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郭晓光 / 邓友全
274.37 KB

A series of catalysts (e.g. FeCl3, Zn(OAc)2, Pb(NO3)2, etc.) were tested for the trans-esterification reaction of 1,6-hexamethylenediamine (HDA) with methyl carbamate (MC), ethyl carbamate (EC), and butyl car-bamate (BC) to afford dialkyl hexamethylene-1,6-dicarbamate (AHDC). By applying the optimized condi-tion, 100% conversion of HDA and 93% yield to diethyl hexamethylene-1,6-dicarbamate (EHDC) could be obtained using FeCl3 as catalyst. The desired products could be precipitated by adding water into the resulting mixture, and the activity of recovered catalyst could be maintained.

Keywords: Non-phosgene; Carbamate; Carbonylation; 1,6-Hexamethylenediamine; Isocyanate

★★★☆☆ Guo XG,Shang JP,Ma XY,et al. Synthesis Of Dialkyl Hexamethylene-1,6-dicarbamate From 1,6-hexamethylenediamine And Alkyl Carbamate Over Fecl3 As Catalyst[J]. Catalysis Communications,2009,10:1248-1251.

李作鹏 / 邓友全
1.94 MB

The in situ electropolymerized-polyaniline (PANI) film (thickness: 5–20 l m) on FTO (fluorine tin oxide) glass doped by various counterions SO2-4, ClO-4 ,BF-4,Cl-, p-toluenesulfonate (TsO-), etc. was prepared with electropolymerized charge capacity of 50–600 mC cm-2. Different doping counterions have great impact on the morphology, electrochemical activity of electropolymerized-PANI film. The electropoly-merized-PANI doped by SO24 anion (PANI-SO4) film with much porous morphology and pore size diam-eter of several micrometers possesses higher reduction current for reduction of I-3 and a low charge-transfer resistance of 1.3 Ω cm2 in comparison with Pt as counter electrode (CE). Dye-sensitized solar cell with PANI-SO4 as CE was assembled, and the device under full sunlight illumination (100 mW cm-2,AM1.5 G) shows 5.6% photovoltaic conversion efficiency, which is comparable to 6.0% of that with Pt CE under the same experimental condition.

Keywords: Dye-sensitized solar cell; Polyaniline; Electropolymerization; Counter electrode

★★★★☆ Li ZP,Ye BX,Hu XD,et al. Facile Electropolymerized-pani As Counter Electrode For Low Cost Dye-sensitized Solar Cell[J]. Electrochemistry Communications,2009,11:1768-1771.

374.62 KB

★★★★☆ Li XL,Ma XY,Shi F,et al. Hydrogen Generation From Formic Acid Decomposition With A Ruthenium Catalyst Promoted By Functionalized Ionic Liquids[J]. Chem.sus.chem.,2010, 3, 71–74.

328.16 KB

★★★★★ Shi F,Man Kin Tes,Cui XJ,et al. Copper-catalyzed Alkylation Of Sulfonamides With Alcohols[J]. Angew. Chem. Int. Ed.,2009,48:5912-5915.

283.07 KB

The N-alkylation of sulfonamides with alcohols is efficiently performed in the presence of easily available copper catalysts via hydrogen borrowing methodology. Applying a copper acetate/potassium carbonate system the reaction of sulfon-ACHTUNGTRENUNGamides and alcohols gave the corresponding secondary amines in excellent yield. In situ HR-MS analysis indicated that bissulfonylated amines are formed under air atmosphere, which act as self-stabilizing ligands for the catalytic system. UV-visible measurements suggest the interaction between the copper centre and the bissulfonylated amine. Reactions of benzyl alcohol-d7 with p-toluenesulfonamide, Nbenzyl-p-toluenesulfonamide or N-benzylidenetolu-ACHTUNGTRENUNGenesulfonamide revealed that the reaction proceeds via a transfer hydrogenation mechanism and the whole process is micro-reversible. Competitive reactions of benzyl alcohol and benzyl alcohol-d7 with ptoluenesulfonamide revealed a kinetic isotope effect (kH/kD) of 3.287 (0.192) for the dehydrogenation of benzyl alcohol and 0.611 (0.033) for the hydrogenation of the N-benzylidene-p-toluACHTUNGTRENUNGenesulfonamide intermediate, which suggests that dehydrogenation of the alcohol is the rate-determining step.

