Design of Functional Cluster using Lattice Space of Zeolite and Analogous Compound as Reaction Field

以沸石及类似化合物的晶格空间为反应场的功能团簇设计

• 批准号: 09650924
• 负责人: MIYAKE Michihiro
• 金额: $ 2.18万
• 依托单位: Okayama University
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for Scientific Research (C)
• 财政年份: 1997
• 资助国家: 日本
• 起止时间: 1997 至 1998
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/grant/KAKENHI-PROJECT-09650924/
• 关键词: Zeolite; Aluminophosphate molecular sieve; Encapsulation; Host-guest reaction; Conducting cluster; Nonlinear optical cluster; Semiconductor cluster; ホスト・ゲスト反応; ニトロアニリン; 硫化物; マイクロクラスター; アルミノリン酸塩モレキュラーシ-ブ; ポリピーロール; ニトロアニリン異性体; 導電性; 非線形光学性

The functional clusters have been synthesized in the lattice space of zeolite Y, aluminophosphate molecular sieve-5 (AlPO _4-5), and so on, and the resulting materials have been characterized in the present research.(1) Pyrrole was encapsulated in two kinds of zeolite Y (NaY and USY) with various concentrations of Cu(II) ions, and the products have been characterized by means of thermoanalytic and spectroscopic methods. Pyrrole was encapsulated as polypyrrole in both NaY and USY with a high concentration of Cu(II) ions, It was found that the polypyrrole fonned in NaY evolved into bipolaron state with increasing Cu(II) content, whereas polypyrrole in USY consisted of polaron and bipolaron states.(2) The encapsulations of thiophen in hexagonal faujasite with Cu(II) ions and pyrrole in zeolite beta with Fe(III) ions have been invesigated and characterized by thermoanalytic and spectroscopic methos. Polythiophen and polypyrrole with electron state of bipolaron were found to be formed in the both lattice spaces, respectively.(3) Nitrophenol (NP) and nitroaniline (NA) isomers were loaded in one-dimensional channels of AlPO4 -5, and the optical properties of the resulting materials (o-NP/, m-NP/, p-NP/, o-NA/, m-NA/, and p-NA/AlPO_4-5) have been characterized, It was found that o-NP/, m-NP/, p-NP/, o-NA/, and m-NA/AlPO_4-5 exhibited nonlinear optical properties (second harmonic generation, SHG) similar to p-NA/AlPO_4-5, and the orders of SHG were m < p < o in NP/AlPO_4-5 series and m < o << p in NA/AlPO_4-5 series, respectively. The SHG intensities of o-NP/, p-NP/, o-NA/, and p-NA/AlPO_4-5 depended on amount of loadings, whereas m-NP/ amd m-NA/AlPO_4-5 hardly did.(4) Semiconductor clusters such as CdS, ZnS, and PbS were synthesized in the lattice space of cancrinite, and the characterization was made. The diffuse-reflectance ultraviolet-visible spectrum revealed that the absorption-edge of CdS cluster blue-shifted, compared with bulk CdS crystal.

本研究在Y沸石、磷酸铝分子筛-5(AlPO_4-5)等晶格空间合成了功能团簇，并对合成的材料进行了表征：(1)用不同浓度的铜(II)将吡咯包裹在两种Y沸石(NaY和USY)中，并用热分析和光谱方法对产物进行了表征。结果表明，随着Cu2+含量的增加，NaY和USY中的聚吡咯均形成双极化子态，而USY中的聚吡咯则由极化子和双极化子两种状态组成。(2)用热分析和光谱方法研究了硫代菲在六方八面沸石中与铜(II)离子的包覆，以及吡咯在β沸石中与Fe(III)离子的包覆。(3)在AlPO4-5的一维孔道中负载了对硝基苯酚(NP)和对硝基苯胺(NA)异构体，并对所得材料(o-NP/，m-NP/，p-NP/，o-NA/，m-NA/，p-NA/AlPO_4-5)的光学性质进行了表征，发现o-NP/，m-NP/，p-NP/，o-Na/，M-Na/AlPO_4-5具有与p-Na/AlPO_4-5相似的非线性光学性质(二次谐波)，其倍频级数为m&lt；Np/AlPO_4-5系列中的P&lt；o和Na/AlPO_4-5系列中的m&lt；o&lt；p。O-NP/、p-NP/、o-Na/和p-Na/AlPO_4-5的倍频强度与负载量有关，而m-NP/和m-Na/AlPO_4-5的倍频强度与负载量几乎无关。漫反射紫外可见光谱表明，与块体晶体相比，硫化镉团簇的吸收边蓝移。

项目成果

M.Sato: "Estimation of chain length of conducting polymers fromed in the faujasite channel" Zeolites and Microporous Crystals. 154-155 (1997)

M.Sato：“八面沸石通道中形成的导电聚合物链长的估计”沸石和微孔晶体。

M.Miyake, M.Matsuda, K.Yagi, H.Uehara, and M.Sato: ""Synthesis of polythiophen cluster in lattice space of hexagonal faujasite"" The Journal of The Faculty of Environmental Science and Technology Okayama University. 2. 137-143 (1997)

M.Miyake、M.Matsuda、K.Yagi、H.Uehara 和 M.Sato：““六方八面沸石晶格空间中聚噻吩簇的合成””冈山大学环境科学技术学院学报。

三宅通博: "六方晶フォージャサイトの格子空間でのポリチオフェンクラスターの合成" 岡山大学環境理工学部研究報告. 2. 137-143 (1997)

三宅道宏：“六方八面沸石晶格空间中的聚噻吩簇的合成”冈山大学环境科学与工程学院的研究报告 2. 137-143 (1997)。

H.Uehara: "Thermal and spectroscopic characterization of polypyrrole formed in zeolite Y" Journal of Materials Chemistry. 8. 2133-2136 (1998)

H.Uehara：“Y 型沸石中形成的聚吡咯的热学和光谱表征”材料化学杂志。

M.Sato, H.Uehara, and M.Miyake: ""Estimation of chain length of conducting polymers formed in the faujasite channel"" Zeolites and Microporous Crystals. 154-155 (1997)

M.Sato、H.Uehara 和 M.Miyake：“八面沸石通道中形成的导电聚合物链长的估计”沸石和微孔晶体。