离子液体与树脂催化合成醋酸正丁酯的动力学比较

以阳离子交换树脂AMBERLYST15和各种离子液体为催化剂,研究了醋酸和正丁醇反应生成醋酸正丁酯的动力学。实验测定了催化剂种类、反应温度和催化剂量对反应速率的影响,并用拟均相模型对实验数据拟合。在实验条件下,发现AMBERLYST15和己内酰胺四氟硼酸盐催化效率很高,表观活化能分别为36.69,37.06kJ/g,指前因子分别为120.0,61.50m3/(g.h)。结果表明,树脂AMBERLYST15和己内酰胺四氟硼酸盐离子液体二类催化反应的活化能相近,指前因子却相差很大,2种催化剂在相同的催化机理下有不同的催化效率。     

丝素蛋白在离子液体中的溶解特性研究

文章以离子液体为溶剂,研究了丝素蛋白在离子液体中的溶解特性。首先研究了丝素蛋白在不同结构的离子液体1-烯丙基-3-甲基咪唑氯化物（[AMIM]C1）和1-丁基-3_-甲基咪唑氯化物（[BMIM]c1）中的溶解速率和溶解度。结果发现,相同条件下,丝素蛋白在[AMIM]cl中具有较快的溶解速率和较大的溶解度;随温度的升高,溶解速度加快,合适的温度为95～105℃;随着丝素蛋白浓度的增大,相同条件下丝素蛋白在离子液体中的溶解速度减慢。XRD结果表明,丝素蛋白的非晶相部分首先被溶解,晶相部分结构被破坏后与溶剂作用逐渐被溶解。采用粘度法测定了丝素蛋白分子质量随溶解时间和温度的变化,结果表明：随加热时间增加和温度升高,蛋白质分子质量减小。为保证丝素蛋白的稳定性和溶解速率,温度一般控制在100℃以下,溶解时间小于5h。     

Effect of various phenol additives on viscosity of SRC blends

Coal-derived liquids are susceptible to oxidative degradation. Two different weight ratios of SRC-I/SRC-II blends, with or without phenol derivatives, have been subjected to accelerated ageing studies. Viscosity, infrared, elemental analysis, molecular weight determination, and solvent analysis are used to examine the properties of the degradation products. On ageing, there is a large increase in the amount of toluene-insoluble material, decrease in oil components, and a relatively constant amount of asphaltenes. The oxygen content increases in the aged toluene-insoluble and asphaltene fractions, and a new absorption at ≈1700 cm^?1 (the C = 0 group) appears in these two fractions only. On the addition of phenol itself and the less hindered phenol derivatives, the original hydrogen-bonding between the acidic and basic fuctional groups in the coal liquids is apparently disrupted because the added phenol can now interact with the proton-accepting species in the liquids, thus leading to a lower viscosity. This does not mean that the unhindered phenols retard the rate of ageing. The original hydrogen-bonding in the coal-derived liquid now gives way to a new hydrogen-bonding, and ageing occurs with the latter. The more hindered phenol derivatives are not as effective as phenol in disrupting the original hydrogen-bonding in the coal-derived liquids.     

A Model for the Estimation of Viscosity of Pure Hydrocarbon Liquids

 

A simple model is developed for the estimation of viscosity of hydrocarbon liquids considering that drag on molecular motion due to thermal energy is balanced by intermolecular attractions. The model equation is validated with National Institute of Standards and Technology data on hydrocarbon liquids (C₃-C₁₀ and C₁₂) considering the effect of molecular shape on drag force. The molecular shape is correlated well with molecular weight of hydrocarbon liquids. The accuracy of the proposed model equation is compared with the correlation. The result showed that the proposed model is more accurate. The proposed model equation predicts the viscosity over a wide range of temperature for C₃-C₂₅ with overall absolute average deviation of 5.13%.     

Low temperature ionothermal synthesis of TiO2 nanomaterials for efficient photocatalytic H2 production,dye degradation and photoluminescence studies

The photocatalytic hydrogen generation is a novel, eco-friendly and favourable method for production of green and clean energy using light energy. In this direction, we report low-temperature ionothermal method for the preparation of TiO₂ nanoparticles (NPs) using methoxy ethyl methyl imidazolium tris (pentafluoroethyl) trifluoro phosphate (MOEMINtf₂) as an ionic liquid (IL) at 120°C for 1 day. The synthesized nanomaterials were examined using different spectrochemical methods like UV-DRS, XRD, FT-IR, TEM, BET and TGA-DTA techniques. The mixed phase TiO₂ is obtained with 81.7% of anatase and 18.3% of rutile phase by the XRD studies, and average crystallite size is found to be ∼7 nm. The stretching of Ti-O bond (∼555 cm⁻¹) and few other bands related to ionic liquid were confirmed by FTIR spectrum. The band gap energy was observed to be ∼3.38 eV by UV-DRS analysis. TEM images reveal spherical shape with an average particles size of about 10 nm. Photocatalytic H₂ generation was carried out using TiO₂ NPs and observed the generation of 553 μmol h⁻¹ g⁻¹ via water splitting reaction. Furthermore, the prepared TiO₂ NPs employed for the photocatalytic degradation of methylene blue dye (84.54%), and photoluminescence studies confirms the obtained material can be used in optoelectronic applications with green emission.     