Keywords: alcohols; alkylation; CN bond formation; copper catalysts; sulfonamides

★★★☆☆ Cui XJ,Shi F,Man Kin Tes,et al. Copper-catalyzed N-alkylation Of Sulfonamides With Benzylic Alcohols: Catalysis And Mechanistic Studies[J]. Adv. Synth. Catal.,2009,351:2949-2958.

乔波涛 / 邓友全
469.31 KB

Ferric hydroxide supported Pd catalyst prepared by a simple co-precipitation method without calcinations at elevated temperatures and only reduced at 50◦C possessed unexpectedly higher activity for CO oxidations even compared with that of supported Au catalysts. XRD and TEM results showed that the support was mixture of Fe(OH)x and Fe3 O4 and Pd was highly dispersed on it. XPS results showed that Pd existed as mixture of oxidation and metal state. The large amount of OH group on the supports may play an important role in O adsorption and activation.

Keywords: Gold; Palladium; CO oxidations; Ferric hydroxide; Low temperature

★★★☆☆ Qiao BT,Liu LQ,Zhang J,et al. Preparation Of Highly Effective Ferric Hydroxide Supported Noble Metal Catalysts For Co Oxidations: From Gold To Palladium[J]. Journal Of Catalysis,2009,261:241-244.

张庆华 / 邓友全
462.03 KB

A new series of ionic liquids composed of three cyclic sulfonium cations and four anions has been synthesized and characterized. Their physicochemical properties, including their spectroscopic characteristics, ion cluster behavior, surface properties, phase transitions, thermal stability, density, viscosity, refractive index, tribological properties, ion conductivity, and electrochemical window have been comprehensively studied. Eight of these salts are liquids at room temperature, at which some salts based on [NO3] and [NTf2] ions exhibit organic plastic crystal behaviors, and all the saccharinbased salts display relatively high refractive indices (1.442–1.594). In addition, some ionic liquids with the [NTf2] ion exhibit peculiar spectroscopic characteristics in FTIR and UV/Vis regions, whilst those salts based on the [DCA] ion show lower viscosities (34.2–62.6 mPas at 20℃) and much higher conductivities (7.6–17.6 mScm-1 at 20℃) than most traditional 1,3-di-ACHTUNGTRENUNGalkylimidazolium salts.

Keywords: electrochemistry · ionic liquids · performance · physicochemical properties · sulfonium ions

★★★★☆ Zhang QH,Liu SM,Li ZP,et al. Novel Cyclic Sulfonium-based Ionic Liquids: Synthesis, Characterization, And Physicochemical Properties[J]. Chem. Eur. J.,2009,15:765-778.

刘乐全 / 邓友全
523.44 KB

Chemoselective hydrogenation of aromatic nitro compounds were first efficiently achieved over Au/Fe(OH)x at 100–120 1C for 1.5–6 h (depending on different substrates) in the presence of CO and H2O.

★★★★☆ Liu LQ,Qiao BT,Chen ZJ,et al. Novel Chemoselective Hydrogenation Of Aromatic Nitro Compounds Over Ferric Hydroxide Supported Nanocluster Gold In The Presence Of Co And H2o[J]. Chemical Communications,2009:653-655.

朱来英 / 邓友全
406.22 KB

本文合成了一系列聚乙烯醇担载离子液体薄膜,并进行了FT-IR, SEM以及DSC表征.通过对模拟汽油脱硫性能的初步研究发现,这一类薄膜对于较低硫含量的体系具有较好的脱硫性能.

★★☆☆☆ 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.

刘乐全 / 邓友全
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.