由金属离子型聚电解质构筑的功能型纳米复合薄膜
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摘要
本论文依照分子设计和超分子合成方法制备出了各种主链上含金属离子型的聚电解质,并通过先进的层层自组装技术制备具有特殊电致变色功能的有机金属型超薄膜以及能对环境刺激快速响应型聚电解质微胶囊,同时对它们的结构和性能之间的内在联系也进行了深入的研究。
本论文主要包含四个部分:
第一,通过超分子配位方法组装出了金属紫精聚阳离子,并且通过层层组装的技术将其和聚阴离子(如聚苯乙烯磺酸钠)构建出了具有电致变色功能的新型电致变色超薄膜;第二,为了提高薄膜变色能力和改善薄膜制备效率,我们设计并成功制备出了具有三明治结构的纳米杂化型电致变色超薄膜。通过层层组装的方法将溶剂热合成的二氧化钛纳米晶体和金属配位型紫精超分子聚电解质以及聚阴离子通过合理的顺序进行三维组装,极大的提高了薄膜的变色度,增加了产品的使用寿命,同时也降低了薄膜制备时间;第三,为了实现由相同主链结构的聚电解质组装制备超薄膜的想法,我们开发出新型环境响应型、主链含二茂铁基团的聚二茂铁硅烷电解质。由该材料制备出的聚电解质胶囊具有对氧化有可控响应的能力,在外界氧化刺激的条件下,自身会发生膨胀现象,直至完全降解,同时降解时间可以通过改变薄膜结构以及外界条件进行调控。最后,首次利用所制备的聚二茂铁硅烷和DNA组装了大孔结构超薄膜材料,提出了利用层层自组装技术制备大孔结构超薄膜材料的新方法,并且通过运用比较的方法对该膜的大孔结构的形成机理作了探讨,为这种方法提供了理论依据。
The design and fabrication of molecular materials has received a lot of attention and dedication in the last decades. It has been demonstrated that the control and tuning of the electronic and/or photonic properties of such materials can be achieved by means of accurate synthesis of tailored molecules. However, a fundamental step towards the effective realization of molecular-based devices relies on the ordered placement of the active components into the nanoscale structure. In this thesis, self-assembly processes are gaining importance in the fabrication of such devices and thin-film or capsules thechnologies are considered to play a major role in future applications.
Our research is focused on the synthesis of metal containg polyelectrolyte and development the intelligent thin film based on them. The thesis is divided into four parts.
1. The molecular modules (ligands) which upon metal ion coordination (here Cobalt(II) is used ) result in metallosupramolecular coordination polyelectrolytes (CoMEPE’s) with electronic properties are obtained. Then the (PSS/CoMEPE)40 films are synthesised by the layer-by-layer electrostatic assembly technique. Such multilayer thin films show the excellent electrochromic responses, i.e. reduction at–1.1 V results in a rapid increase of the absorbance (green colouration) whereas after stepping the potential back to 0.0 V the initial state (red colouration) is recovered. The response time is of the order of seconds in both colouration and“bleaching”processes. The optical contrast is visually noticeable and the optical density of the multilayer film is around 0.16. However, after several cycles a decrease in the absorbance of the film is noticed, which points to lost of material.
2. In order to improve the cyclic life of the electromic film, we try to use other metal ions (Fe(II)) to coordinate with MEPE instead of Cobalt ions. The results do show the improvement of cyclic life. Futhermore, in order to reduce the tedious fabraction processes and enhance the phase constrast; we establish the three-component systems by incorporating TiO2 nanocrystals into the bilayer of PSS/CoMEPE to form a tough and sandwich structure. As compared to the films without the nanocrystal, the hybrid films show a 5-fold increases of the phase contrast and 10-times of the memberane thickness.
3. In this part, a different metal containing polelectrolyte poly(ferrocenylsilane) (PFS) is designed and prepared. Redox-responsive poly(ferrocenylsilane) (PFS) polyanions and polycations, are successfully employed in the electrostatic layer-by-layer supramolecular self-assembly process to form fully free-standing organometallic microcapsules. Microcapsules were obtained by coating the same type of PFS multilayers on colloidal particles (manganese carbonate (MnCO3)) followed by core removal using ethylenediaminetetraacetic acid (EDTA). These capsules displaye desired stability and well-defined integrity. These stable capsules could serve as excellent candidates for the investigation of polyelectrolyte multilayer permeability control triggered by redox stimuli.
