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          Ionic Liquids 離子液體

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          鄧友全,杜正銀
          619.40 KB

          本發明公開了一種室溫離子液體中酮肟經貝克曼重排反應制備酰胺的清潔催化合成方法。本發明的催化劑選自酰氯化合物,酮肟在室溫離子液體中溫和的反應條件下 高轉化高選擇性地生成相應的酰胺,產物可以用水萃取,離子液體能夠循環使用。這種催化重排方法簡單,無污染,不產生固體廢物,是一種綠色清潔催化過程,具 有較好的工業應用前景。

          鄧友全,杜正銀,李作鵬. 一種酮肟經貝克曼重排反應制備酰胺的方法. 200510096932.1. 2008.

          朱來英 / 鄧友全
          406.22 KB

          本文合成了一系列聚乙烯醇擔載離子液體薄膜,并進行了FT-IR, SEM以及DSC表征.通過對模擬汽油脫硫性能的初步研究發現,這一類薄膜對于較低硫含量的體系具有較好的脫硫性能.

          ★★☆☆☆ Zhu LY,Zhang QH,Zhang SG,et al. Preliminary Exploration Of Polyvinylalcohol/ionic Liquids Hybrid Membrane In Desulfurization Of Model Gasoline[J]. 分子催化,2008,22(1):1-4.

          劉樂全 / 鄧友全
          175.36 KB

          An attempt to prepare ferric hydroxide supported Au subnano clusters via modified co-precipitation without any calcination was made. High resolution transmission electron microscopy (HRTEM), X-ray diffraction (XRD) and X-ray photoelectron spectroscopy (XPS) have been employed to study the structure and chemical states of these catalysts. No Au species could be observed in the HRTEM image nor from the XRD pattern, suggesting that the sizes of the Au species in and on the ferric hydroxide support were less than or around 1 nm. Chemoselective hydrogenation of aromatic nitro compounds and a,b-unsaturated aldehydes was selected as a probe reaction to examine the catalytic properties of this catalyst. Under the same reaction conditions, such as 100 ?C and1MPaH2 in the hydrogenation of aromatic nitro compounds, a 96–99% conversion (except for 4-nitrobenzonitrile) with 99% selectivity was obtained over the ferric hydroxide supported Au catalyst, and the TOF values were 2–6 times higher than that of the corresponding ferric oxide supported catalyst with 3–5 nm size Au particles. For further evaluation of this Au catalyst in the hydrogenation of citral and cinnamaldehyde, selectivity towards unsaturated alcohols was 2–20 times higher than that of the corresponding ferric oxide Au catalyst.

          ★★★★☆Liu LQ,Qiao BT,Ma YB,et al. Ferric Hydroxide Supported Gold Subnano Clusters Or Quantum Dots: Enhanced Catalytic Performance In Chemoselective Hydrogenation[J]. Dalton Trans.,2008:2542-2548.

          喬波濤 / 鄧友全
          1.51 MB

          Ferric hydroxide supported Au catalysts prepared with co-precipitation method at room temperature without any heat treatment hereafter exhibited high catalytic activity and selectivity for CO oxidation in air and CO selective oxidation in the presence of H2. With calcination temperature rising, both activity and selectivity decreased. X-ray Photoelectron Spectra (XPS) indicated that Au existed as Au0 and Au+ in the catalyst without heat treatment and even after being calcined at 200 ℃, while after being calcined at 400 ℃, Au existed as Au0 completely. X-ray Diffraction (XRD) and High Resolution Transmission Electron Microscopic (HRTEM) investigations indicated that both the supports and Au species were highly dispersed as nano or sub-nano particles even after being calcined at 200 ℃, but after being calcined at 400 ℃ the supports transformed to crystal Fe2O3 with typical diameter of 30 nm and Au species aggregated to nano-particles with typical diameter of 2–4 nm. HRTEM investigations also suggested that the supports calcined at 200 ℃ were composed of amorphous ferric hydroxide and crystal ferric oxide. Results of computer simulation (CS) showed that O2 was adsorbed on Au crystal cell and then were activated, which should be the key factor for the subsequent reaction. It also suggested that O2 species were more easily adsorbed on Au+ than on Au0, indicating that higher positive charge of the Au species possessed the higher activity for CO oxidation.

          Keywords: Gold catalyst; CO selective oxidation; Preparation; Uncalcined; Low-temperature

          ★★★☆☆ Qiao BT,Zhang J,Liu LQ,et al. Low-temperature Prepared Highly Effective Ferric Hydroxide Supported Gold Catalysts For Carbon Monoxide Selective Oxidation In The Presence Of Hydrogen[J]. Applied Catalysis A: General,2008,340:220-228.

          張娟 / 鄧友全
          554.06 KB

          1-Ethyl-3-methylimidazolium dicyanamide EMImN(CN)2 and S-ethyltetrahydrothiophene dicyanamide EThN(CN)2 physically confined into mesoporous silica gel with pore sizes of 6–8 nm (IL-sg) were synthesized according to a proper sol–gel process. Greatly enhanced fluorescence emissions of dicyanamide based ILs after being confined were exhibited.

          ★★★☆☆ Zhang J,Zhang QH,Shi F,et al. Greatly Enhanced Fluorescence Of Dicyanamide Anion Based Ionic Liquids Confined Into Mesoporous Silica Gel[J]. Chemical Physics Letters,2008,461:229-234.

          張宏哲 / 鄧友全
          607.63 KB

          The non-phosgene carbonylation of 1,6-hexamethylenediamine (HDA) with alkyl carbamates using Y(NO3)3·6H2O as a catalyst and the influence of reaction variables on the yields of dialkyl hexamethylenedicarbamate (HDC) were studied. At 453K and in the presence of 5 wt.% Y(NO3)3·6H2O, nearly 100% HDA conversion and 85% dibutyl hexamethylenedicarbamate (BHDC) isolated yield could be achieved when butyl carbamate (BC) was employed as a carbonyl source. During reaction, an induction periodwas observed, but it almost disappeared by pretreating the catalyst with n-butanol. The FT-IR, X-ray diffraction (XRD) and X-ray photoelectron spectroscopy (XPS) characterizations of the catalyst showed that some transformation occurred when the catalyst was pretreated with n-butanol or employed during reaction, i.e., part decomposition of Y(NO3)3 to Y2O3, conversion from crystal to amorphous state, changes occurring in chemical state of the active species, as well as some subtle interactions between the catalyst and n-butanol. All these observed changes might be the reason resulting in activation of the catalyst.

          Keywords: Green chemistry; Alkyl carbamate; Dialkyl hexamethylenedicarbamate; 1,6-Hexamethylenediamine; Non-phosgene

          ★★★☆☆ Zhang HZ,Guo XG,Zhang QH,et al. Synthesis Of Dialkyl Hexamethylenedicarbamate From 1,6-hexamethylenediamine And Alkyl Carbamate Over Y(no3)3·6h2o Catalyst[J]. Journal Of Molecular Catalysis A: Chemical,2008,296:36-41.

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