TEMPO功能化共轭微孔聚合物催化氧化醇性能

将2,2,6,6-四甲基哌啶氧自由基(TEMPO)嫁接到2,5-二溴苯甲酸侧链,并与1,3,5-三乙炔苯(Ⅰ)通过Sonogashira偶联反应,合成出TEMPO自由基功能化共轭微孔聚合物CMP-3-TEMPO。利用SEM、XRD、FTIR和EPR等测试了CMP-3-TEMPO的形貌和结构组成。催化性能测试结果表明:CMP-3-TEMPO在氧气氛围、较温和条件下(80℃,常压),可将各种一级醇、二级醇以及杂原子醇氧化成相应的醛或酮化合物,转化率为70%～100%。CMP-3-TEMPO经过3次循环利用后,催化性能有所降低,可能的原因是反应过程中CMP-3-TEMPO存在局部解体,导致催化活性位点降低。     

TEMPO功能化共轭微孔聚合物作为高效醇催化氧化剂

2,5-二溴对苯二甲酸通过酰化反应得到了2,5-二溴对苯二甲酰氯(Ⅱ)。接着,中间体Ⅱ与4-氨基-2,2,6,6-四甲基哌啶-1-氧自由基(4-NH2-TEMPO)反应获得了侧链嫁接双2,2,6,6-四甲基哌啶氧自由基(TEMPO)的有机单体。然后,该有机单体与四(4-乙炔基苯)甲烷通过Sonogashira偶联反应,合成了高密度TEMPO自由基功能化的CMP-4-(TEMPO)₂共轭微孔聚合物。利用核磁共振谱(NMR)、扫描电子显微镜(SEM)、X射线衍射(XRD)、红外吸收光谱(FTIR)和电子顺磁共振谱(EPR)对所合成单体及CMP-4-(TEMPO)₂进行了表征。结果表明,CMP-4-(TEMPO)₂由微球和中空纳米管组成,具有较高的比表面积(486m²/g),含有微孔、介孔以及大孔复合孔,孔道含有丰富的TEMPO自由基官能团,可将各种芳香醇和杂原子醇高效、高选择性地氧化成相应的醛和酮。     

三嗪基富氮共轭微孔聚合物的可控合成

本文以N2,N4,N6-三(4-溴苯基)-1,3,5-三嗪-2,4,6-三胺为中心建构模块,通过Buchwald-Hartwig(BH)偶联反应成功制备了三种三嗪基富氮共轭微孔聚合物(TBTT-CMP@1,TBTT-CMP@2,和TBTT-CMP@3),研究表明该类聚合物不仅具有大的比表面积,且骨架具有丰富的π电子。因此,其在吸附、催化等领域有潜在的应用价值。     

共轭微孔聚合物材料的研究进展

共轭微孔聚合物(CMPs)是一类由共价键结合的3D网络结构化合物,由于其热稳定性好,比表面积高以及结构可控等优点,作为一类具有潜在应用前景的多孔材料日益受到重视。重点介绍了CMPs的性质、制备方法和综合应用,并对CMPs在储氢方面存在的不足和未来的研究方向做出了总结和展望。     

含噻吩的共轭微孔聚合物的合成与表征

以对溴碘苯为原料,通过Sonogashira偶联反应,Suzuki偶联反应,八羰基二钴催化的三聚反应,FeCl3氧化关环反应,成功合成了一种未见文献报道的含噻吩的六苯基苯共轭微孔聚合物,该共轭微孔聚合物经XRD测试为无序结构,TG研究结果表明热稳定性良好;其最大吸收峰位于380 nm处,发射出黄色荧光,该共轭微孔聚合物较单体波长发生红移,是聚合后链长增加共轭效应增强的结果。     

噻吩酰胺基共轭聚合物的合成与表征

文章以3-噻吩甲酸为原料,通过三步简单的反应制备出单体2,5-二溴噻吩-3-甲酰正辛胺,再将其与苯并二噻吩(BDT)二锡化物进行Stille偶联反应得到噻吩酰胺基共轭聚合物。通过核磁共振波谱对化学结构进行了表征,利用紫外—可见吸收光谱表征了聚合物溶液和膜的光学性能,用热失重分析仪表征了聚合物的热稳定性,这两个结果表明该聚合物有望用于聚合物太阳能电池中。     

基于共轭微孔聚合物的二维膜材料构筑及其应用

共轭微孔聚合物(CMPs)是典型的多孔有机聚合物,具有丰富的微纳孔和结构可调控性.具有二维结构的CMPs膜材料既保留了CMPs材料的π-共轭骨架和纳米多孔结构,又兼具二维材料优异的可加工性.重点总结了近年来CMPs膜材料的制备方法,包括电化学法、界面聚合法、模板法等;同时介绍了CMPs膜材料在纳滤、分离、抑菌等领域的应用现状;最后指出宏观大尺度CMPs膜的制备技术开发及其微观结构、化学组成与性能调控是未来二维CMPs膜材料的重点发展方向.     

