一步碳化多孔有机材料制备多孔碳及其性能的研究

开发并利用清洁的、可再生的能源是解决环境污染问题和能源短缺的有效方法.碳化含碳量较高的多孔有机材料制备的多孔碳,具有较高的比表面积,良好的物化稳定性,优良的机械性能等优点,在清洁能源的存储、分离、能量的存储与转化领域有广泛的应用.常见的由多孔有机材料制备多孔碳的方法主要是非活化碳化法和活化碳化法.不同的制备方法得到的多孔碳形貌,孔结构各不形同.多孔碳材料自身的结构性质可以影响其应用.合理的设计并调控多孔碳的“孔”,发挥孔尺寸的“筛分效应”可以有效地对气体进行存储和分离.在锂电等能量转化领域,“限域效应”是影响锂电性能的重要因素.多孔碳材料中较小的孔可以限域活性成分,而较大的孔可以快速传输,两种孔的协同效应可以使锂电性能大大提升.本综述系统地归纳了一步碳化多孔有机材料制备多孔碳的方法及其优势,详细地介绍了其在气体吸附、存储、分离以及电化学等领域的应用.最后,结合多孔碳材料的研究现状,提出由多孔有机材料制备多孔碳材料所面临的挑战,同时也展望了多孔碳材料的应用前景.     

胡萝卜基多孔炭的制备及其电化学电容行为

以冷冻干燥获得的多孔胡萝卜为炭源,经过600℃氮气氛围下炭化和KOH活化,获得了多孔结构的炭材料。采用红外光谱、X-射线粉末衍射、扫描电镜、透射电镜、循环伏安、恒流充放电和交流阻抗对多孔炭进行了微结构和电容性能研究。结果表明:通过活化处理,多孔炭的比表面积从7m²·g^-1大幅提高到147m²·g^-1。而且,活化后的多孔炭产生了414F·g^-1的最大比电容,且电流增至4A·g^-1时的电容保持率为74.5%。而未活化的多孔炭最大电容为253F·g^-1,电容保持率仅为45.1%。此外,活化后的多孔炭还具有优异的电化学稳定性。在5A·g^-1电流下循环8000圈后,其电容保持率高达94%。活化后的多孔炭在电容性能方面的极大改善与其比表面积的大幅提高及介孔的增多有密切关系。     

胡萝卜基多孔炭的制备及其电化学电容行为研究

以冷冻干燥获得的多孔胡萝卜为炭源,经过600℃氮气氛围下炭化和KOH活化,获得了多孔结构的炭材料。采用红外光谱、X-射线粉末衍射、扫描电镜、透射电镜、循环伏安、恒流充放电和交流阻抗对多孔炭进行了微结构和电容性能研究。结果表明:通过活化处理,多孔炭的比表面积从7 m²·g^-1大幅提高到147 m²·g^-1。而且,活化后的多孔炭产生了414 F·g^-1的最大比电容,且电流增至4 A·g^-1时的电容保持率为74.5%。而未活化的多孔炭最大电容为253 F·g^-1,电容保持率仅为45.1%。此外,活化后的多孔炭还具有优异的电化学稳定性。在5 A·g^-1电流下循环8 000圈后,其电容保持率高达94%。活化后的多孔炭在电容性能方面的极大改善与其比表面积的大幅提高及介孔的增多有密切关系。     

多孔硅和掺镨多孔硅的光致发光

多孔硅在室温下发出光致荧光展现了硅用作光电子材料和显示技术材料的前景。掺入希土元素可以改善硅的发光性能。本文首次报道多孔硅掺希土的一种新的电化学掺杂方法——恒电位电解,和一种希土硝酸盐-支持电解质-有机溶剂的新电解体系。这一方法和体系的特点是通过采用适当外加电压来控制电解产物,提高掺入的希土浓度,提高发光强度;同时可避免析出使发光不稳定的产物,提高发光稳定性。优化了阳极氧化制备多孔硅的条件和阴极还原制备掺镨多孔硅的条件(镨化合物浓度、溶剂、离子强度、电解电压、时间),获得了光致发光强度高于多孔硅的掺镨多孔硅,并讨论了多孔硅和掺镨多孔硅的光致发光机制。     

