有机胺-多金属氧酸盐超分子化合物的合成、结构及其光、热变色性质研究

近年来随着纳米材料科学、功能材料科学和超分子材料科学等学科的交叉渗透和迅猛发展，设计合成新型的多金属氧酸盐超分子变色材料和研究其结构、性质及变色机理具有重要的理论意义和应用价值。 本文以光致变色材料和热致变色材料的合成、结构与性质的研究为主线，通过水热法和溶液法制备了一系列含氮有机分子多金属氧酸盐的超分子化合物。解析了它们的晶体结构并研究了它们的光致变色与热致变色性质。采用低温固相反应法制备了具有变色特性的纳米氨基酸多金属氧酸盐。主要研究结果如下： 利用水热合成法制备了乙二胺三钼酸盐晶体,发现乙二胺三钼酸盐不仅具有光致变色性质，而且具有热致变色性质。在 365 nm 的紫外光照射下乙二胺三钼酸盐的光致变色样品呈红棕色，而热致变色样品在 180～250 ℃ 之间为蓝黑色。紫外-可见漫反射光谱被用于表征它们的变色性质。FT-IR 和 XRD 的结果确定着色后的样品其晶体结构和钼氧阴离子的骨架不改变，只是发生了轻微的畸变。一系列的光致变色样品和热致变色样品的ESR谱分别保持着各自特征，但二者有明显的差别，这反映出该化合物的热致变色机理与光致变色机理可能有所不同。这一现象是被首次发现和提出的。 利用水热法成功地合成了1, 6-己二胺三钼酸盐及四钼酸盐超分子化合物。单晶X-射线揭示出1, 6-己二胺三钼酸盐是一个新的超分子化合物，在它的晶体结构中，平行于 a 轴的新的无限链[Mo3O10]2–是由扭曲的MoO6八面体通过共边和共角连接的。质子化的己二胺阳离子占据着由无限链[Mo3O10]2–形成的隧道，它们之间以较强的氢键相互作用，形成了一维网络结构。我们发现这两种晶体均展示了新颖的光致变色与热致变色性质。我们利用FTIR、XRD、ESR和XPS对它们的变色性质进行了研究与探索。 选用4, 4'-联吡啶这种线状双基刚性配体, 利用水热法合成了两种4, 4'-联吡啶多金属钼酸盐晶体：一种是化学式为C10H12Mo7N2O23化合物, 另一种是化学式为C10H12Mo3N2O11化合物。测定了前者的晶体结构。两种晶体同样地展示了光致变色和热致变色性质，但后一种化合物有着明显比前一种化合物敏感的光热变色性质。ESR谱揭示出在UV光照射和加热的条件下，两个化合物中的Mo (Ⅵ) 原子均能被还原成Mo(Ⅴ)原子，但仅后一种化合物通过光热着色后有自由基产生。这是否是造成二者光热变色性质差别的原因，有待于今后更深入的研究和探索。 我们利用水溶液法成功地合成了氨基酸多金属氧酸盐晶体。晶体结构分析表明：组氨酸硅钨酸盐基本结构单元由一个[SiW12O40]4–多阴离子和两个质子化的[H2His]2+有机阳离子靠两个氢键相互作用组成。这个化合物展示了一个新颖的三维网络结构。脯氨酸硅钨酸盐的晶体结构正在解析中。在光照或加热后，这两个化合物的颜色由白色变为蓝色。我们利用FTIR、XRD、Raman和ESR研究了它们的光热变色性质。 将低温固相化学反应制备纳米材料的方法应用于纳米氨基酸多金属氧酸盐的制备，选取Silverton型多酸与多种氨基酸反应合成了系列纳米氨基酸-杂多酸电荷转移化合物。苏氨酸((HThr)7PMo12O42•4H2O) 磷钼多酸盐为形状不很规则的二维纳米片，酪氨酸磷钼多酸盐((HTyr)7PMo12O42•5H2O) 为一维纳米棒，丝氨酸磷钼多酸盐((HSer)7PMo12O42•5H2O)和谷氨酸磷钼多酸盐((HGlu)7PMo12O42•4H2O)为零维纳米粒子。有机给体氨基酸的结构对 Silverton 结构杂多化合物的形成起模板剂的作用，从而导致形貌的差异。在紫外光照射下，这些化合物会从白色变成蓝色，且对光比较敏感。

