功能化聚离子液体的设计合成及应用研究

聚离子液体(Poly(ionic liquid)s)是指由离子液体单体聚合生成的,在重复单元上具有阴、阳离子基团的一类离子聚合物。功能化聚离子液体是由功能化离子液体发展而来,兼具离子液体和高分子聚合物的性质。该类研究着眼于结构可控性质,设计合成具有特殊性能的、稳定的、功能化材料。近年来已经在高分子化学、电化学、材料科学及能源科学等领域得到初步应用。本论文综述聚离子液体在固态电解质和聚电解质膜、智能响应性功能材料,以及聚离子液体基碳材料、聚离子液体/碳纳米杂化材料、催化等相关领域的研究与应用。     

多孔聚离子液体的合成与应用

聚离子液体(Poly(ionic liquid)s,PIL)是分子结构中含有离子液体结构单元的一类离子聚合物,兼具离子液体小分子的离子电导性和聚合物可加工性能。多孔聚离子液体材料(Porous PILs),结合了多孔材料大比表面积和聚离子液体的导电性及离子交换等特性,在功能高分子材料、电化学响应材料以及能源科学等领域表现出广泛的应用前景。本文综述了多孔聚离子液体的分子设计与合成方法,及其在智能响应材料、水处理、高效催化、多孔碳材料、生物医用材料等领域的潜在应用。     

聚离子液体的合成及应用

聚离子液体(PILs)是在重复单元上具有阴、阳离子电解质基团的聚合物。此类聚合物结合了离子液体和聚合物的一些性质,近年来在高分子化学和材料科学等领域受到广泛关注。本文将聚离子液体划分为聚阳离子型离子液体、聚阴离子型离子液体、聚两性型离子液体和共聚型离子液体四类并介绍了聚离子液体的性质及各类聚离子液体的合成。此外,本文还对聚离子液体在有机分散剂、纳米复合材料、电化学、吸附剂和分离等方面的应用进行了综述。     

离子液体/凝胶聚合物电解质的制备及其与LiFePO_4的相容性

以1-甲基-3-乙基咪唑六氟磷酸盐(EMIPF6)、聚偏氟乙烯-六氟丙烯(P(VDF-HFP))和六氟磷酸锂(LiPF6)为原料,采用溶液浇铸法制备了离子液体/凝胶聚合物电解质(ILGPE).通过循环伏安(CV)、计时电流法、恒流充放电、电化学阻抗法(EIS)研究了该电解质的离子传输特性以及与锂离子电池正极材料LiFePO4的相容性.结果表明,离子液体/凝胶聚合物电解质的室温电导率为1.650×10-3S·cm-1,电化学稳定窗口达到5.0V.在充放电循环过程中,电极表面形成的钝化膜改善了锂离子脱、嵌可逆性和电极/电解质的界面性质.     

聚季铵盐离子液体材料制备及其对蛋白质吸附性能评价

通过一步合成法制备了两种可聚合季铵盐离子液体功能单体,并通过沉淀聚合法合成了相应的聚离子液体聚合物。对产物进行了核磁共振、扫描电镜、热重分析等表征。结果表明:所制备的两种材料粒径均匀,约为600 nm的椭球形颗粒,颗粒之间有相互粘连。通过对牛血清白蛋白(BSA)、卵清蛋白(OVA)、牛血红蛋白(BHb)、溶菌酶(Lys)、胰蛋白酶(Try)5种蛋白质的吸附性能实验,考察了聚季铵盐离子液体材料对蛋白质的吸附性能。考察结果表明:两种聚离子液体材料均对蛋白质具有一定的吸附性能。其中以4-乙烯基苄氯季铵盐离子液体为功能单体制备的聚离子液体材料对胰蛋白酶的吸附性能最好,是一种具有良好应用前景的材料。     

聚离子液体材料在分离科学中的研究进展

离子液体作为新型离子化试剂,具有诸多优越的物理化学性质,比如:良好的溶解性、导电性、热稳定性、生物相容性及低蒸气压和不易燃等特点,近年来在分析化学领域得到广泛关注。聚离子液体材料结合了离子液体和聚合物的双重性质,已经成为分离科学研究的前沿领域。本文详细讨论了离子液体与目标物之间的多种作用机制,比如亲/疏水作用、氢键作用、离子交换、π - π 堆积及静电吸附作用等等,总结了聚离子液体材料在固相萃取、液相色谱、气相色谱、毛细管电泳及毛细管电色谱等领域的研究进展;最后,对聚离子液体材料的发展前景进行了展望。     

