Synthesis and Structure of Schiff Base Complex Containing＇Cu_4O＇Core

ＳｙｎｔｈｅｓｉｓａｎｄＳｔｒｕｃｔｕｒｅｏｆＳｃｈｉｆｆＢａｓｅＣｏｍｐｌｅｘＣｏｎｔａｉｎｉｎｇ＇Ｃｕ＿４Ｏ＇ＣｏｒｅＭＡＣｈａｎｇ－ｑｉｎ￣＊,ＹＵＺｈｅｎｇ－ｇａｎｇ,ＺＨＡＮＧＷｅｎ－ｘｉｎｇ,ＷＡＮＧＸｕ－ｎｉｎｇａｎｄＪＩＡＮＧＤｅ－ｈ...     

A Study of the Background Absorption of Chitosan in the Graphite Furnace Atomic Absorption Spectrometry

ＡＳｔｕｄｙｏｆｔｈｅＢａｃｋｇｒｏｕｎｄＡｂｓｏｒｐｔｉｏｎｏｆＣｈｉｔｏｓａｎｉｎｔｈｅＧｒａｐｈｉｔｅＦｕｒｎａｃｅＡｔｏｍｉｃＡｂｓｏｒｐｔｉｏｎＳｐｅｃｔｒｏｍｅｔｒｙＴＡＮＧＹｏｕ－ｗｅｎ＊ａｎｄＭＯＳｈｅｎｇ－ｊｕｎ（Ｄｅｐａｒｔｍｅｎ...     

Ab Initio Studies on the Structure and Binding Interaction of M~ CO_2(M=Sc,Ti…Zn)

ＡｂＩｎｉｔｉｏＳｔｕｄｉｅｓｏｎｔｈｅＳｔｒｕｃｔｕｒｅａｎｄＢｉｎｄｉｎｇＩｎｔｅｒａｃｔｉｏｎｏｆＭ＋ＣＯ２（Ｍ＝Ｓｃ,Ｔｉ…Ｚｎ）＊ＦＡＮＨｏｎｇ－Ｊｕｎ,ＺＨＯＮＧＳｈｉ－Ｊｕｎ,ＬＩＵＣｈｕｎ－Ｗａｎ＊＊（ＦｕｊｉａｎＩｎｓｔｉｔｕｔｅｏ...     

Self-consistent Field Crystal Orbital Study on One-dimensional C_(60) Polymer

Ｓｅｌｆ┐ｃｏｎｓｉｓｔｅｎｔＦｉｅｌｄＣｒｙｓｔａｌＯｒｂｉｔａｌＳｔｕｄｙｏｎＯｎｅ┐ｄｉｍｅｎｓｉｏｎａｌＣ６０Ｐｏｌｙｍｅｒ＊ＨＵＡＮＧＹｕａｎ－ｈｅ＊＊,ＣＨＥＮＧｕａｎｇ－ｊｕａｎｄＬＩＵＲｕｏ－ｚｈｕａｎｇ（ＤｅｐａｒｔｍｅｎｔｏｆＣｈ...     

Adsorption of Benzene on the Potassium Exchanged Hbeta Zeolites

ＡｄｓｏｒｐｔｉｏｎｏｆＢｅｎｚｅｎｅｏｎｔｈｅＰｏｔａｓｓｉｕｍＥｘｃｈａｎｇｅｄＨｂｅｔａＺｅｏｌｉｔｅｓＳＨＥＮＪｉａｎ－ｐｉｎｇ；ＭＡＪｕｎ；ＳＵＮＴｉｅａｎｄＪＩＡＮＧＤａ－ｚｈｅｎ（ＤｅｐａｒｔｍｅｎｔｏｆＣｈｅｍｉｓｔｒｙ，ＪｉｌｉｎＵ...     

