树枝形结构“液体分子筛”的设计合成及性质研究

<正>离子液体是由有机阳离子和无机或有机阴离子构成在室温或室温附近温度下呈液体状态的有机物质.而聚合离子液体是一类每个重复单元中带有离子液体基团的特殊的聚电解质.这种功能性的离子液体高聚物在导电材料、有机反应催化、气体吸附以及萃取     

S-烷基噻吩类离子液体及其在染料敏化太阳能电池中的应用

离子液体(或室温熔盐)是含有有机阳离子和一般无机阴离子或有机阴离子的离子材料.它们不含中性分子而且通常具有低于373K的熔点.离子液体的熔点、热和电化学稳定性、粘度,极大地受到阴/阳离子类型的影响,可以通过适当选择阴/阳离子对来调控其亲水性或亲油性错误!未找到引用源.     

室温离子液体在分离分析中的应用

室温离子液体是指室温或接近室温下全部由离子组成的有机液体物质,具有不挥发,不易燃,溶解范围大,对空气和热稳定等特点,作为一种“可设计”型的环境相对友好溶剂,已被成功应用于分离分析领域中。本文重点综述了离子液体近年来在毛细管电泳、液相色谱及气相色谱中的应用进展,也对离子液体在质谱和光谱中的应用作了介绍。     

共价有机框架的合成及其在肿瘤治疗中的应用研究进展

共价有机框架(covalent organic frameworks, COFs)是近年来开发的一种由有机单元连接而成的高结晶性多孔聚合物, 由于具有良好的孔隙率、模块性、结晶性和生物相容性等特点在肿瘤治疗中显示出了良好的应用前景. 本综述总结了已报道的COFs制备方法, 包括溶剂热合成法、机械化学合成法、微波合成法、离子热合成法、界面合成法、室温合成法和纳米尺度COFs的合成方法, 并根据对肿瘤作用机理的差异, 将用于肿瘤治疗的COFs纳米载药系统归纳为药物化疗、光热治疗、光动力学治疗和联合治疗. 此外还讨论了COFs在肿瘤治疗领域所面临的主要挑战和发展趋势.     

有机小分子室温磷光材料的研究进展

室温磷光不仅能直观地反映磷光发光体的激发态跃迁过程,而且在光电、传感、生物成像和信息加密等领域具有广阔的应用前景.因此,近年来室温磷光材料的研究引起了人们越来越多的兴趣与关注,成为发光材料、尤其是有机发光功能材料领域的一个新的研究热点.本综述总结了近年来关于有机小分子室温磷光材料的研究进展,主要围绕基于氢键的室温磷光材料、含有卤素的室温磷光材料、基于给体-受体（D-A）结构的室温磷光材料和具有圆偏振发光（CPL）性质的有机小分子室温磷光材料展开介绍.     

室温磷光凝胶研究进展

室温磷光(RTP)材料因其独特的发光性质和在光电、传感、生物成像及信息加密等领域广阔的应用前景吸引了研究者的兴趣。近年来,科学家探索了各种方法调控有机分子的室温磷光,并通过磷光分子结构设计以及磷光保护基质的构建成功构筑了长寿命和高量子效率的有机室温磷光材料。超分子凝胶作为诱导室温磷光的新基质,具有三维网络结构、热可逆性质及刺激响应性等优势而引起关注。本综述围绕无金属室温磷光凝胶材料和含金属室温磷光凝胶材料,总结了近年来关于室温磷光凝胶材料的研究现状,并在此基础上,简要展望了室温磷光凝胶材料研究的发展趋势。     

S-烷基噻吩类离子液体及其在染料敏化太阳能电池中的应用

离子液体（或室温熔盐）是含有有机阳离子和一般无机阴离子或有机阴离子的离子材料。它们不含中性分子而且通常具有低于373K的熔点。离子液体的熔点、热和电化学稳定性、粘度，极大地受到阴／阳离子类型的影响，可以通过适当选择阴／阳离子对来调控其亲水性或亲油性错误!未找到引用源。     

离子液中的生物催化反应

室温离子液（RTILs）是指主要由有机阳离子和无机或有机阴离子构成的在室温或接近室温下呈液态的盐类．它完全由离子构成，具有许多分子溶剂不可比拟的性能如：低的蒸汽压、高的电传导性、宽的温度范围（300-400℃）、大的电化学窗口和对有机、无机、及高分子化合物好的溶解性等．     

基于室温离子液体的电导型气体传感器

本文利用室温离子液体对水或有机蒸气吸收后其离子导电性的改变,研制了以离子液体BmimPF6为敏感材料的电导型气体传感器.考查了BmimPF6用量对传感器响应的影响,测定了传感器对不同浓度的水蒸汽及乙醇、二氯甲烷等饱和有机蒸气的响应.实验结果显示,该传感器具有制作方便、结构简单、稳定性高及线性范围宽等优点,可被用于不同浓度的水或有机蒸气/氮气混合气氛中,水蒸汽或有机蒸气浓度的测定.此外,还针对该传感器对乙醇等不同饱和有机蒸气响应信号与这些有机溶剂的理化性质参数间的定量关系,采用化学计量学方法进行了建模分析.     

