangement of the {LnO(9)} polyhedra. A new hybrid oxide, Ln(2)O(2)[O(3)S(CH(2))(n)SO(3)], which is supposed to consist of alternating {[Ln(2)O(2)](2+)}(∞) layers and α,ω-organodisulfonate ligands, can be derived from the hydroxide form upon dehydration/dehydroxylation. These hybrid frameworks provide new opportunities to engineer the interlayer chemistry of layered structures and achieve advanced functionalities coupled with the advantages of lanthanide elements.

AgLnSb/sub 2/O/sub 7/ compounds with weberite structure

Energy Technology Data Exchange (ETDEWEB)

Lopatin, S S; Aver' yanova, L N; Belyaev, I N; Zvyagintsev, B I; Dyatlov, Eh V [Rostovskij-na-Donu Gosudarstvennyj Univ. (USSR)

1982-11-01

The interaction between AgSbO/sub 3/ and LnSbO/sub 4/ in the solid phase at 1100-1150 deg C has been investigated. AgLnSb/sub 2/O/sub 7/ compounds with weberite crystal structure are formed in Ln=La, Pr, Nd, Sm cases but in Ln=Eu, Cd, Dy, Er cases the formation of termary oxides of the indicated composition has not been observed. Inasmuch as compounds of the general formula A/sub 2/B/sub 2/O/sub 7/ with average cation radii Rsub(B) >0.60 A and 1.65 <= Rsub(A)/Rsub(B) <= 2.20 can crystallize in weberite, pyrochlore and laminated perovskite-like structurer, conditions of the existence of the above mentioned structures depending on A and B dimensions and electronegativity are discussed.

Red emitting phosphors of Eu3+ doped Na2Ln2Ti3O10 (Ln = Gd, Y) for white light emitting diodes

International Nuclear Information System (INIS)

Zhang, Niumiao; Guo, Chongfeng; Yin, Luqiao; Zhang, Jianhua; Wu, Mingmei

2015-01-01

Highlights: • Layered red phosphors Na 2 Ln 2 Ti 3 O 10 (Ln = Gd, Y):Eu 3+ were prepared. • The synthesis parameters of phosphors were optimized. • PL and thermal stability of the samples were investigated. • LED devices were also fabricated including the present red phosphor. - Abstract: A series of Eu 3+ doped Na 2 Ln 2 Ti 3 O 10 (Ln = Gd, Y) red-emitting phosphors for application in ultraviolet based light emitting diodes (LEDs) were successfully synthesized by a modified sol–gel method. Their structure and luminescent properties were characterized by powder X-ray diffraction (XRD), photoluminescence excitation (PLE) and emission (PL) spectra and absorption spectra, according to these results the optimal compositions and synthesis parameters were determined. In addition, the thermal stabilities of the phosphors were investigated according to the temperature-dependent PL spectra. The red and white-LEDs (W-LEDs) comprising the Na 2 Ln 2 Ti 3 O 10 :Eu 3+ (Ln = Gd, Y) red emitting phosphors were fabricated with a near-ultraviolet (n-UV) chip. In comparison with Na 2 Y 1.4 Eu 0.6 Ti 3 O 10 , the Na 2 Gd 0.6 Eu 1.4 Ti 3 O 10 phosphor offers higher brightness, quantum efficiency, and excellent thermal stability. W-LEDs comprising Na 2 Gd 0.6 Eu 1.4 Ti 3 O 10 showed bright white emission with a color rendering index (Ra) of 82, a color temperature of 2151 K, and Commission Internationale de I’Eclairage (CIE) color coordinates of (0.34, 0.37). The phosphor Na 2 Gd 0.6 Eu 1.4 Ti 3 O 10 is more suitable candidate for application in LEDs

Improving low-temperature performance of spinel LiNi0.5Mn1.5O4 electrode and LiNi0.5Mn1.5O4/Li4Ti5O12 full-cell by coating solid-state electrolyte Li-Al-Ti-P-O

Science.gov (United States)

Bi, Kun; Zhao, Shi-Xi; Huang, Chao; Nan, Ce-Wen

2018-06-01

Octahedral cathode materials LiNi0.5Mn1.5O4 (LNMO), with primary particles size of 300-600 nm are prepared through one-step co-precipitation. Then solid-state electrolyte Li2O-Al2O3-TiO2-P2O5 (LATP) was coated on LNMO to form continuous surface-modification layer. There is no obviously difference of structure, morphology between coated LATP LiNi0.5Mn1.5O4 (LATP-LNMO) and pristine LiNi0.5Mn1.5O4 (P-LNMO). Low-temperature electrochemical performance of P-LNMO and LATP-LNMO electrodes, including charge-discharge capacity, cycle performance, middle discharge voltage and electrochemical impedance spectra (EIS), were measured systematically with three electrode. The results reveal that LATP-LNMO electrode presents superior electrochemical performance at low temperature, compared to P-LNMO electrode. At -20 °C, the capacity retention of LATP-LNMO (61%) is much higher than that of P-LNMO (39%). According to EIS, the enhancement of performance of LATP-LNMO cathode at low temperature can be attribute to LATP coating, which not only promotes lithium-ion diffusion at electrode/electrolyte interface but also decreases the charge transfer resistance. Finally, the electrochemical performances of full cell of LATP-LNMO or P-LNMO cathode vs Li4Ti5O12 anode are investigated. The energy density can be achieved to 270 Wh·Kg-1 at -20 °C if using LATP-LNMO, which is much better than that of P-LNMO.

Investigation of BaMoO4-Ln2(MoO4)3 systems (Ln = Nd, Sm, Yb)

International Nuclear Information System (INIS)

Vakulyuk, V.V.; Evdokimov, A.A.; Khomchenko, G.P.

1982-01-01

Using the methods of X-ray phase and differential-thermal analyses phase ratios in the systems BaMoO 4 -Ln 2 (MoO 4 ) 3 (Ln=Nd, Sm, Yb); BaNd 2 (MoO 4 ) 4 -MaGd 2 (MoO 4 ) are studied. Unit cell parameters and the character of melting of the compounds BaLn 2 (MoO 4 ) 4 are specified. Effect of growth conditions on laminated nature of BaGd 2 (MoO 4 ) 4 monocrystals is studied

Study of LnBaCo{sub 2}O{sub 6-d}elta (Ln = Pr, Nd, Sm and Gd) double perovskites as new cathode material for IT-SOFC

Energy Technology Data Exchange (ETDEWEB)

Chavez, E; Mueller, M; Mogni, L; Caneiro, A, E-mail: mogni@cab.cnea.gov.a [Centro Atomico Bariloche-CNEA, Instituto Balseiro. Av. Bustillo 9500, S. C. de Bariloche 8400 (Argentina)

2009-05-01

Oxides with double perovskites structures of general composition LnBaCo{sub 2}O{sub 6-d}elta (Ln = Pr, Nd, Sm and Gd) were synthesized by solid state reaction with the purpose to evaluate new materials to be used as cathodes in intermediate temperature solid oxide fuel cell (IT-SOFC). A preliminary study about electrochemical properties was performed by impedance spectroscopy between 500 and 800 deg. C under atmosphere of pure O{sub 2}. Symmetrical cells were obtained by spray deposition of LnBaCo{sub 2}O{sub 6-d}elta (Ln = Pr, Nd, Sm and Gd) at both sides of a dense ceramic electrolyte. The impedance spectroscopy measurements as a function of temperatures show a hysteresis loop which could be associated to a tetragonal/orthorhombic phase transition. The existence of this transition was corroborated by high temperature X-Ray diffraction and Differential Scanning Calorimetry measurements.

Structures and magnetic properties of rare earth double perovskites containing antimony or bismuth Ba{sub 2}LnMO{sub 6} (Ln=rare earths; M=Sb, Bi)

Energy Technology Data Exchange (ETDEWEB)

Otsuka, Shumpei, E-mail: m-nis-s-o@ec.hokudai.ac.jp; Hinatsu, Yukio

2015-07-15

A series of double perovskite-type oxides Ba{sub 2}LnMO{sub 6} (Ln=lanthanides; M=Sb, Bi) were synthesized and their structures were studied. The Ln and M are structurally ordered in the rock-salt type at the B-site of the perovskite ABO{sub 3}. For Ba{sub 2}PrBiO{sub 6} and Ba{sub 2}TbBiO{sub 6}, it has been found that the disordering between Ln ion and Bi ion occurs at the B-site of the double perovskite and both the Pr (Tb) and Bi exist in two oxidation state in the same compound from the analysis of the X-ray diffraction and magnetic susceptibility data. Magnetic susceptibility measurements show that all these compounds are paramagnetic and have no magnetic ordering down to 1.8 K. - Graphical abstract: Tolerance factor for Ba{sub 2}LnMO{sub 6} (M=Sb, Bi) plotted against the ionic radius of Ln{sup 3+}. We have found that there is a clear relation between crystal structures and tolerance factors. - Highlights: • The Ln and M ions are structurally ordered in the rock-salt type at the B-site. • The disordering between Pr (Tb) ion and Bi ion occurs at the B-site. • Ba{sub 2}LnMO{sub 6} (M=Sb, Bi) have no magnetic ordering down to 1.8 K.

Magnetic properties of rare earth oxides with perovskite structure

International Nuclear Information System (INIS)

Hinatsu, Yukio

2008-01-01

A perovskite composite oxide is represented by the general formula of ABO 3 . Cations at the B site characterize magnetic properties of the oxide. Many studies have been accumulated for transition metal elements at the B sites. In this report the studies of rare earth elements at the B sites are reviewed. In rare elements, tetravalent ions such as Ce 4+ , Pr 4+ and Tb 4+ can occupy the B sites with Ba and Sr ions at the A sites. Both the SrTbO 3 and BaTbO 3 have an orthorhombic structure and show the antiferromagnetic transition at about 33 K, which is originated from terbium ions coupled antiferromagnetically with the six neighboring terbium ions. A tetravalent praseodymium perovskite SrPrO 3 shows no existence of the magnetic ordering down to 2.0 K. This is in contrast to the result of isomorphous BaPrO 3 , which shows an antiferromagnetic transition at 11.5 K. A double perovskite structure is represented by the formula A 2 LnMO 6 (A=Ba, Sr, Ca; M=Ru, Ir). In a double perovskite compound Ba 2 PrRuO 6 , the Pr 3+ and Ru 5+ ions are arranged with regularity over the six-coordinate B sites. This compound transforms to an antiferromagnetic state below 117 K. Antiferromagnetic transition temperatures T N for isomorphous Sr and Ca show a clear tendency, T N (A=Ba)>T N (Sr)>T N (Ca), in the compounds with the same rare earth elements (Ln). The 6H-perovskite structure Ba 3 LnRu 2 O 9 consists of linkages between LnO 6 octahedra and Ru 2 O 9 dimers made from face-shared RuO 6 octahedra. The 6H-perovskite structure Ba 3 MRu 2 O 9 (M=Sc, Y, La, Nd-Gd, Dy-Lu) have the valence state of Ba 3 M 3+ Ru 2 4.5+ O 9 . The magnetic susceptibilities show a broad maximum at 135-370 K. This magnetic behavior is ascribed to the antiferromagnetic coupling between two Ru ions in a Ru 2 O 9 dimer and to the magnetic interaction between the Ru 2 O 9 dimers. (author)

Significant improvement in performances of LiNi0.5Mn1.5O4 through surface modification with high ordered Al-doped ZnO electro-conductive layer

International Nuclear Information System (INIS)

Sun, Hongdan; Xia, Bingbo; Liu, Weiwei; Fang, Guoqing; Wu, Jingjing; Wang, Haibo; Zhang, Ruixue; Kaneko, Shingo; Zheng, Junwei; Wang, Hongyu; Li, Decheng

2015-01-01

Graphical abstract: Al-doped ZnO (AZO)-coated LiNi 0.5 Mn 1.5 O 4 (LNMO) was prepared by sol–gel method. AZO-coated LNMO electrode shows excellent rate capability and a remarkable improvement in the cyclic performance at a high rate at elevated temperature. - Highlights: • Al-doped ZnO (AZO)-coated LiNi 0.5 Mn 1.5 O 4 (LNMO) was prepared by a traditional sol–gel method. • Al-doped ZnO (AZO) layer grown on the surface of LNMO is high ordered. • At a high rate of 10 C, the discharge capacity of the AZO-coated LNMO electrode can reach 114 mAh g −1 . • Al-doped ZnO (AZO) modification improved cyclic performance of LNMO at high temperatures. - Abstract: Al-doped ZnO (AZO)-coated LiNi 0.5 Mn 1.5 O 4 (LNMO) was prepared by sol–gel method. Transmission electron microscopy (TEM) analysis indicates that AZO layer grown on the surface of LNMO is high ordered. The results of electrochemical performance measurements reveal that the AZO-coated LNMO electrode displays the best rate capability compared with the bare LNMO and ZnO-coated LNMO, even at a high rate of 10 C. The discharge capacity of the AZO-coated LNMO electrode can still reach 114.3 mAh g −1 , about 89% of its discharge capacity at 0.1 C. Moreover, AZO-coated LNMO electrode shows a remarkable improvement in the cyclic performance at a high rate at elevated temperature due to the protective effect of AZO coating layer. The electrode delivers a capacity of 120.3 mAh g −1 with the capacity retention of 95% at 5 C in 50 cycles at 50 °C. The analysis of electrochemical impedance spectra (EIS) indicates that AZO-coated LNMO possesses the lowest charge transfer resistance compared to the bare LNMO and ZnO-coated LNMO, which may be responsible for improved rate capability

X-ray photoelectron spectroscopic study of direct reforming catalysts Ln{sub 0.5}Sr{sub 0.5}Ti{sub 0.5}Mn{sub 0.5}O{sub 3±d} (Ln = La, Nd, and Sm) for high temperature-operating solid oxide fuel cell

Energy Technology Data Exchange (ETDEWEB)

Kim, Keunsoo [Department of Engine Research, Korea Institute of Machinery and Materials, 156 Gajeongbuk-Ro, Daejeon 305-343 (Korea, Republic of); Jeong, Jihoon [Department of Mechanical Engineering, The University of Texas at Austin, Austin, TX 78712 (United States); Azad, Abul K. [Faculty of Integrated Technologies, University Brunei Darussalam, Jalan Tunku Link, Gadong BE1410 (Brunei Darussalam); Jin, Sang Beom [Department of Advanced Materials Science and Engineering, Hanbat National University, 125, Dongseo-Daero, Yusung-Gu, Daejeon 305-719 (Korea, Republic of); Kim, Jung Hyun, E-mail: jhkim2011@hanbat.ac.kr [Department of Advanced Materials Science and Engineering, Hanbat National University, 125, Dongseo-Daero, Yusung-Gu, Daejeon 305-719 (Korea, Republic of)

2016-03-01

Graphical abstract: Measured Ti 2p peaks and deconvolution peaks of Nd{sub 0.5}Sr{sub 0.5}Ti{sub 0.5}Mn{sub 0.5}O{sub 3±d} under oxidizing condition (left) and NSTM under reducing condition (right). - Highlights: • Chemical states of Ln{sub 0.5}Sr{sub 0.5}Ti{sub 0.5}Mn{sub 0.5}O{sub 3±d} (Ln: La, Nd and Sm) were analyzed. • Charge compensation occurred with the reduction of Mn and Ti. • The Nd substitution effect allowed some Ti to convert into a metallic behavioral component. • NSTM and SSTM had a large amount of lattice oxygen; however, LSTM retained a large quantity of adsorbed oxygen. - Abstract: Chemical states of lanthanide doped perovskite for direct reforming anode catalysts, Ln{sub 0.5}Sr{sub 0.5}Ti{sub 0.5}Mn{sub 0.5}O{sub 3±d} (Ln = La, Nd, and Sm) have been studied by X-ray Photoelectron Spectroscopy (XPS) in order to determine the effects of various lanthanide substitution in complex perovskites for high temperature-operating solid oxide fuel cells (HT-SOFC). The charge state of lanthanide ions remained at 3+ and the binding energies of the lanthanide ions in Ln{sub 0.5}Sr{sub 0.5}Ti{sub 0.5}Mn{sub 0.5}O{sub 3±d} were located in a relatively lower range compared to those of conventional lanthanide oxides. Mn and Ti were regarded as charge compensation components in Ln{sub 0.5}Sr{sub 0.5}Ti{sub 0.5}Mn{sub 0.5}O{sub 3±d}; Mn was more influential than Ti. In the cases of substituting Nd and Sm into Ln{sub 0.5}Sr{sub 0.5}Ti{sub 0.5}Mn{sub 0.5}O{sub 3±d}, some portion of Ti showed metallic behavior; the specific Mn satellite peak indicating an electro-catalytic effect had occurred. Three types of oxygen species comprised of lattice oxygen, carbonate species, and adsorbed oxygen species were observed in Ln{sub 0.5}Sr{sub 0.5}Ti{sub 0.5}Mn{sub 0.5}O{sub 3±d} from the O 1s spectra; a high portion of lattice oxygen was observed in both Nd{sub 0.5}Sr{sub 0.5}Ti{sub 0.5}Mn{sub 0.5}O{sub 3±d} (NSTM) and Sm{sub 0.5}Sr{sub 0.5}Ti{sub 0.5}Mn{sub 0.5}O

The effect of lanthanides on color properties of the (Bi2O30.7(Ln2O30.3 compounds

Directory of Open Access Journals (Sweden)

Šulcová P.

2008-01-01

Full Text Available (Bi2O30.7(Ln2O30,3 solid solutions were synthesized as new inorganic yellow and orange pigments and their color properties have been investigated as possible ecological materials. The pigments were prepared by the solid state reaction of mixed oxides (Bi2O30.7(Ln2O30.3 of various rare earth cations (Ln = Eu, Gd, Tm, Yb and Lu. All the synthesized pigment samples were found to have color coordinates, low a* and high b* and exhibit the color from pale light yellow to orange. Reflectance spectra of the samples show high reflectance percentage in the 600 - 700 nm range. Characterization of the (Bi2O30.7(Ln2O30,3 solid solutions suggests that they have a potential to be alternative yellow colorants for paints, inks, plastics, and ceramics.

Significant improvement in performances of LiNi{sub 0.5}Mn{sub 1.5}O{sub 4} through surface modification with high ordered Al-doped ZnO electro-conductive layer

Energy Technology Data Exchange (ETDEWEB)

Sun, Hongdan; Xia, Bingbo [College of Physics, Optoelectronics and Energy & Collaborative Innovation Center of Suzhou Nano Science and Technology, Soochow University, Suzhou 215006 (China); Key Laboratory of Lithium Ion Battery Materials of Jiangsu Province, Institute of Chemical Power Sources, Soochow University, Suzhou 215006 (China); Liu, Weiwei [Changzhou Institute of Energy Storage Materials & Devices, Changzhou 213000 (China); Fang, Guoqing; Wu, Jingjing; Wang, Haibo; Zhang, Ruixue [College of Physics, Optoelectronics and Energy & Collaborative Innovation Center of Suzhou Nano Science and Technology, Soochow University, Suzhou 215006 (China); Key Laboratory of Lithium Ion Battery Materials of Jiangsu Province, Institute of Chemical Power Sources, Soochow University, Suzhou 215006 (China); Kaneko, Shingo [Key Laboratory of Lithium Ion Battery Materials of Jiangsu Province, Institute of Chemical Power Sources, Soochow University, Suzhou 215006 (China); Zheng, Junwei [College of Physics, Optoelectronics and Energy & Collaborative Innovation Center of Suzhou Nano Science and Technology, Soochow University, Suzhou 215006 (China); Key Laboratory of Lithium Ion Battery Materials of Jiangsu Province, Institute of Chemical Power Sources, Soochow University, Suzhou 215006 (China); Wang, Hongyu [Changzhou Institute of Energy Storage Materials & Devices, Changzhou 213000 (China); Li, Decheng, E-mail: lidecheng@suda.edu.cn [College of Physics, Optoelectronics and Energy & Collaborative Innovation Center of Suzhou Nano Science and Technology, Soochow University, Suzhou 215006 (China); Key Laboratory of Lithium Ion Battery Materials of Jiangsu Province, Institute of Chemical Power Sources, Soochow University, Suzhou 215006 (China)

2015-03-15

Graphical abstract: Al-doped ZnO (AZO)-coated LiNi{sub 0.5}Mn{sub 1.5}O{sub 4} (LNMO) was prepared by sol–gel method. AZO-coated LNMO electrode shows excellent rate capability and a remarkable improvement in the cyclic performance at a high rate at elevated temperature. - Highlights: • Al-doped ZnO (AZO)-coated LiNi{sub 0.5}Mn{sub 1.5}O{sub 4} (LNMO) was prepared by a traditional sol–gel method. • Al-doped ZnO (AZO) layer grown on the surface of LNMO is high ordered. • At a high rate of 10 C, the discharge capacity of the AZO-coated LNMO electrode can reach 114 mAh g{sup −1}. • Al-doped ZnO (AZO) modification improved cyclic performance of LNMO at high temperatures. - Abstract: Al-doped ZnO (AZO)-coated LiNi{sub 0.5}Mn{sub 1.5}O{sub 4} (LNMO) was prepared by sol–gel method. Transmission electron microscopy (TEM) analysis indicates that AZO layer grown on the surface of LNMO is high ordered. The results of electrochemical performance measurements reveal that the AZO-coated LNMO electrode displays the best rate capability compared with the bare LNMO and ZnO-coated LNMO, even at a high rate of 10 C. The discharge capacity of the AZO-coated LNMO electrode can still reach 114.3 mAh g{sup −1}, about 89% of its discharge capacity at 0.1 C. Moreover, AZO-coated LNMO electrode shows a remarkable improvement in the cyclic performance at a high rate at elevated temperature due to the protective effect of AZO coating layer. The electrode delivers a capacity of 120.3 mAh g{sup −1} with the capacity retention of 95% at 5 C in 50 cycles at 50 °C. The analysis of electrochemical impedance spectra (EIS) indicates that AZO-coated LNMO possesses the lowest charge transfer resistance compared to the bare LNMO and ZnO-coated LNMO, which may be responsible for improved rate capability.

Phase equilibria in the MgMoO4-Ln2(MoO4)3 (Ln=La,Gd) systems

International Nuclear Information System (INIS)

Fedorov, N.F.; Ipatov, V.V.; Kvyatkovskij, O.V.

1980-01-01

Phase equilibria in the MgMoO 4 -Ln 2 (MoO 4 ) 3 systems (Ln=La, Gd) have been studied by static and dynamic methods of the physico-chemical analysis, using differential thermal, visual-polythermal, crystal-optical, X-ray phase, and infrared spectroscopic methods, and their phase diagrams have been constructed. Phase equilibria in the systems studied are characterized by limited solubility of components in the liquid state, formation of solid solutions on the base of α- and β-forms of Gd 2 (MoO 4 ) 3 . Eutectics in the MgMoO 4 -Ln 2 (MoO 4 ) 3 (Ln=La, Gd) systems corresponds to the composition of 71 mode % La 2 (MoO 4 ) 3 -29 mole % MgMoO 4 , tsub(melt)--935+-5 deg C and 57 mole % Gd 2 (MoO 4 ) 3 -43 mole % MgMoO 4 , tsub(melt)=1020+-5 deg C. The region of glass formation has been established [ru

Studies on the Ln/sub 2/O/sub 3/ (Ln: rare-earth elements)-SrO-V/sub 2/O/sub 3/ system, 1. Phase diagrams at 1400/sup 0/C

Energy Technology Data Exchange (ETDEWEB)

Shin-ike, T [Osaka Dental Coll., Hirakata (Japan); Adachi, G; Shiokawa, J

1980-11-01

Rare-earth oxides Ln/sub 2/O/sub 3/ (Ln : Nd, Eu or Er), strontium oxide SrO and vanadium oxide V/sub 2/O/sub 3/ were mixed in a given molecular ratio, heated at 1400/sup 0/C in vacuum. The products were examined by an x-ray diffraction method to study the phase relations of the ternary systems. On heating, part of the trivalent vanadium was oxidized to the tetravalent state by atmospheric oxygen. In this experimental condition, the following ternary-phase solid solutions were identified: perovskite type Nd sub(1-x)Sr sub(x)VO sub(3-0.1x) (x > 0.3. cubic, x < 0.3: orthorhombic) and Eu sub(1-x)Sr sub(x)VO sub(3-0.1x) (x > 0.4: cubic, x < 0.4: orthorhombic), K/sub 2/NiF/sub 4/ type SrO.Nd sub(1-x)Sr sub(x)VO sub(3-0.1x) (x > 0.3) and SrO.Eu sub(1-x)Sr sub(x)VO sub(3-0.1x) (x > 0.4) and Eu/sub 3/Ti/sub 2/O/sub 7/ type SrO.2Nd sub(1-x)Sr sub(x)VO sub(3-0.1x) (x > 0.3) and SrO.2Eu sub(1-x)Sr sub(x)VO sub(3-0.1x) (x > 0.4). For the Er/sub 2/O/sub 3/-SrO-V/sub 2/O/sub 3/ system, only a mixture of Er/sub 2/O/sub 3/, SrVO sub(2.9), ErVO/sub 3/, SrO and V/sub 2/O/sub 3/ was obtained.

Bi2(Sr, Ln)2CuOz (Ln = Nd, Sm) phases: stability, crystal growth and superconducting properties

International Nuclear Information System (INIS)

Faqir, H.; Kikuchi, M.; Syono, Y.; Mansori, M.; Satre, P.; Sebaoun, A.; Vacquier, G.

2000-01-01

Bi 2 (Sr,Ln) 2 CuO z (Ln = Nd, Sm) single crystals were successfully grown by a self-flux method from stoichiometric and (Bi, Cu)-rich melts. Thermal analysis and thermogravimetry were used to determine stability and the melting sequence of Bi 2 (Sr,Ln) 2 CuO z phases in air. As-grown crystals of the ideal Bi 2 (Sr,Ln) 2 CuO z phase, of dimensions 1x0.5x0.03 mm 3 , exhibit superconducting behaviour with critical temperature T c = 21 K for the Bi 1.9 Sr 1.6 Nd 0.6 CuO z crystal and Tc = 14 K for the Bi 1.8 Sr 1.6 Sm 0.6 CuO z crystal. The compositions of these crystals were homogeneous and close to the stoichiometric composition. We report on the growth of Bi 2 Sr 2-x Sm x CuO z single crystals of large dimensions 9x3x0.03 mm 3 using Bi 2 Sr 1.5 Sm 0.5 CuO z as precursor and Bi 2 CuO 4 as flux. (author)

Syntheses, crystal structures and solid-state properties of the lanthanoid-containing nanoclusters [(Ln{sub 2}PW{sub 10}O{sub 38}){sub 4}(W{sub 3}O{sub 8})(OH){sub 4}(H{sub 2}O){sub 2}]{sup 26-}

Energy Technology Data Exchange (ETDEWEB)

Gupta, Rakesh; Saini, Mukesh Kumar; Hussain, Firasat [Department of Chemistry, University of Delhi (India)

2014-12-15

A series of lanthanoid-substituted polyoxometalates have been synthesized by a self-assembly process in potassium chloride solution by the reaction of dilacunary [P{sub 2}W{sub 19}O{sub 69}(H{sub 2}O)]{sup 14-} with mid- and late-lanthanoid Ln(NO{sub 3}){sub 3}.nH{sub 2}O salts leading to the formation of the tetrameric tungstophosphates [(Ln{sub 2}PW{sub 10}O{sub 38}){sub 4}(W{sub 3}O{sub 8})(OH){sub 4}(H{sub 2}O){sub 2}]{sup 26-} [Ln = Y{sup 3+} (1), Sm{sup 3+} (2), Eu{sup 3+} (3), Gd{sup 3+} (4), Tb{sup 3+} (5), Dy{sup 3+} (6), Ho{sup 3+} (7), Er{sup 3+} (8), Tm{sup 3+} (9), Yb{sup 3+} (10)]. The polyanions were isolated as potassium or mixed-alkali salts. Most of the compounds were characterized by single-crystal X-ray diffraction and various analytical techniques, such as FTIR, UV/Vis, {sup 31}P NMR and photoluminescence spectroscopy, magnetism, as well as thermogravimetric analysis. The FTIR spectra suggest that all the compounds are isomorphous. The crystal structures of these complexes consist of four A-[α-PW{sub 10}O{sub 36}]{sup 7-} units, each incorporating two Ln{sup III} ions to create four Keggin-like anions that further assemble with three additional tungstate units to form a tetramer species with C{sub 2} symmetry. The photoluminescent properties of 3a and 6a were investigated following photoexcitation at room temperature. The magnetic properties of 3a, 4a, 5a and 6a were investigated at room temperature, the complexes exhibiting paramagnetic behaviour. (Copyright copyright 2014 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim)

Phase relations in Ca(Sr)MoO4-Ln2(NoO4)3 systems (Ln = Pr-Lu)

International Nuclear Information System (INIS)

Vakalyuk, V.V.; Evdokimov, A.A.; Berezina, T.A.

1982-01-01

Using the methods of X-ray phase and differential thermal analyses phase ratios in the systems Ca(Sr)MoO 4 -Ln 2 (MoO 4 ) 3 at Ln=Pr-Lu are studied and phase diagrams of the systems CaMoO 4 -Ln 2 (MoO 4 ) 3 , for Ln=Nd, Gd, Yb and SrMoO 4 -Sm 2 (MoO 4 ) 3 are built. It is shown that phase ratios in the systems are similar for the following groups of rare earths: Pr-Sm, Eu-Tb, Ho-Lu. In the first group of systems ordered phase over all subsolidus region are formed, in the second one - ordered phases with scheelite-like structure and wide regions of homogeneity on the basis of Ca(Sr)MoO 4 are formed above the temperature of polymorphous transformation of rare earth molybdates, for the third group of systems intermediate compounds are not detected

Crystallographic and infrared spectroscopic study of bond distances in Ln[Fe(CN)6].4H2O (Ln=lanthanide)

International Nuclear Information System (INIS)

Zhou Xianju; Wong, W.-T.; Faucher, Michele D.; Tanner, Peter A.

2008-01-01

Along with crystallographic data of Ln[Fe(CN) 6 ].4H 2 O (Ln=lanthanide), the infrared spectra are reassigned to examine bond length trends across the series of Ln. The changes in mean Ln-O, Ln-N, C≡N and Fe-C distances are discussed and the bond natures of Ln-N and Ln-O are studied by bond length linear or quadratic fitting and comparisons with relevant ionic radii. The two different C≡N bond distances have been simulated by the covalo-electrostatic model. - Graphical abstract: Crystallographic and FTIR data for Ln[Fe(CN) 6 ].4H 2 O enable the changes in Ln-O, Ln-N, C≡N and Fe-C distances to be determined and modeled across the lanthanide series

Oxidation Behavior of Surface-modified Stainless Steel 316LN in Supercritical-CO{sub 2} Environment

Energy Technology Data Exchange (ETDEWEB)

Kim, Sung Hwan; Heo, Jin Woo; Kim, Hyunm Yung; Jang, Chang Heui [KAIST, Daejeon (Korea, Republic of)

2016-05-15

Compared to other working fluids such as helium or nitrogen, S-CO{sub 2} offers a higher efficiency at operating temperatures of advanced reactors above 550 .deg. C. Moreover, the S-CO{sub 2} cycle is expected to have a significantly smaller footprint compared to other power conversion cycles, resulting in a broader range of applications with lower capital costs. Currently, stainless steel 316 is considered as the candidate structural material for the SFR. In comparison, it is well known that alumina (Al{sub 2}O{sub 3}) have superior oxidation and carburization resistance specifically at higher temperatures where α-Al{sub 2}O{sub 3} may form. Thus, various surface modification techniques have been applied to mostly Ni-base alloys so that a protective and continuous Al-rich oxide layer forms on the surface, conferring superior oxidation and carburization resistance. In this study, SS 316LN was deposited with Al via physical vapor deposition (PVD) method followed by heat treatment processes to develop an Al-rich layer at the surface. The specimens are to be exposed to high temperature S-CO{sub 2} environment to evaluate the oxidation and carburization resistance. Stainless steel 316LN was surface-modified to develop an Al-rich layer for improvement of oxidation behavior in S-CO{sub 2} environment. As the test temperature of 600 .deg. C is not sufficiently high for the formation of protective α-Al{sub 2}O{sub 3} formation, pre-oxidation of surface modified SS 316LN was conducted.

Lanthanide stannate pyrochlores (Ln2Sn2O7; Ln = Nd, Gd, Er) at high pressure.

Science.gov (United States)

Turner, Katlyn M; Tracy, Cameron L; Mao, Wendy L; Ewing, Rodney C

2017-11-09

Lanthanide stannate pyrochlores (Ln2Sn2O7; Ln=Nd, Gd, and Er) were investigated in situ to 50 GPa in order to determine their structural response to compression and compare it to that of lanthanide titanate, zirconate, and hafnate pyrochlores. The cation radius ratio of A3+/B4+ in pyrochlore oxides (A2B2O7) is thought to be the dominant property that influences their compression response. The ionic radius of Sn4+ is intermediate to that of Ti4+, Zr4+, and Hf4+, but the O> bond in stannate pyrochlore is more covalent than the O> bonds in titanates, zirconate, and hafnates. In stannates, the pyrochlore cation and anion sublattices begin to disorder at 0.3 GPa. The extent of sublattice disorder vs. pressure is greater in stannates with a smaller Ln3+ cation. Stannate pyrochlores (Fd-3m) begin a sluggish transformation to a cotunnite-like structure (Pnma) at ~28 GPa; similar transitions have been observed in titanate, zirconate, and hafnate pyrochlore at varying pressures with cation radius ratio. The extent of the phase transition vs. pressure varies directly with the size of the Ln3+ cation. Post-decompression from ~50 GPa, Er2Sn2O7 and Gd2Sn2O7 adopt a pyrochlore structure, rather than the multiscale defect-fluorite + weberite structure adopted by Nd2Sn2O7 that is characteristic of titanate, zirconate, and hafnate pyrochlore treated to similar conditions. Like pyrochlore titanates, zirconates, and hafnates, the bulk modulus, B0, of stannates varies linearly and inversely with cation radius ratio. The trends of bulk moduli in stannates in this study are in excellent agreement with previous experimental studies on stannates, and suggest that the size of the Ln3+ cation is a primary determining factor of B0. Additionally, when normalized to rA/rB, the bulk moduli of stannates are comparable to those of zirconates and hafnates, which vary from titanates. Our results suggest that the cation radius ratio strongly influences the bulk moduli of stannates as well as

Phase relations and crystal structures in the systems (Bi,Ln)2WO6 and (Bi,Ln)2MoO6 (Ln=lanthanide)

International Nuclear Information System (INIS)

Berdonosov, Peter S.; Charkin, Dmitri O.; Knight, Kevin S.; Johnston, Karen E.; Goff, Richard J.; Dolgikh, Valeriy A.; Lightfoot, Philip

2006-01-01

Several outstanding aspects of phase behaviour in the systems (Bi,Ln) 2 WO 6 and (Bi,Ln) 2 MoO 6 (Ln=lanthanide) have been clarified. Detailed crystal structures, from Rietveld refinement of powder neutron diffraction data, are provided for Bi 1.8 La 0.2 WO 6 (L-Bi 2 WO 6 type) and BiLaWO 6 , BiNdWO 6 , Bi 0.7 Yb 1.3 WO 6 and Bi 0.7 Yb 1.3 WO 6 (all H-Bi 2 WO 6 type). Phase evolution within the solid solution Bi 2- x La x MoO 6 has been re-examined, and a crossover from γ(H)-Bi 2 MoO 6 type to γ-R 2 MoO 6 type is observed at x∼1.2. A preliminary X-ray Rietveld refinement of the line phase BiNdMoO 6 has confirmed the α-R 2 MoO 6 type structure, with a possible partial ordering of Bi/Nd over the three crystallographically distinct R sites. - Graphical abstract: A summary of phase relations in the lanthanide-doped bismuth tungstate and bismuth molybdate systems is presented, together with some additional structural data on several of these phases

High-pressure investigations of lanthanoid oxoarsenates. I. Single crystals of scheelite-type Ln[AsO{sub 4}] phases with Ln = La-Nd from monazite-type precursors

Energy Technology Data Exchange (ETDEWEB)

Metzger, Sebastian J.; Ledderboge, Florian; Schleid, Thomas [Stuttgart Univ. (Germany). Inst. fuer Anorganische Chemie; Heymann, Gunter; Huppertz, Hubert [Innsbruck Univ. (Austria). Inst. fuer Allgemeine, Anorganische und Theoretische Chemie

2016-08-01

Transparent single crystals of the scheelite-type Ln[AsO{sub 4}] phases with Ln = La-Nd are obtained by the pressure-induced monazite-to-scheelite type phase transition in a Walker-type module under high-pressure and high-temperature conditions of 11 GPa at 1100-1300 C. Coinciding with this transition, there is an increase in density and a reduction in molar volume of about 4.5 % for the scheelite-type phases (tetragonal, I4{sub 1}/a) for La[AsO{sub 4}] (a = 516.92(4), c = 1186.1(9) pm), Ce[AsO{sub 4}] (a = 514.60(1), c = 1175.44(2) pm), Pr[AsO{sub 4}] (a = 512.63(4), c = 1168.25(9) pm), and Nd[AsO{sub 4}] (a = 510.46(4), c = 1160.32(11) pm) as compared to the well-known monazite-type phases (monoclinic, P2{sub 1}/n). Surprisingly enough, the scheelite-type oxoarsenates(V) exhibit a lower coordination number for the Ln{sup 3+} cations (CN = 8 versus CN = 8 + 1), whereas the isolated tetrahedral [AsO{sub 4}]{sup 3-} anions (d(As-O) = 168.9-169.3 pm for the scheelites as compared to d(As-O) = 167.1-169.9 pm for the monazites) remain almost unchanged. So the densification must occur because of the loss of two edge-connections of the involved [LnO{sub 8+1}]{sup 15-} polyhedra with the [AsO{sub 4}]{sup 3-} tetrahedra in the monazite- resulting in exclusively vertex connected [LnO{sub 8}]{sup 13-} and [AsO{sub 4}]{sup 3-} units in the scheelite-type structure.

Red emitting phosphors of Eu{sup 3+} doped Na{sub 2}Ln{sub 2}Ti{sub 3}O{sub 10} (Ln = Gd, Y) for white light emitting diodes

Energy Technology Data Exchange (ETDEWEB)

Zhang, Niumiao [National Key Laboratory of Photoelectric Technology and Functional Materials Culture Base in Shaanxi Province, National Photoelectric Technology and Functional Materials & Application of Science and Technology International Cooperation Base, Institute of Photonics & Photon-Technology, Northwest University, Xi’an 710069 (China); Guo, Chongfeng, E-mail: guocf@nwu.edu.cn [National Key Laboratory of Photoelectric Technology and Functional Materials Culture Base in Shaanxi Province, National Photoelectric Technology and Functional Materials & Application of Science and Technology International Cooperation Base, Institute of Photonics & Photon-Technology, Northwest University, Xi’an 710069 (China); Yin, Luqiao; Zhang, Jianhua [Key Laboratory of Advanced Display and System Applications (Shanghai University), Ministry of Education, Shanghai 200072 (China); Wu, Mingmei, E-mail: ceswmm@mail.sysu.edu.cn [School of Chemistry and Chemical Engineering, Sun Yat-Sen University, No. 135, Xingang Xi Road, Guangzhou 510275 (China)

2015-06-25

Highlights: • Layered red phosphors Na{sub 2}Ln{sub 2}Ti{sub 3}O{sub 10} (Ln = Gd, Y):Eu{sup 3+} were prepared. • The synthesis parameters of phosphors were optimized. • PL and thermal stability of the samples were investigated. • LED devices were also fabricated including the present red phosphor. - Abstract: A series of Eu{sup 3+} doped Na{sub 2}Ln{sub 2}Ti{sub 3}O{sub 10} (Ln = Gd, Y) red-emitting phosphors for application in ultraviolet based light emitting diodes (LEDs) were successfully synthesized by a modified sol–gel method. Their structure and luminescent properties were characterized by powder X-ray diffraction (XRD), photoluminescence excitation (PLE) and emission (PL) spectra and absorption spectra, according to these results the optimal compositions and synthesis parameters were determined. In addition, the thermal stabilities of the phosphors were investigated according to the temperature-dependent PL spectra. The red and white-LEDs (W-LEDs) comprising the Na{sub 2}Ln{sub 2}Ti{sub 3}O{sub 10}:Eu{sup 3+} (Ln = Gd, Y) red emitting phosphors were fabricated with a near-ultraviolet (n-UV) chip. In comparison with Na{sub 2}Y{sub 1.4}Eu{sub 0.6}Ti{sub 3}O{sub 10}, the Na{sub 2}Gd{sub 0.6}Eu{sub 1.4}Ti{sub 3}O{sub 10} phosphor offers higher brightness, quantum efficiency, and excellent thermal stability. W-LEDs comprising Na{sub 2}Gd{sub 0.6}Eu{sub 1.4}Ti{sub 3}O{sub 10} showed bright white emission with a color rendering index (Ra) of 82, a color temperature of 2151 K, and Commission Internationale de I’Eclairage (CIE) color coordinates of (0.34, 0.37). The phosphor Na{sub 2}Gd{sub 0.6}Eu{sub 1.4}Ti{sub 3}O{sub 10} is more suitable candidate for application in LEDs.

Behaviour of LaAlO 3 +LnTiTaO 6 (Ln= Ce, Pr or Nd)

Indian Academy of Sciences (India)

The 0.1LaAlO3+0.9LnTiTaO6 (Ln= Ce, Pr or Nd) ceramics are prepared through solid state ceramic route. The structure of the materials is studied using X-ray diffraction analysis. The microstructure is analysed using scanning electron microscopy. The dielectric properties in the radio as well as in the microwave frequencies ...

Estimation of tau1 for the host Kramers' Ln3+ ions (Ln = Nd, Sm and Yb) from the EPR linewidths of Gd3+ impurity ions in Ln2(SO4)3.8H2O

International Nuclear Information System (INIS)

Malhotra, V.M.; Buckmaster, H.A.

1981-01-01

It is shown that the EPR linewidth data published by Misra and Mikolajczak for Gd 3+ impurity ions in Ln 2 (SO 4 ) 3 .8H 2 O (Ln = Nd, Sm and Yb) single crystals at 77 and 300 K can be used to estimate the effective spin-lattice relaxation time of Kramers' host ions. The various relaxation mechanisms which are operative in the lanthanides are reviewed and discussed. The estimated relaxation times are shown to be a sensitive function of the host ion energy level splittings and the temperature. The estimated effective spin-lattice relaxation times in these hosts are in reasonable agreement with those expected from a resonance Orbach process

Enhanced visible light-responsive photocatalytic activity of LnFeO3 (Ln = La, Sm) nanoparticles by synergistic catalysis

International Nuclear Information System (INIS)

Li, Li; Wang, Xiong; Zhang, Yange

2014-01-01

Highlights: • LnFeO 3 (Ln = La, Sm) nanoparticles were prepared by a facile sol–gel method. • The samples exhibit superior visible-light-responsive photocatalytic activity. • Synergistic effect will enhance the photodegradation of RhB under visible light. - Abstract: LnFeO 3 (Ln = La, Sm) nanoparticles were prepared by a facile sol–gel method with assistance of glycol at different calcination temperatures. The as-synthesized LnFeO 3 was characterized by X-ray diffraction, transmission electron microscopy, differential scanning calorimeter and thermogravimetric analysis, and UV–vis absorption spectroscopy. The photocatalytic behaviors of LnFeO 3 nanoparticles were evaluated by photodegradation of rhodamine B under visible light irradiation. The results indicate that the visible light-responsive photocatalytic activity of LnFeO 3 nanoparticles was enhanced remarkably by the synergistic effect between the semiconductor photocatalysis and Fenton-like reaction. And a possible catalytic mechanism was also proposed based on the experimental results

Rhombus-shaped tetranuclear [Ln4] complexes [Ln = Dy(III) and Ho(III)]: synthesis, structure, and SMM behavior.

Science.gov (United States)

Chandrasekhar, Vadapalli; Hossain, Sakiat; Das, Sourav; Biswas, Sourav; Sutter, Jean-Pascal

2013-06-03

The reaction of a new hexadentate Schiff base hydrazide ligand (LH3) with rare earth(III) chloride salts in the presence of triethylamine as the base afforded two planar tetranuclear neutral complexes: [{(LH)2Dy4}(μ2-O)4](H2O)8·2CH3OH·8H2O (1) and [{(LH)2Ho4}(μ2-O)4](H2O)8·6CH3OH·4H2O (2). These neutral complexes possess a structure in which all of the lanthanide ions and the donor atoms of the ligand remain in a perfect plane. Each doubly deprotonated ligand holds two Ln(III) ions in its two distinct chelating coordination pockets to form [LH(Ln)2](4+) units. Two such units are connected by four [μ2-O](2-) ligands to form a planar tetranuclear assembly with an Ln(III)4 core that possesses a rhombus-shaped structure. Detailed static and dynamic magnetic analysis of 1 and 2 revealed single-molecule magnet (SMM) behavior for complex 1. A peculiar feature of the χM" versus temperature curve is that two peaks that are frequency-dependent are revealed, indicating the occurrence of two relaxation processes that lead to two energy barriers (16.8 and 54.2 K) and time constants (τ0 = 1.4 × 10(-6) s, τ0 = 7.2 × 10(-7) s). This was related to the presence of two distinct geometrical sites for Dy(III) in complex 1.

Facile in-situ reduction: Crystal growth and magnetic studies of reduced vanadium (III/IV) silicates CaxLn1-xVSiO5 (Ln = Ce-Nd, Sm-Lu, Y)

Science.gov (United States)

Abeysinghe, Dileka; Smith, Mark D.; Morrison, Gregory; Yeon, Jeongho; zur Loye, Hans-Conrad

2018-04-01

A series of lanthanide containing mixed-valent vanadium (III/IV) silicates of the type CaxLn1-xVSiO5 (Ln = Ce-Nd, Sm-Lu, Y) was synthesized as high quality single crystals from a molten chloride eutectic flux, BaCl2/NaCl. Utilizing Ca metal as the reducing agent, an in-situ reduction of V5+ to V3+/4+ as well as of Ce4+ to Ce3+ was achieved. The structures of 14 reported isostructural compounds were determined by single crystal X-ray diffraction. They crystallize in the tilasite (CaMgAsO4F) structure type in the monoclinic space group C2/c. The extended structure contains 1D chains of VO6 octahedra that are connected to each other via SiO4 groups and (Ca/Ln)O7 polyhedra. The magnetic susceptibility and the field dependent magnetization data were measured for CaxLn1-xVSiO5 (Ln = Ce-Nd, Sm, Gd-Lu, Y), and support the existence of antiferromagnetic behavior at low temperatures.

A new continuous two-step molecular precursor route to rare-earth oxysulfides Ln2O2S

International Nuclear Information System (INIS)

De Crom, N.; Devillers, M.

2012-01-01

A continuous two-step molecular precursor pathway is designed for the preparation of rare-earth oxysulfides Ln 2 O 2 S (Ln=Y, La, Pr, Nd, Sm–Lu). This new route involves a first oxidation step leading to the rare-earth oxysulfate Ln 2 O 2 SO 4 which is subsequently reduced to the rare-earth oxysulfide Ln 2 O 2 S by switching to a H 2 –Ar atmosphere. The whole process occurs at a temperature significantly lower than usual solid state synthesis (T≤650 °C) and avoids the use of dangerous sulfur-based gases, providing a convenient route to the synthesis of the entire series of Ln 2 O 2 S. The molecular precursors consist in heteroleptic dithiocarbamate complexes [Ln(Et 2 dtc) 3 (phen)] and [Ln(Et 2 dtc) 3 (bipy)] (Et 2 dtc=N,N-diethyldithiocarbamate; phen=1,10-phenanthroline; bipy=2,2′-bipyridine) and were synthesized by a new high yield and high purity synthesis route. The nature of the molecular precursor determines the minimum synthesis temperature and influences therefore the purity of the final Ln 2 O 2 S crystalline phase. - Graphical abstract: A continuous two-step molecular precursor pathway was designed for the preparation of rare-earth oxysulfides Ln 2 O 2 S (Ln=Y, La, Pr, Nd, Sm–Lu), starting from heteroleptic dithiocarbamate complexes. The influence of the nature of the molecular precursor on the minimum synthesis temperature and on the purity of the final Ln 2 O 2 S crystalline phase is discussed. Highlights: ► A new high yield and high purity synthesis route of rare earth dithiocarbamates is described. ► These compounds are used as precursors in a continuous process leading to rare-earth oxysulfides. ► The oxysulfides are obtained under much more moderate conditions than previously described.

Solution-combustion synthesis of Bi1–xLnxO1⋅ 5 (Ln= Y and La–Yb ...

Indian Academy of Sciences (India)

combustion synthesis of Bi1–LnO1.5 (Ln = Y and La–Yb) oxide ion conductors. Manjunath B Bellakki A S Prakash C Shivakumara M S Hegde A K Shukla. Ceramics and Glasses Volume 29 Issue 4 August 2006 pp 339-345 ...

Observation of Vacancies, Faults, and Superstructures in Ln5Mo2O12 (Ln = La, Y, and Lu) Compounds with Direct Mo-Mo Bonding.

Science.gov (United States)

Colabello, Diane M; Sobalvarro, Elizabeth M; Sheckelton, John P; Neuefeind, Joerg C; McQueen, Tyrel M; Khalifah, Peter G

2017-11-06

Among oxide compounds with direct metal-metal bonding, the Y 5 Mo 2 O 12 (A 5 B 2 O 12 ) structural family of compounds has a particularly intriguing low-dimensional structure due to the presence of bioctahedral B 2 O 10 dimers arranged in one-dimensional edge-sharing chains along the direction of the metal-metal bonds. Furthermore, these compounds can have a local magnetic moment due to the noninteger oxidation state (+4.5) of the transition metal, in contrast to the conspicuous lack of a local moment that is commonly observed when oxide compounds with direct metal-metal bonding have integer oxidation states resulting from the lifting of orbital degeneracy typically induced by the metal-metal bonding. Although a monoclinic C2/m structure has been previously proposed for Ln 5 Mo 2 O 12 (Ln = La-Lu and Y) members of this family based on prior single crystal diffraction data, it is found that this structural model misses many important structural features. On the basis of synchrotron powder diffraction data, it is shown that the C2/m monoclinic unit cell represents a superstructure relative to a previously unrecognized orthorhombic Immm subcell and that the superstructure derives from the ordering of interchangeable Mo 2 O 10 and LaO 6 building blocks. The superstructure for this reason is typically highly faulted, as evidenced by the increased breadth of superstructure diffraction peaks associated with a coherence length of 1-2 nm in the c* direction. Finally, it is shown that oxygen vacancies can occur when Ln = La, producing an oxygen deficient stoichiometry of La 5 Mo 2 O 11.55 and an approximately 10-fold reduction in the number of unpaired electrons due to the reduction of the average Mo valence from +4.5 to +4.05, a result confirmed by magnetic susceptibility measurements. This represents the first observation of oxygen vacancies in this family of compounds and provides an important means of continuously tuning the magnetic interactions within the one

Polymorphism of Bi1-xLnxO1.5 phases (04Ln2O9 (x=0.33; Ln=La, Pr, Nd)

International Nuclear Information System (INIS)

Drache, Michel; Huve, Marielle; Roussel, Pascal; Conflant, Pierre

2003-01-01

The Bi 1-x Ln x O 1.5 solid solutions (Ln=La, Pr, Nd), of the β 2 /β 1 /ε (Bi-Sr-O) structural type, have been investigated in their Ln-rich domains. For Ln=La, Pr, and Nd, the upper limits are 0.35, 0.35 and 0.33, respectively. The Bi 4 Ln 2 O 9 ε phase (x=0.33) appears to be the single definite compound. For Bi 4 La 2 O 9 , Bi 4 Pr 2 O 9 and Bi 4 Nd 2 O 9 , the ε-type cells are respectively: a=9.484(4) A, b=3.982(2) A, c=7.030(3) A, β=104.75(3) deg.; a=9.470(5) A, b=3.945(2) A, c=6.968(4) A, β=104.73(3) deg. and a=9.439(3) A, b=3.944(2) A, c=6.923(2) A, β=105.03(3) deg. . Upon heating, each monoclinic (ε) compound transforms successively into rhombohedral phases (β 2 /β 1 ) and finally into a cubic fluorite-type phase. For La- and Pr-based compounds, all transitions are reversible; for Nd, depending on the thermal treatment, the reversibility of ε→β 2 can be incomplete. These transformations are characterized using X-ray thermodiffractometry, differential thermal analysis, dilatometry and impedance spectroscopy versus temperature. Examination of Bi 4 (Ln, Ln') 2 O 9 samples allows to correlate the evolution of the thermal behavior and of the unit cell parameters, to the lanthanide size. A partial plot of the (Bi 2 O 3 ) 1-x -(La 2 O 3 ) x phase diagram (0≤x≤0.40) is proposed

Investigation of phase relationships in subsolidus region of Ln2O3-MoO3-B2O3 systems

International Nuclear Information System (INIS)

Lysanova, C.V.; Dzhurinskij, B.F.; Komova, M.G.; Tananaev, I.V.

1983-01-01

Phase formation in subsolidus region of Ln 2 O 3 -MoO 3 B 2 O 3 systems (Ln-La, Nd) is studied. Three compounds with mixed oxyanions-boratomolybdates of LnMoBO 6 composition (Ln-La, Ce, Pr, Nd), Ln 2 MoB 2 O 9 (Ln-La, Ce, Pr, Nd, Sm, EU, Gde Tb) Ln 6 Mo 3 B 4 0 24 (Ln-Pr, Nd) are revealed and described

Complexation of amidocarbamoyl phosphine oxides with Ln+3 (Ln = La, Nd, Pm, Sm and Eu) cation series: structural and thermodynamical features

International Nuclear Information System (INIS)

Hosseinnejad, Tayebeh; Kazemi, Tayebeh

2016-01-01

In the present study, we have mainly investigated the nature of interactions in Ln 3+ (Ln = La, Nd, Pm, Sm, Eu) complexes with amidocarbamoyl methyl phosphine oxide (CMPO) and amidocarbamoyl propyl phosphine oxide (CPPO) ligands based on density functional theory (DFT) approaches. In the first step, thermodynamical properties for complexation of CMPO and CPPO ligands with Ln 3+ cation series have been determined in the gas phase and with the presence of three solvents: n-hexane, chloroform and toluene, via polarized continuum model (PCM) computations. The trend of metal-ligand interaction strength has been analyzed and compared with the trend of ionic hardness within the series of lanthanide cations and different size of alkyl chain of amidocarbamoyl phosphine oxide ligand. The calculated thermochemical results in the gas and solution phases reveals that there is a consistency between increasing trend in the hardness of Ln 3+ cation series and also electron-donating property of alkyl chain with increasing in thermodynamical stability of [Ln-CMPO] 3+ and [Ln-CPPO] 3+ complex series. We have also demonstrated that in the complexation reaction of all complex series, using n-hexane as solvent is more favorable thermodynamically than chloroform and toluene. It should be stated that this issue has been observed in many experiments. Finally, analysis of calculated deformation energies and also the variation in bond order of some selected key bonds in CMPO and CPPO ligands and their corresponded Ln 3+ complexes series show a similar trend with increasing in the hardness of Ln 3+ cation series and electron-donating of alkyl chain of amidocarbamoyl phosphine oxide ligand.

General synthesis and structural evolution of a layered family of Ln8(OH)20Cl4 x nH2O (Ln = Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, and Y).

