Li4Ti5O12溶胶-凝胶法合成及其机理研究

The precursors of Li₄Ti₅O₁₂ were prepared from tetrabutyl titanate and lithium acetate by sol-gel process. The Li₄Ti₅O₁₂ samples were synthesized by calcining the gel precursors at 400～900 ℃ in air for 6～20 h. Its reaction mechanism was investigated by infrared spectroscopy(IR), thermogravimetry(TG) and X-ray diffraction(XRD). The effects of sinter-temperature, calcination-time and thermal-treatment for the products were discussed. The samples were characterized by X-ray diffraction(XRD), scanning electron microscopy(SEM). The results showed that the single-phase products were obtained by calcining the gel precursors at 800 ℃ in air for 20 h, the sinter-temperature was lower than that of solid-state method, the particles were narrowly distributed, well crystallized with a size range from 0.3μm to 0.5 μm.     

LiNi1-xMxVO4的红外光谱和拉曼光谱研究

The vanadates of LiNi_1-xM_xVO₄(M=Fe,Co,Ni) containing VO₄ tetrahedrons were synthesized by soft chemical method through a new mild liquid route. The samples sintered at 450℃ for 3h and at 650℃ for 3h are named for LT-LiNiVO₄ and for MT-LiNi_1-xM_xVO₄ respectively. All of the products were measured by X-ray diffraction, IR and Raman spectra respectively. In comparison with IR spectra of V₂O₅ and NiO, the LT-LiNiVO₄ has a strong and broad IR absorption band of VO₄ tetrahedrons located at 600～850cm^-1 with three small splitting peaks corresponding to the asymmetry stretching vibrations of V-O bonds. The results of IR and Raman spectra for MT-LiNi_1-xM_xVO₄ show that the cations of Ni²⁺, Co²⁺, Fe²⁺ have the influences on the frequency shifts of the V-O vibrations.     

锂离子电池正极材料LiMn2O4的合成与晶体结构（英）

Spinel LiMn₂O₄ powders were prepared using two-step synthesis method consisting of solid-state reaction method and citrate modified sol-gel method. The effects of the calcination temperature and the Li/Mn ratio of raw materials were studied on the physicochemical and electrochemical properties of the spinel LiMn₂O₄ powders, such as crystallinity, lattice constant and density. The title compound was characterized by powder X-ray diffraction (XRD), scanning electron microscopy (SEM) and transmission electron microscopy (TEM). Polycrystalline LiMn₂O₄ powers calcined at 750 ℃ were found to be composed of very uniformly-sized microcrystal with an average particle size of 300 nm. The improvement in electrochemical properties was mainly attributed to the process of re-grinding by absolute alcohol.     

锂离子电池用Li4Ti5O12-碳复合材料的制备与电化学性能

Li₄Ti₅O₁₂-C composite was prepared by sol-gel method using ethyl alcohol as solvent, lithium acetate and tetrabutyl titanate as raw materials, and graphite as carbon source. Li₄Ti₅O₁₂-C composites were characterized by thermogravimertric(TG) analysis and differential thermal analysis(DTA), X-ray diffraction(XRD), Fourier transform infrared (FTIR) spectroscopy, scanning electron microscopy (SEM) and electrochemical tests. Results show that Li₄Ti₅O₁₂-C composite with 5% carbon containing can be obtained by annealing the precursor at 600 ℃ for 6 h in N₂ atomsphere. The composites can deliver a specific capacity of 167.1 mAh·g^-1, 99.0% and 105.1% of the capacity can be retained after discharged for 80 times at 0.1C and 2.0C, respectively. Compared with pure Li₄Ti₅O₁₂, Li₄Ti₅O₁₂-C composite shares larger discharge capacity, better cyclability and rate performance.     

In2O3八面体的碳还原法制备及其发光性能研究

In₂O₃ octahedrons were synthesized by carbothermal reduction using In₂O₃ nanoparticles as the source material. The as-synthesized products were characterized by X-ray powder diffraction (XRD), energy dispersive X-ray(EDX), scanning electron microscopy(SEM), transmission electron microscopy(TEM), high-resolution transmission electron microscopy (HRTEM), selected-area electron diffraction analysis(SAED) and Room-temperature photoluminescence(PL) spectroscopy. The results show that the products are single-crystalline In₂O₃ octahedrons, the length of the octahedrons is in the range of 400～3 000 nm; the PL patterns display two peaks located at 447nm and 555 nm upon excitation at 380 nm, and the other two peaks located at 444 nm and 550 nm upon excitation at 325 nm; the excitation pattern shows two peaks located at 274 nm and 371 nm, respectively. The growth mechanism of the In₂O₃ octahedrons is discussed, and the high supersaturation ratio is considered as the key factor.     

