Efficient Synthesis of Dimethyl Ether from Methanol in a Bifunctional Zeolite Membrane Reactor

A sandwich FAU–LTA zeolite dual‐layer membrane has been developed and used as a catalytic membrane reactor for the synthesis of dimethyl ether (DME). In the top H‐FAU layer with mild acidity, methanol is dehydrated to DME. The other reaction product, water, is removed in situ through a hydrophilic Na‐LTA layer, which is located between the porous alumina support and the H‐FAU top layer. The combination of mild acidity with the continuous removal of water results in high methanol conversion (90.9 % at 310 °C) and essentially 100 % DME selectivity. Furthermore, owing to the selective and continuous removal of water through the Na‐LTA membrane, catalyst deactivation can be effectively suppressed.     

Synthesis of a Ferrolite: A Zeolitic All‐Iron Framework

Crystals of the first sodalite‐type zeolite containing an all‐iron framework, a ferrolite, Ba₈(Fe₁₂O₂₄)Na_y(OH)₆?x H₂O, were synthesized using the hydroflux method in nearly quantitative yield. Ba₈(Fe₁₂O₂₄)Na_y(OH)₆?x H₂O crystallizes in the cubic space group with a=10.0476(1) Å. Slightly distorted FeO₄ tetrahedra are linked to form Fe₄O₄ and Fe₆O₆ rings, which in turn yield channels and internal cavities that are characteristic of the sodalite structure. Barium, sodium, and hydroxide ions and water molecules are found in the channels and provide charge balance. Magnetic measurements indicate that the ferrolite exhibits magnetic order up to at least 700 K, with the field‐cooled and zero‐field‐cooled curves diverging. Analysis of the ⁵⁷Fe Mössbauer spectra revealed two spectral components that have equal spectral areas, indicating the presence of two subsets of iron centers in the structure. Dehydrated versions of the ferrolite were also prepared by heating the sample.     

Template–Framework Interactions in Tetraethylammonium‐Directed Zeolite Synthesis

Zeolites, having widespread applications in chemical industries, are often synthesized using organic templates. These can be cost‐prohibitive, motivating investigations into their role in promoting crystallization. Herein, the relationship between framework structure, chemical composition, synthesis conditions and the conformation of the occluded, economical template tetraethylammonium (TEA⁺) has been systematically examined by experimental and computational means. The results show two distinct regimes of occluded conformer tendencies: 1) In frameworks with a large stabilization energy difference, only a single conformer was found (BEA, LTA and MFI). 2) In the frameworks with small stabilization energy differences (AEI, AFI, CHA and MOR), less than the interconversion of TEA⁺ in solution, a heteroatom‐dependent (Al, B, Co, Mn, Ti, Zn) distribution of conformers was observed. These findings demonstrate that host–guest chemistry principles, including electrostatic interactions and coordination chemistry, are as important as ideal pore‐filling.     

Carbon nanotube composite coated platinum electrode for detection of Cr(III) in real samples

This paper demonstrates the application of composite multi-walled carbon nanotube (MWNT) polyvinylchloride (MWNT-PVC) based on 1,5-diphenylcarbazide as chromium ionophore in potentiometric measurement. The sensor shows a good Nernstian slope of 19.52 ± 0.40 mV/decade in a wide linear range concentration of 6.3 × 10⁻⁸ to 1.0 × 10⁻² M for Cr(NO₃)₃. The detection limit of this electrode was found to be 3.2 × 10⁻⁸ M of Cr(NO₃)₃ and is applicable in a pH range of 3.0-6.8. It has a short response time of about 10 s. This chromium electrode has a good selectivity over 16 various metal ions. The practical analytical utility of this electrode was demonstrated by measurement of Cr(III) in drinking water and mineral water samples without any serious preliminary pre-treatment and chromium in multivitamin.     

Optimization of the process variables for the synthesis of cardanol-based novolac-type phenolic resin using response surface methodology

Models capable of predicting the maximum extent of conversion (p) of cardanol-based novolac-type phenolic resin, have been developed using response surface methodology to determine the optimum reaction conditions. Three-dimensional response surface and their contour plot were drawn. The maximum extent of conversion (98.93%) was predicted when the cardanol was condensed with formaldehyde (molar ratio 1:0.652) at 119.84 °C for a time period of 3 h with the catalyst (e.g., citric acid) concentration of 1.988% of total volume of cardanol and formaldehyde. The pH of the reaction mixture was maintained at 3.0. These predicted values for optimum process conditions were in good agreement with experimental data.     

