三维有序交联聚苯乙烯大孔材料的制备及其功能化

利用二氧化硅模板法,采用苯乙烯-二乙烯基苯自由基共聚方法制备了孔径在200～1020nm的三维有序交联聚苯乙烯大孔材料,并在此基础上通过氯甲基化反应对所制备的有序孔材料进行孔壁功能化.对所制备的三位有序交联聚苯乙烯孔材料及氯甲基化后的形貌进行了扫描电子显微镜表征.结果表明,所制备的有序孔材料孔径均一、结构有序,氯甲基化后的孔材料保持了原有孔材料的有序结构.红外光谱分析表明氯甲基基团已被成功地引入了有序孔材料,并且主要发生在苯环的对位.通过热重一滴定分析方法确定了引入到有序孔材料的氯相对含量为5.52mmol/g.     

Eu~(3+)诱导嵌段聚合物的自组装及荧光性能

通过4-氰基-4-乙基三硫代戊酸卞基酯(RAFT)聚合的方法合成具有亲水段和疏水段的嵌段聚合物PS-bPAA。以该两嵌段聚合物、氧化铕、邻菲罗啉、盐酸为原料制备聚合物稀土络合物。由于嵌段聚合物具有亲水段和疏水段,所以在二甲基甲酰胺(DMF)溶剂中,该络合物会形成分散性均一的核壳结构的球形纳米胶束。研究在稀土配合物中聚合物和小分子配体1,10-邻菲罗啉(phen)对Eu~(3+)荧光性能的影响,当PS的聚合度为23,PAA的聚合度为17时,可成功制备出直径30~50nm的纳米胶束,可应用于太阳能电池领域,对稀土在太阳能电池中的应用具有重要意义。     

邻菲罗啉金属配合物的制备及对聚氯乙烯光学性能的影响

研究了配体浓度、反应温度及反应时间对合成以1,10-邻菲罗啉为配体的金属配合物产率的影响,并将以Zn~(2+)、Al~(3+)、Bi~(3+)、Eu~(3+)为中心离子的配合物添加到聚氯乙烯(PVC)塑料中,研究了其对PVC光学性质的影响。得到了制备相应配合物的最佳反应条件:1,10-邻菲罗啉浓度为2mmol/10mL,反应温度为50~70℃,反应时间为1~4h时,邻菲罗啉类金属配合物的产率最高。并且发现ZnP_2、AlP_3、EuP_4对PVC的透光率影响较小,荧光光谱表明,前2种可以有效地将紫外光转换为蓝光,而EuP_4可以将紫外光及蓝绿光转换为特征明显的红色光,而BiP_4对PVC薄膜的透光率有较大的影响(10%),但其具有良好的转光特性。     

一种新型铕三元配合物的制备与荧光性质研究

合成了1个邻菲罗啉衍生物DmPPhen,作为第二配体,以α-噻吩三氟甲酰丙酮作为第一配体制备了1种新颖的三元稀土铕(Eu)配合物发光材料。利用红外光谱、元素分析及核磁氢谱分析了配合物的组成与结构。在常温下研究了配合物的荧光性质,结果表明配合物有很好的荧光性质。     

共价有机聚合物的合成及在燃料电池阴极氧还原反应中的应用

共价有机聚合物(Covalent Organic Polymers,COPs)是一类通过共价键将不同几何构型和长度的有机配体组装成多维度多功能的高水热稳定性的有机多孔材料,具有高比表面积、孔道尺寸可控及结构多样的特性,在能源的转化和储存领域应用前景广阔。围绕COP材料在燃料电池阴极氧还原催化领域中的应用,重点总结了二维、三维及功能化COP材料的合成策略与方法,及几类代表性前驱体(卟啉类、三嗪类、聚苯胺类以及复合类)在氧还原电催化中的调控与性能研究。COP材料的定向裁剪和功能化,可为高效氧还原催化材料的制备提供便捷、丰富、可控的新型合成平台,推动燃料电池新型催化剂的研发,为突破燃料电池工业应用提供新方案。     

