Chemical bond characteristics, thermal expansion property and compressibility of AR(2)O(4) (A = Ca, Sr, Ba; R = rare earths)

Theoretical researches were performed on the CaFe2O4-type binary rare earth oxides AR(2)O(4) (A = Ca, Sr, Ba; R = rare earths) by using chemical bond theory of dielectric description. The chemical bond properties of these crystals were explored, and then the thermal expansion property and compressibility were studied. The theoretical values of linear thermal expansion coefficient (LTEC) and bulk modulus were presented. The calculations revealed that the LTECs and the bulk moduli do have linear relationship with the ionic radii of the rare earths. In the cases of Sc and Y, both the LTEC and bulk modulus values are larger than the lanthanide series. We attribute this to the difference in the electronic configuration between Sc (Y) and lanthanide series. For SrY2O4 and BaY2O4 crystals, the theoretical values of LTEC and bulk modulus agree well with experimental ones.

Implantation of Nafion (R) ionomer into polyvinyl alcohol/chitosan composites to form novel proton-conducting membranes for direct methanol fuel cells

A series of cost-effective, proton-conducting composite membranes, comprising of Nafion (R) ionomer, chitosan (CS). and polyvinyl alcohol (PVA), is successfully prepared. By taking advantage of the strong electrostatic interactions between Nafion (R) ionomer and CS component, Nafion ionomer is effectively implanted into the PVA/CS composite membranes, and improves proton conductivity of the PVA/CS composite membranes. Furthermore, this effect dramatically depends on the composition ratio of PVA/CS, and the optimum conductivity is obtained at the PVA/CS ratio of 1:1. The developed composite membranes exhibit much lower methanol permeability compared with the widely used Nafion (R) membrane, indicating that these novel membranes have great potential for direct methanol fuel cells (DMFCs).

Alternating copolymerization of carbon dioxide and propylene oxide catalyzed by (R,R)-SalenCo(III)-(2,4-dinitrophenoxy) and Lewis-basic cocatalyst

A binary catalyst system of a chiral (R,R)-SalenCo(III)(2,4-dinitrophenoxy) (salen = N,N-bis(3,5-di-tert-butylsalicylidene)-1,2-diphenylethylenediimine) in conjunction with (4-dimethylamino)pyridine (DMAP) was developed to generate the copolymerization of carbon dioxide (CO2) and racemic propylene oxide (rac-PO). The influence of the molar ratio of catalyst components, the operating temperature, and reaction pressure on the yield as well as the molecular weight of polycarbonate were systematically investigated. High yield of turnover frequency (TOF) 501.2 h(-1) and high molecular weight of 70,400 were achieved at an appropriate combination of all variables. The structures of as-prepared products were characterized by the IR, H-1 NMR, C-13 NMR measurements. The linear carbonate linkage, highly regionselectivity and almost 100% carbonate content of the resulting polycarbonate were obtained with the help of these effective catalyst systems under facile conditions.

(R,R)-DPEN-modified Ru/gamma-Al2O3 - An efficient heterogeneous catalyst for enantioselective hydrogenation of acetophenone

An efficient enantioselective catalyst of 5 wt.% Ru/-gamma-Al2O3 modified with R,R-1,2-diphenylethylene-diamine ((R,R)-DPEN) for the hydrogenation of a non-activated aromatic ketone of acetophenone has been investigated, a relatively high enantiomeric excess (ee) of 60.5% was obtained at both the conversion and selectivity larger than 99%, it was about three times higher than the ee values reported up to now for acetophenone hydrogenation with the supported transition metal catalysts modified by chiral reagents. The influences of some reaction parameters such as phosphine ligand, substrate/catalyst/modifier molar ratios, base, solvent, pressure and reaction temperature have been discussed. The chiral modifier of (R,R)-DPEN was very important in controlling the enantioselectivity through adsorption competing with other substrates on the surface of active metal species. The phosphine ligand and base were also important and indispensable in the present reaction.

