本文選題：配合物 + 分子結(jié)構(gòu)　； 參考：《華南理工大學(xué)》2015年碩士論文

【摘要】：在環(huán)境污染日益嚴(yán)重、能源緊缺的21世紀(jì),人們開(kāi)始努力尋找具有可再生的清潔能源來(lái)替代石油、煤炭、天然氣等化石能源。氫氣由于其熱值高、清潔、安全、運(yùn)輸方便、可再生等優(yōu)越的性能,成為人們關(guān)注的焦點(diǎn)。如何通過(guò)簡(jiǎn)單、高效的途徑獲取氫氣已成為全球科學(xué)家們的研究目標(biāo)。自然界中,氫化酶能高效催化水還原生成氫氣,但是這種生物環(huán)境是不可模擬的,不過(guò)這種啟示拉開(kāi)了科學(xué)家對(duì)分子催化劑研究的序幕。本工作致力于通過(guò)設(shè)計(jì)新型配位體和組裝不同類(lèi)型過(guò)渡金屬配合物,尋找新的還原水產(chǎn)氫催化劑。本論文工作包括:1)四種有機(jī)配體的合成:2,3-二(2-羥基苯二胺)-2,3-丁二氰(H2LA),2-吡啶氨基-N,N-二(2-亞甲基-4,6-二氟苯酚)(H2LB),2-吡啶氨基-N,N-二(2-亞甲基-4-甲氧基-6-叔丁基酚)(H2LC),(N,N-二甲基)乙二胺-N,N-二(2,4-二氟苯酚)(H2LD)。2)六種新型配合物的制備和表征:[NiIILA]1,[CuIILA]2,[CoIL’(py)3][CoIIL’2]3[LBMoVI(O)2]4,[LCMoVI(O)2]5,[LDMoVI(O)2]6。3)六種新型配合物的電催化性能研究:六種配合物都具有良好的電催化制氫性能,它們的TOF(turnover frequency)值分別為574(1,p H=6.0),1258(2,p H=5.0),3855(3,p H=7.0),756(4,p H=6.0),493(5,p H=7.0)和88 h-1(6,DMF)。4)催化機(jī)理的初步推論。研究結(jié)果表明,不同金屬離子和不同配體都明顯影響著電催化產(chǎn)氫效率,可以通過(guò)有機(jī)配體的設(shè)計(jì)和配合物的組裝來(lái)提高分子催化劑的電催化產(chǎn)氫效率。特別指出,含有拉電子取代的配體能夠提高配合物的催化制氫效率,推電子取代基配體則會(huì)有相反的效果。長(zhǎng)時(shí)間的控制電位電解實(shí)驗(yàn)數(shù)據(jù)和電解前后的紫外電子光譜數(shù)據(jù)表明6個(gè)配合物的催化能力都具有穩(wěn)定性、耐久性。
[Abstract]:In the 21st century, when environmental pollution is increasingly serious and energy is scarce, people are trying to find renewable clean energy to replace fossil energy such as oil, coal, natural gas and so on. Because of its high calorific value, clean, safe, convenient transportation, renewable and other superior performance, hydrogen has become the focus of attention. How to obtain hydrogen by simple and efficient way has become the research goal of scientists all over the world. In nature, hydrogenase can efficiently catalyze water reduction to produce hydrogen, but this biological environment can not be simulated. However, this revelation opens up the prelude to the study of molecular catalysts. The aim of this work is to find new hydrogen-reducing catalysts by designing new ligands and assembling different types of transition metal complexes. The work of this thesis includes the synthesis of four kinds of organic ligands: 2 ~ (2 +) ~ (3) -dimethylidene-2-hydroxy phenylenediamine (H _ (2) C ~ (2) -N ~ (2) -butyldicyanodioxy (H _ (2) -pyridylamino ~ (2) -N _ (2) -difluorophenol (N ~ (2) -difluorophenol (H _ (2) LBX) -pyridylamino -N (N) -dimethylene _ 2-methyl-4-methoxy -6- tert Ding Ji phenol (H _ 2LC ~ (2) C ~ (2) -N _ (2) -dimethyl) Preparation and characterization of six novel complexes: [NiIILA] 1, [CuIILA] 2, [CoIL'(py)3] [CoIIL'2] 3 [LBMoVI(O)2] 4, [LCMoVI(O)2] 5, [LDMoVI(O)2] 6.3). The TOF(turnover frequency values of them are 574g / h 6.0 / 1258m / 2H ~ (5.0) ~ 3855 / h ~ (7. 0) ~ (756 / H) ~ (6. 0) and 88h-16 ~ (6) DMF 路4) respectively. The results show that the catalytic mechanism of these two compounds is very important and the effect of the activity of the catalyst on the catalytic mechanism is better than that of the control group (P & lt; 0.05) and the catalytic mechanism of the catalyst is 88 h ~ (16) DMF 路4). The results show that different metal ions and different ligands have a significant effect on the efficiency of electrocatalytic hydrogen production, which can be improved by the design of organic ligands and the assembly of complexes. It is pointed out in particular that ligands containing electron-pulling substituents can improve the catalytic hydrogen production efficiency of the complexes, while the push-electron substituted ligands have the opposite effect. The experimental data of controlled potential electrolysis for a long time and the UV electron spectrum data before and after electrolysis show that the catalytic ability of the six complexes is stable and durable.
【學(xué)位授予單位】：華南理工大學(xué)
【學(xué)位級(jí)別】：碩士
【學(xué)位授予年份】：2015
【分類(lèi)號(hào)】：O641.4;TQ116.2

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