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41.
Ab initio energetic calculations based on the density functional theory (DFT) and projector augmented wave (PAW) pseudo-potentials method were performanced to determine the crystal structural parameters and phase transition data of the polymorphic rare-earth sesquioxides Ln2O3 (where Ln=La-Lu, Y, and Sc) with A-type (hexagonal) and B-type (monoclinic) configurations at ground state. The calculated results agree well with the limited experimental data and the critically assessed results. A set of systematic and self-consistent crystal structural parameters, energies and pressures of the phase transition were established for the whole series of the A- and B-type rare-earth sesquioxides Ln2O3. With the increase of the atomic number, the ionic radii of rare-earth elements Ln and the volumes of the sesquioxides Ln2O3 reflect the so-called “lanthanide contraction”. With the increase of the Ln3+-cation radius, the bulk modulus of Ln2O3 decreases and the polymorphic structures show a degenerative tendency. 相似文献
42.
Svilen Bobev Paul H. Tobash Joe D. Thompson John L. Sarrao 《Journal of solid state chemistry》2005,178(6):2091-2103
A number of rare-earth alumo-silicides (R-Al-Si) have been synthesized from the corresponding elements by high-temperature reactions, carried out in excess of aluminum to serve as a flux. Under these experimental conditions, large single crystals of all R-Al-Si ternary phases were readily produced. The crystal structures these ternaries adopt were studied by means of powder and single-crystal X-ray diffraction and were classified as follows: (1) the early rare-earths (R=La, Ce, Pr, Nd, Sm, Gd) yield RAlxSi2−x, x∼1, non-stoichiometric ternary derivatives of the body-centered α-ThSi2-type; (2) the late rare-earths (R=Tb, Dy, Ho, Er, Tm) form stoichiometric R2Al3Si2 compounds that crystallize in the C-centered monoclinic Y2Al3Si2-type; (3) the divalent Eu and Yb produce EuAl2Si2 and YbAl2Si2 with the trigonal CaAl2Si2-type, whereas the last lanthanide element, Lu, forms LuAlSi with C-centered orthorhombic YAlGe-type. These structural trends are reviewed, and the evolution of the basic physical properties such as magnetism, heat capacity and electrical resistivity when moving across the series is described in detail. 相似文献
43.
The polyoxo rare-earth core
(Ln = Y, Gd, and Yb) has been synthesized from the appropriate rare-earth chloride hydrate and K2Se and Se in dmf (dimethylformamide). The cluster core is ligated with a variety of polyselenido chains in addition to a number of dmf molecules. The structure of the Gd8(dmf)13(4-O)(3-OH)12(Se3)(Se4)2(Se5)2 cluster, 1, was determined by X-ray diffraction methods. It is similar to an Eu cluster previously characterized. Two new clusters, Yb8(dmf)11(4-O)(3-OH)12(Se4)2(Se5)2Cl2·dmf, 2, and Y8(dmf)12(4-O)(3-OH)12(Se4)4Cl2·6 dmf, 3, have also been synthesized and characterized. Clusters 2 and 3 have the same octanuclear core of rare-earth atoms as the Gd cluster but contain two chloro ligands in two isomeric conformations in place of the Se
3
2-
ring in the Gd cluster. The geometry of the Ln
8 core is described as a triangulated dodecahedron with 3-OH groups capping the 12 faces. A 4-O atom centers the cluster with close contacts to four Ln atoms in an approximate tetrahedral arrangement. Pertinent crystallographic data are: Compound 1, monoclinic,
, a= 14.410(3) Å, b = 24.439(5) Å, c = 28.927(6) Å, = 101.05(3)°, V = 9998(3) Å3, T = 106(2) K, Z = 4; Compound 2, orthorhombic,
, a = 17.049(9) Å, b = 24.68(1) Å, c = 45.03(2)Å, V = 18,945(16) Å3, T = 153(2) K, Z = 8; Compound 3, monoclinic, C
2h
5
-P21/c, a =18.728(l) Å, b = 29.263( 1) Å, c = 20.548(1) Å, = 90.144(1)°, V = 11,261(1) Å3, T = 153(2) K, Z = 4. 相似文献
44.
Several CaF2 single crystals doped with trivalent rare-earth ions have been grown in the recent years in the form of bulk crystals by using the Bridgman method and in the form of thin films by using the MBE and LPE techniques. The spectroscopic, gain and laser properties of these crystals doped with Pr3+, on the one hand, and with Yb3+, Tm3+ or Er3+ ions, on the other hand, have been studied and are reviewed here for their laser potentials in the red and in the infrared spectral domains, respectively. 相似文献
45.
Three new compounds, LaCuOTe, CeCuOTe, and NdCuOTe, have been synthesized from the respective rare-earth elements, CuO, and a KI flux at 1023 K. The compounds, which have the ZrSiCuAs structure type, are isostructural to LaCuOS, and crystallize in space group P4/nmm of the tetragonal system with two formula units in cells of dimensions at 153 K of , , for LaCuOTe; , , for CeCuOTe; and , , for NdCuOTe. The structure of LnCuOTe (Ln=La, Ce, Nd) is composed of alternating PbO-like [Ln2O2] and anti-PbO-like [Cu2Te2] layers stacked perpendicular to [0 0 1]. The experimental optical band gaps of LaCuOTe and NdCuOTe are 2.31 and 2.26 eV, respectively. At 298 K the electrical conductivity of LaCuOTe is 1.65 S/cm and the Hall mobility is +80.6 cm2 V−1 s−1. The positive values of the Seebeck and Hall coefficients indicate p-type electrical conduction. First-principles theoretical calculations were performed on LaCuOQ (Q=S, Se, Te). In LaCuOTe, Cu 3d and Te 5p orbitals dominate the states near the valence band maximum; the states near the conduction band minimum are composed of Cu 4s, Te 5p, and La 5d orbitals. The larger dispersion of Cu 3d orbitals and the presence of Te 5p orbitals near the valence band maximum are responsible for the larger hole mobility of LaCuOTe compared to LaCuOS and LaCuOSe. 相似文献
46.