Science.gov (United States)

Geng, Fengxia; Matsushita, Yoshitaka; Ma, Renzhi; Xin, Hao; Tanaka, Masahiko; Izumi, Fujio; Iyi, Nobuo; Sasaki, Takayoshi

2008-12-03

The synthesis process and crystal structure evolution for a family of stoichiometric layered rare-earth hydroxides with general formula Ln(8)(OH)(20)Cl(4) x nH(2)O (Ln = Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, and Y; n approximately 6-7) are described. Synthesis was accomplished through homogeneous precipitation of LnCl(3) x xH(2)O with hexamethylenetetramine to yield a single-phase product for Sm-Er and Y. Some minor coexisting phases were observed for Nd(3+) and Tm(3+), indicating a size limit for this layered series. Light lanthanides (Nd, Sm, Eu) crystallized into rectangular platelets, whereas platelets of heavy lanthanides from Gd tended to be of quasi-hexagonal morphology. Rietveld profile analysis revealed that all phases were isostructural in an orthorhombic layered structure featuring a positively charged layer, [Ln(8)(OH)(20)(H(2)O)(n)](4+), and interlayer charge-balancing Cl(-) ions. In-plane lattice parameters a and b decreased nearly linearly with a decrease in the rare-earth cation size. The interlamellar distance, c, was almost constant (approximately 8.70 A) for rare-earth elements Nd(3+), Sm(3+), and Eu(3+), but it suddenly decreased to approximately 8.45 A for Tb(3+), Dy(3+), Ho(3+), and Er(3+), which can be ascribed to two different degrees of hydration. Nd(3+) typically adopted a phase with high hydration, whereas a low-hydration phase was preferred for Tb(3+), Dy(3+), Ho(3+), Er(3+), and Tm(3+). Sm(3+), Eu(3+), and Gd(3+) samples were sensitive to humidity conditions because high- and low-hydration phases were interconvertible at a critical humidity of 10%, 20%, and 50%, respectively, as supported by both X-ray diffraction and gravimetry as a function of the relative humidity. In the phase conversion process, interlayer expansion or contraction of approximately 0.2 A also occurred as a possible consequence of absorption/desorption of H(2)O molecules. The hydration difference was also evidenced by refinement results. The number of coordinated water

Hydrazinium lanthanide oxalates: synthesis, structure and thermal reactivity of N2H5[Ln2(C2O4)4(N2H5)]·4H2O, Ln = Ce, Nd.

Science.gov (United States)

De Almeida, Lucie; Grandjean, Stéphane; Rivenet, Murielle; Patisson, Fabrice; Abraham, Francis

2014-03-28

New hydrazinium lanthanide oxalates N2H5[Ln2(C2O4)4(N2H5)]·4H2O, Ln = Ce (Ce-HyOx) and Nd (Nd-HyOx), were synthesized by hydrothermal reaction at 150 °C between lanthanide nitrate, oxalic acid and hydrazine solutions. The structure of the Nd compound was determined from single-crystal X-ray diffraction data, space group P2₁/c with a = 16.315(4), b = 12.127(3), c = 11.430(2) Å, β = 116.638(4)°, V = 2021.4(7) Å(3), Z = 4, and R1 = 0.0313 for 4231 independent reflections. Two distinct neodymium polyhedra are formed, NdO9 and NdO8N, an oxygen of one monodentate oxalate in the former being replaced by a nitrogen atom of a coordinated hydrazinium ion in the latter. The infrared absorption band at 1005 cm(-1) confirms the coordination of N2H5(+) to the metal. These polyhedra are connected through μ2 and μ3 oxalate ions to form an anionic three-dimensional neodymium-oxalate arrangement. A non-coordinated charge-compensating hydrazinium ion occupies, with water molecules, the resulting tunnels. The N-N stretching frequencies of the infrared spectra demonstrate the existence of the two types of hydrazine ions. Thermal reactivity of these hydrazinium oxalates and of the mixed isotypic Ce/Nd (CeNd-HyOx) oxalate were studied by using thermogravimetric and differential thermal analyses coupled with gas analyzers, and high temperature X-ray diffraction. Under air, fine particles of CeO2 and Ce(0.5)Nd(0.5)O(1.75) are formed at low temperature from Ce-HyOx and CeNd-HyOx, respectively, thanks to a decomposition/oxidation process. Under argon flow, dioxymonocyanamides Ln2O2CN2 are formed.

3d-4f {Co(II)3Ln(OR)4} Cubanes as Bio-Inspired Water Oxidation Catalysts.

Science.gov (United States)

Evangelisti, Fabio; Moré, René; Hodel, Florian; Luber, Sandra; Patzke, Greta Ricarda

2015-09-02

Although the {CaMn4O5} oxygen evolving complex (OEC) of photosystem II is a major paradigm for water oxidation catalyst (WOC) development, the comprehensive translation of its key features into active molecular WOCs remains challenging. The [Co(II)3Ln(hmp)4(OAc)5H2O] ({Co(II)3Ln(OR)4}; Ln = Ho-Yb, hmp = 2-(hydroxymethyl)pyridine) cubane WOC series is introduced as a new springboard to address crucial design parameters, ranging from nuclearity and redox-inactive promoters to operational stability and ligand exchange properties. The {Co(II)3Ln(OR)4} cubanes promote bioinspired WOC design by newly combining Ln(3+) centers as redox-inactive Ca(2+) analogues with flexible aqua-/acetate ligands into active and stable WOCs (max. TON/TOF values of 211/9 s(-1)). Furthermore, they open up the important family of 3d-4f complexes for photocatalytic applications. The stability of the {Co(II)3Ln(OR)4} WOCs under photocatalytic conditions is demonstrated with a comprehensive analytical strategy including trace metal analyses and solution-based X-ray absorption spectroscopy (XAS) investigations. The productive influence of the Ln(3+) centers is linked to favorable ligand mobility, and the experimental trends are substantiated with Born-Oppenheimer molecular dynamics studies.

Hydrazinium lanthanide oxalates: synthesis, structure and thermal reactivity of N_2H_5[Ln_2(C_2O_4)_4(N_2H_5)].4H_2O, Ln = Ce, Nd

International Nuclear Information System (INIS)

De Almeida, Lucie; Grandjean, Stephane; Abraham, Francis; Rivenet, Murielle; Patisson, Fabrice

2014-01-01

New hydrazinium lanthanide oxalates N_2H_5[Ln_2(C_2O_4)_4(N_2H_5)].4H_2O, Ln = Ce (Ce-H_yO_x) and Nd (Nd- H_yO_x), were synthesized by hydrothermal reaction at 150 C between lanthanide nitrate, oxalic acid and hydrazine solutions. The structure of the Nd compound was determined from single-crystal X-ray diffraction data, space group P2_1/c with a = 16.315(4), b = 12.127(3), c = 11.430(2) Angstroms, β = 116.638(4) degrees, V = 2021.4(7) Angstroems"3, Z = 4, and R1 = 0.0313 for 4231 independent reflections. Two distinct neodymium polyhedra are formed, NdO_9 and NdO_8N, an oxygen of one monodentate oxalate in the former being replaced by a nitrogen atom of a coordinated hydrazinium ion in the latter. The infrared absorption band at 1005 cm"-"1 confirms the coordination of N_2H_5"+ to the metal. These polyhedra are connected through μ"2 and μ"3 oxalate ions to form an anionic three-dimensional neodymium-oxalate arrangement. A non-coordinated charge-compensating hydrazinium ion occupies, with water molecules, the resulting tunnels. The N-N stretching frequencies of the infrared spectra demonstrate the existence of the two types of hydrazine ions. Thermal reactivity of these hydrazinium oxalates and of the mixed isotypic Ce/Nd (CeNd-H_yO_x) oxalate were studied by using thermogravimetric and differential thermal analyses coupled with gas analyzers, and high temperature X-ray diffraction. Under air, fine particles of CeO_2 and Ce_0_._5Nd_0_._5O_1_._7_5 are formed at low temperature from Ce-H_yO_x and CeNd-H_yO_x, respectively, thanks to a decomposition/oxidation process. Under argon flow, dioxy-mono-cyanamides Ln_2O_2CN_2 are formed. (authors)

Insertion of water into rare earth oxocuprates (Ln)Ba 2Cu 3O 7-δ

Science.gov (United States)

Günther, Wulf; Schöllhorn, Robert

1996-02-01

The solid state reaction of LnBa 2Cu 3O 7-δ bulk material with water vapour corresponds to a quantitative topotactic reaction of the solid with H 2O to a maximum stoichiometry of LnBa 2Cu 3O 7-δ(H 2O) 1. The reaction proceeds in a temperature window which depends upon the oxygen content (δ) of the starting phase and is correlated with a structural transition via intermediate states. Although the integral copper oxidation state is not affected by the water intercalation, electronic and transport properties are strongly influenced. The insertion of water into these defect perovskites has to be described as a topotactic acid/base process.

Complexation of amidocarbamoyl phosphine oxides with Ln{sup +3} (Ln = La, Nd, Pm, Sm and Eu) cation series: structural and thermodynamical features

Energy Technology Data Exchange (ETDEWEB)

Hosseinnejad, Tayebeh; Kazemi, Tayebeh [Alzahra Univ., Tehran (Iran, Islamic Republic of). Dept. of Chemistry

2016-05-01

In the present study, we have mainly investigated the nature of interactions in Ln{sup 3+} (Ln = La, Nd, Pm, Sm, Eu) complexes with amidocarbamoyl methyl phosphine oxide (CMPO) and amidocarbamoyl propyl phosphine oxide (CPPO) ligands based on density functional theory (DFT) approaches. In the first step, thermodynamical properties for complexation of CMPO and CPPO ligands with Ln{sup 3+} cation series have been determined in the gas phase and with the presence of three solvents: n-hexane, chloroform and toluene, via polarized continuum model (PCM) computations. The trend of metal-ligand interaction strength has been analyzed and compared with the trend of ionic hardness within the series of lanthanide cations and different size of alkyl chain of amidocarbamoyl phosphine oxide ligand. The calculated thermochemical results in the gas and solution phases reveals that there is a consistency between increasing trend in the hardness of Ln{sup 3+} cation series and also electron-donating property of alkyl chain with increasing in thermodynamical stability of [Ln-CMPO]{sup 3+} and [Ln-CPPO]{sup 3+} complex series. We have also demonstrated that in the complexation reaction of all complex series, using n-hexane as solvent is more favorable thermodynamically than chloroform and toluene. It should be stated that this issue has been observed in many experiments. Finally, analysis of calculated deformation energies and also the variation in bond order of some selected key bonds in CMPO and CPPO ligands and their corresponded Ln{sup 3+} complexes series show a similar trend with increasing in the hardness of Ln{sup 3+} cation series and electron-donating of alkyl chain of amidocarbamoyl phosphine oxide ligand.

Effect of ligand substitution on the SMM properties of three isostructural families of double-cubane Mn4Ln2 coordination clusters.

Science.gov (United States)

Akhtar, Muhammad Nadeem; Lan, Yanhua; AlDamen, Murad A; Zheng, Yan-Zhen; Anson, Christopher E; Powell, Annie K

2018-03-06

Three isostructural lanthanide series with a core of MnMnLn 2 are reported. These three families have the formulae of [MnMnLn 2 (μ 4 -O) 2 (H 2 edte) 2 (piv) 6 (NO 3 ) 2 ] {no crystallization solvent, Ln = La, Ce, Pr, Nd, Eu (1-4, 6); solv = 3MeCN, Ln = Sm, Gd, Tb, Dy, Ho, Er, Tm, Yb, Y (5, 7-13)}, where H 2 edte = N,N,N',N'-tetrakis(2-hydroxyethyl)ethylenediamine and piv = pivalate; [MnMnLn 2 (μ 4 -O) 2 (H 2 edte) 2 (benz) 6 (NO 3 ) 2 ], where benz = benzoate, or [MnMnLn 2 (μ 4 -O) 2 (edteH 2 ) 2 (benz) 6 (NO 3 ) 2 ]·2MeCN {Ln = Gd, Tb, Dy (14-16); and [MnMnLn 2 (μ 4 -O) 2 (edteH 2 ) 2 (piv) 8 ].solv {solv = 4MeCN, Ln = La (17); solv = 2MeCN·tol·H 2 O, Ln = Pr, Nd, Sm, Tb (18-20, 22); solv = 2MeCN·H 2 O, Ln = Gd (21). These compounds crystallize in two different systems, namely, monoclinic in the space groups P2 1 /n for 1-4, 6, and 14-16 and C2/c for 5, 7-13, 18-20, and 22 and triclinic in the space group P1[combining macron] for 17 and 21. The crystal structures of these compounds display a face-fused dicubane structure connected by different types of bridged oxygen atoms. Solid-state dc magnetic susceptibility characterization was carried out for 1-22, and fitting showed that Mn III Mn III is antiferromagnetically (AF) coupled and Mn II Mn III , Mn II Ln and Mn III Ln are weakly ferromagnetically coupled. In addition, ac measurements were carried out and showed that only 7, 15, and 22 for Tb, 8 and 16 for Dy, and 20 for Sm exhibited slow magnetization relaxation. In the case of 15, it was possible to determine the energy barrier of the slow-relaxation behavior by fitting peak temperatures to the Arrhenius law, which gave a value of U eff = 21.2 K and a pre-exponential factor of τ 0 = 4.0 × 10 -9 s.

Phase formation in the Li2MoO4-Rb2MoO4-Ln2(MoO4)3 systems and the properties of LiRbLn2(MoO4)4

International Nuclear Information System (INIS)

Basovich, O.M.; Khajkina, E.G.; Vasil'ev, E.V.; Frolov, A.M.

1995-01-01

Phase equilibria within subsolidus range of ternary salt systems Li 2 MoO 4 -Rb 2 MoO 4 -Ln 2 (MoO 4 ) 4 (Ln - Nd, Er) are analyzed. Formation of ternary molybdate LiRbNd 2 (MoO 4 ) 4 is proved along LiNd(MoO 4 ) 2 -RbNd(MoO 4 )-2 cross-section. Phase diagram of this cross-section is plotted. Similar compounds are synthesized for Ln = La-Eu. The parameters of their monoclinic elementary cells are determined. Luminescent properties of LiRbLa 2 (MoO 4 ) 4 -Nd 3+ are studied. 17 refs., 4 figs., 2 tabs

High sensitivity cavity ring down spectroscopy of N_2O near 1.22 µm: (II) "1"4N_2"1"6O line intensity modeling and global fit of "1"4N_2"1"8O line positions

International Nuclear Information System (INIS)

Tashkun, S.A.; Perevalov, V.I.; Karlovets, E.V.; Kassi, S.; Campargue, A.

2016-01-01

In a recent work (Karlovets et al., 2016 [1]), we reported the measurement and rovibrational assignments of more than 3300 transitions belonging to 64 bands of five nitrous oxide isotopologues ("1"4N_2"1"6O, "1"4N"1"5N"1"6O, "1"5N"1"4N"1"6O, "1"4N_2"1"8O and "1"4N_2"1"7O) in the high sensitivity CRDS spectrum recorded in the 7915–8334 cm"−"1 spectral range. The assignments were performed by comparison with predictions of the effective Hamiltonian models developed for each isotopologue. In the present paper, the large amount of measurements from our previous work mentioned above and literature are gathered to refine the modeling of the nitrous oxide spectrum in two ways: (i) improvement of the intensity modeling for the principal isotopologue, "1"4N_2"1"6O, near 8000 cm"−"1 from a new fit of the relevant effective dipole moment parameters, (ii) global modeling of "1"4N_2"1"8O line positions from a new fit of the parameters of the global effective Hamiltonian using an exhaustive input dataset collected in the literature in the 12–8231 cm"−"1 region. The fitted set of 81 parameters allowed reproducing near 5800 measured line positions with an RMS deviation of 0.0016 cm"−"1. The dimensionless weighted standard deviation of the fit is 1.22. As an illustration of the improvement of the predictive capabilities of the obtained effective Hamiltonian, two new "1"4N_2"1"8O bands could be assigned in the CRDS spectrum in the 7915–8334 cm"−"1 spectral range. A line list at 296 K has been generated in the 0–10,700 cm"−"1 range for "1"4N_2"1"8O in natural abundance with a 10"−"3"0 cm/molecule intensity cutoff. - Highlights: • Line parameters of two new "1"4N_2"1"8O bands centered at 7966 cm"−"1 and at 8214 cm"−"1. • Refined sets of the "1"4N_2"1"6O effective dipole moment parameters for ΔP=13,14 series. • Global modeling of "1"4N_2"1"8O line positions and intensities in the 12–8231 cm"−"1 range. • 5800 observed of "1"4N_2"1"8O line positions

Magnetic interactions in rhenium-containing rare earth double perovskites Sr{sub 2}LnReO{sub 6} (Ln=rare earths)

Energy Technology Data Exchange (ETDEWEB)

Nishiyama, Atsuhide; Doi, Yoshihiro; Hinatsu, Yukio, E-mail: hinatsu@sci.hokudai.ac.jp

2017-04-15

The perovskite-type compounds containing both rare earth and rhenium Sr{sub 2}LnReO{sub 6} (Ln=Y, Tb-Lu) have been prepared. Powder X-ray diffraction measurements and Rietveld analysis show that Ln{sup 3+} and Re{sup 5+} ions are structurally ordered at the B site of the perovskite SrBO{sub 3}. Magnetic anomalies are found in their magnetic susceptibility and specific heat measurements at 2.6–20 K for Ln=Y, Tb, Dy, Yb, Lu compounds. They are due to magnetic interactions between Re{sup 5+} ions. The results of the magnetic hysteresis and remnant magnetization measurements for Sr{sub 2}YReO{sub 6} and Sr{sub 2}LuReO{sub 6} indicate that the antiferromagnetic interactions between Re{sup 5+} ions below transition temperatures have a weak ferromagnetic component. The analysis of the magnetic specific heat data for Sr{sub 2}YbReO{sub 6} shows that both the Yb{sup 3+} and Re{sup 5+} ions magnetically order at 20 K. For the case of Sr{sub 2}DyReO{sub 6}, magnetic ordering of the Re{sup 5+} moments occurs at 93 K, and with decreasing temperature, the moments of Dy{sup 3+} ferromagnetically order at 5 K from the measurements of magnetic susceptibility and specific heat. - Graphical abstract: Crystal structure of double perovskite Sr{sub 2}LnReO{sub 6}. Red and black lines show cubic and monoclinic unit cells, respectively. - Highlights: • Double perovskites Sr{sub 2}LnReO{sub 6} (Ln=rare earths) were prepared. • They show an antiferromagnetic transition at 2.6–20 K. • In Sr{sub 2}DyReO{sub 6}, Dy and Re moments magnetically order at 5 and 93 K, respectively.

Crystal structure and phase transition studies in perovskite-type oxides using powder-diffraction techniques and symmetry-mode analysis : SrLnMRuO6 (Ln=La,Pr,Nd; M=Zn,Co,Mg,Ni,Fe) and ALn2CuTi2O9 (A=Ca,Ba; Ln=La,Pr,Nd,Sm)

OpenAIRE

Iturbe Zabalo, Edurne

2013-01-01

La tesis se ha centrado en la síntesis y caracterización estructural de materiales tipo perovskita: SrLnMRuO6 (Ln=La,Pr,Nd; M=Zn,Co,Mg,Ni,Fe) y ALn2CuTi2O9 (A=Ca,Ba; Ln=La,Pr,Nd,Sm). El estudio de las estructuras de los materiales se ha realizado mediante el análisis de los patrones de difracción en polvo de rayos-X, sincrotrón y/o neutrones. En el refinamiento por el método de Rietveld de las estructuras se han sustituido las coordenadas atómicas (el método más común), por coordenadas colect...

Synthesis, crystal and electronic structures, and magnetic properties of LiLn{sub 9}Mo{sub 16}O{sub 35} (Ln=La, Ce, Pr, and Nd) compounds containing the original cluster Mo{sub 16}O{sub 36}

Energy Technology Data Exchange (ETDEWEB)

Gougeon, Patrick; Gall, Philippe [UMR CNRS 6226 - ' ' Sciences Chimiques de Rennes' ' , Universite de Rennes 1 - INSA (France); Cuny, Jerome; Gautier, Regis; Le Polles, Laurent [UMR CNRS 6226 - ' ' Sciences Chimiques de Rennes' ' , Ecole Nationale Superieure de Chimie de Rennes (France); Delevoye, Laurent; Trebosc, Julien [UMR CNRS 8181 - UCCS, ENSCL, Universite Lille Nord de France, Villeneuve d' Ascq (France)

2011-12-02

The new compounds LiLn{sub 9}Mo{sub 16}O{sub 35} (Ln=La, Ce, Pr, and Nd) were synthesized from stoichiometric mixtures of Li{sub 2}MoO{sub 4}, Ln{sub 2}O{sub 3}, Pr{sub 6}O{sub 11} or CeO{sub 2}, MoO{sub 3}, and Mo heated at 1600 C for 48 h in a molybdenum crucible sealed under a low argon pressure. The crystal structure, determined from a single crystal of the Nd member, showed that the main building block is the Mo{sub 16}O{sub 36} unit, the Mo{sub 16} core of which is totally new and results from the fusion of two bioctahedral Mo{sub 10} clusters. It can also be viewed as a fragment of an infinite twin chain of edge-sharing Mo{sub 6} octahedra. The Mo{sub 16}O{sub 36} cluster units share some oxygen atoms to form infinite chains running parallel to the b axis, which are separated by the rare-earth and lithium cations. {sup 7}Li-NMR experiments, carried out at high field on the nonmagnetic LiLa{sub 9}Mo{sub 16}O{sub 35}, provided insights into the local environment of the lithium ions. Magnetic susceptibility measurements confirmed the trivalent oxidation state of the magnetic rare-earth cations and indicated the absence of localized moments on the Mo{sub 16} clusters. The electronic structure of the LiLn{sub 9}Mo{sub 16}O{sub 35} compounds was analyzed using molecular and periodic quantum calculations. The study of the molecular orbital diagrams of isolated Mo{sub 16}O{sub 36} models allowed the understanding of this unique metallic architecture. Periodic density functional theory calculations demonstrated that few interactions occur between the Mo{sub 16} clusters, and predicted semiconducting properties for LiLn{sub 9}Mo{sub 16}O{sub 35} as a band gap of 0.57 eV was computed for the lanthanum phase. (Copyright copyright 2011 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim)

Studies on supercritical hydrothermal syntheses of uranium and lanthanide oxide particles and their reaction mechanisms

Science.gov (United States)

Hwang, DongKi; Tsukahara, Takehiko; Tanaka, Kosuke; Osaka, Masahiko; Ikeda, Yasuhisa

2015-11-01

In order to develop preparation method of raw metal oxide particles for low decontaminated MOX fuels by supercritical hydrothermal (SH) treatments, we have investigated behavior of aqueous solutions dissolving U(VI), Ln(III) (Ln: lanthanide = Ce, Pr, Nd, Sm, Tb), Cs(I), and Sr(II) nitrate or chloride compounds under SH conditions (temperature = 400-500 °C, pressure = 30-40 MPa). As a result, it was found that Ln(NO3)3 (Ln = Ce, Pr, Tb) compounds produce LnO2, that Ln(NO3)3 (Ln = Nd, Sm) compounds are hardly converted to their oxides, and that LnCl3 (Ln = Ce, Pr, Nd, Sm, Tb), CsNO3, and Sr(NO3)2 do not form their oxide compounds. Furthermore, HNO2 species were detected in the liquid phase obtained after treating HNO3 aqueous solutions containing Ln(NO3)3 (Ln = Ce, Pr, Tb) under SH conditions, and also NO2 and NO compounds were found to be produced by decomposition of HNO3. From these results, it was proposed that the Ln oxide (LnO2) particles are directly formed with oxidation of Ln(III) to Ln(IV) by HNO3 and HNO2 species in the SH systems. Moreover, the uranyl ions were found to form U3O8 and UO3 depending on the concentration of HNO3. From these results, it is expected that the raw metal oxide particles for low decontaminated MOX fuels are efficiently prepared by the SH method.

Synthesis, crystal structure, optical and thermal properties of lanthanide hydrogen-polyphosphates Ln[H(PO3)4] (Ln = Tb, Dy, Ho).

Science.gov (United States)

Förg, Katharina; Höppe, Henning A

2015-11-28

Lanthanide hydrogen-polyphosphates Ln[H(PO3)4] (Ln = Tb, Dy, Ho) were synthesised as colourless (Ln = Tb, Dy) and light pink (Ln = Ho) crystalline powders by reaction of Tb4O7/Dy2O3/Ho2O3 with H3PO3 at 380 °C. All compounds crystallise isotypically (P2(1)/c (no. 14), Z = 4, a(Tb) = 1368.24(4) pm, b(Tb) = 710.42(2) pm, c(Tb) = 965.79(3) pm, β(Tb) = 101.200(1)°, 3112 data, 160 parameters, wR2 = 0.062, a(Ho) = 1363.34(5) pm, b(Ho) = 709.24(3) pm, c(Ho) = 959.07(4) pm, β(Ho) = 101.055(1)°, 1607 data, 158 parameters, wR2 = 0.058). The crystal structure comprises two different infinite helical chains of corner-sharing phosphate tetrahedra. In-between these chains the lanthanide ions are located, coordinated by seven oxygen atoms belonging to four different polyphosphate chains. Vibrational, UV/Vis and fluorescence spectra of Ln[H(PO3)4] (Ln = Tb, Dy, Ho) as well as Dy[H(PO3)4]:Ln (Ln = Ce, Eu) and the magnetic and thermal behaviour of Tb[H(PO3)4] are reported.

Generation of H2 and CO by solar thermochemical splitting of H2O and CO2 by employing metal oxides

International Nuclear Information System (INIS)

Rao, C.N.R.; Dey, Sunita

2016-01-01

Generation of H 2 and CO by splitting H 2 O and CO 2 respectively constitutes an important aspect of the present-day concerns with energy and environment. The solar thermochemical route making use of metal oxides is a viable means of accomplishing these reduction reactions. The method essentially involves reducing a metal oxide by heating and passing H 2 O or CO 2 over the nonstoichiometric oxide to cause reverse oxidation by abstracting oxygen from H 2 O or CO 2 . While ceria, perovskites and other oxides have been investigated for this purpose, recent studies have demonstrated the superior performance of perovskites of the type Ln 1−x A x Mn 1−y M y O 3 (Ln=rare earth, A=alkaline earth, M=various +2 and +3 metal ions), in the thermochemical generation of H 2 and CO. We present the important results obtained hitherto to point out how the alkaine earth and the Ln ions, specially the radius of the latter, determine the performance of the perovskites. The encouraging results obtained are exemplefied by Y 0.5 Sr 0.5 MnO 3 which releases 483 µmol/g of O 2 at 1673 K and produces 757 µmol/g of CO from CO 2 at 1173 K. The production of H 2 from H 2 O is also quite appreciable. Modification of the B site ion of the perovskite also affects the performance. In addition to perovskites, we present the generation of H 2 based on the Mn 3 O 4 /NaMnO 2 cycle briefly. - Graphical abstract: Ln 0.5 A 0.5 Mn 1−x M x O 3 (Ln=lanthanide; A=Ca, Sr; M=Al, Ga, Sc, Mg, Cr, Fe, Co) perovskites are employed for the two step thermochemical splitting of CO 2 and H 2 O for the generation of CO and H 2 . - Highlights: • Perovskite oxides based on Mn are ideal for the two-step thermochemical splitting of CO 2 and H 2 O. • In Ln 1−x A x MnO 3 perovskite (Ln=rare earth, A=alkaline earth) both Ln and A ions play major roles in the thermochemical process. • H 2 O splitting is also achieved by the use of the Mn 3 O 4 -sodium carbonate system. • Thermochemical splitting of CO 2 and H

Some crystal chemistry of (Ln,Ce)2CuO4-δ superconductors

International Nuclear Information System (INIS)

Goodman, P.; Keating, A.; Myhra, S.; White, T.J.

1989-01-01

Compounds of the form (Ln, Sr, Ce) 2 CuO 4-δ (Ln = rare earth element) crystallise as the Nd 2 CuO 4 structure type, K 2 NiF 4 structure type or perfectly and imperfectly ordered intergrowths of these parent structures. These structurally similar phases exhibit superconductivity in which the charge carriers are holes (in Sr-doped material) or electrons (in Ce doped material). In this study, X-ray Photoelectron Spectroscopy (XPS) and High Resolution Electron Microscopy (HREM) were used to investigate the charge balancing mechanisms operating in each superconducting regime and the structural changes accompanying compositional variation. It was found that under slightly reducing conditions charge coupled cation substitutions predominate, whilst at low pO 2 ( -5 atm) perfectly ordered oxygen superlattices form. The structural and electronic changes which accompany deoxygenation were observed in situ during XPS and HREM observations. 29 refs., 8 figs., 3 tabs

Host-Sensitized and Tunable Luminescence of GdNbO4:Ln3+ (Ln3+ = Eu3+/Tb3+/Tm3+) Nanocrystalline Phosphors with Abundant Color.

Science.gov (United States)

Liu, Xiaoming; Chen, Chen; Li, Shuailong; Dai, Yuhua; Guo, Huiqin; Tang, Xinghua; Xie, Yu; Yan, Liushui

2016-10-17

Up to now, GdNbO 4 has always been regarded as an essentially inert material in the visible region with excitation of UV light and electron beams. Nevertheless, here we demonstrate a new recreating blue emission of GdNbO 4 nanocrystalline phosphors with a quantum efficiency of 41.6% and host sensitized luminescence in GdNbO 4 :Ln 3+ (Ln 3+ = Eu 3+ /Tb 3+ /Tm 3+ ) nanocrystalline phosphors with abundant color in response to UV light and electron beams. The GdNbO 4 and GdNbO 4 :Ln 3+ (Ln 3+ = Eu 3+ /Tb 3+ /Tm 3+ ) nanocrystalline phosphors were synthesized by a Pechini-type sol-gel process. With excitation of UV light and low-voltage electron beams, the obtained GdNbO 4 nanocrystalline phosphor presents a strong blue luminescence from 280 to 650 nm centered around 440 nm, and the GdNbO 4 :Ln 3+ nanocrystalline phosphors show both host emission and respective emission lines derived from the characterize f-f transitions of the doping Eu 3+ , Tb 3+ , and Tm 3+ ions. The luminescence color of GdNbO 4 :Ln 3+ nanocrystalline phosphors can be tuned from blue to green, red, blue-green, orange, pinkish, white, etc. by varying the doping species, concentration, and relative ratio of the codoping rare earth ions in GdNbO 4 host lattice. A single-phase white-light-emission has been realized in Eu 3+ /Tb 3+ /Tm 3+ triply doped GdNbO 4 nanocrystalline phosphors. The luminescence properties and mechanisms of GdNbO 4 and GdNbO 4 :Ln 3+ (Ln 3+ = Eu 3+ /Tb 3+ /Tm 3+ ) are updated.

The Influence of Oxidation on the Quality of U3O8 Kernels

International Nuclear Information System (INIS)

Damunir; Sukarsono; Indra Suryawan

2002-01-01

The influence of oxidation on quality of U 3 O 8 kernels have been studied. The investigated the influence was changed of time and temperature oxidation of Uranyl-4(ammonia)-2(polyvinyl alcohol) gel on surface area, pore radius, pore volume, porosity and diameter size of U 3 O 8 kernel. The spherical of uranyl-4(ammonia)-2(polyvinyl alcohol) containing 150g U/l were oxidized at 200-800 o C temperature for 2-24 hours, formed U 3 O 8 kernel. After that, the quality of U 3 O 8 kernel were measured by their physical properties i.e. the surface area and pore radius using Surface areameter with N 2 gas as absorbent. The pore volume and porosity using pycnometer with aquabidest of water as a solvent, diameter size using a optical microscope. The experiment results, showed that the time and temperature oxidation of uranyl-4(ammonia)-2(polyvinyl alcohol) grain the influence to quality of U 3 O 8 in formed the surface area of specific, pore radius, pore volume of specific, porosity, and diameter size of U 3 O 8 kernel. The best accurred at 600-800 o C oxidation temperature and oxidation time was 2-5 hours. The resulted quality of U 3 O 8 kernel i.e surface area of specific was 10.84 - 5.99 m 2 /g, pore volume of specific was 10.35x10 -2 - 3.23x10 -2 cc/g, pore radius was 21.05 - 24.62 Angstrom, diameter size was 1264 - 1456 μm and porosity was 49.49 - 21.36 % Vol with Cumulative analysis error was 8.55 % Vol. (author)

First principles investigation of structural, electronic, elastic and thermal properties of rare-earth-doped titanate Ln2TiO5

Directory of Open Access Journals (Sweden)

Hui Niu

2012-09-01

Full Text Available Systematic first-principles calculations based on density functional theory were performed on a wide range of Ln2TiO5 compositions (Ln = La, Ce, Pr, Nd, Sm, Gd, Tb, Dy and Y in order to investigate their structural, elastic, electronic, and thermal properties. At low temperature, these compounds crystallize in orthorhombic structures with a Pnma symmetry, and the calculated equilibrium structural parameters agree well with experimental results. A complete set of elastic parameters including elastic constants, Hill's bulk moduli, Young's moduli, shear moduli and Poisson's ratio were calculated. All Ln2TiO5 are ductile in nature. Analysis of densities of states and charge densities and electron localization functions suggests that the oxide bonds are highly ionic with some degree of covalency in the Ti-O bonds. Thermal properties including the mean sound velocity, Debye temperature, and minimum thermal conductivity were obtained from the elastic constants.

In pursuit of the rhabdophane crystal structure: from the hydrated monoclinic LnPO{sub 4}.0.667H{sub 2}O to the hexagonal LnPO{sub 4} (Ln = Nd, Sm, Gd, Eu and Dy)

Energy Technology Data Exchange (ETDEWEB)

Mesbah, Adel, E-mail: adel.mesbah@cea.fr [ICSM, UMR 5257 CNRS – CEA – ENSCM – Université de Montpellier, Site de Marcoule - Bât 426, BP 17171, 30207 Bagnols/Cèze (France); Clavier, Nicolas [ICSM, UMR 5257 CNRS – CEA – ENSCM – Université de Montpellier, Site de Marcoule - Bât 426, BP 17171, 30207 Bagnols/Cèze (France); Elkaim, Erik [Synchrotron SOLEIL, L' Orme des Merisiers, Saint-Aubin, BP 48, 91192 Gif-sur-Yvette Cedex (France); Szenknect, Stéphanie; Dacheux, Nicolas [ICSM, UMR 5257 CNRS – CEA – ENSCM – Université de Montpellier, Site de Marcoule - Bât 426, BP 17171, 30207 Bagnols/Cèze (France)

2017-05-15

The dehydration process of the hydrated rhabdophane LnPO{sub 4}.0.667H{sub 2}O (Ln = La to Dy) was thoroughly studied over the combination of in situ high resolution synchrotron powder diffraction and TGA experiments. In the case of SmPO{sub 4}.0.667H{sub 2}O (monoclinic, C2), a first dehydration step was identified around 80 °C leading to the formation of SmPO{sub 4}.0.5H{sub 2}O (Monoclinic, C2) with Z =12 and a =17.6264(1) Å, b =6.9704(1) Å, c =12.1141(1) Å, β=133.74(1) °, V =1075.33(1) Å{sup 3}. In agreement with the TGA and dilatometry experiments, all the water molecules were evacuated above 220 °C yielding to the anhydrous form, which crystallizes in the hexagonal P3{sub 1}21 space group with a =7.0389(1) Å, c =6.3702(1) Å and V =273.34(1) Å{sup 3}. This study was extended to selected LnPO{sub 4}.0.667H{sub 2}O samples (Ln= Nd, Gd, Eu, Dy) and the obtained results confirmed the existence of two dehydration steps before the stabilization of the anhydrous form, with the transitory formation of LnPO{sub 4}.0.5H{sub 2}O. - Graphical abstract: The dehydration process of the rhabdophane SmPO{sub 4}.0.667H{sub 2}O was studied over combination of in situ high resolution synchrotron powder diffraction and TGA techniques, a first dehydration was identified around 80 °C leading to the formation of SmPO{sub 4}.0.5H{sub 2}O (Monoclinic, C2). Then above 220 °C, the anhydrous form of the rhabdophane SmPO{sub 4} was stabilized and crystallizes in the hexagonal P3{sub 1}21 space group. - Highlights: • In situ synchrotron powder diffraction was carried out during the dehydration of the rhabdopahe LnPO{sub 4}.0.667H{sub 2}O. • The heat of the rhabdophane LnPO{sub 4}.0.667H{sub 2}O leads to LnPO{sub 4}.0.5H{sub 2}O then to anhydrous rhabdophane LnPO{sub 4}. • LnPO{sub 4}.0.5H{sub 2}O (monoclinic, C2) and LnPO{sub 4} (Hexagonal, P3{sub 1}21) were solved over the use of direct methods.

High performance LiNi0.5Mn1.5O4 cathode by Al-coating and Al3+-doping through a physical vapor deposition method

International Nuclear Information System (INIS)

Sun, Peng; Ma, Ying; Zhai, Tianyou; Li, Huiqiao

2016-01-01

Highlights: • Metal Al was used as an electrical conductive coating material for LiNi 0.5 Mn 1.5 O 4 . • The uniform surface coating layer of metal Al was successfully achieved with adjusted thickness through a physical vapor deposition technology. • Al 3+ -doped LiNi 0.5 Mn 1.5 O 4 can be easily obtained by further directly annealing of Al-coated LiNi 0.5 Mn 1.5 O 4 in air. • The conductive Al-coating layer can greatly improve the rate performance and cycle stability of LiNi 0.5 Mn 1.5 O 4 . - Abstract: In this work, spinel LiNi 0.5 Mn 1.5 O 4 (LNMO) hollow microspheres are synthesized by an impregnation method using microsphere MnO 2 as both the precursor and template. To enhance the electrical conductivity of LNMO, metal Al was employed for the first time as a coating material for LNMO. Though an Electron-beam Vapor Deposition approach, the surface of LNMO can be easily coated by a tight layer of Al nanoparticles with adjusted thickness. Further annealing the Al-coated sample at 800 °C in air, the Al 3+ -doped LNMO can be obtained. The effects of Al-coating and Al 3+ -doping on the sample morphology and structure are investigated by SEM, TEM, XRD and FT-IR. The electrochemical properties of Al-coated LNMO and Al 3+ -doped LNMO are measured with comparison of bare LNMO by charge/discharge tests and electrochemical impedance spectroscopy (EIS). The results show that both Al-coating and Al 3+ -doping can greatly enhance the cycle performance and rate capability of LNMO. Especially for Al-coated LNMO, it shows the lowest battery impedance due to the existence of conductive Al coating layer, thus delivers the best rate performance among the three. The physical coating procedure used in this work may provide a new facile modification approach for other cathode materials.

Solvothermal syntheses, crystal structures, and properties of lanthanide(III) thioarsenates [Ln(dien)2(μ-1κ,2κ2-AsS4)]n (Ln==Sm, Eu, Gd) and [Ln(dien)2(1κ2-AsS4)] (Ln==Tb, Dy, Ho)

International Nuclear Information System (INIS)

Wang, Fang; Tang, Chunying; Chen, Ruihong; Zhang, Yong; Jia, Dingxian

2013-01-01

Solvothermal reactions of Ln 2 O 3 , As and S in diethylenetriamine (dien) at 170 °C for 6 days afforded two structural types of lanthanide thioarsenates with the general formulae [Ln(dien) 2 (μ-1κ,2κ 2 -AsS 4 )] n [Ln=Sm(1), Eu(2), Gd(3)] and [Ln(dien) 2 (1κ 2 -AsS 4 )] [Ln=Tb(4), Dy(5), Ho(6)]. The Ln 2 O 3 oxides were converted to [Ln(dien) 2 ] 3+ complex units in the solvothermal reactions. The As atom binds four S atoms, forming a tetrahedral AsS 4 unit. In 1−3, the AsS 4 units interconnect the [Ln(dien) 2 ] 3+ cations via Ln−S bonds as tridentate μ-1κ,2κ 2 -AsS 4 bridging ligands, resulting in the neutral coordination polymers [Ln(dien) 2 (μ-1κ,2κ 2 -AsS 4 )] n (Ln1). In 4−6, the AsS 4 units coordinate with the Ln 3+ ion of [Ln(dien) 2 ] 3+ as 1κ 2 -AsS 4 chelating ligands to form neutral coordination compounds [Ln(dien) 2 (1κ 2 -AsS 4 )] (Ln2). The Ln 3+ ions are in nine- and eight-coordinated environments in Ln1 and Ln2, respectively. The formation of Ln1 and Ln2 is related with ionic size of the Ln 3+ ions. Optical absorption spectra showed that 1−6 have potential use as semiconductors with the band gaps in the range 2.18−3.21 eV. - Graphical abstract: Two types of Ln-thioarsenates [Ln(dien) 2 (μ-1κ,2κ 2 -AsS 4 )] n and [Ln(dien) 2 (1κ 2 -AsS 4 )] were prepared by solvothermal methods and the soft Lewis basic AsS 4 3– ligand to Ln(III) centers with polyamine co-ligand was obtained. Display Omitted - Highlights: • Lanthanide thioarsenates were prepared by solvothermal methods. • The soft Lewis basic AsS 4 ligand coordinate Ln 3+ ions with coexistence polyamine ligands. • Two structural types of Ln-thioarsenates with structural turnover at Tb were obtained along Ln series. • The Ln-thioarsenates are potential semiconductors with optical band gaps in the range 2.18−3.21 eV

Hydrothermal synthesis of 4ZnO·B2O3·H2O:Ln3 + (Ln = Eu, Tb) phosphors: Morphology-tunable and luminescence properties

Science.gov (United States)

Cao, Shiwei; Jiao, Yang; Han, Weifang; Ge, Chunhua; Song, Bo; Wang, Jie; Zhang, Xiangdong

2018-02-01

4ZnO·B2O3·H2O:Ln3 + (Ln = Eu, Tb) phosphors with different morphologies have been successfully synthesized via one-step hydrothermal method through regulating the molar amount of Eu3 + and Tb3 +. Comprehensive scanning electron microscopy (SEM), X-ray diffraction (XRD) Fourier transform infrared spectrum (FT-IR) and inductively coupled plasma atomic emission spectrometer (ICP-AES) characterizations all confirm that obtained products are 4ZnO·B2O3·H2O:Ln3 + (Ln = Eu, Tb). The experimental results displayed that the morphology and photoluminescence of compounds is regularly changed with increased the molar amount of rare earth ions. For the Eu3 +-doped, Tb3 +-doped and Eu3 +/Tb3 + co-doped 4ZnO·B2O3·H2O phosphors of morphologies, the rod-like structures gradually changed to flower-like structures, fine wire-like structure and hybrid structure, respectively. To their photoluminescence, the Eu3 + shows a red emission (615 nm); the Tb3 + shows a green emission (545 nm); for the Eu3 +/Tb3 + co-doped 4ZnO·B2O3·H2O phosphors, a combination of blue (5d-4f of Eu2 +), green (5D4-7F5 of Tb3 +) and red (5D0-7F2 of Eu3 +) emissions emerges to achieve white emission. In addition, the energy transfer among Eu3 +, Eu2 + and Tb3 + ions was also discussed.

Phase diagrams for the M2MoO4–Ln2(MoO43–Hf(MoO42 systems, where M = Li–Cs, Tl and Ln = La–Lu

Directory of Open Access Journals (Sweden)

Zh. G. Bazarova

2017-12-01

Full Text Available In this paper, the results of systematic studies of complex molybdate systems M2MoO4–Ln2(MoO43–Hf(MoO42 (M = Li–Cs, Tl; Ln = La–Lu are presented. Subsolidus phase diagrams of ternary systems were constructed and new triple molybdates were obtained. The optimum synthesis conditions for poly- and monocrystalline form were determined. According to single-crystal data, the structure of one of the representatives of triple molybdates was determined.

On the structure of rare earth periodates of LnIO5x4H2O (Ln=Pr-Lu, Y)

International Nuclear Information System (INIS)

Shamraj, N.B.; Varfolomeev, M.B.; Saf'yanov, Yu.N.; Kuz'min, Eh.A.; Ilyukhin, V.V.; AN SSSR, Moscow. Inst. Kristallografii)

1977-01-01

The crystal structure of three representatives of an isotypic series of monoclinic periodates of rare earth elements in the series from Pr to Lu and Y was deciphered. The monoclinic cell for all LnIO 5 x4H 2 O contains Z=4 formula units. The architectural motif consists in layers of octahedra of IO 4 (OH) 2 and polyhedra of LnO 5 (H 2 O 3 ) parallel to the (100) plane. Adhesion between the layers is achieved through H-bonds

Tricolor emission Ca3Si2O7:Ln (Ln=Ce, Tb, Eu) phosphors for near-UV white light-emitting-diode

International Nuclear Information System (INIS)

Mao, Zhi-yong; Zhu, Ying-chun; Gan, Lin; Zeng, Yi; Xu, Fang-fang; Wang, Yang; Tian, Hua; Li, Jian; Wang, Da-jian

2013-01-01

Tricolor emission in a same Ca 3 Si 2 O 7 host with independent Ln (Ln=Ce 3+ , Eu 2+ , Tb 3+ ) dopants is demonstrated to construct a near-UV white light emitting diode (LED). The luminescence properties and thermal quenching properties, as well as the applications in near-UV white LED are investigated. These phosphors show typical blue, red, and green, three-basal-color, luminescence in the CIE chromaticity diagram for Ce 3+ , Eu 2+ and Tb 3+ dopants, respectively. Thermal quenching properties show that the luminescence thermal stability strongly depends on the different dopant types; better thermal quenching property of Ce 3+ and Tb 3+ is recorded in comparison with that of Eu 2+ . The white LED prototype fabricated with near-UV chip and as-prepared tricolor phosphors exhibits acceptable CIE chromaticity coordinates (0.32, 0.30) with a CCT of 6000 K and a CRI of 87, indicating the potential application of Ca 3 Si 2 O 7 :Ln phosphors in near-UV white LED. - Highlights: ► Tricolor Ca 3 Si 2 O 7 : Ln phosphors were demonstrated to construct near-UV white LED. ► Eu 2+ doped Ca 3 Si 2 O 7 red-emitting phosphor was confirmed by this work once again. ► Thermal quenching properties for Ca 3 Si 2 O 7 :Ln phosphors were reported for the first time. ► Performances of fabricated white LED indicated the potential application of phosphors.

Corrections to O(α7(lnα)mc2) fine-structure splittings and O(α6(lnα)mc2) energy levels in helium

International Nuclear Information System (INIS)

Zhang, T.

1996-01-01

Fully relativistic formulas for the energy-level shifts arising from no-pair exchange diagrams of two transverse photons plus an arbitrary number of Coulomb photons are derived in closed form within the external potential Bethe-Salpeter formalism. O(α 7 (lnα)mc 2 ) corrections to the fine-structure splittings of helium are obtained and expressed in terms of expectation values of nonrelativistic operators. O(α 7 mc 2 ) operators from exchange diagrams are found in nonrelativistic approximation. O(α 6 m 2 c 2 /M) nucleus-electron operators contributing to the fine-structure splittings are derived. Nonrelativistic operators of O(α 6 mc 2 ) corrections to the triplet levels of helium are presented. Nonrelativistic operators of O(α 6 (lnα)mc 2 ) corrections to the helium singlet levels and to positronium S levels are derived. O(α 6 m 2 c 2 /M) hydrogen and O(α 6 mc 2 ) positronium P levels, and O(α 6 (lnα)mc 2 ) corrections of first order to positronium S levels, are calculated using the derived operators for helium, in agreement with those obtained previously by others, except for one term in corrections to positronium P levels. In addition, the O(α 6 mc 2 ) Dirac energies for hydrogenic non-S levels are exactly reproduced in a perturbative calculation. copyright 1996 The American Physical Society

Crystallization of rare earth germanates in the K2O-Ln2O3-GeO2-H2O at 280 deg C

International Nuclear Information System (INIS)

Panasenko, E.B.; Begunova, R.G.; Sklokina, N.F.

1980-01-01

Crystallization of rare earth germanates in potassium hydroxide solutions is studied at 280 deg C. Stability limits for different crystalline phases are established. Diorthogermanates Ln 2 O 3 x2GeO 3 (three structural modifications) are formed with all lanthanides except lanthanum. Germanates-apatites 7Ln 2 O 3 x9GeO 2 are characteristic for ''large'' lanthanides La-Nd. Alkali germanate of the composition 0.5 K 2 OxLn 2 O 3 xGeO 2 xnH 2 O is realized with the elements of the end of rare earth series, i.e., Tm-Lu. Some properties of the germanates synthesized are considered [ru

Monodisperse and hollow structured Y{sub 2}O{sub 3}:Ln{sup 3+} (Ln = Eu, Dy, Er, Tm) nanospheres: A facile synthesis and multicolor-tunable luminescence properties

Energy Technology Data Exchange (ETDEWEB)

Li, Ruiqing; Zi, Wenwen; Li, Linlin; Liu, Lu; Zhang, Junjun [College of Chemistry, Jilin University, Changchun 130026 (China); Zou, Lianchun, E-mail: zoulianchun@126.com [Teaching Center of Basic Courses, Jilin University, Changchun 130062 (China); Gan, Shucai, E-mail: gansc@jlu.edu.cn [College of Chemistry, Jilin University, Changchun 130026 (China)

2014-12-25

Highlights: • We reported a simple route to synthesize the Y{sub 2}O{sub 3} HNSs. • A possible formation mechanism of the Y{sub 2}O{sub 3} HNSs was proposed. • The Ln-doped Y{sub 2}O{sub 3} HNSs exhibit characteristic emission with different colors. • White-light-emitting phosphor Y{sub 2}O{sub 3}:Tm{sup 3+}, Dy{sup 3+} was also successfully synthesized. - Abstract: A novel, fast and simple method was developed to synthesize the undoped and lanthanide-doped yttrium oxide hollow nanospheres (Y{sub 2}O{sub 3}⋅HNSs) with multicolored downconversion emission under mild conditions by employing poly (acrylic acid sodium salt) microspheres (PAAS MSs) as active templates followed by a subsequent calcination process. The structure, morphology, formation process, and fluorescent properties are well investigated using various techniques. The results show that the samples can be well indexed to the pure cubic phase of Y{sub 2}O{sub 3}. The possible formation mechanism of the PAAS MSs, PAA-Y precursor, and Y{sub 2}O{sub 3} HNSs are proposed and discussed in detail. Upon ultraviolet excitation, the obtained Y{sub 2}O{sub 3}:Ln{sup 3+} (Ln = Eu, Dy, Er, Tm) HNSs exhibit strong red, yellow–green, blue, yellow emission, respectively. Moreover, a novel single-phased and near-UV-pumped white-light-emitting phosphor Y{sub 2}O{sub 3}:Tm{sup 3+}, Dy{sup 3+} was also successfully fabricated through optimizing the molar ratio among Tm{sup 3+} and Dy{sup 3+} in the Y{sub 2}O{sub 3} host. This material may find potential applications in field-emission display devices and white ultraviolet light-emitting diodes (UV LEDs). Furthermore, this synthesis route may be of great significance in the preparation of other hollow spherical materials.

Syntheses, crystal structures and photoluminescence properties of two rare-earth molybdates CsLn(MoO{sub 4}){sub 2} (Ln=Eu, Tb)

Energy Technology Data Exchange (ETDEWEB)

Zhao, Dan; Ma, Fa-Xue; Liu, Bao-Zhong; Fan, Yun-Chang; Han, Xue-Feng; Zhang, Lei; Nie, Cong-Kui [Henan Polytechnic Univ. (China). College of Chemistry and Chemical Engineering

2018-04-01

Single crystals of two cesium rare-earth molybdates CsLn(MoO{sub 4}){sub 2} (Ln=Eu, Tb) have been prepared using the high temperature molten salt (flux) method. Single-crystal X-ray diffraction analyses reveal that they crystallize in the orthorhombic space group Pccm (No. 49) and features a 2D layer structure that is composed of [Ln(MoO{sub 4}){sub 2}]{sub ∞} and [Cs]{sub ∞} layers. Under near-UV light excitation, emission spectrum of CsEu(MoO{sub 4}){sub 2} consists of several sharp lines due to the characteristic electronic transitions of Eu{sup 3+} ions, whereas CsTb(MoO{sub 4}){sub 2} exhibits characteristic green emission of Tb{sup 3+} ions.

Luminescent properties of complexly substituted oxides Ме2Ln8 (XO46O2 (Me=Sr, Ca; Ln=La, Gd, Eu; X= Si, P

Directory of Open Access Journals (Sweden)

A. A. Vasin

2014-11-01

Full Text Available In the current work it is established that the maximum intensity of a luminescence of crystalline phosphors with structure silicate-apatite of general formulae: Ca2Eu8Si6(1-xP6xO26, Sr2Gd7.2Eu0.8Si6(1-xP6xO26 and Ca2La8(1-xEu8xSi6O26 is reached at concentration of europium equal 0,15. The maximum intensity of a luminescence of these substances, at replacement in an anion sublattice of tetrahedrons [SiO4]4- on tetrahedrons [PO4]3- takes place at concentration of phosphorus 0,05.

Synthesis, structures, and luminescent properties of sodium rare-earth metal(III) chloride oxotellurates(IV), Na{sub 2}Ln{sub 3}Cl{sub 3}[TeO{sub 3}]{sub 4} (Ln = Sm, Eu, Gd, Tb, Dy, and Ho)

Energy Technology Data Exchange (ETDEWEB)

Charkin, Dmitri O.; Dorofeev, Sergey G.; Berdonosov, Peter S.; Dolgikh, Valery A. [Department of Chemistry, Lomonosov Moscow State University (Russian Federation); Zitzer, Sabine; Greiner, Stefan; Schleid, Thomas [Institut fuer Anorganische Chemie, Universitaet Stuttgart (Germany); Olenev, Andrei V. [Department of Chemistry, Lomonosov Moscow State University (Russian Federation); Sine Theta Ltd., Moscow (Russian Federation)

2017-11-17

Six sodium rare-earth metal(III) chloride oxotellurates(IV), Na{sub 2}Ln{sub 3}Cl{sub 3}[TeO{sub 3}]{sub 4}, isostructural to Na{sub 2}Y{sub 3}Cl{sub 3}[TeO{sub 3}]{sub 4}, were synthesized by flux techniques and characterized by single-crystal XRD. The compounds crystallize in the monoclinic space group C2/c with lattice constants a = 23.967(1), b = 5.6342(3), c = 16.952(1) Aa, β = 134.456(5) for Ln = Sm, a = 23.932(2), b = 5.6044(5), c = 17.134(1) Aa, β = 135.151(6) for Ln = Eu, a = 23.928(1), b = 5.5928(1), c = 17.1133(8) Aa, β = 135.366(3) for Ln = Gd, a = 23.907(1), b = 5.569(3), c = 16.745(1) Aa, β = 134.205(3) for Ln = Tb, a = 23.870(1), b = 5.547(3), c = 16.665(1) Aa, β = 134.102(3) for Ln = Dy, and a = 23.814(1), b = 5.526(3), c = 16.626(1) Aa, β = 134.016(3) for Ln = Ho and Z = 4. Their crystal structure can be considered as a framework built of intergrowing Ln-O and Na-(O,Cl) slabs with channel walls decorated by tellurium atoms of [TeO{sub 3}]{sup 2-} groups. The luminescent properties of the new compounds due to the Ln{sup 3+} cations are described and discussed. We also discuss the crystal chemistry of various alkali-metal rare-earth metal(III) halide oxochalcogenates(IV). (copyright 2017 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim)

Chemical and structural changes in Ln{sub 2}NiO{sub 4+δ} (Ln=La, Pr or Nd) lanthanide nickelates as a function of oxygen partial pressure at high temperature

Energy Technology Data Exchange (ETDEWEB)

Flura, Aurélien; Dru, Sophie; Nicollet, Clément; Vibhu, Vaibhav; Fourcade, Sébastien; Lebraud, Eric; Rougier, Aline; Bassat, Jean-Marc; Grenier, Jean-Claude, E-mail: grenier@icmcb-bordeaux.cnrs.fr

2015-08-15

The chemical stability of lanthanide nickelates Ln{sub 2}NiO{sub 4+δ} (Ln=La, Pr or Nd) has been studied in the temperature range 25–1300 °C, either in air or at low pO{sub 2} (down to 10{sup −4} atm). Thermal gravimetry analysis (TGA) measurements coupled with X-ray diffraction (XRD) characterization have shown that all compounds retain their K{sub 2}NiF{sub 4}-type structure in these conditions, while remaining over-stoichiometric in oxygen up to 1000 °C. Only Nd{sub 2}NiO{sub 4+δ} starts to decompose into Nd{sub 2}O{sub 3} and NiO above 1000 °C, at pO{sub 2}=10{sup −4} atm. In addition, a careful analysis of the lanthanide nickelates structural features has been performed by in situ XRD, as a function of temperature and pO{sub 2}. For all compounds, a structural transition has been always observed in the temperature range 200–400 °C, in air or at pO{sub 2}=10{sup −4} atm. In addition, their cell volume did not vary upon the variation of the oxygen partial pressure. Therefore, these materials do not exhibit a chemical expansion in these conditions, which is beneficial for a fuel cell application as cathode layers. Additional dilatometry measurements have revealed that a temperature as high as 950 °C for Pr{sub 2}NiO{sub 4+δ} or 1100 °C for La{sub 2}NiO{sub 4+δ} and Nd{sub 2}NiO{sub 4+δ} has to be reached in order to begin the sintering of the material particles, which is of primary importance to obtain an efficient electronic/ionic conduction in the corresponding designed cathode layers. Besides, excellent matching was found between the thermal expansion coefficients of lanthanide nickelates and SOFC electrolytes such as 8wt% yttria stabilized zirconia (8YSZ) or Ce{sub 0.8}Gd{sub 0.2}O{sub 2−δ} (GDC), at least from 400 °C up to 1400 °C in air or up to 1200 °C at pO{sub 2}=10{sup −4} atm. - Graphical abstract: This study reports the good chemical stability of oxygen overstoichiometric Ln2NiO4+δ(Ln = La, Pr or Nd) at high temperatures

Removal of Acid Red 14 from Contaminated Water Using UV/S2O82- Advanced Oxidation Process

Directory of Open Access Journals (Sweden)

Mohammad Hossein Rasoulifard

2012-10-01

Full Text Available The present study investigates the degradation of Acid Red 14 (AR14, commonly used as a textile dye in aqueous medium through the oxidation process by UV /S2O82- under a set of variables concentration of S2O82-, Ag+, AR14 and temperature. Commonly Ag+, heat and UV light can excite S2O82− to sulfate radical form (SO4−•, a stronger oxidant (E0 = 2.60 V than S2O82−, to enhance significantly the oxidation of contaminants. Also the changes in the absorption spectra of AR14 solutions during the photoxidation process showed that decrease of absorption peak of the dye at λmax = 514 nm indicates a rapid degradation of the azo dye. The results of this study suggest that the oxidative treatment of AR14 by peroxydisulfate with UV is a viable option for removal of the textile dyes from effluents.

