过渡金属（铜、钴）—有机纳米聚合物的可控制备及催化和传感性质研究

发布时间：2018-03-04 04:02

本文选题：配位聚合物　切入点：金属有机框架物　出处：《山东师范大学》2017年博士论文　论文类型：学位论文

【摘要】：由金属离子或金属离子簇与多齿有机配体,通过配位键驱动力自组装的金属-有机配位聚合物(Metal-organic coordination polymers,MOCPs),由于其重要分支—金属有机框架物(Metal-organic frameworks,MOFs)的巨大发展,赋予了MOCPs在气体吸附与储存、催化、质子导电、传感及识别等多技术领域不可替代的应用潜力。这一方面受益于构筑MOCPs金属物种和有机前驱体的多样化,另外与其拓扑结构丰富、比表面积高、结构可设计性强、孔道易调控、易功能化等特性直接相关。本文致力于过渡金属(铜、钴)—有机纳米配位聚合物的可控制备及催化还原、电化学传感和电催化水分解性质的研究。主要内容如下:以溶胶-凝胶工艺,室温方便快速的制备了一种微孔-介孔-大孔多级孔共存的金属有机纳米晶Cu L(L=2,4,6-三(3,5-二羧基苯氨基)-1,3,5-三嗪);采用N2吸附、压汞法以及红外光谱(FTIR)、扫描电镜(SEM)和X-射线衍射(XRD)等技术手段,对该多级孔纳米材料的结构和性能进行了表征和测试;研究了多工艺因子对该材料形貌的影响规律;既未活化也未负载纳米贵金属的该多级孔材料,水溶液中表现出高效催化还原4-硝基苯酚、甲基橙、溴酚蓝、溴甲酚绿的活性。合成了一种空间群为P1的新型手性无客体金属有机框架物(Cu_4L_4)n[(H_2L=N-(2-羟基苯基)-L-亮氨酸],开发了(Cu_4L_4)n纳米晶室温快速合成法。采用X-单晶衍射、圆二色谱、FTIR、SEM和XRD等技术手段对该MOF的结构、手性、形貌和晶相进行了表征和分析。(Cu_4L_4)n纳米晶作为手性传感器,直接用于电化学检测R(+)-α-甲基苄胺和S(+)-α-甲基苄胺对映体,不仅表现出高灵敏度、高选择性,并且可迅速定量确定其ee值。利用无表面活性剂室温水溶剂制备技术,基于过渡元素Cu(Ⅱ)-氨基酸MOF纳米线,合成了系列具有高长径比的Co(Ⅱ)Cu(Ⅱ)-氨基酸MOF纳米纤维杂化体,经空气热解后处理,获得了系列复合碳基材均匀负载纳米尺寸氧化铜和氧化钴的一维纳米纤维和二维纳米片,对该系列产品的形貌、晶相和成分进行了系统分析,研究了其不同组成和形貌的纳米材料与电催化析氧反应活性之间的关系和规律。基于高活性异氰酸酯与多元胺室温快速反应的特性,本研究选择芳香族甲苯二异氰酸酯(TDI)与对苯二胺在水和丙酮中逐步沉淀聚合,无需任何稳定剂、致孔剂以及表面改性,一步法制备了富含胺基、脲基的多孔三维聚苯脲(PU)高分子纳米材料,将其与过渡金属Co~(2+)浸渍反应,制得了以配位键驱动力构建的过渡金属Co(Ⅱ)-聚苯脲配位聚合物,将其热解后处理,获得了新型多级孔碳基过渡金属氧化物纳米材料,采用FTIR、SEM、XRD等多技术手段,对合成的系列多形貌产品进行了结构表征和分析,研究其不同组成和形貌的纳米材料与电催化析氧反应性能之间的关系及规律。具有单层空心笼状复合材料表现出显著增强电催化析氧反应的活性,这归因于其多孔结构和复合碳晶及Co_3O_4纳米晶的协同作用。
[Abstract]:By metal ions or metal ion clusters and organic ligand, through coordination bond driven self-assembly of metal organic coordination polymers (Metal-organic, coordination polymers, MOCPs), because of its important branch of metal organic frameworks (Metal-organic, frameworks, MOFs) of the great development, gives the MOCPs in adsorption and gas storage. Catalytic, proton conductivity, potential field sensing and recognition can not be replaced. On the one hand, benefited from the construction of diversified MOCPs metal species and organic precursor, and its topology structure, high specific surface area, pore structure can be designed, easy to control, easy to functional properties are directly related. This paper is devoted to the transition metal (copper, cobalt) - organic nano with controllable preparation and catalytic reduction of polymers, the nature of the decomposition of electrochemical sensing and electrocatalysis of water. The main contents are as follows: to sol Gel process, convenient and fast at room temperature was prepared by a multistage micro meso macro pore coexistence of metal organic nanocrystals (L=2,4,6- Cu L three (3,5- two -1,3,5- three triazine amino carboxyl benzene)); using N2 adsorption, mercury porosimetry and infrared spectroscopy (FTIR), scanning electron microscopy (SEM) and X- ray diffraction (XRD) technique, structure and properties of the hierarchicalporous nano materials were characterized and tested; studied the influence of process factors on the morphology