Surface-modified Nafion (R) membrane by casting proton-conducting polyelectrolyte complexes for direct methanol fuel cells

Surface-modified Nafion (R) membrane was prepared by casting proton-conducting polyelectrolyte complexes on the surface of Nafion (R). The casting layer is homogeneous and its thickness is about 900 nm. The proton conductivity of modified Nafion (R) is slightly lower than that of plain Nafion (R); however, its methanol permeability is 41% lower than that of plain Nafion (R). The single cells with modified Nafion (R) exhibit higher open circuit voltage (OCV = 0.73 V) and maximal power density (P-max = 58 mW cm(-2)) than the single cells with plain Nafion (R) (OCV = 0.67 V, P x = 49 mW cm-2). It is a simple, efficient, cost-effective approach to modifying Nafion (R) by casting proton-conducting materials on the surface of Nafion (R).

Effects R3+ on the photoluminescent properties of Ca2R8(SiO4)(6)O-2 : A (R = Y, La, Gd; A= Eu3+, Tb3+) phosphor films prepared by the sol-gel process

Using CaCO3, metal oxides (all dissolved by nitric acid) and tetraethoxysilane Si(OC2H5)(4) (TEOS) as the main starting materials, Ca2R8(SiO4)(6)O-2:A (R = Y, La, Gd; A = EU3+, Tb3+) phosphor films have been dip-coated on quartz glass substrates through the sol-gel process. X-ray diffraction (XRD), atomic force microscope (AFM), scanning electron microscope (SEM) and photoluminescence (PL) spectra as well as lifetimes were used to characterize the resulting films. The results of XRD indicated that the 1000 degreesC annealed films are isomorphous and crystallize with the silicate oxyapatite structure. AFM and SEM studies revealed that the phosphor films consisted of homogeneous particles ranging from 30 to 90 nm, with an average thickness of 1.30 mum. The Eu3+ and Tb3+ show similar spectral properties independent of R 3, in the films due to their isomorphous crystal structures. However, both the emission intensity and lifetimes of Eu3+ and Tb3+ in Ca2R8(SiO4)(6)O-2 (R = Y, La, Gd) films decrease in the sequence of R = Gd > R = Y > R = La, which have been explained in accordance with the crystal structures.

Luminescence properties of RP1-xVxO4: A (R=Y, Gd, La; A=Sm3+Er3+ x=0, 0.5, 1) thin films prepared by pechini sol-gel process

Thin film phosphors with compositions of RP1-xVxO4: A (R = Y, Gd, La; A = Sm3+, Et3+; x = 0, 0.5, 1) have been prepared by a Pechini sol-gel process. X-Ray diffraction, atomic force microscopy (AFM), photoluminescence excitation and emission spectra were utilized to characterize the thin film phosphors. The results of XRD showed that a solid solution formed in YVxP1-xO4: A film series from x = 0 to x = 1 with zircon structure, which also held for GdVO4: A film. However, LaVO4: A film crystallized with a different structure, monazite. AFM study revealed that the phosphor films consisted of homogeneous particles ranging from 90 to 400 nm depending on the compositions. Upon short ultraviolet excitation, the films exhibit the characteristic Sm(3+ 4)G(5/2)-H-6(J) (J=5/2, 7/2, 9/2) emission in the red region and Er3+ H-2(11/2), S-4(3/2)-I-4(15/2) emission in the green region, respectively With the increase of x values in YVxP1-xO4: SM3+ (Er3+) films, the emission intensity Of SM3+ (Er3+) increases due to the increase of energy transfer probability from VO43- to Sm3+ (Er3+). Due to the structural effects, the Sm3+ (Er3+) shows similar spectral properties in YVO4 and GdVO4 films, which are much different from those in LaVO4 film.

BaMgAl_(10)O_(17)∶R~(2+)(R=Eu,Mn)的真空紫外光谱特性

采用高温固相反应法合成了BaMgAl10 O17∶R(R =Eu ,Mn)荧光体 ,测量了荧光体的真空紫外激发光谱和相应的发射光谱 ,观察到基质吸收带位于 16 5nm附近 ,Mn2 + 离子的吸收位于 170～ 2 40nm范围 ,Eu2 + 离子的 4f→ 5d吸收位于 2 10～ 40 0nm范围。真空紫外光谱特性的研究表明基质与激活离子之间存在较好的能量传递。