BaxCe0.8Y0.2O3-α固体电解质的氧离子导电性

Ba_xCe_0.8Y_0.2O_3-α(x=1.03，1，0.98) solid electrolyte samples show a single phase of orthorhombic perovskite of BaCeO₃. The oxide-ion conduction and transport number were detected in the temperature of 600～1000℃ by electrochemical oxygen permeation (oxygen pumping)， and compared with the results from the oxygen concentration cell. The relation between the ingredient of Ba and oxide-ion conduction was also researched. It was found that these electrolytes exhibited the mixed oxide-ionic and electronic hole conduction under the experimental temperature and oxygen gas. The oxide-ion transport numbers are 0.1～0.6， which are close to the results of the oxygen con-centration cell. They increase as the decrease of Ba content in the samples.     

纳米Mn-Zn铁氧体的制备和研究

Nanosize manganese zinc ferrites were fabricated by hydrothermal precipitation route using Fe₂(SO₄)₃, ZnSO₄·7H₂O, MnSO₄·H₂O as material, then some calcinated at 500 ℃ and studied by XRD, TEM, IR and VSM. The results showed that the products were spinel crystal structure and uniformly sized nanoparticles (15～25 nm) with little aggregation. The analysis of IR showed that the superficial water can be eliminated, but that was embedded in crystal lattice can not be removed by calcinating. The effect Zn content x on the lattice (a) of nanosize Mn_1-xZn_xFe₂O₄ was also discussed. The lattice of nanosize Mn_1-xZn_xFe₂O₄ decreases with x increasing; and its value deviated the standard lattice (a₀) of normal size manganese zinc ferrites. A lot of water was absorbed during the hydrothermal process owing to the large surface of nanosize particles. The change of magnetic properties of Mn_xZn_1-xFe₂O₄ with x increasing was studied: nanosize Mn_xZn_1-xFe₂O₄ particles synthesized by us exhibited peculiar magnetic properties curve with Zn content (x) increasing, Superparamagnetic behaviors of the synthesized ZnFe₂O₄ samples were confirmed by magnetic characterization, which can be explained by the difference between the distribution of the metal ions (Mn²⁺, Zn²⁺ and Fe³⁺) among the tetrahedral (A) and the octahedral (B) sites of nanosize ferrite and that of bulk ferrite.     

共沉淀法制备负热膨胀性ZrW2O8粉体及其粒径控制初探

Negative thermal expansion (NTE) material ZrW₂O₈ powders were synthesized using co-precipitation route. The precursor of ZrW₂O₈ was studied by Thermogravimetric and differential scanning calorimetry (TG-DSC). The structure and morphology of the resulting powders were characterized by Powder X-ray diffraction (XRD) and Scanning electron microscopy (SEM), respectively. The results showed that the samples were single phase of α-ZrW₂O₈ with regular shape. High temperature X-ray diffraction measurement indicated that the thermal expansion coefficient of ZrW₂O₈ was -10.35 × 10^-6 K^-1 in the temperature range from room temperature to 150 ℃, -3.08 ×10^-6 K^-1 from 200 ℃ to 600 ℃ and the average value was -5.38 × 10^-6 K^-1. At the same time, polyethylene glycol (PEG) was used as dispersant to primary control the size of ZrW₂O₈.     

反相微乳液法合成SrTiO3纳米棒

SrTiO₃ nanorods were synthesized in cetanyl trimethyl ammonium bromide (CTAB) reverse microemulsion containing CTAB, n-hexanol, n-octane and water with Ba(OH)₂ as reactants. The effects of different conditions such as ω₀ [ω₀=n_H2O/ n_CTAB], aging time and the concentration of reactants on the formation of the nanorods were studied. Transmission electron microscope (TEM), electron diffraction (ED) and X-ray diffraction(XRD)were used to characterize the morphology and the structure of the synthesized nanorods. The results show that SrTiO₃ nanorods with a length of 260～2 000 nm and a diameter of 50～100 nm belonging to single crystal are single cubic system. The molar ratio of Sr to Ti of products is 1.0 as determinded by ICP.     

LixNi0.8-yCo0.2ZnyOp的合成及电化学性能研究

A series of single-phase Li_xNi_0.8-yCo_0.2Zn_yO_p(0.96 ≤x≤ 1.10， 0 ≤y≤ 0.05， 2 ≤p≤ 2(1+y) ) (different in the y values) were synthesized by a two-step solid state reaction method， in which LiOH·H₂O， Zn-doped spherical Ni(OH)₂ and Co₂O₃ were used as the precursors. The ICP-AES analyses proved that the Zn-doped compounds synthesized had the nonstoichiometric form. The results of the XRD， SEM identified that the uniform particles of the as-prepared materials having a good layered structure were fine， narrowly distributed and well crystallized. The electrochemical performance test was carried out and the results showed that the as-prepared Zn-doped materials had not only a high capacity， but also a better cycling stability characterization than the un-doped one. The Li_1.06Ni_0.75Co_0.22Zn_0.03O_2.03 material has an initial reversible capacity as high as 160.5mAh·g^-1; and a first discharge efficiency 89.2%， and exhibits satisfactory cyclic stability with 90% retainable capacity after 50 cycles.     