47.
Steffen Cychy Sebastian Lechler Zijian Huang Michael Braun Ann Cathrin Brix Peter Blümler Corina Andronescu Friederike Schmid Wolfgang Schuhmann Martin Muhler 《催化学报》2021,42(12):2206-2215
在碱性甘油电氧化反应中,利用电化学傅里叶变换衰减全反射谱红外光谱法,研究了薄膜流动池中滴注硼酸镍催化剂负载量对玻碳电极性能的影响.连续操作的径向流动池包括一个位于内反射元件上方50μm的钻孔电极,可实现红外光谱分析.这是在确定条件下对电催化剂进行简便和可重复筛选的一个适合的方法,同时还提供了对复杂反应(如甘油氧化)产物选择性的检测.通过对泵送电解液进行更耗时的定量高效液相色谱分析,结果表明,衰减全反射红外光谱法可快速鉴定产物.在层流条件下,水中使用0.1 M甘油和1 M KOH,流速为5μL min-1时,甘油转化率较高.转化率和选择性取决于催化剂的负载量,负载量又决定了催化剂层的厚度和粗糙度.由于在更粗糙的膜中停留时间更长有利于再吸附和C-C键断裂,因此当负载量最高达210μg cm-2时,甘油转化率为73%且甲酸选择性接近80%.当最低负载量为13μg cm-2时,甘油转化率达到63%,甲酸选择性降至60%,相应地,C2物种(如乙醇酸盐)选择性较高,为8%.因此,只有催化剂负载量较低时才能形成几微米厚度范围内的薄膜,此时才适合进行优质催化剂的筛选. 相似文献
48.
Fluorescence imaging in the second near-infrared region(900-1700 nm, NIR-II) with a high resolution and penetration depth due to the significantly reduced tissue scattering and autofluorescence has emerged as a useful tool in biomedical fields. Recently, many efforts have been devoted to the development of fluorophores with an emission band covering the long-wavelength end of NIR-II region(1500-1700 nm) to eliminate the autofluorescence. Alternatively, we believe imaging with a narrow bandwidth could also reduce the autofluorescence. As a proof of concept, NaYF4:Yb,Nd@NaYF4 downconversion nanoparticles(DCNPs) with sharp NIR-II emission were synthesized. The luminescence of DCNPs showed a half-peak width of 49 nm centered at 998 nm, which was perfectly matched with a (1000±25) nm bandpass filter. With this filter, we were able to retain most of the emissions from the nanoparticles, while the autofluorescence was largely reduced. After PEGylation, the DCNPs exhibited great performance for blood vessel and tumor imaging in living mice with significantly reduced autofluorescence and interference signals. This work provided an alternative way for the low-autofluorescence imaging and emphasized the importance of narrow emitting rare-earth doped nanoparticles for NIR-II imaging. 相似文献
49.
Danuta M. Czakis-Sulikowska Joanna Radwańska-Doczekalska Teresa Miazek 《Monatshefte für Chemie / Chemical Monthly》1982,113(6-7):827-835
4,4-Dipyridyl and 2,2-dipyridyl complexes of rare-earth perchlorates of the formulaLn(4-dipy)8(ClO4)3HClO4 · 4H2O (Ln=La, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Yb, Lu, Y, 4-dipy=4,4-dipyridyl) andLn(2-dipy)3(ClO4)3 · 6H2O (Ln=Pr, Sm, Eu, Gd, Tb, Dy, Ho, Er, Yb, Lu, Y, 2-dipy = 2,2-dipyridyl) have been synthesized. The IR spectra of these compounds and other physical properties are discussed.
4,4-Dipyridyl- und 2,2-Dipyridylkomplexe von Seltenerdmetallperchloraten
Zusammenfassung Es wurden 4,4-Dipyridylkomplexe des TypsLn(4-dipy)8(ClO4)3HClO4 · · 4 H2O mitLn=La, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Yb, Lu, Y und 2,2-Dipyridylkomplexe des TypsLn(2-dipy)3(ClO4)3 · 6 H2O mitLn=Pr, Sm, Eu, Gd, Tb, Dy, Ho, Er, Yb, Lu und Y dargestellt. Die IR-Spektren und andere physikalische Eigenschaften werden diskutiert.相似文献
50.
The HfFe6Ge6-type compounds Gd0.8L0.2Mn6Sn6 and Tb0.8L0.2Mn6Sn6 (L = Sc, Y, Lu) have been studied by 119Sn Mössbauer spectroscopy. The values of the apparent quadrupolar splitting clearly evidence the easy plane magnetization of the gadolinium compounds and the easy axis one in the terbium compounds. The three tin sites behave differently with the nature and size of the substituting L element. For a given series, the hyperfine field of the Sn2d site is almost unchanged whatever the size of the L element. The hyperfine field of the Sn2e site strongly varies with the L size in relation with atomic displacements. The hyperfine field of the Sn2c site exhibits a more complicated behavior. The field difference in the easy plane and easy axis compounds confirms the angle-dependent anisotropic contribution of the Mn moment to the hyperfine field. The analysis of the results also suggests the play of angle-dependent contributions arising from the rare earth moment. 相似文献