Coordination polyhedra LnFn (Ln=La-Lu) in crystal structure

International Nuclear Information System (INIS)

Vologzhanina, A.V.; Pushkin, D.V.; Serezhkin, V.N.

2006-01-01

Peculiarities of stereochemistry of lanthanides (Ln) surrounded by fluorine atoms were studied by means of the Voronoi-Dirichlet polyhedra (PVD) and method of crossing spheres, 118 compounds are presented in the structure. It has been found that coordination numbers (CN) of Ln atoms change from 6 to 12, nine types of LnF n coordination polyhedra are formed in the process, Ln-F bond lengths have changes by 0.2-0.7 A in accordance to CN. It is found that in spite of significant variation of bond lengths volume of PVD Ln atoms is determined by their nature and oxidation state. It has been found that the change in radii of spherical domains, which volume is equal to the volume of PVD Ln atoms, is accompanied by tetrad-effect [ru

Characteristic charge transport in oxygen-deficiency-controlled LnFeAsO1-y (Ln = La and Nd)

International Nuclear Information System (INIS)

Ishida, Shigeyuki; Nakajima, Masamichi; Tomioka, Yasuhide; Ito, Toshimitsu; Miyazawa, Kiichi; Kito, Hijiri; Lee, Chul-Ho; Ishikado, Motoyuki; Shamoto, Shin-ichi; Iyo, Akira; Eisaki, Hiroshi; Kojima, Kenji M.; Uchida, Shin-ichi

2010-01-01

We have investigated the transport properties of LnFeAsO 1-y (Ln = La, Nd) over a wide range of doping. When we compare the exponent n of resistivity ρ(T)∼T n , a marked difference is found between La and Nd system. In the La system with lower T C ,ρ(T) is always dominated by a T 2 term at low temperatures, showing relatively large magnetoresistance. On the other hand, in the Nd system with higher T C ,ρ(T) is linear on T with a small magnetoresistance. These results indicate that the carriers are subject to stronger scattering in NdFeAsO 1-y , which might be linked to the higher T C .

Ion-irradiation resistance of the orthorhombic Ln_2TiO_5 (Ln = La, Pr, Nd, Sm, Eu, Gd, Tb and Dy) series

International Nuclear Information System (INIS)

Aughterson, Robert D.; Lumpkin, Gregory R.; Ionescu, Mihail; Reyes, Massey de los; Gault, Baptiste; Whittle, Karl R.; Smith, Katherine L.; Cairney, Julie M.

2015-01-01

The response of Ln_2TiO_5 (where Ln is a lanthanide) compounds exposed to high-energy ions was used to test their suitability for nuclear-based applications, under two different but complementary conditions. Eight samples with nominal stoichiometry Ln_2TiO_5 (Ln = La, Pr, Nd, Sm, Eu, Gd, Tb and Dy), of orthorhombic (Pnma) structure were irradiated, at various temperatures, with 1 MeV Kr"2"+ ions in-situ within a transmission electron microscope. In each case, the fluence was increased until a phase transition from crystalline to amorphous was observed, termed critical dose D_c. At certain elevated temperatures, the crystallinity was maintained irrespective of fluence. The critical temperature for maintaining crystallinity, T_c, varied non-uniformly across the series. The T_c was consistently high for La, Pr, Nd and Sm_2TiO_5 before sequential improvement from Eu to Dy_2TiO_5 with T_c's dropping from 974 K to 712 K. In addition, bulk Dy_2TiO_5 was irradiated with 12 MeV Au"+ ions at 300 K, 723 K and 823 K and monitored via grazing-incidence X-ray diffraction (GIXRD). At 300 K, only amorphisation is observed, with no transition to other structures, whilst at higher temperatures, specimens retained their original structure. The improved radiation tolerance of compounds containing smaller lanthanides has previously been attributed to their ability to form radiation-induced phase transitions. No such transitions were observed here. - Highlights: • First ion-irradiation studies on a number of novel compounds including Pr_2TiO_5, Eu_2TiO_5 and Tb_2TiO_5. • Systematic in-situ ion-irradiation study of almost complete Ln_2TiO_5 series (Ln = lanthanides) with orthorhombic crystal structure type. • The first grazing incidence study of bulk irradiated Dy_2TiO_5 looking for irradiation induced phase transition.

Rethinking Sensitized Luminescence in Lanthanide Coordination Polymers and MOFs: Band Sensitization and Water Enhanced Eu Luminescence in [Ln(C15H9O5)3(H2O)3]n (Ln = Eu, Tb).

Science.gov (United States)

Einkauf, Jeffrey D; Kelley, Tanya T; Chan, Benny C; de Lill, Daniel T

2016-08-15

A coordination polymer [Ln(C15H9O9)3(H2O)3]n (1-Ln = Eu(III), Tb(III)) assembled from benzophenonedicarboxylate was synthesized and characterized. The organic component is shown to sensitize lanthanide-based emission in both compounds, with quantum yields of 36% (Eu) and 6% (Tb). Luminescence of lanthanide coordination polymers is currently described from a molecular approach. This methodology fails to explain the luminescence of this system. It was found that the band structure of the organic component rather than the molecular triplet state was able to explain the observed luminescence. Deuterated (Ln(C15H9O9)3(D2O)3) and dehydrated (Ln(C15H9O9)3) analogues were also studied. When bound H2O was replaced by D2O, lifetime and emission increased as expected. Upon dehydration, lifetimes increased again, but emission of 1-Eu unexpectedly decreased. This reduction is reasoned through an unprecedented enhancement effect of the compound's luminescence by the OH/OD oscillators in the organic-to-Eu(III) energy transfer process.

Predictable self-assembled [2×2] Ln(III)4 square grids (Ln = Dy,Tb)-SMM behaviour in a new lanthanide cluster motif.

Science.gov (United States)

Anwar, Muhammad Usman; Thompson, Laurence Kenneth; Dawe, Louise Nicole; Habib, Fatemah; Murugesu, Muralee

2012-05-14

The ditopic carbohydrazone ligand (L1) produces the square, self-assembled [2×2] grids [Dy(4)(L1)(4)(OH)(4)]Cl(2) (1) and [Ln(4)(L1)(4)(μ(4)-O)(μ(2)-1,1-N(3))(4)] (Ln = Dy (2), Tb (3)), with 2 exhibiting SMM behaviour. Two relaxation processes occur with U(eff) = 51 K, 91 K in the absence of an external field, and one with U(eff) = 270 K in the presence of a 1600 Oe optimum field. This journal is © The Royal Society of Chemistry 2012

Kramers non-magnetic superconductivity in LnNiAsO superconductors.

Science.gov (United States)

Li, Yuke; Luo, Yongkang; Li, Lin; Chen, Bin; Xu, Xiaofeng; Dai, Jianhui; Yang, Xiaojun; Zhang, Li; Cao, Guanghan; Xu, Zhu-an

2014-10-22

We investigated a series of nickel-based oxyarsenides LnNiAsO (Ln=La, Ce, Pr, Nd, Sm) compounds. CeNiAsO undergoes two successive anti-ferromagnetic transitions at TN1=9.3 K and TN2=7.3 K; SmNiAsO becomes an anti-ferromagnet below TN≃3.5 K; NdNiAsO keeps paramagnetic down to 2 K but orders anti-ferromagnetically below TN≃1.3 K. Superconductivity was observed only in Kramers non-magnetic LaNiAsO and PrNiAsO with Tc=2.7 K and 0.93 K, respectively. The superconductivity of PrNiAsO is further studied by upper critical field and specific heat measurements, which reveal that PrNiAsO is a weakly coupled Kramers non-magnetic superconductor. Our work confirms that the nickel-based oxyarsenide superconductors are substantially different in mechanism to iron-based ones, and are likely to be described by the conventional superconductivity theory.

Thermal decomposition of heavy rare-earth butanoates, Ln(C₃H₇CO₂)₃ (Ln = Er, Tm, Yb and Lu) in argon

DEFF Research Database (Denmark)

Grivel, Jean-Claude; Yue, Zhao; Tang, Xiao

2016-01-01

was observed in all four compounds, but its course depends on the rare-earth element. Decomposition to sesquioxides proceeds via the formation of dioxymonocarbonates (Ln2O2CO3) and release of 4-heptanone (C3H7COC3H7) as well as carbon dioxide (CO2) without evidence for an intermediate oxobutanoate stage...... of Ln2O2CO3 and Ln2O3. The stability of this intermediate state seems to decrease with the mass of the rare-earth elements. Complete conversion to Ln2O3 is reached at about 1100 °C. The overall thermal decomposition behaviour of the title compounds is different from previous reports for other rare....... During the decomposition of Ln2O2CO3 into the respective sesquioxides (Ln2O3), an intermediate plateau extending from approximately 550 to 850 °C appears in the TG traces. The overall composition during this stage corresponds approximately to Ln2O2.8(CO3)0.2, but the state is more probably a mixture...

Hydrothermal synthesis and photoluminescent properties of hierarchical GdPO4·H2O:Ln3+ (Ln3+ = Eu3+, Ce3+, Tb3+) flower-like clusters

Science.gov (United States)

Amurisana, Bao.; Zhiqiang, Song.; Haschaolu, O.; Yi, Chen; Tegus, O.

2018-02-01

3D hierarchical GdPO4·H2O:Ln3+ (Ln3+ = Eu3+, Ce3+, Tb3+) flower clusters were successfully prepared on glass slide substrate by a simple, economical hydrothermal process with the assistance of disodium ethylenediaminetetraacetic acid (Na2H2L, where L4- = (CH2COO)2N(CH2)2N(CH2COO)24-). In this process, Na2H2L was used as both a chelating agent and a structure-director. The hierarchical flower clusters have an average diameter of 7-12 μm and are composed of well-aligned microrods. The influence of the molar ratio of Na2H2L/Gd3+ and reaction time on the morphology was systematically studied. A possible crystal growth and formation mechanism of hierarchical flower clusters is proposed based on the evolution of morphology as a function of reaction time. The self-assembled GdPO4·H2O:Ln3+ superstructures exhibit strong orange-red (Eu3+, 5D0 → 7F1), green (Tb3+, 5D4 → 7F5) and near ultraviolet emissions (Ce3+, 5d → 7F5/2) under ultraviolet excitation, respectively. This study may provide a new channel for building hierarchically superstructued oxide micro/nanomaterials with optical and new properties.

Generation of H{sub 2} and CO by solar thermochemical splitting of H{sub 2}O and CO{sub 2} by employing metal oxides

Energy Technology Data Exchange (ETDEWEB)

Rao, C.N.R., E-mail: cnrrao@jncasr.ac.in; Dey, Sunita

2016-10-15

Generation of H{sub 2} and CO by splitting H{sub 2}O and CO{sub 2} respectively constitutes an important aspect of the present-day concerns with energy and environment. The solar thermochemical route making use of metal oxides is a viable means of accomplishing these reduction reactions. The method essentially involves reducing a metal oxide by heating and passing H{sub 2}O or CO{sub 2} over the nonstoichiometric oxide to cause reverse oxidation by abstracting oxygen from H{sub 2}O or CO{sub 2}. While ceria, perovskites and other oxides have been investigated for this purpose, recent studies have demonstrated the superior performance of perovskites of the type Ln{sub 1−x}A{sub x}Mn{sub 1−y}M{sub y}O{sub 3} (Ln=rare earth, A=alkaline earth, M=various +2 and +3 metal ions), in the thermochemical generation of H{sub 2} and CO. We present the important results obtained hitherto to point out how the alkaine earth and the Ln ions, specially the radius of the latter, determine the performance of the perovskites. The encouraging results obtained are exemplefied by Y{sub 0.5}Sr{sub 0.5}MnO{sub 3} which releases 483 µmol/g of O{sub 2} at 1673 K and produces 757 µmol/g of CO from CO{sub 2} at 1173 K. The production of H{sub 2} from H{sub 2}O is also quite appreciable. Modification of the B site ion of the perovskite also affects the performance. In addition to perovskites, we present the generation of H{sub 2} based on the Mn{sub 3}O{sub 4}/NaMnO{sub 2} cycle briefly. - Graphical abstract: Ln{sub 0.5}A{sub 0.5}Mn{sub 1−x}M{sub x}O{sub 3} (Ln=lanthanide; A=Ca, Sr; M=Al, Ga, Sc, Mg, Cr, Fe, Co) perovskites are employed for the two step thermochemical splitting of CO{sub 2} and H{sub 2}O for the generation of CO and H{sub 2}. - Highlights: • Perovskite oxides based on Mn are ideal for the two-step thermochemical splitting of CO{sub 2} and H{sub 2}O. • In Ln{sub 1−x}A{sub x}MnO{sub 3} perovskite (Ln=rare earth, A=alkaline earth) both Ln and A ions play major roles

Synthesis and Structures of Two Lanthanide Complexes Containing a Mixed Ligand System: [Ln(Phen)2(L)3(HL)]·H2O [Ln = La, Ce; Phen = Phenanthroline; HL = Salicylic Acid

International Nuclear Information System (INIS)

Iravani, Effat; Nami, Navabeh; Nabizadeh, Fatemeh; Bayani, Elham; Neumueller, Bernhard

2013-01-01

The reaction of LnCl 3 ·7H 2 O [Ln = La (1), Ce (2)] with salicylic acid (HL) and 1,10-phenanthroline (Phen) at 20 .deg. C in H 2 O/ethanol gave after work-up and recrystallization two novel lanthanide complexes with general formula [Ln(Phen) 2 (L) 3 (HL)]·H 2 O. Compounds 1 and 2 were characterized by IR and UV-Vis spectroscopy, TGA, CHN as well as by X-ray analysis. According to these results, compounds 1 and 2 are isostructural and contain Ln 3+ ions with coordination number nine. Complexes 1 and 2 consist of two Phen, one neutral HL and three L anions (two L anions act as monodentate ligands and the third one is chelating to Ln 3+ ). Thermal decomposition led to primary loss of the Phen molecules. Then HL molecules and finally L moieties left the material to give Ln 2 O 3

A series of noncentrosymmetric antimony sulfides Ln{sub 8}Sb{sub 2}S{sub 15} (Ln = La, Pr, Nd) - syntheses, crystal and electronic structures, and NLO properties

Energy Technology Data Exchange (ETDEWEB)

Zhao, Hua-Jun [Laboratory of Applied Research on the Characteristic Resources in the North of Guizhou Province, School of Chemistry and Chemical Engineering, Zunyi Normal College, Guizhou (China); State Key Laboratory of Structural Chemistry, Fujian Institute of Research on the Structure of Matter, Chinese Academy of Sciences, Fuzhou (China); Zhou, Liu-Jiang [State Key Laboratory of Structural Chemistry, Fujian Institute of Research on the Structure of Matter, Chinese Academy of Sciences, Fuzhou (China)

2015-02-15

A series of noncentrosymmetric sulfides Ln{sub 8}Sb{sub 2}S{sub 15} (Ln = La, Pr, Nd) were prepared from stoichiometric mixtures of the elements at 1223 K in an evacuated silica tube. The compounds Ln{sub 8}Sb{sub 2}S{sub 15} with Ln = La and Nd are isostructural to Pr{sub 8}Sb{sub 2}S{sub 15} and crystallize in the tetragonal noncentrosymmetric space group I4{sub 1}cd. Their structure contains discrete [SbS{sub 3}]{sup 3-} trigonal pyramids separated by Ln{sup 3+} cations and S{sup 2-} anions. La{sub 8}Sb{sub 2}S{sub 15} shows second harmonic generation with intensities 1.2 times that of the commercially used IR NLO (nonlinear optics) material AgGaS{sub 2} (at 2.05 μm laser). It exhibits excellent thermal stability up to 663 C. Studies with UV/Vis-NIR diffuse reflectance spectroscopy show that La{sub 8}Sb{sub 2}S{sub 15} has an optical gap of around 2.3 eV, and a DFT study indicates a direct band gap with an electronic transfer excitation of S 3p electrons to a La 5d orbital. (Copyright copyright 2015 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim)

Synthesis, structure, and polymorphism of A{sub 3}LnSi{sub 2}O{sub 7} (A=Na, K; Ln=Sm, Ho, Yb)

Energy Technology Data Exchange (ETDEWEB)

Latshaw, Allison M.; Yeon, Jeongho; Smith, Mark D.; Loye, Hans-Conrad zur, E-mail: zurloye@mailbox.sc.edu

2016-03-15

Four new members of the A{sub 3}LnSi{sub 2}O{sub 7} family, K{sub 3}SmSi{sub 2}O{sub 7}, Na{sub 3}HoSi{sub 2}O{sub 7}, and two polymorphs of Na{sub 3}YbSi{sub 2}O{sub 7}, are reported. K{sub 3}SmSi{sub 2}O{sub 7} crystallizes in the hexagonal space group P6{sub 3}/mcm, Na{sub 3}HoSi{sub 2}O{sub 7} and Na{sub 3}YbSi{sub 2}O{sub 7} crystallize in the hexagonal space group P6{sub 3}/m, and Na{sub 3}YbSi{sub 2}O{sub 7} crystallizes in the trigonal space group P31c. The Na{sub 3}YbSi{sub 2}O{sub 7} composition that crystallizes in P31c is a new structure type. The magnetic properties for the Ho and Yb analogs are reported. - Graphical abstract: The different structure types and polymorphs of the A{sub 3}LnSi{sub 2}O{sub 7} family reported. - Highlights: • Four new members of the A{sub 3}LnSi{sub 2}O{sub 7} family are presented. • Na{sub 3}YbSi{sub 2}O{sub 7} is reported as two polymorphs, one is a new structure type. • Crystals synthesized out of molten fluoride fluxes.

Structure of trihydrated rare-earth acid diphosphates LnHP2O7·3H2O (Ln=La, Er)

International Nuclear Information System (INIS)

Ben Moussa, S.; Ventemillas, S.; Cabeza, A.; Gutierrez-Puebla, E.; Sanz, J.

2004-01-01

In trihydrated lanthanum acid-diphosphates LnHP 2 O 7 ·3H 2 O, prepared from acid LnCl 3 and Na 4 P 2 O 7 solutions (pH=1), two crystal forms were obtained. Layered structures of two representative members of this family have been determined by single-crystal X-ray diffraction (XRD) technique. In the case of orthorhombic LaHP 2 O 7 ·3H 2 O (type I), lanthanum cations are ninefold coordinated and diphosphate groups adopt a staggered (alternated) configuration. In the case of triclinic ErHP 2 O 7 ·3H 2 O (type II), erbium cations are eightfold coordinated and diphosphate groups adopt an eclipsed configuration. In agreement with Infrared (IR) spectroscopic data, a bended configuration for diphosphate groups has been deduced. In both structures, one-dimensional chains of edge-sharing rare-earth polyhedra are linked together by diphosphate groups to form the phosphate layers. In both diphosphates, PO 4 and HPO 4 environments have been identified by 31 P MAS-NMR technique. In the two compounds, OH groups of HPO 4 tetrahedra point out of diphosphate planes interacting with adjacent layers. In La-diphosphate, the interaction between HPO 4 groups and water molecules of adjacent layers is favored; however, in Er-diphosphate, the interaction between phosphate acid groups of contiguous layers is produced. Based on structural information deduced, differences detected in IR and NMR spectra of two disphosphates are discussed

Solvothermal syntheses, crystal structures, and properties of lanthanide(III) thioarsenates [Ln(dien){sub 2}(μ-1κ,2κ{sup 2}-AsS{sub 4})]{sub n} (Ln==Sm, Eu, Gd) and [Ln(dien){sub 2}(1κ{sup 2}-AsS{sub 4})] (Ln==Tb, Dy, Ho)

Energy Technology Data Exchange (ETDEWEB)

Wang, Fang; Tang, Chunying; Chen, Ruihong; Zhang, Yong; Jia, Dingxian, E-mail: jiadingxian@suda.edu.cn

2013-10-15

Solvothermal reactions of Ln{sub 2}O{sub 3}, As and S in diethylenetriamine (dien) at 170 °C for 6 days afforded two structural types of lanthanide thioarsenates with the general formulae [Ln(dien){sub 2}(μ-1κ,2κ{sup 2}-AsS{sub 4})]{sub n} [Ln=Sm(1), Eu(2), Gd(3)] and [Ln(dien){sub 2}(1κ{sup 2}-AsS{sub 4})] [Ln=Tb(4), Dy(5), Ho(6)]. The Ln{sub 2}O{sub 3} oxides were converted to [Ln(dien){sub 2}]{sup 3+} complex units in the solvothermal reactions. The As atom binds four S atoms, forming a tetrahedral AsS{sub 4} unit. In 1−3, the AsS{sub 4} units interconnect the [Ln(dien){sub 2}]{sup 3+} cations via Ln−S bonds as tridentate μ-1κ,2κ{sup 2}-AsS{sub 4} bridging ligands, resulting in the neutral coordination polymers [Ln(dien){sub 2}(μ-1κ,2κ{sup 2}-AsS{sub 4})]{sub n} (Ln1). In 4−6, the AsS{sub 4} units coordinate with the Ln{sup 3+} ion of [Ln(dien){sub 2}]{sup 3+} as 1κ{sup 2}-AsS{sub 4} chelating ligands to form neutral coordination compounds [Ln(dien){sub 2}(1κ{sup 2}-AsS{sub 4})] (Ln2). The Ln{sup 3+} ions are in nine- and eight-coordinated environments in Ln1 and Ln2, respectively. The formation of Ln1 and Ln2 is related with ionic size of the Ln{sup 3+} ions. Optical absorption spectra showed that 1−6 have potential use as semiconductors with the band gaps in the range 2.18−3.21 eV. - Graphical abstract: Two types of Ln-thioarsenates [Ln(dien){sub 2}(μ-1κ,2κ{sup 2}-AsS{sub 4})]{sub n} and [Ln(dien){sub 2}(1κ{sup 2}-AsS{sub 4})] were prepared by solvothermal methods and the soft Lewis basic AsS{sub 4}{sup 3–} ligand to Ln(III) centers with polyamine co-ligand was obtained. Display Omitted - Highlights: • Lanthanide thioarsenates were prepared by solvothermal methods. • The soft Lewis basic AsS{sub 4} ligand coordinate Ln{sup 3+} ions with coexistence polyamine ligands. • Two structural types of Ln-thioarsenates with structural turnover at Tb were obtained along Ln series. • The Ln-thioarsenates are potential semiconductors

Studies on the Ln/sub 2/O/sub 3/ (Ln: rare-earth elements)-SrO-V/sub 2/O/sub 3/ system, 2. Some physical properties for Ln sub(1-x)Sr sub(x)VO sub(3-0. 1x) and SrO. Ln sub(1-x)Sr sub(x)VO sub(3-0. 1x) (Ln: Nd or Eu)

Energy Technology Data Exchange (ETDEWEB)

Shin-ike, T [Osaka Dental Coll., Hirakata (Japan); Adachi, G; Shiokawa, J

1981-01-01

Electrical and magnetic properties of the perovskite type solid solutions, Ln sub(1-x)Sr sub(x)VO sub(3-0.1x) (Ln: Nd or Eu), and the K/sub 2/NiF/sub 4/ type solid solutions, SrO.Ln sub(1-x)Sr sub(x)VO sub(3-0.1x) (Ln: Nd or Eu), were studied in the temperature range 77 - 300 K. The electrical conductivity increased with x for the perovskite type solid solutions and the reverse behavior was observed for the K/sub 2/NiF/sub 4/ type compounds. All the solid solutions examined exhibited a metal-insulator transition at some values of x. Both Nd sub(1-x)Sr sub(x)VO sub(3-0.1x) and Eu sub(1-x)Sr sub(x)VO sub(3-0.1x) were antiferromagnets having a weak ferromagnetism at a low value of x at a low temperature. The K/sub 2/NiF/sub 4/ type solid solutions revealed a weak ferromagnetism at a high value of x at a low temperature.

Monodisperse and core-shell structured SiO{sub 2}-Lu{sub 2}O{sub 3}:Ln{sup 3+} (Ln=Eu, Tb, Dy, Sm, Er, Ho, and Tm) spherical particles: A facile synthesis and luminescent properties

Energy Technology Data Exchange (ETDEWEB)

Xu, Zhenhe, E-mail: xuzh056@163.com [College of Applied Chemistry, Shenyang University of Chemical Technology, Shenyang 100142 (China); Feng, Bin [China National Aviation Fuel Group Corporation, Planning and Development Department, Beijing 100088 (China); Bian, Shasha; Liu, Tao; Wang, Mingli; Gao, Yu; Sun, Di; Gao, Xin [College of Applied Chemistry, Shenyang University of Chemical Technology, Shenyang 100142 (China); Sun, Yaguang, E-mail: yaguangsun@yahoo.com.cn [College of Applied Chemistry, Shenyang University of Chemical Technology, Shenyang 100142 (China)

2012-12-15

The core-shell structured SiO{sub 2}-Lu{sub 2}O{sub 3}:Ln{sup 3+} particles were realized by coating the Lu{sub 2}O{sub 3}:Ln{sup 3+} phosphors onto the surface of non-aggregated, monodisperse and spherical SiO{sub 2} particles by the Pechini sol-gel method. The as-synthesized products were characterized by X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FT-IR), energy-dispersive X-ray (EDX) spectra, scanning electron microscopy (SEM), transmission electron microscopy (TEM), high-resolution transmission electron microscopy (HRTEM), photolumiminescence (PL), and low-voltage cathodoluminescence (CL). The results indicate that the 800 Degree-Sign C annealed sample consists of crystalline Lu{sub 2}O{sub 3} shells and amorphous SiO{sub 2} cores, in spherical shape with a narrow size distribution. The as-obtained particles show strong light emission with different colors corresponding to different Ln{sup 3+} ions under ultraviolet-visible light excitation and low-voltage electron beams excitation, which have potential applications in fluorescent lamps and field emission displays. - Graphical Abstract: Representative SEM and TEM images of the core-shell structured SiO{sub 2}-Lu{sub 2}O{sub 3}:Eu{sup 3+} particles; CIE chromaticity diagram showing the emission colors for SiO{sub 2}-Lu{sub 2}O{sub 3}:Ln{sup 3+}; Multicolor emissions of SiO{sub 2}-Lu{sub 2}O{sub 3}:Ln{sup 3+} particles. Highlights: Black-Right-Pointing-Pointer The core-shell particles were realized by coating the phosphors onto the surface of SiO{sub 2} particles. Black-Right-Pointing-Pointer The sample consists of crystalline Lu{sub 2}O{sub 3} shells and amorphous SiO{sub 2} cores. Black-Right-Pointing-Pointer The particles show different light emission colors corresponding to Ln{sup 3+} ions. Black-Right-Pointing-Pointer They have potential applications in fluorescent lamps and field emission displays.

Topotactic dehydration of the lamellar oxide HK2Ti5NbO14 x H2O: the oxide K4Ti10Nb2O27

International Nuclear Information System (INIS)

Grandin, A.; Borel, M.M.; Hervieu, M.; Raveau, B.

1987-01-01

The lamellar oxide HK 2 Ti 5 NbO 14 x H 2 O can be topotactically dehydrated to K 4 Ti 10 Nb 2 O 27 . Electron diffraction and X-ray diffraction studies of this phase lead to a monoclinic cell with the parameters a = 17.005, b = 3.78, c = 9.01 A and β 92.14 0 . Diffusion streaks on the electron diffraction patterns indicate disorder whereas the existence of two sets of lattices on the same crystal give evidence of the topotactic character of the reaction. A structural model is proposed for K 4 Ti 10 Nb 2 O 27 , which corresponds to the intergrowth of K 3 TiNbO 14 layers with the K 2 Ti 6 O 13 tunnel structure. The possibility of formation of various intergrowths such as (KTi 5 NbO 13 )/sub n/ (HK 2 Ti 5 NbO 14 )/sub n/' is suggested

Comparative magnetic studies of (Sm, Nd) trichloroacetates and their heteronuclear CuLn2(CCl3COO)8.6H2O systems: structure and spectroscopy of a new type of Eu trichloroacetate

International Nuclear Information System (INIS)

Wojciechowski, W.; Legendziewicz, J.; Puchalska, M.; Ciunik, Z.

2004-01-01

Two series of compounds: heteronuclear CuLn 2 (CCl 3 COO) 8 .6H 2 O (Ln = Nd and Sm) and their simple analogues Ln(CCl 3 COO) 3 .2H 2 O (Ln = Eu, Nd, Sm) were synthesized. New Eu(III) trichloroacetate; Eu(CCl 3 COO) 3 .3H 2 O.CH 3 OH was obtained, its molecular structure was determined by X-ray diffraction and compared with the data of respective systems reported earlier. Magnetization was measured and the susceptibility was derived in the limit of low field. Magnetic susceptibilities were calculated and discussed for series of homo- and hetero-nuclear chloroacetates.Untypical hysteresis was found (two loops) in samarium trichloroacetate. This phenomenon is most probably the effect of flops of spins in magnetic fields of 30,000Oe and very weak (if any) interaction intermediated by weak hydrogen bonding between the chains. A similar magnetic behavior was observed in neodymium carboxylate where the magnetic ordering was observed as a result of Nd-Nd interaction at low temperature (1.6K). For this system, the magnetic moment depends on magnitude of the magnetic field and ferromagnetic ordering appears at low temperatures. The strongest interactions of coupled ions and antiferromagnetic ordering with T N =6.5K were found in CuSm 2 (CCl 3 COO) 8 .6H 2 O single crystals.Heisenberg model was applied in the calculations for three interacting ions located linearly. The following relation was derived: χ M =Ng 2 μ β 2 kT(12)+(12)exp(J 2 /kT)+5exp(J 2 /kT)-exp(1,5J 1 /kT)2+2exp(J 2 /kT)+4exp(J 2 /kT)-exp(1,5J 1 /kT) and applied in calculations of the exchange integrals. Mechanism of the exchange interaction was discussed on the basis of the obtained results.

Capacitor Property and Leakage Current Mechanism of ZrO2 Thin Dielectric Films Prepared by Anodic Oxidation

Science.gov (United States)

Kamijyo, Masahiro; Onozuka, Tomotake; Shinkai, Satoko; Sasaki, Katsutaka; Yamane, Misao; Abe, Yoshio

2003-07-01

Polycrystalline ZrO2 thin film capacitors were prepared by anodizing sputter-deposited Zr films. Electrical measurements are performed for the parallel-plate anodized capacitors with an Al-ZrO2-Zr (metal-insulator-metal) structure, and a high capacitance density (0.6 μF/cm2) and a low dielectric loss of nearly 1% are obtained for a very thin-oxide capacitor anodized at 10 V. In addition, the leakage current density of this capacitor is about 1.8 × 10-8 A/cm2 at an applied voltage of 5 V. However, the leakage current is somewhat larger than that of a low-loss HfO2 capacitor. The leakage current density (J) of ZrO2 capacitors as a function of applied electric field (E) was investigated for several capacitors with different oxide thicknesses, by plotting \\ln(J) vs E1/2 curves. As a result, it is revealed that the conduction mechanism is due to the Poole-Frenkel effect, irrespective of the oxide thickness.

High-Pressure Synthesis and Characterization of the Ammonium Yttrium Borate (NH4)YB8O14.

Science.gov (United States)

Schmitt, Martin K; Podewitz, Maren; Liedl, Klaus R; Huppertz, Hubert

2017-11-20

The first high-pressure yttrium borate (NH 4 )YB 8 O 14 was synthesized at 12.8 GPa/1300 °C using a Walker-type multianvil module. The compound crystallizes in the orthorhombic space group Pnma (no. 62) with the lattice parameters a = 17.6375(9), b = 10.7160(5), and c = 4.2191(2) Å. (NH 4 )YB 8 O 14 constitutes a novel structure type but exhibits similarities to the crystal structure of β-BaB 4 O 7 . X-ray single-crystal and powder diffraction, EDX, vibrational spectroscopy as well as quantum chemical calculations were used to characterize (NH 4 )YB 8 O 14 .

Magnetic properties of Aurivillius lanthanide-bismuth (LnFeO3nBi4Ti3O12 (n = 1,2 layered titanates

Directory of Open Access Journals (Sweden)

Tartaj, J.

2008-06-01

Full Text Available Bismuth titanates of Aurivillius layer-structure (BiFeO3nBi4Ti3O12, are of great technological interest because of their applications as non-volatile ferroelectric memories and high-temperature piezoelectric materials. The synthesis and crystallographic characterization of a new family of compounds (LnFeO3nBi4Ti3O12 was recently reported, in which the layers consist of LnFeO3 perovskites with a lanthanide Ln3+ substituting diamagnetic Bi3+. We report herein the magnetic properties of bulk samples, with Ln = Nd, Eu, Gd and Tb, and n = 1 and 2. Single-layer materials are paramagnetic, similar to non-substituted bismuth titanate Bi5FeTi3O15, and show crystal field effects due to the crystallographic environment of Eu3+ and Tb3+. Several anomalies are detected in the magnetization M(T of double-layer (LnFeO32Bi4Ti3O12 compounds, related to the strong magnetism of Tb and Gd, since they weakly appear for Nd and they are absent in the VanVleck Eu3+ ion and in the parent Bi6Fe2Ti3O18 compound.Los titanatos de hierro y bismuto con estructura laminar tipo Aurivillius, (BiFeO3nBi4Ti3O12, tienen un gran interés tecnológico debido a sus aplicaciones como memorias ferroeléctricas no volátiles y como piezoeléctrico cerámico de alta temperatura. La síntesis y la caracterización cristalina de una nueva familia de compuestos (LnFeO3nBi4Ti3O12 han sido recientemente reportadas, en la que el catión diamagnético Bi3+ ha sido sustituido por los paramagnéticos Ln3+ en los bloques de perovskita. Se estudian las propiedades magnéticas de muestras cerámicas en volumen con Ln = Nd, Eu, Gd y Tb, y n = 1 y 2. Los materiales con n=1 son paramagnéticos y similares al no sustituido Bi5FeTi3O15, y muestran efectos de campo cristalino debido al entorno cristalino de Eu3+ y Tb3+. Se han detectado algunas anomalías en la magnetización M(T de los compuestos n=2 (LnFeO32Bi4Ti3O12 que están relacionadas con el fuerte magnetismo de Tb y Gd, que aparecen d

Synthesis and Structures of Two Lanthanide Complexes Containing a Mixed Ligand System: [Ln(Phen){sub 2}(L){sub 3}(HL)]·H{sub 2}O [Ln = La, Ce; Phen = Phenanthroline; HL = Salicylic Acid

Energy Technology Data Exchange (ETDEWEB)

Iravani, Effat [UNiv. of Applied Science and Technology, Tehran (Iran, Islamic Republic of); Nami, Navabeh; Nabizadeh, Fatemeh; Bayani, Elham [Islamic Azad Univ., Mazandaran (Iran, Islamic Republic of); Neumueller, Bernhard [Philipps-Universitat Marburg, Marburg (Germany)

2013-11-15

The reaction of LnCl{sub 3}·7H{sub 2}O [Ln = La (1), Ce (2)] with salicylic acid (HL) and 1,10-phenanthroline (Phen) at 20 .deg. C in H{sub 2}O/ethanol gave after work-up and recrystallization two novel lanthanide complexes with general formula [Ln(Phen){sub 2}(L){sub 3}(HL)]·H{sub 2}O. Compounds 1 and 2 were characterized by IR and UV-Vis spectroscopy, TGA, CHN as well as by X-ray analysis. According to these results, compounds 1 and 2 are isostructural and contain Ln{sup 3+} ions with coordination number nine. Complexes 1 and 2 consist of two Phen, one neutral HL and three L anions (two L anions act as monodentate ligands and the third one is chelating to Ln{sup 3+}). Thermal decomposition led to primary loss of the Phen molecules. Then HL molecules and finally L moieties left the material to give Ln{sub 2}O{sub 3}.

The orthorhombic fluorite related compounds Ln/sub 3/RuO/sub 7/, Ln=Nd, Sm and Eu

International Nuclear Information System (INIS)

Van Berkel, F.P.F.; Ijdo, D.J.W.

1986-01-01

Fluorite-related Ru(V) compound with composition Ln/sub 3/RuO/sub 7/ have been found. These compounds with space group Cmcm adopt a superstructure of the cubic fluorite structure with a/sub orth/=2a/sub c/, b/sub orth/=c/sub orth/=a/sub c/√2. These compounds have the same structure as La/sub 3/NbO/sub 7/

Decanuclear Ln10 Wheels and Vertex-Shared Spirocyclic Ln5 Cores: Synthesis, Structure, SMM Behavior, and MCE Properties.

Science.gov (United States)

Das, Sourav; Dey, Atanu; Kundu, Subrata; Biswas, Sourav; Narayanan, Ramakirushnan Suriya; Titos-Padilla, Silvia; Lorusso, Giulia; Evangelisti, Marco; Colacio, Enrique; Chandrasekhar, Vadapalli

2015-11-16

The reaction of a Schiff base ligand (LH3) with lanthanide salts, pivalic acid and triethylamine in 1:1:1:3 and 4:5:8:20 stoichiometric ratios results in the formation of decanuclear Ln10 (Ln = Dy (1), Tb (2), and Gd (3)) and pentanuclear Ln5 complexes (Ln = Gd (4), Tb (5), and Dy (6)), respectively. The formation of Ln10 and Ln5 complexes are fully governed by the stoichiometry of the reagents used. Detailed magnetic studies on these complexes (1-6) have been carried out. Complex 1 shows a SMM behavior with an effective energy barrier for the reversal of the magnetization (Ueff) = 16.12(8) K and relaxation time (τo) = 3.3×10(-5) s under 4000 Oe direct current (dc) field. Complex 6 shows the frequency dependent maxima in the out-of-phase signal under zero dc field, without achieving maxima above 2 K. Complexes 3 and 4 show a large magnetocaloric effect with the following characteristic values: -ΔSm = 26.6 J kg(-1) K(-1) at T = 2.2 K for 3 and -ΔSm = 27.1 J kg(-1) K(-1) at T = 2.4 K for 4, both for an applied field change of 7 T. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Effect of crystalline electric field on heat capacity of LnBaCuFeO5 (Ln = Gd, Ho, Yb)

Science.gov (United States)

Lal, Surender; Mukherjee, K.; Yadav, C. S.

2018-02-01

Structural, magnetic and thermodynamic properties of layered perovskite compounds LnBaCuFeO5 (Ln = Ho, Gd, Yb) have been investigated. Unlike the iso-structural compound YBaCuFeO5, which shows commensurate antiferromagnetic to incommensurate antiferromagnetic ordering below ∼200 K, the studied compounds do not show any magnetic transition in measured temperature range of 2-350 K. The high temperature heat capacity of the compounds is understood by employing contributions from both optical and acoustic phonons. At low temperature, the observed upturn in the heat capacity is attributed to the Schottky anomaly. The magnetic field dependent heat capacity shows the variation in position of the anomaly with temperature, which appears due to the removal of ground state degeneracy of the rare earth ions, by the crystalline electric field.

Hetero-metallic {3d-4f-5d} complexes: preparation and magnetic behavior of trinuclear [(L(Me2)Ni-Ln){W(CN)(8)}] compounds (Ln = Gd, Tb, Dy, Ho, Er, Y; L(Me2) = Schiff base) and variable SMM characteristics for the Tb derivative.

Science.gov (United States)

Sutter, Jean-Pascal; Dhers, Sébastien; Rajamani, Raghunathan; Ramasesha, S; Costes, Jean-Pierre; Duhayon, Carine; Vendier, Laure

2009-07-06

Assembling bimetallic {Ni-Ln}(3+) units and {W(CN)(8)}(3-) is shown to be an efficient route toward heteronuclear {3d-4f-5d} compounds. The reaction of either the binuclear [{L(Me2)Ni(H(2)O)(2)}{Ln(NO(3))(3)}] complexes or their mononuclear components [L(Me2)Ni] and Ln(NO(3))(3) with (HNBu(3))(3){W(CN)(8)} in dmf followed by diffusion of tetrahydrofuran yielded the trinuclear [{L(Me2)NiLn}{W(CN)(8)}] compounds 1 (Ln = Y), 2a,b (Gd), 3a,b (Tb), 4 (Dy), 5 (Ho), and 6 (Er) as crystalline materials. All of the derivatives possess the trinuclear core resulting from the linkage of the {W(CN)(8)} to the Ni center of the {Ni-Ln} unit. Differences are found in the solvent molecules acting as ligands and/or in the lattice depending on the crystallization conditions. For all the compounds ferromagnetic {Ni-W} and {Ni-Ln} (Ln = Gd, Tb, Dy, and Er} interactions are operative resulting in high spin ground states. Parameterization of the magnetic behaviors for the Y and Gd derivatives confirmed the strong cyano-mediated {Ni-W} interaction (J(NiW) = 27.1 and 28.5 cm(-1)) compared to the {Ni-Gd} interaction (J(NiGd) = 2.17 cm(-1)). The characteristic features for slow relaxation of the magnetization are observed for two Tb derivatives, but these are modulated by the crystal phase. Analysis of the frequency dependence of the alternating current susceptibility data yielded U(eff)/k(B) = 15.3 K and tau(0) = 4.5 x 10(-7) s for one derivative whereas no maxima of chi(M)'' appear above 2 K for the second one.

Bifunctional Zn(II)Ln(III) dinuclear complexes combining field induced SMM behavior and luminescence: enhanced NIR lanthanide emission by 9-anthracene carboxylate bridging ligands.

Science.gov (United States)

Palacios, María A; Titos-Padilla, Silvia; Ruiz, José; Herrera, Juan Manuel; Pope, Simon J A; Brechin, Euan K; Colacio, Enrique

2014-02-03

There were new dinuclear Zn(II)-Ln(III) complexes of general formulas [Zn(μ-L)(μ-OAc)Ln(NO3)2] (Ln(III) = Tb (1), Dy (2), Er (3), and Yb (4)), [Zn(μ-L)(μ-NO3)Er(NO3)2] (5), [Zn(H2O)(μ-L)Nd(NO3)3]·2CH3OH (6), [Zn(μ-L)(μ-9-An)Ln(NO3)2]·2CH3CN (Ln(III) = Tb (7), Dy (8), Er (9), Yb(10)), [Zn(μ-L)(μ-9-An)Yb(9-An)(NO3)3]·3CH3CN (11), [Zn(μ-L)(μ-9-An)Nd(9-An)(NO3)3]·2CH3CN·3H2O (12), and [Zn(μ-L)(μ-9-An)Nd(CH3OH)2(NO3)]ClO4·2CH3OH (13) prepared from the reaction of the compartmental ligand N,N',N″-trimethyl-N,N″-bis(2-hydroxy-3-methoxy-5-methylbenzyl)diethylenetriamine (H2L), with ZnX2·nH2O (X = NO3(-) or OAc(-)) salts, Ln(NO3)3·nH2O, and, in some instances, 9-anthracenecarboxylate anion (9-An). In all these complexes, the Zn(II) ions invariably occupy the internal N3O2 site whereas the Ln(III) ions show preference for the O4 external site, giving rise to a Zn(μ-diphenoxo)Ln bridging fragment. Depending on the Zn(II) salt and solvent used in the reaction, a third bridge can connect the Zn(II) and Ln(III) metal ions, giving rise to triple-bridged diphenoxoacetate in complexes 1-4, diphenoxonitrate in complex 5, and diphenoxo(9-anthracenecarboxylate) in complexes 8-13. Dy(III) and Er(III) complexes 2, 8 and 3, 5, respectively, exhibit field induced single molecule magnet (SMM) behavior, with Ueff values ranging from 11.7 (3) to 41(2) K. Additionally, the solid-state photophysical properties of these complexes are presented showing that ligand L(2-) is able to sensitize Tb(III)- and Dy(III)-based luminescence in the visible region through an energy transfer process (antenna effect). The efficiency of this process is much lower when NIR emitters such as Er(III), Nd(III), and Yb(III) are considered. When the luminophore 9-anthracene carboxylate is incorporated into these complexes, the NIR luminescence is enhanced which proves the efficiency of this bridging ligand to act as antenna group. Complexes 2, 3, 5, and 8 can be considered as dual materials

Highly efficient extraction and oxidative desulfurization system using Na7H2LaW10O36⋅32 H2O in [bmim]BF4 at room temperature.

Science.gov (United States)

Xu, Junhua; Zhao, Shen; Chen, Wei; Wang, Miao; Song, Yu-Fei

2012-04-10

Highly efficient, deep desulfurization of model oil containing dibenzothiophene (DBT), benzothiophene (BT), or 4,6-dimethyldibenzothiophene (4,6-DMDBT) has been achieved under mild conditions by using an extraction and catalytic oxidative desulfurization system (ECODS) in which a lanthanide-containing polyoxometalate Na(7)H(2)LnW(10)O(36)⋅32 H(2)O (LnW(10); Ln = Eu, La) acts as catalyst, [bmim]BF(4) (bmim = 1-butyl-3-methylimidazolium) as extractant, and H(2)O(2) as oxidant. Sulfur removal follows the order DBT>4,6-DMDBT>BT at 30 °C. DBT can be completely oxidized to the corresponding sulfone in 25 min under mild conditions, and the LaW(10)/[bmim]BF(4) system could be recycled for ten times with only slight decrease in activity. Thus, LaW(10) in [bmim]BF(4) is one of the most efficient systems for desulfurization using ionic liquids as extractant reported so far. Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

α-ScVSe2O8, β-ScVSe2O8, and ScVTe2O8: new quaternary mixed metal oxides composed of only second-order Jahn-Teller distortive cations.

Science.gov (United States)

Kim, Yeong Hun; Lee, Dong Woo; Ok, Kang Min

2013-10-07

Three new quaternary scandium vanadium selenium/tellurium oxides, α-ScVSe2O8, β-ScVSe2O8, and ScVTe2O8 have been synthesized through hydrothermal and standard solid-state reactions. Although all three reported materials are stoichiometrically similar, they exhibit different crystal structures: α-ScVSe2O8 has a three-dimensional framework structure consisting of ScO6, VO6, and SeO3 groups. β-ScVSe2O8 reveals another three-dimensional framework composed of ScO7, VO5, and SeO3 polyhedra. ScVTe2O8 shows a layered structure with ScO6, VO4, and TeO4 polyhedra. Interestingly, the constituent cations, that is, Sc(3+), V(5+), Se(4+), and Te(4+) are all in a distorted coordination environment attributable to second-order Jahn-Teller (SOJT) effects. Complete characterizations including infrared spectroscopy, elemental analyses, thermal analyses, dipole moment calculation, and the magnitudes of out-of-center distortions for the compounds are reported. Transformation reactions suggest that α-ScVSe2O8 may change to β-ScVSe2O8, and then to Sc2(SeO3)3·H2O under hydrothermal conditions.

Layered multinary lanthanum oxide [La-Mo-O]; Sojo rantan fukugo sankabutsu ni kansuru kenkyu

Energy Technology Data Exchange (ETDEWEB)

NONE

1997-10-31

Studies have been carried out systematically on properties of oxides including representative transition metal, vanadium, and alkali metals. With respect to Ln2CuO4 (Ln is a rare earth element) being a simple and representative rare earth multinary oxide showing superconductivity, and its related compounds, this paper reports thermal chemistry, superconduction, and making them a superconductor by using soft chemical treatment. The paper also reports centrally on synthesis of new copper oxide superconductors under high pressure, the compositions, structures, superconductive properties of the synthetics, and the relationship between them. It describes phase equilibrium, synthesis, and structures of vanadium multinary oxides being the object of continued studies, and also reports the studies related to structure and phase transfer of NaV6O11 which shows especially interesting properties among the oxides. Studies have also been made on NMR of these compounds and copper oxide superconductors by using magnetic resonance. The paper also describes a method to analyze the structure of quasi-crystal having rotary symmetry which is not allowed in crystals, and has special long-distance order phase. 209 refs., 127 figs., 6 tabs.

Síntesis hidrotermal de monocristales LnMn2O5 (Ln= Y, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho y Er

Directory of Open Access Journals (Sweden)

Señarís Rodríguez, M. A.

2008-08-01

Full Text Available Ten single crystals of the series LnMn2O5 (Ln= Y, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho and Er were synthesized by hydrothermal synthesis in a single step and without subsequent thermal treatments from aqueous solutions of metals salts at 240 ºC. The obtained single crystals have a size of various micrometers and their morphology changes throughout the serie: they are polygonal in the case of the compounds with Ln= Pr, Nd, Sm, Eu and Gd and needle-like in the case of the compounds with Ln= Y, Tb, Dy, Ho and Er. After the analysis of the obtained products employing different conditions of synthesis we attributed the different morphology to a greater growth rate along the c axis when the smaller ions (Y, Tb, Dy, Ho y Er are involved, due to their better adaptation to the compound’s crystal structure.Se han conseguido preparar monocristales de 10 óxidos mixtos de la serie LnMn2O5 (Ln= Y, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho y Er mediante síntesis hidrotermal optimizada, en un único paso y sin tratamientos térmicos posteriores partiendo de las correspondientes sales metálicas en disolución acuosa a 240 ºC. Los monocristales obtenidos son relativamente grandes, de varias micras y su morfología varía a lo largo de la serie: es poligonal en el caso de los compuestos de los lantánidos del inicio de la serie (Ln= Pr, Nd, Sm, Eu y Gd y acicular en el caso de los compuestos de Y y de los lantánidos del final de la serie (Ln= Tb, Dy, Ho y Er. Tras el análisis de los productos obtenidos empleando distintas condiciones de síntesis atribuimos la diferente morfología a una mayor velocidad de crecimiento cristalino a lo largo del eje c cuando intervienen los iones más pequeños (Y, Tb, Dy, Ho y Er debido a la mejor adaptación de éstos últimos a la estructura cristalina del compuesto.

Carbonato-bridged Ni(II)2Ln(III)2 (Ln(III) = Gd(III), Tb(III), Dy(III)) complexes generated by atmospheric CO2 fixation and their single-molecule-magnet behavior: [(μ4-CO3)2{Ni(II)(3-MeOsaltn)(MeOH or H2O)Ln(III)(NO3)}2]·solvent [3-MeOsaltn = N,N'-bis(3-methoxy-2-oxybenzylidene)-1,3-propanediaminato].

