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Intercalated polymer-layered inorganic nanocomposites.

机译：插层聚合物层的无机纳米复合材料。

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摘要

The exfoliation-encapsulative precipitation (EEP) method, which was introduced by Kanatzidis and Bissessur in 1993, is both convenient and general. It enables the formation of an intercalated polymer-layered inorganic nanocomposite when a polymer solution and an inorganic monolayer suspension are mixed. Many MoS 2/polymer nanocomposites were synthesized.; In this dissertation, we expand the investigation of the MoS2 system, contribute a better understanding and provide a better manipulation of the reactions. Moreover, we further develop the EEP method by extending its application to other layered materials such as TaS2, MoO 3, α-RuCl3 and WS2, and by modifying the method so that the intercalation of intractable polymers such as polypyrrole is possible.; In the research, it was found that “LiMoS2” would not be oxidized completely to MoS2 upon exposure to water or air, and the exfoliation of “LiMoS2” in water is a process of solvation of Lix(H2O)yMoS2 (x ∼ 0.18). Like Ax(H2O)yTiS2 (A = Li, Na, K), Lix(H2O)yMoS2 can be exfoliated by stirring. Additional polymers such as polyacrylamide, polyvinylalcohol, polypropylene, polystyrene, polymethylmethacrylate, polybenzimidazole, polyethyleneterephthalate and polypyrrole were encapsulated in MoS2. A convenient method to prepare “LiMoS2” was developed, which uses LiBH4 as a reagent and runs at elevated temperatures (300–350°C). This method can also be used to lithiate other layered transition metal dichalcogenides.; The lithium intercalated materials exfoliate well and encapsulate polymers better than the sodium intercalated materials, at least in the systems of 2H-TaS2 and MoO3. At room temperature, LiBH4 was proven a good lithiation reagent for 2H-TaS2. MoO3 and α-RuCl3. The amount of LiBH4 used in the reaction is crucial to the exfoliation and encapsulation properties of the products. Water-soluble polymers such as poly(ethylene oxide) (PEO) and polyvinylpyrrolidone were intercalated in all three layered materials and polypyrrole was intercalated in RuCl3.; In addition, α-RuCl3/polyaniline nanocomposites, were prepared by the in situ redox intercalative polymerization method, which up to now was only applicable to FeOCl, V2O 5 and VOPO4. The reaction is driven by the reduction of some of the Ru3+ centers to Ru2+ and completed by the participation of ambient oxygen as an electron acceptor.; The large variety of new polymer-nanocomposites thus prepared have many interesting physical properties. For example, TaS2 nanocomposites are superconductors at low temperatures; RuCl3 nanocomposites have adjustable magnetic properties. The arrangement of PEO chains in the interlayer galleries was explored and we believe that MoS2/PEO, TaS2 /PEO and RuCl3/PEO nanocomposites contain in each gallery two sheets of PEO chains in the type-II PEO-HgCl2 complex conformation. The two sheets of PEO chains are believed to have -O- atoms facing each other at the center of the gallery and provide Li+ ions a good two-dimensional migration channel.
机译：Kanatzidis和Bissessur于1993年提出的剥落包裹沉淀法（EEP）既方便又通用。当将聚合物溶液和无机单层悬浮液混合时，它能够形成插层聚合物层的无机纳米复合材料。合成了许多MoS 2 /聚合物纳米复合材料。本文扩大了对MoS 2 体系的研究，为人们更好地理解和提供了更好的反应控制方法。此外，我们通过将其扩展到其他层状材料（如TaS 2 ，MoO 3 ，α-RuCl 3 和WS 2 ，并且通过修改方法，使得可以插入难处理的聚合物（例如聚吡咯）。在研究中发现，“ LiMoS 2 ”在暴露于水或空气后不会被完全氧化为MoS 2 ，并且“ LiMoS ”的剥离2 ”在水中是Li x （H 2 O） y MoS 2 （x〜0.18）。像A x （H 2 O） y TiS 2 （A = Li，Na，K），Li可以通过搅拌除去 x （H 2 O） y MoS 2 。诸如聚丙烯酰胺，聚乙烯醇，聚丙烯，聚苯乙烯，聚甲基丙烯酸甲酯，聚苯并咪唑，聚对苯二甲酸乙二酯和聚吡咯等其他聚合物也被封装在MoS 2 中。开发了一种方便的制备“ LiMoS 2 ”的方法，该方法使用LiBH 4 作为试剂并在高温（300–350°C）下运行。该方法也可用于锂化其他层状过渡金属二硫属化合物。至少在2H-TaS 2 和MoO 3 的系统中，锂插层材料能很好地剥离聚合物，并更好地包裹聚合物。在室温下，LiBH 4 被证明是2H-TaS 2 的优良锂化剂。 MoO 3 和α-RuCl 3 。反应中使用的LiBH 4 的量对于产物的剥离和包封性能至关重要。水溶性聚合物，如聚环氧乙烷（PEO）和聚乙烯吡咯烷酮均插入所有三层材料中，而聚吡咯则插入RuCl 3 中。另外，通过原位氧化还原插层聚合法制备了α-RuCl 3 /聚苯胺纳米复合材料，目前仅适用于FeOCl，V 2 O 5 和VOPO 4 。该反应是由一些Ru 3 + 中心还原为Ru 2 + 所驱动，并通过环境氧作为电子受体的参与而完成的。如此制备的多种新的聚合物-纳米复合材料具有许多令人感兴趣的物理性质。例如，TaS 2 纳米复合材料在低温下是超导体。 RuCl 3 纳米复合材料具有可调节的磁性。探索了层间画廊中PEO链的排列，我们认为MoS 2 / PEO，TaS 2 / PEO和RuCl 3 / PEO纳米复合材料在每个通道中包含两片II型PEO-HgCl 2 复杂构象的PEO链。据信这两条PEO链的-O-原子在长廊的中心彼此面对，并为Li + 离子提供了良好的二维迁移通道。

著录项

  • 作者

    Wang, Lei.;

  • 作者单位

    Michigan State University.;

  • 授予单位 Michigan State University.;
  • 学科 Chemistry Inorganic.
  • 学位 Ph.D.
  • 年度 1999
  • 页码 235 p.
  • 总页数 235
  • 原文格式 PDF
  • 正文语种 eng
  • 中图分类 无机化学;
  • 关键词

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