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.

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.

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.

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.

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.

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.

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.

Microwave enhanced syntheses of 9-boronobenzyladenine derivatives by the reaction of adenine with the corresponding bromomethylphenylboric acid were reported. Microwave irradiation reduced the overnight reaction time of conventional thermal methods to 10 min, provided the desired products and increased the yields up to three times. Preliminary in vitro pharmacological tests were also described.

Keywords: 9-boronobenzyladenines, anti-inflammatory, antitumor, microwave-asisted synthesis

★★★☆☆ Yu XJ,Liu W,Hu WD,et al. Microwave Assisted Synthesis And Biological Activities Of 9-boronobenzyladenine Derivatives[J]. Journal Of Chemical Research,2007:347-349.

A series of ionic liquids (ILs) based on nitrile-functionalized imidazolium, pyridinium, and quaternary ammonium as cations and chlorides and tetrafluoroborate, hexafluorophosphate, dicyanamide, and bis- (trifluoromethanesulfonyl)imide as anions have been prepared and characterized. The physicochemical properties such as spectroscopic, thermal, solubility, surface, electrochemical, tribological, and toxic properties were comparatively studied. The results showed that the incorporation of a CN group to cations could result in remarkable changes in these properties. The reason resulting in such remarkable differences in the properties may be attributed to the conformational changes in the imidazolium groups caused by the interaction between the CN group with other neighboring cations or anions and the enhancement in hydrogen-bonding interactions due to the incorporation of a CN group.

★★★☆☆ Zhang QH,Li ZP,Zhang J,et al. Physicochemical Properties Of Nitrile-functionalized Ionic Liquids[J]. J. Phys. Chem. B,2007,111(11):2864-2872.

A novel series of ionic liquids (ILs) based on N-alkyl- -caprolactam as cations [Cn-CP]+ (Cn ) alkyl with different numbers of C atoms; n ) 6, 8, 10, 12, 16, or 18) containing toluene-p-sulfonate [TS]- and methanesulfonate [MS]- as anions have been synthesized via a one-step atom-economic reaction. Characterizations of these ILs by differential scanning calorimetry, polarizing optical microscopy, variabletemperature powder X-ray diffraction, etc., were conducted. The results showed that the caprolactambased ILs (n≥8) were enantiotropic thermotropic liquid crystals, except for C18-CPMS (monotropic), and displayed smectic A phases. Some properties, such as higher transition enthalpies (e.g., ΔH=83.1 kJ/mol for C18-CPTS), higher specific heat capacities (e.g., Cp=2.85 J/g·K for C16-CPTS) and higher heat storage densities (e.g., sensible heat storage density Es=262.8l MJ/m3 for C16-CPTS; latent heat storage density El=146.0 MJ/m3 for C18-CPTS), were observed. Fluorescence measurements showed that the homologous Cn-CPTS ILs exhibited strong fluorescence behavior. Finally, the test of acute toxicity toward rats showed that these new ILs were less toxic than the popular [BMIm]BF4 IL.

★★★★☆ Yang J,Zhang QH,Zhu LY,et al. Novel Ionic Liquid Crystals Based On N-alkylcaprolactam As Cations[J]. Chem. Mater.,2007,19:2544-2550.