有机—无机杂化纳米材料的组装及性能研究
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摘要
近些年来，有机-无机纳米杂化材料由于其在结构、尺度上的不断匹配，尤其达到纳米尺度范围后，实现了材料在分子、原子等范围内的性质可控，逐渐成为材料科学中最具前途的研究方向之一。由于其将不同的无机元素和有机配体或聚合物引入体系中，使材料不仅具有无机活性中心或有机物各自的相关性质，更可以通过两者之间的相互作用或能量转移，产生许多独特新颖的性能；同时，通过运用不同的反应机理、制备条件以及合成方法等，可以制得形貌结构多样的纳米多孔材料、纳米颗粒材料、纳米薄膜材料等，在光、电、磁性、催化、吸附、药物载体、生物成像等方面展现出良好的应用前景，受到世界范围内相关研究者的极大重视。
然而，如何运用更为简单有效的方法，制备出结构新颖、性能优异的有机-无机纳米杂化材料一直是人们追求的目标。纳米材料的分子自组装技术是指在氢键、静电、疏水亲脂作用、π-π堆积等弱力推动下，分子自发的构筑成具有特殊结构和形状的稳定集合体的技术。它的出现，为液晶、胶束、二维薄膜、三维骨架等多种材料的合成和制备提供了新的思路，开辟了新的捷径，在实际中得到广泛的应用。
因此，根据以上研究背景，本论文致力于运用简洁有效的纳米组装技术，成功合成了介观结构的金属-有机骨架材料、功能化配位聚合物纳米晶复合材料和金属有机多面体纳米笼有序多孔薄膜材料，并对其生成机理、结构组成以及性能应用等方面进行了研究，并取得以下的主要成果：
1.利用协同自组装、配位反应、超分子作用等已知机理和合成策略，通过简洁、有效、普遍的水热合成方法，直接由Cu~(2+)，5-OH-BDC和CTAC在水体系中的协同自组装成功制备出具有介观结构的金属有机骨架材料Cu-(5-OH-BDC)-C16。由XRD和TEM表征可以看出此材料具有高度有序的平面六方结构，并且通过碳链的变化可以得到相应晶格间距的变化；通过IR表征得出在骨架结构中金属铜离子与羧基发生配位，表面活性剂起到模板效应；由ICP、HPLC、EPR、CHN分析可以得出，产物中Cu~(2+)与配体的摩尔比为1:1，并且以一维线性链接的方式构成金属有机骨架结构，体系中的多余的N，H元素来源于NO_3-和H_2O分子，它们在体系中起到了平衡电荷、填补配位点以及促进协同自组装过程等作用；通过类似合成方法，成功合成Co-(5-OH-BDC)-C16和Ni-(5-OH-BDC)-C16介观结构的金属有机骨架材料，表明此合成策略和方法具有一定的规律性和普遍性，具有很好的研究价值和意义。此工作很好的融合了介孔材料和微孔MOF材料领域中的核心思想，为开创出新颖、独特具有广泛实际应用的多功能复合型纳米多级孔材料打下良好的基础。
2.由MOP-OH晶体单元结构拆分再组装的制备思路，与F127的带有羟基的烷基链相互作用，直接包覆制得配位聚合物纳米晶复合材料F127-[MOP-OH]。通过对反应物浓度的改变，不仅可以控制复合材料中纳米晶的颗粒大小（3nm~50nm）和调节复合材料的形貌变化，制得大小均一，单分散性好的纳米球（200nm左右）；有机溶剂中Cu~(2+)释放速率研究表明，产物F127-[MOP-OH]中的[CuL]单元结构更为牢固，具有更为缓慢的Cu~(2+)的释放速率，为产物在防污涂层应用方面打下良好的基础；同时，F127-[MOP-OH]与原晶体材料相比，水中稳定性获得极大提高，并且在对PZA的释放研究中，其药物释放时间显著提高，释放速率更加平稳，为其在生物、医学方面的应用开辟了新的方向。
3.以MOP-SO_3阴离子纳米笼为基元，通过静电作用，与阳离子表面活性剂双十八烷基二甲基氯化铵（DODAMCl）反应，成功制得表面烷基化的纳米笼复合材料{MOP-SO_3}-DODMA。通过1H NMR结果表明DODMACl阳离子端通过强烈的静电相互作用完成对阴离子MOP-SO_3纳米笼组装和包覆，综合TG、CHN、ICP表征结果得出每个MOP-SO_3纳米笼被24个DODMA~+所包覆,同它们的电荷数相匹配；由SAXS，UV-Vis，IR测试结果可知产物中MOP-SO_3纳米笼是以完整的中空球形纳米笼形态存在的（D=3.00.2nm），各种化学键的链接保存完好，其整体结构没有被破坏或发生分解；运用水滴模板法，在空气/水界面进一步将产物组装为{MOP-SO_3}-DODMA多孔蜂窝状薄膜。实验表明，MOP-SO_3完好的存在于多孔薄膜中，当浓度为1.7mg·ml-1时，一张薄膜中会出现不同孔形貌特征的三块区域：气泡状孔薄膜区域、六方排列孔薄膜区域和大孔薄膜区域；溶剂挥发速率和溶液浓度对制备六方有序的多孔薄膜具有重要影响，只有浓度适中，使粒子沉积速率，溶剂挥发速率同水珠模板的形成和排列处于适当的动态平衡中，才能制备出高度有序的六方排列的多孔结构薄膜。此研究成果，对生物大分子的可控组装、多种纳米簇有序结构薄膜的合成及其在气体分离、选择性吸附等方面的应用都具有一定意义。
Recent years, due to the increasing matching between organic and inorganic matterin structures and sizes, especially the material controllability in the range of molecularand atomic level, organic-inorganic hybrid nanomaterials gradually become the mostpromising research direction of material science. Because of the different inorganicelements and organic ligand or polymer coexisted in the system, organic-inorganichybrid nanomaterials not only have their respective nature, but will likely obtainmany special and innovative properties through the interaction between organic andinorganic matter. Meanwhile, through the applications of different reactionmechanisms, the preparation conditions as well as synthetic methods, diversemorphology of nanoporous materials, nanoparticles, nano-film materials can beproduced, which have been widely used in the optics, electricity, magnetics, catalysis,adsorption, drug delivery, bio-imaging and so on. Great attentions have been paid byworldwide researchers.
