用于处理染料废水的配合物-制备与应用

发布时间：2018-04-24 09:08

本文选题：配合物 + 合成　；参考：《北京建筑大学》2017年硕士论文

【摘要】：近年来,废水中有机污染物的去除受到了广泛的关注。一般情况下,有机污染物具有很好的光稳定性,会对环境和生物产生很高的潜在危险。目前越来越多的材料被用来处理废水中的污染物,比如纳米吸附材料、TiO_2光催化材料等,这些材料尽管对废水具有较好的处理效果,但是不利于研究材料与污染物之间的构效关系。因此,探索一种能够有效解决水污染问题并且有利于反应机理探究的新型环境修复材料迫在眉睫。配合物材料是由无机金属离子和有机配体构成的一种新型无机-有机杂化材料。由于具备多样和易调控的结构、可调谐的表面活性位点,配合物在吸附、荧光、催化、化学传感等领域得到了广泛的应用。在环境修复方面,配合物常被用来作为一种有效的吸附剂去除废水中的有机污染物,或在紫外光/可见光/紫外-可见光的照射下作为均相光催化剂来光催化降解有机污染物以及光催化还原CO_2和Cr(VI)。本研究基于晶体工程学设计原理,利用缓慢扩散法和水热法成功合成6种新型功能配合物材料,对其进行结构分析和性能表征,并通过选择典型的有机染料作为吸附或光催化降解的靶物,研究所合成配合物的吸附或光催化性能,并探究其反应机理。主要的研究成果如下:1.本实验根据晶体工程学原理在乙醇/氨水的溶液中通过室温条件下的缓慢扩散法合成一种具有高效吸附和分离效果的新型银基配合物材料[Ag_4(dpe)_4]·(butca)·13H_2O(配合物1)(dpe=1,2-双(4-吡啶基)乙烯,H_4butca=1,2,3,4-丁烷四羧酸),对其进行结构分析和性能表征。通过选择两种阴离子型染料甲基橙(MO)和刚果红(CR),两种阳离子型染料亚甲基蓝(MB)和罗丹明B(Rh B)作为目标靶物来研究配合物1的吸附效果。结果表明:(1)配合物1对阴离子型染料MO和CR具有较高的吸附性能(对MO的最大吸附量为779 mg/g,CR的最大吸附量为739 mg/g);(2)配合物1对MO的吸附动力学过程可用伪一级动力学方程描述,吸附过程符合Langmuir和Freundlich等温线模型;(3)Gibbs自由能变((35)G~0)小于零,焓变(ΔH~0)和熵变(ΔS~0)大于零,表明配合物1对于MO的吸附是一个吸热、自由度逐渐增加的自发反应过程;(4)配合物1能够快速实现MO/MB混合染料的选择性分离,并利用自制的SPE小柱实验验证;(5)配合物1在吸附MO的过程中能实现循环利用并且具有较好的稳定性;(6)配合物1具有良好的杀菌性能以防止生物挂膜现象。2.通过选择新型的有机配体制备了两种具有荧光和光催化性能的配合物材料[Ag_4(dpe)_4]·(btec)(配合物2)和[Ag_4(bpy)_4]·(btec)·12H_2O(配合物3)(dpe=1,2-双(4-吡啶基)乙烯,bpy=4,4′-联吡啶,H_4btec=1,2,4,5-均苯四羧酸),并用单晶X-射线衍射仪(SCXRD)、傅立叶红外变换光谱仪(FTIR)、CNH元素分析仪(EA)、紫外-可见漫反射光谱仪(UV-Vis DRS)及荧光光谱仪(PL)对配合物2和3进行表征。本章中的两种银基配合物材料均由一维的阳离子链[Ag/dpe(bpy)]n n+和离散的btec4-阴离子组成,并通过Ag…Ag和Ag…N作用力、静电作用、π-π堆积作用和氢键作用(除了配合物2)构成三维的类三明治骨架结构。两种配合物材料具有相似的光学能隙和良好的荧光性能,但是在紫外光的照射下对于MO染料的光催化降解效果不同。3.选择合适的金属盐和有机配体利用水热法合成了基于过渡金属钴(Co)、铜(Cu)、锰(Mn)的新型配合物材料[Co(bpy)_2(nbda)_2(H_2O)_2]·2H_2O(配合物4),[Cu(bpy)_2(nbda)_2(H_2O)_2]·2H_2O(配合物5),[Mn(bpy)_2(nbda)_2(H_2O)_2]·2H_2O(配合物6)(bpy=4,4′-联吡啶,H_2nbda=2,3-降茨烷二羧酸),并通过单晶X-射线衍射仪(SCXRD)、元素分析仪(EA)和傅立叶红外变换光谱仪(FTIR)对所制备的样品进行表征。结果表明三种配合物材料具有相似的结构(单斜晶系C2/c),其中配合物中的金属离子由典型的双齿配体bpy连接形成一维的阳离子链[M1(bpy)]n~(2n+)和[M2(bpy)]n~(2n+)(M=(Co)、铜(Cu)、锰(Mn)),并由完全去质子化的配体nbda2-连接形成二维的[M2(bpy)_2(nbda)_2]n阳离子层,在氢键的作用下形成三维的骨架结构。三种配合物对于有机染料甲基橙(MO)、亚甲基蓝(MB)具有不同的光催化性能,并通过异丙醇作为羟基自由基捕捉剂验证HOMO-LUMO的光催化降解机理。
[Abstract]:In recent years, the removal of organic pollutants in waste water has been widely concerned. In general, organic pollutants have good light stability and have high potential hazards to the environment and organisms. At present, more and more materials have been used to deal with pollutants in wastewater, such as nano adsorbents, TiO_2 photocatalytic materials and so on. Although the material has a good treatment effect on the wastewater, it is not conducive to the study of the structure-activity relationship between materials and pollutants. Therefore, it is imminent to explore a new type of environmental remediation material which can effectively solve the problem of water pollution and to explore the mechanism of the reaction. The complex material is composed of inorganic metal ions and organic ligands. A new type of inorganic organic hybrid material has been widely used in fields such as adsorption, fluorescence, catalysis, chemical sensing and so on. In the field of environmental remediation, complexes are often used as an effective adsorbent to remove organic pollutants in wastewater, or in the environment. UV / visible light / UV visible light is used as homogeneous photocatalyst to photocatalytic degradation of organic pollutants and photocatalytic reduction of CO_2 and Cr (VI). Based on the principle of crystal engineering design, 6 new functional complexes were synthesized by the slow diffusion method and hydrothermal method. The structure and performance characterization of the materials were successfully synthesized by the slow diffusion method and the hydrothermal method. By selecting typical organic dyes as a target for adsorption or photocatalytic degradation, the adsorption and photocatalytic properties of the synthesized complexes are studied and their reaction mechanisms are investigated. The main achievements are