微生物发酵诱导多孔材料: 制备方法和应用

微生物发酵作为一种新的制备多孔材料的方式, 将微生物发酵工程与发泡工程有机结合起来, 克服了传统制备方法需要特殊设备、 操作复杂、 后处理繁琐、 化学药品污染和成本昂贵等缺点, 受到了广泛关注.本文基于微生物发酵多孔材料的研究, 围绕多孔材料的定义和多孔水凝胶的分类及制备方式进行总结.针对微生物发酵诱导制备多孔材料的制备方法, 综合评述了该方法在染料吸附、 海水蒸发脱盐、 电磁屏蔽以及制备新型功能性生物材料等方面的应用.最后, 对微生物诱导制备多孔材料的未来发展进行了展望.     

高活性硫化铅电极的制备及在量子点敏化太阳能电池中的应用

为了提高量子点敏化纳晶薄膜太阳能电池的光电转换效率,我们通过连续在酸和多硫溶液中处理铅片制备了对多硫电解液具有高电催化活性的硫化铅电极.通过电化学阻抗谱测试评价所制备硫化铅电极的催化活性,从而确定制备高效硫化铅电极的最佳条件.以在最佳条件下制备的硫化铅为对电极、CdSe量子点敏化TiO2纳晶薄膜为工作电极和多硫电解液组装成量子点敏化太阳能电池.光电性能测试结果表明所制备的电极具有良好的催化活性和光电转换性能.与已报导的方法相比,新方法大幅度地减少制备过程所需的时间,但却提高了所制备的硫化铅对电极的催化活性.通过X射线衍射和扫描电镜测试表征了硫化铅的生成过程,探讨了催化活性提高的原因.     

PEMFC膜电极组件(MEA)制备方法的评述*

膜电极组件(MEA)是质子交换膜燃料电池的核心部件.本文在简述MEA结构的基础上,根据MEA制备过程中催化层支撑体不同,将目前已有的多种MEA制备方法分为两类制备模式:以GDL为支撑体和以PEM为支撑体的制备模式.文中对这些制备方法的特点进行了详细评述,对MEA制备方法的发展趋势进行了展望,认为以PEM为支撑体的制备模式是今后MEA制备的主要发展方向.     

催化裂解CH4制备碳纳米管的影响因素

以柠檬酸法制备的Fe-MgO、Co-MgO和Ni-MgO为催化剂,CH4为碳源气,H2为还原气,在873、973和1073 K制备出碳纳米管,通过TEM和拉曼光谱表征,讨论了催化剂、制备温度、反应时间等因素对碳纳米管形貌、产率和内部结构的影响.结果表明:不同的催化剂在相同的温度下制备的碳纳米管的形态和内部结构有很大的差异.其中Fe-MgO催化剂制备的碳纳米管管径粗,且大小不均匀,而Ni-MgO催化剂制备的碳纳米管管径较细、较均匀.碳纳米管的产率随着裂解温度的变化而改变.Fe-MgO催化剂制备碳纳米管的产率随制备温度的升高而提高,而Ni-MgO催化剂制备碳纳米管的产率随制备温度的升高而降低.Fe-MgO催化剂制备碳纳米管,在1073K甚至更高的制备温度才能达到其最高产率.Co-MgO催化剂制备碳纳米管的产率在973 K左右产率较高,而用Ni-MgO催化剂制备碳纳米管,则在873 K甚至更低的制备温度就能达到最高产率.反应时间与碳纳米管的产率不成正比,有一最佳反应时间,如Ni-MgO催化剂的最佳反应时间为2 h.     

Ce-Zr-La-Al2O3的制备及负载的单Pd三效催化剂

采用共沉淀和浸渍两种方法制备了Ce-Zr-La-Al2O3(CZLA),对其进行了N2吸附和X射线衍射分析.以CZLA为载体制备了2%Pd/CZLA三效催化剂,并对催化剂进行了程序升温还原和活性测试.结果表明,两种方法制备的CZLA均具有较好的结构、织构和储氧性能,共沉淀法制备的CZLA具有更好的抗老化性能.以CZLA为载体所制备的单Pd三效催化剂表现出低的起燃温度、优异的三效性能,特别是优异的转化NO性能及抗老化性能.     