Science.gov (United States)

Sakamoto, Soichiro; Fujinami, Takeshi; Nishi, Koshiro; Matsumoto, Naohide; Mochida, Naotaka; Ishida, Takayuki; Sunatsuki, Yukinari; Re, Nazzareno

2013-06-17

Atmospheric CO2 fixation of [Ni(II)(3-MeOsaltn)(H2O)2]·2.5H2O [3-MeOsaltn = N,N'-bis(3-methoxy-2-oxybenzylidene)-1,3-propanediaminato], Ln(III)(NO3)3·6H2O, and triethylamine occurred in methanol/acetone, giving a first series of carbonato-bridged Ni(II)2Ln(III)2 complexes [(μ4-CO3)2{Ni(II)(3-MeOsaltn)(MeOH)Ln(III)(NO3)}2] (1Gd, 1Tb, and 1Dy). When the reaction was carried out in acetonitrile/water, it gave a second series of complexes [(μ4-CO3)2{Ni(II)(3-MeOsaltn)(H2O)Ln(III)(NO3)}2]·2CH3CN·2H2O (2Gd, 2Tb, and 2Dy). For both series, each Ni(II)2Ln(III)2 structure can be described as two di-μ-phenoxo-bridged Ni(II)Ln(III) binuclear units bridged by two carbonato CO3(2-) units to form a carbonato-bridged (μ4-CO3)2{Ni(II)2Ln(III)2} structure. The high-spin Ni(II) ion has octahedral coordination geometry, and the Ln(III) ion is coordinated by O9 donor atoms from Ni(II)(3-MeOsaltn), bidentate NO3(-), and one and two oxygen atoms of two CO3(2-) ions. The NO3(-) ion for the first series roughly lie on Ln-O(methoxy) bonds and are tilted toward the outside, while for the second series, the two oxygen atoms roughly lie on one of the Ln-O(phenoxy) bonds due to the intramolecular hydrogen bond. The temperature-dependent magnetic susceptibilities indicated a ferromagnetic interaction between the Ni(II) and Ln(III) ions (Ln(III) = Gd(III), Tb(III), Dy(III)) for all of the complexes, with a distinctly different magnetic behavior between the two series in the lowest-temperature region due to the Ln(III)-Ln(III) magnetic interaction and/or different magnetic anisotropies of the Tb(III) or Dy(III) ion. Alternating-current susceptibility measurements under the 0 and 1000 Oe direct-current (dc) bias fields showed no magnetic relaxation for the Ni(II)2Gd(III)2 complexes but exhibited an out-of-phase signal for Ni(II)2Tb(III)2 and Ni(II)2Dy(III)2, indicative of slow relaxation of magnetization. The energy barriers, Δ/kB, for the spin flipping were estimated from the Arrhenius

Structural evolution of bias sputtered LiNi0.5Mn1.5O4 thin film cathodes for lithium ion batteries

International Nuclear Information System (INIS)

Su, Shih-Hsuan; Chiu, Kuo-Feng; Leu, Hoang-Jyh

2014-01-01

LiNi 0.5 Mn 1.5 O 4 (LNMO) thin films have been deposited on stainless steel substrates using radio frequency (f = 13.56 MHz) magnetron sputtering, followed by thermal annealing in ambient atmosphere. Various negative biases were applied on the substrates during deposition. The structural evolution of LNMO thin films under different negative biases has been investigated and characterized by X-ray diffraction. All of the deposited films exhibit a crystalline spinel structure with a space group of Fd-3m, which is a so-called disordered phase. The results also indicate that particle size decreases with increasing negative bias. The electrochemical properties of the LNMO thin films as cathode materials for lithium ion batteries were investigated. Two distinctive voltage plateaus at ∼ 4.7 V and at ∼ 4.0 V (vs. Li + /Li) can be observed in the discharge curves, corresponding to the reactions of the disordered phase. The capacity of LNMO thin film electrodes under suitable negative bias can be optimized. - Highlights: • LiNi 0.5 Mn 1.5 O 4 thin films have been deposited on stainless steel substrates. • Various negative biases were applied on the substrates during deposition. • The particle sizes of LNMO thin films decrease with increasing negative bias

Gauthierite, KPb[(UO{sub 2}){sub 7}O{sub 5}(OH){sub 7}].8H{sub 2}O, a new uranyl-oxide hydroxy-hydrate mineral from Shinkolobwe with a novel uranyl-anion sheet-topology

Energy Technology Data Exchange (ETDEWEB)

Olds, Travis A. [Notre Dame Univ., IN (United States). Dept. of Civil and Environmental Engineering and Earth Sciences; Plasil, Jakub [ASCR, Prague (Czech Republic). Inst. of Physics; Kampf, Anthony R. [Natural History Museum of Los Angeles County, Los Angeles, CA (United States). Mineral Sciences Dept.; Skoda, Radek [Masaryk Univ., Brno (Czech Republic). Dept. of Geological Sciences; Burns, Peter C. [Notre Dame Univ., IN (United States). Dept. of Civil and Environmental Engineering and Earth Sciences; Notre Dame Univ., IN (United States). Dept. of Chemistry and Biochemistry,; Cejka, Jiri [National Museum, Prague (Czech Republic). Dept. of Mineralogy and Petrology; Bourgoin, Vincent; Boulliard, Jean-Claude [Pierre et Marie Curie Univ., Paris (France). Association Jean Wyart, Collection des Mineraux de Jussieu

2017-03-15

Gauthierite, KPb[(UO{sub 2}){sub 7}O{sub 5}(OH){sub 7}].8H{sub 2}O, is a new uranyl-oxide hydroxy-hydrate mineral from the Shinkolobwe Mine, Democratic Republic of Congo, Africa. It occurs on a matrix of uraninite-bearing quartz gangue associated with soddyite and a minor metazeunerite.metatorbernite series mineral. It is a product of oxidation.hydration weathering of uraninite. Gauthierite is monoclinic, P2{sub 1}/c, with a = 29.844(2) Aa, b = 14.5368(8) Aa, c = 14.0406(7) Aa, β = 103.708(6) , V = 5917.8(6)Aa{sup 3} and Z = 8. Prismatic crystals have pronounced lengthwise striations and reach about 1mm in length. Gauthierite is yellowish orange with a light orange streak and vitreous lustre. The Mohs hardness is ∝ 3 to 4. It is brittle with an uneven fracture and perfect cleavage on {0 1 0}. The calculated density based on the empirical formula is 5.437 g/cm{sup 3}. Optically, gauthierite is biaxial (-), with α = 1.780(5), β = 1.815(5), γ = 1.825(5) (white light), 2V{sub meas.} = 58(1) ; dispersion is extreme (r>>v). The optical orientation is X = b, Y∼a{sup *}, Z∼c (or X = b, Y and a=14 in obtuse β); it is pleochroic with X very pale yellow, Y and Z orange-yellow; X<O 1.29, PbO 7.17, UO{sub 3} 82.10, H{sub 2}O 8.78 (structure), total 99.34 wt.%. The empirical formula (based on 34 O a.p.f.u.) is: K{sub 0.67}Pb{sub 0.78}U{sub 7}O{sub 34}H{sub 23.77}. The ideal formula is KPb[(UO{sub 2}){sub 7}O{sub 5}(OH){sub 7}](H{sub 2}O){sub 8}, which requires K{sub 2}O 1.90, PbO 9.00, UO{sub 3} 80.74, H{sub 2}O 8.35, total 100 wt.%. Raman and infrared spectral data confirm the presence of UO{sub 2}{sup 2+}, OH{sup -} and molecular H{sub 2}O. The eight strongest powder X-ray diffraction lines are [d{sub obs} in Aa (hkl) I{sub rel}]: 7.28 (020,400) 49, 3.566 (040, -802, -204) 67, 3.192 (622, -224) 100, 2.541 (-842,-244) 18, 2.043 (406) 14, 2.001 (662,-264, 14.2.0) 23, 1.962 (426,-146) 14, and 1

Hydrothermal synthesis, structure, and optical properties of two nanosized Ln{sub 26} rate at CO{sub 3} (Ln=Dy and Tb) cluster-based lanthanide-transition-metal-organic frameworks (Ln MOFs)

Energy Technology Data Exchange (ETDEWEB)

Zhang, Yu; Huang, Lian; Miao, Hao; Wan, Hong Xiang; Mei, Hua; Liu, Ying [State Key Laboratory of Materials-Oriented Chemical Engineering, Nanjing Tech University (China); Xu, Yan [State Key Laboratory of Materials-Oriented Chemical Engineering, Nanjing Tech University (China); State Key Laboratory of Coordination Chemistry, Nanjing Tech University (China)

2015-02-16

Two Ln{sub 26} rate at CO{sub 3} (Ln=Dy and Tb) cluster-based lanthanide-transition-metal-organic frameworks (Ln MOFs) formulated as [Dy{sub 26}Cu{sub 3}(Nic){sub 24}(CH{sub 3}COO){sub 8}(CO{sub 3}){sub 11}(OH){sub 26}(H{sub 2}O){sub 14}]Cl . 3 H{sub 2}O (1; HNic=nicotinic acid) and [Tb{sub 26}NaAg{sub 3}(Nic){sub 27}(CH{sub 3}COO){sub 6}(CO{sub 3}){sub 11}(OH){sub 26}Cl(H{sub 2}O){sub 15}] . 7.5 H{sub 2}O (2) have been successfully synthesized by hydrothermal methods and characterized by IR, thermogravimetric analysis (TGA), elemental analysis, and single X-ray diffraction. Compound 1 crystallizes in the monoclinic space group Cc with a=35.775(12) Aa, b=33.346(11) Aa, c=24.424(8) Aa, β=93.993(5) , V=29065(16) Aa{sup 3}, whereas 2 crystallizes in the triclinic space group P anti 1 with a=20.4929(19) Aa, b=24.671(2) Aa, c=29.727(3) Aa, α=81.9990(10) , β=88.0830(10) , γ=89.9940(10) , V=14875(2) Aa{sup 3}. Structural analysis indicates the framework of 1 is a 3D perovskite-like structure constructed out of CO{sub 3} rate at Dy{sub 26} building units and Cu{sup +} centers by means of nicotinic acid ligand bridging. In 2, however, nanosized CO{sub 3} rate at Tb{sub 26} units and [Ag{sub 3}Cl]{sup 2+} centers are connected by Nic{sup -} bridges to give rise to a 2D structure. It is worth mentioning that this kind of 4d-4f cluster-based MOF is quite rare as most of the reported analogous compounds are 3d-4f ones. Additionally, the solid-state emission spectra of pure compound 2 at room temperature suggest an efficient energy transfer from the ligand Nic{sup -} to Tb{sup 3+} ions, which we called the ''antenna effect''. Compound 2 shows a good two-photon absorption (TPA) with a TPA coefficient of 0.06947 cm GM{sup -1} (1 GM = 10{sup -50} cm{sup 4} s photon{sup -1}), which indicates that compound 2 might be a good choice for third-order nonlinear optical materials. (copyright 2015 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim)

Changes in irradiated LnSiAlO(N) glasses at a microscopic scale

Energy Technology Data Exchange (ETDEWEB)

Dauce, R. [UMR CNRS 6512, Verres et ceramiques, Institut de Chimie, Universite de Rennes 1, F-35042 Rennes Cedex (France) and CE Cadarache, DEC/SESC, F-13018 St. Paul Lez Durances Cedex (France)]. E-mail: rachel.dauce@freenet.de; Sangleboeuf, J.-C. [LARMAUR, FRE CNRS 2717, Universite de Rennes 1, F-35042 Rennes Cedex (France); Verdier, P. [UMR CNRS 6512, Verres et ceramiques, Institut de Chimie, Universite de Rennes 1, F-35042 Rennes Cedex (France)

2006-06-15

Six oxide and oxynitride glasses from three different M-Ln-Si-Al-O(-N) systems (where M is an alkaline-earth and Ln a rare earth) have been irradiated by Kr, Ni and S ions, with different energies varying from 350 to 700 MeV. Neither micro-bubble formation nor crystallisation are evidenced, but the irradiated glasses exhibit an anisotropic deformation under the ion beam. The main crack mode developed during scratching is shifted from radial for the pristine glasses to lateral for all the irradiated glasses. The hardness of each glass decreases when irradiated for all the incident ions used. This decrease appears to be in close relation with the electronic stopping power of the incident particle, and is associated with a change in the indentation mechanism (from normal to anomalous behaviour). The evolution of the scratches in the material depth confirms the change in deformation mechanism and the strong dependence between the hardness of the irradiated material and the electronic stopping power of the incident ion. Three phenomena can be the source of the changes in the properties: the creation of internal stresses during irradiation, the creation of point defects and the cross-linking of the silicate network.

Enhancement of superconductivity near the pressure-induced semiconductor-metal transition in the BiS₂-based superconductors LnO₀.₅F₀.₅BiS₂ (Ln = La, Ce, Pr, Nd).

Science.gov (United States)

Wolowiec, C T; White, B D; Jeon, I; Yazici, D; Huang, K; Maple, M B

2013-10-23

Measurements of electrical resistivity were performed between 3 and 300 K at various pressures up to 2.8 GPa on the BiS2-based superconductors LnO0.5F0.5BiS2 (Ln=Pr, Nd). At lower pressures, PrO0.5F0.5BiS2 and NdO0.5F0.5BiS2 exhibit superconductivity with critical temperatures Tc of 3.5 and 3.9 K, respectively. As pressure is increased, both compounds undergo a transition at a pressure Pt from a low Tc superconducting phase to a high Tc superconducting phase in which Tc reaches maximum values of 7.6 and 6.4 K for PrO0.5F0.5BiS2 and NdO0.5F0.5BiS2, respectively. The pressure-induced transition is characterized by a rapid increase in Tc within a small range in pressure of ∼0.3 GPa for both compounds. In the normal state of PrO0.5F0.5BiS2, the transition pressure Pt correlates with the pressure where the suppression of semiconducting behaviour saturates. In the normal state of NdO0.5F0.5BiS2, Pt is coincident with a semiconductor-metal transition. This behaviour is similar to the results recently reported for the LnO0.5F0.5BiS2 (Ln=La, Ce) compounds. We observe that Pt and the size of the jump in Tc between the two superconducting phases both scale with the lanthanide element in LnO0.5F0.5BiS2 (Ln=La, Ce, Pr, Nd).

Electrochemical and Electronic Charge Transport Properties of Ni-Doped LiMn2O4 Spinel Obtained from Polyol-Mediated Synthesis

Directory of Open Access Journals (Sweden)

Shuo Yang

2018-05-01

Full Text Available LiNi0.5Mn1.5O4 (LNMO spinel has been extensively investigated as one of the most promising high-voltage cathode candidates for lithium-ion batteries. The electrochemical performance of LNMO, especially its rate performance, seems to be governed by its crystallographic structure, which is strongly influenced by the preparation methods. Conventionally, LNMO materials are prepared via solid-state reactions, which typically lead to microscaled particles with only limited control over the particle size and morphology. In this work, we prepared Ni-doped LiMn2O4 (LMO spinel via the polyol method. The cycling stability and rate capability of the synthesized material are found to be comparable to the ones reported in literature. Furthermore, its electronic charge transport properties were investigated by local electrical transport measurements on individual particles by means of a nanorobotics setup in a scanning electron microscope, as well as by performing DFT calculations. We found that the scarcity of Mn3+ in the LNMO leads to a significant decrease in electronic conductivity as compared to undoped LMO, which had no obvious effect on the rate capability of the two materials. Our results suggest that the rate capability of LNMO and LMO materials is not limited by the electronic conductivity of the fully lithiated materials.

Comparison of UVC/S2O8 2- with UVC/H2O2 in terms of efficiency and cost for the removal of micropollutants from groundwater

DEFF Research Database (Denmark)

Antoniou, Maria; Andersen, Henrik Rasmus

2015-01-01

' concentrations were tested with atrazine alone and in the micropollutants' mixture and it was decided to use 11.8mgL(-1) S2O8(2-) and 14.9mgL(-1) H2O2 for further testing since is closer to industrial applications and to minimize the residual oxidant concentration. Changes of the matrix composition......This study compared the UVC/S2O8(2-) system with the more commonly used AOP in water industry, UVC/H2O2, and examined whether the first one can be an economically feasible alternative technology. Atrazine and 4 volatile compounds (methyl tert-butyl ether, cis-dichlorethen, 1,4-dioxane and 1......-through reactor to simulate industrial applications. Initial experiments on the activation of oxidants with a LP lamp indicated that S2O8(2-) is photolysed about 2.3times faster than H2O2 and that the applied treatment times were not sufficient to utilize the majority of the oxidant. The effect of oxidants...

Relating surface chemistry and oxygen surface exchange in LnBaCo2O(5+δ) air electrodes.

Science.gov (United States)

Téllez, Helena; Druce, John; Kilner, John A; Ishihara, Tatsumi

2015-01-01

The surface and near-surface chemical composition of electroceramic materials often shows significant deviations from that of the bulk. In particular, layered materials, such as cation-ordered LnBaCo2O(5+δ) perovskites (Ln = lanthanide), undergo surface and sub-surface restructuring due to the segregation of the divalent alkaline-earth cation. These processes can take place during synthesis and processing steps (e.g. deposition, sintering or annealing), as well as at temperatures relevant for the operation of these materials as air electrodes in solid oxide fuel cells and electrolysers. Furthermore, the surface segregation in these double perovskites shows fast kinetics, starting at temperatures as low as 400 °C over short periods of time and leading to a decrease in the transition metal surface coverage exposed to the gas phase. In this work, we use a combination of stable isotope tracer labeling and surface-sensitive ion beam techniques to study the oxygen transport properties and their relationship with the surface chemistry in ordered LnBaCo2O(5+δ) perovskites. Time-of-Flight Secondary-Ion Mass Spectrometry (ToF-SIMS) combined with (18)O isotope exchange was used to determine the oxygen tracer diffusion (D*) and surface exchange (k*) coefficients. Furthermore, Low Energy Ion Scattering (LEIS) was used for the analysis of the surface and near surface chemistry as it provides information from the first mono-atomic layer of the materials. In this way, we could relate the compositional modifications (e.g. cation segregation) taking place at the electrochemically-active surface during the exchange at high temperatures and the oxygen transport properties in double perovskite electrode materials to further our understanding of the mechanism of the surface exchange process.

Synthesis and characterization of LnAg(WO{sub 4})(MoO{sub 4})

Energy Technology Data Exchange (ETDEWEB)

Fernandez-Martinez, F. [Universidad Politecnica de Madrid, E.U.I.T. Industrial, Ronda de Valencia 3, 28012 Madrid (Spain)], E-mail: francisco.fernandezm@upm.es; Colon, C.; Montero, J.L.; Atanes, E. [Universidad Politecnica de Madrid, E.U.I.T. Industrial, Ronda de Valencia 3, 28012 Madrid (Spain); Rivero, C. [Universidad Politecnica de Madrid, E.T.S.I. Telecomunicaciones, Avda. Complutense s/n, Ciudad Universitaria, 28040 Madrid (Spain)

2008-02-28

Polycrystalline LnAg(WO{sub 4})(MoO{sub 4}) powders, with Ln = La to Lu and Y, have been obtained by ceramic method. Rietveld refinement for all compounds reveals that they present tetragonal symmetry, space group I4{sub 1}/a (No. 88), where the Ln{sup 3+}/Ag{sup +} ions are located in the 4a atomic positions, since the W/Mo are randomly distributed into 4b crystal sites. In these compounds, a and b lattice parameters take values between those corresponding to tungstate and molybdate compounds. A progressive decrease in the lattice parameters is observed in going from La to Lu derivatives as a consequence of the well-known lanthanide contraction.

Preliminary Ionization Efficiencies of 11C and 14O with the LBNL ECR Ion Sources

International Nuclear Information System (INIS)

Xie, Z.Q.; Cerny, J.; Guo, F.Q.; Joosten, R.; Larimer, R.M.; Lyneis, C.M.; McMahan, P.; Norman, E.B.; O'Neil, J.P.; Powell, J.; Rowe, M.W.; VanBrocklin, H.F.; Wutte, D.; Xu, X.J.; Haustein, P.

1998-01-01

High charge states, up to fully stripped 11 C and 14 O ion, beams have been produced with the electron cyclotron resonance ion sources (LBNL, ECR and AECR-U) at Lawrence Berkeley National Laboratory. The radioactive atoms of 11 C and 14 O were collected in batch mode with an LN 2 trap and then bled into the ECR ion sources. Ionization efficiency as high as 11% for 11 C 4+ was achieved

Ultrafast atomic layer-by-layer oxygen vacancy-exchange diffusion in double-perovskite LnBaCo2O5.5+δ thin films.

Science.gov (United States)

Bao, Shanyong; Ma, Chunrui; Chen, Garry; Xu, Xing; Enriquez, Erik; Chen, Chonglin; Zhang, Yamei; Bettis, Jerry L; Whangbo, Myung-Hwan; Dong, Chuang; Zhang, Qingyu

2014-04-22

Surface exchange and oxygen vacancy diffusion dynamics were studied in double-perovskites LnBaCo2O5.5+δ (LnBCO) single-crystalline thin films (Ln = Er, Pr; -0.5 atoms in the LnBCO thin films is taking the layer by layer oxygen-vacancy-exchange mechanism. The first principles density functional theory calculations indicate that hydrogen atoms are present in LnBCO as bound to oxygen forming O-H bonds. This unprecedented oscillation phenomenon provides the first direct experimental evidence of the layer by layer oxygen vacancy exchange diffusion mechanism.

Equivalence of chemical and external pressures in RCoLnO

Energy Technology Data Exchange (ETDEWEB)

Prando, Giacomo; Ortix, Carmine; Kataev, Vladislav [Leibniz-Institut fuer Festkoerper- und Werkstoffforschung (IFW), Dresden (Germany); Profeta, Gianni [SPIN-CNR e Dipartimento di Fisica, Universita dell' Aquila (Italy); Sanna, Samuele [Dipartimento di Fisica, Universita di Pavia (Italy); Khasanov, Rustem [Laboratory for Muon Spin Spectroscopy, Paul Scherrer Institut, Villigen (Switzerland); Pal, Anand; Awana, Veer [National Physical Laboratory (CSIR), New Delhi (India); Buechner, Bernd [Leibniz-Institut fuer Festkoerper- und Werkstoffforschung (IFW), Dresden (Germany); Institut fuer Festkoerperphysik, Technische Universitaet Dresden (Germany); De Renzi, Roberto [Dipartimento di Fisica, Universita di Parma e CNISM (Italy)

2015-07-01

We report on the local magnetic properties of the series of ferromagnetic (FM) materials RCoLnO (R = La, Pr, Nd, Sm; Ln = As, P) as investigated by means of muon spin spectroscopy under pressure P and electron spin resonance (ESR). The effect of P is shown to be quantitatively equivalent to the chemical lattice shrinkage triggered by the different ionic radii of R ions. This is verified for both experimental-dependent quantities (i.e., magnetic field at the muon site) and for intrinsically material-dependent properties (i.e., FM critical temperature T{sub C}). Results of ESR in a wide range of temperature and magnetic field clearly display that magnetism is of localized nature, despite the overall metallic behaviour of these materials.

2-D and 3-D phosphotungstate-based TM-Ln heterometallic derivatives constructed from dimeric [Ln({alpha}-PW{sub 11}O{sub 39}){sub 2}]{sup 11-} fragments and copper-organic complex linkers

Energy Technology Data Exchange (ETDEWEB)

Shang, Sensen [Institute of Molecular and Crystal Engineering, College of Chemistry and Chemical Engineering, Henan University, Kaifeng, Henan 475004 (China); Zhao, Junwei, E-mail: zhaojunwei@henu.edu.cn [Institute of Molecular and Crystal Engineering, College of Chemistry and Chemical Engineering, Henan University, Kaifeng, Henan 475004 (China); State Key Laboratory of Structural Chemistry, Fujian Institute of Research on the Structure of Matter, Chinese Academy of Sciences, Fuzhou, Fujian 350002 (China); Chen, Lijuan [Institute of Molecular and Crystal Engineering, College of Chemistry and Chemical Engineering, Henan University, Kaifeng, Henan 475004 (China); Basic Experiment Teaching Center, Henan University, Kaifeng, Henan 475004 (China); Li, Yuye; Zhang, Jingli; Li, Yanzhou [Institute of Molecular and Crystal Engineering, College of Chemistry and Chemical Engineering, Henan University, Kaifeng, Henan 475004 (China); Niu, Jingyang, E-mail: jyniu@henu.edu.cn [Institute of Molecular and Crystal Engineering, College of Chemistry and Chemical Engineering, Henan University, Kaifeng, Henan 475004 (China)

2012-12-15

Three organic-inorganic hybrid TM-Ln heterometallic phosphotungstates [Cu(dap){sub 2}(H{sub 2}O)][Cu(dap){sub 2}]{sub 3.5}[La({alpha}-HPW{sub 11}O{sub 39}){sub 2}]{center_dot}6H{sub 2}O (1) [Cu(dap){sub 2}(H{sub 2}O)]{sub 0.5}[Cu(dap){sub 2}]{sub 4}[Nd({alpha}-HPW{sub 11}O{sub 39}){sub 2}]{center_dot}4H{sub 2}O (2) and [Cu(dap){sub 2}(H{sub 2}O)]{sub 2}[Cu(dap){sub 2}]{sub 3.5}[Eu({alpha}-PW{sub 11}O{sub 39}){sub 2}]{center_dot}6H{sub 2}O (3) (dap=1,2-diaminopropane) have been hydrothermally synthesized and structurally characterized by elemental analyses, IR spectra, optical diffuse reflectance spectra, powder X-ray diffraction (PXRD), thermogravimetric (TG) analyses and single-crystal X-ray diffraction. Their common features are that 1-3 all consist of asymmetric sandwich-type subunits [Ln({alpha}-PW{sub 11}O{sub 39}){sub 2}]{sup 11-} and [Cu(dap){sub 2}]{sup 2+} bridges. Both 1 and 2 display the 2-D (4,4)-topological sheets whereas 3 exhibits the 3-D 5-connected (4{sup 6}{center_dot}6{sup 4}) topological framework. The magnetic properties of 2 and 3 and the luminescence performance of 3 have been measured. - Graphical Abstract: Three TM-Ln heterometallic phosphotungstates 1-3 have been synthesized and characterized by elemental analyses, IR spectra, optical diffuse reflectance spectra, X-ray diffraction, thermogravimetric analyses magnetic susceptibility and luminescent properties. Highlights: Black-Right-Pointing-Pointer Cu{sup II}-Ln{sup III} heterometallic polyoxometalates. Black-Right-Pointing-Pointer 2-D and 3-D organic-inorganic hybrid phosphotungstates. Black-Right-Pointing-Pointer 2-D and 3-D structures consisting of Cu{sup II}-Ln{sup III} heterometals.

Synthesis and characterization of K2Ln2/3Ta2O7·nH2O (Ln= La, Pr, Nd), layered tantalates photo catalysts for water splitting

International Nuclear Information System (INIS)

Valencia S, H.; Tavizon, G.; Pfeiffer, H.; Acosta, D.; Negron M, A.

2015-01-01

Three compounds of the K 2 Ln 2/3 Ta 2 O 7 (Ln = La, Nd, Pr) cation-deficient Ruddlesden-Popper series were prepared by the Pechini (polymeric complex) method. The crystal structures of the hydrated form of these compounds were determined by Rietveld analysis of the X-ray power diffraction data and High Resolution Transmission Electron Microscopy (HRTEM). The samples were also analyzed to determine specific area (Bet), degree of hydration (Thermogravimetric analysis), and photo catalytic activity for hydrogen evolution from water and aqueous methanol solution. (Author)

Chiral Silver-Lanthanide Metal-Organic Frameworks Comprised of One-Dimensional Triple Right-Handed Helical Chains Based on [Ln7(μ3-OH)8]13+ Clusters.

Science.gov (United States)

Guo, Yan; Zhang, Lijuan; Muhammad, Nadeem; Xu, Yan; Zhou, Yunshan; Tang, Fang; Yang, Shaowei

2018-02-05

Three new isostructural chiral silver-lanthanide heterometal-organic frameworks [Ag 3 Ln 7 (μ 3 -OH) 8 (bpdc) 6 (NO 3 ) 3 (H 2 O) 6 ](NO 3 )·2H 2 O [Ln = Eu (1), Tb (2, Sm (3); H 2 bpdc = 2,2'-bipyridine-3,3'-dicarboxylic acid] based on heptanuclear lanthanide clusters [Ln 7 (μ 3 -OH) 8 ] 13+ comprised of one-dimensional triple right-handed helical chains were hydrothermally synthesized. Various means such as UV-vis spectroscopy, IR spectroscopy, elemental analysis, powder X-ray diffraction, and thermogravimetric/differential thermal analysis were used to characterize the compounds, wherein compound 3 was crystallographically characterized. In the structure of compound 3, eight μ 3 -OH - groups link seven Sm 3+ ions, forming a heptanuclear cluster, [Sm 7 (μ 3 -OH) 8 ] 13+ , and the adjacent [Sm 7 (μ 3 -OH) 8 ] 13+ clusters are linked by the carboxylic groups of bpdc 2- ligands, leading to the formation of a one-dimensional triple right-handed helical chain. The adjacent triple right-handed helical chains are further joined together by coordinating the pyridyl N atoms of the bpdc 2- ligands with Ag + , resulting in a chiral three-dimensional silver(I)-lanthanide(III) heterometal-organic framework with one-dimensional channels wherein NO 3 - anions and crystal lattice H 2 O molecules are trapped. The compounds were studied systematically with respect to their photoluminescence properties and energy-transfer mechanism, and it was found that H 2 bpdc (the energy level for the triplet states of the ligand H 2 bpdc is 21505 cm -1 ) can sensitize Eu 3+ luminescence more effectively than Tb 3+ and Sm 3+ luminescence because of effective energy transfer from bpdc 2- to Eu 3+ under excitation in compound 1.

Metal–organic frameworks assembled from lanthanide and 2,5-pyridinedicaboxylate with cubane-like [Ln{sub 4}(OH){sub 4}] building units

Energy Technology Data Exchange (ETDEWEB)

Abdelbaky, Mohammed S.M. [Departamentos de Química Física y Analítica y Química Orgánica e Inorgánica, University of Oviedo—CINN, Oviedo 33006 (Spain); Amghouz, Zakariae, E-mail: amghouz.uo@uniovi.es [Departamentos de Química Física y Analítica y Química Orgánica e Inorgánica, University of Oviedo—CINN, Oviedo 33006 (Spain); Servicios Científico-Técnicos, University of Oviedo—CINN, Oviedo 33006 (Spain); Fernández-Zapico, Eva; García-Granda, Santiago; García, José R. [Departamentos de Química Física y Analítica y Química Orgánica e Inorgánica, University of Oviedo—CINN, Oviedo 33006 (Spain)

2015-09-15

Lanthanide–organic frameworks based on 2,5-pyridinedicaboxylate (25p) ligand, formulated as [Yb{sub 4}(OH){sub 4}(25p){sub 4}(H{sub 2}O){sub 3}]·H{sub 2}O (25pYb), [Y{sub 4}(OH){sub 4}(25p){sub 4}(H{sub 2}O){sub 3}]·H{sub 2}O (25pY-1) and [Y{sub 6}(OH){sub 8}(25p){sub 5}(H{sub 2}O){sub 2}] (25pY-2), have been obtained as single phases under hydrothermal conditions. 25pYb and 25pY-1 are isostructural, and crystallize in the triclinic space group, P-1, with a=8.6075(5) Å, b=14.8478(7) Å, c=15.9164(9) Å, α=86.277(4)°, β=80.196(5)°, γ=81.785(4)°, and a=8.7166(6) Å, b=14.966(1) Å, c=15.966(1) Å, α=86.260(6)°, β=80.036(6)°, γ=81.599(6)°, respectively. 25pY-2 crystallizes in the monoclinic space group, P2{sub 1}/c, with a=24.9117(17) Å, b=13.7340(8) Å, c=14.3385(10) Å, β=100.551(7)°. 25pYb and 25pY-2 have been structurally characterized by single-crystal X-ray diffraction. The 25pYb structure is based on tetranuclear cubane-like [Yb{sub 4}(OH){sub 4}]{sup 8+} clusters, which are interconnected to eight neighbouring clusters through teen surrounding 25p ligands leading to neutral 3D framework, while the structure of 25pY-2 is based on two independent cuban-like [Y{sub 4}(OH){sub 4}]{sup 8+} clusters, which are joined together through Y1 cation leading to the formation of hexanuclear [Y{sub 6}(OH){sub 8}]{sup 10+} clusters, which in turn are joined via Y2 cation resulting in infinite inorganic chain extending along c-axis, and each chain is interconnected to six adjacent chains through 25p ligands leading finally to 3D framework. The luminescence properties of Eu{sup 3+} and Tb{sup 3+} doped 25pY-1 and 25pY-2 compounds have also been investigated. All materials has been characterized by powder X-ray diffraction, thermal analyses (TG–SDTA–MS), FTIR spectroscopy, C–H–N elemental analysis, scanning electron microscopy (SEM-EDX), and powder X-ray thermodiffraction. - Graphical abstract: Nowadays, lanthanide–organic frameworks (LOFs) attract

Bi3+ sensitized Y2WO6:Ln3+ (Ln=Dy, Eu, and Sm) phosphors for solar spectral conversion.

Science.gov (United States)

Huang, M N; Ma, Y Y; Xiao, F; Zhang, Q Y

2014-01-01

The phosphors of Y2WO6:Bi3+, Ln3+ (Ln=Dy, Eu and Sm) were synthesized by solid-state reaction in this study. The crystal structure, photoluminescence properties and energy transfer mechanism were investigated. By introducing Bi3+ ions, the excitation band of the phosphors was broadened to be 250-380 nm, which could be absorbed by the dye-sensitized solar cells (DSSCs). The overlap between excitation of W-O groups/Bi3+ and the emission of Ln3+ (Dy, Eu, and Sm) indicated that the probability of energy transfer from W-O groups and Bi3+ to Ln3+. The energy transfer efficiency from Bi3+ to Ln3+ (Ln=Dy, Eu and Sm) are calculated to be 16%, 20% and 58%. This work suggested that Y2WO6:Bi3+, Ln3+ (Ln=Dy, Eu and Sm) might be a promising ultraviolet-absorbing luminescent converter to enhance the photoelectrical conversion efficiency of dye-sensitized solar cells (DSSCs). Copyright © 2013 Elsevier B.V. All rights reserved.

The quaternary arsenide oxides Ce{sub 9}Au{sub 5-x}As{sub 8}O{sub 6} and Pr{sub 9}Au{sub 5-x}As{sub 8}O{sub 6}

Energy Technology Data Exchange (ETDEWEB)

Bartsch, Timo; Hoffmann, Rolf-Dieter; Poettgen, Rainer [Univ. Muenster (Germany). Inst. fuer Anorganische und Analytische Chemie

2016-07-01

The quaternary gold arsenide oxides Ce{sub 9}Au{sub 5-x}As{sub 8}O{sub 6} and Pr{sub 9}Au{sub 5-x}As{sub 8}O{sub 6} were synthesized from the rare earth elements (RE), rare earth oxides, arsenic and gold powder at maximum annealing temperatures of 1173 K. The structures were refined from single crystal X-ray diffractometer data: Pnnm, a=1321.64(6) pm, b=4073.0(3), c=423.96(2), wR2=0.0842, 3106 F{sup 2} values, 160 variables for Ce{sub 9}Au{sub 4.91(4)}As{sub 8}O{sub 6} and Pnnm, a=1315.01(4), b=4052.87(8), c=420.68(1) pm, wR2=0.0865, 5313 F{sup 2} values, 160 variables for Pr{sub 9}Au{sub 4.75(1)}As{sub 8}O{sub 6}. They represent a new structure type and show a further extension of pnictide oxide crystal chemistry. A complex polyanionic gold arsenide network [Au{sub 5}As{sub 8}]{sup 15-} (with some disorder in the gold substructure) is charge compensated with polycationic strands of condensed edge-sharing O rate at RE{sub 4/4} and O rate at RE{sub 4/3} tetrahedra ([RE{sub 4}O{sub 3}]{sub 2}{sup 12+}) as well as RE{sup 3+} cations in cavities.

Phase-Tunable Synthesis of Monodisperse YPO4:Ln3+ (Ln = Ce, Eu, Tb) Micro/Nanocrystals via Topotactic Transformation Route with Multicolor Luminescence Properties.

Science.gov (United States)

Shao, Baiqi; Feng, Yang; Zhao, Shuang; Yuan, Senwen; Huo, Jiansheng; Lü, Wei; You, Hongpeng

2017-06-05

A novel aqueous-based and phase-selected synthetic strategy toward YPO 4 :Ln 3+ (Ln = Ce, Eu, Tb) micro/nanocrystals was developed by selecting specific precursors whose structure topotactically matches with the target ones. It was found that layered yttrium hydroxide (LYH) induced the formation of hexagonal-phased h-YPO 4 ·0.8H 2 O with the crystalline relationship of [001]LYH//[0001]h-YPO 4 ·0.8H 2 O, while the amorphous Y(OH)CO 3 favored the formation of tetragonal-phased t-YPO 4 . We also systematically investigated the influence of Na 2 CO 3 /NaH 2 PO 4 feeding ratio on the evolutions of morphology and size of the h-YPO 4 ·0.8H 2 O sample, and we also obtained a novel mesoporous nanostructure for t-YPO 4 single crystalline with closed octahedron shape for the first time. Besides, the multicolor and phase-dependent luminescence properties of the as-obtained h-YPO 4 ·0.8H 2 O and t-YPO 4 micro/nanocrystals were also investigated in detail. Our work may provide some new guidance in synthesis of nanocrystals with target phase structure by rational selection of precursor with topotactic structural matching.

Crystallographic origin of cycle decay of the high-voltage LiNi0.5Mn1.5O4 spinel lithium-ion battery electrode.

Science.gov (United States)

Pang, Wei Kong; Lu, Cheng-Zhang; Liu, Chia-Erh; Peterson, Vanessa K; Lin, Hsiu-Fen; Liao, Shih-Chieh; Chen, Jin-Ming

2016-06-29

High-voltage spinel LiNi0.5Mn1.5O4 (LNMO) is considered a potential high-power-density positive electrode for lithium-ion batteries, however, it suffers from capacity decay after extended charge-discharge cycling, severely hindering commercial application. Capacity fade is thought to occur through the significant volume change of the LNMO electrode occurring on cycling, and in this work we use operando neutron powder diffraction to compare the structural evolution of the LNMO electrode in an as-assembled 18650-type battery containing a Li4Ti5O12 negative electrode with that in an identical battery following 1000 cycles at high-current. We reveal that the capacity reduction in the battery post cycling is directly proportional to the reduction in the maximum change of the LNMO lattice parameter during its evolution. This is correlated to a corresponding reduction in the MnO6 octahedral distortion in the spinel structure in the cycled battery. Further, we find that the rate of lattice evolution, which reflects the rate of lithium insertion and removal, is ∼9 and ∼10% slower in the cycled than in the as-assembled battery during the Ni(2+)/Ni(3+) and Ni(3+)/Ni(4+) transitions, respectively.

A family of acetato-diphenoxo triply bridged dimetallic Zn(II)Ln(III) complexes: SMM behavior and luminescent properties.

Science.gov (United States)

Oyarzabal, Itziar; Artetxe, Beñat; Rodríguez-Diéguez, Antonio; García, JoséÁngel; Seco, José Manuel; Colacio, Enrique

2016-06-21

Eleven dimetallic Zn(II)-Ln(III) complexes of the general formula [Zn(µ-L)(µ-OAc)Ln(NO3)2]·CH3CN (Ln(III) = Pr (1), Nd (2), Sm (3), Eu (4), Gd (5), Tb (6), Dy (7), Ho (8), Er (9), Tm (10), Yb (11)) have been prepared in a one-pot reaction from the compartmental ligand N,N'-dimethyl-N,N'-bis(2-hydroxy-3-formyl-5-bromo-benzyl)ethylenediamine (H2L). In all these complexes, the Zn(II) ions occupy the internal N2O2 site whereas the Ln(III) ions show preference for the O4 external site. Both metallic ions are bridged by an acetate bridge, giving rise to triple mixed diphenoxido/acetate bridged Zn(II)Ln(III) compounds. The Nd, Dy, Er and Yb complexes exhibit field induced single-ion magnet (SIM) behaviour, with Ueff values ranging from 14.12 to 41.55 K. The Er complex shows two relaxation processes, but only the second relaxation process with an energy barrier of 21.0 K has been characterized. The chromophoric L(2-) ligand is able to act as an "antenna" group, sensitizing the near-infrared (NIR) Nd(III) and Yb(III)-based luminescence in complexes 2 and 11 and therefore, both compounds can be considered as magneto-luminescent materials. In addition, the Sm(III), Eu(III) and Tb(III) derivatives exhibit characteristic emissions in the visible region.

The role of Ln

NARCIS (Netherlands)

Katayama, Y.; Kayumi, T.; Ueda, J.; Dorenbos, P.; Viana, B; Tanabe, S

2017-01-01

In this paper, Mn2+ and Ln3+ (Ln = Eu, Yb) co-doped MgGeO3 phosphors were prepared using a solid state reaction technique, and their optical properties were investigated. Mn2+-doped samples exhibit persistent luminescence in the red region, peaking at 677 nm, because of the 4T1 → 6A1 transition of

Near-infrared photoluminescence in La0.98AlO3: 0.02Ln3+(Ln = Nd/Yb) for sensitization of c-Si solar cells

Science.gov (United States)

Sawala, N. S.; Koparkar, K. A.; Bajaj, N. S.; Omanwar, S. K.

2016-05-01

The host matrix LaAlO3 was synthesized by conventional solid state reaction method in which the Nd3+ ions and Yb3+ ions successfully doped at 2mol% concentrations. The phase purity was confirmed by X ray powder diffraction (XRD) method. The photoluminescence (PL) properties were studied by spectrophotometer in near infra red (NIR) and ultra violet visible (UV-VIS) region. The Nd3+ ion doped LaAlO3 converts a visible (VIS) green photon (587 nm) into near infrared (NIR) photon (1070 nm) while Yb3+ ion doped converts ultra violet (UV) photon (221 nm) into NIR photon (980 nm). The La0.98AlO3: 0.02Ln3+(Ln = Nd / Yb) can be potentiality used for betterment of photovoltaic (PV) technology. This result further indicates its potential application as a luminescence converter layer for enhancing solar cells performance.

Lanthanide stannate pyrochlores (Ln2Sn2O7; Ln  =  Nd, Gd, Er) at high pressure

Science.gov (United States)

Turner, Katlyn M.; Tracy, Cameron L.; Mao, Wendy L.; Ewing, Rodney C.

2017-12-01

Lanthanide stannate pyrochlores (Ln2Sn2O7; Ln  =  Nd, Gd, and Er) were investigated in situ to 50 GPa in order to determine their structural response to compression and compare their response to that of lanthanide titanate, zirconate, and hafnate pyrochlores. The cation radius ratio of A3+/B4+ in pyrochlore oxides (A2B2O7) is thought to be the dominant feature that influences their response on compression. The ionic radius of Sn4+ is intermediate to that of Ti4+, Zr4+, and Hf4+, but the 〈Sn-O〉 bond in stannate pyrochlore is more covalent than the 〈B-O〉 bonds in titanates, zirconate, and hafnates. In stannates, based on in situ Raman spectroscopy, pyrochlore cation and anion sublattices begin to disorder with the onset of compression, first measured at 0.3 GPa. The extent of sublattice disorder versus pressure is greater in stannates with a smaller Ln3+ cation. Stannate pyrochlores (Fd-3m) begin a sluggish transformation to an orthorhombic, cotunnite-like structure at ~28 GPa similar transitions have been observed in titanate, zirconate, and hafnate pyrochlores at varying pressures (18-40 GPa) with cation radius ratio. The extent of the phase transition versus pressure varies directly with the size of the Ln3+ cation. Post-decompression from ~50 GPa, Er2Sn2O7 and Gd2Sn2O7 adopt a pyrochlore structure, rather than the multi-scale defect-fluorite  +  weberite-type structure adopted by Nd2Sn2O7 that is characteristic of titanate, zirconate, and hafnate pyrochlores under similar conditions. Like pyrochlore titanates, zirconates, and hafnates, the bulk modulus, B 0, of stannates varies linearly and inversely with cation radius ratio from 1 1 1 GPa (Nd2Sn2O7) to 251 GPa (Er2Sn2O7). The trends of bulk moduli in stannates in this study are in excellent agreement with previous experimental studies on stannates and suggest that the size of the Ln3+ cation is the primary determining factor of B 0. Additionally, when normalized to r A

(La, Pr)0.8Sr0.2FeO3-δ-Sm 0.2Ce0.8O2-δ composite cathode for proton-conducting solid oxide fuel cells

KAUST Repository

Chen, Yonghong

2014-08-01

Mixed rare-earth (La, Pr)0.8Sr0.2FeO 3-δ-Sm0.2Ce0.8O2-δ (LPSF-SDC) composite cathode was investigated for proton-conducting solid oxide fuel cells based on protonic BaZr0.1Ce0.7Y 0.2O3-δ (BZCY) electrolyte. The powders of La 0.8-xPrxSr0.2FeO3-δ (x = 0, 0.2, 0.4, 0.6), Sm0.2Ce0.8O2-δ (SDC) and BaZr0.1Ce0.7Y0.2O3-δ (BZCY) were synthesized by a citric acid-nitrates self-propagating combustion method. The XRD results indicate that La0.8-xPrxSr 0.2FeO3-δ samples calcined at 950 °C exhibit perovskite structure and there are no interactions between LPSF0.2 and SDC at 1100 °C. The average thermal expansion coefficient (TEC) of LPSF0.2-SDC, BZCY and NiO-BZCY is 12.50 × 10-6 K-1, 13.51 × 10-6 K-1 and 13.47 × 10-6 K -1, respectively, which can provide good thermal compatibility between electrodes and electrolyte. An anode-supported single cell of NiO-BZCY|BZCY|LPSF0.2-SDC was successfully fabricated and operated from 700 °C to 550 °C with humidified hydrogen (∼3% H2O) as fuel and the static air as oxidant. A high maximum power density of 488 mW cm -2, an open-circuit potential of 0.95 V, and a low electrode polarization resistance of 0.071 Ω cm2 were achieved at 700 °C. Preliminary results demonstrate that LPSF0.2-SDC composite is a promising cathode material for proton-conducting solid oxide fuel cells. © 2014, Hydrogen Energy Publications, LLC. Published by Elsevier Ltd. All rights reserved.

Decomposition of 1,4-dioxane by advanced oxidation and biochemical process.

Science.gov (United States)

Kim, Chang-Gyun; Seo, Hyung-Joon; Lee, Byung-Ryul

2006-01-01

This study was undertaken to determine the optimal decomposition conditions when 1,4-dioxane was degraded using either the AOPs (Advanced Oxidation Processes) or the BAC-TERRA microbial complex. The advanced oxidation was operated with H2O2, in the range 4.7 to 51 mM, under 254 nm (25 W lamp) illumination, while varying the reaction parameters, such as the air flow rate and reaction time. The greatest oxidation rate (96%) of 1,4-dioxane was achieved with H2O2 concentration of 17 mM after a 2-hr reaction. As a result of this reaction, organic acid intermediates were formed, such as acetic, propionic and butyric acids. Furthermore, the study revealed that suspended particles, i.e., bio-flocs, kaolin and pozzolan, in the reaction were able to have an impact on the extent of 1,4-dioxane decomposition. The decomposition of 1,4-dioxane in the presence of bio-flocs was significantly declined due to hindered UV penetration through the solution as a result of the consistent dispersion of bio-particles. In contrast, dosing with pozzolan decomposed up to 98.8% of the 1,4-dioxane after 2 hr of reaction. Two actual wastewaters, from polyester manufacturing, containing 1,4-dioxane in the range 370 to 450 mg/L were able to be oxidized by as high as 100% within 15 min with the introduction of 100:200 (mg/L) Fe(II):H202 under UV illumination. Aerobic biological decomposition, employing BAC-TERRA, was able to remove up to 90% of 1,4-dioxane after 15 days of incubation. In the meantime, the by-products (i.e., acetic, propionic and valeric acid) generated were similar to those formed during the AOPs investigation. According to kinetic studies, both photo-decomposition and biodegradation of 1,4-dioxane followed pseudo first-order reaction kinetics, with k = 5 x 10(-4) s(-1) and 2.38 x 10(-6) s(-1), respectively. It was concluded that 1,4-dioxane could be readily degraded by both AOPs and BAC-TERRA, and that the actual polyester wastewater containing 1,4-dioxane could be successfully

Li{sub 35}Ln{sub 9}Si{sub 30}N{sub 59}O{sub 2}F with Ln = Ce, Pr - highly condensed nitridosilicates

Energy Technology Data Exchange (ETDEWEB)

Lupart, Saskia; Durach, Dajana; Schnick, Wolfgang [Department Chemie, Lehrstuhl fuer Anorganische Festkoerperchemie, Ludwig-Maximilians-Universitaet Muenchen (Germany)

2011-10-15

The isotypic nitridosilicates Li{sub 35}Ln{sub 9}Si{sub 30}N{sub 59}O{sub 2}F (Ln = Ce, Pr) were synthesized by reaction of LnF{sub 3} and LiN{sub 3} with Si(NH){sub 2} in liquid lithium flux in weld shut tantalum ampoules. The crystal structures of the isotypic compounds were solved and refined on the basis of single-crystal X-ray diffraction (P anti 3c1 (no. 165), Z = 2; Li{sub 35}Ce{sub 9}Si{sub 30}N{sub 59}O{sub 2}F:, a = 1479.9(2), c = 1538.3(3) pm, R{sub 1} = 0.0526, 1671 data, 175 parameters; Li{sub 35}Pr{sub 9}Si{sub 30}N{sub 59}O{sub 2}F: a = 1477.3(2), c = 1533.9(3) pm, R{sub 1} = 0.0441, 1331 data, 175 parameters). The silicate substructure represents a 3D network of all side corner sharing SiN{sub 4} tetrahedra. At one discrete and not condensed mixed anion position an atomic ratio O:F = 2:1 is assumed in order to achieve charge neutrality. With an atomic ratio Si:N = 30:59, the degree of condensation of the silicate substructure is slightly above κ = 1/2. Accordingly, there are triply crosslinking N{sup [3]} atoms in the silicate substructure. The obtained structures prove that by employing the lithium flux technique not only nitridosilicates with a low degree of condensation can be obtained by using rather mild reaction conditions at low temperatures. Lattice energy calculations (MAPLE) and EDX measurements confirmed the electrostatic bonding interactions and the chemical composition. (Copyright copyright 2011 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim)

Structural characterization of M(IV)1-xLn(III)xO2-x/2 (M = Ce, Th) mixed-oxides prepared from oxalate precursors. Multi-parametric study of dissolution and microstructural evolution

International Nuclear Information System (INIS)

Horlait, D.

2011-01-01

In the framework of Gen IV program development, several physico-chemical properties of some foreseen fuels, including the chemical durability, have to be evaluated. In this aim, a study was undertaken on M(IV) 1-x Ln(III) x O 2 (M=Ce,Th) model compounds prepared from oxalate precursors. The fluorite-type structure of CeO 2 and ThO 2 remains stable up to x ≅ 0.4, the substitution of M(IV) by Ln(III) occurring simultaneously to the formation of oxygen vacancies. For higher x values, a cubic superstructure is formed as a result of oxygen vacancies ordering. The normalized dissolution rates of such solids were found to be strongly enhanced by the Ln(III) fraction. On the contrary, the nature of the M(IV) and Ln(III) elements did not modify significantly the normalized dissolution rates. The effect of temperature and acid concentration suggested the existence of surface-controlling dissolution reactions. Simultaneously, the microstructural evolution of both powdered and sintered samples revealed some important changes in the reactive surface during dissolution tests. ESEM images allowed observing the existence of preferential dissolution sites located at grains boundaries and around crystalline defects, leading to the formation of corrosion pits. In addition, the formation of gelatinous phases, acting as diffusion barriers (thus slowing down the dissolution process) was also evidenced. (author) [fr

Systematics in the electron transport and magnetic properties of LnBO3 perovskites

International Nuclear Information System (INIS)

Ganguly, P.; Rao, C.N.R.

1980-01-01

Systematics in the electrical and magnetic properties of transition metal perovskites LnBO 3 (Ln = rare-earth ion, B = 3d transition metal) with the variation of Ln and B ions are reviewed. The electrical resistivity and activation energy of LnBO 3 compounds increase with the decreasing size of the Ln 3+ ion for a given B ion. The low-spin to high-spin transition temperature of Co 3+ ion in LnCoO 3 similarly increase with the decrease in size of Ln 3+ while the magnetic ordering temperatures in LnVO 3 , LnFeO 3 , LnCrO 3 and LnSrCo 2 O 6 decrease with decreasing size of the rare-earth ion. These results may be understood in terms of the increasing acidity of the rare earth ion with decreasing size and the competition between the Ln 3+ and the B 3+ ions for covalency with the oxygen ions. The effect of this competition on the metal oxygen covalency and crystal field parameter is discussed in relation to the results obtained and Goodenough's phase diagram. The possibility of d-f exchange interaction in Lasub(1-x)Lnsub(x)NiOsub(3) is also discussed in the light of ESR results. (auth.)

High-pressure synthesis and magnetic behavior of A-site columnar-ordered double perovskites, LnMn(Ga{sub 0.5}Ti{sub 0.5}){sub 2}O{sub 6} (Ln = Sm, Gd)

Energy Technology Data Exchange (ETDEWEB)

Shimura, Gen; Niwa, Ken; Shirako, Yuichi; Hasegawa, Masashi [Department of Crystalline Materials Science, Nagoya University, 464-8601, Nagoya (Japan)

2017-01-26

A-site columnar-ordered double perovskites, LnMn(Ga{sub 0.5}Ti{sub 0.5}){sub 2}O{sub 6} (Ln = Sm, Gd), were successfully synthesized under high pressure and high temperature (6 GPa, 1375 K). From the synchrotron powder X-ray diffraction patterns, all of the diffraction peaks can be indexed by the P4{sub 2}/nmc space group with lattice parameters a, c ∼ 2a{sub p} (a{sub p}: primitive cubic perovskite lattice) and no ordering of the B-site cations. Rietveld analysis of the synchrotron powder X-ray diffraction patterns and Curie-Weiss fitting of their magnetizations reveal that the ionic formulae of these perovskites are Ln{sup 3+}Mn{sup 2+}(Ga{sup 3+}{sub 0.5}Ti{sup 4+}{sub 0.5}){sub 2}O{sup 2-}{sub 6}. SmMn(Ga{sub 0.5}Ti{sub 0.5}){sub 2}O{sub 6} shows canted-antiferromagnetic behavior, whereas GdMn(Ga{sub 0.5}Ti{sub 0.5}){sub 2}O{sub 6} exhibits two different magnetic states at low temperature depending on the applied magnetic field and shows an unusual magnetization curve. These magnetic behaviors originate by decreasing the antiferromagnetic interaction by substituting Ga{sup 3+}(d{sup 10}) for Ti{sup 4+}(d{sup 0}) and by decreasing the ferromagnetic interaction between columnar-ordered Ln{sup 3+} and Mn{sup 2+}. (copyright 2017 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim)

Microstructure and tensile properties of oxide dispersion strengthened Fe–14Cr–0.3Y2O3 and Fe–14Cr–2W–0.3Ti–0.3Y2O3

International Nuclear Information System (INIS)

Auger, M.A.; Castro, V. de; Leguey, T.; Monge, M.A.; Muñoz, A.; Pareja, R.

2013-01-01

Two ODS ferritic steels with nominal compositions (wt.%): Fe–14Cr–0.3Y 2 O 3 and Fe–14Cr–2W–0.3Ti–0.3Y 2 O 3 have been produced by mechanical alloying and consolidation by hot isostatic pressing. The microstructure and tensile properties of these materials after being forged and heat-treated at 1123 K have been investigated to clarify the interrelation between composition, microstructure and mechanical properties. The second-phase precipitates in these alloys have been analyzed by high-angle annular dark-field imaging in scanning TEM mode and electron diffraction. Fe–14Cr–2W–0.3Ti–0.3Y 2 O 3 exhibits a duplex microstructure consisting of large recrystallized grains, as large as 1.5 μm, and unrecovered regions containing submicron equiaxed grains. In addition, three types of secondary phase particles have been found: large M 23 C 6 particles containing W and Cr, (Cr + Ti) rich spherical particles with diameters between 50 and 500 nm, and fine (Y + Ti) oxide particles with sizes below 30 nm. In contrast, Fe14CrY shows a uniform structure of equiaxed grains, with sizes in the range 0.5–3 μm, containing a fine dispersion of Y oxide particles ( 2 O 3 at temperatures up to 773 K, but the opposite appears to occur beyond this temperature

Magnetic properties of cyano-bridged Ln3+-M3+ complexes. Part I: trinuclear complexes (Ln3+ = La, Ce, Pr, Nd, Sm; M3+ = FeLS, Co) with bpy as blocking ligand.

Science.gov (United States)

Figuerola, Albert; Ribas, Joan; Llunell, Miquel; Casanova, David; Maestro, Miguel; Alvarez, Santiago; Diaz, Carmen

2005-10-03

The reaction of Ln(NO3)3(aq) with K3[Fe(CN)6] or K3[Co(CN)6] and 2,2'-bipyridine in water/ethanol led to eight trinuclear complexes: trans-[M(CN)4(mu-CN)2{Ln(H2O)4(bpy)2}2][M(CN)6].8H2O (M = Fe3+ or Co3+, Ln = La3+, Ce3+, Pr3+, Nd3+, and Sm3+). The structures for the eight complexes [La2Fe] (1), [Ce2Fe] (2), [Pr2Fe] (3), [Nd2Fe] (4), [Ce2Co] (5), [Pr2Co] (6), [Nd2Co] (7), and [Sm2Co] (8) have been solved; they crystallize in the triclinic space group P and are isomorphous. They exhibit a supramolecular 3D architecture through hydrogen bonding and pi-pi stacking interactions. A stereochemical study of the nine-vertex polyhedra of the lanthanide ions, based on continuous shape measures, is presented. No significant magnetic interaction was found between the lanthanide(III) and the iron(III) ions.

Crystal structure of fluorite-related Ln3SbO7 (Ln=La–Dy) ceramics studied by synchrotron X-ray diffraction and Raman scattering

International Nuclear Information System (INIS)

Siqueira, K.P.F.; Borges, R.M.; Granado, E.; Malard, L.M.; Paula, A.M. de; Moreira, R.L.; Bittar, E.M.; Dias, A.

2013-01-01

Ln 3 SbO 7 (Ln=La, Pr, Nd, Sm, Eu, Gd, Tb and Dy) ceramics were synthesized by solid-state reaction in optimized conditions of temperature and time to yield single-phase ceramics. The crystal structures of the obtained ceramics were investigated by synchrotron X-ray diffraction, second harmonic generation (SHG) and Raman scattering. All samples exhibited fluorite-type orthorhombic structures with different oxygen arrangements as a function of the ionic radius of the lanthanide metal. For ceramics with the largest ionic radii (La–Nd), the ceramics crystallized into the Cmcm space group, while the ceramics with intermediate and smallest ionic radii (Sm–Dy) exhibited a different crystal structure belonging to the same space group, described under the Ccmm setting. The results from SHG and Raman scattering confirmed these settings and ruled out any possibility for the non-centrosymmetric C222 1 space group describing the structure of the small ionic radii ceramics, solving a recent controversy in the literature. Besides, the Raman modes for all samples are reported for the first time, showing characteristic features for each group of samples. - Graphical abstract: Raman spectrum for La 3 SbO 7 ceramics showing their 22 phonon modes adjusted through Lorentzian lines. According to synchrotron X-ray diffraction and Raman scattering, this material belongs to the space group Cmcm. - Highlights: • Ln 3 SbO 7 ceramics belonging to the space groups Cmcm and Ccmm are synthesized. • SXRD, SHG and Raman scattering confirmed the orthorhombic structures. • Ccmm instead of C222 1 is the correct one based on SHG and Raman data

Facile design and synthesis of Li-rich nanoplates cathodes with habit-tuned crystal for lithium ion batteries

Science.gov (United States)

Li, Jili; Jia, Tiekun; Liu, Kai; Zhao, Junwei; Chen, Jian; Cao, Chuanbao

2016-11-01

Li-ion batteries with high-energy and high-power density are pursued to apply in the electronic vehicles and renewable energy storage systems. In this work, layered Li-rich transition-metal oxide cathode Li1.2Ni0.2Mn0.6O2 nanoplates with enhanced growth of {010} planes (LNMO-NP) is successfully synthesized through a facile and versatile strategy. Ethylene glycol plays an important role in the formation of LNMO-NP nanoplates with {010} electrochemically active surface planes exposure. As cathode for Li-ion batteries, LNMO-NP demonstrates a high specific discharge capacity of 270.2 mAh g-1 at 0.1 C (1 C = 300 mA g-1) and an excellent rate capability. The good electrochemical performance can be attributed to the nanoplates with the growth of {010} electrochemically active planes which is in favor of Li+ intercalation/deintercalation.

