纳米CuO的形貌控制合成及其性能研究

The CuO nanocrystals were prepared by quick-precipitation and hydrolysis method respectively, using Cu(Ac)₂ and NaOH as starting materials. The as-prepared CuO nanocrystals were characterized by XRD, TEM, XPS, UV-Visible absorption spectroscopy and BET. The catalysis of CuO nanocrystals of different morphologies on ammonium perchlorate decomposition was investigated by thermal analysis. Results indicated the variation in temperature for NaOH addition played an important role in the shape of the CuO nanocrystals in precipitation method. Well-dispersed spherical CuO nanocrystals with an average size of 6 nm could be obtained when NaOH was added at 100 ℃ and spindle-shaped CuO nanocrystals exceeding 100 nm in diameter were obtained when NaOH was added at room temperature. Needle-shaped CuO nanocrystals could be prepared by the hydrolysis method, and the presence of small amounts of cetyltrimethylammonium bromide (CTAB) could make needle-shaped CuO well dispersed. The catalytic activity of CuO nanocrystals of different morphologies on ammonium perchlorate decomposition was high. The 2% of spherical CuO nanocrystals could make higher decomposition temperature of ammonium perchlorate decreased to 102 ℃. The exothermic quantity of decomposition was from 590 J·g^-1 up to 1 420 J·g^-1.     

纳米铜粉对高氯酸铵热分解的影响

The decomposition behaviour of ammonium perchlorate (AP) has been investigated in the presence of Cu nanopowder by DTA. The results show that nanometer Cu powder decreased the first and second thermal decomposition temperature of AP by 35.1 ℃ and 130.2 ℃, respectively, and the DTA heat release of AP in the presence of Cu nanopowders increased to 1.20 kJ·g^-1, showing good catalytic effect on the thermal decomposition of AP. The catalytic effect of Cu micron-size powder on the thermal decomposition of AP was less than that of Cu nanopowder. With the increase in content, Cu nanopowder enhanced its catalytic effect on the high temperature decomposition of AP, however, it weakened its catalytic effect on the low temperature decomposition of AP. The mechanism of catalysis for the thermal decomposition of AP is as follows: (1) metal oxider acts as the intermedium in the process of election tranfer, (2) Cu nanopowder reacts with the decomposed product of AP, (3) Cu nanopowder has special surface effect.     

Nonisothermal crystallization and morphology of poly(butylene succinate)/layered double hydroxide nanocomposites

Biodegradable poly(butylene succinate) (PBS) and layered double hydroxide (LDH) nanocomposites were prepared via melt blending in a twin-screw extruder. The morphology and dispersion of LDH nanoparticles within PBS matrix were characterized by transmission electron microscopy (TEM), which showed that LDH nanoparticles were found to be well distributed at the nanometer level. The nonisothermal crystallization behavior of nanocomposites was extensively studied using differential scanning calorimetry (DSC) technique at various cooling rates. The crystallization rate of PBS was accelerated by the addition of LDH due to its heterogeneous nucleation effect; however, the crystallization mechanism and crystal structure of PBS remained almost unchanged. In kinetics analysis of nonisothermal crystallization, the Ozawa approach failed to describe the crystallization behavior of PBS/LDH nanocomposites, whereas both the modified Avrami model and the Mo method well represented the crystallization behavior of nanocomposites. The effective activation energy was estimated as a function of the relative degree of crystallinity using the isoconversional analysis. The subsequent melting behavior of PBS and PBS/LDH nanocomposites was observed to be dependent on the cooling rate. The POM showed that the small and less perfect crystals were formed in nanocomposites.     

PREPARATION OF POLY（METHYL METHACRYLATE）/LAYERED DOUBLE HYDROXIDES NANOCOMPOSITES via in situ SOLUTION POLYMERIZATION

An exfoliated layered double hydroxides/poly(methyl methacrylate)(LDHs/PMMA)nanocomposite was prepared by in situ solution polymerization of methyl methacrylate(MMA)in the presence of 4-vinylbenzenesulfonate intercalated LDHs(MgAl-VBS LDHs).MgAl-VBS LDHs was prepared by the ion exchange method,and the structure and composition of the MgA1-VBS LDHs were determined by X-ray diffraction(XRD),infrared spectroscopy and elemental analysis.XRD and transmission electron microscopy(TEM)were employed to examine the structure of LDHs/PMMA nanocomposite.It was indicated that the LDHs layers were well exfoliated and dispersed in the PMMA matrix.The grafting of PMMA onto LDHs was confirmed by the extraction result and the weight fraction of grafted PMMA increased as the weight fraction of LDHs in the nanocomposites increased.     