However, the organic-inorganic hybrid nanomaterials with the novel structure andexcellent performance, which are synthesized by more simple and effective method,have always been the goal pursued by scientists. Molecular self-assembly technologyis the process method of the molecules spontaneously built into a stable structure andspecial shape of the aggregates, which is driven by hydrogen bonding, electrostatic,hydrophobic, lipophilic role, π-π stacking. The rise of molecular self-assembly technology has provided new ideas and a improvement for the synthesis of liquidcrystals, micelles, two-dimensional film in practice.
Therefore, in accordance with the above background, this thesis is committed touse a simple and effective nano-assembly technique, and successfully synthesize amesoscopic structure of the metal-organic framework materials, functionalcoordination polymer nano-crystal composite materials and surface functionalizedmetal-organic polyhedron nanocages thin film materials with ordered honeycombarchitectures. The formation mechanism, structural composition and properties havebeen investigated and major achievements have been made as following:
1. Based on the known synthetic mechanism and strategies of cooperativeself-assembly, through a simple, effective, widespread hydrothermal synthesis method,coordination reaction and supramolecular interaction, through a simple, effective andwidespread hydrothermal method, the mesostructured metal-organic frameworkmaterials Cu-(5-OH-BDC)-C16have been prepared directly with the cooperativeself-assembly of Cu~(2+),5-OH-BDC and CTAC in aqueous system. This material hasshown a highly ordered hexagonal structure and a corresponding increase of unit cellsize with increase of surfactant chain length with the XRD and TEM characterization.IR spectra could prove the phenyl hydroxyl might participate in the reaction duringthe self-assembly progress and the coordination between the carboxyl and metal ionsto form frameworks of the materials. Through the analysis of ICP, HPLC, EPR, CHN,it could conclude that the chain connective construction between mononuclear Cu~(2+)and ligand is the most possible structures existd in the framework with the molar ratioof Cu~(2+)to ligand at1:1, and the redundant N, H element quite likely come from thenitrate and water molecules, which could play important parts in the system. TheCo-(5-OH-BDC)-C16and of Ni-(5-OH-BDC)-C16mesostructured metal-organicframework materials have also been successfully synthesized by similar syntheticmethods, which could shown a certain regularity and universality of the syntheticstrategy and method. This work well integrate the core idea in the field of mesoporousmaterials and microporous MOF materials, which make a foundation to create new and unique multi-functional nanoporous materials with a wide range of practicalapplications.