基底表面构建单原子催化剂与催化性能研究进展

近年来,单原子催化剂因其较高的催化活性和选择性等优点而受到了人们的广泛关注.我们综述了以C, Si, Ti, Al为基底的单原子催化剂的制备方法,并对以不同材料基底制备单原子催化剂的制备方法、形成机理及优势特点进行了比较.通过对单原子制备、表征方法及催化活性的概述,以期对制备单原子催化剂提供一定的借鉴和指导.研究表明,单原子催化剂的制备已从贵金属单原子催化剂向过渡金属单原子催化剂进行了转变.单原子催化剂的基底也不再仅仅局限于单一的形式.这些转变为单原子催化剂向传统催化领域迈进提供了可能.我们同时也对单原子催化剂在工业上的应用进行了介绍.     

超临界CO2法制备头孢唑啉钠脂质体

采用超临界CO2(scCO2)流体代替有机溶剂一步法制备了头孢唑啉钠药物载体脂质体. 研究了该脂质体的尺寸、稳定性和药物的包封率. 结果表明, 脂质体的尺寸和稳定性依赖于制备压力, 脂质体对头孢唑啉钠的包封率与乙醇和脂浓度有关, 采用超临界CO2法制备脂质体的药物包封率比采用薄膜分散法(Bangham method)制备的包封率高.     

Y2O3:Er3+粒子的微波制备

采用微波法和溶胶-凝胶法制备了(Y2O3:Er3+)粒子. 微波法制备过程中烧结温度降低到600 ℃. 980 nm激光激发下得到550 和660 nm两个上转换发射带. 微波法制备的上转换材料得到了强的红光发射和弱的绿光发射, 溶胶-凝胶法制备的材料得到了强的绿色发射和弱的红光发射. 结果表明, 微波促进了S6对称性的形成, S6对称性促进了红光的发射.     

改进的微乳液聚合制备的聚甲基丙烯酸甲酯的力学和光学性能研究

研究了改进的微乳液聚合方法制备的聚甲基丙烯酸甲酯(PMMA)的力学和光学性能, 并与本体聚合制备的PMMA相比较. 研究结果表明, 由改进的微乳液聚合制备的PMMA具有较高的Tg和富间规度, 在较宽的温度范围内具有较高的力学模量. 此外, 它的拉伸强度、拉伸模量及断裂伸长率均比本体聚合制备的PMMA样品高. PMMA的折光率与制备方法关系不大, 但由改进的微乳液聚合制备的PMMA样品消光系数更小, 更加透明. 这说明由改进的微乳液聚合方法制备的PMMA具有更广泛的应用前景.     

高活性硫化铅电极的制备及在量子点敏化太阳能电池中的应用

为了提高量子点敏化纳晶薄膜太阳能电池的光电转换效率,我们通过连续在酸和多硫溶液中处理铅片制备了对多硫电解液具有高电催化活性的硫化铅电极. 通过电化学阻抗谱测试评价所制备硫化铅电极的催化活性,从而确定制备高效硫化铅电极的最佳条件. 以在最佳条件下制备的硫化铅为对电极、CdSe量子点敏化TiO₂纳晶薄膜为工作电极和多硫电解液组装成量子点敏化太阳能电池. 光电性能测试结果表明所制备的电极具有良好的催化活性和光电转换性能. 与已报导的方法相比,新方法大幅度地减少制备过程所需的时间,但却提高了所制备的硫化铅对电极的催化活性. 通过X射线衍射和扫描电镜测试表征了硫化铅的生成过程,探讨了催化活性提高的原因.     