Crystallization behavior, thermal and mechanical properties of PHBV/graphene nanosheet composites

Biodegradable poly(3-hydroxybutyrate-co-3-hydroxyvalerate) (PHBV)/graphene nanosheet (GNS) composites were prepared via a solution-casting method at low GNS loadings in this work. Transmission electron microscopy revealed that a fine dispersion of GNSs was achieved in the PHBV matrix. The thermal properties of the nanocomposites were investigated by thermogravimetric analysis, and the results showed that the thermal stability of PHBV was significantly improved with a very low loading of GNSs. Nonisothermal melts crystallization behavior, spherulitic morphology and crystal structure of neat PHBV and the PHBV/GNSs nanocomposites were investigated, and the experimental results indicated that crystallization behavior of PHBV was enhanced by the presence of GNSs due to the heterogeneous nucleation effect; however, the two-dimensional (2D) GNSs might restrict the mobility of the PHBV chains in the process of crystal growing. Dynamic mechanical analysis studies showed that the storage modulus of the PHBV/GNSs nanocomposites was greatly improved.     

纳米钯粒子的超声制备与表征

Monodispersed nano-Pd particles were prepared by sonochemical reduction of a 1∶12 molar mixture of palladium(Ⅱ) chloride(PdCl₂), and sodium dodecyl sulfate (SDS) in double deionized aqueous solution. The reducing substance was characterized by transmission electron microscopy (TEM) with selected area electron diffraction (SAED), Fourier transform infrared (FTIR) and X-ray photo electron specstropy analysis (XPS). The results show that the reduction of Pd(Ⅱ) to metallic Pd is achieved and that the obtained suspensions have a long life period. The Pd nanoparticles are highly dispersed and uniform in size (in the range of 1～10 nm). The protective effect of SDS for Pd nanoparticles was investigated and the results indicate that there are interactions between Pd and SDS.     

PROPERTIES AND MORPHOLOGY OF UNSATURATED POLYESTER/ACRYLATE-TERMINATED POLYURETHANE/ORGANOMONTMORILLONITE NANOCOMPOSITES

Unsaturated polyester resin （UPR）/acrylate-terminated polyurethane （ATPU）/organo-modified montmorillonite （OMMT） nanocomposites were prepared by the in situ intercalative polymerization method. Samples were prepared by the sequential mixing, i.e. mixture of the ATPU and styrene （S） and OMMT were prepared in the first step; UPR was then added to the pre-intercalates of ATPU/S/OMMT. Results indicate that the mechanical properties and thermal properties of UPR/ATPU/OMMT nanocomposites greatly depend on the amount of ATPU and OMMT. Results show that the addition of ATPU could increase the impact strength of UPR/ATPU composites, but the tensile strength, flexural strength and heat resistance of the materials are obviously decreased. When the weight ratio between UPR, ATPU and OMMT were 82：15：3, the impact strength and heat distortion-temperature of nanocomposite were greatly improved, meanwhile there was little change for other properties of the nanocomposites. The synergistic enhancement effects of ATPU and OMMT on the composites were observed. The structures and morphology of the composites were investigated by X-ray diffraction, scanning electron microscopy and transmission electron microscopy.     

Synthesis and Analysis of Tm3+ Doped YF3 Upconversion Luminescent Nano-materials

<正>Upconversion(UC)phosphor Tm~(3+)doped YF_3 nano-crystals were prepared by hydrothermal method under different conditions and characterized by Field Transmission electron microscopy(TEM),Scanning electron microscopy(SEM)and X-ray diffraction(XRD).Their UC luminescence properties were studied by fluorescence spectrophotometer with 980 nm diode laser excitation,and impact of different grain sizes and morphology on the UC luminescence intensity was discussed.The fluorescence decay lifetime was calculated by Multi-exponential function fitting method.Results show that UC emission intensity was enhanced with the reduction of grain size,and the decay lifetime is 0.60 us.     

石墨负载Pt催化剂的制备、表征及活性研究

Pt/graphite catalyst was prepared by incipient wetness impregnation using H₂PtCl₆·6H₂O as precursor. The catalyst was characterized by SEM, XRD, XPS and its degradation ability for oxalic acid was evaluated. The preparation parameters, including the reduction temperature, Pt loading and pyrolysis were studied. The optimal preparation conditions were 350 ℃ with Pt loading of 1.0%. Results show that the loading of Pt can significantly enhance catalytic activity of graphite and that Pt/graphite catalytic ozonation can effectively remove oxalic acid in aqueous solution. The BET surface area of graphite is much smaller than that of activated carbon, however, the catalytic activity of Pt/graphite towards oxalic acid degradation is higher than that of Pt/AC. The XPS results indicate that the active phase at catalyst surface is in the form of Pt⁰. Compared with that of reduction process in hydrogen, the activity of Pt/graphite catalyst decreases when it is prepared by pyrolysis in air due to the lower Pt dispersion on graphite surface.     