Synthesis and characterization of K{sub 2}Ln{sub 2/3}Ta{sub 2}O{sub 7}·nH{sub 2}O (Ln= La, Pr, Nd), layered tantalates photo catalysts for water splitting

Energy Technology Data Exchange (ETDEWEB)

Valencia S, H.; Tavizon, G. [UNAM, Instituto de Quimica, Ciudad Universitaria, 04510 Ciudad de Mexico (Mexico); Pfeiffer, H. [UNAM, Instituto de Investigaciones en Materiales, Ciudad Universitaria, 04510 Ciudad de Mexico (Mexico); Acosta, D. [UNAM, Instituto de Fisica, Ciudad Universitaria, 04510 Ciudad de Mexico (Mexico); Negron M, A., E-mail: hvalencia@utp.edu.co [UNAM, Instituto de Ciencias Nucleares, Ciudad Universitaria, 04510 Ciudad de Mexico (Mexico)

2015-07-01

Three compounds of the K{sub 2}Ln{sub 2/3}Ta{sub 2}O{sub 7} (Ln = La, Nd, Pr) cation-deficient Ruddlesden-Popper series were prepared by the Pechini (polymeric complex) method. The crystal structures of the hydrated form of these compounds were determined by Rietveld analysis of the X-ray power diffraction data and High Resolution Transmission Electron Microscopy (HRTEM). The samples were also analyzed to determine specific area (Bet), degree of hydration (Thermogravimetric analysis), and photo catalytic activity for hydrogen evolution from water and aqueous methanol solution. (Author)

Synthesis and characterisation of the n = 2 Ruddlesden–Popper phases Ln2Sr(Ba)Fe2O7 (Ln = La, Nd, Eu)

International Nuclear Information System (INIS)

Gurusinghe, Nicola N.M.; Figuera, Juand de la; Marco, José F.; Thomas, Michael F.; Berry, Frank J.; Greaves, Colin

2013-01-01

Graphical abstract: - Highlights: • Some Ruddlesden–Popper phases have been characterised. • Substitution on the A site influences cationic order. • The magnetic moment redirects with temperature - Abstract: A series of n = 2 Ruddlesden–Popper phases A 2 B 2 O 7 of composition Ln 2 Sr(Ba)Fe 2 O 7 (Ln = La, Nd, Eu) have been prepared. La 2 SrFe 2 O 7 and La 2 BaFe 2 O 7 crystallise in the tetragonal space group I4/mmm. The structures of Eu 2 SrFe 2 O 7 and Nd 2 SrFe 2 O 7 are best described in space group P4 2 /mnm. Substitution on the A site with smaller lanthanide- and larger alkaline metal- ions leads to enhanced cationic order in these phases and reflects increasing differences in cationic radii. All the compounds are antiferromagnetically ordered between 298 and 2 K. In La 2 SrFe 2 O 7 the magnetic moment lies along [1 1 0] at all temperatures between 298 and 2 K whereas in La 2 BaFe 2 O 7 the magnetic moment at 298 K lies along the crystallographic x-axis but redirects from the [1 0 0] to the [1 1 0] direction between 210 and 190 K and is retained in this direction until 2 K. In Nd 2 SrFe 2 O 7 the magnetic moment at 298 K lies along [1 1 0] but rotates from [1 1 0] to [0 0 1] between 17 and 9 K. A series of 57 Fe Mössbauer spectra recorded from La 2 SrFe 2 O 7 between 290 and 600 K indicate a magnetic ordering temperature of T N ≥ 535 K

Inflammatory effects induced by selected limonene oxidation products: 4-OPA, IPOH, 4-AMCH in human bronchial (16HBE14o-) and alveolar (A549) epithelial cell lines.

Science.gov (United States)

Lipsa, Dorelia; Leva, Paolo; Barrero-Moreno, Josefa; Coelhan, Mehmet

2016-11-16

Limonene, a monoterpene abundantly present in most of the consumer products (due to its pleasant citrus smell), easily undergoes ozonolysis leading to several limonene oxidation products (LOPs) such as 4-acetyl-1-methylcyclohexene (4-AMCH), 4-oxopentanal (4-OPA) and 3-isopropenyl-6-oxoheptanal (IPOH). Toxicological studies have indicated that human exposure to limonene and ozone can cause adverse airway effects. However, little attention has been paid to the potential health impact of specific LOPs, in particular of IPOH, 4-OPA and 4-AMCH. This study evaluates the cytotoxic effects of the selected LOPs on human bronchial epithelial (16HBE14o-) and alveolar epithelial (A549) cell lines by generating concentration-response curves using the neutral red uptake assay and analyzing the inflammatory response with a series of cytokines/chemokines. The cellular viability was mostly reduced by 4-OPA [IC 50 =1.6mM (A549) and 1.45mM (16HBE14o-)] when compared to IPOH [IC 50 =3.5mM (A549) and 3.4mM (16HBE14o-)] and 4-AMCH [IC 50 could not be calculated]. As a result from the inflammatory response, IPOH [50μM] induced an increase of both IL-6 and IL-8 secretion in A549 (1.5-fold change) and in 16HBE14o- (2.8- and 7-fold change respectively). 4-OPA [50μM] treatment of A549 increased IL-6 (1.4-times) and IL-8 (1.3-times) levels, while in 16HBE14o- had an opposite effect. A549 treated with 4-AMCH [50μM] elevate both IL-6 and IL-8 levels by 1.2-times, while in 16HBE14o- had an opposite effect. Based on our results, lung cellular injury characterized by inflammatory cytokine release was observed for both cell lines treated with the selected chemicals at concentrations that did not affect their cellular viability. Copyright © 2016 The Authors. Published by Elsevier Ireland Ltd.. All rights reserved.

A comparative study of the magnetic properties and phase separation behavior of the rare earth cobaltates, Ln 0.5Sr0.5CoO3 (Ln=rare earth)

International Nuclear Information System (INIS)

Kundu, Asish; Sarkar, R.; Pahari, B.; Ghoshray, A.; Rao, C.N.R.

2007-01-01

A comparative study of the magnetic properties of a few members of the Ln 0.5 Sr 0.5 CoO 3 family with different radii of the A-site cations, A >, in the range 1.19-1.40 A has been carried out. The apparent T c (where the magnetization undergoes an abrupt increase) decreases markedly with A > as well as the size-disorder arising from the mismatch in the size of the A-site cations. The value of the magnetization at low temperatures decreases markedly with decrease in A > or increase in size-disorder, suggesting that the relative proportion of the ferromagnetic (FM) species decreases relative to that of the paramagnetic (PM) species. Such a variation of the FM/PM ratio with composition and temperature is evidenced from the Moessbauer spectra of La 0.5 Sr 0.5 CoO 3 as well. The variation of the FM/PM ratio with A > and size-disorder, as well as a local-probe study using 59 Co Nuclear magnetic resonance spectroscopy suggest that electronic phase separation is an inherent feature of the Ln 0.5 Sr 0.5 CoO 3 type cobaltates, with the nature of the different magnetic species in the phase-separated system varying with A > and size disorder. - Graphical abstract: Variation of (a) T c and (b) FC magnetization at 1000 Oe with A > at 120 K in Ln 0.5 Sr 0.5 CoO 3 and Dy 0.34 Nd 0.16 Sr 0.40 Ca 0.10 CoO 3

Controllable synthesis of Ln3+ (Ln = Tb, Eu) doped zinc phosphate nano-/micro-structured materials: phase, morphology and luminescence properties

Science.gov (United States)

Yue, Dan; Lu, Wei; Li, Chunyang; Zhang, Xinlei; Liu, Chunxia; Wang, Zhenling

2014-01-01

Ln3+ (Ln = Tb, Eu) doped zinc phosphate tetrahydrate (ZPT:Ln3+) and ammonium zinc phosphate (AZP:Ln3+) nano-/micro-structured materials were synthesized in aqueous solution without the addition of any structure-directing agent. The phase structures, morphologies and luminescence properties of the as-synthesized samples were investigated by X-ray diffraction (XRD), scanning electron microscopy (SEM), energy dispersive X-ray spectroscopy (EDX), transmission electron microscopy (TEM), photoluminescence (PL) spectroscopy and lifetime. These investigations indicate that different phosphate sources MnH(3-n)PO4 (M = NH4+ or Na+, n = 1, 2, 3) can lead to the altering of morphology from nanosheet to microflower, but have no significant effect on the phase structure of the samples. The microlump, nanosheet, and microflower (constructed by the primary microlumps or nanosheets) of orthorhombic ZPT:Ln3+ could be selectively prepared by adjusting the pH value from 3.5 to 7.0. A mixture of orthorhombic ZPT:Ln3+ and monoclinic AZP:Ln3+ with a microflower morphology was obtained when the pH value was adjusted to 8.0. Monoclinic AZP:Ln3+ microplate, microcube and nanoparticle morphologies were obtained at pH values of 8.5, 9.0 and 11.0 respectively. The phase transformation and growth mechanism of the diverse morphologies were proposed, and ZPT:Ln3+ (Ln3+ = Eu or Tb) samples exhibit red or green emission under the excitation of UV light.Ln3+ (Ln = Tb, Eu) doped zinc phosphate tetrahydrate (ZPT:Ln3+) and ammonium zinc phosphate (AZP:Ln3+) nano-/micro-structured materials were synthesized in aqueous solution without the addition of any structure-directing agent. The phase structures, morphologies and luminescence properties of the as-synthesized samples were investigated by X-ray diffraction (XRD), scanning electron microscopy (SEM), energy dispersive X-ray spectroscopy (EDX), transmission electron microscopy (TEM), photoluminescence (PL) spectroscopy and lifetime. These

Pembuatan La0,8Ca0,2MnO3 sebagai Katoda pada Solid Oxide Fuel Cell (SOFC dan Karakteristiknya

Directory of Open Access Journals (Sweden)

Riska Ekawati

2007-06-01

Full Text Available The making of La0,8Ca0,2MnO3 cathode material of solid oxide fuel cell from lanthanum oxide (La2O3, calcium oxide (CaO, and manganese carbonate hydrate (MnCO3.H2O has been done using tape casting method. Time of firing the La0,8Ca0,2MnO3 varied. The values of t = 30 minutes, 60 minutes and 120 minutes. Microstructure of these materials was analyzed and characterized by means of their electric conductivity, XRD (x ray diffraction and SEM (scanning electron microscope. It is found that formulated micro structure is orthorhombic. The result of measurement shows that density is in linear (positive correlation with increasing of holding time of firing, porosity and coefficient of thermal expansion is negatively correlated with density and electric conductivity is in linear (positive correlation with increase density.

Synthesis and crystal structure analysis of titanium bismuthide oxide, Ti{sub 8}BiO{sub 7}

Energy Technology Data Exchange (ETDEWEB)

Amano, Shinsaku; Yamane, Hisanori, E-mail: yamane@tagen.tohoku.ac.jp

2016-08-05

Silver metallic luster columnar single crystals of a novel compound, Ti{sub 8}BiO{sub 7}, were synthesized using a bismuth flux. Ti{sub 8}BiO{sub 7} having a new structure type crystallizes in an orthorhombic cell, a = 7.8473(4) Å, b = 16.8295(10) Å, c = 3.0256(2) Å, space group: Cmmm. The Ti atoms enter the sites of isosceles-triangle 3-fold and rectangular 4-fold coordination of O atoms and the site of octahedral 6-fold coordination of O and Bi atoms. O atoms are in the rectangles, tetrahedra, and orthogonal pyramids of Ti atoms. The electrical resistivity measured for a Ti{sub 8}BiO{sub 7} single crystal in the c-axis direction was 6.2 × 10{sup −7} Ωm at 300 K and 1.3 × 10{sup −7} Ωm at 10 K. - Highlights: • A novel bismuthide oxide containing titanium, Ti{sub 8}BiO{sub 7}, was synthesized. • Single crystals of Ti{sub 8}BiO{sub 7} were grown by heating a mixture of Ti and Bi{sub 2}O{sub 3}. • Single crystal X-ray diffraction revealed that Ti{sub 8}BiO{sub 7} has a new structure type. • O atoms and Bi atoms are surrounded by Ti atoms in the structure. • Metallic conduction of Ti{sub 8}BiO{sub 7} was exhibited.

Ordered oxygen deficient '112'perovskites, LnBaCo2 O5⋅ 50 ...

Indian Academy of Sciences (India)

... Refresher Courses · Symposia · Live Streaming. Home; Journals; Bulletin of Materials Science; Volume 32; Issue 3. Ordered oxygen deficient '112' perovskites, LnBaCo2O5.50+: complex magnetism and transport properties. B Raveau Md Motin Seikh V Pralong V Caignaert. Volume 32 Issue 3 June 2009 pp 305-312 ...

Ternary phosphates in Ca3(PO4)2-Na3Ln(PO4)2 (Ln-Nd, Eu, Er) systems

International Nuclear Information System (INIS)

Lazoryak, B.I.; Ivanov, L.N.; Strunenkova, T.V.; Golubev, V.N.; Viting, B.N.

1990-01-01

Ternary phosphates, formed in Ca 3 (PO 4 ) 2 -Na 3 Ln(PO 4 ) 2 (Ln-Nd, Eu, Er) systems were investigated by the methods of X-ray phase, luminescent analyses and IR spectroscopy. 5 regions of homogeneity were found. Two of them (I and II) were distinguished for all systems. Samples in the region of up to 14.285 mol.% Na 3 Ln(PO 4 ) 2 crystallize on the basis of β-Ca 3 (PO 4 ) 2 structure, and in other homogeneity regions - on the basis of β-K 2 SO 4 structure

Kinetics of CO Oxidation over Unloaded and Pd-Loaded α-Fe2O3 Spherical Submicron Powder Catalysts: Photoacoustic Investigations at Low Pressure

Directory of Open Access Journals (Sweden)

Joong-Seok Roh

2018-02-01

Full Text Available In this study, α-Fe2O3 spherical particles with an average diameter of approximately 200 nm were synthesized by a solvothermal method for use as both a catalyst and medium for a Pd catalyst. The kinetics of CO oxidation over powders of α-Fe2O3 spherical particles and 14 wt % Pd/α-Fe2O3 spherical particles were measured in a static reactor by using a CO2 laser-based photoacoustic technique. The total pressure was fixed at 40 Torr for the CO/O2/N2 mixture for temperatures in the range of 225–350 °C. The variation in the CO2 photoacoustic signal with the CO2 concentration during CO oxidation was recorded as a function of time, and the CO2 photoacoustic data at the early reaction stage was used to estimate the rates of CO2 formation. Based on plots of ln(rate vs. 1/T, apparent activation energies were calculated as 13.4 kcal/mol for the α-Fe2O3 submicron powder and 13.2 kcal/mol for the 14 wt % Pd/α-Fe2O3 submicron powder. Reaction orders with respect to CO and O2 were determined from the rates measured at various partial pressures of CO and O2 at 350 °C. The zero-order of the reaction with respect to Po2 was observed for CO oxidation over α-Fe2O3 submicron powder, while 0.48 order to Po2 was observed for CO oxidation over Pd/α-Fe2O3 submicron powder. The partial orders with respect to PCO were determined as 0.58 and 0.54 for the α-Fe2O3, and the Pd/α-Fe2O3 submicron powders, respectively. The kinetic results obtained from both catalysts were compared with those for the α-Fe2O3 fine powder catalysts and were used to understand the reaction mechanism.

Treatment of landfill leachate biochemical effluent using the nano-Fe3O4/Na2S2O8 system: Oxidation performance, wastewater spectral analysis, and activator characterization.

Science.gov (United States)

Liu, Zhanmeng; Li, Xian; Rao, Zhiwei; Hu, Fengping

2018-02-15

Nano-Fe 3 O 4 was used as heterogeneous catalyst to activate Na 2 S 2 O 8 for the generation of the sulfate radicals (SO 4 - ) to oxidize the residual pollutants in landfill leachate biochemical effluent. The oxidation performance, wastewater spectral analysis and activator characterization were discussed. Oxidation experimental result shows that nano-Fe 3 O 4 has obvious catalytic effect on Na 2 S 2 O 8 and can significantly enhance the oxidation efficiencies of Na 2 S 2 O 8 on landfill leachate biochemical effluent, with COD and color removals above 63% and 95%, respectively. Based on the analyses of three-dimensional excitation emission matrix fluorescence spectrum (3DEEM), ultraviolet-visible spectra (UV-vis), and Fourier Transform infrared spectroscopy (FTIR) of wastewater samples before and after treatment, it can be concluded that the pollution level of dissolved organic matter (DOM) declined and that the humic acid (HA) fractions were efficiently degraded into small molecules of fulvic acid (FA) fractions with less weight and stable structure. Compared to the raw wastewater sample, the aromaticity and substituent groups of the DOM were lessened in the treated wastewater sample. Moreover, the main structure of the organics and functional groups were changed by the Fe 3 O 4 /Na 2 S 2 O 8 system, with substantial decrease of conjugated double bonds. The micro morphology of nano-Fe 3 O 4 was characterized before and after reaction by the methods of scanning electron microscope spectra (SEM), X-ray diffraction pattern (XRD), and X-ray photoelectron spectroscopy (XPS). The XRD pattern analysis showed that nano-Fe 3 O 4 was oxidized into r-Fe 2 O 3 and that the particle size of it also became smaller after reaction. XPS was employed to analyze the content and iron valence on the nano-Fe 3 O 4 surface, and it can be found that the ratio of Fe 3+ /Fe 2+ decreased from 1.8 before reaction to 0.8 after reaction. From the SEM analysis after the treatment, it was

Quantitative Evidence for Lanthanide-Oxygen Orbital Mixing in CeO2, PrO2, and TbO2.

Science.gov (United States)

Minasian, Stefan G; Batista, Enrique R; Booth, Corwin H; Clark, David L; Keith, Jason M; Kozimor, Stosh A; Lukens, Wayne W; Martin, Richard L; Shuh, David K; Stieber, S Chantal E; Tylisczcak, Tolek; Wen, Xiao-Dong

2017-12-13

Understanding the nature of covalent (band-like) vs ionic (atomic-like) electrons in metal oxides continues to be at the forefront of research in the physical sciences. In particular, the development of a coherent and quantitative model of bonding and electronic structure for the lanthanide dioxides, LnO 2 (Ln = Ce, Pr, and Tb), has remained a considerable challenge for both experiment and theory. Herein, relative changes in mixing between the O 2p orbitals and the Ln 4f and 5d orbitals in LnO 2 are evaluated quantitatively using O K-edge X-ray absorption spectroscopy (XAS) obtained with a scanning transmission X-ray microscope and density functional theory (DFT) calculations. For each LnO 2 , the results reveal significant amounts of Ln 5d and O 2p mixing in the orbitals of t 2g (σ-bonding) and e g (π-bonding) symmetry. The remarkable agreement between experiment and theory also shows that significant mixing with the O 2p orbitals occurs in a band derived from the 4f orbitals of a 2u symmetry (σ-bonding) for each compound. However, a large increase in orbital mixing is observed for PrO 2 that is ascribed to a unique interaction derived from the 4f orbitals of t 1u symmetry (σ- and π-bonding). O K-edge XAS and DFT results are compared with complementary L 3 -edge and M 5,4 -edge XAS measurements and configuration interaction calculations, which shows that each spectroscopic approach provides evidence for ground state O 2p and Ln 4f orbital mixing despite inducing very different core-hole potentials in the final state.

Near-infrared photoluminescence in La{sub 0.98}AlO{sub 3}: {sub 0.02}Ln{sup 3+}(Ln = Nd/Yb) for sensitization of c-Si solar cells

Energy Technology Data Exchange (ETDEWEB)

Sawala, N. S., E-mail: nssawala@gmail.com; Koparkar, K. A.; Omanwar, S. K. [Department of Physics, SantGadge Baba Amravati University, Amravati - MH, 444602 (India); Bajaj, N. S. [Department of Physics, Toshniwal Art, Commerce and Science College, Sengoan, Hingoli - MH (India)

2016-05-06

The host matrix LaAlO{sub 3} was synthesized by conventional solid state reaction method in which the Nd{sup 3+} ions and Yb{sup 3+} ions successfully doped at 2mol% concentrations. The phase purity was confirmed by X ray powder diffraction (XRD) method. The photoluminescence (PL) properties were studied by spectrophotometer in near infra red (NIR) and ultra violet visible (UV-VIS) region. The Nd{sup 3+} ion doped LaAlO{sub 3} converts a visible (VIS) green photon (587 nm) into near infrared (NIR) photon (1070 nm) while Yb{sup 3+} ion doped converts ultra violet (UV) photon (221 nm) into NIR photon (980 nm). The La{sub 0.98}AlO{sub 3}: {sub 0.02}Ln{sup 3+}(Ln = Nd / Yb) can be potentiality used for betterment of photovoltaic (PV) technology. This result further indicates its potential application as a luminescence converter layer for enhancing solar cells performance.

A novel method for stoichiometric reduction of (U{sub 3}O{sub 8},PuO{sub 2}) and its controlled oxidation using microwave

Energy Technology Data Exchange (ETDEWEB)

Singh, G., E-mail: gitendars@barctara.gov.in [Advanced Fuel Fabrication Facility (AFFF), Bhabha Atomic Research Centre, Tarapur, 401 502 (India); Kumar, Pradeep [Integrated Fuel Fabrication Facility, Bhabha Atomic Research Centre, Mumbai, 400 085 (India); Aher, S.; Purohit, P.; Khot, P.M. [Advanced Fuel Fabrication Facility (AFFF), Bhabha Atomic Research Centre, Tarapur, 401 502 (India); Prakash, Amrit [Radio-Metallurgy Division, Bhabha Atomic Research Centre, Mumbai, 400 085 (India); Das, D.K.; Behere, P.G.; Afzal, Mohd [Advanced Fuel Fabrication Facility (AFFF), Bhabha Atomic Research Centre, Tarapur, 401 502 (India)

2016-10-15

We report a process for stoichiometric reduction of U{sub 3}O{sub 8} and (U{sub 3}O{sub 8},PuO{sub 2}) mixed oxide powders using an indigenously developed 2.4 GHz microwave processing system. The process parameters were optimized by interpreting reduction kinetic curves at a temperature which is 150 °C lower than the conventional reduction. The process improved the sinterability of the powder which was evaluated in terms of average particle size, BET specific surface area and bulk density. A quick method for controlled oxidation of the reduced powder to incorporate a controlled amount of hyper-stoichiometry was demonstrated by modifying the same reduction process. The percent reduction was measured experimentally using O:(U + Pu) ratio. The X-ray diffraction analysis confirmed the various phases present. The process is novel considering shorter processing cycle, lower temperature processing, improved powder properties, energy efficiency and cost effectiveness. - Highlights: • A process for stoichiometric reduction of (U{sub 3}O{sub 8},PuO{sub 2}) was demonstrated using 2.4 GHz microwave. • A simple and quick method for obtaining controlled hyper-stoichiometry in the reduced powder was successfully demonstrated. • The process is novel relative to conventional methods in terms of time and energy economy and sinter-activity.

A robust NiO-Sm0.2Ce0.8O1.9 anode for direct-methane solid oxide fuel cell

KAUST Repository

Tian, Dong

2015-07-02

In order to directly use methane without a reforming process, NiO-Sm0.2Ce0.8O1.9 (NiO-SDC) nanocomposite anode are successfully synthesized via a one-pot, surfactant-assisted co-assembly approach for direct-methane solid oxide fuel cells. Both NiO with cubic phase and SDC with fluorite phase are obtained at 550 °C. Both NiO nanoparticles and SDC nanoparticles are highly monodispersed in size with nearly spherical shapes. Based on the as-synthesized NiO-SDC, two kinds of single cells with different micro/macro-porous structure are successfully fabricated. As a result, the cell performance was improved by 40%-45% with the new double-pore NiO-SDC anode relative to the cell performance with the conventional NiO-SDC anode due to a wider triple-phase-boundary (TPB) area. In addition, no significant degradation of the cell performance was observed after 60 hours, which means an increasing of long term stability. Therefore, the as-synthesized NiO-SDC nanocomposite is a promising anode for direct-methane solid oxide fuel cells.

Microstructure and tensile properties of oxide dispersion strengthened Fe–14Cr–0.3Y{sub 2}O{sub 3} and Fe–14Cr–2W–0.3Ti–0.3Y{sub 2}O{sub 3}

Energy Technology Data Exchange (ETDEWEB)

Auger, M.A., E-mail: mauger@fis.uc3m.es [Departamento de Física, Universidad Carlos III de Madrid, 28911 Leganés (Spain); Castro, V. de; Leguey, T.; Monge, M.A.; Muñoz, A.; Pareja, R. [Departamento de Física, Universidad Carlos III de Madrid, 28911 Leganés (Spain)

2013-11-15

Two ODS ferritic steels with nominal compositions (wt.%): Fe–14Cr–0.3Y{sub 2}O{sub 3} and Fe–14Cr–2W–0.3Ti–0.3Y{sub 2}O{sub 3} have been produced by mechanical alloying and consolidation by hot isostatic pressing. The microstructure and tensile properties of these materials after being forged and heat-treated at 1123 K have been investigated to clarify the interrelation between composition, microstructure and mechanical properties. The second-phase precipitates in these alloys have been analyzed by high-angle annular dark-field imaging in scanning TEM mode and electron diffraction. Fe–14Cr–2W–0.3Ti–0.3Y{sub 2}O{sub 3} exhibits a duplex microstructure consisting of large recrystallized grains, as large as 1.5 μm, and unrecovered regions containing submicron equiaxed grains. In addition, three types of secondary phase particles have been found: large M{sub 23}C{sub 6} particles containing W and Cr, (Cr + Ti) rich spherical particles with diameters between 50 and 500 nm, and fine (Y + Ti) oxide particles with sizes below 30 nm. In contrast, Fe14CrY shows a uniform structure of equiaxed grains, with sizes in the range 0.5–3 μm, containing a fine dispersion of Y oxide particles (<30 nm) homogeneously distributed inside the grains, as well as large carbide and oxide particles. Tensile tests performed over the temperature range 273–973 K have revealed that the alloy containing W and Ti has lower yield and tensile strengths than Fe–14Cr–0.3Y{sub 2}O{sub 3} at temperatures up to 773 K, but the opposite appears to occur beyond this temperature.

Determination of the constants of the solubility product of Ln(OH){sub 3} and the effect of the chloride ions on the lanthanum hydrolysis, praseodymium and lutetium in aqueous solutions of ion force 2 Molar; Determinacion de las constantes del producto de solubilidad de Ln(OH){sub 3} y el efecto de los iones cloruro sobre la hidrolisis de lantano, praseodimio y lutecio en soluciones acuosas de fuerza ionica 2 Molar

Energy Technology Data Exchange (ETDEWEB)

Lopez G, H.D

2005-07-01

The behavior of lanthanum (III), praseodymium (III), and lutetium (III) was studied in 2 M NaClO{sub 4} (aq) and 2 M NaCl (aq) at 303 K and free -CO{sub 2} conditions. Solubility diagrams (p Ln(aq)-pC{sub H}) were obtained by means of a radiochemical method. The pC{sub H} borderlines of saturation and unsaturation zones of the solutions and solubility product constants for Ln(OH){sub 3} were determined from these diagrams. The fitting of the solubility equation to the experimental values of p Ln(aq)-pC{sub H} diagrams allowed the calculation of the first hydrolysis and solubility product constants. Independently, the stability constants for the first species of hydrolysis were determined by means of pH titrations, the data were treated with the program SUPERQUAD and fitted to the mean ligand number equation. The stability constants for the species LnCl{sup 2+} were as well calculated in 2M ionic strength and 303 K from the hydrolysis constant values obtained in both perchlorate and chloride media. The values obtained for La, Pr and Lu were: logK{sub ps}: 21.11 {+-} 0.09, 19.81 {+-} 0.11 and 18.10 {+-} 0.13 in 2M NaClO{sub 4}; logK{sub ps}: 22.22 {+-} 0.09, 21.45 {+-} 0.14 and 18.52 {+-} 0.29 in 2M NaCl; log {beta}{sub 1}: - 8.64 {+-} 0.02, - 8.37 {+-} 0.01 and - 7.95 {+-} 0.11 in 2M NaClO{sub 4}; log {beta}{sub 1}{sup /} : - 9.02 {+-} 0.11, - 8.75 {+-} 0.01 and - 8.12 {+-} 0.03 in 2M NaCl and the values for log {beta}{sub 1,Cl} were - 0.0255, - 0.155 and - 0.758, respectively. (Author)

Crystal structures of [Ln(NO33(μ2-bpydo2], where Ln = Ce, Pr or Nd, and bpydo = 4,4′-bipyridine N,N′-dioxide: layered coordination networks containing 44 grids

Directory of Open Access Journals (Sweden)

Michael L. Stromyer

2016-01-01

Full Text Available Three isostructural coordination networks of Ce, Pr, and Nd nitrate with 4,4′-bipyridine N,N′-dioxide (bpydo are reported, namely poly[[tris(nitrato-κ2O,O′cerium(III]-bis(μ2-4,4′-bipyridine N,N′-dioxide-κ2N:N′], [Ce(NO33(C10H8N2O22], poly[[tris(nitrato-κ2O,O′praeseodymium(III]-bis(μ2-4,4′-bipyridine N,N′-dioxide-κ2N:N′], [Pr(NO33(C10H8N2O22], and poly[[tris(nitrato-κ2O,O′neodymium(III]-bis(μ2-4,4′-bipyridine N,N′-dioxide-κ2N:N′], [Nd(NO33(C10H8N2O22]. All three compounds are isostructural to the previously reported La analogue. The asymmetric unit of [Ln(NO33(μ2-bpydo2] contains one lanthanide cation, two bpydo ligands, and three nitrate anions. Both bpydo ligands act as end-to-end μ2-bridges and display nearly ideal cis and gauche conformations, respectively. The bpydo ligands link the ten-coordinate LnIII cations, forming interdigitating 44 grid-like layers extending parallel to (-101, where interdigitation of layers is promoted by C—H...O interactions between nitrate anions and bpydo ligands. The interdigitated layers are linked to sets of neighboring layers via further C—H...O and π–π interactions.

Carbon-14-labeled 2,3,7,8- and 1,2,7,8-tetrachlorodibenzofuran

International Nuclear Information System (INIS)

Gray, A.P.; McClellan, W.J.; Dipinto, V.M.

1981-01-01

Both 2,3,7,8- and 1,2,7,8- tetrachlorodibenzofuran -U 14 C, specific activity 57 mCi/mmol, have been obtained in low yield but at > 98% purity via Pschorr cyclization of o-phenoxyaniline -U 14 C, chlorination of the resultant dibenzofuran and separation of the tetrachloro isomers by hplc. The lower yields obtained in the Pschorr cyclization of 'hot' o-phenoxyaniline in comparison with the 'cold' material are postulated to result from enhanced homolytic relative to heterolytic cleavage of the 'hot' diazonium ion leading to a 'hot' free radical which polymerizes. The completely anomalous results observed in the attempted palladium acetate-mediated cyclization of diphenyl ether- U 14 C are likewise interpreted in terms of the intervention of a 'hot' free radical. (author)

New lanthanide hydrogen phosphites LnH (P03H)2 2H20

International Nuclear Information System (INIS)

Durand, J.; Tijani, N.; Cot, L.; Loukili, M.; Rafiq, M.

1988-01-01

LnH ((P0 3 H) 2 2H 2 0 is prepared from lanthanide oxide and phosphorous acid with Ln = La, Y, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er or Tm. By thermal gravimetric analysis LnH (P0 3 H) 2 and LnH 2 P 2 0 5 (P0 3 H) 2 are obtained. The three salts are orthorhombic. Parameters and space groups are given for the three salts of each lanthanide. 4 tabs., 13 refs

Towards hybrid biocompatible magnetic rHuman serum albumin-based nanoparticles: use of ultra-small (CeLn)3/4+ cation-doped maghemite nanoparticles as functional shell

Science.gov (United States)

Israel, Liron L.; Kovalenko, Elena I.; Boyko, Anna A.; Sapozhnikov, Alexander M.; Rosenberger, Ina; Kreuter, Jörg; Passoni, Lorena; Lellouche, Jean-Paul

2015-01-01

Human serum albumin (HSA) is a protein found in human blood. Over the last decade, HSA has been evaluated as a promising drug carrier. However, not being magnetic, HSA cannot be used for biomedical applications such as magnetic resonance imaging (MRI) and magnetic drug targeting. Therefore, subsequent composites building on iron oxide nanoparticles that are already used clinically as MRI contrast agents are extensively studied. Recently and in this context, innovative fully hydrophilic ultra-small CAN-stabilized maghemite ((CeLn)3/4+-γ-Fe2O3) nanoparticles have been readily fabricated. The present study discusses the design, fabrication, and characterization of a dual phase hybrid core (rHSA)-shell ((CeLn)3/4+-γ-Fe2O3 NPs) nanosystem. Quite importantly and in contrast to widely used encapsulation strategies, rHSA NP surface-attached (CeLn)3/4+-γ-Fe2O3 NPs enabled to exploit both rHSA (protein functionalities) and (CeLn)3/4+-γ-Fe2O3 NP surface functionalities (COOH and ligand L coordinative exchange) in addition to very effective MRI contrast capability due to optimal accessibility of H2O molecules with the outer magnetic phase. Resulting hybrid nanoparticles might be used as a platform modular system for therapeutic (drug delivery system) and MR diagnostic purposes.

La0.8Sr0.2Co0.8Ni0.2O3-δ impregnated oxygen electrode for H2O/CO2 co-electrolysis in solid oxide electrolysis cells

Science.gov (United States)

Zheng, Haoyu; Tian, Yunfeng; Zhang, Lingling; Chi, Bo; Pu, Jian; Jian, Li

2018-04-01

High-temperature H2O/CO2 co-electrolysis through reversible solid oxide electrolysis cell (SOEC) provides potentially a feasible and eco-friendly way to convert electrical energy into chemicals stored in syngas. In this work, La0.8Sr0.2Co0.8Ni0.2O3-δ (LSCN) impregnated Gd0.1Ce0.9O1.95 (GDC)-(La0.8Sr0.2)0.95MnO3-δ (LSM) composite oxygen electrode is studied as high-performance electrode for H2O/CO2 co-electrolysis. The LSCN impregnated cell exhibits competitive performance with the peak power density of 1057 mW cm-2 at 800 °C in solid oxide fuel cell (SOFC) mode; in co-electrolysis mode, the current density can reach 1.60 A cm-2 at 1.5 V at 800 °C with H2O/CO2 ratio of 2/1. With LSCN nanoparticles dispersed on the surface of GDC-LSM to maximize the reaction active sites, the LSCN impregnated cell shows significant enhanced electrochemical performance at both SOEC and SOFC modes. The influence of feed gas composition (H2O-H2-CO2) and operating voltages on the performance of co-electrolysis are discussed in detail. The cell shows a very stable performance without obvious degradation for more than 100 h. Post-test characterization is analyzed in detail by multiple measurements.

Determination of the constants of the solubility product of Ln(OH)3 and the effect of the chloride ions on the lanthanum hydrolysis, praseodymium and lutetium in aqueous solutions of ion force 2 Molar

International Nuclear Information System (INIS)

Lopez G, H.D.

2005-01-01

The behavior of lanthanum (III), praseodymium (III), and lutetium (III) was studied in 2 M NaClO 4 (aq) and 2 M NaCl (aq) at 303 K and free -CO 2 conditions. Solubility diagrams (p Ln(aq)-pC H ) were obtained by means of a radiochemical method. The pC H borderlines of saturation and unsaturation zones of the solutions and solubility product constants for Ln(OH) 3 were determined from these diagrams. The fitting of the solubility equation to the experimental values of p Ln(aq)-pC H diagrams allowed the calculation of the first hydrolysis and solubility product constants. Independently, the stability constants for the first species of hydrolysis were determined by means of pH titrations, the data were treated with the program SUPERQUAD and fitted to the mean ligand number equation. The stability constants for the species LnCl 2+ were as well calculated in 2M ionic strength and 303 K from the hydrolysis constant values obtained in both perchlorate and chloride media. The values obtained for La, Pr and Lu were: logK ps : 21.11 ± 0.09, 19.81 ± 0.11 and 18.10 ± 0.13 in 2M NaClO 4 ; logK ps : 22.22 ± 0.09, 21.45 ± 0.14 and 18.52 ± 0.29 in 2M NaCl; log β 1 : - 8.64 ± 0.02, - 8.37 ± 0.01 and - 7.95 ± 0.11 in 2M NaClO 4 ; log β 1 / : - 9.02 ± 0.11, - 8.75 ± 0.01 and - 8.12 ± 0.03 in 2M NaCl and the values for log β 1,Cl were - 0.0255, - 0.155 and - 0.758, respectively. (Author)

Carbon-14 immobilization via the Ba(OH)2.8H2O process

International Nuclear Information System (INIS)

Haag, G.L.; Nehls, J.W. Jr.; Young, G.C.

1983-03-01

The airborne release of 4 C from varous nuclear facilities has been identified as a potential biohazard due to the long half-life of 14 C (5730 y) and the ease with which it may be assimilated into the biosphere. At ORNL, technology has been developed for the removal and immobilization of this radionuclide. Prior studies have indicated that 14 C will likely exist in the oxidized form as CO 2 and will contribute slightly to the bulk CO 2 concentration of the gas stream, which is airlike in nature (approx. 330 ppmv CO 2 ). The technology that has been developed utilizes the CO 2 -Ba(OH) 2 .8H 2 O gas-solid reaction with the mode of gas-solid contacting being a fixed bed. The product, BaCO 3 , possesses excellent thermal and chemical stability, prerequisites for the long-term disposal of nuclear wastes. For optimal process operation, studies have indicated that an operating window of adequate size does exist. When operating within the window, high CO 2 removal efficiency (effluent concentrations 99%), and an acceptable pressure drop across the bed (3 kPa/m at a superficial velocity of 13 cm/s) are possible. This paper addresses three areas of experimental investigation: (1) microscale studies on 150-mg samples to provide information concerning surface properties, kinetics, and equilibrium vapor pressures; (2) macroscale studies on large fixed beds (4.2 kg of reactant) to determine the effects of humidity, temperature, and gas flow rate upon bed pressure drop and CO 2 breakthrough; and (3) design, construction, and initial operation of a pilot unit capable of continuously processing a 34-m 3 /h (20-ft 3 /min) air-based gas stream

Crystal structure of 4-RbHo(PO3)4, 4-RbTm(PO3)4 and 4-CsEr(PO3)4

International Nuclear Information System (INIS)

Maksimova, S.I.; Palkina, K.K.; Chibiskova, N.T.

1982-01-01

X-ray structural study of 4-RbLn(PO 3 ) 4 (Ln=Mo, Tm) and 4-CsEr(PO 3 ) 4 is carried out. The compounds are crystallized in monoclinic crystal system, sp. gr P2 1 /n. Parameters of their unit cell, atom coordinates, anisotropic heat parameters, interatomic distances and valent angles are given. 4-RbHo(PO 3 ) 4 , 4-RbTm(PO 3 ) 4 , 4-CsEr(PO 3 ) 4 are isostructural to previously studied TlNd(PO 3 ) and 4-RbNd(PO 3 ) 4 . Using as an example the structural type 4-M 1 Ln(PO 3 ) 4 it is shown that the change of the shortest distances Ln-Ln, M 1 -M 1 and M 1 -Ln, as well as of degree of polymorphous chain corrugation to a higher extent depends on rare earth atom dimensions, than on monovalent metal ion dimensions [ru

A high-power narrow-linewidth optical parametric oscillator based on PPMgLN

International Nuclear Information System (INIS)

Peng, Y F; Wei, X B; Xie, G; Gao, J R; Li, D M; Wang, W M

2013-01-01

A high-power and narrow-linewidth tunable optical parametric oscillator based on PPMgLN is presented. The phase matching type e → e + e is used to avoid the walk-off effect and utilize the maximum nonlinear coefficient d 33 (27.4 pm V −1 ) of the PPMgLN crystal (5 mol% MgO doped). When the pump power of the 1064 nm laser is 50 W and the temperature of the PPMgLN crystal is 100 °C, average output power of 15.8 W is obtained with a slope efficiency of 40.6%. The 1.655 μm signal and 2.98 μm idler output powers are 9.5 W and 6.3 W, respectively. The linewidth of the 1.655 μm signal laser is 1.00 nm before compression and 0.05 nm after compression. The compression ratio is 20. The linewidth of the 2.98 μm idler laser is within 0.30–0.63 nm based on theoretical analysis of the linewidth of the 1064 nm pump laser and 1.655 μm signal laser. The output wavelength can be tuned from 1.6 to 1.8 μm and from 3.1 to 2.7 μm by changing the temperature of the 31.2 μm PPMgLN crystal from 30 to 200 °C. (paper)

Dissolution of LnYSiAlO glass (Ln=La or Ce) in aqueous media. Part 3. Influence of β irradiation on structure and hydrolysis mechanisms

International Nuclear Information System (INIS)

Gavarini, S.; Carrot, F.; Trocellier, P.; Boizot, B.; Matzen, G.

2003-01-01

LnYSiAlO glasses (Ln=La or Ce) are considered as potential matrices for the specific storage of minor actinides. β particles emitted during the disintegration of fission products may cause important modifications to the glass network through electronic excitation and ionization. The influence of these processes on the structure of two analogous compositions of glass, involving La or Ce, and the consequences for their chemical durability were studied. Monoliths of glasses were irradiated with electrons that had been accelerated to 2.5 MeV and samples were then leached in static bidistilled water for one month at 90 C. Raman spectrometry, 27 Al MAS-NMR and EPR spectrometry experiments, performed after irradiation, globally indicated weak structural modifications. The two main effects of irradiation were an increase of the (Al IV )/(Al VI +Al V ) ratio and the formation of a paramagnetic center in the case of La-glass (g∼1.99). The former observation could indicate a slight migration and segregation of the rare earth, preferentially surrounded by highly charged Al V and Al VI units initially. The second point could be correlated with a change in the oxidation state of one of the La-glass component. The reason why no similar paramagnetic center is created during irradiation for Ce-glass is not well understood but a possible charge trapping process involving Ce(III)/Ce(IV) is developed. Finally, leaching solution analysis indicated that normalized elemental releases are almost unchanged after irradiation for both of the La and Ce-glass. The globally weak influence of β irradiation on this family of glass is subsequent to the low mobility of the major components that form high field strength bonds with oxygen

Synthesis, Characterization, and Catalytic Applications of Transition Metal Oxide/Carbonate Nanomaterials

Science.gov (United States)

Jin, Lei

2011-12-01

This thesis contains two parts: 1) Studies of novel synthesis methods and characterization of advanced functional manganese oxide octahedral molecular sieves (OMS) and their applications in Li/Air batteries, solvent free toluene oxidations, and ethane oxydehydrogenation (ODH) in the presence of CO2, recycling the green house gas. 2) Development of unique Ln2O2CO3 (Ln = rare earth) layered materials and ZnO/La2O2CO3 composites as clean energy biofuel catalysts. These parts are separated into five different focused topics included in this thesis. The first topic presents studies of catalytic activities of a single step synthesized gamma-MnO2 octahedral molecular sieve nano fiber in solvent free atmospheric oxidation of toluene with molecular oxygen. Solvent free atmospheric oxidation of toluene is a notoriously difficult liquid phase oxidation process due to the challenge of oxidizing sp³ hybridized carbon in inactive hydrocarbons. The synthesized gamma-MnO2 showed excellent catalytic activity and good selectivity under the mild atmospheric reflux system. Under optimized conditions, a 47.8% conversion of toluene, along with 57% selectivity of benzoic acid and 15% of benzaldehyde were obtained. The effects of reaction time, amount of catalyst and initiator, and the reusability of the catalyst were investigated. The second topic involves developing titanium containing gamma-MnO 2 (TM) hollow spheres as electrocatalysts in Li/Air Batteries. Li/air batteries have recently attracted interest because they have the largest theoretical specific energy (11,972 Wh.kg-1) among all practical electrochemical couples. In this study, unique hollow aspheric materials were prepared for the first time using a one-step synthesis method and fully characterized by various techniques. These prepared materials were found to have excellent electrocatalytic activation as cathode materials in lithium-air batteries with a very high specific capacity (up to 2.3 A.h/g of carbon). The third

The phase transition of the incommensurate phases β-Ln(PO3)3(Ln=Y,Tb…Yb), crystal structures of α-Ln(PO3)3(Ln=Y,Tb…Yb) and Sc(PO3)3

Science.gov (United States)

Höppe, Hennig A.

2009-07-01

The incommensurately modulated room-temperature phases β-Ln(PO3)3(Ln=Y,Tb…Yb) undergo a topotactic phase transition monitored by vibrational spectroscopy below 180 K leading to α-Ln(PO3)3(Ln=Y,Dy…Yb), above 200 K the incommensurate phases are reobtained. The low-temperature phases exhibit a new structure type (α-Dy(PO3)3, P21/c, Z=12,a=14.1422(6), b=20.0793(9),c=10.1018(4) A˚, β=127.532(3)∘). α-Tb(PO3)3 is isotypic with Gd(PO3)3(α-Tb(PO3)3, I2/a,Z=16,a=25.875(6), b=13.460(3), c=10.044(2) A˚, β=119.13(3)∘). The symmetry relations between the involved phases of the phase transition are discussed. The crystal structure of Sc(PO3)3 is isotypic with that of Lu(PO3)3 and C-type phosphates. The polyphosphates consist of infinite zig-zag chains of corner-sharing PO4 tetrahedra, the cations are coordinated sixfold in an almost octahedral arrangement. To confirm the quality of the determined crystal structures the deviation of the phosphate tetrahedra from ideal symmetry was determined and discussed.

Tunable emission in Ln3+ (Ce3+/Dy3+, Ce3+/Tb3+) doped KNa3Al4Si4O16 phosphor synthesized by combustion method

Science.gov (United States)

Kolte, M. M.; Pawade, V. B.; Bhattacharya, A. B.; Dhoble, S. J.

2018-05-01

Ln3+ (Ln = Ce3+/Dy3+, Ce3+/Tb3+) doped KNa3Al4Si4O16 phosphor has been synthesized by Combustion method (CS) at 550° C successfully. Ln3+ (Ln = Ce3+, Dy3+, Tb3+) ions when doped in KNa3Al4Si4O16 host lattice, it shows blue and green emission band under the near Ultraviolet (NUV) excitation wavelength. The Photoluminescence excitation (PLE) and emission spectra are observed due to f-f and d-f transition of rare earth ions. Also, an effective energy transfer (ET) study from Ce3+ → Dy3+ and Ce3+ → Tb3+ ions has been studied and confirmed on the basis of Dexter-Foster theory. Further synthesized phosphor is well characterized by XRD, SEM, TEM and decay time measurement. However, the analysis of crystallite size, lattice strain has been studied by using theoretical as well as experimental techniques. Hence, the observed tunable emission in Ln3+ doped KNa3Al4Si4O16 phosphor may be applicable for solid state lighting technology.

Series of isostructural planar lanthanide complexes [Ln(III)4(mu3-OH)2(mdeaH)2(piv)8] with single molecule magnet behavior for the Dy4 analogue.

Science.gov (United States)

Abbas, Ghulam; Lan, Yanhua; Kostakis, George E; Wernsdorfer, Wolfgang; Anson, Christopher E; Powell, Annie K

2010-09-06

A series of five isostructural tetranuclear lanthanide complexes of formula [Ln(4)(mu(3)-OH)(2)(mdeaH)(2)(piv)(8)], (mdeaH(2) = N-methyldiethanolamine; piv = pivalate; Ln = Tb (1), Dy (2), Ho (3), Er (4), and Tm (5)) have been synthesized and characterized. These clusters have a planar "butterfly" Ln(4) core. Magnetically, the Ln(III) ions are weakly coupled in all cases; the Dy(4) compound 2 shows Single Molecule Magnet (SMM) behavior.

Thickness measurement of a thin hetero-oxide film with an interfacial oxide layer by X-ray photoelectron spectroscopy

Science.gov (United States)

Kim, Kyung Joong; Lee, Seung Mi; Jang, Jong Shik; Moret, Mona

2012-02-01

The general equation Tove = L cos θ ln(Rexp/R0 + 1) for the thickness measurement of thin oxide films by X-ray photoelectron spectroscopy (XPS) was applied to a HfO2/SiO2/Si(1 0 0) as a thin hetero-oxide film system with an interfacial oxide layer. The contribution of the thick interfacial SiO2 layer to the thickness of the HfO2 overlayer was counterbalanced by multiplying the ratio between the intensity of Si4+ from a thick SiO2 film and that of Si0 from a Si(1 0 0) substrate to the intensity of Si4+ from the HfO2/SiO2/Si(1 0 0) film. With this approximation, the thickness levels of the HfO2 overlayers showed a small standard deviation of 0.03 nm in a series of HfO2 (2 nm)/SiO2 (2-6 nm)/Si(1 0 0) films. Mutual calibration with XPS and transmission electron microscopy (TEM) was used to verify the thickness of HfO2 overlayers in a series of HfO2 (1-4 nm)/SiO2 (3 nm)/Si(1 0 0) films. From the linear relation between the thickness values derived from XPS and TEM, the effective attenuation length of the photoelectrons and the thickness of the HfO2 overlayer could be determined.

Structural anomalies, spin transitions and charge disproportionation in LnCoO.sub.3./sub..

Czech Academy of Sciences Publication Activity Database

Knížek, Karel; Jirák, Zdeněk; Hejtmánek, Jiří; Henry, P.; André, G.

2008-01-01

Roč. 103, č. 7 (2008), 07B703/1-07B703/3 ISSN 0021-8979 R&D Projects: GA ČR GA202/06/0051 Institutional research plan: CEZ:AV0Z10100521 Keywords : LnCoO 3 * neutron diffraction * thermal expansion * spin-state transition Subject RIV: BM - Solid Matter Physics ; Magnetism Impact factor: 2.201, year: 2008

Expanding rare-earth oxidation state chemistry to molecular complexes of holmium(II) and erbium(II).

Science.gov (United States)

MacDonald, Matthew R; Bates, Jefferson E; Fieser, Megan E; Ziller, Joseph W; Furche, Filipp; Evans, William J

2012-05-23

The first molecular complexes of holmium and erbium in the +2 oxidation state have been generated by reducing Cp'(3)Ln [Cp' = C(5)H(4)SiMe(3); Ln = Ho (1), Er (2)] with KC(8) in the presence of 18-crown-6 in Et(2)O at -35 °C under argon. Purification and crystallization below -35 °C gave isomorphous [(18-crown-6)K][Cp'(3)Ln] [Ln = Ho (3), Er (4)]. The three Cp' ring centroids define a trigonal-planar geometry around each metal ion that is not perturbed by the location of the potassium crown cation near one ring with K-C(Cp') distances of 3.053(8)-3.078(2) Å. The metrical parameters of the three rings are indistinguishable within the error limits. In contrast to Ln(2+) complexes of Eu, Yb, Sm, Tm, Dy, and Nd, 3 and 4 have average Ln-(Cp' ring centroid) distances only 0.029 and 0.021 Å longer than those of the Ln(3+) analogues 1 and 2, a result similar to that previously reported for the 4d(1) Y(2+) complex [(18-crown-6)K][Cp'(3)Y] (5) and the 5d(1) La(2+) complex [K(18-crown-6)(Et(2)O)][Cp″(3)La] [Cp″ = 1,3-(Me(3)Si)(2)C(5)H(3)]. Surprisingly, the UV-vis spectra of 3 and 4 are also very similar to that of 5 with two broad absorptions in the visible region, suggesting that 3-5 have similar electron configurations. Density functional theory calculations on the Ho(2+) and Er(2+) species yielded HOMOs that are largely 5d(z(2)) in character and supportive of 4f(10)5d(1) and 4f(11)5d(1) ground-state configurations, respectively.

Novel curcumin analogue 14p protects against myocardial ischemia reperfusion injury through Nrf2-activating anti-oxidative activity

Energy Technology Data Exchange (ETDEWEB)

Li, Weixin [Department of Cardiology, The 5th Affiliated Hospital of Wenzhou Medical University, Lishui, Zhejiang (China); Chemical Biology Research Center, School of Pharmaceutical Science, Wenzhou Medical University, Wenzhou, Zhejiang (China); Wu, Mingchai [Department of Pharmacy, The Third Affiliated Hospital of Wenzhou Medical University, Wenzou, Zhejiang (China); Tang, Longguang; Pan, Yong; Liu, Zhiguo [Chemical Biology Research Center, School of Pharmaceutical Science, Wenzhou Medical University, Wenzhou, Zhejiang (China); Zeng, Chunlai [Department of Cardiology, The 5th Affiliated Hospital of Wenzhou Medical University, Lishui, Zhejiang (China); Wang, Jingying [Chemical Biology Research Center, School of Pharmaceutical Science, Wenzhou Medical University, Wenzhou, Zhejiang (China); Wei, Tiemin, E-mail: lswtm@sina.com [Department of Cardiology, The 5th Affiliated Hospital of Wenzhou Medical University, Lishui, Zhejiang (China); Liang, Guang, E-mail: wzmcliangguang@163.com [Chemical Biology Research Center, School of Pharmaceutical Science, Wenzhou Medical University, Wenzhou, Zhejiang (China)

2015-01-15

Background: Alleviating the oxidant stress associated with myocardial ischemia reperfusion has been demonstrated as a potential therapeutic approach to limit ischemia reperfusion (I/R)-induced cardiac damage. Curcumin, a natural compound with anti-oxidative activity, exerts beneficial effect against cardiac I/R injury, but poor chemical and metabolic stability. Previously, we have designed and synthesized a series of mono-carbonyl analogues of curcumin (MACs) with high stability. This study aims to find new anti-oxidant MACs and to demonstrate their effects and mechanisms against I/R-induced heart injury. Methods: H9c2 cells challenged with H{sub 2}O{sub 2} or TBHP were used for in vitro bio-screening and mechanistic studies. The MDA, H{sub 2}O{sub 2} and SOD levels in H9C2 cells were determined, and the cell viability was assessed by MTT assay. Myocardial I/R mouse models administrated with or without the compound were used for in vivo studies. Results: The in vitro cell-based screening showed that curcumin analogues 8d and 14p exhibited strong anti-oxidative effects. Pre-treatment of H9c2 cells with 14p activated Nrf2 signaling pathway, attenuated H{sub 2}O{sub 2}-increased MDA and SOD level, followed by the inhibition of TBHP-induced cell death and Bax/Bcl-2–caspase-3 pathway activation. Silencing Nrf2 significantly reversed the protective effects of 14p. In in vivo animal model of myocardial I/R, administration of low dose 14p (10 mg/kg) reduced infarct size and myocardial apoptosis to the same extent as the high dose curcumin (100 mg/kg). Conclusion: These data support the novel curcumin analogue 14p as a promising antioxidant to decrease oxidative stress and limit myocardial ischemia reperfusion injury via activating Nrf2. - Highlights: • Mono-carbonyl analogue of curcumin, 14p, exhibited better chemical stability. • Compound 14p inhibited TBHP-induced apoptosis through activating Nrf2 in vitro. • Compound 14p limited myocardial ischemia

Synthesis, structure, luminescent, and magnetic properties of carbonato-bridged Zn(II)2Ln(III)2 complexes [(μ4-CO3)2{Zn(II)L(n)Ln(III)(NO3)}2] (Ln(III) = Gd(III), Tb(III), Dy(III); L(1) = N,N'-bis(3-methoxy-2-oxybenzylidene)-1,3-propanediaminato, L(2) = N,N'-bis(3-ethoxy-2-oxybenzylidene)-1,3-propanediaminato).

