多孔聚合物储氢材料研究进展

综述多孔聚合物储氢材料自具微孔聚合物、共轭微孔聚合物、超交联聚合物的合成方法及储氢性质的研究进展.分析影响储氢材料的储氢性能因素,并与其他多孔储氢材料的储氢性能进行比较.     

共轭微孔聚合物的合成及其光催化性能研究

共轭多孔聚合物由于其丰富的制备方法、良好的光热稳定性以及可调的能带结构，在可见光催化中展现了广阔的应用前景.本文采用Pd催化的Suzuki-Miyaura交叉偶联反应制备了共轭微孔聚合物CMP1和线性聚合物LP2，通过扫描电子显微镜（SEM）和X射线衍射（XRD）对聚合物的形貌和结构进行表征.通过紫外可见漫反射光谱（DRS）研究了两种聚合物的光学性质，结果表明共轭微孔聚合物CMP1的可见光吸收能力明显优于LP2.通过循环伏安（CV）测试得到两种聚合物的导带位置，两种聚合物的能带结构位置均满足光催化NADH再生的热力学条件.通过电化学测试分析了两种聚合物的光电流响应和电化学阻抗，与线性聚合物LP2相比，共轭微孔聚合物CMP1具有更快的光激发响应和电荷迁移速率.最后将两种聚合物用于光催化NADH再生实验以研究其光催化活性，CMP1和LP2对NADH再生的效率分别为58.3%和50%，表明共轭微孔聚合物光催化剂具有优异的催化活性.     

封存类甲烷型一维水带的微孔配位聚合物

水热条件下,4,4′-联吡啶、硝酸镍与咪唑甲酸反应,使咪唑甲酸脱羧构筑了配位聚合物{[Ni（4,4′-bipy）（H2O）（HCOO）2].4H2O}n（其中4,4′-bipy=4,4′-联吡啶,HCOO=甲酸根）,通过元素分析、X-射线单晶衍射等技术对其结构进行了表征。配合物属单斜晶系,空间群Cc,a=1.04 862（2）nm,b=2.0 061（4）nm,c=0.81 072（16）nm,β=102.59（3）°;Z=4,R=0.0679,wR=0.1 337。在配合物中,甲酸根和4,4′-联吡啶分别与Ni（Ⅱ）配位,形成具有＂CdSO4（6581）＂拓扑结构的三维微孔网络,微孔尺寸为1.0 028 nm×1.0 486 nm,有趣的是,微孔配位聚合物主体了一种新型类甲烷结构的一维水带,其是由（H2O）4水簇通过氢键相互作用共点拓展而成。     

HPAM／AlCit交联聚合物溶液微孔膜过滤行为研究

分别采用孔径为1．2μm醋酸纤维素树脂核微孔滤膜及2μm混合纤维素树脂热压滤膜,考察了HPAM／AlGit交联聚合物溶液在恒压并流微过滤条件下的微孔膜过滤行为。结果表明,随反应时间的延长,该交联聚合物溶液中交联聚合物线团的数目逐渐增加,对于核微孔滤膜,其封堵作用遵循表面过滤机理,侧重反映封堵过程中交联聚合物线团的粒子特性;而对于网络型热压滤膜,过滤实验中交联聚合物线团对滤膜的封堵作用逐步由深度过滤过渡到表面过滤,侧重反映交联聚合物线团封堵非均—孔径滤膜所具有的非均匀封堵特征,即遵循大孔到中孔到小孔的封堵过程。     

微孔配位聚合物{[Cu(4-PTZ)]·H2O}n的合成与晶体结构

在水热条件下,利用四唑吡啶（4-PTZ）、Cu2（OH）2CO3反应获得了一种新型微孔配合物[Cu（4-PTZ）].H2O（其中4-PTZ=四唑吡啶）,通过X-射线单晶衍射技术测定了晶体结构。配合物属单斜晶系,空间群P21/c,晶胞参数：a=5.7 176（5）nm,b=16.7 670（14）nm,c=9.3 620（8）nm;α=90.000°,β=97.480（10）°,γ=90.000°。中心Cu（Ⅰ）原子分别与1个4-PTZ中的吡啶N原子及另外3个4-PTZ中的四唑N原子配位形成畸变的四面体构型。在配合物中,4-PTZ的四唑基团采用μ3桥连方式连接紧邻Cu（Ⅰ）原子,沿c轴形成一维共边双股螺旋链,进而通过4-PTZ吡啶环的连接作用拓展为具有（42.63.8）拓扑结构的三维微孔配位聚合物。     

HPAM/AlCit交联聚合物溶液微孔膜过滤行为研究

分别采用孔径为 1.2 μm醋酸纤维素树脂核微孔滤膜及 2 μm混合纤维素树脂热压滤膜 ,考察了HPAM/AlCit交联聚合物溶液在恒压并流微过滤条件下的微孔膜过滤行为。结果表明 ,随反应时间的延长 ,该交联聚合物溶液中交联聚合物线团的数目逐渐增加 ,对于核微孔滤膜 ,其封堵作用遵循表面过滤机理 ,侧重反映封堵过程中交联聚合物线团的粒子特性 ;而对于网络型热压滤膜 ,过滤实验中交联聚合物线团对滤膜的封堵作用逐步由深度过滤过渡到表面过滤 ,侧重反映交联聚合物线团封堵非均一孔径滤膜所具有的非均匀封堵特征 ,即遵循大孔到中孔到小孔的封堵过程     