高密度TEMPO功能化CMPs作为高效醇催化氧化剂

以2,5-二溴对苯二甲酸为原料，通过酰化反应，获得酰氯中间体，并与4-氨基-2,2,6,6-四甲基哌啶-1-氧自由基（4-amino-2,2,6,6-tetramethylpiperidine-1-oxyl, 4-NH2-TEMPO）反应，获得侧链嫁接双TEMPO（2,2,6,6-tetramethylpiperidine-1-oxyl, TEMPO）自由基的有机单体。将该有机单体与四（4-乙炔基苯）甲烷通过Sonogashira偶联反应，合成高密度TEMPO自由基功能化的CMP-4-(TEMPO)2共轭微孔聚合物。利用核磁共振谱（NMR）、扫描电子显微镜（SEM）、粉末X射线衍射（PXRD）、红外吸收光谱（FT-IR）和电子顺磁共振谱（EPR）等表征手段研究了所合成单体及CMP-4-(TEMPO)2的结构特点。CMP-4-(TEMPO)2由微球和中空纳米管组成，具有较高的比表面积（486 m2/g），含有微孔、介孔以及大孔复合孔，孔道含有丰富的TEMPO自由基官能团，可将各种芳香醇和杂原子醇高效、高选择性氧化成相应的醛和酮。     

过渡金属催化5-羟甲基糠醛合成2,5-呋喃二甲酸研究进展

随着绿色合成理念的不断提升,以具有高催化活性、高稳定性及价格低廉等优势的过渡金属催化剂代替强氧化剂和贵金属催化剂催化氧化5-羟甲基糠醛(HMF)制备精细化学品,逐渐成为研究者关注的焦点。本文综述了近年来廉价过渡金属基催化剂用于催化HMF氧化制备2,5-呋喃二甲酸(FDCA)的相关研究,对该领域的最新研究进行了叙述,重点介绍了锰基、铜基、铁/钴基、镍基及其他催化体系在HMF氧化反应中的应用,主要包括锰基金属氧化物、CuCl_(2)催化体系、Fe_(3)O_(4)-CoO_(x)的磁性催化体系等。此外,在介绍上述催化剂的基础上,还对廉价过渡金属基催化剂催化HMF氧化制备FDCA的发展前景进行了展望。     

贮氢合金催化共轭二烯烃类聚合物双键加氢的研究

研究了共轭二烯烃类聚合物在贮氢合金氢化物存在下双键加氢的情况。结果表明AB；型贮氢合金[包括LaNi5和MINi5-x(CoMnAl)8]可催化NBR、NR、BR、SBS等共轭二烯烃聚合物双键加氢，其氢化度分别可达33．5％、31．1％、45．8％、32．3％。采用IR、^1H NMR、碘量分析法等手段对加氢产物进行了分析，表明聚合物中双键加氢的同时，NBR中的-C≡N和SBS中的苯环不受影响。此外。研究结果还表明合金组成、表面处理方式等对贮氢合金催化共轭二烯烃类聚合物双键加氢活性有影响。合金氢化物在共轭二烯烃类聚合物双键加氢过程中具有提供氢源与催化双重功能。     

Design,preparation and application of conjugated microporous polymers

Conjugated microporous polymers (CMPs) are of great interest because these types of materials have high specific surface area and pore diameters less than 2 nm. CMPs have found applications in the fields of hydrogen storage, heterogeneous catalysts, gas‐permeable membranes and light‐emitting organics. A large number of recent reports have demonstrated that CMPs can be prepared using several approaches like noble metal‐mediated ethynyl, Sonogashira–Hagihara coupling, Suzuki coupling and Yamamoto coupling reactions. In this review, the synthetic routes, functionalization and potential applications of CMPs are systematically introduced. © 2013 Society of Chemical Industry     

Symmetry-dependent photocatalysis of conjugated microporous polymers based on pyrene for oxygenation of sulfides with O2

To date, conjugated microporous polymers (CMPs) have been developed into multifaceted photocatalysts. Here, two CMPs based on pyrene with the linkages of thiazolo[5,4-d]thiazole (TzTz) are prepared for visible light photocatalysis. The dimension of the molecular building block’s symmetry on the property and activity of CMPs is systematically investigated. Py(4)-TzTz-CMP with a pyrene building block of D_2h symmetry gives rise to better optoelectronic property than Py(2)-TzTz-CMP with a pyrene building block of C₂ symmetry. Therefore, Py(4)-TzTz-CMP photocatalyst is endowed with superior conversions for the green light-promoted oxygenation of sulfides with O₂. Intriguingly, mechanistic explorations disclose that both superoxide and singlet oxygen are responsible for the production of the target sulfoxides. This work gives insight into the rational design of highly active CMP photocatalysts for selective chemical transformations.     