CharacterizationofHydroxylgroupsinDealuminatedzeoliteHZSM－5bySolid，State1HNMR＊

ＣｈａｒａｃｔｅｒｉｚａｔｉｏｎｏｆＨｙｄｒｏｘｙｌｇｒｏｕｐｓｉｎＤｅａｌｕｍｉｎａｔｅｄｚｅｏｌｉｔｅＨＺＳＭ－５ｂｙＳｏｌｉｄ,Ｓｔａｔｅ１ＨＮＭＲ＊ＤＥＮＧＦｅｎｇ￣ａ,ＤＵＹｏｕ－ｒｕ￣ａ＊＊,ＹＥＣｈａｏ－ｈｕｉ￣ａＷＡＮＧＪｉｎｇ－ｚｈ...     

SYNTHESIS OF PROPYLENE CARBONATECATALYZED BY ANION EXCIIANGE RESINS

ＳＹＮＴＨＥＳＩＳＯＦＰＲＯＰＹＬＥＮＥＣＡＲＢＯＮＡＴＥＣＡＴＡＬＹＺＥＤＢＹ　ＡＮＩＯＮＥＸＣＩＩＡＮＧＥＲＥＳＩＮＳＨｏｎｇＺＨＵ；Ｌｉ－ＢａｎＣＨＥＮ（ＧｕａｎｇｚｈｏｕＩｎｓｔｉｔｕｔｅｏｆＣｈｅｍｉｓｔｒｙ，ＡｃａｄｅｌｎｉａＳｉｎｉｃａ...     

Structures and Vibrational Spectra of C_2 and LaC_2~ Clusters

ＳｔｒｕｃｔｕｒｅｓａｎｄＶｉｂｒａｔｉｏｎａｌＳｐｅｃｔｒａｏｆＣ２ａｎｄＬａＣ＋２Ｃｌｕｓｔｅｒｓ＊ＷＵＺｈｉ－ｊｉａｎ，ＭＥＮＧＱｉｎｇ－ｂｏａｎｄＺＨＡＮＧＳｉ－ｙｕａｎ＊＊（ＣｈａｎｇｃｈｕｎＩｎｓｔｉｔｕｔｅｏｆＡｐｐｌｉｅｄＣｈｅｍｉｓ...     

Stereochemistry of Acetone Condensation on Solid Base Catalysts

ＳｔｅｒｅｏｃｈｅｍｉｓｔｒｙｏｆＡｃｅｔｏｎｅＣｏｎｄｅｎｓａｔｉｏｎｏｎＳｏｌｉｄＢａｓｅＣａｔａｌｙｓｔｓＷＡＮＧＹｕ－ｈｕａｎ;ａｎｄＷＡＮＧＧｕｏ－ｊｉａ（ＤｅｐａｒｌｍｅｎｔｏｆＣｈｅｍｉｓｔｒｙ,ＪｉｌｉｎＵｎｉｖｅｒｓｉｔｙ．Ｃｈａｎ...     

Syntheses and Studies of PEG-b-PNIPA Block Polymers

ＳｙｎｔｈｅｓｅｓａｎｄＳｔｕｄｉｅｓｏｆＰＥＧ┐ｂ┐ＰＮＩＰＡＢｌｏｃｋＰｏｌｙｍｅｒｓＣＡＯＷｅｉ－ｘｉａｏ＊＊ａｎｄＺＨＡＮＧＴａｏ（ＣｏｌｅｇｅｏｆＣｈｅｍｉｓｔｒｙａｎｄＭｏｌｅｃｕｌａｒＥｎｇｉｎｅｒｉｎｇ，ＰｅｋｉｎｇＵｎｉｖｅｒｓｉｔ...     