Autowave cryopolymerization of epichlorohydrin initiated by brittle fracture of solid samples at 77 K

The autowave polymerization of preliminarily radiolyzed glassy epichlorohydrin at 77 K has been performed. The progressing wave of polymerization is initiated through the local brittle fracture of the sample. The velocity of propagation of the reaction wave front achieves 15 mm/s at a preliminary irradiation dose of 680 kGy. The progressing wave of polymerization is realized via the positive feedback between the chemical transformation in the solid and its brittle fracture because of temperature or density gradients arising in the course of reaction. The process proceeds according to the cationic mechanism via opening of the epoxide ring in epichlorohydrin.     

Effect of the structure of carboxylic acids on activation parameters for catalytic acidolysis of epichlorohydrin

We have studied the effect of temperature and the structure of the reagent on the rate of the reaction between 1-chloro-2,3-epoxypropane (epichlorohydrin) and aliphatic monocarboxylic acids in the presence of an ammonium salt: (3-chloro-2-hydroxypropyl)trimethylammonium chloride, obtained from trimethylammonium chloride and epichlorohydrin. We have done a correlation analysis of the effect of the substituent within the structure of the carboxylic acid and the temperature on the reaction rate. Using ab initio quantum chemical methods, we have estimated the structures and energy parameters of the transition states for the limiting step of the process, and have formulated hypotheses for the reaction mechanism.     

Modeling of the mechanism for the acidolysis of epichlorohydrin by aliphatic and aromatic carboxylic acids catalyzed by amines

A model was constructed for the mechanism of the reaction of aliphatic and aromatic carboxylic acids with epichlorohydrin catalyzed by tertiary amines. A mechanism for the catalysis of the transfer of the anion of the nucleophilic reagent by an ion pair was proposed taking account of the kinetic data and selected chemical and mathematical models.     

Perfectly alternating copolymerization of CO2 and epichlorohydrin using cobalt(III)-based catalyst systems

Selective transformations of carbon dioxide and epoxides into biodegradable polycarbonates by the alternating copolymerization of the two monomers represent some of the most well-studied and innovative technologies for potential large-scale utilization of carbon dioxide in chemical synthesis. For the most part, previous studies of these processes have focused on the use of aliphatic terminal epoxides or cyclohexene oxide derivatives, with only rare reports concerning the synthesis of CO(2) copolymers from epoxides containing electron-withdrawing groups such as styrene oxide. Herein we report the production of the CO(2) copolymer with more than 99% carbonate linkages from the coupling of CO(2) with epichlorohydrin, employing binary and bifunctional (salen)cobalt(III)-based catalyst systems. Comparative kinetic studies were performed via in situ infrared measurements as a function of temperature to assess the activation barriers for the production of cyclic carbonate versus copolymer involving two electronically different epoxides: epichlorohydrin and propylene oxide. The relative small activation energy difference between copolymer versus cyclic carbonate formation for the epichlorohydrin/CO(2) process (45.4 kJ/mol) accounts in part for the selective synthesis of copolymer to be more difficult in comparison with the propylene oxide/CO(2) case (53.5 kJ/mol). Direct observation of the propagating polymer-chain species from the binary (salen)CoX/MTBD (X = 2,4-dinitrophenoxide and MTBD = 7-methyl-1,5,7-triazabicyclo[4.4.0]dec-5-ene) catalyst system by means of electrospray ionization mass spectrometry confirmed the perfectly alternating nature of the copolymerization process. This observation in combination with control experiments suggests possible intermediates involving MTBD in the CO(2)/epichlorohydrin copolymerization process.     