基于二(1,2,3-三氮唑)吡啶共轭微孔聚合物的制备及其催化性能研究

以合成的2,6-双(1-(4-(9H-咔唑-9-基)苯基)-1H-1,2,3-三唑-4-基)吡啶(CPTP)为单体,采用氯仿为溶剂、无水三氯化铁为催化剂,通过氧化偶联方式合成一种共轭微孔聚合物(PCPTP).利用红外光谱、固体核磁碳谱、紫外可见漫反射谱等表征聚合物的结构和性质.实验结果表明,PCPTP具有很强的可见光吸收能力,可以有效催化可见光诱导N-取代四氢异喹啉的α-氧化反应,且可重复回收使用多次.密度泛函理论(DFT)计算结果表明,聚合物的电子供体-受体(DA)结构是PCPTP具有高效光催化性能的重要因素.     

一种基于噻吩的共轭有机多孔聚合物的合成及其光催化性能研究

共轭多孔聚合物(CPPs)具有扩展的共轭体系和多孔性,是一种具有广阔应用前景的非均相无金属光催化剂.本文中,我们报道一种基于噻吩的有机多孔聚合物的设计和制备,首先利用Suzuki偶联反应合成出单体3,3',5,5'-四(噻吩-2-基)-1,1'-联苯,再以三氯化铁为催化剂催化噻吩偶联,成功制备一种共轭有机多孔聚合物(PTB).这种聚合物光吸收可达到800 nm,比表面积为699.8 m~2·g~(-1),并且中孔和微孔共存.在非均相体系中,这种催化剂对胺氧化偶联表现出有效的光催化性能,反应产率可达94%,并且亚胺为其唯一产物.     

含苯乙酯基共轭微孔聚合物的合成与表征

成功合成了新型单体3,5-二溴苯甲酸(1-苯乙基)酯(RO),其收率高达86％.以R0和1,3,5-三[(4-乙炔基)苯基]苯为单体,采用Sonogashira偶联反应,首次成功制备了含苯乙酯基共轭微孔聚合物(CMP-E),其收率为78％.采用核磁氢谱、傅立叶变换红外光谱、全自动气体吸附分析、扫描电镜和热失重分析等测试...     

MMA-EDMA聚合物微球型和包覆硅胶型填料的制备与色谱性能

以Methyl methacrylate(MMA)和Ethylene dimethacrylate(EDMA)作为单体制备了多孔聚合物微球型(PG)和硅胶基质聚合物包覆型填料(PCSG).经电子显微镜、元素分析、尺寸排阻色谱和反相液相色谱对多孔聚合物微球粒径、硅胶基质聚合物包覆程度、交联剂添加对填料微孔构造的影响、非极性和极性化合物的色谱保留行为进行了评价和讨论.结果显示:PG和PCSG填料制备过程中形成了与C18填料不同的微孔结构;PG填料的大微孔体积Vb最大,PCSG填料小微孔体积Va最大.PG和PCSG填料的小微孔体积Va的不同导致填料表面具有相同的MMA高分子链却表现出不同的疏水性能;大微孔体积Vb的存在使填料对大体积芳香族化合物分离表现出了与C18填料不同的立体选择性.PG和PCSG填料因其表面残留有相同的MMA高分子链,使其对极性芳香族化合物表现出了相似的色谱保留行为.PCSG填料的柱效能介于C18和PG填料之间.     

Control of conformational and interpolymer effects in conjugated polymers.

The role of conjugated polymers in emerging electronic, sensor and display technologies is rapidly expanding. In spite of extensive investigations, the intrinsic spectroscopic properties of conjugated polymers in precise conformational and spatial arrangements have remained elusive. The difficulties of obtaining such information are endemic to polymers, which often resist assembly into single crystals or organized structures owing to entropic and polydispersity considerations. Here we show that the conformation of individual polymers and interpolymer interactions in conjugated polymers can be controlled through the use of designed surfactant poly(p-phenylene-ethynylene) Langmuir films. We show that by mechanically inducing reversible conformational changes of these Langmuir monolayers, we can obtain the precise interrelationship of the intrinsic optical properties of a conjugated polymer and a single chain's conformation and/or interpolymer interactions. This method for controlling the structure of conjugated polymers and establishing their intrinsic spectroscopic properties should permit a more comprehensive understanding of fluorescent conjugated materials.     

