混合溶剂前体法制备纳米CuO粉体及其性能表征

Nano-CuO was prepared by heating nano-Cu₂(OH)₂CO₃ precursors in different calcination temperatures. The precursor was synthesized from water-alcohol mixed solution of Cu(Ac)₂ using mixed solution of NaOH and Na₂CO₃as precipitants. XRD, FT-IR, TEM, TG-DTA and surface area measurement techniques were used to investigate the properties of the CuO powder. The results show that the spherical, well dispersed nano-CuO powder with the average size of 15 nm and higher catalytic activity for H₂O₂ decomposition was obtained at 300 ℃. With the increasing of calcination temperature, crystal of CuO grows up, agglomeration of the powder becomes heavier and catalytic activity decreases. FT-IR patterns revealed that the vibration fine structure of Cu-O bond in nano-CuO powder disappears and main absorption is red-shifted with the average size of nano-CuO reducing.     

Si5P6O25∶Tb3+的结构与荧光性质

Tb³⁺ ions were incorporated in P-Si matrix material through a sol-gel process. Luminescence properties of Tb³⁺ as a function of dopant， firing temperature， composition and structure of matrices were investigated. The gels synthesized by the reaction of P₂O₅ or H₃PO₄ with tetraethoxy silane and TbCl₃ as dopant were fired in air from the temperature 25～1000℃ to form P-Si crystalline phase. The crystal structure was determined by powder X-ray diffraction. Si₅O(PO₄)₆ were the only crystalline phase and belong to hexagonal crystal system. The emission of ⁵D₄-⁷F₅(～545nm) transition of Tb³⁺ in the P-Si system is composed of two peaks. The amount of doping Tb³⁺ varied from 0.664% to 1.644%， and no obvious concentration quenching was observed in this doping concentra-tion range. The intensity of Tb³⁺ emission increased with firing temperature increasing and becomes stable at 800～1000℃.     

La2O2S∶Mn2+荧光粉的微波合成及其荧光特性

Using La₂(SO₄)3 and the active carbon powder as reactants, La₂O₂S∶Mn²⁺ red phosphor was synthesized by microwave radiation method. The phosphor was characterized by means of X-ray diffraction (XRD), scanning electron microscopy (SEM), laser-diffraction size analyzer and fluorospectrophotometer. The XRD analysis showed that the phosphor was pure phase La₂O₂S. The phosphor of La₂O₂S∶Mn²⁺ showed hexagonal crystal structure with diverse shapes, such as spherical and rod, with average particle size of 10.22 μm. The emission and excitation spectra of the phosphor were determined by fluorospectrophotometer and the results showed that the excitation spectrum of the phosphor under 600 nm emission wavelength was excitation bands between 250 nm and 350 nm with a peak value of 303 nm. Then ,when exicited under UV 303 nm, the phosphor showed broad band emission of 550~700 nm with a peak at 607 nm. In addition, the optimal effects were obtained for the phosphor preparation when the concentration of the activator Mn²⁺ was x_Mn=0.01, the ratio of C and O (n_C / n_O) in the reactants was 0.6∶1, and the time of reaction was about 1 h. La₂O₂S∶Mn²⁺ has strong absorption of UV spectrum and can emit bright red light.     

钛酸锌的制备及其对高氯酸铵热分解的催化性能

ZnTiO₃ nanocrystals were prepared by sol-gel method, using Zn(NO₃)₂ and Ti(C₄H₉O)₄ in the topic. The as-prepared ZnTiO₃ nanocrystals were characterized by XRD, FTIR and TEM, and the catalytic performance of ZnTiO₃ nanocrystals of different contents for the ammonium perchlorate(AP)decomposition was investigated by thermal analysis. The results indicate that ZnTiO₃ with pure cube structure can be synthesized at 600 ℃ by this procedure,which was spheroid with particle size of about 60~100 nm. The results expressed that the low temperature decomposition peaks of AP is advanced by 17 ℃ and the high temperature decomposition peaks of AP is advanced by 24 ℃ when adding 5% nanoparticle ZnTiO₃ powder. The catalytic effects of ZnTiO₃ powders on the high temperature decomposition of AP are less than that of nanometer metal powders, but all the micron metal powders decrease the low decomposition temperature of AP.     