Freezing-point of mixtures of H 2 16 O and H 2 18 O

Freezing-point depression of mixtures of H ₂ ¹⁶ O and H ₂ ¹⁸ O were measured. The results showed that the freezing point of the mixture rose linearly with an increase in the molal concentration of H ₂ ¹⁸ O. The results suggested the formation of a solid solution of H ₂ ¹⁶ O and H ₂ ¹⁸ O by freezing, similar to that formed by H ₂ O–D ₂ O, and that H ₂ ¹⁸ O behaves as a different molecule than H ₂ ¹⁶ O.     

Ca2+-Mg2+-Zn2+体系在水溶性聚磷酸铵溶液中螯合规律的研究

近年来,水溶性聚磷酸铵在液体肥料和复合肥料的领域受到了广泛的关注,并在发达国家中得到了大面积的推广及应用。在pH值为5.5~8.0、温度为278.15 K~323.15 K的条件下,本文采用滴定法研究Ca_²⁺-Mg_²⁺-Zn_²⁺体系在聚磷酸铵溶液中的螯合规律。实验结果表明：相同质量分数的聚磷酸铵溶液对金属离子的螯合量会随着体系中Ca_²⁺、Mg_²⁺、Zn_²⁺的摩尔浓度的变化而变化;随着温度的升高而逐渐降低;随着pH的增加而逐渐增加;随着聚合度的升高而逐渐增加。采用傅里叶红外光谱对聚磷酸铵和A₁B₃C₃体系的螯合物进行表征。     

Ab initio investigations of the bound rovibrational levels of NeH 2 + , NeHD+, and NeD 2 +

Summary Bound rovibrational levels have been calculated for NeH ₂ ⁺ , NeHD⁺, and NeD ₂ ⁺ using three recent fits to an accurateab initio PES. The NeH ₂ ⁺ molecule behaves essentially as a linear molecule, the predicted rotational constant is 2.57 cm^–1. The fundamental frequencies are 811, 1189, and 1748 cm^–1 for the Ne-H ₂ ⁺ stretch, the Ne-H ₂ ⁺ bend and H ₂ ⁺ stretching modes, respectively.Dedicated to the 60th birthday of Prof. W. Kutzelnigg, Bochum     

Study of the vibrational spectra of SO2, H2O and D2O using the U(4) algebraic model

Using the U(4) algebraic model, in this work we report a study of the vibrational spectra of SO₂, H₂0¹⁸ and D₂O¹⁶. The inclusion of intermode couplings in algebraic models has been stated to give a deep insight into detailed spectroscopy for these bent XY₂ molecules. Improved set of algebraic parameters has been reported to provide improved RMS deviations for these molecules.     

ZrW1.7ⅥW0.3ⅤO7H0.3(OH)2·2H2O的合成与表征

分别利用微乳液水热法和酸蒸气水热法合成了杂多蓝化合物ZrW1.7ⅥW0.3ⅤO7H0.3(OH)2·2H2O.XRD测定结果表明,该化合物与ZrMo2O7(OH)2·2H2O具有相同晶体结构类型.使用Rietveld方法对产物进行了结构精修,并计算出了键参数和键价.运用EPR技术测定了该化合物中W的价态,并利用XPS能谱测定了W/W的比例.利用价键和规则,指出ZrW1.7ⅥW0.3ⅤO7H0.3(OH)2·2H2O中的W—O3—H0.15存在羟基化现象,并对杂多蓝化合物的红外吸收光谱进行了指认.     

氨基酸-BrO-3-Mn2+-H2SO4-丙酮体系的振荡反应

This paper, Using potentiometric method, first reports the oscillating behavior of five amino acids (L-methionine, L-cystine, L-tryptophan, L-serine, L-tyrosine) in a new oscillating system of amino acid-BrO_3~--Mn~(2+)-H_2SO_4-acetone. The effect of many factors on oscillation have been investigated. According to Arrhenius equation, the apparent activation energy of the oscillatary induction period and oscillation period of five oscillating systems are obtained within temperature range of 20～37 ℃.     