2. The NMOF-organic hybrid materials of F127-[MOP-OH] has been obtainedthrough the MOP-OH crystal cell structure splitted and reorganized in the system ofF127methanol solution. The change of concentration of reactants can not only controlthe particle size of the nanocrystals in the composite (3nm to50nm), but adjustmorphology of the material with uniform size and good monodisperse nanospheres(200nm). The studies of Cu~(2+)released rate experiment in organic solvents have shownthat the [CuL] unit structure of F127-[MOP-OH] is more solid and the Cu~(2+)releaserate of the product is more slowly than [MOP-OH] crystall, which make a goodfoundation for anti-fouling coatings applications. Furthermore, compared to theoriginal crystal materials, the stability of F127-[MOP-OH] in water has been greatlyimproved. In the experiment of PZA release, the NMOF-organic hybrid material hasexhibited more stable release rate and longer drug release time, which opened up newareas of applications in biology or medicine directions.
3. The surface alkylation of nanocage composite material {MOP-SO_3}-DODMAhas been successfully prepared with the anion metal-organic nanocage MOP-SO_3andcationic surfactant DODAMCl through electrostatic interaction.1H NMR shows thatDODMACl cationic side is fixed in anionic MOP-SO_3nanocages through a strongelectrostatic interaction. Due to the caculation of TG、CHN、ICP test, it could beproved that every MOP-SO_3were surrounded by about24DODMA~+; Throughthe analysis of SAXS, UV-Vis, IR, it could conclude that MOP-SO_3nanocages in theproduct is intact hollow spherical shape (D=3.0±0.2nm) and all bond bindings ofnanocages preserved the well. With the water droplets templating method, the surfacefunctionalized MOP-SO_3nanocages film with ordered honeycomb architectures hasbeen successfully obtained. The experiments show that the MOP-SO_3nanocages arealso intact in the porous film. At the concentration of1.7mg·ml-1, a film will appearthree different pore morphology regions: alveoli-like porous domains, hexagonalporous domains and huge porous domains. The solvent evaporation rate and solute concentration play an imortant influence on the preparation of hexagonal porous films.When the particle deposition rate, solvent evaporation rate and the formation andarrangement of water droplets template are in the appropriate dynamic balance, highlyordered hexagonal arrangement films could possibly be obtained. Due to theaggregating similarity of metal-organic macroionic unit and viral capsid, theself-assembly method of metal-organic nanocages could also make a good foundationfor organization or controllability of biological macromolecules (protein, nucleic acidetc.) in biology or medicine domains.
然而，如何运用更为简单有效的方法，制备出结构新颖、性能优异的有机-无机纳米杂化材料一直是人们追求的目标。纳米材料的分子自组装技术是指在氢键、静电、疏水亲脂作用、π-π堆积等弱力推动下，分子自发的构筑成具有特殊结构和形状的稳定集合体的技术。它的出现，为液晶、胶束、二维薄膜、三维骨架等多种材料的合成和制备提供了新的思路，开辟了新的捷径，在实际中得到广泛的应用。
因此，根据以上研究背景，本论文致力于运用简洁有效的纳米组装技术，成功合成了介观结构的金属-有机骨架材料、功能化配位聚合物纳米晶复合材料和金属有机多面体纳米笼有序多孔薄膜材料，并对其生成机理、结构组成以及性能应用等方面进行了研究，并取得以下的主要成果：