Eu3+离子在Ca2PbO4一维结构基质中的发光研究

A Eu³⁺-doped Ca₂PbO₄ with one-dimensional structure was prepared with a solid-state reaction method and its characteristics were investigated. The XRD results show that the substitution of Ca²⁺ by Eu³⁺ has no influence on the structure of Ca₂PbO₄. Under the excitation of ultraviolet light， the Ca₂PbO₄:Eu³⁺ phosphor exhibits strong red emission at about 618 nm which is assigned to the ⁵D₀- ⁷F₂ electric-dipole transition. The compounds Sr₂CeO₄ and Ca₂SnO₄ have the same crystal symmetry as that of Ca₂PbO₄ and it is found that the emission intensity of Ca₂PbO₄∶Eu³⁺ is higher than that of Sr₂CeO₄∶Eu³⁺ and lower than that of Ca₂SnO₄∶Eu³⁺. The excitation spectrum of Ca₂PbO₄∶Eu³⁺ appears to be a broad band with two peaks at about 289 nm and 340 nm. The former peak is attributed to the Eu³⁺-O₂- charge transfer transition， while the latter one may be related to the absorption of Ca₂PbO₄ host or its crystal defects.     

由乙氧基铅配合物制备纳米PbO

Lead complex was directly synthesized by electrochemical dissolution of lead in a cell without separating the cathode and anode. The product was characterized by FTIR, Raman spectra and ¹H NMR. The xerogel was prepared by a direct sol-gel of the electrolyte solution and then dryness of it. The xerogel was heated at 450 ℃ for 2 h to obtain the nano-PbO powder. FTIR, XRD, and TEM were used to investigate the structure of nano-PbO. The results show that the lead complex is Pb(OEt)₂(acac)₂, which contains acac- group and could prevent the precursor from hydrolysis and sintering during the calcinations process. The nano-PbO of 20～30 nm was thus obtained in a high purity by drying at 450 ℃.     

由镁、铝醇盐配合物合成纳米粒子MgAl2O4尖晶石

Mg and Al alkoxide complex was synthesized in a cell without battery separator by electrochemical dissolution of aluminum for 6 h and magnesium for 1.8 h at 45 ℃ in ethanol solution of 0.04 mol·dm^-3 (Bu₄N)Br with a current density of 100 mA·cm^-2. IR and Raman spectroscopy were used to characterize the structure of the precursor of MgAl₂O₄. The results show that the current efficiency attains 98.4% and the precursor is MgAl₂(OCH₂CH₃)₅(acac)₃. The acac^- group-containing precursor could prevent it from agglomeration. The xerogel was obtained by drying in vacuum for 24 h and hydrolysis under pH≈8.5 of the precursor, which was heated at 350 ℃ for 2 h to obtain the nano-MgAl₂O₄ powder. XRD and TEM were used to investigate the structure of nano-MgAl₂O₄. The result suggests that the xerogel with an average particle size of 10 nm and the Nano-sized Spinel MgAl₂O₄ Particle of 12 nm thus obtained are with high purity.     

发光材料BaAl2Si2O8∶Eu2+的物相结构与发光性能

A phosphor, Ba_0.97Al₂Si₂O₈∶Eu²⁺, was synthesized by high temperature solid-phase method at different temperatures. The samples were characterized by TG/DTA, XRD and fluorescence spectroscopy. The results show that the main phase for host of these luminescence materials is barium feldspar BaAl₂Si₂O₈∶Eu²⁺ and there is a transition from hexagonal crystal system to monoclinic crystal system in the process of the sintering of barium feldspar. The luminescent phenomen of barium feldspar with hexagonal structure can not be observed under the excitation of ultraviolet lamp of 365 nm while the barium feldspar with monoclinic structure has excellent luminescence properties. The excitation spectra of all these samples show broad band spectra ranging from 250～390 nm with peak at λ_ex of 357 nm,which indicates that these samples can be effectively excited by near ultraviolet ; the emission spectra range from 380～600 nm with peak at λ_em of 433 nm. The luminescent intensity increases then decreases with the concentration of doping Eu²⁺ ions. When the concentration of dopants is 2.5mol%, the luminescent intensity reaches the maximum value. When the concentration of Eu²⁺ ions changes from 0.5mol% to 2.5mol%, the emission peak has a red shift from 427 nm to 440 nm.     

