Self‐Assembly and Gelation of Poly(aryl ether) Dendrons Containing Hydrazide Units: Factors Controlling the Formation of Helical Structures

Self‐assembly of AB₂ and AB₃ type low molecular weight poly(aryl ether) dendrons that contain hydrazide units were used to investigate mechanistic aspects of helical structure formation during self‐assembly. The results suggest that there are three important aspects that control helical structure formation in such systems with acyl hydrazide/hydrazone linkage: i) J‐type aggregation, ii) the hydrogen‐bond donor/acceptor ability of the solvent, and iii) the dielectric constant of the solvent. The monomer units self‐assemble to form dimer structures through hydrogen‐bonding and further assembly of the hydrogen‐bonded dimers leads to macroscopic chirality in the present case. Dimer formation was confirmed by NMR spectroscopy and by mass spectrometry. The self‐assembly in the system was driven by hydrogen‐bonding and π–π stacking interactions. The morphology of the aggregates formed was examined by scanning electron microscopy, and the analysis suggests that aprotic solvent systems facilitate helical fibre formation, whereas introduction of protic solvents results in the formation of flat ribbons. This detailed mechanistic study suggests that the self‐assembly follows a nucleation–elongation model to form helical structures, rather than the isodesmic model.     

Efficient dye-sensitized solar cells based on CNTs and Zr-doped TiO2 nanoparticles

The light scattering, harvesting and adsorption effects in dye-sensitized solar cells (DSSCs) are studied by preparation of coated carbon nanotubes (CNTs) with TiO₂ and Zr-doped TiO₂ nanoparticles in the forms of mono- and double-layer cells. X-ray diffraction (XRD) analysis reveals that the phase composition of Zr-doped TiO₂ electrode is a mixture of anatase and rutile phases with major rutile content, whereas it is the same mixture with major anatase content for coated CNTs with TiO₂. Furthermore, the average crystallite size of Zr-doped TiO₂ electrode is slightly decreased with Zr introduction. Field emission scanning electron microscope (FE-SEM) images show that the porosity of Zr-doped TiO₂ electrodes is higher than that of undoped electrode, enhancing dye adsorption. UV–visible spectroscopy analysis reveals that the absorption onset of Zr-doped TiO₂ electrodes is slightly shifted to longer wavelength (the red-shift) in comparison with that of undoped TiO₂ electrode. Moreover, the band gap energy of TiO₂ nanoparticles is decreased by Zr introduction, enhancing light absorption. It is found that electron injection of monolayer TiO₂ electrode is improved by introduction of 0.025 mol% Zr, resulted in enhancement of its power conversion efficiency (PCE) up to 6.81% compared with 6.17% for pure TiO₂ electrode. Moreover, electron transport and light scattering are enhanced by incorporation of 0.025 wt% coated CNTs with TiO₂ in the over-layer of double layer electrode. Therefore, double layer solar cell composed of 0.025 mol% Zr-doped TiO₂ nanoparticles as the under-layer and mixtures of these nanoparticles and 0.025 wt% coated CNTs with TiO₂ as the over-layer shows the highest PCE of 8.19%.     

锂离子电池用聚合物电解质的最新进展II.含液聚合物电解质

由于干态聚合物电解质目前还不能满足聚合物锂离子电池的应用要求,人们致力于开发含液体增塑剂的聚合物电解质,包括凝胶型和微孔型两类体系。本文综述了含液聚合物电解质的最新进展,重点论述了各种新体系和新方法。     

溶胶-凝胶制备技术与新型催化材料Ⅲ.溶胶粒子表面修饰方法制备催化膜

提出用溶胶粒子表面修饰方法，结合溶胶凝胶技术制备无机催化膜．该方法的基本原理是利用合适的金属配合物在胶粒表面的吸附作用，经溶胶凝胶过程，将活性组分结合到无机膜中．实验测定结果表明：（ＮｉＥＤＴＡ）２－，ＶＯ－３，ＭｏＯ２－４，（Ｐｄ（ＮＨ３）４）２＋，ＰｄＣｌ２－４，ＰｔＣｌ２－６和ＲｈＣｌ３－６可用来修饰ＡｌＯＯＨ溶胶．以Ｐｄ／γＡｌ２Ｏ３催化膜的制备为例，经三次溶胶凝胶过程，可制得无裂缺的厚度为９μｍ的Ｐｄ／γＡｌ２Ｏ３催化膜，膜材料的平均孔直径为６ｎｍ，Ｐｄ被均匀地分布在膜的顶层，其平均粒径为２３ｎｍ．     

Mg_(0.15)Zn_(0.85)O:Tb合金薄膜的阴极射线发光性质研究

采用溶胶凝胶方法成功地制备了掺杂稀土铽离子的 Zn O和 Mg0 .1 5Zn0 .85薄膜。通过对 X射线衍射结果的分析表明 ,稀土离子替代了 Zn2 +的格位 ,进入了半导体基质的晶格中。从阴极射线发光结果可以发现 ,在Mg0 .1 5Zn0 .85O基质中 ,可以观察到来源于稀土铽离子各能级的发射 ,而 Zn O:Tb的薄膜只能观察到较强的铽离子 5D4 — 7F5能级的跃迁。这可能是由于 Mg0 .1 5Zn0 .85O基质的能隙 (3 .65 e V)比 Zn O更宽 (3 .3 e V) ,其对铽离子的能量传递更有效的缘故。     

