本文關(guān)鍵詞：多羧酸類金屬—有機(jī)雜化材料的功能化設(shè)計(jì)及其性質(zhì)研究　出處：《蘇州大學(xué)》2015年碩士論文　論文類型：學(xué)位論文

  更多相關(guān)文章： 多羧酸類配體 氣體選擇性吸附 晶體結(jié)構(gòu)轉(zhuǎn)變 能量可控釋放

【摘要】：晶體工程學(xué)為實(shí)現(xiàn)分子堆積的可設(shè)計(jì)性和可控合成,并進(jìn)而實(shí)現(xiàn)材料的功能化提供了豐富的途徑。金屬-有機(jī)框架作為晶體工程學(xué)中的一類重要研究對(duì)象,以其結(jié)構(gòu)穩(wěn)定、設(shè)計(jì)多樣、易于合成的優(yōu)點(diǎn),受到人們的廣泛關(guān)注。而羧酸根容易與金屬離子螯合形成穩(wěn)定結(jié)構(gòu),所以多羧酸類配體通常被認(rèn)為是構(gòu)建金屬-有機(jī)框架的優(yōu)秀結(jié)構(gòu)單元。本文主要利用水熱與溶劑熱合成的方法,通過控制反應(yīng)溫度、改變配體、調(diào)整反應(yīng)物比例、調(diào)節(jié)酸堿度等策略合成了6個(gè)多羧酸基的金屬-有機(jī)框架材料。采用X-射線單晶衍射確定了所獲晶體的原子結(jié)構(gòu),并通過粉末X-射線衍射、紅外光譜、熱重分析、氣體吸附、量熱分析等表征方法對(duì)產(chǎn)物的結(jié)構(gòu)以及性質(zhì)進(jìn)行了分析。主要內(nèi)容如下:1.雙羧基微孔框架的設(shè)計(jì)、合成,及其氣體選擇性吸附性質(zhì)的研究。溶劑熱條件下,將間苯二甲酸(1,3-H2bdc)和對(duì)苯二甲酸(1,4-H2bdc)分別引入硝酸銦(In(NO3)3)體系中,獲得了兩種具有不同孔狀結(jié)構(gòu)的金屬-有機(jī)雜化材料,化合物1和化合物2:[H2In3O(OH)3(1,3-bdc)3](1)[HIn(1,4-bdc)2](2)化合物1中的孔道被其內(nèi)部的苯環(huán)所阻擋,沒有表現(xiàn)出對(duì)氣體的良好的吸附能力。化合物2則在1 atm下對(duì)CO2和N2具有較高的吸附選擇性,而且擁有良好的結(jié)構(gòu)與氣體吸附量的穩(wěn)定性。2.能量的儲(chǔ)存與pH控制釋放。水熱條件下,將1,3-二吡啶基丙烷(bpp)引入到醋酸鈷(Co(Ac)2)和均苯四羧酸(1,2,4,5-H4btec)體系當(dāng)中,制備了化合物3。將化合物3的樣品放入酸性水溶液,保持常溫常壓(NTP:~298 K,1 atm),依次獲得了化合物4,5和6:[Co5(OH)2(bpp)(btec)2]2?H2O(3)[Co2(H2O)4(bpp)2(Hbtec)2]?5H2O?H2bpp(4)[Co2(H2O)2(OH)(bpp)2(Hbpp)(btec)]?5H2O(5)[Co3(H2O)4(Hbpp)2(btec)2]?6H2O(6)值得一提的是,如果將原料混合,不經(jīng)水熱處理,空氣中保持常溫常壓(NTP:~298 K,1 atm),會(huì)直接獲得化合物6。將化合物6加水進(jìn)行水熱處理又會(huì)獲得化合物3。在化合物轉(zhuǎn)變的過程當(dāng)中,體系的能量變化可以通過體系溫度的波動(dòng)以及理論計(jì)算得到驗(yàn)證。進(jìn)一步實(shí)驗(yàn)表明,這種轉(zhuǎn)變過程是可以通過調(diào)節(jié)體系的pH值來控制的。
[Abstract]:For crystal engineering design and implementation of controllable synthesis of molecular packing, and then realize the function of material provides a rich way. Metal organic framework as an important research object in crystal engineering, with its stable structure, design diversity, the advantages of easy synthesis, people pay more and more attention. And the CMC easy acid chelating with metal ions to form a stable structure, so the multicarboxylic acids are usually considered excellent building blocks of metal organic frameworks. This paper mainly uses the method of hydrothermal and solvothermal synthesis, by controlling the reaction temperature, reactant ratio change of ligand, adjustment, more than 6 carboxylic acid metal organic frameworks the material synthesized pH adjustment strategies are determined. The atomic structure of the crystal by X- ray diffraction and by powder X- ray diffraction, infrared spectroscopy, thermogravimetric analysis, gas adsorption, Calorimetry characterization methods of the product structure and properties are analyzed. The main contents are as follows: design, synthesis of 1. double carboxyl microporous framework, and Study on gas selective adsorption properties. Under solvothermal conditions, the benzene between two formic acid (1,3-H2bdc) and terephthalic acid (1,4-H2bdc) were introduced into indium nitrate (In (NO3 3)) system, obtained with two different porous metal organic hybrid materials, compounds 1 and 2:[H2In3O (OH) 3 (1,3-bdc) 3] (1) [HIn (1,4-bdc) 2] (2) channels in compound 1 is blocked by the Department of the benzene ring, did not show the the gas has good adsorption capability. The adsorption selectivity of compound 2 under 1 atm of CO2 and N2 is high, the release of stored energy control and the stability of pH.2. and has a good structure and gas adsorption capacity. Under hydrothermal conditions, 1,3- two pyridyl propane (BPP) into vinegar 閰擱挻(Co(Ac)2)鍜屽潎鑻洓緹ч吀(1,2,4,5-H4btec)浣撶郴褰撲腑,鍒跺浜?jiǎn)鍖栧悎鐗?.灝嗗寲鍚堢墿3鐨勬牱鍝佹斁鍏ラ吀鎬ф按婧舵恫,淇濇寔甯告俯甯稿帇(NTP:~298 K,1 atm),渚濇鑾峰緱浜?jiǎn)鍖栧悎鐗?,5鍜，

本文編號(hào)：1378040