Studies on crystal transition of polyamide 11 nanocomposites by variable-temperature X-ray diffraction

Polyamide I1 （PAll） and its nanocomposites with different organoclay loadings were prepared by melt-compounding and subsequent pelletizing. The crystal phase transitions of PAl 1 and its clay nanocomposites were investigated by variable-temperature X-ray diffraction. It was found that the Brill transition of the nanocomposite was 20 K higher than that of the neat PAl 1 for both heating and cooling processes. The PAl 1 d-spacings of the nanocomposites were observed to be smaller than those of the neat PAl 1 for melt crystallization. The constraints imposed by the addition of layered clay, restricting the thermal expansion of the polymer chains, are probably responsible for such a reduction of the d-spacing.     

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%.     

Synthesis of 1-benzyloxypyrazin-2(1H)-one derivatives

Different approaches for the synthesis of 1-benzyloxypyrazin-2(1H)-one derivatives from simple amino acids have been investigated. A library of 33 precursors for the preparation of N-hydroxy pyrazinones was obtained in moderate to good yields.     

Toward new camptothecins. Part 6: Synthesis of crucial ketones and their use in Friedländer reaction

In the context of the preparation of camptothecin and luotonin A analogs, the synthesis of some key keto-precursors and their use in Friedländer condensation are described. This paper also focuses on the stability of these keto intermediates and emphasizes the major differences between indolizinones and pyrroloquinazolinones series. Noteworthy is also the report of some original structures isolated as by-products of some experiments.     

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.     

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.     

KMnO4-mediated oxidative CN bond cleavage of tertiary amines: Synthesis of amides and sulfonamides

KMnO₄-mediated oxidative CN bond cleavage of tertiary amines producing secondary amine was introduced, which was trapped by electrophiles (acyl chloride and sulfonyl chloride) to form amides and sulfonamides. The reaction could take place at mild condition, tolerating a wide range of function groups and affording products in moderate to excellent yields.     

Chemistry of heterocyclic compounds at the A. E. Favorsky Irkutsk Institute of Chemistry, Siberian Branch of the Russian Academy of Sciences, over 50 years (Review)

The review contains a concise historical account and information on the most significant researches undertaken by the staff at the A. E. Favorsky Irkutsk Institute of Chemistry, Siberian Branch of the Russian Academy of Sciences on the Chemistry of Heterocyclic Compounds. Dedicated to Academician of the Russian Academy of Sciences B. A. Trofimov on his 70th jubilee. Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 10, pp. 1443–1502, October, 2008.     

A general and convenient synthesis of 4-(tosylmethyl)semicarbazones and their use in amidoalkylation of hydrogen,heteroatom, and carbon nucleophiles

A general synthesis of previously unknown semicarbazone-based α-amidoalkylating reagents, 4-(tosylmethyl)semicarbazones, has been developed. The synthesis involved three-component condensation of semicarbazones of aliphatic or aromatic aldehydes with the same or other aldehydes and p-toluenesulfinic acid. The scope and limitations of this reaction were investigated. The compounds obtained were demonstrated to be an efficient α-(4-semicarbazono)alkylating agents. They were reacted with H- (sodium borohydride), O- (sodium methylate), S- (sodium phenylthiolate), N- (pyrrolidine, sodium succinimide), P- (trialkyl phosphites), and C-nucleophiles (sodium diethyl malonate) to give the corresponding products of the tosyl group substitution, 4-substituted semicarbazones, including analogues of nitrofurazone. Among the prepared compounds tested in vitro for antibacterial and antifungal activity, three nitrofuryl-containing semicarbazones exhibited high biological activities with minimum inhibitory concentration (MIC) values of 8–32 μg/mL.     

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.     

Synthesis of novel chiral bidentate hydroxyalkyl-N-heterocyclic carbene ligands and their application in palladium-catalyzed Mizoroki–Heck couplings and asymmetric addition of diethylzinc to benzaldehyde

A small library of new chiral bidentate hydroxyalkyl-imidazolium salts 1 is conveniently synthesized on multi-gram scale from inexpensive and commercially available chiral pool amino acids. The corresponding carbenes, generated by deprotonation of imidazolium salts 1, in combination with palladium(II) chloride were tested in the Mizoroki–Heck coupling reaction. The most significant results in terms of yields and reactivities were achieved with low catalyst loading. The catalytic activities of these imidazolium salts were also investigated in the asymmetric addition of diethylzinc to benzaldehyde. The use of MgO nanoparticles as an additive in conjunction with these ligands played a crucial role in increasing the efficiency of these reactions.