Effects of MoO3 Amounts on Sintering and Electrical Properties of Ce0.8Nd0.2O1.9

The high purity (Ce_0.8Nd_0.2O_1.9)_1-x(MoO₃)_x(x=0, 0.005, 0.010, 0.020; Ce_0.8Nd_0.2O_1.9=NDC) solid solutions were prepared by modified sol-gel method. The structures and electric conductivities were characterized by X-ray diffraction(XRD), field-emission scanning electron microscopy(FESEM) and electrochemical impedance spectroscopy( EIS). The XRD results show that the materials were pure phase with a cubic fluorite structure. Compared to the undoped-NDC samples, MoO3 doped-NDC showed higher sintered density(over 96%) at reduced sintering temperature. The electric conductivity(σ_t) of (Ce_0.8Nd_0.2O_1.9)_1-x(MoO₃)_x at 400 ℃ was 9.58×10^–4 S/cm when x=0.010, which was higher than that of undoped-NDC samples(σ_t=3.29×10^–4 S/cm). The obtained optimal amount of the MoO₃ was x=0.010 in this system.     

Formation of stabilized zirconia with rare earth fluorides

New reactions to prepare stabilized zirconia using rare earth fluorides as the solid electrolyte have been examined by means of X-ray diffraction, DTA and EPMA methods. The eleven rare earth fluorides of yttrium and samarium through lutetium reacted with ZrO₂ to form new types of stabilized zirconias (LnFSZ) consisting of the ternary system of ZrO₂-Ln₂O₃-LnF₃. (2x+3y)ZrO₂ + (4y+2z)LnF₃ = 2(ZrO₂)_x(Ln₂O₃)_z + 3yZrF₄) where x, y and z represent the stabilizing composition at which the homogeneous solid solution with the fluorite structure is formed, and x + y + z + = 1. This reactions begins to take place at about 600 C and is completed by firing at temperatures ranging from 1000 to 1300 °C for a few hours in an argon atmosphere.     

Effects of doping Fe cations on crystal structure and thermal expansion property of Yb2Mo3O12

Crystal structures and thermal expansion properties of Yb_(2-x)Fe_xMo_3O_(12)(x=0.0,0.6,1.0,1.1,1.4) solid solutions have been studied by X-ray powder diffraction(XRPD) at different temperatures.Rietveld analysis of the XRPD data shows that Yb_(2-x)Fe_xMo_3O_(12) solid solutions adopt orthorhombic structure and have variable thermal expansion coefficients controlled by the ratio of Yb~(3+) to Fe~(3+).Yb_2Mo_3O_(12) shows anisotropic negative thermal expansion property,induced by the reductions in average Yb-O-Mo angle and average apparent Mo2-O bond length with increasing temperatures.As more Yb~(3+) substituted by Fe~(3+),the linear thermal expansion coefficients of Yb_(2-x)Fe_xMo_3O_(12) increase from negative to positive.A near-zero thermal expansion coefficient of 0.55×10~(-6)K~(-1) for Yb_(0.6)Fe_(1.4)Mo_3O_(12) is observed in the temperature range of 573-873 K     

Structural evolutions of the n-heneicosane and n-tricosane molecular alloys at 293 K

A structural study of odd-numbered n-alkane (C_n) binary mixtures (C₂₁ : C₂₃) was carried out on powder samples using a Guinier-de Wolff camera with increasing concentration of n-C₂₃ at 293 K.

Despite the reports in the literature, these molecular alloys do not form an orthorhombic continuous homogeneous solid solution to C₂₁ from C₂₃ at “low temperature”. Instead, as already observed in two even-numbered C_n systems, X-ray diffraction results show the existence of seven solid solutions as the molar concentration of C₂₃ increases: four terminal solid solutions, denoted β₀(C₂₁)β₀(C₂₃), isostructural with the “low temperature” phase of pure C₂₁ and C₂₃ (Pbcm), β′₀(C₂₁) and β′₀(C₂₃), identical to the phase β′₀ which appears in pure C₂₃ above the δ transition, and three orthorhombic intermediate solid solutions, designated β″₁, β′₁ and β″₂.

On the basis of powder X-ray photographs, the phases β″₁ and β″₂ (C₂₁ : C₂₃) are indistinguishable, and they are isostructural with the intermediate solid solution β″ of the even-numbered C_n binary systems (C₂₂ : C₂₄) and (C₂₄ : C₂₆). The phase β′₁(C₂₁ : C₂₃) is also isostructural with the two indistinguishable intermediate solid solutions β′₁ and β′₂ of the molecular alloys (C₂₂ : C₂₄) and (₂₄ : C₂₆).

