【摘要】：自然界利用并固定太陽(yáng)能的有效方法之一就是光合作用。光合系統(tǒng)是植物利用太陽(yáng)能固定CO_2產(chǎn)生氧氣的重要作用方式,近年來(lái),人們一直致力于研究固定太陽(yáng)能和人工催化水氧化產(chǎn)生O_2。因此,合成具有優(yōu)良性能的水氧化催化劑成為人們的研究熱點(diǎn)。具有半夾心結(jié)構(gòu)的過(guò)渡金屬有機(jī)化合物由于空間結(jié)構(gòu)新穎,便于修飾,易于溶解,還能夠調(diào)節(jié)氧化還原性能而受到廣大研究工作者的關(guān)注。而且已有很多報(bào)道都有力的說(shuō)明半夾心結(jié)構(gòu)的過(guò)渡金屬化合物的催化水氧化的能力。本文合成了幾種過(guò)渡金屬與有機(jī)配體的化合物,通過(guò)對(duì)化合物結(jié)構(gòu)的設(shè)計(jì)、合成、表征和性能檢測(cè)來(lái)證明該種類(lèi)型的化合物更適于作為水氧化催化劑,并能更好的穩(wěn)定化合物的空間結(jié)構(gòu),增加化合物的活性。論文的主體部分主要包括以下三個(gè)方面:一、合成了新的基于金屬釕的半夾心化合物[η-6-CyRu(L)(H_2O)](L為配體4-吡啶-2-乙烯基-8羥基喹啉,Cy為對(duì)甲基異丙基苯)對(duì)其進(jìn)行了表征,得到了該化合物的晶體數(shù)據(jù)以及各項(xiàng)特征數(shù)據(jù)。同時(shí)通過(guò)循環(huán)伏安法檢測(cè)該化合物的氧化還原性能,對(duì)數(shù)據(jù)進(jìn)行了必要的分析。二、用金屬有機(jī)化合物β-萘酚偶氮對(duì)苯磺酸鈉(L2)與后過(guò)渡金屬銅、鎳、鈷、錳的硝酸鹽水合物合成了新的金屬偶氮類(lèi)化合物,表征了這些化合物的結(jié)構(gòu)和特征,并研究了它們的光學(xué)和電化學(xué)性能,通過(guò)電化學(xué)性能的研究發(fā)現(xiàn)在這四個(gè)化合物中,Co的偶氮類(lèi)化合物的氧化還原性能最好。三、通過(guò)金屬銅的硝酸鹽與有機(jī)化合物3-(2-偶氮吡啶)-2-萘酚(L3)制備新型金屬有機(jī)化合物。通過(guò)核磁、單晶衍射、紅外光譜等手段表征了該化合物的結(jié)構(gòu)。通過(guò)熱重(TGA)、紫外可見(jiàn)(UV-vis)光譜、電化學(xué)等手段分別研究了化合物的穩(wěn)定性,電子結(jié)構(gòu),以及電化學(xué)性能,取得了良好的結(jié)果。用循環(huán)伏安法檢測(cè)化合物的氧化還原性能,發(fā)現(xiàn)在pH=11時(shí)該性能最強(qiáng)。另外,將該偶氮類(lèi)化合物應(yīng)用于化學(xué)水氧化,以Ce(Ⅳ)鹽作為氧化劑,取得了非常好的效果。上述研究結(jié)果表明,后過(guò)渡金屬有機(jī)配合物在催化水氧化領(lǐng)域有著巨大潛力,為進(jìn)一步探索后過(guò)渡金屬水氧化催化劑奠定了基礎(chǔ),也為通過(guò)人工光合作用開(kāi)發(fā)太陽(yáng)能提供了更多的實(shí)驗(yàn)依據(jù)和理論基礎(chǔ)。
[Abstract]:Photosynthesis is one of the effective ways to use and fix solar energy in nature. Photosynthetic system is an important way for plants to use solar energy to immobilize CO_2 to produce oxygen. In recent years, people have been working on fixed solar energy and artificial catalytic water oxidation to produce O _ 2s. Therefore, the synthesis of water oxidation catalysts with excellent performance has become a hot research topic. Transition metal-organic compounds with semi-sandwich structure have attracted much attention due to their novel space structure, easy modification, easy dissolution, and the ability to regulate redox properties. Moreover, there have been many reports on the catalytic water oxidation ability of semi-sandwich transition metal compounds. In this paper, several compounds of transition metal and organic ligands were synthesized. By designing, synthesizing, characterizing and testing the structure of the compounds, it was proved that these compounds are more suitable as catalysts for water oxidation. And it can stabilize the space structure of the compound and increase the activity of the compound. The main contents of this thesis are as follows: firstly, a new semi-sandwich compound based on ruthenium [畏-6-CyRu (L) (H _ 2O] (L is ligand 4pyridine-2-vinyl-8-hydroxyquinoline) has been synthesized. The Cy was characterized by p-methylisopropylbenzene, and the crystal data and characteristic data of the compound were obtained. At the same time, the redox properties of the compound were determined by cyclic voltammetry, and the data were analyzed. Secondly, new metal azo compounds were synthesized from sodium 尾 -naphthol azobenzenesulfonate (L _ 2) and nitrate hydrates of post-transition metal copper, nickel, cobalt and manganese. The structures and characteristics of these compounds were characterized. Their optical and electrochemical properties were studied. The results showed that the Co azo compounds had the best redox performance among the four compounds. Third, a novel organometallic compound was prepared by nitrates of copper and organic compound 3- (2-azopyridine) -2-naphthol (L3). The structure of the compound was characterized by NMR, single crystal diffraction and infrared spectroscopy. The stability, electronic structure and electrochemical properties of the compounds were studied by thermogravimetric (TGA), UV-Vis (UV-vis) spectroscopy and electrochemistry, respectively. Good results were obtained. The redox properties of the compounds were determined by cyclic voltammetry. It was found that the redox property was the strongest at 11:00 pH=. In addition, the azo compound was applied to chemical water oxidation and Ce (鈪，

本文編號(hào)：2387265