本文關(guān)鍵詞： 金屬-有機(jī)配位聚合物 晶體結(jié)構(gòu) 催化 磁性 穩(wěn)定性　出處：《青島科技大學(xué)》2017年碩士論文　論文類型：學(xué)位論文

【摘要】：金屬-有機(jī)配位聚合物(metal-organic coordination polymers)是由有機(jī)配體與金屬離子構(gòu)筑的一種新興晶態(tài)材料,因?yàn)橛袡C(jī)配體種類繁多且金屬中心離子配位方式較為復(fù)雜,所以配位聚合物具有多變的結(jié)構(gòu)和優(yōu)異的性能,在氣體的吸附與分離、催化、光電磁及藥物儲(chǔ)存與緩釋等諸多領(lǐng)域展現(xiàn)出了極大的應(yīng)用價(jià)值,受到了研究者的廣泛關(guān)注。本論文中,我們采用了常規(guī)的水熱及溶劑熱的合成方法,構(gòu)筑了8個(gè)結(jié)構(gòu)新穎的金屬-有機(jī)配位聚合物材料,并對(duì)它們的結(jié)構(gòu)進(jìn)行了表征,對(duì)它們的性能做了初步探索,總結(jié)了這類材料的合成、結(jié)構(gòu)及性能規(guī)律。具體研究?jī)?nèi)容如下:(1)選用5,5-(quinoxaline-5,8-diyl)-diisophthalate(H4L1)作為橋連配體,與金屬鈷離子構(gòu)筑了兩個(gè)具有三維框架結(jié)構(gòu)的配位聚合物WN-1和WN-2。探究了WN-1的催化活性,表現(xiàn)為惰性;后將材料進(jìn)行緩慢熱處理制備了新型Co基催化材料,CoOx物種以3-5 nm左右的粒子均勻鑲嵌在碳骨架中,該催化劑在硝基苯加氫反應(yīng)中僅需要10 min即可將底物幾乎完全轉(zhuǎn)化,相同條件下其催化活性明顯高于氧化鈷(40 min轉(zhuǎn)化10%)和碳載氧化鈷(40 min轉(zhuǎn)化2%)催化劑。與傳統(tǒng)的非貴金屬氧化物催化劑相比,通過(guò)高溫焙燒配位聚合物所得的Co基催化材料CoOx具有更高的催化活性。(2)利用水熱及溶劑熱的合成方法,基于含氮羧酸配體6-(3-pyridyl)isophthalic acid(H2pip),通過(guò)輔助配體的調(diào)節(jié),成功構(gòu)筑了一系列具有不同維度(從零維、二維到三維)的金屬-有機(jī)配位聚合物(WN-3—WN-6)。實(shí)驗(yàn)表明WN-4和WN-5具有良好的熱穩(wěn)定性及有機(jī)溶劑穩(wěn)定性,甚至在沸水中連續(xù)煮72 h、在乙醇中浸泡72 h后掃描XRD,其結(jié)構(gòu)依然沒有坍塌。此外,磁性測(cè)試表明,WN-4和WN-5也展現(xiàn)出了反鐵磁性。(3)選取了一個(gè)與H2pip類似的有機(jī)配體2-(pyridin-4-yl)terephthalic acid(H2pta),依舊采用簡(jiǎn)單的溶劑熱方法合成了兩個(gè)多孔金屬-有機(jī)配位聚合物,這兩個(gè)結(jié)構(gòu)的孔道尺寸較大,分別為52.8%及35.4%,可進(jìn)一步探究其吸附性能。
[Abstract]:Metal organic coordination polymers (metal-organic coordination polymers) is a new crystalline material formed by organic ligands and metal ions and organic ligands because of the variety and center of metal ion coordination method is complex, so the coordination polymer has changeable structure and excellent performance in adsorption and separation, catalysis, gas. Photoelectric and magnetic fields of drug storage and release showed great application value, has attracted much attention of researchers. In this thesis, we use the conventional synthetic method hydrothermalsolvothermal, constructed 8 novel metal organic coordination polymers, and their structure the characterization, made a preliminary exploration on their performance, summarizes the synthesis of this kind of materials, structure and properties of the law. The specific contents are as follows: (1) using 5,5- (quinoxaline-5,8-diyl) -diisoph Thalate (H4L1) as bridging ligand and metal cobalt ion has constructed two three-dimensional frame structure coordination polymer of WN-1 and WN-2. on the catalytic activity of WN-1, after the material is inert; slow heat treatment of new Co based catalytic materials were prepared, CoOx species with about 3-5 nm particle uniform embedded in the carbon skeleton, the catalyst requires only 10 min substrate can be almost completely transformed in the hydrogenation of nitrobenzene in the same conditions, the catalytic activity was significantly higher than that of cobalt oxide (40 min 10%) and carbon supported cobalt oxide (40 min 2%) catalyst. Compared with the traditional non noble metal oxide catalysts the Co based catalyst CoOx through high temperature roasting coordination polymer obtained has higher catalytic activity. (2) synthesized by hydrothermal method and solvothermal, nitrogen ligands based on 6- (3-pyridyl) isophthalic acid (H2pip), assisted by the Ligand regulation, the successful construction of a series of different dimensions (from zero dimensional, two-dimensional to three-dimensional) metal organic coordination polymers (WN-3 - WN-6). The results showed that WN-4 and WN-5 have good thermal stability and stability in organic solvents, even in boiling water for boiling 72 h in ethanol for 72 h after XRD scanning, the structure is still not collapsed. In addition, the magnetic test shows that WN-4 and WN-5 also show antiferromagnetism. (3) the selection of a H2pip like ligand 2- (pyridin-4-yl) terephthalic acid (H2pta), still using a simple solvothermal method two porous metal organic coordination polymer synthesis, the two structure of the pore size is larger, respectively 52.8% and 35.4%, can be used to investigate the adsorption performance.