Electrochemical sensors for the simultaneous determination of zinc,cadmium and lead using a Nafion/ionic liquid/graphene composite modified screen-printed carbon electrode

A simple, low cost, and highly sensitive electrochemical sensor, based on a Nafion/ionic liquid/graphene composite modified screen-printed carbon electrode (N/IL/G/SPCE) was developed to determine zinc (Zn(II)), cadmium (Cd(II)), and lead (Pb(II)) simultaneously. This disposable electrode shows excellent conductivity and fast electron transfer kinetics. By in situ plating with a bismuth film (BiF), the developed electrode exhibited well-defined and separate peaks for Zn(II), Cd(II), and Pb(II) by square wave anodic stripping voltammetry (SWASV). Analytical characteristics of the BiF/N/IL/G/SPCE were explored with calibration curves which were found to be linear for Zn(II), Cd(II), and Pb(II) concentrations over the range from 0.1 to 100.0 ng L⁻¹. With an accumulation period of 120 s detection limits of 0.09 ng mL⁻¹, 0.06 ng L⁻¹ and 0.08 ng L⁻¹ were obtained for Zn(II), Cd(II) and Pb(II), respectively using the BiF/N/IL/G/SPCE sensor, calculated as 3σ value of the blank. In addition, the developed electrode displayed a good repeatability and reproducibility. The interference from other common ions associated with Zn(II), Cd(II) and Pb(II) detection could be effectively avoided. Finally, the proposed analytical procedure was applied to detect the trace metal ions in drinking water samples with satisfactory results which demonstrates the suitability of the BiF/N/IL/G/SPCE to detect heavy metals in water samples and the results agreed well with those obtained by inductively coupled plasma mass spectrometry.     

负载型Pt/CeO_2-Al_2O_3催化剂的制备及其脱氢性能

通过超声辅助共沉淀法制备了具有高比表面积、大孔容和大孔径的CeO_2-Al_2O_3复合载体,并以此制备了一系列负载型Pt/CeO_2-Al_2O_3催化剂,采用XRD、氮吸附、NH3-TPD、SEM和TEM等方法对复合载体和催化剂进行了表征;以甲基环己烷为模型化合物,考察了Pt/CeO_2-Al_2O_3催化剂的脱氢性能,研究了载体中Ce/Al物质的量比及反应温度对其催化脱氢性能的影响。结果表明,当Ce/Al物质的量比为0.5时,Pt/CeO_2-Al_2O_3催化剂在450℃下具有较高的脱氢性能;甲基环己烷转化率达到88.53%,甲苯的选择性达94.63%。     

Structure and tribological properties of Cu–PU–PTFE composite coatings prepared by low‐energy electron beam dispersion with glow discharge

Polytetrafluoroethylene (PTFE) composite coatings doped copper acetate and polyurethane (PU) were prepared on rubber substrate by low‐energy electron beam dispersion technique. The effects of dopant and glow discharge treatment on the surface morphology, structure and tribological properties of the coatings were investigated. The results showed that Cu–PTFE composite coatings form uniform surface and dense column structure with spherical aggregations under glow discharge treatment. PU coating shows the large size of protuberance structure but PU–PTFE coating presents spherical structure. Both of the coatings become relative dense and smooth after discharge treatment, and Cu–PU–PTFE composite coatings possess a smoother surface and lower polar component of surface energy. Cu doping weakens the crystallinity and ordering degree of composite coatings, but glow discharge increases the ordering degree and branched structure of C―H groups. Friction experiment indicated that Cu fails to improve the wear resistance of PTFE coatings but glow discharge treatment can do it. Cu–PU–PTFE coatings after discharge treatment have the higher wear resistance and lower coefficient of friction. Copyright © 2016 John Wiley & Sons, Ltd.     

天然高分子复合羟基磷灰石材料的制备与应用

羟基磷灰石(HA)是人类与动物骨骼中主要无机物组成成分,因其具有良好的生物相容性、生物活性和骨传导作用,作为新型合成生物材料已应用于骨组织的修复与替代技术。本文在介绍HA主要制备方法(如:沉淀法、乳液法、水热反应法、溶胶-凝胶法、机械化学法、固态合成法、水解法、超声化学法、热解法、模板法和电沉积法等)和应用的基础上,重点综述了各类天然高分子与HA复合材料的制备及应用研究进展。天然高分子,如:纤维素、淀粉、甲壳素、壳聚糖、蛋白(包括胶原蛋白、明胶、角蛋白、丝蛋白和植物蛋白)等,与HA复合后制备的天然高分子复合羟基磷灰石材料,在保持其生物相容性的同时,又能改善复合材料的机械性能与生物活性,使其可用于医用材料、载体材料和吸附分离材料。最后,本文指出为了满足生物体内的特殊环境(如强的韧性、与骨生长速度匹配性能等)及不同领域的要求,天然高分子复合HA材料需要发展的方向。     

锂硫电池用多孔碳/硫复合正极材料的研究

锂硫电池具有高的理论比容量和理论能量密度,被认为是当前最有前景的二次电池体系之一。现阶段锂硫电池的研究工作主要集中于高性能硫正极材料的设计与合成。具有优良的导电性、良好的结构稳定性和多孔结构的纳米碳材料,比如活性碳、介孔碳、超小微孔碳、多级结构多孔碳、空心碳球和空心碳纤维,充分满足了锂硫电池正极材料对碳基体的要求。本文综述了近年来多孔碳/硫复合材料作为硫正极的研究进展。总结了以具有不同结构特征的多孔碳基体负载硫组装的锂硫电池的电化学性能,并分析了不同多孔结构对性能的影响。最后在此基础上,从多孔碳/硫复合正极材料的设计和合成的角度,展望了其未来的发展趋势。