4. we introduce a new method to prepare macroporous films, which are fabricated by DNA and strong polyelectrolyte based on LBL assembly method. Then we try to interpret this phenoment.and introduce a new method to prepare macroporous film.
本论文主要包含四个部分:
第一,通过超分子配位方法组装出了金属紫精聚阳离子,并且通过层层组装的技术将其和聚阴离子(如聚苯乙烯磺酸钠)构建出了具有电致变色功能的新型电致变色超薄膜;第二,为了提高薄膜变色能力和改善薄膜制备效率,我们设计并成功制备出了具有三明治结构的纳米杂化型电致变色超薄膜。通过层层组装的方法将溶剂热合成的二氧化钛纳米晶体和金属配位型紫精超分子聚电解质以及聚阴离子通过合理的顺序进行三维组装,极大的提高了薄膜的变色度,增加了产品的使用寿命,同时也降低了薄膜制备时间;第三,为了实现由相同主链结构的聚电解质组装制备超薄膜的想法,我们开发出新型环境响应型、主链含二茂铁基团的聚二茂铁硅烷电解质。由该材料制备出的聚电解质胶囊具有对氧化有可控响应的能力,在外界氧化刺激的条件下,自身会发生膨胀现象,直至完全降解,同时降解时间可以通过改变薄膜结构以及外界条件进行调控。最后,首次利用所制备的聚二茂铁硅烷和DNA组装了大孔结构超薄膜材料,提出了利用层层自组装技术制备大孔结构超薄膜材料的新方法,并且通过运用比较的方法对该膜的大孔结构的形成机理作了探讨,为这种方法提供了理论依据。
The design and fabrication of molecular materials has received a lot of attention and dedication in the last decades. It has been demonstrated that the control and tuning of the electronic and/or photonic properties of such materials can be achieved by means of accurate synthesis of tailored molecules. However, a fundamental step towards the effective realization of molecular-based devices relies on the ordered placement of the active components into the nanoscale structure. In this thesis, self-assembly processes are gaining importance in the fabrication of such devices and thin-film or capsules thechnologies are considered to play a major role in future applications.
Our research is focused on the synthesis of metal containg polyelectrolyte and development the intelligent thin film based on them. The thesis is divided into four parts.
1. The molecular modules (ligands) which upon metal ion coordination (here Cobalt(II) is used ) result in metallosupramolecular coordination polyelectrolytes (CoMEPE’s) with electronic properties are obtained. Then the (PSS/CoMEPE)40 films are synthesised by the layer-by-layer electrostatic assembly technique. Such multilayer thin films show the excellent electrochromic responses, i.e. reduction at–1.1 V results in a rapid increase of the absorbance (green colouration) whereas after stepping the potential back to 0.0 V the initial state (red colouration) is recovered. The response time is of the order of seconds in both colouration and“bleaching”processes. The optical contrast is visually noticeable and the optical density of the multilayer film is around 0.16. However, after several cycles a decrease in the absorbance of the film is noticed, which points to lost of material.
2. In order to improve the cyclic life of the electromic film, we try to use other metal ions (Fe(II)) to coordinate with MEPE instead of Cobalt ions. The results do show the improvement of cyclic life. Futhermore, in order to reduce the tedious fabraction processes and enhance the phase constrast; we establish the three-component systems by incorporating TiO2 nanocrystals into the bilayer of PSS/CoMEPE to form a tough and sandwich structure. As compared to the films without the nanocrystal, the hybrid films show a 5-fold increases of the phase contrast and 10-times of the memberane thickness.
3. In this part, a different metal containing polelectrolyte poly(ferrocenylsilane) (PFS) is designed and prepared. Redox-responsive poly(ferrocenylsilane) (PFS) polyanions and polycations, are successfully employed in the electrostatic layer-by-layer supramolecular self-assembly process to form fully free-standing organometallic microcapsules. Microcapsules were obtained by coating the same type of PFS multilayers on colloidal particles (manganese carbonate (MnCO3)) followed by core removal using ethylenediaminetetraacetic acid (EDTA). These capsules displaye desired stability and well-defined integrity. These stable capsules could serve as excellent candidates for the investigation of polyelectrolyte multilayer permeability control triggered by redox stimuli.
4. we introduce a new method to prepare macroporous films, which are fabricated by DNA and strong polyelectrolyte based on LBL assembly method. Then we try to interpret this phenoment.and introduce a new method to prepare macroporous film.
引文
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