X-ray Crystal Structure of (CNSSS)2(M)2 (M = AsF6 −, SbF6 −, Sb2F11 −)

The crystal structures of (CNSSS)₂(AsF₆)₂, (CNSSS)₂(SbF6)₂, and two phases of (CNSSS)₂(Sb₂F₁₁)₂ have been determined. The AsF₆ ^?, SbF₆ ^?, and α-Sb₂F₁₁ ^? salts crystallize as reddish-brown plates whereas the β-Sb₂F₁₁ ^? salt crystallizes as green rods. The dication ^ß+SSSNCCNSSS^+ß (1²⁺) is the same in all four structures and consists of two 7π rings linked by a sp²-sp² C-C bond (1.462 Å in 1 (AsF₆)₂). The packing in the four structures is similar with stacks of dications along the a-axis and alternating sheets of dications and anions lying in the bc-plane. The differences in the dication-dication contacts is reflected in the variable temperature magnetic data.     

SO42-改性后的TiO2(锐钛和/或金红石)表面上MoO3的分散性质研究

采用红外(IR)、拉曼(Raman)、X-射线衍射(XRD)、程序升温还原(TPR)等方法考察了经硫酸根改性后的金红石(SR)与锐钛矿(SA)的混合比例变化时的负载型催化剂，MoO₃ / TiO₂(SR+SA)，的一些物理化学性质(如活性组分MoO₃的分散行为、表面酸碱性、氧化还原性)的变化规律。结果表明：对于MoO₃ / TiO₂(SR+SA)样品，低含量MoO₃表面分散时倾向于优先与混合载体中的改性金红石(SR)发生作用；TiO₂载体表面SO₄^2-的存在，使得载体表面产生了新的酸性位，导致样品中表面分散的钼物种主要以聚合八面体状态存在。     

Theoretical study of the triplet excited state of PtPOP and the exciplexes M-PtPOP (M = Tl, Ag) in solution and comparison with ultrafast X-ray scattering results

The [Pt₂(H₂P₂O₅)₄]⁴⁻ ions in the ground and excited states and the excited-state complexes M-[Pt₂(H₂P₂O₅)₄]³⁻ and M₂-[Pt₂(H₂P₂O₅)₄]²⁻ (M = Ag, Tl) were studied in solution with various density functional theory (DFT) functionals from Gaussian 09 and Amsterdam Density Functional (ADF) programs. Calculated results were compared with ultrafast X-ray solution scattering data. Time dependent DFT (TD-DFT) calculations with the B3PW91 functional and unrestricted open shell calculations with the mPBE functional produce good agreement with the experimental results. Compared to gas phase calculations, the surrounding solvent is found to play an important role to shorten the Pt-Pt and M-Pt (M = Ag, Tl) bond lengths, lowering the molecular orbital energies and influences the molecular orbital transitions upon excitation, which stabilizes the excited transient molecules in solution.     

ZUR KENNTNIS DES NATRIUMDIPHENYLPHOSPHINOFORMIATS Ph2PCOONa1

Abstract

Ph ₂ PCOONa 2, hergestellt dutch Reaktion von Ph₂PNa mit CO₂, wird in protischen Medien rasch unter Bildung von Ph₂PH and CO₂ hydrolysiert. Die Hydrolyse verlauft in Natronlauge sehr viel langsamer and es bilden sich zusätzlich geringe Mengen Ph₂P(O)O^? und HCOO^?, Aus 2 and stöchiometrischen Mengen RI bilden sich tertiäre Phosphine Ph₂PR (R[dbnd]Me, Et) während mit überschüssigem MeI das Phosphoniumsalz [Ph₂PMe₂]I erhalten wird. Ph₂PCOOMe, Ph₂PCOOSiMe₃ bzw. Ph₂PCSSNa wurden durch Umsetzung von 2 mit (MeO)₂SO₂, Me₃SiCl bzw. CS₂ synthetisiert. Ph₂P(O)ONa and Ph₂P(S)SNa entstanden bei der Reaktion von 2 mit O₂ oder S₈ in Benzol.

Concerning Sodiumdiphenylphosphinoformiate Ph2PCOONa¹.

Ph₂PCOONa 2, prepared from Ph₂PNa and CO₂, is readily hydrolyzed in protic media with formation of Ph ₂ PH and CO₂. Hydrolysis is much slower in NaOH and small quantities of Ph₂P(O)O^? and HCOO^? are additionally formed. Reactions of 2 with RI in stoichiometrical amounts gave tertiary phosphines Ph₂PR (R[dbnd]Me, Et) while the phosphonium compound [Ph₂PMe₂]I resulted from 2 and MeI in excess. Ph₂PCOOMe, Ph₂PCOOSiMe₃ or Ph₂PCSSNa were obtained from 2 and (MeO)₂SO₂, Me₃SiCl or CS₂. Ph₂P(O)ONa and Ph₂P(S)SNa were isolated when 2 was reacted with O₂ or S₈ in benzene.