From this study and our other laboratory results, the sequences of appearance of the solid solutions and the structural identities between these phases are established at “low temperature” for all the binary molecular alloys of consecutive C_n (odd-odd, even-even or odd-even: 19 < n < 27) when increasing the solute concentration.     

Thiocyanato adducts of chromium(II) carboxylates and the molecular structure of tetraethyl-ammonium tetra-μ-propionatodiisothio-cyanatodichromate(II)

X-Ray crystallographic studies on [NEt₄]₂[Cr₂[(O₂CC₂H₅)₄(NCS)₂] show that the Cr–Cr separation (2.467Å) in the dinuclear anion is one of the longest known. The thiocyanato groups are N-bonded, and the results emphasize the known sensitivity of the quadruple Cr–Cr bond to the nature of the axial ligands. The compound crystallises in the tetragonal space group P4/mnc with two molecules per unit cell, the dimensions of which are a = b = 9.785(1), c = 21.186(2) Å. Magnetic investigations from room to liquid nitrogen temperature on the tetra-μ-propionato complex and on [NMe₄]₂ [Cr₂(O₂CCH₃)₄(NCS)₂] show that both complexes have been obtained free from paramagnetic chromium(III) impurities. Their weak paramagnetic susceptibilities (X_cr is approx. 200 x 10⁻⁶ cm³ mol⁻¹ at 295 K and 50 x 10⁻⁶cm³mol⁻¹ at 90 K) are inherent, and are ascribed to temperature independent paramagnetism at low temperature plus para-magnetism arising from slight population of the triplet state (2J 700 cm⁻¹, g = 2, N = 50 x 10⁻⁶cm³mol⁻¹) at higher temperatures.     

Calorimetric study on oxidation of alumina supported rhodium by dioxygen

Rhodium particles in nanometer size were prepared by impregnating alumina powders with aqueous solutions containing rhodium salts. The dispersion (D) of rhodium crystallites on the prepared samples was estimated by dioxygen adsorption measured at 300 K. Phenomena of oxidizing the supported crystallites with 2.5 × 10⁴ Pa O₂ in a temperature range between 280 and 870 K were calorimetrically studied. Extent of oxidation may be distinguished into three stages, i.e., adsorption on surface (T < 300 K), progressive penetration into bulk, and formation of a stable bulk oxide (T> 700 K), on raising the oxidation temperature. Heat of dioxygen adsorption varies only slightly with the dispersion (D) of rhodium and has a value of 294 ± 6 kJ (mol O₂)⁻¹. Chemical stoichiometry of the bulk oxide formed, however, varies with the dispersion of rhodium crystallites. A dioxide (RhO₂) (_f H = 225 ± 3 kJ (mol O₂)⁻¹) and a sesquioxide (Rh₂O₃) (_f H = 273 ± 3 kJ (mol O₂)⁻¹) was formed at D < 60% and D> 80%,     

The mechanism of 2-methylbutene-2 hydrohalogenation in solid phase

Complexes and reactions of 2-methylbutene-2 with hydrohalogen (HCl, HBr) have been studied in solid phase at 80–150 K. It has been found that 2-methylbutene-2 forms with HX complexes of 1:1 and 1:2 composition. Hydrohalogenation proceeds via the rearrangement of complex 2HX·C₅H₁₀ into complex of the addition product with HX. Kinetic equation depends on the reagents ratio. In excess of HX (1< HX:C₅H₁₀< 10) reaction can be described by the first order kinetic equation. If the ratio HX:C₅H₁₀ is more than 10, reaction is described by polychronous kinetic law. The effective activation energy of solid phase hydrohalogenation does not exceed 20 kJ/mole. The molecular mechanism of hydrohalogenation in solid phase has been proposed.     