正钛酸胶溶法制纳米TiO2薄膜及性能表征

The Nanometer TiO₂ thin film was prepared by sol method with titanic acid precursor from industrial TiOSO₄ solution. The characters of the sol and the factors affecting sol formation were investigated by ζ electricity potential. The crystalline structure, particle size, appearance shape and photo-catalytic activity were characterized by XRD, SEM, TEM and spectrophotometer. The study show: (1) pH value and HNO₃concentration effected importantly on the forming process and stability of the sol. The thermodynamic condition for forming sol is pH=0.5～1.5. The lower the HNO₃concentration,the more stable the sol. The ζ electricity potential of the sol, with 5% HNO₃as gluing reagent, was up to 48 mV, and shelf life of the sol could more than 10 months. (2) The film, made from the sol and crystallized at 400 ℃, had the characters of anatase structure and crystal size of 18.5 nm by XRD analysis. The SEM imagines show that TiO₂ film was with the characteristics of tight surface structure, The TEM imagine showed the mean particle size is about 20 nm. The photo-degrading test data indicate that the photo-degrading rate to methyl orange solution of 20 mg·L^-1 was more than 84% in 5 hours.     

铁、氮共掺杂二氧化钛粉末的制备及光催化活性

Using TiCl₄ as the titanium source, nanoparticles of TiO₂ doped with nitrogen(N-TiO₂) were synthesized by triethylamine. TiO₂ powder codoped with iron and nitrogen(Fe/N-TiO₂) were prepared by adsorption-deposition of Fe³⁺ on N-TiO₂ and calcining at 400 ℃ for 2 h. From the XPS results for N1s binding energy at 399.6 eV and 396.6 eV, it is proposed that the partial N atoms as substitution atoms replace for O atoms in TiO₂ lattice. The onset of the absorption spectrum of Fe/N-TiO₂ has a 45 nm red-shift compared with that of TiO₂. The results of photocatalytic degradation of methylene blue solution indicate that Fe/N-TiO₂(0.45% Fe³⁺) has a higher activity. Its photocatalytic activity is about 2 times as high as that of pure TiO₂ under UV-light, and 3 times under sunlight. Doping of nitrogen in TiO₂ enhances photoresponse in visible light region and doping of Fe³⁺ reduces the recombination of electrons and holes. Both of the above effects are beneficial for improving the performances of Fe/N-TiO₂ photocatalyst.     

二氧化碳和丙烯直接合成甲基丙烯酸的NiPMo/TiO2催化剂的研究

用溶胶-凝胶法以磷钼酸(MPA)的镍盐溶液水解钛酸四丁酯制备了NiPMo/TiO2催化剂.使用ICP、 XRD、 TG-DTA、 IR、 TPD-MS和微反应技术研究了催化剂的化学组成、热稳定性、化学吸附性质和催化反应性能.杂多钼酸盐与TiO2通过O2-在TiO2表面发生了键合.在623 K下,杂多阴离子仍保持原有的Keggin结构.CO2在Lewis酸位Ni(Ⅱ)和Lewis碱位Ni-O-Mo的桥氧协同作用下生成CO2卧式吸附态Ni(Ⅱ)←O-(CO)←(O--Ni).丙烯有多种吸附态在催化剂上吸附.在563 K、 1 MPa和空速1500 h-1的反应条件下,丙烯的摩尔转化率为3.2%,产物MAA选择性为95%.     

α-Amino acid derived enaminones and their application in the synthesis of N-protected methyl 5-substituted-4-hydroxypyrrole-3-carboxylates and other heterocycles

A new and simple synthesis of novel N-protected methyl 5-substituted-4-hydroxypyrrole-3-carboxylates, which exist in equilibrium with their 4-oxo tautomers, has been developed in two steps starting from N-protected α-amino acids. The key intermediates are enaminones, which can also be isolated, characterized, and used for the construction of other functionalized heterocycles, before they spontaneously decompose to pyrrole products. 4-Hydroxypyrroles are prone to partial aerial oxidation but can be efficiently alkylated or reduced to stable polysubstituted pyrrolidine derivatives.     