离子自组装方法在偶氮光响应材料制备中的应用

偶氮光响应材料在光信息存储,光学器件制造等领域具有广阔的应用前景。离子自组装技术是近几年发展起来的制备超分子功能材料的一种新方法。本文首先对偶氮光响应材料的制备方法以及离子自组装技术的基本原理做了简单的介绍。然后分4类对离子自组装方法在偶氮光响应材料制备中的应用进行了综述,主要包括带电荷小分子染料与反电荷表面活性剂组装、聚电解质与反电荷偶氮小分子组装、高支化大分子与偶氮小分子组装以及环糊精与含偶氮聚电解质组装。最后对该领域的发展趋势和研究热点进行了展望。     

室温离子液体电解质与锂离子电池正极材料的相容性

室温离子液体作为新一代软功能介质材料,其电化学性质正在引起人们的广泛关注。本文综述了室温离子液体电解质在用于锂离子电池时与正极材料相容性的研究状况,总结了不同室温离子液体电解质与锂离子电池正极材料相容性的基本规律,从正极材料和室温离子液体两个方面探讨了改善室温离子液体/正极材料相容性的基本途径。     

离子型电活性聚合物驱动器的研究进展

近年来软驱动材料在可穿戴设备、医疗健康器件、软体机器人等领域中的重要应用引起了学术界和工业界的关注。在软驱动材料中,电活性聚合物材料(EAP)是一种在电场刺激下能够改变形状或尺寸的软驱动材料,可分为电子型和离子型EAP。与电子型EAP相比,离子型电活性聚合物(IEAP)驱动器因具有较低驱动电压,在医疗器械和可穿戴设备上具有显著的应用优势。近年来,随着电极材料和离子液体基聚合物凝胶电解质材料的发展,大大改善了传统IEAP驱动器的响应速度慢、大气中的耐久性差、电致变形和应力小等缺点。本综述中,我们较全面地总结了IEAP材料的类型以及其研究进展,包括基于离子聚合物-金属复合材料(IPMC)、导电聚合物材料(CP)、巴基凝胶(Bucky-gel)材料和离子凝胶(IG)材料等。此外,还总结了不同类型IEAP驱动器的机电耦合机制、性能和应用进展并讨论了IEAP驱动器未来发展趋势和面对的挑战。     

基于离子液体的炭材料制备、改性及应用

离子液体因其熔点低、液态温域宽、蒸气压低、热稳定性高、电导率高、电化学窗口宽、结构可设计及对许多化合物的亲和性等系列性能而引起人们广泛关注。离子液体在炭材料制备、改性领域展示出了良好的前景及巨大的应用潜力,可直接作为碳源,经过高温炭化实现杂原子掺杂制备多孔炭材料;离子液体也可充当反应介质和致孔剂,将生物质转化为多孔炭材料;此外,由于离子液体与炭材料相容性较好,可以用于多孔炭材料改性制备炭复合材料。基于离子液体的炭材料在电催化、超级电容器、吸附分离及生物医学等领域具有潜在的应用价值。本文总结了基于离子液体炭材料的制备、改性及应用最新研究进展,并着重介绍了其在能源和环境相关领域的应用。     

Robust Aqua Material: A Pressure‐Resistant Self‐Assembled Membrane for Water Purification

“Aqua materials” that contain water as their major component and are as robust as conventional plastics are highly desirable. Yet, the ability of such systems to withstand harsh conditions, for example, high pressures typical of industrial applications has not been demonstrated. We show that a hydrogel‐like membrane self‐assembled from an aromatic amphiphile and colloidal Nafion is capable of purifying water from organic molecules, including pharmaceuticals, and heavy metals in a very wide range of concentrations. Remarkably, the membrane can sustain high pressures, retaining its function. The robustness and functionality of the water‐based self‐assembled array advances the idea that aqua materials can be very strong and suitable for demanding industrial applications.     