1.利用协同自组装、配位反应、超分子作用等已知机理和合成策略，通过简洁、有效、普遍的水热合成方法，直接由Cu~(2+)，5-OH-BDC和CTAC在水体系中的协同自组装成功制备出具有介观结构的金属有机骨架材料Cu-(5-OH-BDC)-C16。由XRD和TEM表征可以看出此材料具有高度有序的平面六方结构，并且通过碳链的变化可以得到相应晶格间距的变化；通过IR表征得出在骨架结构中金属铜离子与羧基发生配位，表面活性剂起到模板效应；由ICP、HPLC、EPR、CHN分析可以得出，产物中Cu~(2+)与配体的摩尔比为1:1，并且以一维线性链接的方式构成金属有机骨架结构，体系中的多余的N，H元素来源于NO_3-和H_2O分子，它们在体系中起到了平衡电荷、填补配位点以及促进协同自组装过程等作用；通过类似合成方法，成功合成Co-(5-OH-BDC)-C16和Ni-(5-OH-BDC)-C16介观结构的金属有机骨架材料，表明此合成策略和方法具有一定的规律性和普遍性，具有很好的研究价值和意义。此工作很好的融合了介孔材料和微孔MOF材料领域中的核心思想，为开创出新颖、独特具有广泛实际应用的多功能复合型纳米多级孔材料打下良好的基础。
2.由MOP-OH晶体单元结构拆分再组装的制备思路，与F127的带有羟基的烷基链相互作用，直接包覆制得配位聚合物纳米晶复合材料F127-[MOP-OH]。通过对反应物浓度的改变，不仅可以控制复合材料中纳米晶的颗粒大小（3nm~50nm）和调节复合材料的形貌变化，制得大小均一，单分散性好的纳米球（200nm左右）；有机溶剂中Cu~(2+)释放速率研究表明，产物F127-[MOP-OH]中的[CuL]单元结构更为牢固，具有更为缓慢的Cu~(2+)的释放速率，为产物在防污涂层应用方面打下良好的基础；同时，F127-[MOP-OH]与原晶体材料相比，水中稳定性获得极大提高，并且在对PZA的释放研究中，其药物释放时间显著提高，释放速率更加平稳，为其在生物、医学方面的应用开辟了新的方向。
3.以MOP-SO_3阴离子纳米笼为基元，通过静电作用，与阳离子表面活性剂双十八烷基二甲基氯化铵（DODAMCl）反应，成功制得表面烷基化的纳米笼复合材料{MOP-SO_3}-DODMA。通过1H NMR结果表明DODMACl阳离子端通过强烈的静电相互作用完成对阴离子MOP-SO_3纳米笼组装和包覆，综合TG、CHN、ICP表征结果得出每个MOP-SO_3纳米笼被24个DODMA~+所包覆,同它们的电荷数相匹配；由SAXS，UV-Vis，IR测试结果可知产物中MOP-SO_3纳米笼是以完整的中空球形纳米笼形态存在的（D=3.00.2nm），各种化学键的链接保存完好，其整体结构没有被破坏或发生分解；运用水滴模板法，在空气/水界面进一步将产物组装为{MOP-SO_3}-DODMA多孔蜂窝状薄膜。实验表明，MOP-SO_3完好的存在于多孔薄膜中，当浓度为1.7mg·ml-1时，一张薄膜中会出现不同孔形貌特征的三块区域：气泡状孔薄膜区域、六方排列孔薄膜区域和大孔薄膜区域；溶剂挥发速率和溶液浓度对制备六方有序的多孔薄膜具有重要影响，只有浓度适中，使粒子沉积速率，溶剂挥发速率同水珠模板的形成和排列处于适当的动态平衡中，才能制备出高度有序的六方排列的多孔结构薄膜。此研究成果，对生物大分子的可控组装、多种纳米簇有序结构薄膜的合成及其在气体分离、选择性吸附等方面的应用都具有一定意义。
Recent years, due to the increasing matching between organic and inorganic matterin structures and sizes, especially the material controllability in the range of molecularand atomic level, organic-inorganic hybrid nanomaterials gradually become the mostpromising research direction of material science. Because of the different inorganicelements and organic ligand or polymer coexisted in the system, organic-inorganichybrid nanomaterials not only have their respective nature, but will likely obtainmany special and innovative properties through the interaction between organic andinorganic matter. Meanwhile, through the applications of different reactionmechanisms, the preparation conditions as well as synthetic methods, diversemorphology of nanoporous materials, nanoparticles, nano-film materials can beproduced, which have been widely used in the optics, electricity, magnetics, catalysis,adsorption, drug delivery, bio-imaging and so on. Great attentions have been paid byworldwide researchers.
However, the organic-inorganic hybrid nanomaterials with the novel structure andexcellent performance, which are synthesized by more simple and effective method,have always been the goal pursued by scientists. Molecular self-assembly technologyis the process method of the molecules spontaneously built into a stable structure andspecial shape of the aggregates, which is driven by hydrogen bonding, electrostatic,hydrophobic, lipophilic role, π-π stacking. The rise of molecular self-assembly technology has provided new ideas and a improvement for the synthesis of liquidcrystals, micelles, two-dimensional film in practice.
