ZnO clusters encapsulated inside micropores of zeolites studied by UV Raman and laser-induced luminescence spectroscopies

Using microporous zeolites as host, sub-nanometric ZnO clusters were prepared in the micropores of the host by the incipient wetness impregnation method. A small amount of sub-nanometric ZnO clusters were introduced into the channels of HZSM-5 zeolite, whereas a large quantity of sub-nanometric ZnO clusters can be accommodated in the supercages of HY zeolite and no macrocrystalline ZnO exists on the extra surface of the HY material. The vibrations of the zeolite framework and ZnO were characterized by UV Raman spectroscopy. The optical properties of these ZnO clusters were studied by UV-visible absorption spectroscopy and laser-induced luminescence spectroscopy. It is found that there are strong host-guest interactions between the framework oxygen atoms of zeolite and ZnO clusters influencing the motions of the framework oxygen atoms. The interaction may be the reason why ZnO clusters are stabilized in the pores of zeolites. Different from bulk ZnO materials, these sub-nanometric ZnO clusters exhibit their absorption onset below 265 nm and show a purple luminescence band (centered at 410-445 nm) that possesses high quantum efficiency and quantum size effect. This purple luminescence band most likely originates from the coordinatively unsaturated Zn sites in sub-nanometric ZnO clusters. On the other hand, the differences in the pore structure between HZSM-5 and HY zeolites cause the absorption edge and the purple luminescence band of ZnO clusters in ZnO/HZSM-5 show a red shift in comparison with those of ZnO clusters in ZnO/HY.

几种植物生长调节物质对大花蕙兰组培原球茎增殖的影响

采用KC培养基 ,分别添加不同浓度的BA、KT、NAA及KT +NAA组合 ,对大花蕙兰初代培养已分化出的原球茎进行了继代培养。结果发现 :①BA可加快原球茎的增殖速度 ,但浓度超过0 .5mg/L后增殖速度有所下降 ,且原球茎变小呈暗绿色。②KT的促进增殖效果好于BA ,但浓度超过 1 .0mg/L时 ,增殖速度也有所下降 ,原球茎变小。③NAA促进原球茎增殖的效果明显好于BA、和KT ,但浓度大于 1 .0mg/L后增殖不再加快 ,而且部分原球茎有变褐现象。④在KT 0 .5～ 0 .7mg+NAA 0 .7～ 1 .0mg/L范围组合的KC培养基上 ,大花蕙兰原球茎增殖的速度和质量是比较理想的。考虑到较低的细胞分裂素和植物生长素有利于植物增殖过程中遗传性的稳定 ,选择KT0 .5mg+NAA 0 .7mg/L的KC培养基作为大花蕙兰原球茎增殖培养基

On the induction period of methane aromatization over Mo-based catalysts

The behavior of different species during the temperature-programmed surface reaction (TPSR) of methane over various catalysts is traced by an online mass spectrometer, It is demonstrated that the transformation of MoO3 to molybdenum carbide hinders the activation of methane as well as the succeeding aromatization in the TPSR, If this transformation process is done before the reaction, the temperature needed for methane activation and benzene formation will be greatly lowered (760 and 847 K, respectively). On the basis of comparison of the catalytic behavior of molybdenum supported on different zeolites, it is suggested that the initial activation of methane is the rate-determining step of this reaction. For the cobalt catalysts supported on HMCM-22 or Mo catalysts supported on TiO2, no benzene formation could be observed during the TPSR, However, the prohibition of benzene formation is different in nature over these two catalysts: the former lacks the special properties exhibited by molybdenum carbide, which can continuously activate methane even when multiple layers of carbonaceous species are formed on its surface, while the latter cannot accomplish the aromatization reaction since there are no Bronsted acid sites to which the activated intermediates can migrate, although the activation of methane can be achieved on it. Only for the catalysts that possess both of these properties, together with the special channel structure of zeolite, can efficient methane aromatization be accomplished. (C) 2000 Academic Press.