of the materials; neither activation of the hierarchical porous materials are not supported noble metal nano, aqueous solution shows high catalytic reduction of nitro 4- phenol, methyl orange, bromophenol blue, bromocresol green activity. The synthesis of a new chiral space group P1 no object metal organic framework (Cu_4L_4) n[(H_2L=N- (2- hydroxyphenyl) -L-] leucine (Cu_4L_4), the development of the rapid synthesis of N nanocrystals at room temperature. By using X- diffraction. Round Two FTIR, chromatography, structure, SEM and XRD techniques on the MOF chiral morphology and crystal phase were characterized and analyzed. (Cu_4L_4) n nanocrystals as chiral sensors for direct electrochemical detection of R (+) - alpha methyl benzylamine and S (+) - alpha - methylbenzylamine enantiomers that not only exhibits high sensitivity, high selectivity, and rapid quantitative determination of the EE value. Using a surfactant free room temperature solvent preparation technology, transition elements based on Cu (II) - amino acid MOF nanowires synthesized a series of high aspect ratio Co (II) Cu (II) - amino acids MOF nano fiber hybrid, the air was pyrolysis postprocessing, one-dimensional nano fiber and two-dimensional nano film series composite carbon substrate uniformly loaded nanometer sized copper oxide and cobalt oxide, on the morphology of the products, crystal phase and the components of system analysis, study the different composition and morphology of nano materials and electrical The relationship between law and catalytic activity. The oxygen evolution reaction characteristics of fast reaction of high active isocyanate and amine at room temperature based on this study, selection of toluene diisocyanate (TDI) and polymerization of benzene amine two gradually precipitated in water and acetone, without any stabilizer, porogenic agent and surface modified amine rich by one step method, urea based three-dimensional porous polystyrene (PU) urea polymer nano materials, and the transition metal Co~ (2+) were prepared by impregnation reaction with transition metal Co a key driving force of construction (II) - poly urea coordination polymers, the pyrolysis postprocessing, obtained a new hierarchical porous carbon based transition metal oxide nano materials, using FTIR, SEM, XRD and other technical means, for the synthesis of a series of multimorphologies products were characterized and analyzed between the different composition and morphology of nano materials and the electrocatalytic performance for oxygen evolution reaction The relationship between single layer and hollow cage composite shows remarkable enhancement of the activity of electro catalytic oxygen evolution, which is attributed to the synergistic effect of porous structure and composite carbon and Co_3O_4 nanocrystals.

【学位授予单位】：山东师范大学
【学位级别】：博士
【学位授予年份】：2017
【分类号】：O641.4

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