Synthesis and electrochemical performances of amorphous carbon-coated Sn–Sb particles as anode material for lithium-ion batteries

The amorphous carbon coating on the Sn–Sb particles was prepared from aqueous glucose solutions using a hydrothermal method. Because the outer layer carbon of composite materials is loose cotton-like and porous-like, it can accommodate the expansion and contraction of active materials to maintain the stability of the structure, and hinder effectively the aggregation of nano-sized alloy particles. The as-prepared composite materials show much improved electrochemical performances as anode materials for lithium-ion batteries compared with Sn–Sb alloy and carbon alone. This amorphous carbon-coated Sn–Sb particle is extremely promising anode materials for lithium secondary batteries and has a high potentiality in the future use.     

A 3D Organically Synthesized Porous Carbon Material for Lithium‐Ion Batteries

We report the first organically synthesized sp–sp³ hybridized porous carbon, OSPC‐1. This new carbon shows electron conductivity, high porosity, the highest uptake of lithium ions of any carbon material to‐date, and the ability to inhibit dangerous lithium dendrite formation. The new carbon exhibits exceptional potential as anode material for lithium‐ion batteries (LIBs) with high capacity, excellent rate capability, long cycle life, and potential for improved safety performance.     

A Sustainable Freeze‐Drying Route to Porous Polysaccharides with Tailored Hierarchical Meso‐ and Macroporosity

Bio‐derived polysaccharide aerogels are of interest for a broad range of applications. To date, these aerogels have been obtained through the time‐ and solvent‐intensive procedure of hydrogel fomation, solvent exchange, and scCO2 drying, which offers little control over meso/macropore distribution. A simpler and more versatile route is developed, using freeze drying to produce highly mesoporous polysaccharide aerogels with various degrees of macroporosity. The hierarchical pore distribution is controlled by addition of different quantities of t‐butanol (TBA) to hydrogels before drying. Through a systematic study an interesting relationship between the mesoporosity and t‐butanol/water phase diagram is found, linking mesoporosity maxima with eutectic points for all polysaccharides studied (pectin, starch, and alginic acid). Moreover, direct gelation of polysaccharides in aqueous TBA offers additional time savings and the potential for solvent reuse. This finding is a doorway to more accessible polysaccharide aerogels for research and industrial scale production, due to the widespread accessibility of the freeze drying technology and the simplicity of the method.

     

Pumping through Porous Hydrophobic/Oleophilic Materials: An Alternative Technology for Oil Spill Remediation

Recently, porous hydrophobic/oleophilic materials (PHOMs) have been shown to be the most promising candidates for cleaning up oil spills; however, due to their limited absorption capacity, a large quantity of PHOMs would be consumed in oil spill remediation, causing serious economic problems. In addition, the complicated and time‐consuming process of oil recovery from these sorbents is also an obstacle to their practical application. To solve the above problems, we apply external pumping on PHOMs to realize the continuous collection of oil spills in situ from the water surface with high speed and efficiency. Based on this novel design, oil/water separation and oil collection can be simultaneously achieved in the remediation of oil spills, and the oil sorption capacity is no longer limited to the volume and weight of the sorption material. This novel external pumping technique may bring PHOMs a step closer to practical application in oil spill remediation.     

甲壳素基新材料研究进展

甲壳素/壳聚糖良好的生物相容性、生物可降解性及独特的生理活性使其成为非常有应用价值的天然高分子材料,当前已成为新材料领域的研究热点.甲壳素/壳聚糖具有良好的可加工性能,可固定贵金属、半导体纳米材料等活性催化物质,同时其本身也具有催化作用,是一类绿色环境友好的高分子催化材料.良好的生物相容性和生物可降解性使甲壳素/壳聚糖...     

Synthesis of poly{[bis(diethynylphenyl)silylene]phenylene}s with highly heat-resistant properties and an application to conducting materials

Poly{[bis(3,5-diethynylphenyl)silylene]-p-phenylene} was prepared by the reaction of poly[(diethoxysilylene)-p-phenylene] with 3,5-bis(trimethylsilylethynyl)phenyllithium, followed by desilylation of the resulting substitution product. The present polymer exhibited extremely high heat-resistance and their thermogravimetric analysis (TGA) in a nitrogen atmosphere showed the temperature of 5% weight loss (Td₅) of 791 °C. Total weight loss at 1000 °C in TGA was determined to be 6% based on the initial weight. Treatment of a polymer film on a quartz plate at 1200 °C in vacuo led to the formation of a conducting thin film with a thickness of 74 nm and a conductivity of 9 S/cm.