纳米氧化钛-乙二醇溶胶溶液的研究

选用了钛酸丁酯、硬脂酸和乙二醇作为表面活性剂，采用表面化学修饰和表面物理修饰2种方法修饰纳米氧化钛，然后分散在乙二醇溶剂中形成溶胶溶液．并通过红外光谱仪、紫外分光计、原子力显微镜，分析了表面化学修饰后的纳米氧化钛表面化学结构的变化，观测了纳米氧化钛溶胶在乙二醇溶剂中稳定性．试验结果表明表面活性剂与纳米氧化钛的表面的不饱和键之间形成了新的化学结构，粒子表面可能接枝上有机长链，提高了纳米粒子在溶剂中的相容性．表面化学修饰后的纳米氧化钛与乙二醇溶剂形成了较稳定的溶胶体系，而且纳米溶胶粒径较小．表面活性剂添加量与纳米粒子添加量控制在(1～1．2)：1时，可以获得纳米溶胶粒径较小，同时溶胶稳定性较好的纳米氧化钛-乙二醇溶胶体系．     

Resistivity－temperature characteristics of sol gel YBa2Cu3Oy samples synthesized in flowing oxygen atmosphere

The relationship of resistivity versus synthesizing temperature of sol gel YBa_2Cu_3O_y samples was studied when prepared under flowing oxygen conditions. A set of high-temperature ρ－T curves was obtained for the whole process. After the sample finished the test measuring, its resistivity was ρ_{300}=9.83×10^{-3 }Ω·cm at room temperature. The ρ－T curve also showed that the orthorhombic－tetragonal phase transformation of sol-gel YBa_2Cu_3O_y sample occurred at 581℃ for the sample in the rising temperature process, but at 613℃ in the cooling process, lower than that of the samples made by using the conventional powder metallurgy methods.     

Two‐stage copolycondensation of preformed oligomers with bisphenols by tosyl chloride/dimethylformamide/pyridine from distributions of resulting oligomers determined by a combination of gel permeation chromatography and NMR

A two‐stage co‐oligomerization of the oligomers initially formed from an equimolar mixture of isophthalic acid (IPA) and terephthalic acid (TPA) and 2,2‐bis(4‐hydroxyphenyl)propane (BPA, 50 mol %) with bisphenols (BPs, 20 mol %) was carried out using a tosyl chloride/dimethylformamide/pyridine condensing agent. The distributions of the resulting oligomers (n_x‐mers), which were quenched with methanol, were determined by a combination of gel permeation chromatography (GPC) and NMR. These distributions (presented by molar percentage) were conveniently calculated with the equation n_x (mol %) = n_x (% mol by GPC) × n₀ (mol % by NMR)/n₀ (% mol by GPC), where n_x (% mol) = n_x (wt % by GPC)/its molecular weight. The results showed the distributions of the preformed IPA/TPA‐BPA oligomers to be in fairly good accord with those obtained directly from GPC and to be supported by the NMR results. The calculation was applied to the co‐oligomers prepared up to a reaction of 0.7, at which there was an increase in the number of higher oligomers indivisible by GPC and the distributions could no longer be determined by molar percentage. The calculated distributions are discussed in relation to the results of copolycondensation. The sequence distributions in the resulting co‐oligomers, which were also examined by NMR, are compared with those in the copolymers. © 2003 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 44–51, 2004     

Synthesis and characterization of alt‐bipyridinylene‐phenylene copolymers containing ruthenium(II) complexes

Poly{bis(4,4′‐tert‐butyl‐2,2′‐bipyridine)–(2,2′‐bipyridine‐5,5′‐diyl‐[1,4‐phenylene])–ruthenium(II)bishexafluorophosphate} ( 3a ), poly{bis(4,4′‐tert‐butyl‐2,2′‐bipyridine)–(2,2′‐bipyridine‐4,4′‐diyl‐[1,4‐phenylene])–ruthenium(II)bishexafluorophosphate} ( 3b ), and poly{bis(2,2′‐bipyridine)–(2,2′‐bipyridine‐5,5′‐diyl‐[1,4‐phenylene])–ruthenium(II)bishexafluorophosphate} ( 3c ) were synthesized by the Suzuki coupling reaction. The alternating structure of the copolymers was confirmed by ¹H and ¹³C NMR and elemental analysis. The polymers showed, by ultraviolet–visible, the π–π* absorption of the polymer backbone (320–380 nm) and at a lower energy attributed to the d–π* metal‐to‐ligand charge‐transfer absorption (450 nm for linear 3a and 480 nm for angular 3b ). The polymers were characterized by a monomodal molecular weight distribution. The degree of polymerization was approximately 8 for polymer 3b and 28 for polymer 3d . © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 2911–2919, 2004