Science.gov (United States)

Ehama, Kiyomi; Ohmichi, Yusuke; Sakamoto, Soichiro; Fujinami, Takeshi; Matsumoto, Naohide; Mochida, Naotaka; Ishida, Takayuki; Sunatsuki, Yukinari; Tsuchimoto, Masanobu; Re, Nazzareno

2013-11-04

Carbonato-bridged Zn(II)2Ln(III)2 complexes [(μ4-CO3)2{Zn(II)L(n)Ln(III)(NO3)}2]·solvent were synthesized through atmospheric CO2 fixation reaction of [Zn(II)L(n)(H2O)2]·xH2O, Ln(III)(NO3)3·6H2O, and triethylamine, where Ln(III) = Gd(III), Tb(III), Dy(III); L(1) = N,N'-bis(3-methoxy-2-oxybenzylidene)-1,3-propanediaminato, L(2) = N,N'-bis(3-ethoxy-2-oxybenzylidene)-1,3-propanediaminato. Each Zn(II)2Ln(III)2 structure possessing an inversion center can be described as two di-μ-phenoxo-bridged {Zn(II)L(n)Ln(III)(NO3)} binuclear units bridged by two carbonato CO3(2-) ions. The Zn(II) ion has square pyramidal coordination geometry with N2O2 donor atoms of L(n) and one oxygen atom of a bridging carbonato ion at the axial site. Ln(III) ion is coordinated by nine oxygen atoms consisting of four from the deprotonated Schiff-base L(n), two from a chelating nitrate, and three from two carbonate groups. The temperature-dependent magnetic susceptibilities in the range 1.9-300 K, field-dependent magnetization from 0 to 5 T at 1.9 K, and alternating current magnetic susceptibilities under the direct current bias fields of 0 and 1000 Oe were measured. The magnetic properties of the Zn(II)2Ln(III)2 complexes are analyzed on the basis of the dicarbonato-bridged binuclear Ln(III)-Ln(III) structure, as the Zn(II) ion with d(10) electronic configuration is diamagnetic. ZnGd1 (L(1)) and ZnGd2 (L(2)) show a ferromagnetic Gd(III)-Gd(III) interaction with J(Gd-Gd) = +0.042 and +0.028 cm(-1), respectively, on the basis of the Hamiltonian H = -2J(Gd-Gd)ŜGd1·ŜGd2. The magnetic data of the Zn(II)2Ln(III)2 complexes (Ln(III) = Tb(III), Dy(III)) were analyzed by a spin Hamiltonian including the crystal field effect on the Ln(III) ions and the Ln(III)-Ln(III) magnetic interaction. The Stark splitting of the ground state was so evaluated, and the energy pattern indicates a strong easy axis (Ising type) anisotropy. Luminescence spectra of Zn(II)2Tb(III)2 complexes were observed, while those

Synthesis and characterisation of the n = 2 Ruddlesden–Popper phases Ln{sub 2}Sr(Ba)Fe{sub 2}O{sub 7} (Ln = La, Nd, Eu)

Energy Technology Data Exchange (ETDEWEB)

Gurusinghe, Nicola N.M. [School of Chemistry, The University of Birmingham, Edgbaston, Birmingham B15 2TT (United Kingdom); Figuera, Juand de la; Marco, José F. [Instituto de Quimica-Fisica “Rocasolano”, CSIC, Serrano 119, 28006 Madrid (Spain); Thomas, Michael F. [Department of Physics, University of Liverpool, Liverpool. L69 3BX (United Kingdom); Berry, Frank J., E-mail: f.j.berry.1@bham.ac.uk [School of Chemistry, The University of Birmingham, Edgbaston, Birmingham B15 2TT (United Kingdom); Greaves, Colin [School of Chemistry, The University of Birmingham, Edgbaston, Birmingham B15 2TT (United Kingdom)

2013-09-01

Graphical abstract: - Highlights: • Some Ruddlesden–Popper phases have been characterised. • Substitution on the A site influences cationic order. • The magnetic moment redirects with temperature - Abstract: A series of n = 2 Ruddlesden–Popper phases A{sub 2}B{sub 2}O{sub 7} of composition Ln{sub 2}Sr(Ba)Fe{sub 2}O{sub 7} (Ln = La, Nd, Eu) have been prepared. La{sub 2}SrFe{sub 2}O{sub 7} and La{sub 2}BaFe{sub 2}O{sub 7} crystallise in the tetragonal space group I4/mmm. The structures of Eu{sub 2}SrFe{sub 2}O{sub 7} and Nd{sub 2}SrFe{sub 2}O{sub 7} are best described in space group P4{sub 2}/mnm. Substitution on the A site with smaller lanthanide- and larger alkaline metal- ions leads to enhanced cationic order in these phases and reflects increasing differences in cationic radii. All the compounds are antiferromagnetically ordered between 298 and 2 K. In La{sub 2}SrFe{sub 2}O{sub 7} the magnetic moment lies along [1 1 0] at all temperatures between 298 and 2 K whereas in La{sub 2}BaFe{sub 2}O{sub 7} the magnetic moment at 298 K lies along the crystallographic x-axis but redirects from the [1 0 0] to the [1 1 0] direction between 210 and 190 K and is retained in this direction until 2 K. In Nd{sub 2}SrFe{sub 2}O{sub 7} the magnetic moment at 298 K lies along [1 1 0] but rotates from [1 1 0] to [0 0 1] between 17 and 9 K. A series of {sup 57}Fe Mössbauer spectra recorded from La{sub 2}SrFe{sub 2}O{sub 7} between 290 and 600 K indicate a magnetic ordering temperature of T{sub N} ≥ 535 K.

Syntheses, structures and properties of three new two-dimensional Cu(I)-Ln(III) heterometallic coordination polymers based on 2,2'-dipyridyl-5,5'-dicarboxylate ligands.

Science.gov (United States)

Zhao, Junwei; Cheng, Yamin; Shang, Sensen; Zhang, Fang; Chen, Li; Chen, Lijuan

2013-12-01

Three new two-dimensional Cu(I)-Ln(III) heterometallic coordination polymers [Ln(III)Cu2(I)(Hbpdc)4] · Cl · xH2O [Ln(III) = La(III), x = 8 (1); Ln(III) = Pr(III), x=9 (2); Ln(III) = Eu(III), x = 8 (3)] (H2bpdc = 2,2'-bipyridyl-5,5'-dicarboxylic acid) have been prepared under hydrothermal conditions and structurally characterized by elemental analyses, inductively coupled plasma atomic emission spectrometry (ICP-AES) analyses, IR spectra, X-ray photoelectron spectroscopy (XPS) and single-crystal X-ray diffraction. X-ray diffraction indicates that the isomorphic 1-3 display the two-dimensional sheet structure constructed from [Cu(I)(Hbpdc)2](-) fragments through Ln(3+) connectors. Moreover, the solid-state photoluminescence measurements of 3 indicate that the Eu(III) ions, Hbpdc(-) ligands and Cu(I) cations make contributions to its luminescent properties simultaneously. Copyright © 2013 Elsevier B.V. All rights reserved.

Structure and bulk modulus of Ln-doped UO{sub 2} (Ln = La, Nd) at high pressure

Energy Technology Data Exchange (ETDEWEB)

Rittman, Dylan R., E-mail: drittman@stanford.edu [Department of Geological Sciences, Stanford University, Stanford, CA 94305 (United States); Park, Sulgiye; Tracy, Cameron L. [Department of Geological Sciences, Stanford University, Stanford, CA 94305 (United States); Zhang, Lei [Peter A. Rock Thermochemistry Laboratory and NEAT ORU, University of California Davis, Davis, CA 95616 (United States); Department of Chemical Engineering and Materials Science, University of California Davis, Davis, CA 95616 (United States); Palomares, Raul I.; Lang, Maik [Department of Nuclear Engineering, University of Tennessee, Knoxville, TN 37996 (United States); Navrotsky, Alexandra [Peter A. Rock Thermochemistry Laboratory and NEAT ORU, University of California Davis, Davis, CA 95616 (United States); Department of Chemical Engineering and Materials Science, University of California Davis, Davis, CA 95616 (United States); Mao, Wendy L. [Department of Geological Sciences, Stanford University, Stanford, CA 94305 (United States); Stanford Institute for Materials and Energy Sciences, SLAC National Accelerator Laboratory, Menlo Park, CA 94025 (United States); Ewing, Rodney C. [Department of Geological Sciences, Stanford University, Stanford, CA 94305 (United States)

2017-07-15

The structure of lanthanide-doped uranium dioxide, Ln{sub x}U{sub 1-x}O{sub 2-0.5x+y} (Ln = La, Nd), was investigated at pressures up to ∼50–55 GPa. Samples were synthesized with different lanthanides at different concentrations (x ∼ 0.2 and 0.5), and all were slightly hyperstoichiometric (y ∼ 0.25–0.4). In situ high-pressure synchrotron X-ray diffraction was used to investigate their high-pressure phase behavior and determine their bulk moduli. All samples underwent a fluorite-to-cotunnite phase transformation with increasing pressure. The pressure of the phase transformation increased with increasing hyperstoichiometry, which is consistent with results from previous computational simulations. Bulk moduli are inversely proportional to both the ionic radius of the lanthanide and its concentration, as quantified using a weighted cationic radius ratio. This trend was found to be consistent with the behavior of other elastic properties measured for Ln-doped UO{sub 2}, such as Young's modulus. - Highlights: •Ln-doped UO{sub 2} transforms from fluorite to cotunnite at high pressure. •Transition pressure increases with increasing hyperstoichiometry. •Bulk modulus decreases with increasing Ln-dopant radius and concentration.

The phase transition of the incommensurate phases β-Ln(PO3)3(Ln=Y,Tb...Yb), crystal structures of α-Ln(PO3)3(Ln=Y,Tb...Yb) and Sc(PO3)3

International Nuclear Information System (INIS)

Hoeppe, Hennig A.

2009-01-01

The incommensurately modulated room-temperature phases β-Ln(PO 3 ) 3 (Ln=Y,Tb...Yb) undergo a topotactic phase transition monitored by vibrational spectroscopy below 180 K leading to α-Ln(PO 3 ) 3 (Ln=Y,Dy...Yb), above 200 K the incommensurate phases are reobtained. The low-temperature phases exhibit a new structure type (α-Dy(PO 3 ) 3 ,P2 1 /c,Z=12,a=14.1422(6),b=20.0793(9),c=10.1018(4)A, β=127.532(3) 0 ). α-Tb(PO 3 ) 3 is isotypic with Gd(PO 3 ) 3 (α-Tb(PO 3 ) 3 ,I2/a,Z=16,a=25.875(6),b=13.460(3),c=10.044(2)A, β=119.13(3) 0 ). The symmetry relations between the involved phases of the phase transition are discussed. The crystal structure of Sc(PO 3 ) 3 is isotypic with that of Lu(PO 3 ) 3 and C-type phosphates. The polyphosphates consist of infinite zig-zag chains of corner-sharing PO 4 tetrahedra, the cations are coordinated sixfold in an almost octahedral arrangement. To confirm the quality of the determined crystal structures the deviation of the phosphate tetrahedra from ideal symmetry was determined and discussed. - Abstract: Basic structure from which all crystal structures of the late lanthanoids' polyphosphates at room temperature and below can be derived.

High-pressure syntheses of lanthanide polysulfides and polyselenides LnX_1_._9 (Ln = Gd-Tm, X = S, Se)

International Nuclear Information System (INIS)

Mueller, Carola J.; Schwarz, Ulrich; Doert, Thomas

2012-01-01

The polysulfides LnS_1_._9 and polyselenides LnSe_1_._9 of the lanthanide metals from gadolinium to thulium were prepared by high-pressure high-temperature synthesis. The compounds adopt the tetragonal CeSe_1_._9 structure type in space group P4_2/n (No. 86) with lattice parameters of 8.531 Aa ≤ a ≤ 8.654 Aa and 15.563 Aa ≤ c ≤ 15.763 Aa for the sulfides and 8.869 Aa ≤ a ≤ 9.076 Aa and 16.367 Aa ≤ c ≤ 16.611 Aa for the selenides. The atomic pattern consists of puckered double slabs [LnX]"+ and planar chalcogenide layers with ten possible chalcogen positions, of which eight are occupied by chalcogen atoms forming dinuclear X_2"2"- dianions, one by a single X"2"- ion and one remaining vacant. This resembles a √5 x √5 x 2 superstructure of the ZrSSi aristotype. Structural relationships to the aristotype and the related lanthanide polychalcogenides LnX_2_-_δ (Ln = La-Tm, X = S-Te, δ = 0 - 0.3) are discussed. The samples synthesized under high-pressure conditions (p > 1 GPa) decompose slowly under release of sulfur or selenium at ambient conditions. The crystal structure of a partially degraded thulium-polysulfide sample can be described as an incommensurate variant of the original TmS_1_._9 motif. Additionally, the isostructural ternary compound Gd(S_1_-_xSe_x)_1_._9 was synthesized and characterized by powder X-ray diffraction. (Copyright copyright 2012 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim)

An Efficient Synthesis of Phenols via Oxidative Hydroxylation of Arylboronic Acids Using (NH42S2O8

Directory of Open Access Journals (Sweden)

Claudia A. Contreras-Celedón

2014-01-01

Full Text Available A mild and efficient method for the ipso-hydroxylation of arylboronic acids to the corresponding phenols was developed using (NH42S2O8 as an oxidizing agent. The reactions were performed under metal-, ligand-, and base-free conditions.

Oxidative stress augments toll-like receptor 8 mediated neutrophilic responses in healthy subjects

Directory of Open Access Journals (Sweden)

Matsunaga Kazuto

2009-06-01

Full Text Available Abstract Background Excessive oxidative stress has been reported to be generated in inflamed tissues and contribute to the pathogenesis of inflammatory lung diseases, exacerbations of which induced by viral infections are associated with toll-like receptor (TLR activation. Among these receptors, TLR8 has been reported as a key receptor that recognizes single-strand RNA virus. However, it remains unknown whether TLR8 signaling is potentiated by oxidative stress. The aim of this study is to examine whether oxidative stress modulates TLR8 signaling in vitro. Methods Human peripheral blood neutrophils were obtained from healthy non-smokers and stimulated with TLR 7/8 agonist imidazoquinoline resiquimod (R848 in the presence or absence of hydrogen peroxide (H2O2. Neutrophilic responses including cytokine release, superoxide production and chemotaxis were examined, and the signal transduction was also analyzed. Results Activation of TLR8, but not TLR7, augmented IL-8 release. The R848-augmented IL-8 release was significantly potentiated by pretreatment with H2O2 (p L-cysteine reversed this potentiation. The combination of H2O2 and R848 significantly potentiated NF-kB phosphorylation and IkBα degradation. The H2O2-potentiated IL-8 release was suppressed by MG-132, a proteosome inhibitor, and by dexamethasone. The expressions of TLR8, myeloid differentiation primary response gene 88 (MyD88, and tumor necrosis factor receptor-associated factor 6 (TRAF6 were not affected by H2O2. Conclusion TLR8-mediated neutrophilic responses were markedly potentiated by oxidative stress, and the potentiation was mediated by enhanced NF-kB activation. These results suggest that oxidative stress might potentiate the neutrophilic inflammation during viral infection.

Reconsideration of Orth I and Orth II Phases in Ln-System Superconductors

Science.gov (United States)

Liu, Yue-Wei; Wang, Lu; Zhang, Han

2006-02-01

A block model is used to calculate the combinative energy in LnBa2Cu3O7-x (Ln=Y, Er, Nd) systems, and the energy has no difference for orth-I and orth-II in the plateau range. Namely, no matter what phase it is, when the oxygen deficiency is in the range of δ~0.35-0.55, the plateau appears in the energy -δ curves, and the combinative energy has close correlation with the Tc value. The result in the present work gives some hints to reconsider the role of the order of oxygen defects or its effect on superconductivity in LnBa2Cu3O7-x. The existence of the orth-II seems not to be the reason for the plateau in the Tc curve. This is an important problem for LnBa2Cu3O7-x and some suggestion is given in the discussion.

A highly sensitive fluorescence quenching method for perphenazine detection based on its catalysis of K{sub 2}S{sub 2}O{sub 8} oxidizing rhodamine 6G

Energy Technology Data Exchange (ETDEWEB)

Zhang, Lihong; Huang, Qitong; Lin, Changqing [Department of Food and Biological Engineering, Zhangzhou Institute of Technology, Zhangzhou, 363000 (China); Lin, Xiaofeng [College of Chemistry and Environment, Minnan Normal University, Zhangzhou, 363000 (China); Huang, Yiqun [Zhangzhou Affiliated Hospital of Fujian Medical University, Zhangzhou 363000 (China); Liu, Jiaming, E-mail: mnsdljm@163.com [College of Chemistry and Environment, Minnan Normal University, Zhangzhou, 363000 (China); Ma, Xudong, E-mail: maxudong005@hotmail.com [Zhangzhou Affiliated Hospital of Fujian Medical University, Zhangzhou 363000 (China)

2014-12-15

In this paper, the fluorescence spectra of Rhod 6G (rhodamine 6G)–K{sub 2}S{sub 2}O{sub 8}–PPH (perphenazine) were studied. We found that Rhod 6G existed in the form of Rhod 6G{sup +} under the conditions of 60 °C, 10 min and pH 5.42, and Rhod 6G{sup +} can emit strong and stable fluorescence. Further study showed that when PPH and Rhod 6G{sup +} coexisted, the ester exchange reaction carried out between -OH of PPH and -COOC{sub 2}H{sub 5} of Rhod 6G{sup +} to produced Rhod 6G{sup +}–PPH compound. More interestingly, K{sub 2}S{sub 2}O{sub 8} could oxidize Rhod 6G{sup +} and quench its RTP signal, while PPH was oxidized to red compound PPH′ by K{sub 2}S{sub 2}O{sub 8}, and Rhod 6G{sup +}–PPH′ and PPH were produced in the ester exchange reaction between the -OH of PPH′ and the -COOC{sub 2}H{sub 5} of Rhod 6G{sup +}–PPH. In the above process, PPH catalyzed K{sub 2}S{sub 2}O{sub 8} oxidizing Rhod 6G, which caused the fluorescence signal of the system to quench sharply. Hence, a catalytic fluorescence quenching method for the determination of residual PPH has been developed based on the its catalyzing K{sub 2}S{sub 2}O{sub 8} oxidize rhodamine 6G. This sensitive, accurate, simple and selective fluorescence quenching method was used to determine residual PPH in biological samples with the results consisting with those obtained by high performance liquid chromatography (HPLC), showing good accuracy. The structures of Rhod 6G{sup +}, PPH and Rhod 6G{sup +}–PPH were characterized by infrared spectra. The reaction mechanism of the determination of PPH was also discussed. - Highlights: • Fluorescence for the determination of perphenazine (PPH) had been established. • This method had high sensitivity (limit of detection was 3.3×10{sup −14} g mL{sup −1}). • This method had been applied to determination of PPH in biological samples. • Structures of Rhod 6G{sup +}, PPH and Rhod 6G{sup +}–PPH were characterized by infrared spectra. • Mechanism

Three isostructural one-dimensional Ln(III) chains with distorted cubane motifs showing dual fluorescence and slow magnetic relaxation/magnetocaloric effect.

Science.gov (United States)

Li, Yan; Yu, Jia-Wen; Liu, Zhong-Yi; Yang, En-Cui; Zhao, Xiao-Jun

2015-01-05

Three new homometallic lanthanide complexes with mixed carboxylate-modified rigid ligands, [Ln(μ3-OH)(na)(pyzc)]n (na(-) = 1-naphtholate, pyzc(-) = 2-pyrazinecarboxylate, Ln = Dy (1), Yb (2), and Gd (3)), were solvothermally synthesized, and their structures and magnetic as well as photophysical properties were completely investigated. Complexes 1-3 are crystallographically isostructural, exhibiting linear chains with four bidentate bridging μ-COO(-) moieties encapsulated cubic {Ln4(μ3-OH)4}(8+) clusters repeatedly extended by 4-fold chelating-bridging-pyzc(-) connectors. Magnetically, the former two complexes with highly anisotropic Dy(III) and weak anisotropic Yb(III) ions in the distorted NO7 triangular dodecahedron coordination environment display field-induced slow relaxation of magnetization. Fitting the dynamic magnetic data to the Arrhenius law gives energy barrier ΔE/kB = 39.6 K and pre-exponential factor τo = 1.52 × 10(-8) s for 1 and ΔE/kB = 14.1 K and τo = 2.13 × 10(-7) s for 2. By contrast, complex 3 with isotropic Gd(III) ion and weak intracluster antiferromagnetic coupling shows a significant cryogenic magnetocaloric effect, with a maximum -ΔSm value of 30.0 J kg(-1) K(-1) at 2.5 K and 70 kOe. Additionally, the chromophoric na(-) and pyzc(-) ligands can serve as antenna groups, selectively sensitizing the Dy(III)- and Yb(III)-based luminescence of 1 and 2 in the UV-visible region by an intramolecular energy transfer process. Thus, complexes 1-3, incorporating field-induced slow magnetic magnetization and interesting luminescence together, can be used as composite magneto-optical materials. More importantly, these interesting results further demonstrate that the mixed-ligand system with rigid carboxylate-functionalized chromophores can be excellent candidates for the preparations of new bifunctional magneto-optical materials.

U3O8 obtained from metallic uranium

International Nuclear Information System (INIS)

Lopez, Marisol; Gonzalez, Alfredo; Pasqualini, Enrique E.

2003-01-01

Enriched uranium oxide, U 3 O 8 , used as nuclear powder in MTR's, can be obtained by direct oxidation of metallic uranium at 800 C degrees. Maximum density, 8.2 gr/cm 3 , is achieved after grinding and a high temperature treatment at 1400 C degrees. All the process is highly controllable and performed in dry environments. (author)

Cobalt Oxide Catalysts Supported on CeO2–TiO2 for Ethanol Oxidation and N2O Decomposition.

Czech Academy of Sciences Publication Activity Database

Jirátová, Květa; Kovanda, F.; Balabánová, Jana; Koloušek, D.; Klegová, A.; Pacultová, K.; Obalová, L.

2017-01-01

Roč. 12, č. 1 (2017), s. 121-139 ISSN 1878-5190. [Pannonian Symposium on Catalysis. Siófok, 19.09.2016-23.09.2016] R&D Projects: GA ČR GA14-13750S Institutional support: RVO:67985858 Keywords : cobalt oxide catalysts * ethanol total oxidation * N2O decomposition Subject RIV: CI - Industrial Chemistry, Chemical Engineering OBOR OECD: Chemical process engineering Impact factor: 1.264, year: 2016

Electric Field Generation and Control of Bipartite Quantum Entanglement between Electronic Spins in Mixed Valence Polyoxovanadate [GeV14O40]8.

Science.gov (United States)

Palii, Andrew; Aldoshin, Sergey; Tsukerblat, Boris; Borràs-Almenar, Juan José; Clemente-Juan, Juan Modesto; Cardona-Serra, Salvador; Coronado, Eugenio

2017-08-21

As part of the search for systems in which control of quantum entanglement can be achieved, here we consider the paramagnetic mixed valence polyoxometalate K 2 Na 6 [GeV 14 O 40 ]·10H 2 O in which two electrons are delocalized over the 14 vanadium ions. Applying a homogeneous electric field can induce an antiferromagnetic coupling between the two delocalized electronic spins that behave independently in the absence of the field. On the basis of the proposed theoretical model, we show that the external field can be used to generate controllable quantum entanglement between the two electronic spins traveling over a vanadium network of mixed valence polyoxoanion [GeV 14 O 40 ] 8- . Within a simplified two-level picture of the energy pattern of the electronic pair based on the previous ab initio analysis, we evaluate the temperature and field dependencies of concurrence and thus indicate that the entanglement can be controlled via the temperature, magnitude, and orientation of the electric field with respect to molecular axes of [GeV 14 O 40 ] 8- .

Spectrophotometric investigation of addition compounds between neodymium (III) and europium (III) perchorates and hexafluorophosphate and cyclic ligants with two oxygen in opposite position

International Nuclear Information System (INIS)

Oliveira, M.A.S.

1986-01-01

Addition compounds between Nd 3+ and Eu 3+ perchlorates and hexafluorophosphates with trans-1,4-dithino-1,4-dioxide (TDTD), pyrazine-1,4-dioxide (pyzDO), 2,5 - piperazinedione (pdo) and 1-4-diazabicyclo /2,2,2/-octane-1,4-dioxide or triethylenediamine dioxide (TEDADO) were prepared. The lanthanide content was determined by complexometric titration with EDTA. Carbon, hydrogen and nitrogen were determined by microanalytical procedures and water by the Karl Fischer method. The following stoichiometries were determined: Nd(ClO 4 ) 3 .6TDTD.8H 2 O; Eu(ClO 4 ) 3 .6TDTD.4H 2 O; Ln(PF 6 ) 3 .4TDTD.4H 2 O; Ln(ClO 4 ) 3 .4pyzDO; Ln(ClO 4 ) 3 .4pdo; Ln(ClO 4 ) 3 .3TEDADO.3H 2 O; Ln(PF 6 ) 3 .3TEDADO.3H 2 O (Ln = Nd 3+ and Eu 3+ ). X-ray powder patterns of the perchlorates show that the compounds of neodymium and europium with the respective ligands are isomorphous. The samme occurs in relation to Nd 3+ and Eu 3+ hexafluorophosphates. The results of the infared spectra, Raman spectra, absorption electronic spectra and fluorescence electronic spectra are also presented. (author) [pt

Benzylic oxidation of gemfibrozil-1-O-beta-glucuronide by P450 2C8 leads to heme alkylation and irreversible inhibition.

Science.gov (United States)

Baer, Brian R; DeLisle, Robert Kirk; Allen, Andrew

2009-07-01

Gemfibrozil-1-O-beta-glucuronide (GEM-1-O-gluc), a major metabolite of the antihyperlipidemic drug gemfibrozil, is a mechanism-based inhibitor of P450 2C8 in vitro, and this irreversible inactivation may lead to clinical drug-drug interactions between gemfibrozil and other P450 2C8 substrates. In light of this in vitro finding and the observation that the glucuronide conjugate does not contain any obvious structural alerts, the current study was conducted to determine the potential site of GEM-1-O-gluc bioactivation and the subsequent mechanism of P450 2C8 inhibition (i.e., modification of apoprotein or heme). LC/MS analysis of a reaction mixture containing recombinant P450 2C8 and GEM-1-O-gluc revealed that the substrate was covalently linked to the heme prosthetic heme group during catalysis. A combination of mass spectrometry and deuterium isotope effects revealed that a benzylic carbon on the 2',5'-dimethylphenoxy group of GEM-1-O-gluc was covalently bound to the heme of P450 2C8. The regiospecificity of substrate addition to the heme group was not confirmed experimentally, but computational modeling experiments indicated that the gamma-meso position was the most likely site of modification. The metabolite profile, which consisted of two benzyl alcohol metabolites and a 4'-hydroxy-GEM-1-O-gluc metabolite, indicated that oxidation of GEM-1-O-gluc was limited to the 2',5'-dimethylphenoxy group. These results are consistent with an inactivation mechanism wherein GEM-1-O-gluc is oxidized to a benzyl radical intermediate, which evades oxygen rebound, and adds to the gamma-meso position of heme. Mechanism-based inhibition of P450 2C8 can be rationalized by the formation of the GEM-1-O-gluc-heme adduct and the consequential restriction of additional substrate access to the catalytic iron center.

Oxidation of 1-butene over uranium oxide (UO3)-antimony oxide (Sb2O3) catalysts

NARCIS (Netherlands)

Simons, T.; Houtman, P.N.; Schuit, G.C.A.

1971-01-01

The oxidative dehydrogenation of butene to butadiene over U-Sb catalysts was investigated. The presence of two compds., (UO2)Sb3O7 and Sb3U3O14, reported by Grasselli and Callahan (1969), was confirmed with (UO2)Sb3O7 being the actual catalyst. The reaction is first order in butene and zero order in

Structural and physical properties of a novel misfit-layered cobalt oxide (CaOH)1.14CoO2

International Nuclear Information System (INIS)

Isobe, Masaaki; Shizuya, Mitsuyuki; Takayama-Muromachi, Eiji

2007-01-01

We have studied crystal structure and physical properties of a new layered cobalt oxide (CaOH) 1.14 CoO 2 . The compound is a composite crystal which consists of two interpenetrating subsystems of the CdI 2 -type CoO 2 layer and the rock-salt-type double CaOH atomic layer. The two subsystems have incommensurate periodicity along the a-axis, resulting in modulated crystal structure due to the inter-subsystem interaction. We found that the observed physical properties originate in the electronic state with a 'low-carrier-density limit' in the cobalt t 2g band

Magnetic properties and crystal field effects in TlLnX2 compounds (X=S, Se, Te)

International Nuclear Information System (INIS)

Duczmal, M.; Pawlak, L.

1997-01-01

Ternary thallium lanthanide chalcogenides TlLnX 2 (X=S, Se or Te) crystallize in the α-NaFeO 2 type of structure (R anti 3m). Each kind of the metal ions, surrounded by the distorted chalcogenide octahedra, forms separate layers. The TlX 6 octahedra are strongly elongated and the LnX 6 octahedra slightly shrunk along the threefold axis. The deformations of the coordination polyhedra and the cell volumes change regularly with the lanthanide ionic radii. The difference between the experimental and the calculated M-X distances increases on going from sulphides to tellurides, as a result of the growing covalent character of the bonds. The crystal field parameters were estimated from the high field magnetization (0-14 T) assuming trigonal distortion of the octahedral symmetry of LnX 6 polyhedra. The second-order crystal field parameters were found to correlate with the deformation of the lanthanide ions' environments. No magnetic transition was observed down to 4.2 K. (orig.)

[Mechanism and performance of styrene oxidation by O3/H2O2].

Science.gov (United States)

He, Jue-Cong; Huang, Qian-Ru; Ye, Qi-Hong; Luo, Yu-Wei; Zhang, Zai-Li; Fan, Qing-Juan; Wei, Zai-Shan

2013-10-01

It can produce a large number of free radicals in O3/H2O2, system, ozone and free radical coupling oxidation can improve the styrene removal efficiency. Styrene oxidation by O3/H2O2 was investigated. Ozone dosage, residence time, H2o2 volume fraction, spray density and molar ratio of O3/C8H8 on styrene removal were evaluated. The experimental results showed that styrene removal efficiency achieved 85.7%. The optimal residence time, H2O2, volume fraction, spray density and O3/C8H8 molar ratio were 20. 6 s, 10% , 1.72 m3.(m2.h)-1 and 0.46, respectively. The gas-phase degradation intermediate products were benzaldehyde(C6H5CHO) and benzoic acid (C6H5 COOH) , which were identified by means of gas chromatography-mass spectrometry(GC-MS). The degradation mechanism of styrene is presented.

Releasing metal catalysts via phase transition: (NiO)0.05-(SrTi0.8Nb0.2O3)0.95 as a redox stable anode material for solid oxide fuel cells.

Science.gov (United States)

Xiao, Guoliang; Wang, Siwei; Lin, Ye; Zhang, Yanxiang; An, Ke; Chen, Fanglin

2014-11-26

Donor-doped perovskite-type SrTiO3 experiences stoichiometric changes at high temperatures in different Po2 involving the formation of Sr or Ti-rich impurities. NiO is incorporated into the stoichiometric strontium titanate, SrTi0.8Nb0.2O3-δ (STN), to form an A-site deficient perovskite material, (NiO)0.05-(SrTi0.8Nb0.2O3)0.95 (Ni-STN), for balancing the phase transition. Metallic Ni nanoparticles can be released upon reduction instead of forming undesired secondary phases. This material design introduces a simple catalytic modification method with good compositional control of the ceramic backbones, by which transport property and durability of solid oxide fuel cell anodes are largely determined. Using Ni-STN as anodes for solid oxide fuel cells, enhanced catalytic activity and remarkable stability in redox cycling have been achieved. Electrolyte-supported cells with the cell configuration of Ni-STN-SDC anode, La0.8Sr0.2Ga0.87Mg0.13O3 (LSGM) electrolyte, and La0.6Sr0.4Co0.2Fe0.8O3 (LSCF) cathode produce peak power densities of 612, 794, and 922 mW cm(-2) at 800, 850, and 900 °C, respectively, using H2 as the fuel and air as the oxidant. Minor degradation in fuel cell performance resulted from redox cycling can be recovered upon operating the fuel cells in H2. Such property makes Ni-STN a promising regenerative anode candidate for solid oxide fuel cells.

Magnetism of cyano-bridged Ln3+-M3+ complexes. Part II: one-dimensional complexes (Ln3+ = Eu, Tb, Dy, Ho, Er, Tm; M3+ = Fe or Co) with bpy as blocking ligand.

Science.gov (United States)

Figuerola, Albert; Ribas, Joan; Casanova, David; Maestro, Miguel; Alvarez, Santiago; Diaz, Carmen

2005-10-03

The reaction of Ln(NO3)3(aq) with K3[Fe(CN)6] or K3[Co(CN)6] and 2,2'-bipyridine in water/ethanol led to 13 one-dimensional complexes: trans-[M(CN)4(mu-CN)2Ln(H2O)4(bpy)]n.4nH2O.1.5nbpy (Ln = Eu3+, Tb3+, Dy3+, Ho3+, Er3+, Tm3+, Lu3+; M = Fe3+, Co3+). The structures for [EuFe]n (1), [TbFe]n (2), [DyFe]n (3), [HoFe]n (4), [ErFe]n (5), [TmFe]n (6), [LuFe]n (7), [EuCo]n (8), [TbCo]n (9), [DyCo]n (10), [HoCo]n (11), [ErCo]n (12), and [TmCo]n (13) have been solved: they crystallize in the triclinic space group P and are isomorphous. They exhibit a supramolecular architecture created by the interplay of coordinative, hydrogen bonding, and pi-pi interactions. A stereochemical study of the eight-vertex polyhedra of the lanthanide ions, based on continuous shape measures, is presented. The Ln3+-Fe3+ interaction is antiferromagnetic in [DyFe]n and [TbFe]n. For [EuFe]n, [HoFe]n, [ErFe]n, and [TmFe]n, there is no sign of any significant interaction. The magnetic behavior of [DyFe]n suggests the onset of weak long-range ferromagnetic ordering at 2.5 K.

Synthesis, surface modification/decoration of luminescent–magnetic core/shell nanomaterials, based on the lanthanide doped fluorides (Fe3O4/SiO2/NH2/PAA/LnF3)

International Nuclear Information System (INIS)

Runowski, Marcin; Lis, Stefan

2016-01-01

The synthesized magnetite nanoparticles (10–15 nm) were successfully coated with amine modified silica nanoshell, which led to the formation of core/shell type nanostructures (30–50 nm). The as-prepared nanoparticles were surface modified with polyacrylic acid (PAA) via electrostatic interactions of –NH 2 and –COOH groups. Afterwards, the surface PAA molecules acted as complexing agents of the introduced lanthanide (Ln 3+ ) ions. Subsequently, the as-prepared nanostructures were surface decorated with luminescent LnF 3 nanoparticles, forming Eu 3+ or Tb 3+ doped Fe 3 O 4 /SiO 2 /NH 2 /PAA/LnF 3 nanomaterials (50–100 nm). The obtained luminescent–magnetic products exhibited simultaneously bright red or green emission under UV lamp irradiation (λ ex =254 nm), and a response for the applied magnetic field (strong magnet attracts the colloidal particles, dispersed in aqueous medium). After the synthesis, properties of the nanomaterials were investigated by powder X-ray diffraction (XRD) technique, transmission electron microscopy (TEM), infrared spectroscopy (IR) and spectrofluorometry (analysis of excitation/emission spectra and luminescence decay curves). Such advanced nanomaterials can be potentially used in multimodal imaging, targeted therapies and as multifunctional contrast agents, novel luminescent–magnetic tracers, protection of documents, etc. - Highlights: • Luminescent–magnetic nanomaterials Fe 3 O 4 /SiO 2 /NH 2 /PAA/LnF 3 were synthesized. • Core/shell nanostructures were obtained by surface modification of nanoparticles. • Luminescent lanthanide fluoride nanoparticles doped with Eu 3+ and Tb 3+ ions. • Multifunctional core/shell nanostructures exhibited red or green emission. • Nanomaterials formed stable aqueous colloids.

Synthesis, Crystal Structures, Magnetic Properties, and Theoretical Investigation of a New Series of NiII-LnIII-WV Heterotrimetallics: Understanding the SMM Behavior of Mixed Polynuclear Complexes.

Science.gov (United States)

Vieru, Veacheslav; Pasatoiu, Traian D; Ungur, Liviu; Suturina, Elizaveta; Madalan, Augustin M; Duhayon, Carine; Sutter, Jean-Pascal; Andruh, Marius; Chibotaru, Liviu F

2016-12-05

The polynuclear compounds containing anisotropic metal ions often exhibit efficient barriers for blocking of magnetization at fairly arbitrary geometries. However, at variance with mononuclear complexes, which usually become single-molecule magnets (SMM) under the sole requirement of a highly axial crystal field at the metal ion, the factors influencing the SMM behavior in polynuclear complexes, especially, with weakly axial magnetic ions, still remain largely unrevealed. As an attempt to clarify these conditions, we present here the synthesis, crystal structures, magnetic behavior, and ab initio calculations for a new series of Ni II -Ln III -W V trimetallics, [(CN) 7 W(CN)Ni(H 2 O)(valpn)Ln(H 2 O) 4 ]·H 2 O (Ln = Y 1, Eu 2, Gd 3, Tb 4, Dy 5, Lu 6). The surprising finding is the absence of the magnetic blockage even for compounds involving strongly anisotropic Dy III and Tb III metal ions. This is well explained by ab initio calculations showing relatively large transversal components of the g-tensor in the ground exchange Kramers doublets of 1 and 4 and large intrinsic tunneling gaps in the ground exchange doublets of 3 and 5. In order to get more insight into this behavior, another series of earlier reported compounds with the same trinuclear [W V Ni II Ln III ] core structure, [(CN) 7 W(CN)Ni(dmf)(valdmpn)Ln(dmf) 4 ]·H 2 O (Ln = Gd III 7, Tb III 8a, Dy III 9, Ho III 10), [(CN) 7 W(CN)Ni(H 2 O)(valdmpn)Tb(dmf) 2.5 (H 2 O) 1.5 ]·H 2 O·0.5dmf 8b, and [(CN) 7 W(CN)Ni(H 2 O)(valdmpn)Er(dmf) 3 (H 2 O) 1 ]·H 2 O·0.5dmf 11, has been also investigated theoretically. In this series, only 8b exhibits SMM behavior which is confirmed by the present ab initio calculations. An important feature for the entire series is the strong ferromagnetic coupling between Ni(II) and W(V), which is due to an almost perfect trigonal dodecahedron geometry of the octacyano wolframate fragment. The reason why only 8b is an SMM is explained by positive zero-field splitting on the nickel

Lattice dynamics of cubic Cs2NaLnX6 and CsNaLn1-xLn'xX6 elpasolites

International Nuclear Information System (INIS)

Acevedo, R.; Poblete, V.; Alzamora, R.; Venegas, R.; Navarro, G.; Henriquez, C.

1999-01-01

Crystal lattice dynamics of stoichiometric Cs 2 NaLnX 6 and nonstoichiometric CsNaLn 1-x Ln' x X 6 , 0.01 ≤ x ≤ 0.10, Ln and Ln' are trivalent positive lanthanide ions and X is chlorine or bromine, were studied.. Phonon dispersion relations were computed for similar compound, Cs 2 UBr 6 , and vibronic absorption spectra with reduced number of required input parameters are considered on the basis of proposed model. (author)

Magnetism of cyano-bridged hetero-one-dimensional Ln3+-M3+ complexes (Ln3+ = Sm, Gd, Yb; M3+ = FeLS, Co).

Science.gov (United States)

Figuerola, Albert; Diaz, Carmen; Ribas, Joan; Tangoulis, Vassilis; Sangregorio, Claudio; Gatteschi, Dante; Maestro, Miguel; Mahía, José

2003-08-25

The reaction of Ln(NO(3))(3).aq with K(3)[Fe(CN)(6)] or K(3)[Co(CN)(6)] and 2,2'-bipyridine in water led to five one-dimensional complexes: trans-[M(CN)(4)(mu-CN)(2)Ln(H(2)O)(4) (bpy)](n)().XnH(2)O.1.5nbpy (M = Fe(3+) or Co(3+); Ln = Sm(3+), Gd(3+), or Yb(3+); X = 4 or 5). The structures for [Fe(3)(+)-Sm(3+)] (1), [Fe(3)(+)-Gd(3+)] (2), [Fe(3)(+)-Yb(3+)] (3), [Co(3)(+)-Gd(3+)] (4), and [Co(3)(+)-Yb(3+)] (5) have been solved; they crystallize in the triclinic space P1 and are isomorphous. The [Fe(3+)-Sm(3+)] complex is a ferrimagnet, its magnetic studies suggesting the onset of weak ferromagnetic 3-D ordering at 3.5 K. The [Fe(3+)-Gd(3+)] interaction is weakly antiferromagnetic. The isotropic nature of Gd(3+) allowed us to evaluate the exchange interaction (J = 0.77 cm(-)(1)).

OXIDATIVE DEHYDROGENATION OF PROPANE BY RARE EARTH PHOSPHATES SUPPORTED ON AL-PILC

Directory of Open Access Journals (Sweden)

Carolina De Los Santos

2012-12-01

Full Text Available Catalytic activity in propane oxidative dehydrogenation of rare earth phosphates LnPO4 (where Ln = La, Ce, Pr, Nd, Sm and of the same supported by an aluminum pillared clay, of high specific surface area, is presented. The solids were characterized by TGA, XRD, nitrogen adsorption and immediate analysis after reaction in order to determine eventual carbon formation. Catalytic assays were performed at temperatures in the range 400oC-600oC, the reaction mixture was C3H8/O2/Ar = 10/10/80. All the catalysts were active. The reaction products were H2, CO, CO2, CH4, C2H4 and C3H6 and there were no organic oxygenated compounds detected. Although all the investigated systems were active, the Al-PILC supported catalysts presented a higher activity than the bulk materials. In this context, the samarium supported catalyst showed a propene yield increase from 4% to 10% compared with bulk samarium phosphate at 600°C. This effect was attributed to the increase in the specific surface area.

Electrochemical properties of composite cathodes using Sm doped layered perovskite for intermediate temperature-operating solid oxide fuel cell

Science.gov (United States)

Baek, Seung-Wook; Azad, Abul K.; Irvine, John T. S.; Choi, Won Seok; Kang, Hyunil; Kim, Jung Hyun

2018-02-01

SmBaCo2O5+d (SBCO) showed the lowest observed Area Specific Resistance (ASR) value in the LnBaCo2O5+d (Ln: Pr, Nd, Sm, and Gd) oxide system for the overall temperature ranges tested. The ASR of a composite cathode (mixture of SBCO and Ce0.9Gd0.1O2-d) on a Ce0.9Gd0.1O2-d (CGO91) electrolyte decreased with respect to the CGO91 content; the percolation limit was also achieved for a 50 wt% SBCO and 50 wt% CGO91 (SBCO50) composite cathode. The ASRs of SBCO50 on the dense CGO91 electrolyte in the overall temperature range of 500-750 °C were relatively lower than those of SBCO50 on the CGO91 coated dense 8 mol% yttria-stabilized zirconia (8YSZ) electrolyte for the same temperature range. From 750 °C and for all higher temperatures tested, however, the ASRs of SBCO50 on the CGO91 coated dense 8YSZ electrolyte were lower than those of the CGO91 electrolyte. The maximum power densities of SBCO50 on the Ni-8YSZ/8YSZ/CGO91 buffer layer were 1.034 W cm-2 and 0.611 W cm-2 at 800 °C and 700 °C.

Influence of microstructural change of the interface between Nd2Fe14B and Nd-O phases on coercivity of Nd-Fe-B films by oxidation and subsequent low-temperature annealing

International Nuclear Information System (INIS)

Matsuura, Masashi; Tezuka, Nobuki; Sugimoto, Satoshi; Goto, Ryota

2011-01-01

This study provides the influence of microstructural change of the interface between Nd 2 Fe 14 B and Nd-O phases on coercivity of Nd-Fe-B thin films during annealing at low temperature (∼350 deg. C). All films were prepared by using ultra high vacuum (UHV) magnetron sputtering, and the Nd-Fe-B layer was oxidized under Ar gas atmosphere (O 2 content; ∼2 Vol.ppm). Then, the films were annealed at 250-350 deg. C under UHV condition. After oxidation, the coercivity of Nd-Fe-B film decreased to around 40% of the coercivity of as-deposited Nd-Fe-B film. The Nd-rich phase changed from α-Nd to amorphous Nd(-O), and the interface of Nd 2 Fe 14 B/Nd(-O) became rough. In the Nd-Fe-B films oxidized and subsequent annealed at 350 deg. C, the coercivity decreased to around 20%. In the films, poly crystalline hcp Nd 2 O 3 phase crystallized in Nd-rich phase, and there were some steps at the surface of Nd 2 Fe 14 B phase contacting with hcp Nd 2 O 3 phase. Regardless of crystal orientation of Nd 2 Fe 14 B, the microstructural changes of the interface described above were observed.

Preparation and melting of uranium from U3O8

International Nuclear Information System (INIS)

Hur, Jin-Mok; Choi, In-Kyu; Cho, Soo-Haeng; Jeong, Sang-Mun; Seo, Chung-Seok

2008-01-01

In this paper, we report on the preparation and melting of uranium in association with a spent nuclear fuel conditioning process. U 3 O 8 powder was electrochemically reduced in a mixture of molten LiCl-Li 2 O (∼3 wt.% of Li 2 O in LiCl) at 650 deg. C resulting in the formation of uranium and Li 2 O with a yield of >99%. When the powder of uranium with a residual LiCl-Li 2 O salt was heated in order to melt the metal, the uranium oxidation to UO 2 due to the reaction with Li 2 O was observed. We were able to synthesize FeU 6 by using a Fe based cathode during the U 3 O 8 reduction procedure. FeU 6 could be melted to below the temperatures where the oxidation of uranium by Li 2 O occurred. The idea of compound formation and melting is applicable to the melting and casting of a spent nuclear fuel which contains oxidative residual salts due to its conditioning in a molten salt

Syntheses, crystal structures and properties of series of 4d–4f ln(III)–Ag(I) heterometallic coordination polymers

Energy Technology Data Exchange (ETDEWEB)

Ran, Xing-Rui [School of Chemistry and Environment, South China Normal University, Guangzhou 510006 (China); Wang, Ning [School of Materials Science and Engineering, Nanyang Technological University, 50 Nanyang Avenue, Singapore 639798 (Singapore); Xie, Wei-Ping; Xiong, Yan-Ju; Cheng, Qian [School of Chemistry and Environment, South China Normal University, Guangzhou 510006 (China); Long, Yi [School of Materials Science and Engineering, Nanyang Technological University, 50 Nanyang Avenue, Singapore 639798 (Singapore); Yue, Shan-Tang, E-mail: yuesht@scnu.edu.cn [School of Chemistry and Environment, South China Normal University, Guangzhou 510006 (China); Guangzhou Key Laboratory of Materials for Energy Conversion and Storage, Guangzhou (China); Liu, Ying-Liang [College of Science, South China Agricultural University, Guangzhou 510642 (China)

2015-05-15

By control of the experimental parameters such as ligands, pH value and reacting temperature, series of three-dimensional (3D) 4d–4f Ln(III)–Ag(I) porous coordination polymers (PCPs) with interesting chain-layer construction, namely, ([Ln{sup III}Ag{sup I}(na)(ina)(ox)]·2(H{sub 2}O)){sub n} [Ln=Sm(1), Eu(2), Gd(3), Tb(4), Dy(5), Ho(6), Y(7), Yb(8)], have been successfully synthesized under hydrothermal conditions and structurally characterized. All the complexes are characterized by elemental analyses, FT-IR spectroscopy, Powder X-ray diffraction (PXRD) and thermogravimetric analyses (TGA). Furthermore, the luminescence properties of compounds 2 and 4 and the magsnetic properties of complexes 3 and 5 were also investigated in detail. - Graphical abstract: Series of three-dimensional (3D) 4d–4f Ln(III)–Ag(I) porous coordination polymers (PCPs) with interesting chain-layer construction which are featured by tetranuclear Ln{sub 2}Ag{sub 2} and ‘non-linear’ N–Ag–N linkages. - Highlights: • Complexes 1–8 are first built by three kinds of organic ligands based on nicotinic acid and isonicotinic acid. • PCPs 1–8 are featured by tetranuclear Ln{sub 2}Ag{sub 2} and ‘non-linear’ N–Ag–N linkages. • The total solvent-accessible volume of PCP 2 comprises 11.6% of the crystal volume after dislodging the free water molecules. • Complexes 2 and 4 exhibit characteristic lanthanide-centered luminescence, while compounds 3 and 5 show antiferromagnetic behaviors.

Effects of Out-of-Plane Disorder on the Nodal Quasiparticle and Superconducting Gap in Single-Layer Bi_2Sr_1.6Ln_0.4CuO_6 delta (Ln = La, Nd, Gd)

Energy Technology Data Exchange (ETDEWEB)

Hashimoto, M.

2011-01-04

How out-of-plane disorder affects the electronic structure has been investigated for the single-layer cuprates Bi{sub 2}Sr{sub 1.6}Ln{sub 0.4}CuO{sub 6+{delta}} (Ln = La, Nd, Gd) by angle-resolved photoemission spectroscopy. We have observed that, with increasing disorder, while the Fermi surface shape and band dispersions are not affected, the quasi-particle width increases, the anti-nodal gap is enhanced and the superconducting gap in the nodal region is depressed. The results indicate that the superconductivity is significantly depressed by out-of-plane disorder through the enhancement of the anti-nodal gap and the depression of the superconducting gap in the nodal region.

Synthesis, structures, and luminescent properties of lanthanide complexes with triphenylphospine oxide

Energy Technology Data Exchange (ETDEWEB)

Ma, Yan; Xu, Shan; Wang, Xin; Li, Yue-Xue; Jin, Qiong-Hua [Department of Chemistry, Capital Normal University, Beijing (China); Liu, Min [The College of Materials Science and Engineering, Beijing University of Technology (China); Xin, Xiu-Lan [School of Food and Chemical Engineering, Beijing Technology and Business University (China)

2017-07-03

Seven lanthanide complexes [Ln(OPPh{sub 3}){sub 3}(NO{sub 3}){sub 3}] (1-3) (OPPh{sub 3} = triphenylphosphine oxide, Ln = Nd, Sm, Gd), [Dy(OPPh{sub 3}){sub 4}(NO{sub 3}){sub 2}](NO{sub 3}) (4), [Ln(OPPh{sub 3}){sub 3}(NO{sub 3}){sub 3}]{sub 2} (5-7) (Ln = Pr, Eu, Gd) were synthesized by the reactions of different lanthanide salts and OPPh{sub 3} ligand in the air. These complexes were characterized by single-crystal X-ray diffraction analysis, elemental analysis, IR and fluorescence spectra. Structure analysis shows that complexes 1-4 are mononuclear complexes formed by OPPh{sub 3} ligands and nitrates. The asymmetric units of complexes 5-7 consist of two crystallographic-separate molecules. Complex 1 is self-assembled to construct a 2D layer-structure of (4,4) net topology by hydrogen bond interactions. The other complexes show a 1D chain-like structure that was assembled by OPPh{sub 3} ligands and nitrate ions through C-H..O interactions. Solid emission spectra of compounds 4 and 6 are assigned to the characteristic fluorescence of Tb{sup 3+} (λ{sub em} = 480, 574 nm) and Eu{sup 3+} (λ{sub em} = 552, 593, 619, 668 nm). (copyright 2017 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim)

TEMPERATURE TRENDS OF THE PERMITTIVITY IN COMPLEX OXIDES OF RARE-EARTH ELEMENTS WITH PEROVSKITE-TYPE STRUCTURE

Directory of Open Access Journals (Sweden)

A.G.Belous

2003-01-01

Full Text Available Ceramic materials based on complex oxides with both the perovskite structure (Ln2/3Nb2O6 and the structure of tetragonal tungsten bronze (Ba6-xLn8+2x/3Ti18O54 have been investigated over a wide frequency and temperature ranges. The results obtained for certain structures denote the presence of the temperature anomalies of dielectric parameters (ε, tanδ. These anomalies occur over the wide frequency range including submilimeter (SMM wavelength range, and are related neither with the processing peculiarities nor with the presence of the phase transitions. Temperature behavior of the permittivity has been considered in terms of the polarization mechanism based on the elastic-strain lattice oscillations. It has been assumed that the observed anomalies could be ascribed to a superposition of harmonic and anharmonic contribution to lattice oscillations that determines τε sign and magnitude.

From Ba3Ta5O14N to LaBa2Ta5O13N2: Decreasing the optical band gap of a photocatalyst

International Nuclear Information System (INIS)

Anke, B.; Bredow, T.; Pilarski, M.; Wark, M.; Lerch, M.

2017-01-01

Yellow LaBa 2 Ta 5 O 13 N 2 was successfully synthesized as phase-pure material crystallizing isostructurally to previously reported Ba 3 Ta 5 O 14 N and mixed-valence Ba 3 Ta V 4 Ta IV O 15 . The electronic structure of LaBa 2 Ta 5 O 13 N 2 was studied theoretically with the range-separated hybrid method HSE06. The most stable structure was obtained when lanthanum was placed on 2a and nitrogen on 4h sites confirming Pauling's second rule. By incorporating nitrogen, the measured band gap decreases from ∼3.8 eV for the oxide via 2.74 eV for Ba 3 Ta 5 O 14 N to 2.63 eV for the new oxide nitride, giving rise to an absorption band well in the visible-light region. Calculated fundamental band gaps confirm the experimental trend. The atom-projected density of states has large contributions from N2p orbitals close to the valence band edge. These are responsible for the observed band gap reduction. Photocatalytic hydrogen formation was investigated and compared with that of Ba 3 Ta 5 O 14 N revealing significantly higher activity for LaBa 2 Ta 5 O 13 N 2 under UV-light. - Graphical abstract: X-ray powder diffraction pattern of LaBa 2 Ta 5 O 13 N 2 with the results of the Rietveld refinements. Inset: Unit cell of LaBa 2 Ta 5 O 13 N 2 and polyhedral representation of the crystal structure. - Highlights: • Synthesis of a new oxide nitride LaBa 2 Ta 5 O 13 N 2 . • Refinement of the crystal structure. • Quantum chemical calculations provided band gap close to the measured value. • New phase shows a higher photocatalytic H 2 evolution rate compared to prior tested Ba 3 Ta 5 O 14 N.

New structural and electrical data on Bi-Mo mixed oxides with a structure based on [Bi12O14]∞ columns

International Nuclear Information System (INIS)

Vannier, R.N.; Abraham, F.; Nowogrocki, G.; Mairesse, G.

1999-01-01

The authors recently described a new family of oxide anion conductors with a structure based on [Bi 12 O 14 ] ∞ columns (Journal of Solid State Chemistry 122, 394 (1996)). The parent compound of this series can be formulated as Bi 26 Mo 10 O 69 and formation of a solid solution, in the Bi 2 O 3 -MoO 3 binary system, in the range 2.57 ≤ Bi/Mo ≤ 2.77 was established. The stoichiometry of this series was questioned by R. Enjalbert et al. (Journal of Solid State Chemistry 131, 236 (1997)), but confirmed by D.J. Buttrey et al. (Materials Research Bulletin 32, 947 (1997)). The first part of this paper is devoted to a refutation of criticisms by R. Enjalbert et al. In the second part, a comparison with other Bi 2 O 3 -based oxide anion conductors enables the authors to propose an iono-covalent description of this novel structure type, taking into account all the structural and electrical features, especially new neutron powder diffraction refinement and conductivity measurements under variable oxygen partial pressures

Synthesis, crystal structure, and physical properties of the Gd{sub 3}BiO{sub 3} and Gd{sub 8}Bi{sub 3}O{sub 8} phases

Energy Technology Data Exchange (ETDEWEB)

Forbes, Scott; Yuan, Fang [Department of Chemistry and Chemical Biology, McMaster University, 1280 Main Street West, Hamilton, Ontario, Canada L8S 4M1 (Canada); Kosuda, Kosuke; Kolodiazhnyi, Taras [Institute for Materials Science, 1-1 Namiki, Tsukuba, Ibaraki 305-0044 (Japan); Mozharivskyj, Yurij, E-mail: mozhar@mcmaster.ca [Department of Chemistry and Chemical Biology, McMaster University, 1280 Main Street West, Hamilton, Ontario, Canada L8S 4M1 (Canada)

2016-01-15

The second and third known rare-earth bismuthide oxides, Gd{sub 3}BiO{sub 3} and Gd{sub 8}Bi{sub 3}O{sub 8}, have been discovered via high temperature reactions at 1300 °C. Like its Gd–Sb–O counterparts, the Gd{sub 3}BiO{sub 3} and Gd{sub 8}Bi{sub 3}O{sub 8} phases crystallize in the monoclinic C2/m space group, with the latter containing disordered Bi atoms along the b direction of the unit cell. Unlike the RE{sub 8}Sb{sub 3}O{sub 8} series, the formation of the Gd{sub 3}BiO{sub 3} phase does not necessarily precede the formation of Gd{sub 8}Bi{sub 3}O{sub 8}, which is likely due to the difficulty of accommodating bismuth in the RE–O framework due to its larger size. Physical property measurements performed on a pure Gd{sub 8}Bi{sub 3}O{sub 8} sample reveal semiconducting behavior. Although electronic structure calculations predict metallic behavior due to an unbalanced electron count, the semiconducting behavior originates from the Anderson localization of the Bi p states near the Fermi level as a result of atomic disorder. - Graphical abstract: Reaction of GdBi and Gd{sub 2}O{sub 3} at high temperatures yields Gd–Bi–O phases. - Highlights: • Gd{sub 3}BiO{sub 3} and Gd{sub 8}Bi{sub 3}O{sub 8}, the second and third rare-earth bismuthide oxides, have been discovered. • Gd{sub 3}BiO{sub 3} and Gd{sub 8}Bi{sub 3}O{sub 8} are isostructural with RE{sub 3}SbO{sub 3} and RE{sub 8}Sb{sub 3}O{sub 8}. • Gd{sub 8}Bi{sub 3}O{sub 8} displays semiconducting behavior despite an unbalanced electron count. • Anderson localization of Bi p states results in semiconducting behavior in Gd{sub 8}Bi{sub 3}O{sub 8}.