【學(xué)位授予單位】：青島科技大學(xué)
【學(xué)位級(jí)別】：碩士
【學(xué)位授予年份】：2017
【分類號(hào)】：O641.4

【參考文獻(xiàn)】

相關(guān)期刊論文 前8條

1 Tingting Wang;Yanyuan Jia;Qiang Chen;Rui Feng;Shouyi Tian;Tong-Liang Hu;Xian-He Bu;;A new luminescent metal-organic framework for selective sensing of nitroaromatic explosives[J];Science China(Chemistry);2016年08期

2 Bin Wang;Hui Yang;Ya-Bo Xie;Yi-Bo Dou;Min-Jian Zhao;Jian-Rong Li;;Controlling structural topology of metal-organic frameworks with a desymmetric 4-connected ligand through the design of metal-containing nodes[J];Chinese Chemical Letters;2016年04期

3 LU HuiYing;YAN Yan;TONG XiaoQiang;YAN WenFu;YU JiHong;XU RuRen;;The structure-directing effect of n-propylamine in the crystallization of open-framework aluminophosphates[J];Science China(Chemistry);2014年01期

4 TIAN Dan;LIU SuiJun;ZHANG DaShuai;CHANG Ze;HU TongLiang;BU XianHe;;Syntheses, structures and magnetic properties of three Co(Ⅱ)coordination architectures based on a flexible multidentate carboxylate ligand and different N-donor ligands[J];Science China(Chemistry);2013年12期

5 劉彬文;曾卉一;趙中燕;鄭發(fā)鯤;郭國(guó)聰;黃錦順;;Syntheses and Single-crystal Structures of New Deficient Compounds in the R_6B_2C_2Q_(14)Family[J];結(jié)構(gòu)化學(xué);2013年10期

6 仝曉強(qiáng);盧慧英;黃湃;閆文付;于吉紅;徐如人;;新型三維開放骨架磷酸鋁[C_4H_(14)N_2][Al_4P_5O_(19)OH]的合成、表征及結(jié)構(gòu)導(dǎo)向研究[J];無(wú)機(jī)化學(xué)學(xué)報(bào);2013年08期

7 楊鑫;傅瑞標(biāo);胡勝民;黃藝輝;盛天錄;吳新濤;;Three New Zn(Ⅱ)/Cd(Ⅱ) Coordination Polymers Constructed with 2-Mercaptonicotinic Acid and 1,2-Di(4-pyridyl)ethylene: Syntheses and Structure Analysis[J];結(jié)構(gòu)化學(xué);2013年01期

8 霍衛(wèi)峰;李乙;盧君然;于吉紅;徐如人;李晶;;一種在無(wú)機(jī)晶體結(jié)構(gòu)中檢索特定子結(jié)構(gòu)的計(jì)算機(jī)方法[J];物理化學(xué)學(xué)報(bào);2012年03期

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