多孔液体在气体捕集与分离领域的应用

多孔液体是指具有永久性孔隙的液体材料,其将多孔固体的有序规整孔道和液体的流动性等诸多优点相结合,在气体捕集与分离领域表现出巨大的应用潜力,成为新的研究热点。本文首先简单阐述了多孔液体的概念及分类,并总结了多孔液体形成的必要条件;然后分别详细综述了三类多孔液体的合成进展,并阐述了多孔液体在气体捕集与分离方面的应用,着重介绍了近五年的研究进展;最后对其现存的挑战及未来展望进行了总结。     

光化学氧化对多孔硅稳定性及SO2传感性能影响

采用光化学氧化方法对多孔硅进行后处理,获得具有良好稳定性的氧化多孔硅;采用SEM、AFM、FT-IR进行表征;通过SO2传感实验,评价其光致发光谱的变化。结果表明,采用电化学阳极氧化制备的新鲜多孔硅在空气中稳定性较差,SEM图表明其膜层分布有120×40μm的长方形小块,光化学氧化后使该长方形小块进一步分裂变细;AFM图表明,新鲜制备的多孔硅经稳定化处理后,表面硅柱宽度由700～750 nm变为300～350 nm,高度由50～58 nm变为40 nm;出现Si—O键(1 114 cm-1)和OSi—H键(2 249 cm-1)的振动峰;该氧化多孔硅在SO2介质中呈可逆的荧光猝灭特征,荧光峰的位置不随SO2浓度变化而发生移动,稳定性较好。     

悬浮缩聚法制备腰果酚醛树脂多孔微球的特性

悬浮缩聚法制备腰果酚醛树脂多孔微球的特性;悬浮缩聚;腰果酚醛树脂;多孔微球     

多孔Co(OH)2的制备及其超电容特性

多孔Co(OH)2的制备及其超电容特性;多孔氢氧化钴;电化学电容器;超电容     

位错对阳极氧化铝多孔薄膜纳米孔阵列结构的影响

多孔铝氧化物薄膜;电解质强度;位错对阳极氧化铝多孔薄膜纳米孔阵列结构的影响     

多孔壳聚糖膜的制备及对水中游离余氯的吸附性能

多孔壳聚糖膜的制备及对水中游离余氯的吸附性能;多孔壳聚糖膜;游离余氯;吸附动力学     

微乳液聚合制备多孔高吸油甲基丙烯酸酯类树脂的研究

研究了双连续相微乳液聚合制备多孔高吸油树脂,以甲基丙烯酸甲酯(MMA)、丙烯酸丁酯(BA)为共聚单体(油相),水(H2O)/乙醇(EtOH)为混合水相,2,2′-偶氮二异丁腈(AIBN)为引发剂,采用十二烷基硫酸钠(SDS)和复配十二烷基硫酸钠/吐温80(SDS/T80)两种乳化体系,调节油相和水相比例,配制出双连续相微乳液.聚合在无搅拌下进行.研究了乳化体系、混合水相含量、单体配比、交联剂和引发剂用量等因素对树脂吸油性能的影响.结果表明,多孔高吸油树脂比同系无孔树脂的吸油速率大大提高,最快可以在2min内达到吸油饱和.树脂对苯,四氢呋喃,四氯化碳的吸油倍率分别达到15.5g/g,15.5g/g,31.7g/g.     

双连续相微乳液辐射聚合制备多孔材料的研究

利用6 0 Co γ射线在室温下辐照双连续相微乳液体系以制备多孔聚合物材料 ,试图在控制多孔材料的微孔结构形态和减少微乳液聚合过程中的相分离方面做一些探索 .通过电导率的测量分析微乳液的结构类型 ,并确定微乳液的双连续相区域范围 .微乳液聚合后所得的样品的孔结构和聚合前的微乳液结构类型有关 ,扫描电镜和热重分析的结果表明双连续相微乳液在聚合时容易发生相分离 ,未必能够得到开孔结构的聚合物 .但适当控制聚合前微乳液的组成 ,如选择合适的水油比例、交联剂的用量和加入一些功能性单体 (如甲基丙烯酸或丙烯酸钠 ) ,可以有效地抑制相分离 ,调节所得聚合物的结构形态 .     