Synthesis of ZrO2-8%CeO2 and ZrO2-8%Y2O3 by polymeric precursors route

International Nuclear Information System (INIS)

Macedo, D.A.; Macedo, M.C.; Melo, D.M.A.; Nascimento, R.M.; Rabelo, A.A.

2006-01-01

The stabilization of zirconia in the cubical and tetragonal structures comes gaining importance because of its excellent thermal stability, chemical resistance, mechanical properties and oxygen conductivity. Its main applications include electrolytes of high temperature fuel cells, sensors of oxygen and electrochemical reactors. In this work the polymeric precursors route was used to synthesize ZrO 2 -8 mol% Y 2 O 3 and ZrO 2 -8 mol%CeO 2 . In this process the dopant concentration, besides making possible the stabilization of distinct structures, influences in the morphologic characteristics of the powders synthesized. The characterization of the powders was carried through X-ray diffraction for existing phases verification and average crystallite size, thermogravimetric analysis, specific surface area measures, particles size distribution by laser scattering and the powder morphology was observed using scanning electronic microscopy. The powder only calcined at 700 deg C had presented of average crystallite size of 6,77 nm for ZrO 2 -8%Y 2 O 3 and 7,14 nm for ZrO 2 -CeO 2 . (author)

Joint dissolution and oxidation behaviour of 316LN steel at 550 C. in liquid sodium containing low concentration of oxygen - 15417

International Nuclear Information System (INIS)

Courouau, J.L.; Rivollier, M.; Lorentz, V.; Tabarant, M.

2015-01-01

The sodium cooled fast reactor is selected in France as the 4. generation of nuclear power plant. 4. generation's reactor vessel, primary loop structures and heat exchangers will be made of austenitic stainless steels (316LN). To assess reactor service life time, corrosion of austenitic stainless steel by liquid sodium is studied in normal operating conditions as well as in transient conditions either expected or not. Oxygen, one of the main impurities, but present in trace amounts (1 to 10 μg/g or ppm weight), plays a major role on corrosion phenomena of the steel, although not totally understood yet. Literature reports an increased dissolution rate of steel or even of pure iron with increasing oxygen content although no thermodynamically stable iron oxide exists at low oxygen content. Oxygen is only known to form sodium chromite scale (NaCrO 2 ), those behaviour is, however, little documented. Based on corrosion tests performed in the static sodium test device (CorroNa) at 550 C. degrees for an oxygen content initially of about 1 ppm in weight or lower, and about 5-10 ppm after 4600 h of test, either a really small dissolution rate or small sodium chromite scale formation (NaCrO 2 ) are observed. Dissolution and carburation are observed for specimen immersed since the beginning of the test, while oxidation is the main feature observed for the specimen immersed during the last periods of the test. Some aspects of the morphologies of this oxide scale obtained by scanning electron microscopy (SEM) or transmission electron microscopy (TEM) as well as by Glow Discharge Optical Emission Spectroscopy (GD-OES) are presented. Discussions and explanations of these apparently opposing results are given based on thermodynamic analysis, as well as their possible consequences for reactor operation. (authors)

Co-Mn-Al Mixed Oxides as Catalysts for Ammonia Oxidation to N2O.

Czech Academy of Sciences Publication Activity Database

Ludvíková, Jana; Jablońska, M.; Jirátová, Květa; Chmielarz, L.; Balabánová, Jana; Kovanda, F.; Obalová, L.

2016-01-01

Roč. 42, č. 3 (2016), s. 2669-2690 ISSN 0922-6168 R&D Projects: GA ČR GA14-13750S Institutional support: RVO:67985858 Keywords : Co-Mn-Al mixed oxide s * catalytic ammonia oxidation * N2O production * mechanochemical production Subject RIV: CI - Industrial Chemistry, Chemical Engineering Impact factor: 1.369, year: 2016

Magnetic ordering and electrical resistivity in Co0.2Zn0.8Fe2O4 spinel oxide

International Nuclear Information System (INIS)

Bhowmik, R.N.; Ranganathan, R.; Ghosh, B.; Kumar, S.; Chattopadhyay, S.

2008-01-01

We report the magnetic, Moessbauer spectroscopy and resistivity measurements in order to understand the electronic behaviour of bulk Co 0.2 Zn 0.8 Fe 2 O 4 spinel oxide. The effect of magnetic order on electrical behaviour is observed from the resistivity measurements in the absence and presence of magnetic field. The analysis of Moessbauer spectra suggests the absence of Fe 2+ ions in the system, which implies that complete hopping of charge carriers between localized Fe 3+ /Co 2+ and Fe 2+ /Co 3+ pair of ions in B sublattice is not the favourable mechanism in Co 0.2 Zn 0.8 Fe 2 O 4 . We suggest that electrical behaviour of the present sample may be consistent with a model of fractional charge transfer via Fe B 3+ -O 2- -Co B 2+ superexchange path

Facilely solving cathode/electrolyte interfacial issue for high-voltage lithium ion batteries by constructing an effective solid electrolyte interface film

International Nuclear Information System (INIS)

Xu, Jingjing; Xia, Qingbo; Chen, Fangyuan; Liu, Tao; Li, Li; Cheng, Xueyuan; Lu, Wei; Wu, Xiaodong

2016-01-01

The cathode/electrolyte interface stability is the key factor for the cyclic performance and the safety performance of lithium ion batteries. Suppression of consuming key elements in the electrode materials is essential in this concern. In this purpose, we investigate a facile strategy to solve interfacial issue for high-voltage lithium ion batteries by adding an oxidable fluorinated phosphate, Bis(2,2,2-trifluoroethyl) Phosphite (BTFEP), as a sacrificial additive in electrolyte. We demonstrate that BTFEP additive could be oxidized at slightly above 4.28 V which is a relatively lower voltage than that of solvents, and the oxidative products facilitate in-situ forming a stable solid electrolyte interphase (SEI) film on the cathode surface. The results manifest the SEI film validly restrains the generation of HF and the interfacial side reaction between high-voltage charged LiNi 0.5 Mn 1.5 O 4 (LNMO) and electrolyte, hence, the dissolution of Mn and Ni is effectively suppressed. Finally, the cyclic performance of LNMO after 200 cycles was remarkably improved from 68.4% in blank electrolyte to 95% in 1 wt% BTFEP-adding electrolyte.

Pressure induced Amorphization of Ln1/3(Nb,Ta)O3

International Nuclear Information System (INIS)

Melchior, A.; Noked, O.; Sterer, E.; Shuker, R.

2014-01-01

The research focuses on the phenomenon of pressure induced amorphization (PIA) in Ln1/3MO3, Ln - La,Pr,Nd and M-Nb,Ta. In most pressure induced phase transitions the material changes from a crystalline phase to another crystalline phase. However, if this transition is kinetically hindered, the increased free energy due to the applied pressure will result in a structural collapse to an amorphous intermediate phase. This phenomenon is known as pressure induced amorphization

Determination of Debye temperatures and Lamb-Mössbauer factors for LnFeO3 orthoferrite perovskites (Ln  =  La, Nd, Sm, Eu, Gd)

Science.gov (United States)

Scrimshire, A.; Lobera, A.; Bell, A. M. T.; Jones, A. H.; Sterianou, I.; Forder, S. D.; Bingham, P. A.

2018-03-01

Lanthanide orthoferrites have wide-ranging industrial uses including solar, catalytic and electronic applications. Here a series of lanthanide orthoferrite perovskites, LnFeO3 (Ln  =  La Nd; Sm; Eu; Gd), prepared through a standard stoichiometric wet ball milling route using oxide precursors, has been studied. Characterisation through x-ray diffraction and x-ray fluorescence confirmed the synthesis of phase-pure or near-pure LnFeO3 compounds. 57Fe Mössbauer spectroscopy was performed over a temperature range of 10 K-293 K to observe hyperfine structure and to enable calculation of the recoil-free fraction and Debye temperature (θ D) of each orthoferrite. Debye temperatures (Ln  =  La 474 K Nd 459 K Sm 457 K Eu 452 K Gd 473 K) and recoil-free fractions (Ln  =  La 0.827; Nd 0.817; Sm 0.816; Eu 0.812; Gd 0.826) were approximated through minimising the difference in the temperature dependent experimental centre shift and theoretical isomer shift, by allowing the Debye temperature and isomer shift values to vary. This method of minimising the difference between theoretical and actual values yields Debye temperatures consistent with results from other studies determined through thermal analysis methods. This displays the ability of variable-temperature Mössbauer spectroscopy to approximate Debye temperatures and recoil-free fractions, whilst observing temperature induced transitions over the temperature range observed. X-ray diffraction and Rietveld refinement show an inverse relationship between FeO6 octahedral volume and approximated Debye temperatures. Raman spectroscopy show an increase in the band positions attributed to soft modes of Ag symmetry, Ag(3) and Ag(5) from La to GdFeO3 corresponding to octahedral rotations and tilts in the [0 1 0] and [1 0 1] planes respectively.

Effect of Preparation Methods on Al2O3 Supported CuO-CeO2-ZrO2 Catalysts for CO Oxidation

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Gaurav Rattan

2012-12-01

Full Text Available To examine the effect of preparation methods, four catalyst samples having same composition (CuCe5.17Zr3.83Ox/g-Al2O3 (15wt% were prepared by four different methods for CO oxidation. The catalysts were prepared by co-impregnation, citric acid sol-gel, urea nitrate combustion and urea gelation co-precipitation methods, and characterized by BET, XRD, TGA/DSC and SEM. The The air oxidation of CO was carried out in a tubular fixed bed reactor under the following operating conditions: catalyst weight - 100 mg, temperature - ambient to 250 oC, pressure - atmospheric, 2.5% CO in air, total feed rate - 60 ml/min.  It was observed that the catalytic activity greatly influenced by the preparation methods. The highest activity of the catalyst prepared by the sol gel method appeared to be associated with its largest BET surface area. All the four catalysts were active for CO oxidation and did not show deactivation of catalytic activity for 50 hours of continuous runs. The ranking order of the preparation methods of the catalyst is as follows: sol-gel > co-impregnation > urea gelation > urea nitrate combustion. Copyright © 2012 by BCREC UNDIP. All rights reservedReceived: 14th June 2012, Revised: 8th September 2012, Accepted: 19th September 2012[How to Cite: G. Rattan, R. Prasad, R.C.Katyal. (2012. Effect of Preparation Methods on Al2O3 Supported CuO-CeO2-ZrO2 Catalysts for CO Oxidation. Bulletin of Chemical Reaction Engineering & Catalysis, 7(2: 112-123. doi:10.9767/bcrec.7.2.3646.112-123] [How to Link / DOI: http://dx.doi.org/10.9767/bcrec.7.2.3646.112-123 ] | View in 

Mitigation of chromium poisoning of cathodes in solid oxide fuel cells employing CuMn1.8O4 spinel coating on metallic interconnect

Science.gov (United States)

Wang, Ruofan; Sun, Zhihao; Pal, Uday B.; Gopalan, Srikanth; Basu, Soumendra N.

2018-02-01

Chromium poisoning is one of the major reasons for cathode performance degradation in solid oxide fuel cells (SOFCs). To mitigate the effect of Cr-poisoning, a protective coating on the surface of interconnect for suppressing Cr vaporization is necessary. Among the various coating materials, Cu-Mn spinel coating is considered to be a potential candidate due to their good thermal compatibility, high stability and good electronic conductivity at high temperature. In this study, Crofer 22 H meshes with no protective coating, those with commercial CuMn2O4 spinel coating and the ones with lab-developed CuMn1.8O4 spinel coating were investigated. The lab-developed CuMn1.8O4 spinel coating were deposited on Crofer 22 H mesh by electrophoretic deposition and densified by a reduction and re-oxidation process. With these different Crofer 22 H meshes (bare, CuMn2O4-coated, and CuMn1.8O4-coated), anode-supported SOFCs with Sr-doped LaMnO3-based cathode were electrochemically tested at 800 °C for total durations of up to 288 h. Comparing the mitigating effects of the two types of Cu-Mn spinel coatings on Cr-poisoning, it was found that the performance of the denser lab-developed CuMn1.8O4 spinel coating was distinctly better, showing no degradation in the cell electrochemical performance and significantly less Cr deposition near the cathode/electrolyte interface after the test.

Lanthanide(III) complexes with μ-SnSe{sub 4} and μ-Sn{sub 2}Se{sub 6} linkers. Solvothermal syntheses and properties of new Ln(III) selenidostannates decorated with linear polyamine

Energy Technology Data Exchange (ETDEWEB)

Liu, Shuzhen; Sun, Peipei; Shen, Yali; Han, Jingyu; Sun, Hui; Jia, Dingxian [Soochow Univ., Suzhou (China). College of Chemistry, Chemical Engineering and Materials Science

2017-06-01

New lanthanide-selenidostannate complexes [{La(peha)(Cl)}{La(peha)(NO_3)}(μ-1κ{sup 2}:2κ{sup 2}-SnSe{sub 4})] (1), [H{sub 2}trien][{La(trien)_2}{sub 2}(μ-1-κ:2κ-Sn{sub 2}Se{sub 6})][Sn{sub 2}Se{sub 6}].H{sub 2}O (2) and [{Ln(tepa)(μ-OH)}{sub 2}(μ-1κ:2κ-Sn{sub 2}Se{sub 6})]{sub n}.nH{sub 2}O (Ln=Sm(3), Eu(4)) were prepared by solvothermal methods in pentaethylenehexamine (peha), triethylenetetramine (trien) and tetraethylenepentamine (tepa), respectively. Acting as a tetradentate chelating and bridging ligand, μ-1κ{sup 2}:2κ{sup 2}-SnSe{sub 4}, the tetrahedral SnSe{sub 4} unit joins {La(peha)(Cl)}{sup 2+} and {La(peha)(NO_3)}{sup 2+} complex fragments to generate the neutral coordination compound 1. The tetradentate μ-1κ{sup 2}:2κ{sup 2} bridge in 1 represents a new coordination mode for the SnSe{sub 4} tetrahedron. In 2, dinuclear [Sn{sub 2}Se{sub 6}]{sup 4-} anions are formed of SnSe{sub 4} tetrahedra via edge-sharing. One [Sn{sub 2}Se{sub 6}]{sup 4-} anion acts as a bidentate bridging ligand in a μ-1κ:2κ coordination mode to join two {La(trien)_2}{sup 3+} units, and the other [Sn{sub 2}Se{sub 6}]{sup 4-} anion exists as a free charge compensating ion. In 3 and 4, the [Sn{sub 2}Se{sub 6}]{sup 4-} anion connects binuclear [{Ln(tepa)(μ-OH)}{sub 2}]{sup 2+}(Ln=Sm, Eu) units with a bidentate μ-1κ:2κ mode, giving neutral coordination polymers [{Ln(tepa)(μ-OH)}{sub 2}(μ-1κ:2κ-Sn{sub 2}Se{sub 6})]{sub n}. The La(2){sup 3+} ion in 1 is in a 10-fold coordination environment of LaN{sub 6}O{sub 2}Se{sub 2}, whereas the La(1){sup 3+} ions in 1 and 2 are in 9-fold coordinated environments forming polyhedra LaN{sub 6}ClSe{sub 2} and LaN{sub 8}Se, respectively. The Sm{sup 3+} and Eu{sup 3+} ions in 3 and 4 are both in an 8-fold coordination environment of LnN{sub 5}O{sub 2}Se. Compounds 1-4 exhibit optical band gaps between 2.21 and 2.42 eV. Their thermal stabilities were investigated by thermogravimetric analyses.

Kinetics and mechanism of auto- and copper-catalyzed oxidation of 1,4-naphthohydroquinone.

Science.gov (United States)

Yuan, Xiu; Miller, Christopher J; Pham, A Ninh; Waite, T David

2014-06-01

Although quinones represent a class of organic compounds that may exert toxic effects both in vitro and in vivo, the molecular mechanisms involved in quinone species toxicity are still largely unknown, especially in the presence of transition metals, which may both induce the transformation of the various quinone species and result in generation of harmful reactive oxygen species. In this study, the oxidation of 1,4-naphthohydroquinone (NH2Q) in the absence and presence of nanomolar concentrations of Cu(II) in 10 mM NaCl solution over a pH range of 6.5-7.5 has been investigated, with detailed kinetic models developed to describe the predominant mechanisms operative in these systems. In the absence of copper, the apparent oxidation rate of NH2Q increased with increasing pH and initial NH2Q concentration, with concomitant oxygen consumption and peroxide generation. The doubly dissociated species, NQ(2-), has been shown to be the reactive species with regard to the one-electron oxidation by O2 and comproportionation with the quinone species, both generating the semiquinone radical (NSQ(·-)). The oxidation of NSQ(·-) by O2 is shown to be the most important pathway for superoxide (O2(·-)) generation with a high intrinsic rate constant of 1.0×10(8)M(-1)s(-1). Both NSQ(·-) and O2(·-) served as chain-propagating species in the autoxidation of NH2Q. Cu(II) is capable of catalyzing the oxidation of NH2Q in the presence of O2 with the oxidation also accelerated by increasing the pH. Both the uncharged (NH2Q(0)) and the mono-anionic (NHQ(-)) species were found to be the kinetically active forms, reducing Cu(II) with an intrinsic rate constant of 4.0×10(4) and 1.2×10(7)M(-1)s(-1), respectively. The presence of O2 facilitated the catalytic role of Cu(II) by rapidly regenerating Cu(II) via continuous oxidation of Cu(I) and also by efficient removal of NSQ(·-) resulting in the generation of O2(·-). The half-cell reduction potentials of various redox couples at neutral p

Effects of chronic nitric oxide synthase inhibition on V'O2max and exercise capacity in mice.

Science.gov (United States)

Wojewoda, M; Przyborowski, K; Sitek, B; Zakrzewska, A; Mateuszuk, L; Zoladz, J A; Chlopicki, S

2017-03-01

Acute inhibition of NOS by L-NAME (N ω -nitro-L-arginine methyl ester) is known to decrease maximal oxygen consumption (V'O 2max ) and impair maximal exercise capacity, whereas the effects of chronic L-NAME treatment on V'O 2max and exercise performance have not been studied so far. In this study, we analysed the effect of L-NAME treatment, (LN2 and LN12, respectively) on V'O 2max and exercise capacity (in maximal incremental running and prolonged sub-maximal incremental running tests), systemic NO bioavailability (plasma nitrite (NO 2 - ) and nitrate (NO 3 - )) and prostacyclin (PGI 2 ) production in C57BL6/J mice. Mice treated with L-NAME for 2 weeks (LN2) displayed higher V'O 2max and better running capacity than age-matched control mice. In LN2 mice, NO bioavailability was preserved, as evidenced by maintained NO 2 - plasma concentration. PGI 2 production was activated (increased 6-keto-PGF 1α plasma concentration) and the number of circulating erythrocytes (RBC) and haemoglobin concentration were increased. In mice treated with L-NAME for 12 weeks (LN12), NO bioavailability was decreased (lower NO 2 - plasma concentration), and 6-keto-PGF 1α plasma concentration and RBC number were not elevated compared to age-matched control mice. However, LN12 mice still performed better during the maximal incremental running test despite having lower V'O 2max . Interestingly, the LN12 mice showed poorer running capacity during the prolonged sub-maximal incremental running test. To conclude, short-term (2 weeks) but not long-term (12 weeks) treatment with L-NAME activated robust compensatory mechanisms involving preservation of NO2- plasma concentration, overproduction of PGI 2 and increased number of RBCs, which might explain the fully preserved exercise capacity despite the inhibition of NOS.

An anti CuO{sub 2}-type metal hydride square net structure in Ln{sub 2}M{sub 2}As{sub 2}H{sub x} (Ln = La or Sm, M = Ti, V, Cr, or Mn)

Energy Technology Data Exchange (ETDEWEB)

Mizoguchi, Hiroshi; Park, SangWon; Hosono, Hideo [Tokyo Institute of Technology, Yokohama (Japan). Materials Research Center for Element Strategy; Hiraka, Haruhiro; Ikeda, Kazutaka; Otomo, Toshiya [High-Energy Accelerator Research Organization (KEK), Tsukuba (Japan). Inst. of Materials Structure Science

2015-03-02

Using a high pressure technique and the strong donating nature of H{sup -}, a new series of tetragonal La{sub 2}Fe{sub 2}Se{sub 2}O{sub 3}-type layered mixed-anion arsenides, Ln{sub 2}M{sub 2}As{sub 2}H{sub x}, was synthesized (Ln=La or Sm, M=Ti, V, Cr, or Mn; x∼3). In these compounds, an unusual M{sub 2}H square net, which has anti CuO{sub 2} square net structures accompanying two As{sup 3-} ions, is sandwiched by (LaH){sub 2} fluorite layers. Notably, strong metal-metal bonding with a distance of 2.80 Aa was confirmed in La{sub 2}Ti{sub 2}As{sub 2}H{sub 2.3}, which has metallic properties. In fact, these compounds are situated near the boundary between salt-like ionic hydrides and transition-metal hydrides with metallic characters.

Interaction between uranium oxide alloyed with Al2O3·SiO2 and pyrocarbon coating during irradiation of micro fuel elements

International Nuclear Information System (INIS)

Chernikov, A.S.; Khromov, Y.F.; Svistunov, D.E.; Chuiko, E.E.

1989-01-01

The thermodynamics of the interaction between uranium oxide and carbon was previously studied in the presence of Al 2 O 3 ·SiO 2 , SiC, and UC 1.86 ; in this case, the quantity of the reacting substances does not have any effect on the attainment of the equilibrium state. Based on the obtained results, it is interesting to study the characteristic features of the interaction between the alloyed UO x cores (kernels) with the PyC-coating under the conditions involving irradiation of the micro fuel elements with thermal neutrons and the formation of solid fission products. The data concerning the characteristics of a micro fuel element (the weight of the core, its composition, etc.) are useful for carrying out a quantitative evaluation of the additives required for fixing the alkali-earth fission products by obtaining stable compounds of aluminosilicates with Ba, Sr, Rb, and Cs at different levels of depletion (burnup) of the oxide fuel. An analysis of the interaction processes in such a complex system as the irradiated alloyed uranium oxide fuel located in a micro fuel element is carried out by comparing the chemical potential of oxygen (RT ln P O 2 ) for the competing constituents of the system

Nano-oxide nucleation in a 14Cr-ODS steel elaborated by reactive-inspired ball-milling: Multiscale characterizations

International Nuclear Information System (INIS)

Brocq, M.; Legendre, F.; Sakasegawa, H.; Radiguet, B.; Cuvilly, F.; Pareige, P.; Mathon, M.H.

2009-01-01

Oxide dispersion strengthened (ODS) steels are promising structural materials for both fusion and fission Generation IV reactors. Indeed, they exhibit excellent mechanical and creep properties and radiation resistance thanks to a fine and dense dispersion of complex nanometric oxides. ODS steels are usually elaborated by ball-milling iron based and yttrium oxide powders and then by thermomechanical treatments. It is expected that ball-milling dissolves yttrium oxides in the metallic matrix and that annealing induces nano-oxide precipitation. However the formation mechanism remains unclear and as a consequence the process is still uncontrolled. In this context, we proposed a new approach based on reactive ball milling of iron oxide (Fe 2 O 3 ), yttria (YFe 3 ) and iron based alloy in a dedicated instrumented ball-milling device. Also, a fine scale characterization, after each step of the process including ball-milling, is performed. A Fe-14Cr-2W-1Ti-0.8Y-0.2O (%wt) ODS steel was synthesized by reactive ball-milling and was characterized at very fine scale in both as-milled and as-annealed state. Atom Probe Tomography (APT) and Small Angle Neutron Scattering (SANS) were combined. After ballmilling, most of Y and O were, as expected, in solution in the ferritic matrix but some complex Y-Ti nano-oxides were also observed, indicating that oxide nucleation can start during ball-milling. With annealing the number of nano-oxides increases. In this presentation, experimental results of APT and SANS will be detailed and compared with what is usually observed in ODS steels elaborated by conventional ball milling. Finally, a formation mechanism of nano-oxides deduced from these results will be proposed. (author)

Exploration of the Singlet O2 Oxidation of 8-Oxoguanine by Guided-Ion Beam Scattering and Density Functional Theory: Changes of Reaction Intermediates, Energetics, and Kinetics upon Protonation/Deprotonation and Hydration.

Science.gov (United States)

Sun, Yan; Lu, Wenchao; Liu, Jianbo

2017-02-09

8-Oxo-7,8-dihydro-2'-deoxyguanosine (8-oxodGuo) is one of the most common DNA lesions resulting from reactive oxygen species and ionizing radiation, and is involved in mutagenesis, carcinogenesis, and cell death. Notably, 8-oxodGuo is more reactive toward singlet (a 1 Δ g ) O 2 than the undamaged guanosine, and the lesions arising from the secondary oxidation of 8-oxodGuo are more mutagenic. Herein the 1 O 2 oxidation of free base 8-oxoguanine (8-oxoG) was investigated at different initial conditions including protonated [8-oxoG + H] + , deprotonated [8-oxoG - H] - , and their monohydrates. Experiment was carried out on a guided-ion beam scattering tandem mass spectrometer. Measurements include the effects of collision energy (E col ) on reaction cross sections over a center-of-mass E col range from 0.1 to 0.5 eV. The aim of this study is to quantitatively probe the sensitivity of the early stage of 8-oxoG oxidation to ionization and hydration. Density functional theory and Rice-Ramsperger-Kassel-Marcus calculations were performed to identify the intermediates and the products along reaction pathways and locate accessible reaction potential energy surfaces, and to rationalize reaction outcomes from energetic and kinetic points of view. No product was observed for the reaction of [8-oxoG + H] + ·W 0,1 (W = H 2 O) because insurmountable barriers block the addition of 1 O 2 to reactant ions. Neither was [8-oxoG - H] - reactive with 1 O 2 , in this case due to the rapid decay of transient intermediates to starting reactants. However, the nonreactivity of [8-oxoG - H] - was inverted by hydration; as a result, 4,5-dioxetane of [8-oxoG - H] - was captured as the main oxidation product. Reaction cross section for [8-oxoG - H] - ·W + 1 O 2 decreases with increasing E col and becomes negligible above 0.3 eV, indicating that the reaction is exothermic and has no barriers above reactants. The contrasting oxidation behaviors of [8-oxoG + H] + ·W 0,1 and [8-oxoG - H] - ·W 0

Prism inside. Spectroscopic and magnetic properties of the lanthanide(III) chloride oxidotungstates(VI) Ln{sub 3}Cl{sub 3}[WO{sub 6}] (Ln = La - Nd, Sm - Tb)

Energy Technology Data Exchange (ETDEWEB)

Dorn, Katharina V.; Blaschkowski, Bjoern; Hartenbach, Ingo [Institute for Inorganic Chemistry, University of Stuttgart (Germany); Foerg, Katharina; Netzsch, Philip; Hoeppe, Henning A. [Institute for Physics, University of Augsburg (Germany)

2017-11-17

The lanthanide(III) chloride oxidotungstates(VI) with the formula Ln{sub 3}Cl{sub 3}[WO{sub 6}] for Ln = La - Nd, Sm - Tb were synthesized by solid-state reactions utilizing the respective lanthanide trichloride, lanthanide sesquioxide (where available), and tungsten trioxide together with lithium chloride as flux. The title compounds crystallize hexagonally in space group P6{sub 3}/m (no. 176, a = 941-909, c = 543-525 pm, Z = 2). The structures comprise crystallographically unique Ln{sup 3+} cations surrounded by six O{sup 2-} and four Cl{sup -} anions (C.N. = 10) forming distorted tetracapped trigonal prisms as well as rather uncommon trigonal prismatic [WO{sub 6}]{sup 6-} units, whose edges are coordinated by nine Ln{sup 3+} cations. Thus, a {sup 3}{sub ∞}{([WO_6]Ln"e_9_/_3)"3"+} framework (e = edge-sharing) is created, which contains tube-shaped channels along [001] lined with chloride anions. To elucidate the spectroscopic and magnetic properties of the obtained pure phase samples, single-crystal Raman (for Ln = La - Nd, Sm-Tb), diffuse reflectance (for Ln = La, Pr, Nd, Gd), and luminescence spectroscopy (for bulk Ln{sub 3}Cl{sub 3}[WO{sub 6}] (Ln = La, Eu, Gd, Tb) and Eu{sup 3+}- or Tb{sup 3+}-doped derivatives of La{sub 3}Cl{sub 3}[WO{sub 6}] and Gd{sub 3}Cl{sub 3}[WO{sub 6}], respectively) were performed and their temperature-dependent magnetic moments (for Ln = Pr, Nd, Gd) were determined. (copyright 2017 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim)

Insights into magnetic interactions in a monodisperse Gd{sub 12}Fe{sub 14} metal cluster

Energy Technology Data Exchange (ETDEWEB)

Zheng, Xiu-Ying; Zhang, Hui; Liu, Pengxin; Du, Ming-Hao; Han, Ying-Zi; Wei, Rong-Jia; Kong, Xiang-Jian; Long, La-Sheng; Zheng, Lan-Sun [Collaborative Innovation Center of Chemistry for Energy Materials, State Key Lab. of Physical Chemistry of Solid Surface and Dept. of Chemistry, College of Chemistry and Chemical Engineering, Xiamen Univ. (China); Wang, Zhenxing; Ouyang, Zhong-Wen [Wuhan National High Magnetic Field Center and School of Physics, Huazhong University of Science and Technology, Wuhan (China); Zhuang, Gui-Lin [College of Chemcal Engineering, Zhejiang University of Technology, Hangzhou (China)

2017-09-11

The largest Ln-Fe metal cluster [Gd{sub 12}Fe{sub 14}(μ{sub 3}-OH){sub 12}(μ{sub 4}-OH){sub 6}(μ{sub 4}-O){sub 12}(TEOA){sub 6}(CH{sub 3}COO){sub 16}(H{sub 2} O){sub 8}].(CH{sub 3}COO){sub 2}(CH{sub 3}CN){sub 2}.(H{sub 2}O){sub 20} (1) and the core-shell monodisperse metal cluster of 1 a rate at SiO{sub 2} (1 a=[Gd{sub 12}Fe{sub 14}(μ{sub 3}-OH){sub 12}(μ{sub 4}-OH){sub 6}(μ{sub 4}-O){sub 12}(TEOA){sub 6}(CH{sub 3}COO){sub 16} (H{sub 2}O){sub 8}]{sup 2+}) were prepared. Experimental and theoretical studies on the magnetic properties of 1 and 1 a rate at SiO{sub 2} reveal that encapsulation of one cluster into one silica nanosphere not only effectively decreases intermolecular magnetic interactions but also significantly increases the zero-field splitting effect of the outer layer Fe{sup 3+} ions. (copyright 2017 Wiley-VCH Verlag GmbH and Co. KGaA, Weinheim)

Luminescence and magnetic properties of novel nanoparticle-sheathed 3D Micro-Architectures of Fe0.5R0.5(MoO4)1.5:Ln3+ (R = Gd3+, La3+), (Ln = Eu, Tb, Dy) for bifunctional application

Science.gov (United States)

Krishnan, Rajagopalan; Thirumalai, Jagannathan; Kathiravan, Arunkumar

2015-01-01

For the first time, we report the successful synthesis of novel nanoparticle-sheathed bipyramid-like and almond-like Fe0.5R0.5(MoO4)1.5:Ln3+ (R = Gd3+, La3+), (Ln = Eu, Tb, Dy) 3D hierarchical microstructures through a simple disodium ethylenediaminetetraacetic acid (Na2EDTA) facilitated hydrothermal method. Interestingly, time-dependent experiments confirm that the assembly-disassembly process is responsible for the formation of self-aggregated 3D architectures via Ostwald ripening phenomena. The resultant products are characterized by x-ray diffraction (XRD), field emission scanning electron microscopy (FESEM), high resolution transmission electron microscopy (HRTEM), photoluminescence (PL), and magnetic measurements. The growth and formation mechanisms of the self-assembled 3D micro structures are discussed in detail. To confirm the presence of all the elements in the microstructure, the energy loss induced by the K, L shell electron ionization is observed in order to map the Fe, Gd, Mo, O, and Eu components. The photo luminescence properties of Fe0.5R0.5(MoO4)1.5 doped with Eu3+, Tb3+, Dy3+ are investigated. The room temperature and low temperature magnetic properties suggest that the interaction between the local-fields introduced by the magnetic Fe3+ ions and the R3+ (La, Gd) ions in the dodecahedral sites determine the magnetism in Fe0.5R0.5(MoO4)1.5:Eu3+. This work provides a new approach to synthesizing the novel Fe0.5R0.5(MoO4)1.5:Ln3+ for bi-functional magnetic and luminescence applications.

Processing and microstructure characterisation of oxide dispersion strengthened Fe–14Cr–0.4Ti–0.25Y2O3 ferritic steels fabricated by spark plasma sintering

International Nuclear Information System (INIS)

Zhang, Hongtao; Huang, Yina; Ning, Huanpo; Williams, Ceri A.; London, Andrew J.; Dawson, Karl; Hong, Zuliang; Gorley, Michael J.; Grovenor, Chris R.M.; Tatlock, Gordon J.; Roberts, Steve G.; Reece, Michael J.; Yan, Haixue; Grant, Patrick S.

2015-01-01

Highlights: • Nanostructured ODS steels were successfully produced by SPS. • Presence of Y 2 Ti 2 O 7 nanoclusters was confirmed by synchrotron XRD and microscopy. • The chemistry of nanoclusters tested by ATP indicated they are Y–Ti–O oxides. - Abstract: Ferritic steels strengthened with Ti–Y–O nanoclusters are leading candidates for fission and fusion reactor components. A Fe–14Cr–0.4Ti + 0.25Y 2 O 3 (14YT) alloy was fabricated by mechanical alloying and subsequently consolidated by spark plasma sintering (SPS). The densification of the 14YT alloys significantly improved with an increase in the sintering temperature. Scanning electron microscopy and electron backscatter diffraction revealed that 14YT SPS-sintered at 1150 °C under 50 MPa for 5 min had a high density (99.6%), a random grain orientation and a bimodal grain size distribution (<500 nm and 1–20 μm). Synchrotron X-ray diffraction patterns showed bcc ferrite, Y 2 Ti 2 O 7 , FeO, and chromium carbides, while transmission electron microscopy and atom probe tomography showed uniformly dispersed Y 2 Ti 2 O 7 nanoclusters of <5 nm diameter and number density of 1.04 × 10 23 m −3 . Due to the very much shorter consolidation times and lower pressures used in SPS compared with the more usual hot isostatic pressing routes, SPS is shown to be a cost-effective technique for oxide dispersion strengthened (ODS) alloy manufacturing with microstructural features consistent with the best-performing ODS alloys

Electrochemical reduction behavior of U3O8 powder in a LiCl molten salt

International Nuclear Information System (INIS)

Jeong, Sang Mun; Shin, Ho-Sup; Hong, Sun-Seok; Hur, Jin-Mok; Do, Jae Bum; Lee, Han Soo

2010-01-01

The reduction path of the U 3 O 8 powder vol-oxidized at 1200 deg. C has been determined by a series of electrochemical experiments in a 1 wt.% Li 2 O/LiCl molten salt. Various reaction intermediates are observed by during electrolysis of U 3 O 8 . The formation of the metallic uranium is caused from two different reduction paths, a direct reduction of uranium oxide and an electro-lithiothermic reduction. As the uranium oxide is converted to the metallic uranium, the lithium metal is more actively formed in the cathode basket. The reducibility of the rare earth oxides with the U 3 O 8 powder has been tested by constant voltage electrolysis. The results suggest the advanced vol-oxidation could lead to the enhancement in the reducibility of the rare earth fission products.

Ba(OH)2.8H2O process for the removal and immobilization of carbon-14. Final report

International Nuclear Information System (INIS)

Haag, G.L.; Holladay, D.W.; Pitt, W.W. Jr.; Young, G.C.

1986-01-01

The airborne release of 14 C from various nuclear facilities has been identified as a potential biohazard due to the long half-life of 14 C (5730 years) and the ease with which it may be assimilated into the biosphere. At ORNL, technology has been developed for the removal and immobilization of this radionuclide. Prior studies have indicated that 14 C will likely exist in the oxidized form as CO 2 and will contribute slightly to the bulk CO 2 concentration of the gas stream, which is air-like in nature (approx.300 ppM/sub v/ CO 2 ). The technology that has been developed utilizes the CO 2 -Ba(OH) 2 .8H 2 O gas-solid reaction with the mode of gas-solid contacting being a fixed bed. The product, BaCO 3 , possesses excellent thermal and chemical stability, prerequisites for the long-term disposal of nuclear wastes. For optimal process operation, studies have indicated that an operating window of adequate size does exist. When operating within the window, high CO 2 removal efficiency (effluent concentrations 99%), and an acceptable pressure drop across the bed (3 kPa/m at a superficial velocity of 13 cm/s) are possible. Three areas of experimental investigation are reported: (1) microscale studies on 150-mg samples to provide information concerning surface properties, kinetics, and equilibrium vapor pressures; (2) macroscale studies on large fixed beds (4.2 kg of reactant) to determine the effects of humidity, temperature, and gas flow rate upon bed pressure drop and CO 2 breakthrough; and (3) design, construction, and operation of a pilot unit capable of continuously processing a 34-m 3 /h (20-ft 3 /min) air-based gas stream

High-pressure synthesis and single-crystal structure elucidation of the indium oxide-borate In{sub 4}O{sub 2}B{sub 2}O{sub 7}

Energy Technology Data Exchange (ETDEWEB)

Ortner, Teresa S.; Vitzthum, Daniela; Heymann, Gunter; Huppertz, Hubert [Department of General, Inorganic and Theoretical Chemistry, Centre of Chemistry and Biomedicine (CCB), Leopold-Franzens-University Innsbruck (Austria)

2017-12-29

The indium oxide-borate In{sub 4}O{sub 2}B{sub 2}O{sub 7} was synthesized under high-pressure/high-temperature conditions at 12.5 GPa/1420 K using a Walker-type multianvil apparatus. Single-crystal X-ray structure elucidation showed edge-sharing OIn{sub 4} tetrahedra and B{sub 2}O{sub 7} units building up the oxide-borate. It crystallizes with Z = 8 in the monoclinic space group P2{sub 1}/n (no. 14) with a = 1016.54(3), b = 964.55(3), c = 1382.66(4) pm, and β = 109.7(1) . The compound was also characterized by powder X-ray diffraction and vibrational spectroscopy. (copyright 2017 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim)

Interplay of structural chemistry and magnetism in perovskites; A study of CaLn2Ni2WO9; Ln=La, Pr, Nd

Science.gov (United States)

Chin, Chun-Mann; Paria Sena, Robert; Hunter, Emily C.; Hadermann, Joke; Battle, Peter D.

2017-07-01

Polycrystalline samples of CaLn2Ni2WO9 (Ln=La, Pr, Nd) have been synthesized and characterised by a combination of X-ray and neutron diffraction, electron microscopy and magnetometry. Each composition adopts a perovskite-like structure with a 5.50, b 5.56, c 7.78 Å, β 90.1° in space group P21/n. Of the two crystallographically distinct six-coordinate sites, one is occupied entirely (Ln=Pr) or predominantly (Ln=La, Nd) by Ni2+ and the other by Ni2+ and W6+ in a ratio of approximately 1:2. None of the compounds shows long-range magnetic order at 5 K. The magnetometry data show that the magnetic moments of the Ni2+ cations form a spin glass below 30 K in each case. The Pr3+ moments in CaPr2Ni2WO9 also freeze but the Nd3+ moments in CaNd2Ni2WO9 do not. This behaviour is contrasted with that observed in other (A,A')B2B'O9 perovskites.

Precipitation of HNbO{sub 3} at the Ti:LiNbO{sub 3} surface

Energy Technology Data Exchange (ETDEWEB)

Kalabin, Ivan E.; Grigorieva, Tatiana I.; Pokrovsky, Lev D.; Atuchin, Victor V

2004-03-30

The conditions of HNbO{sub 3} precipitation on the lithium niobate single-crystal and titanium diffused lithium niobate, LiNbO{sub 3} (LN) were studied. It has been shown, that the maximum of HNbO{sub 3} precipitation corresponds to the highest humidity of atmosphere at the annealing temperatures of 800-850 deg. C for 5-10 h. Moreover, the application of humid atmosphere during the annealing of LN at 600-850 deg. C does not ensure in full measure the lack of LiNb{sub 3}O{sub 8} precipitation.

An anti CuO{sub 2}-type metal hydride square net structure in Ln{sub 2}M{sub 2}As{sub 2}H{sub x} (Ln = La or Sm, M = Ti, V, Cr, or Mn)

Energy Technology Data Exchange (ETDEWEB)

Mizoguchi, Hiroshi; Park, SangWon; Hosono, Hideo [Materials Research Center for Element Strategy, Tokyo Institute of Technology, Yokohama 226-8503 (Japan); Hiraka, Haruhiro; Ikeda, Kazutaka; Otomo, Toshiya [Institute of Materials Structure Science, High-Energy Accelerator Research Organization (KEK), Tsukuba 305-0801 (Japan)

2015-03-02

Using a high pressure technique and the strong donating nature of H{sup -}, a new series of tetragonal La{sub 2}Fe{sub 2}Se{sub 2}O{sub 3}-type layered mixed-anion arsenides, Ln{sub 2}M{sub 2}As{sub 2}H{sub x}, was synthesized (Ln=La or Sm, M=Ti, V, Cr, or Mn; x∼3). In these compounds, an unusual M{sub 2}H square net, which has anti CuO{sub 2} square net structures accompanying two As{sup 3-} ions, is sandwiched by (LaH){sub 2} fluorite layers. Notably, strong metal-metal bonding with a distance of 2.80 Aa was confirmed in La{sub 2}Ti{sub 2}As{sub 2}H{sub 2.3}, which has metallic properties. In fact, these compounds are situated near the boundary between salt-like ionic hydrides and transition-metal hydrides with metallic characters. (copyright 2015 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim)

Chemical quality and oxidative stability of extra virgin olive oils from San Juan province (Argentina).

Science.gov (United States)

Ceci, Liliana N; Mattar, Susana B; Carelli, Amalia A

2017-10-01

This study provides information about the chemical quality (quality indices, fatty acid profile, total polyphenols (PPs), tocopherols and pigments) and oxidative stability index (OSI) of virgin olive oils of Arbequina, Changlot Real and Coratina cultivars (San Juan province, Argentina). The influence of the cultivar and the effect of earlier harvest dates on the yields (OY), quality and OSI of the oils were also evaluated. All the oils were classified as extra virgin. The OY (L/100kg) averaged: Arbequina=13.2, Changlot Real=21.3, Coratina=18.3. The oleic acid (O) percentage, oleic to linoleic plus linolenic ratio [O/(L+Ln)], PPs and OSI were highly dependent on cultivar (Arbequina8h up to 10.6-19.0h, Changlot: from 6.0-12.1h up to 13.7-36.9h and Coratina: from 20.5-26.0h up to 24.6-42.4h) due to a more favorable O/(L+Ln) ratio and antioxidant composition. Regional producers are recommended to bring forward the harvest season to obtain oils with better chemical and nutritional quality, higher oxidative stability and a fatty acid profile according to the IOC trade standard. Copyright © 2017 Elsevier Ltd. All rights reserved.

Unprecedented reduction of the uranyl ion [UO2]2+ into a polyoxo uranium(IV) cluster: synthesis and crystal structure of the first f-element oxide with a M6(micro3-O)8 core.

Science.gov (United States)

Berthet, Jean-Claude; Thuéry, Pierre; Ephritikhine, Michel

2005-07-21

The smooth comproportionation reaction of the U(VI) and U(III) complexes UO2(OTf)2 and U(OTf)3, afforded the hexanuclear U(IV) oxide cluster [U6(micro3-O)8(micro2-OTf)8(py)8], a rare example of a metal oxide with a M6(micro3-O)8 core.

Fate of citalopram during water treatment with O3, ClO2, UV and fenton oxidation

DEFF Research Database (Denmark)

Hörsing, Maritha; Kosjek, Tina; Andersen, Henrik Rasmus

2012-01-01

In the present study we investigate the fate of citalopram (CIT) at neutral pH using advanced water treatment technologies that include O3, ClO2 oxidation, UV irradiation and Fenton oxidation. The ozonation resulted in 80% reduction after 30 min treatment. Oxidation with ClO2 removed >90% CIT...... at a dosage of 0.1 mg L−1. During UV irradiation 85% reduction was achieved after 5 min, while Fenton with addition of 14 mg L−1 (Fe2+) resulted in 90% reduction of CIT. During these treatment experiments transformation products (TPs) were formed from CIT, where five compounds were identified by using high...

RE{sub 2}B{sub 8}O{sub 15} (RE = La, Pr, Nd). Syntheses of three new rare earth borates isotypic to Ce{sub 2}B{sub 8}O{sub 15}

Energy Technology Data Exchange (ETDEWEB)

Glaetzle, Matthias; Hoerder, Gregor J.; Huppertz, Hubert [Innsbruck Univ. (Austria). Inst. fuer Allgemeine, Anorganische und Theoretische Chemie

2016-08-01

The rare earth borates RE{sub 2}B{sub 8}O{sub 15} (RE = La, Pr, Nd) were synthesized in a Walker-type multianvil apparatus under conditions of 5.5 GPa and 1100 C. Starting from the corresponding rare earth oxides and boron oxide, the syntheses yielded crystalline products of all new compounds that allowed crystal structure analyses based on single-crystal X-ray diffraction data for La{sub 2}B{sub 8}O{sub 15} and Nd{sub 2}B{sub 8}O{sub 15}. The compound Pr{sub 2}B{sub 8}O{sub 15} could be characterized via X-ray powder diffractometry. The results show that the new compounds crystallize isotypically to Ce{sub 2}B{sub 8}O{sub 15} in the monoclinic space group P2/c. The infrared spectra of RE{sub 2}B{sub 8}O{sub 15} (RE = La, Pr, Nd) have also been studied.

Modeling 4f–4f intensity parameters as a function of structural distortions in Ln(2,2′-bipyridine-1,1′-dioxide){sub 4}(ClO{sub 4}){sub 3} complexes (Ln=Pr{sup 3+}, Nd{sup 3+})

Energy Technology Data Exchange (ETDEWEB)

Carneiro, A.N. [Departamento de Química Fundamental, Universidade Federal de Pernambuco-CCEN, Cidade Universitária, Recife-PE 50670-901 (Brazil); Huskowska, E.; Gawryszewska, P. [Faculty of Chemistry, Wroclaw University, 14 F. Joliot-Curie Street, Wroclaw (Poland); Legendziewicz, J., E-mail: janina.legendziewicz@chem.uni.wroc.pl [Faculty of Chemistry, Wroclaw University, 14 F. Joliot-Curie Street, Wroclaw (Poland); Malta, O.L. [Departamento de Química Fundamental, Universidade Federal de Pernambuco-CCEN, Cidade Universitária, Recife-PE 50670-901 (Brazil)

2016-01-15

This work reports on the influence of structural distortions on 4f–4f intensity parameters. These distortions in the first coordination sphere were applied to two complexes with similar structures, Ln(bpyO{sub 2}){sub 4}(ClO{sub 4}){sub 3} (Ln=Pr{sup 3+}, Nd{sup 3+} ions and bpyO{sub 2}=2,2′-bipyridine-1,1′-dioxide). The 4f–4f intensity theory and the PM3/Sparkle model were used. It is concluded that larger distortions are predicted in the case of the Pr complex, and that this point might contribute to the rationalization of the much higher values of the Ω{sub λ} intensity parameters in the Pr complex than in the Nd one. - Highlights: • The influence of structural distortions on 4f–4f intensity parameters was demonstrated for Nd and Pr complexes with 2,2′-bipyridine-1,1′-dioxide.

Nanoparticles of La0.8Ca0.2Fe0.8Ni0.2O3-δ perovskite for solid oxide fuel cell application

International Nuclear Information System (INIS)

Ortiz-Vitoriano, N.; Ruiz de Larramendi, I.; Gil de Muro, I.; Ruiz de Larramendi, J.I.; Rojo, T.

2010-01-01

Polycrystalline samples of La 0.8 Ca 0.2 Fe 0.8 Ni 0.2 O 3-δ (LCFN) with perovskite type structure have been prepared by combustion, freeze drying, citrate-gel process and liquid mix method. The analysis of X-ray powder diffraction indicated that the samples were single phase and crystallized in an orthorhombic (space group, Pnma no. 62) structure. Transmission electron microscopy (TEM) analysis on the synthesized powder at 600 o C by liquid mix method showed clusters of 150 nm formed by nanoparticles of 20 nm. Electrochemical performance of LCFN cathodes, which are used for intermediate temperature solid oxide fuel cells, were investigated. The polarization resistance was studied using two different electrolytes: Y-doped zirconia (YSZ) and Sm-doped ceria (SDC). The dc four-probe measurement exhibits a total electrical conductivity, over 100 S cm -1 at T ≥ 600 o C, pointing out that strontium can be substituted for the cheaper calcium cation without destroying the electrochemical properties. Experimental results indicate that nanoparticles have more advantages in terms of smaller particle size and better electrochemical performance.

Dark ambient degradation of Bisphenol A and Acid Orange 8 as organic pollutants by perovskite SrFeO3−δ metal oxide

International Nuclear Information System (INIS)

Leiw, Ming Yian; Guai, Guan Hong; Wang, Xiaoping; Tse, Man Siu; Ng, Chee Mang; Tan, Ooi Kiang

2013-01-01

Highlights: • Perovskite SFO prepared by high temperature and high-energy ball milling process. • SFO metal oxide shows good efficiency in degrading and mineralizing BPA. • Rapid decoloration of AO8 was achieved in the presence of SFO metal oxide. • O 2 · − is the predominant ROS for dark oxidative degradation of BPA and AO8. -- Abstract: Current advanced oxidation processes (AOPs) are chemically and energetically intensive processes, which are undesirable for cost-effective and large-scale system water treatment and wastewater recycling. This study explored the Strontium Ferrite (SFO) metal oxide on the degradation of highly concentrated organic pollutants under dark ambient condition without any external stimulants. The SFO particles with single perovskite structure were successfully synthesized with a combined high temperature and high-energy ball milling process. An endocrine disruptor, Bisphenol A (BPA) and an azo dye, Acid Orange 8 (AO8) were used as probe organic pollutants. BPA was completely degraded with 83% of mineralization in 24 h while rapid decoloration of AO8 was achieved in 60 min and complete breakdown into primary intermediates and aliphatic acids occurred in 24 h under the treatment of dispersed SFO metal oxide in water. Such efficient degradation could be attributed to the enhanced adsorption of these anionic pollutants on positively charged ball-milled SFO metal oxide surface, resulted in higher degradation activity. Preliminary degradation mechanisms of BPA and AO8 under the action of SFO metal oxide were proposed. These results showed that the SFO metal oxide could be an efficient alternative material as novel advanced oxidation technology for low cost water treatment

On some factors affecting the nonstoichiometry in U 3O 8

Science.gov (United States)

Fujino, Takeo; Tagawa, Hiroaki; Adachi, Takeo

1981-03-01

The nonstoichiometry of U 3O 8 was studied under various conditions. The {O}/{U} atom ratios obtained by the oxidation of uranium metal in air followed by cooling with moderate rates (method 1) are 2.67 ± 0.01 in the temperature range 700 900°C and 2.662 ± 0.005 at 1000°C and are generally larger than the ratio by thermogravimetry. If the oxidation was carried out in a crucible with a lid, a compositional peak was observed at 900 950°C, which did not appear for the U 3O 8 samples from UO 2. The U 3O 8 made from UO 2 by method 1 have {O}/{U} ratios 2.655 ± 0.005 (700° C), 2.653 ± 0.004 (800° C), 2.648 ± 0.004 (900° C) and 2.645 ± 0.003 (1000° C). Differences were observed in the O/U ratios of heating and cooling series. X-ray diffraction analysis showed several additional peaks other than those of α-U 3O 8 for the samples which exhibited the compositional peak.

Host-sensitized luminescence properties in CaNb2O6:Ln(3+) (Ln(3+) = Eu(3+)/Tb(3+)/Dy(3+)/Sm(3+)) phosphors with abundant colors.

Science.gov (United States)

Li, Kai; Liu, Xiaoming; Zhang, Yang; Li, Xuejiao; Lian, Hongzhou; Lin, Jun

2015-01-05

A series of Ln(3+) (Ln(3+) = Eu(3+)/Tb(3+)/Dy(3+)/Sm(3+)) ion doped CaNb2O6 (CNO) phosphors have been prepared via the conventional high-temperature solid-state reaction route. The X-ray diffraction (XRD) and structure refinement, diffuse reflection, photoluminescence (PL), and fluorescent decay curves were used to characterize the as-prepared samples. Under UV radiation, the CNO host present a broad emission band from about 355 to 605 nm centered around 460 nm originating from the NbO6 octahedral groups, which has spectral overlaps with the excitation of f-f transitions of Eu(3+)/Tb(3+)/Dy(3+)/Sm(3+) in CNO:Eu(3+)/Tb(3+)/Dy(3+)/Sm(3+) samples. They show both host emission and respective emission lines derived from the characteristic f-f transitions of activators, which present different emission colors owing to the energy transfer from the NbO6 group in the host to Eu(3+)/Tb(3+)/Dy(3+)/Sm(3+) with increasing activator concentrations. The decreases of decay lifetimes of host emissions in CNO:Eu(3+)/Tb(3+)/Dy(3+)/Sm(3+) demonstrate the energy transfer from the hosts to Eu(3+)/Tb(3+)/Dy(3+)/Sm(3+). The energy transfer mechanisms in CNO:Eu(3+)/Tb(3+)/Dy(3+) phosphors have been determined to be a resonant type via dipole-dipole mechanisms. For CNO:Sm(3+), the metal-metal charge transfer transition (MMCT) might contribute to the different variations of decay lifetimes and emission intensity from CNO:Eu(3+)/Tb(3+)/Dy(3+) samples. The best quantum efficiency is 71.2% for CNO:0.01/0.02Dy(3+). The PL properties of as-prepared materials indicate the promising application in UV-pumped white-emitting lighting diodes field.

Ultra-violet absorption cross sections of isotopically substituted nitrous oxide species: 14N14NO, 15N14NO, 14N15NO and 15N15NO

Directory of Open Access Journals (Sweden)

P. von Hessberg

2004-01-01

Full Text Available The isotopically substituted nitrous oxide species 14N14NO, 15N14NO, 14N15NO and 15N15NO were investigated by ultra-violet (UV absorption spectroscopy. High precision cross sections were obtained for the wavelength range 181 to 218nm at temperatures of 233 and 283K. These data are used to calculate photolytic isotopic fractionation constants as a function of wavelength. The fractionation constants were used in a three-dimensional chemical transport model in order to simulate the actual fractionation of N2O in the stratosphere, and the results were found to be in good agreement with field studies.

Thermodynamic modeling of La2O3-SrO-Mn2O3-Cr2O3 for solid oxide fuel cell applications

DEFF Research Database (Denmark)

Povoden-Karadeniz, E.; Chen, Ming; Ivas, Toni

2012-01-01

The thermodynamic La–Sr–Mn–Cr–O oxide database is obtained as an extension of thermodynamic descriptions of oxide subsystems using the calculation of phase diagrams approach. Concepts of the thermodynamic modeling of solid oxide phases are discussed. Gibbs energy functions of SrCrO4, Sr2.67Cr2O8......, Sr2CrO4, and SrCr2O4 are presented, and thermodynamic model parameters of La–Sr–Mn–Chromite perovskite are given. Experimental solid solubilities and nonstoichiometries in La1xSrxCrO3d and LaMn1xCrxO3d are reproduced by the model. The presented oxide database can be used for applied computational...... thermodynamics of traditional lanthanum manganite cathode with Cr-impurities. It represents the fundament for extensions to higher orders, aiming on thermodynamic calculations in noble symmetric solid oxide fuel cells...