微孔共轭聚合物的合成调控及其吸附研究进展

微孔共轭聚合物(CMPs)具有高比表面积以及高孔隙率等性质,是一类重要的吸附材料。本文综述了CMPs材料的合成、调控及其在吸附领域应用的研究现状,归纳总结了不同偶联方式制备的CMPs所具有的不同特点,讨论了反应单体的结构和比例以及反应溶剂、反应温度、催化剂用量和反应添加物等参数对CMPs的分子结构、形貌和孔道孔隙的影响规律,明确了制备CMPs适宜的调控策略。同时介绍了CMPs在重金属和有机物等污染物吸附上的应用,并对CMPs未来研究方向进行了展望。     

Synthesis and photocurrent response of porphyrin-containing conjugated polymers

In recent years conjugated polymers have attracted considerable attention because of their potential appli- cations in the fields of light emitting diodes, photo- voltaic devices, and sensors[1―7]. In the fabrication of semiconductor photovoltaic devices…     

K 4169合金铸件的常温疲劳断裂行为

摘要：
通过在某K4169合金精密大型熔模铸件本体典型承力结构处取样而进行常温疲劳试验,并结合疲劳断口的分析与凝固过程的温度场模拟,对其疲劳断裂机制进行探讨.结果表明,不同结构试样的疲劳寿命差异显著,其疲劳失效与微观疏松缺陷及其分布有关.早期的疲劳失效试样中存在大量的疏松缺陷,而疲劳性能较好的试样的疏松缺陷很少.当疏松缺陷较少时,疲劳裂纹主要沿晶间Laves相和碳化物扩展;当疏松缺陷较多时,裂纹主要经疏松缺陷而加速扩展并导致试样的早期失效.
关键词：
K4169合金; 疲劳断裂; 疏松缺陷; 模拟
中图分类号： TG 111.8
文献标志码： A     

Progress in photonic and optoelectronic active polymers and organic solids

The progress of the researches in photonic and optoelectronic active polymers and organic solids in recent two decades is reviewed with particular attention to the excellent achievements of Chinese scientists. The recent progress in the areas of conducting polymers, organic light-emitting diodes, photoelectric conversion material, material for information storage, and nonlinear optical polymers is introduced. The peculiarities of organic photonic and optoelectronic active materials are briefly compared with those of inorganic photonic and optoelectronic materials.     

Highly sensitive biosensors based on water-soluble conjugated polymers

Conjugated, conductive polymers are a kind of important organic macromolecules, which has found applications in a variety of areas. The application of conjugated polymers in developing fluorescent biosensors represents the merge of polymer sciences and biological sciences. Conjugated polymers are very good light harvesters as well as fluorescent polymers, and they are also “molecular wires”.Through elaborate designs, these important features, i.e.efficient light harvesting and electron/energy transfer, can be used as signal amplification in fluorescent biosensors. This might significantly improve the sensitivity of conjugated polymer-based biosensors. In this article, we reviewed the application of conjugated polymers, via either electron transfer or energy transfer, to detections of gene targets, antibodies or enzymes. We also reviewed recent efforts in conjugated polymer-based solid-state sensor designs as well as chip-based multiple target detection. Possible directions in this conjugated polymer-based biosensor area are also discussed.     

基于水溶性共轭聚合物的蛋白质荧光传感器

化学和生物传感器研究领域对新传感材料的开发越来越依赖.探讨了基于荧光信号放大共轭聚合物的蛋白质传感器的最新进展;共轭聚合物可作为高效电子/能量传递载体这一特性是其高灵敏度检测/信号放大的根源;详细介绍了数种传感策略.     

咪唑基配位聚合物

含咪唑基配体的配位聚合物，有其独特的光学、磁性、催化和生物活性，并具备配合物和复合高分子的特点，在应用新材料、分子识别和自组装等方面有广阔的应用前景。本就咪唑基有机配体中连接咪唑的有机基团的差异，对含咪唑基配体的配位聚合物进行了分类研究。     

有机聚合物及小分子材料的电致发光器件

论述了有机聚合物及小分子材料的电致发光原理 ,发光二极管的结构及影响器件稳定性、寿命的原因 ,总结了目前该领域所取得的成果 ,展望了下世纪有机发光材料的应用前景和商业化可能性 .     

A homochiral metal-organic porous material for enantioselective separation and catalysis

Inorganic zeolites are used for many practical applications that exploit the microporosity intrinsic to their crystal structures. Organic analogues, which are assembled from modular organic building blocks linked through non-covalent interactions, are of interest for similar applications. These range from catalysis, separation and sensor technology to optoelectronics, with enantioselective separation and catalysis being especially important for the chemical and pharmaceutical industries. The modular construction of these analogues allows flexible and rational design, as both the architecture and chemical functionality of the micropores can, in principle, be precisely controlled. Porous organic solids with large voids and high framework stability have been produced, and investigations into the range of accessible pore functionalities have been initiated. For example, catalytically active organic zeolite analogues are known, as are chiral metal-organic open-framework materials. However, the latter are only available as racemic mixtures, or lack the degree of framework stability or void space that is required for practical applications. Here we report the synthesis of a homochiral metal-organic porous material that allows the enantioselective inclusion of metal complexes in its pores and catalyses a transesterification reaction in an enantioselective manner. Our synthesis strategy, which uses enantiopure metal-organic clusters as secondary building blocks, should be readily applicable to chemically modified cluster components and thus provide access to a wide range of porous organic materials suitable for enantioselective separation and catalysis.