發(fā)布時(shí)間：2018-05-30 06:51

  本文選題：納米片 + 陰離子表面活性劑�。� 參考：《南京郵電大學(xué)》2017年碩士論文

【摘要】：配位聚合物二維納米材料具有高比表面積、易于成膜、表面化學(xué)可修飾等優(yōu)勢,使其成為當(dāng)前化學(xué)和材料學(xué)家關(guān)注的焦點(diǎn)。本課題圍繞卟啉配體、C_2、C_3對稱性苯羧酸類配體,提出陰離子表面活性劑輔助策略,并成功實(shí)現(xiàn)了一系列不同種類配位聚合物二維納米結(jié)構(gòu)的可控合成,主要研究工作如下:1.以5,10,15,20-四(4-吡啶基)卟啉和5,10,15,20-四(4-羧基苯基)卟啉為基本構(gòu)筑單元,通過陰離子表面活性劑輔助配位組裝法合成了多種單分散金屬卟啉納米片,并系統(tǒng)研究了表面活性劑種類、反應(yīng)時(shí)間和溫度對納米片合成的影響,對納米片形貌、聚集態(tài)結(jié)構(gòu)進(jìn)行了系統(tǒng)表征,結(jié)果表明該策略成功制備了分散性、穩(wěn)定性良好、尺寸均勻的M-TPyP/TCPP納米片。通過納米片的XRD、吸收光譜及TG數(shù)據(jù)分析,我們猜測當(dāng)金屬卟啉某一晶面的金屬離子濃度最高,SDS會通過靜電作用優(yōu)先吸附于該晶面,通過封端作用限制該晶面生長速率,誘導(dǎo)晶體發(fā)生各向異性生長,進(jìn)而抑制晶體三維方向中某一維度的生長,生成2D片狀結(jié)構(gòu)。2.以上述卟啉體系為研究對象,選用帶不同電荷的表面活性劑CTAB及PVP,相同的實(shí)驗(yàn)條件下,SEM測試結(jié)果表明CTAB和PVP條件下金屬卟啉晶體更傾向于生成零維、三維納米結(jié)構(gòu),如Cu/Zn-TPyP多面體、CuTCPP花簇結(jié)構(gòu)等,XRD圖譜表明該條件下樣品與SDS體系具有不同空間群和優(yōu)勢晶面,UVVis圖譜中Cu/Zn-TPyP晶體Soret帶吸收峰發(fā)生了藍(lán)移,配體卟啉分子間發(fā)生了明顯的H-聚集。而SDS條件下,Cu/Zn-TPyP納米片樣品吸收峰紅移,均發(fā)生了典型的J-聚集。實(shí)驗(yàn)結(jié)果表明金屬卟啉納米晶發(fā)生了與SDS不同的生長過程,二者主要通過特定形狀膠束輔助金屬卟啉完成組裝過程,從而實(shí)現(xiàn)對金屬卟啉納米晶的可控制備。3.實(shí)現(xiàn)了基于1,4-對苯二甲酸(H_2BDC)和1,3,5-均苯三甲酸(H_3BTC)配體的MOF-5及HKUST-1納米片制備,并研究了SDS、CTAB及PVP對配位聚合物納米結(jié)構(gòu)形貌的影響。
[Abstract]:Coordination polymer two-dimensional nanomaterials have the advantages of high specific surface area, easy film formation and surface chemically modifiable, which make them become the focus of current chemistry and materials scientists. In this paper, a novel anionic surfactant assistant strategy was proposed around the porphyrin ligand C _ 2C _ 3 symmetric benzene carboxylic acid ligands, and a series of coordinated polymers were successfully synthesized. The main research work is as follows: 1: 1. Several mono-dispersed metalloporphyrin nanocrystals were synthesized by anionic surfactant assisted coordination assembly method, using 5 ~ (10) ~ 10 ~ (10) ~ 15 ~ (15) -tetra-4-pyridyl) porphyrin and 5 ~ (10) ~ 10 ~ (15) ~ 15 ~ (15) -tetra-4-carboxyphenyl) porphyrin as the basic building unit, and the types of surfactants were systematically studied. The effects of reaction time and temperature on the synthesis of M-TPyP/TCPP nanoparticles were investigated. The morphology and structure of the nanoparticles were systematically characterized. The results showed that the M-TPyP/TCPP nanoparticles with good dispersion, good stability and uniform size were successfully prepared by this strategy. Based on the analysis of the XRD, absorption spectra and TG data of the nanoparticles, we speculate that when the concentration of metal ions on a metalloporphyrin crystal plane is the highest, SDS will be preferentially adsorbed on the crystal surface by electrostatic action, and the growth rate of the crystal surface will be limited by the capping action. The anisotropic growth of crystals is induced, which inhibits the growth of one dimension in the three-dimensional direction of the crystal and generates 2D flake structure. 2. Taking the porphyrin system as the research object, the surface active agents CTAB and PVP with different charge were selected. The results showed that the metalloporphyrin crystals under the same experimental conditions were more inclined to form zero-dimensional and three-dimensional nanostructures under the same experimental conditions. For example, the structure of Cu/Zn-TPyP polyhedron CuTCPP clusters shows that there is blue shift in the absorption peak of Cu/Zn-TPyP crystal Soret band and obvious H- aggregation between the ligand porphyrin molecules in the Cu/Zn-TPyP crystal Soret band spectra under the condition that the sample and SDS system have different space groups and dominant crystal planes. On the other hand, the red shift of absorption peak of CuZn-TPyP nanocrystals under SDS condition is typical J-aggregation. The experimental results show that metalloporphyrin nanocrystals have a different growth process than SDS, and they mainly complete the assembly process of metalloporphyrins by special shape micelles, so as to realize the controllable preparation of metalloporphyrin nanocrystals. 3. The preparation of MOF-5 and HKUST-1 nanochips based on the ligands of 1h2BDCand 1h2BDCand 1h2BDCand H3BTC2BDC) were carried out, and the effects of PVP and DS-CTAB on the morphology of coordination polymer nanostructures were studied.
【學(xué)位授予單位】：南京郵電大學(xué)
【學(xué)位級別】：碩士
【學(xué)位授予年份】：2017
【分類號】：O634;TB383.1

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本文編號：1954354