双核铜和铁金属配合物的水氧化催化性质研究

发布时间：2018-05-03 16:40

本文选题：铜金属配合物 + 铁金属配合物　；参考：《广西大学》2016年硕士论文

【摘要】：氢气是清洁的可再生能源,发展氢能源被认为是可持续地解决能源问题的一种重要方式。地球上有丰富的水资源,利用水作为原料制备氢气被认为是最经济的一种方法。在水分解成氢气和氧气的过程中,水氧化生成氧气的半反应是复杂的四电子过程,而且具有较高的能垒,是一个瓶颈问题。因此,如何合成高效稳定的水氧化催化剂是重要的研究课题。过渡金属配合物具有丰富的光学、氧化还原性质和催化性能而备受关注。已报道的金属配合物水氧化催化剂主要以含有Ru、Ir等贵金属元素的配合物为主。近年来,有关Mn、Cu、Fe、Co等非贵金属配合物水氧化催化剂的报道不断地出现。与贵金属催化剂相比,这些第一过渡系金属配合物的水氧化催化剂的成本较低,具有广阔的应用前景。在本研究工作中,合成了双核铜和铁金属配合物,并研究了它们的水氧化催化活性。研究内容包括：1.合成了两个双核铜配合物[Cu2(tpbn)(CH3OH)4(ClO4)2](ClO4)2 (1)和[Cu2(tpbn)(CioH8N2)2](C104)4(CH3COCH3)2 (2) (CioH8N2=2,2'-bipyridine, tpbn=(N,N,N\N'-四(2-吡啶甲基)-1,4-丁二胺)。通过X-ray单晶衍射对配合物的结构进行了分析鉴定,配合物(1)中的Cu(Ⅱ)属于六配位的八面体构型,配合物(2)中的Cu(Ⅱ)属于五配位的四方锥构型,其中每个tpbn分子螯合和桥联两个Cu(Ⅱ)离子。2.在醋酸钠-氢氧化钠的缓冲溶液中,以过硫酸氢钾作为氧化剂,测定了双核铜配合物在不同pH值、不同浓度条件下的水氧化催化活性。其中,(1)在pH=12.50的缓冲溶液中催化活性较好,转化数(TON)为2.4。(2)在pH=12.50的缓冲溶液中催化活性较好,转化数为3.8。 (1)和(2)的电催化活性研究表明,在pH=12.50的醋酸钠-氢氧化钠的缓冲溶液中,(1)和(2)催化水氧化的起始电压约为0.8 V。3.合成了三个双核铁的配合物[Fe2O(C12H8N2)4](H2O)2(ClO4)4(3) (C12H8N2= 1,10-邻菲罗啉)、[Fe20(CioH8N2)4](H20)2(C104)4 (4) (C10H8N2=2,2’-联吡啶)、[Fe2O(Ci2Hi2N2)4](H2O)2(ClO4)4 (5) (C12H12N2=4,4'-二甲基-2,2'-联吡啶),并研究了它们的水氧化催化性能。在醋酸钠-醋酸的缓冲溶液中,以过硫酸氢钾作为氧化剂,测定配合物(3)-(5)在不同pH值、不同浓度条件下的催化活性。其中,(3)在pH=4.50的缓冲溶液中催化活性较好,TON为3.8；(4)在pH=3.45的缓冲溶液中催化活性较好,TON为7.7；(5)在pH=7.00的缓冲溶液中催化活性较好,TON为12.3。(3)、(4)和(5)的电催化活性研究表明,在pH=7.50的醋酸钠-醋酸的缓冲溶液中,(3)、(4)和(5)的催化水氧化起始电压约为1.20 V。
[Abstract]:Hydrogen is a clean and renewable energy, and the development of hydrogen energy is considered as an important way to solve the energy problem sustainably. There is a rich water resource on the earth. It is considered the most economical way to make hydrogen by using water as raw material. In the process of water decomposition into hydrogen and oxygen, the semi reaction of water oxidation to oxygen is complex. The four electronic process, with high energy barrier, is a bottleneck problem. Therefore, how to synthesize high efficient and stable water oxidation catalyst is an important research topic. The transition metal complexes have been paid much attention to with rich optical, redox properties and catalytic properties. The reported metal complex water oxidation catalyst mainly contains R U, Ir and other noble metal complexes are the main complexes. In recent years, reports of non precious metal complexes such as Mn, Cu, Fe and Co have been reported continuously. Compared with the noble metal catalysts, the cost of the water oxidation catalysts for these first transition metal complexes has a low cost and has a broad application prospect. Nuclear copper and iron metal complexes have been studied and their catalytic activity for water oxidation is studied. The contents of the study include: 1. the synthesis of two binuclear copper complexes [Cu2 (tpbn) (CH3OH) 4 (ClO4) 2] (ClO4) 2 (1) and [Cu2 (CioH8N2) 2] (C104) 4 (CH3COCH3) 2 (2). The structure of the complex is identified by single crystal diffraction. The Cu (II) in the complex (1) belongs to the six coordination eight body configuration, and the Cu (II) in the complex (2) belongs to the five coordination tetragonal cone configuration, in which each tpbn molecule chelation and the bridged two Cu (II) ion.2. are in the buffer solution of sodium acetate sodium hydroxide, with potassium persulfate as the buffer solution. As oxidizer, the catalytic activity of the dual core copper complex under different pH and different concentration conditions was determined. (1) the catalytic activity was better in the buffer solution of pH=12.50, and the conversion number (TON) was 2.4. (2) in pH=12.50 buffer solution, and the conversion number of 3.8. (1) and (2) electrocatalytic activity showed that in pH=12.50 In the buffer solution of sodium acetate - sodium hydroxide, the starting voltage of (1) and (2) catalyzed water oxidation is about 0.8 V.3. synthesis of three biuclear complexes, [Fe2O (C12H8N2) 4] (H2O) 2 (ClO4) 4 (3) (C12H8N2= 1,10- adjacent phenanthroline), [Fe20 (CioH8N2) 4] (H20) 2 (4) (4)) 4 (5) 2=4,4'- two methyl -2,2'- bipyridine) and their catalytic performance in water oxidation. In the buffer solution of sodium acetate acetic acid, the catalytic activity of the complex (3) - (5) under the different pH and different concentration conditions was determined in the buffer solution of sodium acetate acetic acid. Among them, (3) in the buffer solution of pH=4.50, the catalytic activity was better, TON was 3.8; (4) in pH The catalytic activity of =3.45's buffer solution is better, TON is 7.7, and (5) in pH=7.00 buffer solution, the catalytic activity is better, TON is 12.3. (3), (4) and (5) electrocatalytic activity studies show that the starting voltage of catalytic water oxidation of (3), (4) and (5) in the buffer solution of sodium acetate acetic acid in pH=7.50 is about 1.20 V..

【学位授予单位】：广西大学
【学位级别】：硕士
【学位授予年份】：2016
【分类号】：O641.4

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