Reduction of U3O8 to U by a metallic reductant, Li

International Nuclear Information System (INIS)

Jin-Mok Hur; Sun-Seok Hong; Hansoo Lee

2010-01-01

Reduction of U 3 O 8 was investigated for the recycling of spent oxide fuel from a commercial nuclear power plant. The possible reduction methods were proposed and compared. Based on the thermodynamic analysis, Li metal was selected as a reductant. The optimum reaction temperature for the reduction of U 3 O 8 was investigated at the wider reaction temperature range. The adverse oxidation of U metal by Li 2 O at 1,000 deg C was experimentally verified. Ellingham diagram was constructed to investigate the extent of the uranium oxides reduction when the reaction was carried out above melting point of U metal. (author)

Oxidation of iodide and iodine on birnessite (delta-MnO2) in the pH range 4-8.

Science.gov (United States)

Allard, Sébastien; von Gunten, Urs; Sahli, Elisabeth; Nicolau, Rudy; Gallard, Hervé

2009-08-01

The oxidation of iodide by synthetic birnessite (delta-MnO(2)) was studied in perchlorate media in the pH range 4-8. Iodine (I(2)) was detected as an oxidation product that was subsequently further oxidized to iodate (IO(3)(-)). The third order rate constants, second order on iodide and first order on manganese oxide, determined by extraction of iodine in benzene decreased with increasing pH (6.3-7.5) from 1790 to 3.1M(-2) s(-1). Both iodine and iodate were found to adsorb significantly on birnessite with an adsorption capacity of 12.7 microM/g for iodate at pH 5.7. The rate of iodine oxidation by birnessite decreased with increasing ionic strength, which resulted in a lower rate of iodate formation. The production of iodine in iodide-containing waters in contact with manganese oxides may result in the formation of undesired iodinated organic compounds (taste and odor, toxicity) in natural and technical systems. The probability of the formation of such compounds is highest in the pH range 5-7.5. For pH iodine is quickly oxidized to iodate, a non-toxic and stable sink for iodine. At pH >7.5, iodide is not oxidized to a significant extent.

The single crystal structure determination of Ln{sub 6}MnSb{sub 15} (Ln=La, Ce), Ln{sub 6}Mn{sub 1-x}Zn{sub x}Sb{sub 15} (x∝0.5), and Ln{sub 6}ZnSb{sub 15} (Ln=La-Pr)

Energy Technology Data Exchange (ETDEWEB)

Benavides, Katherine A.; McCandless, Gregory T.; Chan, Julia Y. [Texas Univ., Dallas, Richardson, TX (United States). Dept. of Chemistry and Biochemistry

2017-09-01

Single crystals of Ln{sub 6}MnSb{sub 15} (Ln=La, Ce), Ln{sub 6}Mn{sub 1-x}Zn{sub x}Sb{sub 15} (x∝0.5), and Ln{sub 6}ZnSb{sub 15} (Ln=La-Pr) have been successfully grown and the compounds adopt the orthorhombic Ln{sub 6}MnSb{sub 15} structure type (space group Immm), with a∝4.3 Aa, b∝15 Aa, and c∝19 Aa. This structure is comprised of antimony nets and antimony ribbons which exhibit positional disorder at connecting points between antimony substructures, in addition to two partially occupied transition metal sites. The unit cell volumes of the La analogs displayed a systematic decrease upon Zn substitution. However, for the Ce{sub 6}Mn{sub 1-x}Zn{sub x}Sb{sub 15} and Pr{sub 6}Mn{sub 1-x}Zn{sub x}Sb{sub 15} (x∝0.5), the volumes deviate from linearity as observed in the parent compounds.

Narrow spectral emission CaMoO{sub 4}: Eu{sup 3+}, Dy{sup 3+}, Tb{sup 3+} phosphor crystals for white light emitting diodes

Energy Technology Data Exchange (ETDEWEB)

Khanna, A. [Smart Lighting Engineering Research Center, 110, 8th Street, Troy, New York, 12180 (United States); Electrical, Computer and Systems Engineering Department, Rensselaer Polytechnic Institute, 110, 8th Street, Troy, New York, 12180 (United States); Dutta, P.S., E-mail: duttap@rpi.edu [Smart Lighting Engineering Research Center, 110, 8th Street, Troy, New York, 12180 (United States); Electrical, Computer and Systems Engineering Department, Rensselaer Polytechnic Institute, 110, 8th Street, Troy, New York, 12180 (United States)

2013-02-15

Alkaline earth metal molybdates are promising candidates as a host material for high efficiency narrow spectral emission phosphors. These phosphors could potentially be used for the fabrication of phosphor-converted light emitting diodes (pc-LEDs). Phosphor crystals of calcium molybdate doped with rare earth dopant Ln{sup 3+}(Ln=Eu, Dy, Tb) grown using flux growth method have been shown to exhibit higher excitation efficiency than the powders synthesized by solid-state reaction process. Molybdenum (VI) oxide has been found to be a suitable flux for growing large size optically transparent high quality crystals at a temperature around 1100 Degree-Sign C. Using the excitation wavelengths of 465 nm, 454 nm and 489 nm for CaMoO{sub 4}: Eu{sup 3+}, CaMoO{sub 4}: Dy{sup 3+} and CaMoO{sub 4}: Tb{sup 3+}, respectively, intense emission lines at wavelengths of 615 nm, 575 nm and 550 nm were observed. The optimized doping concentrations of 12%, 2% and 5% for Eu{sup 3+}, Dy{sup 3+} and Tb{sup 3+}, respectively, provided the highest luminescence intensity. - Graphical Abstract: CaMoO{sub 4}: Eu{sup 3+} phosphor crystals grown using a molybdenum (VI) oxide flux exhibited around 1.5 times the emission intensity of powders obtained from solid-state reaction at the same synthesis temperature. These crystals were found to efficiently emit 615 nm red light when excited by near UV light up to a wavelength of 395 nm. Highlights: Black-Right-Pointing-Pointer CaMoO{sub 4}: Ln{sup 3+} (Ln=Eu{sup 3+}, Dy{sup 3+}, Tb{sup 3+}) phosphor crystals were successfully grown using high temperature flux (solutions) containing molybdenum (VI) oxide or lithium chloride. Black-Right-Pointing-Pointer Narrow spectral emission at 615 nm, 575 nm and 550 nm, respectively, was observed from CaMoO{sub 4}: Ln{sup 3+} (Ln=Eu{sup 3+}, Dy{sup 3+}, Tb{sup 3+}) phosphor crystals. Black-Right-Pointing-Pointer The optimized doping concentrations of Eu{sup 3+}, Dy{sup 3+}, Tb{sup 3+} in CaMoO{sub 4} for highest

Rare earth metals, rare earth hydrides, and rare earth oxides as thin films

International Nuclear Information System (INIS)

Gasgnier, M.

1980-01-01

The review deals with pure rare earth materials such as rare earth metals, rare earth hydrides, and rare earth oxides as thin films. Several preparation techniques, control methods, and nature of possible contaminations of thin films are described. These films can now be produced in an extremely well-known state concerning chemical composition, structure and texture. Structural, electric, magnetic, and optical properties of thin films are studied and discussed in comparison with the bulk state. The greatest contamination of metallic rare earth thin films is caused by reaction with hydrogen or with water vapour. The compound with an f.c.c. structure is the dihydride LnH 2 (Ln = lanthanides). The oxygen contamination takes place after annealing at higher temperatures. Then there appears a compound with a b.c.c. structure which is the C-type sesquioxide C-Ln 2 O 3 . At room atmosphere dihydride light rare earth thin films are converted to hydroxide Ln(OH) 3 . For heavy rare earth thin films the oxinitride LnNsub(x)Osub(y) is observed. The LnO-type compound was never seen. The present review tries to set the stage anew for the investigations to be undertaken in the future especially through the new generations of electron microscopes

Synthesis, structural approach and electronic properties of V{sub 18}O{sub 45}, (N{sub 2}C{sub 6}H{sub 14}){sub 6}: a new organically templated vanadium oxide exhibiting V{sub 2}O{sub 5} layer topology

Energy Technology Data Exchange (ETDEWEB)

Sicard, M.; Maignan, A. [Laboratoire Crismat-ISMRa UMR 6508, 14 - Caen (France); Riou, D. [Universite de Versailles St Quentin, Institut Lavoisier UMR CNRS 8637, 78 - Versailles (France)

2002-02-01

V{sub 18}O{sub 45}, (N{sub 2}C{sub 6}H{sub 14}){sub 6} was hydrothermally synthesized in the form of thin platelets. Its structural approach was investigated by single crystal X-ray diffraction (non-centrosymmetric P2{sub 1} (No 4) monoclinic space group with a 10.7713(3) Angstrom, b = 11.2697(3) Angstrom, c = 29.7630(9) Angstrom, {beta} = 93.924(1) deg., V = 3604.4(2) Angstrom{sup 3}, Z = 2). V{sub 18}O{sub 45}, (N{sub 2}C{sub 6}H{sub 14}){sub 6} exhibits a lamellar structure built up from the stacking of vanadium oxide slabs between which the di-protonated 1,4-di-aza-bi-cyclo[2.2.2]octane organic cations are intercalated. The oxide layers are topologically similar to those encountered in the parent vanadium penta-oxide V{sub 2}O{sub 5} but exhibiting here a mixed valence V{sup IV}/V{sup V} with a ratio equal to 2. The electronic conductivity measurements performed on the crystals show that the resistivity curves are described by an Arrhenius law with an activation energy of 0.16 eV. (authors)

UV Photolysis of Chloramine and Persulfate for 1,4-Dioxane Removal in Reverse-Osmosis Permeate for Potable Water Reuse.

Science.gov (United States)

Li, Wei; Patton, Samuel; Gleason, Jamie M; Mezyk, Stephen P; Ishida, Kenneth P; Liu, Haizhou

2018-06-05

A sequential combination of membrane treatment and UV-based advanced oxidation processes (UV/AOP) has become the industry standard for potable water reuse. Chloramines are used as membrane antifouling agents and therefore carried over into the UV/AOP. In addition, persulfate (S 2 O 8 2- ) is an emerging oxidant that can be added into a UV/AOP, thus creating radicals generated from both chloramines and persulfate for water treatment. This study investigated the simultaneous photolysis of S 2 O 8 2- and monochloramine (NH 2 Cl) on the removal of 1,4-dioxane (1,4-D) for potable-water reuse. The dual oxidant effects of NH 2 Cl and S 2 O 8 2- on 1,4-D degradation were examined at various levels of oxidant dosage, chloride, and solution pH. Results showed that a NH 2 Cl-to-S 2 O 8 2- molar ratio of 0.1 was optimal, beyond which the scavenging by NH 2 Cl of HO • , SO 4 •- , and Cl 2 •- radicals decreased the 1,4-D degradation rate. At the optimal ratio, the degradation rate of 1,4-D increased linearly with the total oxidant dose up to 6 mM. The combined photolysis of NH 2 Cl and S 2 O 8 2- was sensitive to the solution pH due to a disproportionation of NH 2 Cl at pH lower than 6 into less-photoreactive dichloramine (NHCl 2 ) and radical scavenging by NH 4 + . The presence of chloride transformed HO • and SO 4 •- to Cl 2 •- that is less-reactive with 1,4-D, while the presence of dissolved O 2 promoted gaseous nitrogen production. Results from this study suggest that the presence of chloramines can be beneficial to persulfate photolysis in the removal of 1,4-D; however, the treatment efficiency depends on a careful control of an optimal NH 2 Cl dosage and a minimal chloride residue.

Complexes of o-Vanillin oxime with La(III), Ce(III), Nd(III), Sm(III), Gd(III), Tb(III), Dy(III), Ho(III) and Yb(III)

International Nuclear Information System (INIS)

Dhar, M.L.; Gupta, V.K.; Singh, Onkar

1988-01-01

Ten complexes of lanthanides with o-vanillin oxime have been swynthesised and characterised. The composition of the complexes as determined by elemental and thermal analyses, infrared electronic spectral and magnetic moment studies is [Ln(C 8 H 8 NO 3 ) 3 .XH 2 O], where X=2 when Ln=La, Ce, Pr, Nd, Sm and X=3 when Ln=Gd, Dy, Tb, Ho, Yb; C 8 H 8 NO 3 - represents the anion of the ligand. (author). 16 refs., 2 figs., 2 tables

Dark ambient degradation of Bisphenol A and Acid Orange 8 as organic pollutants by perovskite SrFeO{sub 3−δ} metal oxide

Energy Technology Data Exchange (ETDEWEB)

Leiw, Ming Yian, E-mail: LEIW0003@e.ntu.edu.sg [School of Electrical and Electronic Engineering, Nanyang Technological University, 50 Nanyang Avenue, Singapore 639798 (Singapore); GlobalFoundries Singapore Pte. Ltd., 60 Woodlands Industrial Park D Street 2, Singapore 738406 (Singapore); Guai, Guan Hong [GlobalFoundries Singapore Pte. Ltd., 60 Woodlands Industrial Park D Street 2, Singapore 738406 (Singapore); School of Chemical and Biomedical Engineering and Center for Advanced Bionanosystems, Nanyang Technological University, 70 Nanyang Drive, Singapore 637457 (Singapore); Wang, Xiaoping [School of Civil and Environmental Engineering, Nanyang Technological University, 50 Nanyang Avenue, Singapore 639798 (Singapore); Tse, Man Siu [School of Electrical and Electronic Engineering, Nanyang Technological University, 50 Nanyang Avenue, Singapore 639798 (Singapore); Ng, Chee Mang [GlobalFoundries Singapore Pte. Ltd., 60 Woodlands Industrial Park D Street 2, Singapore 738406 (Singapore); Tan, Ooi Kiang [School of Electrical and Electronic Engineering, Nanyang Technological University, 50 Nanyang Avenue, Singapore 639798 (Singapore)

2013-09-15

Highlights: • Perovskite SFO prepared by high temperature and high-energy ball milling process. • SFO metal oxide shows good efficiency in degrading and mineralizing BPA. • Rapid decoloration of AO8 was achieved in the presence of SFO metal oxide. • O{sub 2}·{sup −} is the predominant ROS for dark oxidative degradation of BPA and AO8. -- Abstract: Current advanced oxidation processes (AOPs) are chemically and energetically intensive processes, which are undesirable for cost-effective and large-scale system water treatment and wastewater recycling. This study explored the Strontium Ferrite (SFO) metal oxide on the degradation of highly concentrated organic pollutants under dark ambient condition without any external stimulants. The SFO particles with single perovskite structure were successfully synthesized with a combined high temperature and high-energy ball milling process. An endocrine disruptor, Bisphenol A (BPA) and an azo dye, Acid Orange 8 (AO8) were used as probe organic pollutants. BPA was completely degraded with 83% of mineralization in 24 h while rapid decoloration of AO8 was achieved in 60 min and complete breakdown into primary intermediates and aliphatic acids occurred in 24 h under the treatment of dispersed SFO metal oxide in water. Such efficient degradation could be attributed to the enhanced adsorption of these anionic pollutants on positively charged ball-milled SFO metal oxide surface, resulted in higher degradation activity. Preliminary degradation mechanisms of BPA and AO8 under the action of SFO metal oxide were proposed. These results showed that the SFO metal oxide could be an efficient alternative material as novel advanced oxidation technology for low cost water treatment.

Covalency in lanthanides. An X-ray absorption spectroscopy and density functional theory study of LnCl6(x-) (x = 3, 2).

Science.gov (United States)

Löble, Matthias W; Keith, Jason M; Altman, Alison B; Stieber, S Chantal E; Batista, Enrique R; Boland, Kevin S; Conradson, Steven D; Clark, David L; Lezama Pacheco, Juan; Kozimor, Stosh A; Martin, Richard L; Minasian, Stefan G; Olson, Angela C; Scott, Brian L; Shuh, David K; Tyliszczak, Tolek; Wilkerson, Marianne P; Zehnder, Ralph A

2015-02-25

Covalency in Ln-Cl bonds of Oh-LnCl6(x-) (x = 3 for Ln = Ce(III), Nd(III), Sm(III), Eu(III), Gd(III); x = 2 for Ln = Ce(IV)) anions has been investigated, primarily using Cl K-edge X-ray absorption spectroscopy (XAS) and time-dependent density functional theory (TDDFT); however, Ce L3,2-edge and M5,4-edge XAS were also used to characterize CeCl6(x-) (x = 2, 3). The M5,4-edge XAS spectra were modeled using configuration interaction calculations. The results were evaluated as a function of (1) the lanthanide (Ln) metal identity, which was varied across the series from Ce to Gd, and (2) the Ln oxidation state (when practical, i.e., formally Ce(III) and Ce(IV)). Pronounced mixing between the Cl 3p- and Ln 5d-orbitals (t2g* and eg*) was observed. Experimental results indicated that Ln 5d-orbital mixing decreased when moving across the lanthanide series. In contrast, oxidizing Ce(III) to Ce(IV) had little effect on Cl 3p and Ce 5d-orbital mixing. For LnCl6(3-) (formally Ln(III)), the 4f-orbitals participated only marginally in covalent bonding, which was consistent with historical descriptions. Surprisingly, there was a marked increase in Cl 3p- and Ce(IV) 4f-orbital mixing (t1u* + t2u*) in CeCl6(2-). This unexpected 4f- and 5d-orbital participation in covalent bonding is presented in the context of recent studies on both tetravalent transition metal and actinide hexahalides, MCl6(2-) (M = Ti, Zr, Hf, U).

Effect of anode firing on the performance of lanthanum and nickel co-doped SrTiO3 (La0.2Sr0.8Ti0.9Ni0.1O3-δ) anode of solid oxide fuel cell

Science.gov (United States)

Park, Byung Hyun; Choi, Gyeong Man

2015-10-01

Perovskite oxides have potential for use as alternative anode materials in solid oxide fuel cells (SOFCs) due to stability in anode atmosphere; donor-doped SrTiO3 (e.g., La0.2Sr0.8TiO3-δ) is a good candidate for this purpose. Electro-catalytic nanoparticles can be produced in oxide anodes by the ex-solution method, e.g., by incorporating Ni into a perovskite oxide in air, then reducing the oxide in H2 atmosphere. In this study, we varied the temperature (1100, 1250 °C) and atmosphere (air, H2) of La0.2Sr0.8Ti0.9Ni0.1O3-δ (LSTN) anode firing to control the degree of Ni ex-solution and microstructure. LSTN fired at 1250 °C in H2 showed the best anodic performance for scandia-stabilized zirconia (ScSZ) electrolyte-supported cells in H2 and CH4 fuels due to the favorable microstructure and Ni ex-solution.

Transuranium element incorporation into the β-U3O8 uranyl sheet

International Nuclear Information System (INIS)

Miller, M.L.; Burns, P.C.; Ewing, R.C.; Finch, R.J.

1997-01-01

Spent nuclear fuel (SNF) is unstable under oxidizing conditions. Although recent studies have determined the paragenetic sequence for uranium phases that result from the corrosion of SNF, there are only limited data on the potential of alteration phases for the incorporation of transuranium elements. The crystal chemical characteristics of transuranic elements (TUE) are to a certain extent similar to uranium; thus TUE incorporation into the sheets of uranyl oxide hydrate structures can be assessed by examination of the structural details of the β-U 3 O 8 sheet type. The sheets of uranyl polyhedra observed in the crystal structure of β-U 3 O 8 also occur in the mineral billietite, where they alternate with α-U 3 O 8 type sheets. Preliminary crystal structure determinations for the minerals ianthinite, and wyartite, indicate that these phases also contain β-U 3 O 8 type sheets. The β-U 3 O 8 sheet anion topology contains triangular, rhombic, and pentagonal sites in the proportions 2:1:2. In all structures containing β-U 3 O 8 type sheets, the triangular sites are vacant. The pentagonal sites are filled with U 6+ O 2 forming pentagonal bipyramids. The rhombic dipyramids filling the rhombic sites contain U 6+ O 2 in billietite, U 4+ O 2 in β-U 3 O 8 , U 4+ (H 2 O) 2 in ianthinite, and U 4+ O 3 in wyartite-II. Interlayer species include: H 2 O (billietite, wyartite II, and ianthinite), Ba 2+ (billietite) Ca 2+ wyartite II, and Co 3 2- wyartite II; there is no interlayer in β-U 3 O 8 . The similarity of known TUE coordination polyhedra with those of U suggests that the β-U 3 O 8 sheet will accommodate TUE substitution coupled with variations in apical anion configuration and interlayer population providing the required charge balance

High-pressure synthesis and characterization of new actinide borates, AnB4O8 (An=Th, U).

Science.gov (United States)

Hinteregger, Ernst; Hofer, Thomas S; Heymann, Gunter; Perfler, Lukas; Kraus, Florian; Huppertz, Hubert

2013-11-18

New actinide borates ThB4O8 and UB4O8 were synthesized under high-pressure, high-temperature conditions (5.5 GPa/1100 °C for thorium borate, 10.5 GPa/1100 °C for the isotypic uranium borate) in a Walker-type multianvil apparatus from their corresponding actinide oxide and boron oxide. The crystal structure was determined on basis of single-crystal X-ray diffraction data that were collected at room temperature. Both compounds crystallized in the monoclinic space group C2/c (Z=4). Lattice parameters for ThB4O8: a=1611.3(3), b=419.86(8), c=730.6(2) pm; β=114.70(3)°; V=449.0(2) Å(3); R1=0.0255, wR2=0.0653 (all data). Lattice parameters for UB4O8: a=1589.7(3), b=422.14(8), c=723.4(2) pm; β=114.13(3)°; V=443.1(2) Å(3); R1=0.0227, wR2=0.0372 (all data). The new AnB4O8 (An=Th, U) structure type is constructed from corner-sharing BO4 tetrahedra, which form layers in the bc plane. One of the four independent oxygen atoms is threefold-coordinated. The actinide cations are located between the boron-oxygen layers. In addition to Raman spectroscopic investigations, DFT calculations were performed to support the assignment of the vibrational bands. © 2013 The Authors. Published by Wiley-VCH Verlag GmbH & Co. KGaA. This isan open access article under the terms of the Creative Commons AttributionLicense, which permits use, distribution and reproduction in any medium,provided the original work is properly cited.

Crystal structure and optical property of complex perovskite oxynitrides ALi0.2Nb0.8O2.8N0.2, ANa0.2Nb0.8O2.8N0.2, and AMg0.2Nb0.8O2.6N0.4 (A = Sr, Ba)

Science.gov (United States)

Moon, Keon Ho; Avdeev, Maxim; Kim, Young-Il

2017-10-01

Oxynitride type complex perovskites AM0.2Nb0.8O3-xNx (A = Sr, Ba; M = Li, Na, Mg) were newly synthesized by the solid state diffusion of Li+, Na+, or Mg2+ into the layered oxide, A5Nb4O15, with concurrent O/N substitution. Neutron and synchrotron X-ray Rietveld refinement showed that SrLi0.2Nb0.8O2.8N0.2, SrNa0.2Nb0.8O2.8N0.2, and SrMg0.2Nb0.8O2.6N0.4 had body-centered tetragonal symmetry (I4/mcm), while those with A = Ba had simple cubic symmetry (Pm 3 ̅ m). In the tetragonal Sr-compounds, the nitrogen atoms were localized on the c-axial 4a site. However, the octahedral cations, M/Nb (M = Li, Na, Mg) were distributed randomly in all six compounds. The lattice volume of AM0.2Nb0.8O3-xNx was dependent on various factors including the type of A and the electronegativity of M. Compared to the simple perovskites, ANbO2N (A = Sr, Ba), AM0.2Nb0.8O3-xNx had wider band gaps (1.76-2.15 eV for A = Sr and 1.65-2.10 eV for A = Ba), but significantly lower sub-gap absorption.

Synthesis, surface modification/decoration of luminescent–magnetic core/shell nanomaterials, based on the lanthanide doped fluorides (Fe{sub 3}O{sub 4}/SiO{sub 2}/NH{sub 2}/PAA/LnF{sub 3})

Energy Technology Data Exchange (ETDEWEB)

Runowski, Marcin; Lis, Stefan, E-mail: blis@amu.edu.pl

2016-02-15

The synthesized magnetite nanoparticles (10–15 nm) were successfully coated with amine modified silica nanoshell, which led to the formation of core/shell type nanostructures (30–50 nm). The as-prepared nanoparticles were surface modified with polyacrylic acid (PAA) via electrostatic interactions of –NH{sub 2} and –COOH groups. Afterwards, the surface PAA molecules acted as complexing agents of the introduced lanthanide (Ln{sup 3+}) ions. Subsequently, the as-prepared nanostructures were surface decorated with luminescent LnF{sub 3} nanoparticles, forming Eu{sup 3+} or Tb{sup 3+} doped Fe{sub 3}O{sub 4}/SiO{sub 2}/NH{sub 2}/PAA/LnF{sub 3} nanomaterials (50–100 nm). The obtained luminescent–magnetic products exhibited simultaneously bright red or green emission under UV lamp irradiation (λ{sub ex}=254 nm), and a response for the applied magnetic field (strong magnet attracts the colloidal particles, dispersed in aqueous medium). After the synthesis, properties of the nanomaterials were investigated by powder X-ray diffraction (XRD) technique, transmission electron microscopy (TEM), infrared spectroscopy (IR) and spectrofluorometry (analysis of excitation/emission spectra and luminescence decay curves). Such advanced nanomaterials can be potentially used in multimodal imaging, targeted therapies and as multifunctional contrast agents, novel luminescent–magnetic tracers, protection of documents, etc. - Highlights: • Luminescent–magnetic nanomaterials Fe{sub 3}O{sub 4}/SiO{sub 2}/NH{sub 2}/PAA/LnF{sub 3} were synthesized. • Core/shell nanostructures were obtained by surface modification of nanoparticles. • Luminescent lanthanide fluoride nanoparticles doped with Eu{sup 3+} and Tb{sup 3+} ions. • Multifunctional core/shell nanostructures exhibited red or green emission. • Nanomaterials formed stable aqueous colloids.

Substitution studies of Mn and Fe in Ln{sub 6}W{sub 4}Al{sub 43} (Ln=Gd, Yb) and the structure of Yb{sub 6}Ti{sub 4}Al{sub 43}

Energy Technology Data Exchange (ETDEWEB)

Treadwell, LaRico J.; Watkins-Curry, Pilanda [Department of Chemistry, Louisiana State University, Baton Rouge, LA 70803 (United States); Department of Chemistry, University of Texas at Dallas, Richardson, TX 75080 (United States); McAlpin, Jacob D. [Department of Chemistry, Louisiana State University, Baton Rouge, LA 70803 (United States); Prestigiacomo, Joseph; Stadler, Shane [Department of Physics and Astronomy, Louisiana State University, Baton Rouge, LA 70803 (United States); Chan, Julia Y., E-mail: Julia.Chan@utdallas.edu [Department of Chemistry, Louisiana State University, Baton Rouge, LA 70803 (United States); Department of Chemistry, University of Texas at Dallas, Richardson, TX 75080 (United States)

2014-02-15

The synthesis and characterization of Mn- and Fe-substituted Ln{sub 6}W{sub 4}Al{sub 43} (Ln=Gd, Yb) and Yb{sub 6}Ti{sub 4}Al{sub 43} are reported. The compounds adopt the Ho{sub 6}Mo{sub 4}Al{sub 43} structure type with lattice parameters of a∼11 Å and c∼17.8 Å with structural site preferences for Mn and Fe. The magnetization of Yb{sub 6}W{sub 4}Al{sub 43} is sensitive to Mn and Fe doping, which is evident by an increase in the field dependent magnetization. Gd{sub 6}W{sub 4}Al{sub 43}, Gd{sub 6}W{sub 4}Al{sub 42.31(11)}Mn{sub 0.69(11)}, and Gd{sub 6}W{sub 4}Al{sub 41.69(12)}Fe{sub 1.30(12)} order antiferromagnetically in the ab- and c-directions at 15, 14, and 13 K, respectively, with positive Weiss constants, suggesting the presence of ferromagnetic exchange interactions. Anisotropic magnetization data of Gd{sub 6}W{sub 4}Al{sub 43−y}T{sub y} (T=Mn, Fe) analogs are discussed. - Graphical abstract: The magnetic susceptibility of Ln{sub 6}W{sub 4−x}Al{sub 43−y}T{sub x+y} (Ln = Gd, Yb; T= Mn, Fe). Display Omitted - Highlights: • Single crystals of Ln{sub 6}W{sub 4−x}Al{sub 43−y}T{sub x+y} were grown with Al-flux. • Anisotropic magnetic behavior were determined on single crystals. • Gd{sub 6}W{sub 4−x}Al{sub 43−y}T{sub x+y} (T=Mn, Fe) analogs order antiferromagnetically.

Axially symmetric U-O-Ln- and U-O-U-containing molecules from the control of uranyl reduction with simple f-block halides

International Nuclear Information System (INIS)

Arnold, Polly L.; Cowie, Bradley E.; Suvova, Marketa; Zegke, Markus; Love, Jason B.; Magnani, Nicola; Colineau, Eric; Griveau, Jean-Christophe; Caciuffo, Roberto

2017-01-01

The reduction of U"V"I uranyl halides or amides with simple Ln"I"I or U"I"I"I salts forms highly symmetric, linear, oxo-bridged trinuclear U"V/Ln"I"I"I/U"V, Ln"I"I"I/U"I"V/Ln"I"I"I, and U"I"V/U"I"V/U"I"V complexes or linear Ln"I"I"I/U"V polymers depending on the stoichiometry and solvent. The reactions can be tuned to give the products of one- or two-electron uranyl reduction. The reactivity and magnetism of these compounds are discussed in the context of using a series of strongly oxo-coupled homo- and heterometallic poly(f-block) chains to better understand fundamental electronic structure in the f-block. (copyright 2017 Wiley-VCH Verlag GmbH and Co. KGaA, Weinheim)

Axially symmetric U-O-Ln- and U-O-U-containing molecules from the control of uranyl reduction with simple f-block halides

Energy Technology Data Exchange (ETDEWEB)

Arnold, Polly L.; Cowie, Bradley E.; Suvova, Marketa; Zegke, Markus; Love, Jason B. [EaStCHEM School of Chemistry, University of Edinburgh (United Kingdom); Magnani, Nicola; Colineau, Eric; Griveau, Jean-Christophe; Caciuffo, Roberto [European Commission, Directorate for Nuclear Safety and Security, Joint Research Centre, Karlsruhe (Germany)

2017-08-28

The reduction of U{sup VI} uranyl halides or amides with simple Ln{sup II} or U{sup III} salts forms highly symmetric, linear, oxo-bridged trinuclear U{sup V}/Ln{sup III}/U{sup V}, Ln{sup III}/U{sup IV}/Ln{sup III}, and U{sup IV}/U{sup IV}/U{sup IV} complexes or linear Ln{sup III}/U{sup V} polymers depending on the stoichiometry and solvent. The reactions can be tuned to give the products of one- or two-electron uranyl reduction. The reactivity and magnetism of these compounds are discussed in the context of using a series of strongly oxo-coupled homo- and heterometallic poly(f-block) chains to better understand fundamental electronic structure in the f-block. (copyright 2017 Wiley-VCH Verlag GmbH and Co. KGaA, Weinheim)

Experimental thermochemistry of neptunium oxides: Np2O5 and NpO2

Science.gov (United States)

Zhang, Lei; Dzik, Ewa A.; Sigmon, Ginger E.; Szymanowski, Jennifer E. S.; Navrotsky, Alexandra; Burns, Peter C.

2018-04-01

Neptunium (Np) compounds are important in the nuclear fuel cycle because of the buildup and long half-life (2.14 Ma) of Np-237 in nuclear waste, especially during long-term disposal in a geological repository. Neptunium in environmental conditions exists mainly in two oxidation states (+5 and + 4) and can substitute for uranium and/or rare earths in solid phases. Yet thermochemical data for solid neptunium compounds are scarce, despite being critical for evaluating the environmental transport of this radioactive and toxic element. Although high temperature oxide melt solution calorimetry has proven very useful in obtaining thermodynamic data for the formation of uranium and thorium oxide materials, it has not yet been applied to transuranium compounds. Continuing a program at Notre Dame to study the thermodynamics of transuranium compounds, we report the first determination of the enthalpies of drop solution of well-characterized neptunium oxides (Np2O5 and NpO2) using oxide melt solution calorimetry in molten sodium molybdate solvent at 973 K. The enthalpy of the decomposition reaction, Np2O5(cr) = 2NpO2(cr) + 1/2O2(g) at 298 K, is determined to be 7.70 ± 5.86 kJ/mol, and this direct measurement is consistent with existing thermodynamic data. The calorimetric methodology is straightforward and produces reliable data using milligram quantities of radioactive materials, and can be applied to many other transuranium compounds.

Preparation of ammonium sulfate, calcium oxide and rare earth concentrate from phospho-gypsum

International Nuclear Information System (INIS)

Andrianov, A.M.; Rusin, N.F.; Dejneka, G.F.; Zinchenko, T.A.; Burova, T.I.

1978-01-01

A technological scheme is proposed which gives ammonium sulfate, purified (from admixtures of silicon, iron, titanium, aluminium) calcium oxide with direct yield of calcium 91% and rare-earth concentrate, containing 5.6% of Ln 2 O 3 with direct yield of 99.5%

A screen-printed Ce 0.8Sm 0.2O 1.9 film solid oxide fuel cell with a Ba 0.5Sr 0.5Co 0.8Fe 0.2O 3- δ cathode

Science.gov (United States)

Zhang, Yaohui; Huang, Xiqiang; Lu, Zhe; Liu, Zhiguo; Ge, Xiaodong; Xu, Jiahuan; Xin, Xianshuang; Sha, Xueqing; Su, Wenhui

Screen-printing technology was developed to fabricate Ce 0.8Sm 0.2O 1.9 (SDC) electrolyte films onto porous NiO-SDC green anode substrates. After sintering at 1400 °C for 4 h, a gas-tight SDC film with a thickness of 12 μm was obtained. A novel cathode material of Ba 0.5Sr 0.5Co 0.8Fe 0.2O 3- δ was subsequently applied onto the sintered SDC electrolyte film also by screen-printing and sintered at 970 °C for 3 h to get a single cell. A fuel cell of Ni-SDC/SDC (12 μm)/Ba 0.5Sr 0.5Co 0.8Fe 0.2O 3- δ provides the maximum power densities of 1280, 1080, 670, 370, 180 and 73 mW cm -2 at 650, 600, 555, 505, 455 and 405 °C, respectively, using hydrogen as fuel and stationary air as oxidant. When dry methane was used as fuel, the maximum power densities are 876, 568, 346 and 114 mW cm -2 at 650, 600, 555 and 505 °C, respectively. The present fuel cell shows excellent performance at lowered temperatures.

Family of defect-dicubane Ni4Ln2 (Ln = Gd, Tb, Dy, Ho) and Ni4Y2 complexes: rare Tb(III) and Ho(III) examples showing SMM behavior.

Science.gov (United States)

Zhao, Lang; Wu, Jianfeng; Ke, Hongshan; Tang, Jinkui

2014-04-07

Reactions of Ln(III) perchlorate (Ln = Gd, Tb, Dy, and Ho), NiCl2·6H2O, and a polydentate Schiff base resulted in the assembly of novel isostructural hexanuclear Ni4Ln2 complexes [Ln = Gd (1), Tb (2), Dy (3), Ho (4)] with an unprecedented 3d-4f metal topology consisting of two defect-dicubane units. The corresponding Ni4Y2 (5) complex containing diamagnetic Y(III) atoms was also isolated to assist the magnetic studies. Interestingly, complexes 2 and 3 exhibit SMM characteristics and 4 shows slow relaxation of the magnetization. The absence of frequency-dependent in-phase and out-of-phase signals for the Ni-Y species suggests that the Ln ions' contribution to the slow relaxation must be effectual as previously observed in other Ni-Dy samples. However, the observation of χ″ signals with zero dc field for the Ni-Tb and Ni-Ho derivatives is notable. Indeed, this is the first time that such a behavior is observed in the Ni-Tb and Ni-Ho complexes.

Mono(pyridine-N-oxide) analog of DOTA as a suitable organic reagent for a sensitive and selective fluorimetric determination of Ln(III) ions

Energy Technology Data Exchange (ETDEWEB)

Vanek, Jakub [Department of Chemistry, Faculty of Science, Masaryk University, Kotlarska 2, 611 37 Brno (Czech Republic); Central European Institute of Technology (CEITEC), Masaryk University, Kamenice 5, 625 00 Brno (Czech Republic); Lubal, Premysl, E-mail: lubal@chemi.muni.cz [Department of Chemistry, Faculty of Science, Masaryk University, Kotlarska 2, 611 37 Brno (Czech Republic); Central European Institute of Technology (CEITEC), Masaryk University, Kamenice 5, 625 00 Brno (Czech Republic); Sevcikova, Romana [Department of Chemistry, Faculty of Science, Masaryk University, Kotlarska 2, 611 37 Brno (Czech Republic); Polasek, Miloslav; Hermann, Petr [Department of Inorganic Chemistry, Faculty of Science, Charles University, Hlavova 2030, 128 40, Prague (Czech Republic)

2012-08-15

The mono(pyridine-N-oxide) analog of the H{sub 4}dota macrocylic ligand, H{sub 3}do3a-py{sup NO}, is capable of forming thermodynamically stable and kinetically inert Ln(III) complexes. Its Eu(III) and Tb(III) complexes display a strong long-lived fluorescence as a result of the antenna effect of the pyridine-N-oxide fluorophore in the reagent. It is shown that H{sub 3}do3a-py{sup NO} can be used as a fluorogenic reagent for the determination of Eu(III) and Tb(III) at pH 6.5 and c{sub L}=1 mM. At an excitation wavelength of 286 nm, the emission maxima are 615 nm (Eu(III)-complex), and 547 nm (Tb(III)complex). Detection limits are at concentrations around 1.0 {mu}M and linearity of the method spans over 2 orders of magnitude. The method was applied to artificial and real samples (spiked mineral waters, extracts from cathode ray tube luminophore dust) and gave satisfactory results. The method is simple, rapid, and hardly interfered by other metal ions. - Graphical Abstract: A DOTA-like ligand with pyridine-N-oxide pendant arm is used for a quick, selective and sensitive determination of Eu{sup 3+} and Tb{sup 3+} ions through sensitized emission with excitation at 286 nm. The presented fluorimetric method is not interfered by transition metal or other lanthanide(III) ions and has a high dynamic range. Highlights: Black-Right-Pointing-Pointer Quick, selective and sensitive determination of Eu{sup 3+}/Tb{sup 3+} ions was developed. Black-Right-Pointing-Pointer Sensitized emission with excitation at 286 nm through pyridine-N-oxide pendant arm. Black-Right-Pointing-Pointer No interference of transition metal or other Ln(III) ions within high dynamic range.

The synthesis of 8-β-[(methylsulfinyl-[18O])-methyl]-6-propylergoline

International Nuclear Information System (INIS)

Wheeler, W.J.

1987-01-01

The synthesis of 18 O-labeled 8-Β-[(methylsulfinyl)-methyl]-6-propyl-ergoline(pergolide-[ 18 O]-sulfoxide) of undetermined stereochemistry by the reaction of 8-Β-(methylthiomethyl)-6-propyl-ergoline (pergolide) with bis-(4-methoxyphenyl)-selen-[ 18 O]-oxide in acetic acid is described. Although the yields were low and the incorporation of 18 O was not high, this procedure represents a convenient method for the preparation of 18 O-labeled sulfoxides of pergolide and other sulfides present in compounds for which the usual methods are inappropriate. (author)

Ruthenium nanoparticles supported on CeO2 for catalytic permanganate oxidation of butylparaben.

Science.gov (United States)

Zhang, Jing; Sun, Bo; Guan, Xiaohong; Wang, Hui; Bao, Hongliang; Huang, Yuying; Qiao, Junlian; Zhou, Gongming

2013-11-19

This study developed a heterogeneous catalytic permanganate oxidation system with ceria supported ruthenium, Ru/CeO2 (0.8‰ as Ru), as catalyst for the first time. The catalytic performance of Ru/CeO2 toward butylparaben (BP) oxidation by permanganate was strongly dependent on its dosage, pH, permanganate concentration and temperature. The presence of 1.0 g L(-1) Ru/CeO2 increased the oxidation rate of BP by permanganate at pH 4.0-8.0 by 3-96 times. The increase in Ru/CeO2 dosage led to a progressive enhancement in the oxidation rate of BP by permanganate at neutral pH. The XANES analysis revealed that (1) Ru was deposited on the surface of CeO2 as Ru(III); (2) Ru(III) was oxidized by permanganate to its higher oxidation state Ru(VI) and Ru(VII), which acted as the co-oxidants in BP oxidation; (3) Ru(VI) and Ru(VII) were reduced by BP to its initial state of Ru(III). Therefore, Ru/CeO2 acted as an electron shuttle in catalytic permanganate oxidation process. LC-MS/MS analysis implied that BP was initially attacked by permanganate or Ru(VI) and Ru(VII) at the aromatic ring, leading to the formation of various hydroxyl-substituted and ring-opening products. Ru/CeO2 could maintain its catalytic activity during the six successive runs. In conclusion, catalyzing permanganate oxidation with Ru/CeO2 is a promising technology for degrading phenolic pollutants in water treatment.

Degradation kinetics and mechanism of β-lactam antibiotics by the activation of H2O2 and Na2S2O8 under UV-254 nm irradiation

International Nuclear Information System (INIS)

He, Xuexiang; Mezyk, Stephen P.; Michael, Irene; Fatta-Kassinos, Despo; Dionysiou, Dionysios D.

2014-01-01

Graphical abstract: - Highlights: • Removal efficiency was comparable at different UV fluence rates but same fluence. • Reducing pH to 3 or 2 did not inhibit the removal of nitrobenzene by UV/S 2 O 8 2− . • 1.84 × 10 −14 M [HO • ] ss and 3.10 × 10 −13 M [SO 4 • − ] ss in UV/S 2 O 8 2− were estimated. • HO • reacted faster with the β-lactams than SO 4 • − but sharing similar byproducts. • Transformation pathways included hydroxylation, hydrolysis and decarboxylation. - Abstract: The extensive production and usage of antibiotics have led to an increasing occurrence of antibiotic residuals in various aquatic compartments, presenting a significant threat to both ecosystem and human health. This study investigated the degradation of selected β-lactam antibiotics (penicillins: ampicillin, penicillin V, and piperacillin; cephalosporin: cephalothin) by UV-254 nm activated H 2 O 2 and S 2 O 8 2− photochemical processes. The UV irradiation alone resulted in various degrees of direct photolysis of the antibiotics; while the addition of the oxidants improved significantly the removal efficiency. The steady-state radical concentrations were estimated, revealing a non-negligible contribution of hydroxyl radicals in the UV/S 2 O 8 2− system. Mineralization of the β-lactams could be achieved at high UV fluence, with a slow formation of SO 4 2− and a much lower elimination of total organic carbon (TOC). The transformation mechanisms were also investigated showing the main reaction pathways of hydroxylation (+16 Da) at the aromatic ring and/or the sulfur atom, hydrolysis (+18 Da) at the β-lactam ring and decarboxylation (–44 Da) for the three penicillins. Oxidation of amine group was also observed for ampicillin. This study suggests that UV/H 2 O 2 and UV/S 2 O 8 2− advanced oxidation processes (AOPs) are capable of degrading β-lactam antibiotics decreasing consequently the antibiotic activity of treated waters

Improving the SMM and luminescence properties of lanthanide complexes with LnO9 cores in the presence of ZnII: an emissive Zn2Dy single ion magnet.

Science.gov (United States)

Fondo, Matilde; Corredoira-Vázquez, Julio; Herrera-Lanzós, Antía; García-Deibe, Ana M; Sanmartín-Matalobos, Jesús; Herrera, Juan Manuel; Colacio, Enrique; Nuñez, Cristina

2017-12-12

Mononuclear complexes of stoichiometry [Ln(H 3 L)(H 2 O)(NO 3 )](NO 3 ) 2 (Ln = Tb, 1; Dy, 2, Er, 3), which crystallise with different solvates, and the heterotrinuclear compound [Zn 2 Dy(L)(NO 3 ) 3 (OH)] (4) can be obtained with the same H 3 L compartmental ligand. The single X-ray crystal structure of the mononuclear complexes shows a LnO 9 core with a muffin-like disposition while the geometry of the DyO 9 core in 4 seems to be closer to spherical capped square antiprism. The analysis of the magnetic properties of all the complexes demonstrates that the mononuclear lanthanide compounds do not show slow relaxation of the magnetization, even when the samples are diluted with a diamagnetic matrix and subjected to a dc applied field of 1000 Oe. Nevertheless, the heterotrinuclear dysprosium complex 4·3H 2 O is a field-induced single ion magnet, with an estimated U eff barrier of 59 K. The luminescence characterisation of all the metal complexes in methanol solution at 298 K also shows a notable increase in the fluorescence emission of the heterotrinuclear complex with respect to the mononuclear ones, in such a way that 4 can be defined as a fluorescent single ion magnet.

Magneto, spectral and thermal studies of lanthanum and lanthanide(3) bromide and nitrate complexes of 2,2'bipyridine mono N-oxide

International Nuclear Information System (INIS)

Agarwal, R.K.

1988-01-01

Lanthanide(3) bromide and nitrate complexes of 2,2'-bipyridine mono N-oxide (BipyNO) having the composition Ln(BipyNO) 3 Br 3 and Ln(BipyNO) 2 (NO 3 ) 3 (Ln=La, Ce, Pr, Nd, Sm, Gd, Tb, Dy, Ho and Yb) have been prepared and characterized by means of conductance, molecular weight, magnetic and spectral studies. The ligand acts as a bidentate O,N-chelating agent. The coordination number nine or ten for lanthanide ions has been assigned to these complexes. 3 tabs., 25 refs. (author)

Influence of C3H8O3 in the electrolyte on characteristics and corrosion resistance of the microarc oxidation coatings formed on AZ91D magnesium alloy surface

International Nuclear Information System (INIS)

Wu Di; Liu Xiangdong; Lu Kai; Zhang Yaping; Wang Huan

2009-01-01

Ceramic coatings were fabricated on AZ91D Mg-alloy substrate by microarc oxidation in Na 2 SiO 3 -NaOH-Na 2 EDTA electrolytes with and without C 3 H 8 O 3 addition. The effects of different concentrations of C 3 H 8 O 3 contained in the electrolyte on coatings thickness were investigated. The surface morphologies, RMS roughness, phase compositions and corrosion resistance property of the ceramic coatings were analyzed by scanning electron microscopy (SEM), atomic force microscopy (AFM), X-ray diffraction (XRD), and electrochemical corrosion test respectively. It is found that the addition of C 3 H 8 O 3 into silicate electrolyte leads to increase of the unit-area adsorptive capacity of the negative ions at anode-electrolyte interface and thus improves the compactness and corrosion resistance of the MAO coating. The coating thickness decreases gradually with the increase of concentrations of C 3 H 8 O 3 in the electrolyte. The oxide coating formed in base electrolyte containing 4 mL/L C 3 H 8 O 3 exhibits the best surface appearance, the lowest surface RMS roughness (174 nm) and highest corrosion resistance. In addition, both ceramic coatings treated in base electrolyte with and without C 3 H 8 O 3 are mainly composed of periclase MgO and forsterite Mg 2 SiO 4 phase, but no diffraction peak of Mg phase is found in the patterns.

Determinación del coeficiente piroeléctrico del sistema ferroeléctrico cerámico de Pb0.88Ln0.08Ti0.98Mn0.02O3 (Ln=La, Sm, Eu y su aplicación en detectores de infrarrojo

Directory of Open Access Journals (Sweden)

Suaste-Gómez, E.

2004-12-01

Full Text Available In this work the dielectric and pyroelectric characteristics of the ferroelectric ceramic system of Pb0.88(Ln0.08Ti0.98Mn0.02O3 (Ln = La, Sm, Eu are studied in order to determine its usefulness as infrared dectectors. Dielectric constant and pyroelectric coefficient of the ceramics were determined. This material with perovskite structure presented a phase transition from tetragonal to cubic on the heating process, besides of presenting high values of dielectric constant. Values of figure of merit for infrared detection Rv=pi/εr were calculated. The results were compared with other materials used as infrared detectors.En este trabajo se estudian las características dieléctricas y piroeléctricas del sistema ferroléctrico cerámico de Pb0.88(Ln0.08Ti0.98 Mn0.02O3 (Ln = La, Sm, Eu para determinar su utilidad como detectores de infrarrojo. Se determinó la constante dieléctrica y el coeficiente piroeléctrico de las cerámicas. Este material con estructura de perovskita presentó una transición de fase tetragonal a cúbica en el proceso de calentamiento, además de presentar altos valores de la constante dieléctrica. Se obtuvieron valores de la figura de mérito para detección infrarroja Rv=pi/εr Los resultados se compararon con otros materiales usados como detectores de infrarrojo.

Nonheme oxoiron(IV) complexes of pentadentate N5 ligands: spectroscopy, electrochemistry, and oxidative reactivity

OpenAIRE

Wang, Dong; Ray, Kallol; Collins, Michael J.; Farquhar, Erik R.; Frisch, Jonathan R.; Gomez, Laura; Jackson, Timothy A.; Kerscher, Marion; Waleska, Arkadius; Comba, Peter; Costas, Miquel; Que, Lawrence, Jr.

2013-01-01

Oxoiron(IV) species have been found to act as the oxidants in the catalytic cycles of several mononuclear nonheme iron enzymes that activate dioxygen. To gain insight into the factors that govern the oxidative reactivity of such complexes, a series of five synthetic S = 1 [FeIV(O)(LN5)]2+ complexes has been characterized with respect to their spectroscopic and electrochemical properties as well as their relative abilities to carry out oxo transfer and hydrogen atom abstraction. The Fe=O units...

Atomic layer deposition of calcium oxide and calcium hafnium oxide films using calcium cyclopentadienyl precursor

International Nuclear Information System (INIS)

Kukli, Kaupo; Ritala, Mikko; Sajavaara, Timo; Haenninen, Timo; Leskelae, Markku

2006-01-01

Calcium oxide and calcium hafnium oxide thin films were grown by atomic layer deposition on borosilicate glass and silicon substrates in the temperature range of 205-300 o C. The calcium oxide films were grown from novel calcium cyclopentadienyl precursor and water. Calcium oxide films possessed refractive index 1.75-1.80. Calcium oxide films grown without Al 2 O 3 capping layer occurred hygroscopic and converted to Ca(OH) 2 after exposure to air. As-deposited CaO films were (200)-oriented. CaO covered with Al 2 O 3 capping layers contained relatively low amounts of hydrogen and re-oriented into (111) direction upon annealing at 900 o C. In order to examine the application of CaO in high-permittivity dielectric layers, mixtures of Ca and Hf oxides were grown by alternate CaO and HfO 2 growth cycles at 230 and 300 o C. HfCl 4 was used as a hafnium precursor. When grown at 230 o C, the films were amorphous with equal amounts of Ca and Hf constituents (15 at.%). These films crystallized upon annealing at 750 o C, showing X-ray diffraction peaks characteristic of hafnium-rich phases such as Ca 2 Hf 7 O 16 or Ca 6 Hf 19 O 44 . At 300 o C, the relative Ca content remained below 8 at.%. The crystallized phase well matched with rhombohedral Ca 2 Hf 7 O 16 . The dielectric films grown on Si(100) substrates possessed effective permittivity values in the range of 12.8-14.2

Synthesis, second-harmonic generation (SHG), and photoluminescence (PL) properties of noncentrosymmetric bismuth selenite solid solutions, Bi2-xLnxSeO5 (Ln = La and Eu; x = 0-0.3)

Science.gov (United States)

Qi, Hai-Xin; Jo, Hongil; Oh, Seung-Jin; Ok, Kang Min

2018-02-01

A series of La3+ or Eu3+-doped noncentrosymmetric (NCS) bismuth selenite solid solutions, Bi2-xLnxSeO5 (x = 0.1, 0.2, and 0.3), have been successfully synthesized via standard solid-state reactions under vacuum with Bi2O3, La2O3 (or Eu2O3), and SeO2 as starting materials. Crystal structures and phase purities of the resultant materials were thoroughly characterized by powder X-ray diffraction using the Rietveld method. The results clearly show that the reported materials crystallize in the orthorhombic space group, Abm2 (No. 39), and exhibit pseudo-three-dimensional frameworks consisting of BiO3, BiO5, and SeO3 polyhedra that share edges and corners. Detailed diffraction studies indicate that the cell volume of Bi2-xLnxSeO5 decreases with an increasing amount of Ln3+ on the Bi3+ sites. However, no ordering between Ln3+ and Bi3+ was observed in the Bi2-xLnxSeO5 solid solutions. Powder second-harmonic generation (SHG) measurements, using 1064 nm radiation, reveal that SHG efficiencies of Bi2-xLnxSeO5 solid solutions continuously decrease as more Ln3+ cations are added to the sites of polarizable Bi3+ cations. Photoluminescence (PL) measurements on Bi2-xEuxSeO5 exhibit three specific emission peaks at 592, 613, and 702 nm (5D0 → 7F1, 2, 4) owing to the 4f-4f intrashell transitions of Eu3+ ions.

Efeito de doses de adubo 4-14-8 na competição entre tomateiro e Solanum americanum em convivência intra e interespecífica Effect of fertilizer 4-14-8 doses on competition between tomato and Solanum americanum under intra- and inter-specific coexistence

Directory of Open Access Journals (Sweden)

B.P. Silva

2010-01-01

Full Text Available O tomateiro (Lycopersicum esculentum é uma das mais importantes hortaliças produzidas no mundo, porém sua produtividade pode ser reduzida em função da convivência com Solanum americanum (maria-pretinha. O objetivo desta pesquisa foi avaliar o efeito da adubação na relação de interferência intra e interespecífica entre plantas de tomateiro e S. americanum. Duas plantas em condições de convivência intra e interespecífica, por espécie, foram plantadas em vasos e adubadas com 13, 18 e 24 g de 4-14-8 por vaso, sendo avaliadas características de crescimento de ambas as espécies aos 90 dias após o transplante das plantas. A adubação com 4-14-8 estimulou o desenvolvimento da área foliar e da massa seca de caules, folhas e frutos de S. americanum, além da área foliar e da massa seca de folhas e frutos do tomateiro. A convivência interespecífica proporcionou maior altura de plantas de S. americanum, bem como menor altura e massa seca de folhas e frutos do tomateiro. Houve interação dos fatores adubação e convivência somente para o tomateiro, sendo a altura e a massa seca de folhas da cultura influenciadas negativamente quando submetidas às maiores doses de adubo e à competição com S. americanum.Tomato (Lycopersicum esculentum is one of the leading vegetable crops grown worldwide, but its productivity may be reduced due to coexistence with Solanum americanum (black nightshade. This work aimed to evaluate the effect of fertilization on intra- and inter-specific interference between tomato and S. americanum plants. Two plants in intra- and inter-specific coexistence conditions of both species were planted in pots and fertilized with 13, 18 and 24 g of 4-14-8 per pot to evaluate the growth characteristics of both species at 90 days after transplanting. The 4-14-8 fertilization stimulated the development of the leaf area and dry mass of stems, leaves and fruit of S. americanum, consequently and equally influencing the leaf

Proportioning of U3O8 powder

International Nuclear Information System (INIS)

Cermak, V.; Markvart, M.; Novy, P.; Vanka, M.

1989-01-01

The tests are briefly described or proportioning U 3 O 8 powder of a granulometric grain size range of 0-160 μm using a vertical screw, a horizontal dual screw and a vibration dispenser with a view to proportioning very fine U 3 O 8 powder fractions produced in the oxidation of UO 2 fuel pellets. In the tests, the evenness of proportioning was assessed by the percentage value of the proportioning rate spread measured at one-minute intervals at a proportioning rate of 1-3 kg/h. In feeding the U 3 O 3 in a flame fluorator, it is advantageous to monitor the continuity of the powder column being proportioned and to assess it radiometrically by the value of the proportioning rate spread at very short intervals (0.1 s). (author). 10 figs., 1 tab., 12 refs

Oxidation kinetics of (B6O) boron oxide

International Nuclear Information System (INIS)

Makarov, V.S.; Solov'ev, N.E.; Ugaj, Ya.A.

1987-01-01

Reactivity of B 6 O to oxygen is investigated. It is shown that the process of B 6 O oxidation in the air in the temperature range 760-1150 K results in the maximum transformation degree equal to 0.35. At the initial stages oxidation proceeds in kinetic regime, at final stages - in diffusion one, and high viscosity of B 2 O 3 probably affects the oxidation process