用NMR、FT-IR、DSC和AFM的方法研究PP-b-PE的结构与性能

聚丙烯是一种优异的高分子材料，但其低温抗冲击性能欠佳，因而限制了其应用范围。采用PP与PE嵌段共聚来改善PP的抗冲击性能是世界上目前行之有效的方法，因而引起人们的重视。由于聚丙烯嵌段共聚物（PP-b-PE）是由多组分组成的复杂体系，对其组成和链的结构仍不十分清楚。因此，本工作选取国外（6组）和国内（5组）共计11组PP-b-PE样品，分别对其结构、性能及其影响因素进行了研究，为实际应用提供了依据。为了保证能将PP-b-PE中的橡胶成分抽提出来，先将PP-b-PE样品用二甲苯溶解，之后加入甲醇沉淀、过滤、干燥，最后用正庚烷抽提，使得PP-b-PE样品中正庚烷的不可溶物与可溶物完全分离。其中，可溶物即为橡胶，不可溶物为塑料。再利用高温核磁共振谱仪（NMR）、示差扫描量热仪（DSC）和傅立汗卜变换红外谱仪（FT-IR）等先进的分析技术手段进行结构分析，并用原子力显微镜（AFM）观察生产过程中样品的形貌。实验和分析结果表明：在正庚烷可溶物中含有低熔点的聚丙烯和嵌段长度不同且能结晶的聚乙烯；并且还含有属于乙丙无规共聚物橡胶部分的n值小于4的（-CH2-）n结构，以及嵌有结晶性的丙烯和乙烯链节。正庚烷的不可溶物主要为聚丙烯，及少量聚乙烯。对于不同物性的PP-b-PE而言，正庚烷不可溶物决定了其刚性，正庚烷可溶物决定了其韧性，并由其粘度比决定了橡胶在聚丙烯中的分布情况。用AFM来研究PP-b-PE中的橡胶颗粒的分布情况是非常好的分析方法。PP-b-PE样品中橡胶的含量及其组成成分将对PP-b-PE的性能产生很大的影响。国内用浆液法生产的PP-b-PE样品中橡胶含量相对于用液一气相法和气相法生产的要少，但在其正庚烷不可溶物中含有较多的乙烯。从而可以用控制乙烯的含量来改善其抗冲击性能，这是浆液法与液一气相法和气相法的最大区别。液一气相法和气相法生产的PP-b-PE样品中的正庚烷可溶物的含量和结构十分接近。结果表明，本文采用多种不同的先进的分析方法和实验手段对PP-b-PE的结构与性能的研究是一条有效可行的实验途径。

RAMAN PHONONS OF SILICON WIRES

Using the Keating model and the Raman polarizability of Alben et al., the phonon Raman spectra of silicon wires are calculated. With the calculation results, the Raman spectra of porous silicon of some published papers are analyzed. Until now different authors have had different views on the luminescence mechanism of porous silicon, which may mainly result from the fact that they had different samples.

NEAR-RESONANT RAMAN-SCATTERING FROM GAAS/ALAS SUPERLATTICES

This article presents the results of near-resonant Raman scattering measurements on GaAs/AlAs superlattices at room temperature. A strong enhancement of GaAs LO phonon-even modes resulted owing to a dipole-allowed Frohlich interaction in superlattices. Similar to the previous results, the LO phonon-even modes in a polarized configuration are observed. In contrast to previous work, however, what we observed in depolarized configurations is the LO phonon-odd modes instead of even modes. It is confirmed that the selection rules for near-resonant Raman scattering from LO phonons in this kind of superlattices are the same as those for off-resonant scattering. From the second-order Raman scattering, it is confirmed that polarized second-order Raman scattering spectra consist of overtones and combinations of two even modes, and depolarized second-order Raman scattering spectra consist of combinations of an even mode and an odd mode. Our experimental results coincide with the predictions using the recently developed Huang-Zhu model. A brief discussion on interface modes and their combination with confined modes is also presented.

STUDY OF RAMAN-SPECTRA OF ZNSE-ZNTE STRAINED LAYER SUPERLATTICES

The Raman spectra of the II-VI wide band-gap compound ZnSe-ZnTe semiconductor strained-layer superlattices have been studied. The relations between the Raman shifts of the longitudinal optical phonon modes and the superlattice-structure parameters have been determined. When the layer thickness exceeds 40 angstrom, the change of the LO phonon-mode frequency shifts with the layer thickness is minimal, whereas when the layer thickness is smaller than 40 angstrom, great shifts have been observed. We estimate that the critical thickness of ZnSe-ZnTe SLS is about 40 angstrom. We have also found that the shifts induced by strain are much larger than the red shifts due to confinement.

NEAR-RESONANCE RAMAN-SCATTERING OF LONGITUDINAL OPTICAL PHONON MODES AND INTERFACE MODES IN GAAS/ALAS SUPERLATTICES

The near-resonance Raman scattering of GaAs/AlAs superlattices is investigated at room temperature. Owing to the resonance enhancement of Frohlich interaction, the scattering intensity of even LO confined modes with A1 symmetry becomes much stronger than that of odd modes with B2 symmetry. The even modes were observed in the polarized spectra, while the odd modes appear in the depolarized spectra as in the off-resonance case. The second-order Raman spectra show that the polarized spectra are composed of the overtone and combinations of even modes, while the depolarized spectra are composed of the combinations of one odd mode and one even mode. The results agree well with the selection rules predicted by the microscopic theory of Raman scattering in superlattices, developed recently by Huang and co-workers. In addition, the interface modes and the combinations of interface modes and confined modes are also observed in the two configurations.

RAMAN-SCATTERING BY LO PHONONS IN (GAAS)N1/(ALAS)N2 ULTRATHIN-LAYER SUPERLATTICES

Raman spectra of (GaAs)n1/(AlAs)n2 ultrathin-layer superlattices were measured at room temperature and under off-resonance conditions. The experimental results show that there are two effects in ultrathin-layer superlattices: the confinement effect of LO phonons and the alloy effect. It is found that the relative intensity of the disorder-activated TO mode can give a measure of the alloy effect. The Raman spectra of one-monolayer superlattices measured in various scattering configurations are very similar to those of the Al0.5Ga0.5As alloy, and thus the alloy effect is prominent. However, in the case of monolayer number n greater-than-or-equal-to 4, the confined effect is prominent, while the alloy effect is only shown as an interface effect.