Therefore, in accordance with the above background, this thesis is committed touse a simple and effective nano-assembly technique, and successfully synthesize amesoscopic structure of the metal-organic framework materials, functionalcoordination polymer nano-crystal composite materials and surface functionalizedmetal-organic polyhedron nanocages thin film materials with ordered honeycombarchitectures. The formation mechanism, structural composition and properties havebeen investigated and major achievements have been made as following:
1. Based on the known synthetic mechanism and strategies of cooperativeself-assembly, through a simple, effective, widespread hydrothermal synthesis method,coordination reaction and supramolecular interaction, through a simple, effective andwidespread hydrothermal method, the mesostructured metal-organic frameworkmaterials Cu-(5-OH-BDC)-C16have been prepared directly with the cooperativeself-assembly of Cu~(2+),5-OH-BDC and CTAC in aqueous system. This material hasshown a highly ordered hexagonal structure and a corresponding increase of unit cellsize with increase of surfactant chain length with the XRD and TEM characterization.IR spectra could prove the phenyl hydroxyl might participate in the reaction duringthe self-assembly progress and the coordination between the carboxyl and metal ionsto form frameworks of the materials. Through the analysis of ICP, HPLC, EPR, CHN,it could conclude that the chain connective construction between mononuclear Cu~(2+)and ligand is the most possible structures existd in the framework with the molar ratioof Cu~(2+)to ligand at1:1, and the redundant N, H element quite likely come from thenitrate and water molecules, which could play important parts in the system. TheCo-(5-OH-BDC)-C16and of Ni-(5-OH-BDC)-C16mesostructured metal-organicframework materials have also been successfully synthesized by similar syntheticmethods, which could shown a certain regularity and universality of the syntheticstrategy and method. This work well integrate the core idea in the field of mesoporousmaterials and microporous MOF materials, which make a foundation to create new and unique multi-functional nanoporous materials with a wide range of practicalapplications.
2. The NMOF-organic hybrid materials of F127-[MOP-OH] has been obtainedthrough the MOP-OH crystal cell structure splitted and reorganized in the system ofF127methanol solution. The change of concentration of reactants can not only controlthe particle size of the nanocrystals in the composite (3nm to50nm), but adjustmorphology of the material with uniform size and good monodisperse nanospheres(200nm). The studies of Cu~(2+)released rate experiment in organic solvents have shownthat the [CuL] unit structure of F127-[MOP-OH] is more solid and the Cu~(2+)releaserate of the product is more slowly than [MOP-OH] crystall, which make a goodfoundation for anti-fouling coatings applications. Furthermore, compared to theoriginal crystal materials, the stability of F127-[MOP-OH] in water has been greatlyimproved. In the experiment of PZA release, the NMOF-organic hybrid material hasexhibited more stable release rate and longer drug release time, which opened up newareas of applications in biology or medicine directions.
3. The surface alkylation of nanocage composite material {MOP-SO_3}-DODMAhas been successfully prepared with the anion metal-organic nanocage MOP-SO_3andcationic surfactant DODAMCl through electrostatic interaction.1H NMR shows thatDODMACl cationic side is fixed in anionic MOP-SO_3nanocages through a strongelectrostatic interaction. Due to the caculation of TG、CHN、ICP test, it could beproved that every MOP-SO_3were surrounded by about24DODMA~+; Throughthe analysis of SAXS, UV-Vis, IR, it could conclude that MOP-SO_3nanocages in theproduct is intact hollow spherical shape (D=3.0±0.2nm) and all bond bindings ofnanocages preserved the well. With the water droplets templating method, the surfacefunctionalized MOP-SO_3nanocages film with ordered honeycomb architectures hasbeen successfully obtained. The experiments show that the MOP-SO_3nanocages arealso intact in the porous film. At the concentration of1.7mg·ml-1, a film will appearthree different pore morphology regions: alveoli-like porous domains, hexagonalporous domains and huge porous domains. The solvent evaporation rate and solute concentration play an imortant influence on the preparation of hexagonal porous films.When the particle deposition rate, solvent evaporation rate and the formation andarrangement of water droplets template are in the appropriate dynamic balance, highlyordered hexagonal arrangement films could possibly be obtained. Due to theaggregating similarity of metal-organic macroionic unit and viral capsid, theself-assembly method of metal-organic nanocages could also make a good foundationfor organization or controllability of biological macromolecules (protein, nucleic acidetc.) in biology or medicine domains.
引文
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