Chemical Modification of Poly(epichlorohydrin) Using Montmorillonite Clay

Cationic ring opening polymerization of epichlorohydrin (1) and acetic anhydride in the presence of Maghnite- H (Mag-H＋) as a catalyst afforded, ω-diacetylated poly(epichlorohydrin) (P1) in a moderate yield and molecular weight without formation of side products and degradation. P1 was chemically modified with morpholine (2), piperidine (3) and pyrrolidine (4) into the corresponding new functional poly(epichlorohydrin)s (P2—P4) in a moderate reaction conversion . The conversion of P1 into P2—P4 was confirmed by using FTIR and NMR spectroscopy and the yield was calculated from the elemental analysis data according to the mole fraction concept. The obtained functional polymers were further characterized by thermal analysis which showed a substantial increase of the glass transition temperature (Tg). Thus, the chemical modification of α,ω-acetylated PECH using Mag-H＋ offers a simple method for obtaining functional polymers. Mag-H＋ is a montmorillonite sheet silicate clay exchanged with proton.     

Reaction of 2-chloroindole-3-carbaldehyde with epihalogenohydrins. Tandem oxirane-opening—1,3-oxazole-closure process

Reaction of 2-chloroindole-3-carbaldehyde with epibromohydrin gives the expected 1-(oxiran-2-ylmethyl) derivative. However the analogous reaction with epichlorohydrin leads to the formation of the oxazolo[3,2-a]indole skeleton. Some chemical properties of this tricyclic system were investigated. Its reaction with secondary amines unexpectedly proceeds with the opening of the oxazole ring.     

Synthesis and characterization of hyperbranched polymer with epoxide-terminated group and application as modifier for epoxy/polyamide system

Hyperbranched polymer with epoxide-terminated group was synthesized through end-capping reaction between hyperbranched polymer with hydroxyl-terminated group and epichlorohydrin. The chemical structure of the synthesized polymer was characterized by ATR-IR and ¹H NMR spectroscopy. The influence of hyperbranched polymer content on the mechanical properties and fracture toughness of epoxy/polyamide systems was investigated. The toughening mechanism was discussed basing on observing the fracture surface morphologies of epoxy/polyamide/ hyperbranched polymer system.     

多乙酰氧基硅烷与环氧氯丙烷的开环反应

本文详细地研究了在5-叔丁基呋喃甲酸铬的存在下,多乙酰氧基硅烷与环氧氯丙烷的开环反应及其产物。     

Macrophage activation in vitro by chemically cross-linked (1----3)-beta-D-glucans

The chemical cross-linking of soluble (1----3)-beta-D-glucans having molecular weights of 21000 (CL 3 h) and 6400 (CL 6 h), and laminarin (CL LAMI), which showed negligible biological activity, by epichlorohydrin provided rigid particles. These particles showed no gel-to-sol transition upon the addition of sodium hydroxide. We compared the effects of chemical cross-linking on the biological activities of glucans. The alternative complement pathway was not activated by any of the cross-linked glucans. Glucose consumption, lysosomal enzyme release, and interleukin-1 production by mouse resident peritoneal macrophages incubated in vitro were strongly induced by CL 3 h, CL 6 h and CL LAMI. However, cross-linked dextran, Sephadex, did not exhibit any of these biological activities. These results suggested that chemical cross-linking of (1----3)-beta-D-glucans enhances macrophage activities without opsonization by complement components.     

气相色谱法分析阳离子醚化剂中残存的环氧氯丙烷和1,3-二氯丙醇

建立了液体阳离子醚化剂中残存的环氧氯丙烷、1,3-二氯丙醇的气相色谱分析法。用苯甲酸甲酯萃取样品,对两组分都有很高的萃取率。选用HP-5 30　m毛细管柱,一次进样能同时测定两组分,两组分达到完全分离,且均在萃取剂前出峰,因而减少了峰扩散,提高了检测灵敏度。检测的线性范围:环氧氯丙烷5～590 mg/kg,1,3-二氯丙醇21～480 mg/kg;检测限:环氧氯丙烷1.2 mg/kg,1,3-二氯丙醇2.2 mg/kg;回收率：环氧氯丙烷95.93%～103.42%,相对标准偏差(RSD)2.4%～10.