利用正交法研究丁香幼胚离体培养的影响因素

利用正交法研究5种不同因素(糖、胚龄、Gln、BA、NAA)对丁香幼胚萌发及成苗的影响,筛选出最佳的幼胚离体培养条件为在Monnier+0.1mg·L-1BA+0.001mg·L-1NAA+400mg·L-1Gln+50g·L-1糖培养基上培养胚龄为50d的丁香幼胚,同时发现Gln的加入量对丁香幼胚离体培养的萌发率有显著影响。

日本落叶松微体繁殖及植株再生

日本落叶松的微体繁殖中 ,茎诱导阶段WPM +Zea 1.0 0mg/L +IAA 1.0 0mg/L、SH +Zea 0 .2 0mg/L +IAA 0 .0 5mg/L或改良MS +Zea 0 .0 1～ 0 .5 0mg/L等 3种培养基均适用 ,诱导效率与供体材料的质量有关 ,取材以初春芽苞萌动时为好。根诱导阶段的培养基为改良MS +NAA 0 .10mg/L +IBA 0 .30mg/L +0 .15 %AC(活性炭 ) ,低剂量的AC ,夜间降低培养温度至 2 0℃并与继代培养相结合 ,可促进生根率的提高。实验经 8次继代培养成功地实现了根、茎器官的再生。对于成龄材料 ,认为反复继代可能是最有效的恢复幼年生长特性的途径之一。同时指出微体繁殖过程中应当注意遗传材料的异质性对诱导效率的影响。

Controllable synthesis of VSB-5 micirospheres and microrods: Growth mechanism and selective hydrogenation catalysis

Nanoporous VSB-5 nickel phosphate molecular sieves with relatively well controllable sizes and morphology of microspheres assembled from nanorods were synthesized at 140 degrees C over a short time in the presence of hexamethylenetetramine (HMT) by a facile hydrothermal method. The pH value, reaction time, and ratio of HMT to NaHPO2-H2O crucially influence the morphology and quality of the final products.

Selective oxidation of cyclohexane with hydrogen peroxide in the presence of copper pyrophosphate

Liquid phase oxidation of cyclohexane was carried out under mild reaction condition over copper pyrophosphate catalyst in CH3CN using hydrogen peroxide as an oxidant at the temperature between 25 and 80 degrees C. The copper pyrophosphate catalyst was characterized by means of XRD, FT-IR and water contact angle measurement. It was found that appropriate surface hydrophobicity is the key factor for the excellent performance of the catalyst. In addition, a significant improvement for the cyclohexane conversion in the presence of organic acid was observed.

Carbon dioxide/propylene oxide coupling reaction catalyzed by chromium salen complexes

A series of chromium/Schiff base complexes N,N'-bis(salicylidene)-1,2-phenylenediamino chromium(III) X were prepared and employed for the alternating copolymerization of carbon dioxide with racemic propylene oxide in the presence of (4-dimethylamino)pyridine. The effect of the complex structure and reaction conditions on the catalytic activity, the poly(propylene carbonate)/cyclic carbonate (PPC/PC) selectivity, and the polymer head-to-tail linkages was examined. The experiments indicated that N,N'-bis(3,5-di-tert-butylsalicylidene)-1,2-phenylenediamino chromium(III) (NO3) exhibited the highest PPC/PC selectivity as well as polymer head-to-tail linkages and N,N'-bis(3,5-dichlorosalicylidene)-1,2-phenylenediimino chromiu(III) (NO3) possessed the highest catalytic activity among these chromium/Schiff base complexes. The structure of the produced copolymer was characterized by the IR, H-1 NMR, and C-13 NMR measurements.

Surface-appropriate lipophobicity - Application in isobutene oligomerization over Teflon-modified silica-supported 12-silicotungstic acid

A series of silica-supported 12-silicotungstic acid catalysts (H4SiW12O40, abbreviated as HSiW), modified with various loadings of Teflon (HSiW/SiO2-Teflon), were prepared by an impregnation method. The surface properties of the catalysts were studied by means of X-ray diffraction (XRD), scanning electron microscopy (SEM), BET, infrared (IR) spectroscopy, NH3-TPD and the Drop Shape Analysis (DSA). SEM results combined with energy-dispersive X-ray (EDX) measurements of HSiW/SiO2-Teflon revealed that F-compound (Teflon) is effectively coated on the catalyst surface. The contact angles for water and oil of 50 wt% HSiW/SiO2 and HSiW/SiO2-Teflon indicate that HSiW/SiO2-Teflon catalyst enhances not only the surface hydrophobicity but also the surface lipophobicity by means of the addition of Teflon. Silica-supported 12-silicotungstic acid modified with Teflon exhibits higher C-8(=) selectivity and longer lifetime than that of silica-supported 12-silicotungstic acid in isobutene oligomerization. Thus, surface-appropriate lipophobicity of catalysts may be effective for decreasing the interaction between coke precursors and the catalyst surface and for removing deposited coke more easily.