Specific intramolecular aromatic CH insertion of diazosulfonamides

The chemoselectivity in the intramolecular CH insertion of various diazosulfonamides has been experimentally studied. The results reveal that the aliphatic 1,4-, 1,5-, or 1,6-C(sp³)?H insertions of diazosulfonamides are not accessible, while the aromatic 1,5-C(sp²)?H insertion can be realized specifically by adjusting the diazo-adjacent group. In addition, the general chemoselectivities in the intramolecular CH insertions of diazosulfonyl compounds are summarized. Generally, diazosulfones undergo both aromatic 1,5-C(sp²)?H and aliphatic 1,5- and 1,6-C(sp³)?H insertions, while diazosulfonates undergo aliphatic 1,5- and 1,6-C(sp³)?H insertions. However, diazosulfonamides only undergo aromatic 1,5-C(sp²)?H insertion.     

N-Heterocyclic carbene-palladacyclic complexes: synthesis,characterization and their applications in the C-N coupling and α-arylation of ketones using aryl chlorides

N-Heterocyclic carbene-palladacyclic complexes 3 were successfully achieved in a one-pot procedure under mild conditions. The structure of 3a was unambiguously confirmed by X-ray single crystal diffraction and it was an active catalyst in the Buchwald-Hartwig amination and α-arylation of ketones even at very low catalyst loadings (0.01?mol%).     

CoFe2O4自形成磁性液体场致结构化对磁化的影响

The Langevin paramagnetic theory can’t describe the relation between magnetization of ferrofluids and applied magnetic field. The structuralization of ferrofluids, which is considered the main influence factor of the magnetization, is regarded. The part of magnetization works is deposited when the structure is forming. This action influences the magnetization of ferrofluids directly or indirectly. On the base of the “compressing” model, the Langevin function that usually describes the magnetization of ferrofluid is modified, and a well-fitted curve is obtained. An equation of the relation between the equivalent volume fraction after being “compressed” and the intensity of magnetic field is discovered, which approximately describes the process of magnetization. The relation between the approximate initial susceptibility and the volume fraction can be obtained from modified formula.     

Iodine-mediated oxidative Pictet-Spengler reaction using terminal alkyne as the 2-oxoaldehyde surrogate for the synthesis of 1-aroyl-β-carbolines and fused-nitrogen heterocycles

An efficient iodine-mediated oxidative Pictet-Spengler reaction in dimethyl sulphoxide (DMSO) using terminal alkynes as the 2-oxoaldehyde surrogate for the synthesis of aryl (9H-pyrido[3,4-b]indol-1-yl)methanones is described. The scope of the protocol includes the total synthesis of Fascaplysin, Eudistomins Y₁ and Y₂. The methodology is extended for preparing pyrrolo[1,2-a]-quinoxaline and indolo[1,5-a]quinoxaline derivatives. The utility of 1-aroyl-β-carbolines was demonstrated by performing palladium-catalyzed β-carboline directed ortho-C(sp2)-H functionalization of the phenyl ring with thiomethyl (SMe) group using DMSO as source and for accessing 4-aryl-canthin-6-ones.     

Facile synthesis of bicyclic 1-arylpyrazol-5-ones

In this Letter, we described a facile method for constructing fused bicyclic 1-arylpyrazol-5-one ring system. We employed various methylene-containing carboxylic acids as the substrates and proved that the pyrazolone ring closure requires activated methylene group in intermediate II. Accordingly, a series of structurally diversified, fused bicyclic 1-arylpyrazol-5-ones was prepared in moderate to high yields using the requisite substrates.     

Highly regioselective Buchwald–Hartwig amination at C-2 of 2,4-dichloropyridine enabling a novel approach to 2,4-bisanilinopyridine (BAPyd) libraries

The highly regioselective Buchwald–Hartwig amination at C-2 of the cheap and readily accessible reagent, 2,4-dichloropyridine with a range of anilines and heterocyclic amines is described. This new methodology is robust and provides a facile access to 4-chloro-N-phenylpyridin-2-amines on 0.25 mol scale. These intermediates undergo a further Buchwald–Hartwig amination at higher temperature to enable rapid exploration of the chemical space at C-4 and to provide a library of 2,4-bisaminopyridines.     

Sulfur-directed metal-free and regiospecific methyl C(sp3)–H imidation of thioanisoles

Regiospecific and direct imidation of the methyl C(sp³)–H bond of thioanisoles is realized under mild and metal-free conditions with N-fluorobis(benzenesulfonyl)imide as an oxidant and nitrogen source. Proposed mechanism suggests that thionium ion intermediates and a Pummerer-type reaction are involved. The imidation has advantages such as high step-economy, excellent functionality tolerance, and regiospecificity, giving structurally diverse imidation products.