一种新型稀土铕配合物的制备及荧光性能研究

本文以2,6-二(4-乙氧基苯甲酰基)吡啶(L)和1,10-邻菲罗琳为配体,设计并制备了新型的稀土铕离子三元配合物EuL(Phen)2(Phen=1,10-邻菲罗啉),通过核磁共振氢谱和红外光谱对结构进行了表征。研究表明,配合物具有很好的溶剂化效应,溶液体系的荧光强度与溶剂的极性有关,极性越小体系荧光强度越大;固体配合物在593nm和620nm处有较强的Eu~(3+)特征发射峰,以620nm处的荧光强度最强,2处峰强度比值为4.57,配合物单色性较好,是一种具有很好的应用前景的红光材料。     

新型芳香族多羧酸配体1,3,5-三(间苯二甲酸)的合成与表征

为了增加金属有机骨架材料对氢气的吸附势能叠加量以及得到配位不饱和的金属中心,从而提高材料对氢气的吸附焓,改善材料在常温下的储氢性能,通过SUZUKI偶联反应,设计合成了新型芳香多羧酸配体1,3,5-三(间苯二甲酸)。该新配体集中了合成NOTT-112和MOF-177的配体的特点。与合成NOTT-112的配体相比,新配体减少一个苯环的尺寸,将使聚合物材料的孔尺寸相应减小,增加对氢气的吸附势能叠加量。与合成MOF-177的配体相比,新配体的羧酸配位数增加1倍,将使聚合物中的晶体结构更加多样化。可以预测,用新配体合成的新型金属有机骨架材料可以兼顾NOTT-112及MOF-177的性能,对吸附储氢材料的研究开发具有重要意义。     

功能化介孔氧化铝材料的制备及应用进展

介孔氧化铝因其在催化、吸附等领域具有巨大的应用前景,而受到国内外研究学者的广泛关注。随着工业化生产要求的不断提高,普通介孔氧化铝的使用逐渐受到限制,制备高性能的功能化介孔氧化铝材料将具有重大意义。功能化介孔氧化铝材料具有较高的催化活性、较强的机械和水热稳定性,不仅在催化、吸附领域受到极大重视,而且延伸到光学、医学等重要领域。综述了功能化介孔氧化铝材料的主要制备方法,包括原位合成法和浸渍法,并对两种方法存在的优缺点进行了比较。同时详细介绍了功能化介孔氧化铝材料的种类以及在催化、吸附分离和其它领域的应用,并展望了功能化介孔氧化铝材料的发展及应用前景。     

可用于纸张防火的新型高分子材料的制备与性能研究

以二苯甲酰甲烷(DBM)为第一配体,1.10-邻菲罗啉(phen)为第二配体,合成了稀土铽配合物,并通过红外、核磁、元素分析和质谱等手段对配合物进行了表征。在一定条件下,将此稀土配合物加入甲基丙烯酸(MAA)和苯乙烯(St)聚合体系中进行聚合,制备了一种高分子复合材料,并对高分子材料进行了紫外、荧光、热重(TG)分析。结果表明:这种材料的分解温度大于220℃;在350 nm和262 nm处有较强的紫外吸收;其荧光光谱发出较强的稀土Tb3+特征吸收峰。研究表明,所得的高分子复合材料具有较好的紫外吸收性和较高的热稳定性,阻燃实验证明,平均碳化度为9.7 cm,说明所得高分子复合材料具有较好的阻燃性。     

稀土席夫碱邻菲罗啉三元配合物的合成及活性研究

以席夫碱[N,N′,-双(2,4-二羟基苯甲醛)缩邻苯二胺](L)和邻菲罗啉为配体,与稀土金属离子配位合成了稀土席夫碱邻菲罗啉三元配合物REM(o-phen)2Cl.2H2O(M=La3+、Pr3+、Nd3+、Sm3+),并利用红外光谱、紫外-可见光谱、元素分析和摩尔电导率仪对其结构进行了分析表征,同时将该类配合物应用于生物活性抑菌试验。结果表明,所有配合物对大肠杆菌、金黄色葡萄球菌和白色念珠菌都有较好的抑菌作用,且配合物RESm(o-phen)2Cl.2H2O的抑菌活性最好。     