过渡金属配合物与铀酰-有机框架复合:两例新型铀/铜异金属配合物的合成、晶体结构及其性能研究

在水热条件下,将铜金属配合物插入到铀酰有机框架化合物中,合成了两例新型铀/铜异金属杂化配合物[Cu(bipy)(UO₂)(bdc)₂·H₂O]_n(1),{[Cu(phen)(UO₂)(bdc)(bc)(H₂O)]·H₂O}_n(2)(bipy=2,2′-联吡啶,bdc=对苯二甲酸,phen=1,10-邻菲罗琳,bc=苯甲酸),并通过X射线单晶衍射对其结构进行了表征。配合物1属于单斜晶系,P2₁/c空间群,M_r=833.99,a=7.9077(5)A,b=23.1076(13)A,c=14.6172(8)A,β=101.4180(10)°,V=2618.1(3)A³,Z=4,D_c=2.116 g·cm-3,μ=7.056 mm^-1,F(000)=3003,最终偏离因子R=0.0210,wR=0.0560。配合物2属于单斜晶系,P2/c空间群,Mr=829.99,a=7.9327(2)A,b=11.6546(3)A,c=13.8618(4)A,β=96.2230(10)°,V=1274.01(6)A³,Z=2,Dc=2.164 g·cm^-3,μ=7.247 mm^-1,F(000)=786,最终偏离因子R=0.0273,wR=0.0749。在对苯二甲酸配体桥联下这两个配合物都具有三维异金属网络结构(CCDC:860177,1;CCDC:857137,2)。此外,测试了配合物1和2的固态紫外-可见吸收光谱并研究了配合物1的固态荧光性能。     

New temperature effect on tunneling reaction in hydrogen, alkane, and ethanol in the solid phase

Rate constants for the tunneling reaction (HD + D → h + D₂) in solid HD increase steeply with increasing temperature above 5 K, while they are almost constant below 4.2 K. The apparent activation energy for the tunneling reaction above 5 K is 95 K, which is consistent with the energy (91–112 K) for vacancy formation in solid hydrogen. The results above 5 K were explained by the model that the tunneling reaction was accelerated by a local motion of hydrogen molecules and hydrogen atoms. The model of the tunneling reaction assisted by the local motion of the reactans and products was applied to the temperature dependence of the proton-transfer tunneling reaction (C₆H₆⁻ + C₂H₅OH → C₆H₇ + C₂H₅O⁻) in solid ethanol, the tunneling elimination of H₂ molecule of H₂ molecule ((CH₃)₂ CHCH(CH₃)₂⁺ → (CH₃)₂ C = C(CH₃)₂⁺ + H₂) in solid 2,3-dimethylbutane, and the selective tunneling reaction of H atoms in solid neo-C₅H₁₂-alkane mixtures.     

Two New Piperazine Templated Lanthanide Sulfates with 2D Corrugated Layered Crystal Structures

Two new piperazine templated lanthanide sulfates (C₄N₂H₁₂)_1.5[Ln(SO₄)₃(H₂O)]·H₂O[Ln=Gd(1), Tb(2)] have been synthesized solvothermally and structurally characterized by single crystal X-ray diffraction(XRD), infrared(IR) spectroscopy, thermal analysis, fluorescent spectra and inductively coupled plasma(ICP). Single crystal X-ray diffraction reveals that both compounds 1 and 2 crystallized in the monoclinic crystal system, with space group P2₁/c and cell dimensions: a=0.64468(19) nm, b=2.9979(9) nm, c=0.9818(3) nm, β=101.271(4)°, V=1.8608(10) nm³, Z=4 for compound 1; a=0.64259(19) nm, b=3.0010(9) nm, c=0.9812(3) nm, β=101.229(4)°, V=1.8560(10) nm³, Z=4 for compound 2. Compounds 1 and 2 are isomorphous and have similar 2D corrugated inorganic frameworks fabricated via the connection of single chains and S2O₄ groups, while fully protonated piperazine cations and water molecules are located between the inorganic layers. The solid state luminescent properties of compound 2 were investigated and it displayed a typical luminescent property of Tb³⁺ with excitation wavelength at 371 nm.