發(fā)布時(shí)間：2018-01-27 12:13

  本文關(guān)鍵詞： 金屬-有機(jī)框架化合物 熒光檢測 氣體吸附 儲氫材料　出處：《華中師范大學(xué)》2015年碩士論文　論文類型：學(xué)位論文

【摘要】：本論文以晶體工程學(xué)原理為依據(jù),從金屬-有機(jī)框架(metal-organic frameworks, MOFs)晶體材料的功能性與應(yīng)用出發(fā),主要研究這類化合物的合成、拓?fù)浣Y(jié)構(gòu)和多功能性質(zhì),旨在探索金屬有機(jī)框架晶體材料的結(jié)構(gòu)多樣性,并在結(jié)構(gòu)研究的基礎(chǔ)上,探究具有新穎拓?fù)浣Y(jié)構(gòu)的金屬有機(jī)框架晶體材料的性質(zhì)應(yīng)用。本論文選擇具有不同配位構(gòu)型的芳香羧酸配體及中性橋聯(lián)配體與過渡金屬離子構(gòu)筑了10個(gè)金屬有機(jī)框架化合物,并測定了其單晶結(jié)構(gòu),重點(diǎn)研究了這些化合物在氣體吸附、熒光檢測、儲氫等方面的性質(zhì)。本論文包含五個(gè)部分的內(nèi)容,第一個(gè)部分簡單介紹了金屬有機(jī)框架化合物(MOFs)的相關(guān)概念以及這類材料的合成方法與影響因素,并介紹了目前多孔及熒光MOFs的研究進(jìn)展。第二個(gè)部分以共軛噻吩三羧酸：Benzo-(1,2;3,4; 5,6)-tris(thiophene-2'-carboxylic acid) (H3BTTC)為有機(jī)連接體通過溶劑熱方法合成并表征了2個(gè)三維的微孔化合物：Cu6(BTTC)4(H2O)6·xS(化合物1)和[(CH3)2NH2]3[(Cu4Cl)3(BTTC)8]·yS(化合物2,S代表未配位的溶劑分子),它們都是由切角八面體組成的,并且含有納米級的孔道,顯示不同的拓?fù)浣Y(jié)構(gòu)�；衔�1對氫氣分子和二氧化碳分子顯示出較高的吸附焓,這主要是由于在化合物1的孔道表面存在暴露的金屬銅位點(diǎn)。尤其,活化的化合物1顯示出了對某些氣體分子高效的分離效率,例如在室溫條件下從氮?dú)�、二氧化碳和甲烷氣體中分離出二氧化碳。第三個(gè)部分以芳香三羧酸：3,5-bis(4'-carboxylphenoxy)benzoic acid (H3BCPBA)為主要配體,中性橋聯(lián)配體4,4'二咪唑基聯(lián)苯(bimb)為輔助配體,合成了4個(gè)MOFs: [Co2(BCPBA)2(bimb)2(DMA)2(H2O)2]n(化合物3)、[Mn3(BCPBA)2(DMA)2(H2O)2]n(化合物4)、[Cu3(BCPBA)2(bimb)3(DMA)3(H2O)5]n (化合物5)和[Cd2(BCPBA)2(bimb)2(DMA)2(H2O)]n(化合物6)。它們都是三維的網(wǎng)絡(luò)結(jié)構(gòu),其中化合物3和6為異質(zhì)同構(gòu),它們的結(jié)構(gòu)中配體H3BCPBA有一個(gè)羧基沒有參與配位；化合物6具有較強(qiáng)的熒光,通過熒光淬滅實(shí)現(xiàn)了對五類物質(zhì)定量的選擇性檢測(溶劑小分子acetone、農(nóng)藥Methyl parathion、硝基苯類化合物、Cr2O72-、Cu2+、Ni2+),化合物6有可能成為一個(gè)較好的熒光檢測材料；化合物4和5的結(jié)構(gòu)中都含有孔道,通過PLATON計(jì)算得到其孔洞有效率分別為16.2%和25%,金屬原子上都有水分子參與配位,配位的水分子可以很容易地通過加熱或是抽真空的方法移除,活化后的化合物4和5能選擇性地吸附C02分子。第四個(gè)部分以芳香二羧酸：3-((4'-carboxybenzyl)oxy)benzoic acid (3,4'-H2CBOB)和4-((2'-carboxybenzyl)oxy)benzoic acid (4,2'-H2CBOB)為主要配體,4,4'-二咪唑基聯(lián)苯(bimb)為輔助配體,合成了4個(gè)MOFs:[Ni(4,2'-CBOB)2(bimb)2(H2O)]n(化合物7)、[Ni(4,2'-CBOB)3(bimb)2]n(化合物8)、[Co(4,2'-CBOB)3(bimb)2]n(化合物9)和[Cd4(3,4'-CBOB)6(bimb)4]n(化合物10)�；衔�7、8和9為二維的網(wǎng)狀結(jié)構(gòu),其中化合物8和9為異質(zhì)同構(gòu)；化合物10是一個(gè)三維的網(wǎng)絡(luò)結(jié)構(gòu),具有較強(qiáng)的熒光,通過熒光淬滅實(shí)現(xiàn)了對五類物質(zhì)定量的選擇性檢測(溶劑小分子acetone、農(nóng)藥Methyl parathion、硝基苯類化合物、Cr2O72-、Cu2+),化合物10有可能成為一個(gè)較好的熒光檢測材料。第五個(gè)部分對本論文的研究成果做了簡單小結(jié),提出了研究的創(chuàng)新點(diǎn),并對MOFs作為氣體吸附材料及熒光材料的應(yīng)用前景進(jìn)行了展望。
[Abstract]:In this paper, the principle of crystal engineering as the basis, from metal organic frameworks (metal-organic, frameworks, MOFs) function and application of crystal materials, mainly studies the synthesis of these compounds, topological structure and multifunctional properties, in order to explore the structure of metal organic framework crystal material diversity, and based on the study of the structure. Research of properties of metal organic framework crystal materials with novel topological structure. 10 metal organic frameworks constructed in this paper with different configuration of aromatic carboxylic acid ligands and neutral ligands and transition metal ions, its crystal structure was determined, focusing on the fluorescence detection of these compounds in gas adsorption properties. Hydrogen storage and so on. This thesis consists of five parts, the first part briefly introduces the metal organic frameworks (MOFs) related concepts The factors and methods of synthesis of this kind of material and influence, and introduces the research progress of porous and fluorescence of MOFs. The second part in three: Benzo- conjugated thiophene carboxylic acid (1,2; 3,4; 5,6) -tris (thiophene-2'-carboxylic acid) (H3BTTC) as the organic solvent through the connection methods of thermal synthesis and characterization of 2 three the microporous compounds: Cu6 (BTTC) 4 (H2O) 6 - xS (compound 1) and [(CH3) 2NH2]3[(Cu4Cl) 3 (BTTC) 8] - yS (compound 2, S represents the distribution of solvent molecules), they are composed of eight corner cutting surface body, and containing nano the channel shows different topologies. 1 compounds of hydrogen molecules and carbon dioxide showed higher enthalpy of adsorption, which is mainly due to the presence of copper sites exposed in compound 1 pore surface. Especially, the activation of the 1 compounds showed on the separation efficiency of some high molecular gases, such as 瀹ゆ俯鏉′歡涓嬩粠姘皵,浜屾哀鍖栫⒊鍜岀敳鐑鋒皵浣撲腑鍒嗙鍑轟簩姘у寲紕，

本文編號：1468449