LaMgAl_(11)O_(19)∶R(R=Tb,Mn)的真空紫外光谱特性

采用高温固相反应法合成了LaMgAl11O19∶R(R=Mn,Tb)荧光体,测量了荧光体的真空紫外激发光谱和相应的发射光谱,观察到基质吸收带位于170nm附近,Mn2+离子的吸收位于170～510nm范围,Tb3+离子的4f 5d吸收位于170～250nm范围。在147nm激发下,它们发射绿光。真空紫外光谱特性的研究表明,基质与激活离子之间存在较好的能量传递。

钙改性对r-Al2O3的高温热稳定性的影响

中国科学院山西煤炭化学研究所

Photochemical synthesis, characterization and X-ray crystal structure of dodecamolybdophosphate tetrabutylammonium heteropoly blue (Bu4N)(4)[PMo12O40]center dot 2DMF center dot H2O

In this paper, we will report the preparation of a mixed-valence polyoxometalate compound (Bu4N)(4)[PMo12O40].2DMF.H2O (TBA = tetrabutylammonium; DMF = N,N-dimethyl formamide). The title compound has been photochemically synthesized and characterized by using elemental analysis, IR, solid diffusion reflectance electronic spectra, ESR spectra, XPS, CV and X-ray single-crystal analysis. The crystal lographic data are as follows: monoclinic, P2(1)/c, a = 14.124(3), b = 17.481(4), c = 22.744(5) Angstrom, beta = 101.66(3)degrees, V = 5500(2) Angstrom(3), C70H160Mo12N6O43P, M-r = 2956.29, Z = 2, D-c = 1.785 g/cm(3), F(000) = 2970 and mu(MoKalpha) = 1.412 mm(-1). The structure has been refined to R = 0.0638 and wR = 0.1975 by full-matrix least-squares methods. The title compound is composed of four tetrabutylammonium cations, one [(PMoMo11O40)-Mo-V](4-) heteropoly anion, two N,N-dimethyl formamide and one H2O molecule.

12-钼磷酸四丁基铵杂多蓝的光化学合成表征与晶体结构

用450W高压汞灯照射H3PMo12O40·5H2O和（Bu4N）Br���TBA）的DMF（N,N-二甲基甲酰胺）溶液,合成了12-钼磷酸四丁基铵杂多蓝（Bu4N）4[PMo12O40]·2DMF·H2O,用元素分析,IR,固体漫反射电子光谱,ESR,XPS和CV等进行了表征。晶体结构分析表明,标题化合物属单斜晶系,空间群P21/c,晶胞参数a=14.124（3）,b=17.481（4）,c=22.744（5）A,β=101.66（3）°,V=5500（2）A3,C70H160Mo12N6O43P,Mr=2956.29,Z=2,Dc=1.785g/cm3,F（000）=2970,μ（MoKα）=1.412mm-1,R=0.0638,wR=0.1975。标题化合物是由4个四丁基铵阳离子、1个12-钼磷混合价杂多阴离子[PMo12O40]4-、2个DMF分子和1个水分子构成。

La_(0.5)R_(0.5)Ba_2Cu_3O_7,Pr_(0.5)R_(0.5)Ba_2Cu_3O_7以及RBa_2Cu_3O_7(R=稀土)的键共价性计算

使用复杂晶体化学键理论计算了La0 .5R0 .5Ba2 Cu3O7(R =Pr,Nd ,Sm ,Eu ,Gd ,Dy ,Y ,Ho,Er,Tm ,Yb ,Lu) (La-R12 3) ,Pr0 .5R0 .5Ba2 Cu3O7(R =La ,Nd ,Sm ,Eu ,Gd ,Dy ,Ho ,Y ,Er,Tm ,Yb ,Lu) (Pr -R12 3)以及RBa2 Cu3O7(R =La ,Pr,Nd ,Sm ,Eu ,Gd ,Dy ,Ho ,Y ,Er,Tm) (R12 3)中Cu—O键的键共价性 ,结果表明Pr-R12 3,La-R12 3,以及R12 3都应具有超导性 ,而实验结果是La0 .5Pr0 .5Ba2 Cu3O7,R0 .5Pr0 .5Ba2 Cu3O7(R =La,Nd ,Sm ,Eu ,Gd)无超导性 .产生这种矛盾的原因尚不明确 ,需要做进一步的研究.