室温离子液体电解质与锂离子电池碳负极材料的相容性

室温离子液体电解质与碳负极材料间的相容性是其应用于锂离子电池的关键问题之一.本文总结了室温离子液体电解质体系与碳负极材料相容性的研究现状和微观机制,阐述了不同种类的室温离子液体与碳负极材料相容性的规律和存在的问题以及改善方法.     

卟啉-硫醚基共价有机框架材料用于氧还原反应电催化剂

氧还原反应（ORR）是能进行能量存储的核心电化学过程。由于它的动力学速率缓慢,因此亟需制备出高活性的电催化剂来促进这一反应的速率。二维共价有机框架材料（2D COFs）的π-π堆积结构可赋予骨架高导电率,并且一维有序的孔道有利于促进中间反应体传输。因此,其在可再生能源领域中具有良好的应用前景,并有望作为能量存储与转化的强大催化平台。本文通过向2D COFs中引入金属卟啉单元及硫醚单元成功制备了两个2D COFs （JUC-600和JUC-601）。通过多种表征手段证明,这两个2D COFs均具有AA堆积的sql拓扑结构。通过电化学测试表明,Co²⁺配位的JUC-601具有更正的ORR起始电势（0.825 V）和半波电势（0.7 V）、更高的活性表面积（7.8 mF/cm²）,更低的Tafel斜率（58 mV/dec）。这主要是由于JUC-601的高比表面积和高孔隙率使得中间产物能更易在COFs的表面和孔道中接触和传输。此外,Co²⁺-卟啉单元以及硫醚单元的存在使其骨架整体的电子结构发生了变化,更有利于电子转移。这一工作不仅开发了新的二维卟啉-硫醚基COFs材料,同时也拓展了2D COFs材料在电催化领域的应用。     

Piezochromism in Dynamic Three-Dimensional Covalent Organic Frameworks

Piezochromic materials with pressure-dependent photoluminescence tuning properties are important in many fields, such as mechanical sensors, security papers, and storage devices. Covalent organic frameworks (COFs), as an emerging class of crystalline porous materials (CPMs) with structural dynamics and tunable photophysical properties, are suitable for designing piezochromic materials, but there are few related studies. Herein, we report two dynamic three-dimensional COFs based on aggregation-induced emission (AIE) or aggregation-caused quenching (ACQ) chromophores, termed JUC-635 and JUC-636 (JUC=Jilin University China), and for the first time, study their piezochromic behavior by diamond anvil cell technique. Due to the various luminescent groups, JUC-635 has completely different solvatochromism and molecular aggregation behavior in the solvents. More importantly, JUC-635 with AIE effect exhibits a sustained fluorescence upon pressure increase (≈3 GPa), and reversible sensitivity with high-contrast emission differences (Δλ_em=187 nm) up to 12 GPa, superior to other CPMs reported so far. Therefore, this study will open a new gate to expand the potential applications of COFs as exceptional piezochromic materials in pressure sensing, barcoding, and signal switching.     

Stable Thiophene-sulfur Covalent Organic Frameworks for Oxygen Reduction Reaction(ORR)

Exploring novel materials deriving from earth resources to substitute for platinum(Pt) electrocatalyst to promote oxygen reduction reaction(ORR) of fuel cell cathode is very important. Herein, we have exploited two crystallographic thiophene-sulfur covalent organic frameworks(COFs), termed JUC-607 and JUC-608, as electrocatalysts that exhibited good ORR performances. These thiophene-sulfur COFs exhibited high stability, and their functional groups acting as active centers in the ORR can be precisely determined. Notably, due to a larger aperture for mass transfer and electrons transport, JUC-608 displayed a growing electrochemical performance, leading to a better ORR activity. Thus, this study will provide a new strategy for designing heteroatom-based COF materials for high-performance electrochemical catalysis.     