胶体晶体模板法合成有序大孔聚甲基丙烯酸甲酯

以离心沉降技术组装的二氧化硅胶体晶体为模板,从同种尺寸的二氧化硅微球出发,合成了孔的结构和形貌不同的两种有序大孔聚甲基丙烯酸甲酯。采用扫描电镜对模板、复合物及聚合物的形貌和微观结构进行了观察和表征。实验结果表明,所合成的聚甲基丙烯酸甲酯具有高度有序的多孔结构,模板的热处理工艺对孔的形状和连通性均有重要影响。     

Macroporous Membranes with Highly Ordered and Three-Dimensionally Interconnected Spherical Pores

We have demonstrated the fabrication of highly ordered three-dimensional macroporous membranes with crystalline assemblies of monodispersed mesoscale particles (∼200 nm to ∼10 μm in diameter) as templates. We filled the void spaces among the particles with a UV-curable liquid prepolymer by capillary action. Subsequent solidification of the prepolymer and dissolution of the particles yielded a membrane film consisting of a highly organized and three-dimensionally interconnected framework of spherical pores. The pores are uniform in size, with dimensions defined by the diameter of the particles. The pores are completely exposed on both top and bottom surfaces of the membrane film. In addition to those applications associated with conventional macroporous materials, the macroporous membranes fabricated here are potentially useful as photonic bandgap structures or as supports for the fabrication of diffractive optical sensors due to their specified and highly ordered structures.     

气-液界面二元共沉积法制备三维有序大孔SiO2

采用乳液聚合法制备粒径为229nm的单分散聚苯乙烯(PS)微球,以单分散PS微球和粒径为10nm的硅溶胶为原料,采用蒸发自组装法在气-液界面上二元共沉积,制备了大孔SiO2材料。结果表明,当SiO2体积分数为11%时,大孔SiO2材料呈现有序规整的FCC结构,其填充率为42%,收缩率仅为2%。低温N2吸附表明该材料在大孔孔壁上存在6.4nm左右的介孔,是一种具有大孔/介孔复合孔道结构的功能材料。     

Preparation and photoluminescence properties of three-dimensionally ordered macroporous ZrO2:Eu3+

Three-dimensionally ordered macroporous (3DOM) ZrO2:Eu3+ (0.5%, 1%, 2% and 5%) were successfully prepared using a polystyrene (PS) colloidal crystal template in combination with a sol-gel method. The structure, morphology, porosity, and optical properties of the materials were well characterized by X-ray diffraction (XRD), Field emission scanning electron micrograph (FESEM), N2 adsorption, and photoluminescence (PL) spectra. The results indicated that the closely packed material exhibited three-dimensional ordering of pores and a strong red (5)D0-->(7)F2 transitions under charge transfer excitation. Strong PL and abundant porosity are of particular interest and give this multifunctional material future potential.     

Fabrication and characterization of ordered macroporous semiconductors CdS by colloidal crystal template

The synthesis and characterization of a highly ordered macroporous CdS with regular arrays of spherical pores comparable to optical wavelengths are discussed. The sample has been successfully fabricated using colloidal crystal of poly (styrene-acrylic) (PSA) spheres as templates. The pore size is tunable in the range of 100-400 nm based on the size of PSA spheres. Transmission electron microscope (TEM) and scanning electron microscope (SEM) show that the exactly three-dimensional structure of the template has been imprinted in the final materials. XRD pattern indicates that the walls of the macroporous material are composed of 4 nm CdS nanoparticles making the absorption spectrum shift blue. The sample was also characterized by Raman spectroscopy and photo luminescent spectra (PL).     

Highly ordered three-dimensional macroporous carbon spheres for determination of heavy metal ions

An effective voltammetric method for detection of trace heavy metal ions using chemically modified highly ordered three dimensional macroporous carbon spheres electrode surfaces is described. The highly ordered three dimensional macroporous carbon spheres were prepared by carbonization of glucose in silica crystal bead template, followed by removal of the template. The highly ordered three dimensional macroporous carbon spheres were covalently modified by cysteine, an amino acid with high affinities towards some heavy metals. The materials were characterized by physical adsorption of nitrogen, scanning electron microscopy, and transmission electron microscopy techniques. While the Fourier-transform infrared spectroscopy was used to characterize the functional groups on the surface of carbon spheres. High sensitivity was exhibited when this material was used in electrochemical detection (square wave anodic stripping voltammetry) of heavy metal ions due to the porous structure. And the potential application for simultaneous detection of heavy metal ions was also investigated.     

