基于后过渡金属的有机化合物的水氧化催化剂的设计合成和性能研究
发布时间：2018-12-19 18:00
【摘要】：自然界利用并固定太阳能的有效方法之一就是光合作用。光合系统是植物利用太阳能固定CO_2产生氧气的重要作用方式,近年来,人们一直致力于研究固定太阳能和人工催化水氧化产生O_2。因此,合成具有优良性能的水氧化催化剂成为人们的研究热点。具有半夹心结构的过渡金属有机化合物由于空间结构新颖,便于修饰,易于溶解,还能够调节氧化还原性能而受到广大研究工作者的关注。而且已有很多报道都有力的说明半夹心结构的过渡金属化合物的催化水氧化的能力。本文合成了几种过渡金属与有机配体的化合物,通过对化合物结构的设计、合成、表征和性能检测来证明该种类型的化合物更适于作为水氧化催化剂,并能更好的稳定化合物的空间结构,增加化合物的活性。论文的主体部分主要包括以下三个方面:一、合成了新的基于金属钌的半夹心化合物[η-6-CyRu(L)(H_2O)](L为配体4-吡啶-2-乙烯基-8羟基喹啉,Cy为对甲基异丙基苯)对其进行了表征,得到了该化合物的晶体数据以及各项特征数据。同时通过循环伏安法检测该化合物的氧化还原性能,对数据进行了必要的分析。二、用金属有机化合物β-萘酚偶氮对苯磺酸钠(L2)与后过渡金属铜、镍、钴、锰的硝酸盐水合物合成了新的金属偶氮类化合物,表征了这些化合物的结构和特征,并研究了它们的光学和电化学性能,通过电化学性能的研究发现在这四个化合物中,Co的偶氮类化合物的氧化还原性能最好。三、通过金属铜的硝酸盐与有机化合物3-(2-偶氮吡啶)-2-萘酚(L3)制备新型金属有机化合物。通过核磁、单晶衍射、红外光谱等手段表征了该化合物的结构。通过热重(TGA)、紫外可见(UV-vis)光谱、电化学等手段分别研究了化合物的稳定性,电子结构,以及电化学性能,取得了良好的结果。用循环伏安法检测化合物的氧化还原性能,发现在pH=11时该性能最强。另外,将该偶氮类化合物应用于化学水氧化,以Ce(Ⅳ)盐作为氧化剂,取得了非常好的效果。上述研究结果表明,后过渡金属有机配合物在催化水氧化领域有着巨大潜力,为进一步探索后过渡金属水氧化催化剂奠定了基础,也为通过人工光合作用开发太阳能提供了更多的实验依据和理论基础。
[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，
本文编号：2387265
[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，
本文编号：2387265
本文链接：https://www.wllwen.com/kejilunwen/huaxue/2387265.html
教材专著
