本文選題：配合物 + 合成�。� 參考：《北京建筑大學》2017年碩士論文

【摘要】：近年來,廢水中有機污染物的去除受到了廣泛的關注。一般情況下,有機污染物具有很好的光穩(wěn)定性,會對環(huán)境和生物產(chǎn)生很高的潛在危險。目前越來越多的材料被用來處理廢水中的污染物,比如納米吸附材料、TiO_2光催化材料等,這些材料盡管對廢水具有較好的處理效果,但是不利于研究材料與污染物之間的構效關系。因此,探索一種能夠有效解決水污染問題并且有利于反應機理探究的新型環(huán)境修復材料迫在眉睫。配合物材料是由無機金屬離子和有機配體構成的一種新型無機-有機雜化材料。由于具備多樣和易調(diào)控的結構、可調(diào)諧的表面活性位點,配合物在吸附、熒光、催化、化學傳感等領域得到了廣泛的應用。在環(huán)境修復方面,配合物常被用來作為一種有效的吸附劑去除廢水中的有機污染物,或在紫外光/可見光/紫外-可見光的照射下作為均相光催化劑來光催化降解有機污染物以及光催化還原CO_2和Cr(VI)。本研究基于晶體工程學設計原理,利用緩慢擴散法和水熱法成功合成6種新型功能配合物材料,對其進行結構分析和性能表征,并通過選擇典型的有機染料作為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,并探究其反應機理。主要的研究成果如下:1.本實驗根據(jù)晶體工程學原理在乙醇/氨水的溶液中通過室溫條件下的緩慢擴散法合成一種具有高效吸附和分離效果的新型銀基配合物材料[Ag_4(dpe)_4]·(butca)·13H_2O(配合物1)(dpe=1,2-雙(4-吡啶基)乙烯,H_4butca=1,2,3,4-丁烷四羧酸),對其進行結構分析和性能表征。通過選擇兩種陰離子型染料甲基橙(MO)和剛果紅(CR),兩種陽離子型染料亞甲基藍(MB)和羅丹明B(Rh B)作為目標靶物來研究配合物1的吸附效果。結果表明:(1)配合物1對陰離子型染料MO和CR具有較高的吸附性能(對MO的最大吸附量為779 mg/g,CR的最大吸附量為739 mg/g);(2)配合物1對MO的吸附動力學過程可用偽一級動力學方程描述,吸附過程符合Langmuir和Freundlich等溫線模型;(3)Gibbs自由能變((35)G~0)小于零,焓變(ΔH~0)和熵變(ΔS~0)大于零,表明配合物1對于MO的吸附是一個吸熱、自由度逐漸增加的自發(fā)反應過程;(4)配合物1能夠快速實現(xiàn)MO/MB混合染料的選擇性分離,并利用自制的SPE小柱實驗驗證;(5)配合物1在吸附MO的過程中能實現(xiàn)循環(huán)利用并且具有較好的穩(wěn)定性;(6)配合物1具有良好的殺菌性能以防止生物掛膜現(xiàn)象。2.通過選擇新型的有機配體制備了兩種具有熒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-雙(4-吡啶基)乙烯,bpy=4,4′-聯(lián)吡啶,H_4btec=1,2,4,5-均苯四羧酸),并用單晶X-射線衍射儀(SCXRD)、傅立葉紅外變換光譜儀(FTIR)、CNH元素分析儀(EA)、紫外-可見漫反射光譜儀(UV-Vis DRS)及熒光光譜儀(PL)對配合物2和3進行表征。本章中的兩種銀基配合物材料均由一維的陽離子鏈[Ag/dpe(bpy)]n n+和離散的btec4-陰離子組成,并通過Ag…Ag和Ag…N作用力、靜電作用、π-π堆積作用和氫鍵作用(除了配合物2)構成三維的類三明治骨架結構。兩種配合物材料具有相似的光學能隙和良好的熒光性能,但是在紫外光的照射下對于MO染料的光催化降解效果不同。3.選擇合適的金屬鹽和有機配體利用水熱法合成了基于過渡金屬鈷(Co)、銅(Cu)、錳(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′-聯(lián)吡啶,H_2nbda=2,3-降茨烷二羧酸),并通過單晶X-射線衍射儀(SCXRD)、元素分析儀(EA)和傅立葉紅外變換光譜儀(FTIR)對所制備的樣品進行表征。結果表明三種配合物材料具有相似的結構(單斜晶系C2/c),其中配合物中的金屬離子由典型的雙齒配體bpy連接形成一維的陽離子鏈[M1(bpy)]n~(2n+)和[M2(bpy)]n~(2n+)(M=(Co)、銅(Cu)、錳(Mn)),并由完全去質(zhì)子化的配體nbda2-連接形成二維的[M2(bpy)_2(nbda)_2]n陽離子層,在氫鍵的作用下形成三維的骨架結構。三種配合物對于有機染料甲基橙(MO)、亞甲基藍(MB)具有不同的光催化性能,并通過異丙醇作為羥基自由基捕捉劑驗證HOMO-LUMO的光催化降解機理。
[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.

【學位授予單位】：北京建筑大學
【學位級別】：碩士
【學位授予年份】：2017
【分類號】：X703

【參考文獻】

相關期刊論文 前5條

1 郭廣亮;王崇臣;王鵬;;生物陶吸附酸性品紅的性能[J];環(huán)境化學;2014年05期

2 趙德明;張譚;張建庭;徐新華;;微波輔助二氧化氯氧化降解苯酚[J];化工學報;2011年07期

3 鄒照華;何素芳;韓彩蕓;張六一;羅永明;;重金屬廢水處理技術研究進展[J];水處理技術;2010年06期

4 劉中立;李篤;王玉琨;;前線軌道理論在有機化學中的應用[J];化學通報;1983年10期

5 陳爾廷;唐立中;;八一年諾貝爾化學獎獲得者福井謙一及其理論[J];化學通報;1982年05期

相關碩士學位論文 前1條

1 杜晶晶;納米孔洞金屬—有機骨架的選擇性吸附與催化性質(zhì)研究[D];安徽大學;2011年

，

本文編號：1796019