基于四硫富瓦烯的无金属共价有机框架材料用于高效电催化析氧反应

共价有机框架(COFs)在电催化析氧反应(OER)中的应用得到了广泛的关注。然而,大多数无金属共价有机框架(COFs)的导电性较差,不利于OER反应。四硫富瓦烯(TTF)是一种良好的电子供体,具有快速的电子转移能力,将TTF整合到共价有机框架骨架中将有助于电子的转移。在此,我们报道了一种基于四硫富瓦烯的二维无金属共价有机框架材料,JUC-630。与不含四硫富瓦烯的同类材料(Etta-Td COF)相比,JUC-630具有较低的过电位(400 mV)和塔菲尔斜率(104 mV∙dec⁻¹)。本研究提出了合理设计功能基元的策略,这有助于大大提高COF材料的OER催化活性。     

具有高气态碘吸附的二维介孔共价有机框架

合成了一种新型的二维介孔共价有机框架(COF)材料JUC-573. 粉末X射线衍射、 氮气吸附-脱附和热重等表征结果表明合成的COF材料具有高结晶度、 高比表面积以及良好的热稳定性. 在333 K、 常压条件下, 该材料表现出优异的碘吸附能力, 且吸附量高达4.15 g/g. 这是由于在JUC-573中规则定向的垂直一维介孔孔道能够有效地避免碘吸附后的堵塞, 从而优化了材料的吸附能力. JUC-573可多次循环用于气态碘的捕获且保持几乎不变的吸附量.     

偶氮苯功能化的光响应共价有机框架材料

通过后修饰的方法, 在共价有机框架(COFs)材料JUC-500的孔道中引入光敏性的偶氮苯小分子, 合成了具有光热刺激响应的共价有机框架材料JUC-501. 在紫外线和加热作用下, 孔道中的偶氮苯会发生可逆的顺-反异构变化, 对染料污染物甲基橙(MO)表现出优异的可逆吸附与释放性能.     

Selective alkylation of phenol with tert-butyl alcohol catalyzed by [bmim]PF6

Alkylation of phenol with tert-butyl alcohol (TBA) in a room temperature ionic liquid, 1-butyl-3-methylimidazoliumhexafluorophosphate ([bmim]PF₆), has been investigated. The effects of various parameters such as reaction temperature, reaction time, reactant ratio (mol ratio of phenol to that of TBA), and the amount of the ionic liquid used were studied. The [bmim]PF₆ ionic liquid was found to catalyze the reaction with high conversion and good selectivity.     

Designing Thiophene-Enriched Fully Conjugated 3D Covalent Organic Framework as Metal-Free Oxygen Reduction Catalyst for Hydrogen Fuel Cells

The application of three-dimensional (3D) covalent organic frameworks (COFs) in renewable energy fields is greatly limited due to their non-conjugated skeletons. Here, we design and successfully synthesize a thiophene-enriched fully conjugated 3D COF (BUCT-COF-11) through an all-thiophene-linked saddle-shaped building block (COThTh-CHO). The BUCT-COF-11 exhibits excellent semiconducting property with intrinsic metal-free oxygen reduction reaction (ORR) activity. Using the COF as cathode catalyst, the assembled anion-exchange membrane fuel cells (AEMFCs) exhibited a high peak power density up to 493 mW cm⁻². DFT calculations reveal that thiophene introduction in the COF not only improves the conductivity but also optimizes the electronic structure of the sample, which therefore boosts the ORR performance. This is the first report on the application of COFs as metal-free catalysts in fuel cells, demonstrating the great potential of fully conjugated 3D COFs as promising semiconductors in energy fields.     

Silica-supported boric acid with ionic liquid: a novel recyclable catalytic system for one-pot three-component Mannich reaction

A rapid and efficient silica-supported boric acid/ionic liquid ([bmim][PF?]), catalyzed, one-pot three-component Mannich reaction has been carried out to synthesize β-amino carbonyl compounds at room temperature. The reaction afforded desired products in excellent yields with moderate to good diastereoselectivity. The method provides a novel modification of three-component Mannich reaction in terms of mild reaction conditions, clean reaction profiles, low amount of catalyst, recyclability of catalyst and a simple workup procedure. The present report first time describes the preparation of H?BO?-SiO? catalyst and its use with [bmim][PF?], to synthesize Mannich products. The catalyst can be reused at least seven times.     

A Two-dimensional Covalent Organic Framework for Iodine Adsorption

Radioactive iodine is a notorious pollutant in gas radioactive nuclear waste due to its radiation hazard, volatility, chemical toxicity, and high mobility. Therefore, developing a material with high efficiency-specific iodine capture is significant. Covalent organic framework(COF) has attracted significant attention as a new crystalline porous organic material. Due to its large specific surface and high chemical stability, it is an excellent alternative to adsorbents. Herein, we report a chemically stable two-dimensional COF(termed JUC-609) with specific adsorption of iodine. Adsorption experiments show that JUC-609 has an excellent iodine adsorption capacity as high as 5.9 g/g under 353 K and normal pressure condition, and iodine adsorption after multiple cycles is still maintained. Our study thus promotes the potential application of COFs in the field of environment-related applications.