as follows: 1. the experiment is based on the principle of crystal engineering in ethanol / ammonia solution by the slow diffusion method at room temperature. A new type of silver based complex material [Ag_4 (DPE) _4] (butca) 13H_2O (butca) / 13H_2O (dpe=1,2- double (4- pyridyl) ethylene, and H_4butca=1,2,3,4- butane four carboxylic acid) with high efficiency adsorption and separation effect was analyzed and characterized for its structure and properties. Two cationic dyes were selected by selecting two kinds of anionic dyes methyl orange (MO) and Congo red (CR). Methylene blue (MB) and Luo Danming B (Rh B) are used as target targets to study the adsorption effect of complex 1. The results show that (1) the complexes 1 have high adsorption properties for anionic dyes MO and CR (the maximum adsorption capacity for MO is 779 mg/g, the maximum adsorption amount of CR is 739 mg /g); (2) the adsorption kinetics of the ligand 1 for MO is a pseudo first order The kinetic equation describes the adsorption process in accordance with the Langmuir and Freundlich isotherm models; (3) the free energy change ((35) G~0) of Gibbs is less than zero, the enthalpy change (delta H~0) and entropy change (delta S~0) are greater than zero, indicating that the adsorption of the complex 1 for MO is a spontaneous reaction process of endothermic and gradual increase of degree of freedom; (4) the complex 1 of the complex can quickly realize the MO/MB mixed dye. Selective separation, and using the self-made SPE columella test, (5) the complex 1 can be recycled and has good stability during the adsorption of MO; (6) the coordination compound 1 has good bactericidal properties to prevent the biofilm phenomenon.2. prepared two kinds of fluorescent and photocatalytic properties by selecting new organic ligands. Compound material [Ag_4 (DPE) _4] (BTEC) (complex 2) and [Ag_4 (bpy) _4]. (BTEC). 12H_2O (complex 3) (dpe=1,2- double (4- pyridyl) ethylene, bpy=4,4 '- bipyridine, benzene four carboxylic acid), and using single crystal diffraction ray diffractometer, Fu Liye infrared transform spectrometer, ultraviolet visible diffuse light The spectrometers (UV-Vis DRS) and fluorescence spectrometer (PL) are used to characterize complexes 2 and 3. The two types of silver based complex materials in this chapter are composed of one dimensional cationic chain [Ag/dpe (bpy)]n n+ and discrete btec4- anions, and through Ag... Ag and Ag... N force, electrostatic action, pion pion accumulation and hydrogen bonding (except for complex 2) constitute a three dimensional sandwich skeleton structure. The two complex materials have similar optical gap and good fluorescence properties, but the photocatalytic degradation effect of MO dyes under ultraviolet light is different.3. selection suitable metal salt and organic A novel ligand based on transition metal cobalt (Co), copper (Cu), manganese (Mn), [Co (nbda) _2 (H_2O) _2] 2H_2O (complex 4) was synthesized by the hydrothermal method. Single crystal X- ray diffractometer (SCXRD), element analyzer (EA) and Fu Liye infrared transform spectrometer (FTIR) are used to characterize the prepared samples. The results show that the three complex materials have similar structure (monoclinic C2/c), in which the metal ions in the complexes form a one-dimensional cationic chain [M1 (bpy)]n with a canonical double dentate ligand bpy. ~ (2n+) and [M2 (bpy)]n~ (2n+) (M= (Co), copper (Cu), manganese (Mn)), and formed by a fully deprotonated ligand nbda2- connection to form a two-dimensional [M2 (bpy) cationic layer, forming a three-dimensional skeleton structure under the action of hydrogen bonds. The three complexes have different photocatalytic properties for organic dye methyl orange and methylene blue. Propanol was used as a hydroxyl radical scavenger to verify the photocatalytic degradation mechanism of HOMO-LUMO.

【学位授予单位】：北京建筑大学
【学位级别】：硕士
【学位授予年份】：2017
【分类号】：X703

【参考文献】