Lipase-catalyzed enantioselective esterifications using different microemulsion-based gels

Chiral esters with high optical purity have been synthesized at 298.2 K from racemic 2-octanol and alkanoic acids using the commerical lipases fromChromobacterium viscosum (CV) orCandida sp. (SP 525) immobilized in microemulsion-based gelatin gels. The microemulsions consisted of water and alkanes stabilized by the anionic surfactant sodium 1,4-bis(2-ethylhexyl) sulfosuccinate (AOT) and the naturally occurring zwitterionic surfactant soybean lecithin, respectively. The enzymes were solubilized both in water-in-oil (W/O) microemulsions and in microemulsions with a bicontinuous structure. Different microstructures of the gels were chosen since the enzyme may undergo conformational changes in different environments resulting in different catalytic efficiencies toward competing substrates. Therefore, it is of great fundamental interest to know the phase behaviour and the microstructures of the used microemulsion systems. Phase diagrams were determined at 298.2 K for the systems water-hexane-AOT and ethanol/water (11)-hexadecane-soybean lecithin. The former system exhibited a large one-phase W/O microemulsion region, while in the latter a small one-phase region with bicontinuous structure was present. The kinetic enantiomeric ratios (E-values), as determined from enantiomeric excess (e.e.) values at a conversion below 0.5, were higher both in the W/O microemulsion as well as in the bicontinuous microemulsion using the SP 525 lipase, than using the CV lipase. On the other hand, the conversions were higher using gels based on W/O microemulsions (AOT stabilized) than using gels based on microemulsions with a bicontinuous structure (lecithin stabilized).     

Synthesis of sponge-like polymer dispersions via polymerization of bicontinuous microemulsions

Polymer gels with high water content are made by polymerization of hydrophilic/hydrophobic monomer mixtures in bicontinuous microemulsions. These structures can be described as a heterophasic, bicontinuous polymer colloid-in-water structure, the characteristic length of which is only indirectly influenced by the original microemulsion mixture.The structure formation and phase changes throughout the polymerization reaction are followed with rheology, polarization microscopy, and scanning and transmission electron microscopy. It is shown that already the very first formed polymer changes disturb the bicontinuous phase structure and nucleate a vesicular phase; with further consumption of the monomer mixture, at least three other phase transitions can be detected, ending with a simple globular surfactant structure.Although direct templating of the original mesomorphous structure does not occur, the existence of the diverse lyotropic phases influences the final structure. It is shown that simple dilution changes the characteristic length of the network elements from about 2 m down to 50 nm. This is explained by a combination of a nucleation-and-growth mechanism with the influence of a restricted colloidal stability in anisometric lyotropic phases.     

AM/(2-甲基丙烯酰氧乙基)三甲基氯化铵/2-丙烯酰胺基-2-甲基丙基磺酸钠的反相微乳液共聚合动力学研究

通过实验绘制了失水山梨醇单月桂酸酯(Span20)-聚氧乙烯山梨醇酐单脂酸酯(Tween80)复配乳化剂、丙烯酰胺、(2-甲基丙烯酰氧乙基)三甲基氯化铵、2-丙烯酰胺基-2-甲基丙基磺酸钠和环己烷的拟三元相图.采用过硫酸铵-亚硫酸氢钠氧化还原引发剂,通过动力学研究,得到了聚合反应的表观活化能为68.10 kJ/mol,并分别得到了聚合速率与产物特性粘数的动力学关系式Rp∝[M]1.74[APS]0.60[E]-1.28,[η]∝[M]0.78[APS]-0.23[E]-0.71,分析了单体浓度、引发剂浓度、乳化剂浓度对共聚合反应速率Rp和共聚物特性粘数[η]作用及影响的原因,在动力学研究的基础上初步探讨了聚合机理.     