Forced convective heat transfer between assemblages of spherical particles and power‐law non‐Newtonian liquids with velocity slip at the interface

Heat transfer from spheres can be influenced by a varying degree of slip at the fluid‐particle interface along with the rheology of the surrounding continuous liquid and adjacent spheres. Thus in this study, the effects of dimensionless velocity slip parameter (λ) along with power‐law fluid rheology and other pertinent kinematic flow and heat transfer parameters on isotherm contours, local and average Nusselt numbers of assemblages of spherical slip particles are presented. This is done by adopting a segregated approach where dimensionless momentum and energy equations are solved by SMAC algorithm formulated in spherical coordinates within the finite difference formulation. Before obtaining new results, grid independence studies for either extreme values of power‐law consistency index of non‐Newtonian fluids are carried out. Finally, the major contribution of this study is the development of a correlative equation for the average Nusselt number of assemblages of spherical slip particles in power‐law fluids based on the present results (5880 data points) as a function of pertinent dimensionless parameters.     

Comparison of nitrogen bases generated via HCl precipitation and ion exchange chromatography

Nitrogen base fractions were prepared from a heavy coal-derived liquid via two commonly accepted laboratory procedures and partially characterized. Significant differences in the composition of the two fractions suggest strongly that extreme caution should be exercised in interpreting and comparing the results of base characterization studies in which different base isolation procedures are used.     

Chemical diffusion in bulk glass-forming Pd40Cu30Ni10P20 melts

Interdiffusion and self-diffusion of bulk metallic glass-forming Pd–Cu–Ni–P alloys have been investigated above the liquidus temperature at 993 K by the long-capillary method. Good agreement between the calculated partial mixing enthalpies and observed uphill-diffusion was found. The flow direction of uphill-diffusing elements is towards regions with the highest negative heat of mixing.     

Imidazolium‐functionalized norbornene ionic liquid block copolymer and silica composite electrolyte membranes for lithium‐ion batteries

Imidazolium‐functionalized norbornene and benzene‐functionalized norbornene were synthesized and copolymerized via ring‐opening metathesis polymerization to afford a polymeric ionic liquid (PIL) block copolymers {5‐norbornene‐2‐methyl benzoate‐block ‐5‐norbornene‐2‐carboxylate‐1‐hexyl‐3‐methyl imidazolium bis[(trifluoromethyl)sulfonyl]amide [P(NPh‐b ‐NIm‐TFSI)]} with good thermal stability. On this basis, the solid electrolyte, P(NPh‐b ‐NIm‐TFSI)–lithium bis(trifluoromethanesulfonyl)imide (LiTFSI), through blending with LiTFSI, and the nanosilica composite electrolyte, P(NPh‐b ‐NIm‐TFSI)–LiTFSI–SiO₂, through blending with LiTFSI and nanosilica, were prepared. The effects of the PILs and silica compositions on the properties, morphology, and ionic conductivity were investigated. The ionic conductivity was enhanced by an order of magnitude compared to that of polyelectrolytes with lower PIL compositions. In addition, the ionic conductivity of the nanosilica composite polyelectrolyte was obviously improved compared with that of the P(NPh‐b ‐NIm‐TFSI)–LiTFSI polyelectrolyte and increased progressively up to a maximum with increasing silica content when SiO₂ was 10 wt % or lower. The best conductivity of the P(NPh‐b ‐NIm‐TFSI)–20 wt % LiTFSI–10 wt % SiO₂ composite electrolyte with 7.7 × 10^?5 S/cm at 25 °C and 1.3 × 10^?3 S/cm at 100 °C were obtained, respectively. All of the polyelectrolytes exhibited suitable electrochemical stability windows. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134 , 44884.     

Hydrogen bioelectrooxidation in ionic liquids: From cytochrome c3 redox behavior to hydrogenase activity

Electrochemistry of polyheme bacterial cytochrome c₃ and catalytic oxidation of hydrogen by two different bacterial [NiFe] hydrogenases were investigated for the first time in pure room-temperature ionic liquids (RTILs) as electrolyte. Direct electrochemical response of Desulfovibrio vulgaris Hildenborough cytochrome c₃ (DvH cytc₃) adsorbed at a pyrolytic graphite (PG) electrode was observed in the RTILs used in this work: 1-butyl-3-methylimidazolium tetrafluoroborate (BmimBF4), 1-ethyl-3-methylimidazolium tetrafluoroborate (EmimBF4) and 1-ethyl-3-methylimidazolium bis(trifluoromethanesulfonyl)imide (EmimNTf2). The electrochemical signal differed however from that obtained in aqueous buffer, and depended on the type of RTIL. UV–vis measurements as well as transfer experiments from aqueous buffer to RTILs or RTILs to aqueous buffer strongly suggested that the protein was not denatured in the presence of RTILs. EmimNTf2, as a hydrophobic non-water-miscible RTIL, was demonstrated to stabilize the native form of DvH cytc₃. Moreover it allowed an amount of electroactive DvH cytc₃ 30-fold higher than observed in aqueous buffer. Catalytic oxidation of H₂ via Desulfovibrio fructosovorans [NiFe] hydrogenase (Df Hase) mediated by DvH cytc₃ failed however. Further investigation suggested that Df Hase could be inhibited in the presence of RTILs. Reasons for such an inhibition were explored, including the blocking up of the substrate channels. By using hyperthermophilic [NiFe] membrane-bound hydrogenase from Aquifex aeolicus (Aa Hase) an efficient direct catalytic oxidation process was obtained in mixed aqueous buffer/RTILs electrolytes, although direct H₂ oxidation was not observed in pure RTIL. Chronoamperometric experiments showed that Aa Hase could afford 80% RTILs in aqueous buffer, thus giving the opportunity of future electrolytes with uncommon and variable properties for biofuel cell design.