模板辅助电化学沉积三维有序大孔Fe-Ni合金膜

三维有序大孔磁性材料在光子晶体和新功能磁性材料方面具有潜在优势.采用电化学沉积方法制备三维有序大孔Fe-Ni合金,将聚苯乙烯(PS)微球在ITO导电玻璃上自组装高度有序的胶体晶体阵列作为模板,向模板空隙中电沉积Fe-Ni合金,去除PS模板后获得六方密排多孔结构的Fe-Ni合金薄膜.采用金相显微镜和扫描电子显微镜对多孔薄膜的微观结构进行表征,结果表明,多孔薄膜孔径的大小由模板聚苯乙烯微粒的粒径决定,不同孔径的薄膜由于布拉格衍射呈现出不同的颜色.通过调整沉积时间和沉积温度可以控制有序大孔材料的结构和厚度.     

Fabrication of Transferable Perforated Isoporous Membranes on Versatile Solid Substrates via the Breath Figure Method

Isoporous separation membranes have received considerable attention because of the high‐resolution performance and energy‐saving characteristics. Isoporous membranes prepared by the breath figure method rely on special substrates such as water and ice because solid substrates such as polyethylene terephthalate films, which are widely used in commercial processes, often lead to nonthrough pores. In this work, it is found that highly ordered through‐pore membranes can be fabricated on hydrophilic glass surface when using polymers that are able to form ordered membranes at low concentrations. On the basis of this finding, a facile strategy is proposed to fabricate isoporous membranes on various solid substrates by introducing a water‐soluble polymer interlayer. The multifunctional interlayer promotes the spreading of membrane‐forming solutions, enables the formation of through pores, and simplifies the transfer to macroporous supports to form composite membranes. The versatility of the proposed strategy is verified by using different substrates including highly hydrophobic polytetrafluoroethylene film and using different water‐soluble polymers as the interlayer. Furthermore, the high‐resolution separation performance of the isoporous composite membranes has been demonstrated by the filtration of yeasts under gravitational pressure.     

Fabrication of hydroxyapatite with highly ordered macroporous frame by colloidal templating method

Three-dimensional, highly ordered macroporous frame of hydroxyapatite has been fabricated via a template-assisted colloidal processing technique. In the present method, colloidal template was first prepared with SiO₂ spheres by gravitational sedimentation, which was then infiltrated with hydroxyapatite precursor prepared by the sol-gel process. The resulting hydroxyapatite replicated the three-dimensionally ordered macroporous structure of SiO₂ template. Modified by H₂O₂, the SiO₂ spheres could be packed into better ordered templates. After removal of the template by immersing in NaOH solution, the well-ordered macroporous frame made from HA was obtained. The arrangement of the pore structure was hexagonal close-packed and pore sizes could be controlled by changing the sizes of SiO₂ spheres. The resulting highly ordered macroporous frame of hydroxyapatite could have potential applications in the biomedical field.     

三维规则排列的大孔钛硅混合氧化物的制备与表征

以聚苯乙烯微球离心后形成的三维规则排列的胶晶作模板,用钛酸丁酯和正硅酸乙酯分别和水、乙醇等配制成的混合溶胶填充微球之间的间隙,然后原位形成凝胶,最后通过焙烧(<5℃/min;300℃,5h;570℃,5～10h,空气流速1L/min)除去微球得到三维规则排列的大孔钛硅混合氧化物.样品表面可观察到五颜六色的彩光.样品的SEM图表明,球形孔大小均匀,排列整齐,孔壁填充完全.孔径在500nm左右,孔的排列呈面心立方结构,孔与孔之间由小孔窗相互交连.较高的溶胶浓度有利于溶胶的填充,容易形成孔壁较厚的坚固的三维骨架.低浓度得到的样品孔壁薄,缺陷多,易脆裂.样品的EDS表明Si/Ti的摩尔比为2.7,XRD研究表明孔壁具有无定形的结构.