Retention of structure in microemulsion polymerization: formation of nanolatices

Polymerization of styrene-in-water microemulsions by photoinitiation using the initiator 2,2'-dimethoxy-2-phenyl acetophenone (DMPA) produces small nanolatices of the same size as the parent microemulsion (radius = 24-31 angstroms). This behavior is distinct from previously applied methods where significant particle growth accompanies the polymerization reaction. NMR measurements confirmed that polymerization is complete in under an hour and small-angle neutron scattering established the microemulsion structure before and after polymerization. The approach may be of more general application where retention of structure is sought in microemulsion-based polymer templating procedures.     

Synthesis and Characterization of Hydrogel Nanoparticles Through Inverse Microemulsion Polymerization of 2-Acrylamido-2-methyl-1-propanesulfonic Acid

Nanosized hydrogel particles prepared through inverse microemulsion polymerization of 2-acrylamido-2-methyl-1-propanesulfonic acid, using the combination of an oil soluble emulsifier (SPAN80) with a water soluble emulsifier (TWEEN 80), and precise determination of HLB range related to the formation of stable single phase microemulsions.

The effect of crosslink density, water phase to oil phase ratio, and the hydrophilic-lipophilic balance (HLB) value on polymerization rate, particle size, and swelling ratio were investigated. It found that polymerization rate and particle size are strongly dependent on the water phase to oil phase ratio. Hydrogel samples prepared using oil soluble and water soluble initiators and the results showed that the initiator type had a great influence on monomer conversion and particle size. Effect of pH on equilibrium swelling of hydrogels was studied by dynamic light scattering and hydrogels showed pH-independent swelling behavior in a broad range of pH values. We also reported and discussed the crosslink density distribution in nanogels prepared by inverse microemulsion polymerization.     

The effect of structure of oil phase, surfactant and co-surfactant on the physicochemical and electrochemical properties of bicontinuous microemulsion

Efforts were made to prepare bicontinuous microemulsions with ten different oil phases involving aliphatic, linear, and aromatic hydrocarbons as oil phases, two co-surfactants (n-butanol and n-pentanol) and two surfactants: cationic (CTAB) and anionic (SDS). Different weight percentages were employed for the preparation of cationic and anionic surfactant based microemulsions as reported in the literature. Out of the 40 compositions (10 oil phasesx2 co-surfactantsx2 surfactants) thus selected only 28 systems showed stable bicontinuous microemulsion phase. This behavior is explained on the basis of the structures of various constituents present in the microemulsions. Viscosity variations of stable bicontinuous microemulsions are found to depend mainly on the nature of co-surfactant. Conductivity behavior on the other hand depends mainly on the weight percentage and composition of aqueous phase. The solubility of pyrene in the oil phase determines the excimer formation and fluorescence behavior in microemulsions. The electron transfer property of both the water-soluble and the oil-soluble redox systems does not depend on the oil phase and the co-surfactant. The significance and importance of characterizing well defined bicontinuous microemulsions is thus highlighted.     

有机硅聚丙烯酸酯微乳液的合成与性能

有机硅聚丙烯酸酯微乳液的合成与性能;硅氧烷     

Sugar-based microemulsion glass templates

Complex fluids comprising of surfactants with water and/or oil form a rich variety of dynamic self-assembled structures, ranging from spherical swollen micelles, viscous rod-like micelles, and bicontinuous microemulsions to ordered liquid crystalline phases. The wide range of practical and specialized applications of complex fluids has made them the subject of intense research for many decades. Here, we demonstrate for the first time how bicontinuous microemulsions containing equal masses of oil and sugar can be driven to the glassy state without phase separation at ambient temperatures by controlled desiccation of sugar-rich microemulsions. The robust nanostructure of these microemulsion glasses allows polymerization of hydrophobic liquid monomers within the interstices of the glassy microemulsion template without macroscopic phase separation. Yet after polymerization, the sugar and surfactant template can be easily removed by dissolution in water.