Altering the emission properties of conjugated polymers

Many technological applications that have had tremendous impact on our society and lifestyle are exploiting the emission properties of organic species such as conjugated polymers and organic small‐molecule semiconductors. The most prominent case‐in‐point here are possibly organic light‐emitting diodes, which have found use in information displays, touch screens and beyond. To further advance the rapid development of these powerful and versatile technologies, it will be of paramount importance to gain fundamental insights about which strategies and processes we can employ to alter, control and eventually enhance the emission properties of this interesting class of material. In this work, we focus on macromolecular systems and review the most important categories of tools that can be employed to efficiently alter their emission properties by manipulating their molecular architecture and electronic structure; by influencing their molecular ordering, packing motifs and overall microstructure; as well as by utilizing the ability of some of these materials to respond to external stimuli and other physical parameters (pressure, light exposure etc.) and/or to interact with other compounds, including systems of different functionalities. © 2015 Society of Chemical Industry     

新型金属-有机骨架配位聚合物（MOF）的研究龈

金属有机骨架配位聚合物结构多样,性质独特,具有广泛的应用前景,它已成为近几年来一个热门的研究领域,如今它因H2存储方面的潜力受到广泛关注。本文简要介绍该类配位聚合物作为一种新型的多孔材料,在结构和性能方面的研究进展。     

Two-photon absorption properties of hyperbranched conjugated polymers with triphenylamine as the core

Two new hyperbranched phenylene vinylenes (HPVs) with triphenylamine as the core, 2,5-dihexyloxyl substituted phenylene vinylene as the connecting unit, and electron-donating triphenylamine or electron-deficient nitrobenzene as the different terminal groups were synthesized by modified Wittig polymerization reaction. Their one- and two-photon absorption (TPA) properties have been investigated. The two-photon absorption cross sections of the two polymers were performed by open-aperture Z-scan experiment using 120 femtosecond (fs) pulse, and their TPA cross section were determined to be 1.43 and 0.64×10⁻²⁰ cm⁴/GW per repeating unit at 800 nm, respectively. In chloroform, HPVs exhibit intense frequency up-converted fluorescence under the excitation of 120 fs pulses at 800 nm with the peaks located at 544 and 554 nm, respectively.     

Catechol-functionalized microporous organic polymer as supported media for Pd nanoparticles and its high catalytic activity

We report a new hydroxyl functionalized microporous organic polymer (MOPOH) based on the polymerization of catechol with terephthalaldehyde using phenolic resin-inspired chemistry. This catechol-decorated material, with surface area of 874 m² g⁻¹ and micro, mesopores, facilitates the immobilization and dispersion of Pd nanoparticles (NPs) on the polymer matrix. The surface area of the created composite (Pd@MOPOH) decreases to 419 m² g⁻¹ and the pore size distribution is narrowly distributed at 1.54 nm due to the filling of mesopores. The CO₂ capture capacities for MOPOH and Pd@MOPOH at 273 K and 1 bar are 13.4 and 9.2 wt%, respectively. The resultant Pd NPs are crystalline and uniform with a mean diameter of 4.8 nm. The well-dispersed Pd@MOPOH exhibits excellent catalytic activity toward the model reduction of 4-nitrophenol into 4-aminophenol. Significantly, nearly no Pd leaching is detected during the catalytic cycles, showing active and durable nature of the heterogeneous nanocatalyst.     

供电子基取代联苯胺类共轭聚合物的光电性质及电化学性能

通过取代基修饰增强联苯胺单元供电子性,使其与缺电子的苯甲醛单元共聚,基于简单结构设计合成了一组具有给体-受体型结构的聚联苯胺基共轭聚合物聚物。采用H NMR、FT-IR,XRD对单体及聚合物进行了结构表征,表明各目标产物成功制得。通过Uv-vis、Uv-vis-DRS、循环伏安、计时电位、交流阻抗以及循环性能测试对各共聚物进行了光电性质及电化学性能测试。结果表明,引入甲氧基后制得的共轭聚合物P3分子链共轭程度较高,结晶性较佳,光学带隙E_g^opt为2.09 eV,该样品具有较高的HOMO及较低的LUMO值,分别为-5.15 eV和-3.06 eV,呈现更好的氧化还原性,相应地也表现出较佳的电化学电容特性。0.3 A/g时,P3恒流充放电首次放电比电容达1030 F/g,经700次循环仍保持在530 F/g。