本文選題：銅金屬配合物 + 鐵金屬配合物��； 參考：《廣西大學(xué)》2016年碩士論文

【摘要】：氫氣是清潔的可再生能源,發(fā)展氫能源被認(rèn)為是可持續(xù)地解決能源問題的一種重要方式。地球上有豐富的水資源,利用水作為原料制備氫氣被認(rèn)為是最經(jīng)濟(jì)的一種方法。在水分解成氫氣和氧氣的過程中,水氧化生成氧氣的半反應(yīng)是復(fù)雜的四電子過程,而且具有較高的能壘,是一個瓶頸問題。因此,如何合成高效穩(wěn)定的水氧化催化劑是重要的研究課題。過渡金屬配合物具有豐富的光學(xué)、氧化還原性質(zhì)和催化性能而備受關(guān)注。已報道的金屬配合物水氧化催化劑主要以含有Ru、Ir等貴金屬元素的配合物為主。近年來,有關(guān)Mn、Cu、Fe、Co等非貴金屬配合物水氧化催化劑的報道不斷地出現(xiàn)。與貴金屬催化劑相比,這些第一過渡系金屬配合物的水氧化催化劑的成本較低,具有廣闊的應(yīng)用前景。在本研究工作中,合成了雙核銅和鐵金屬配合物,并研究了它們的水氧化催化活性。研究內(nèi)容包括：1.合成了兩個雙核銅配合物[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)。通過X-ray單晶衍射對配合物的結(jié)構(gòu)進(jìn)行了分析鑒定,配合物(1)中的Cu(Ⅱ)屬于六配位的八面體構(gòu)型,配合物(2)中的Cu(Ⅱ)屬于五配位的四方錐構(gòu)型,其中每個tpbn分子螯合和橋聯(lián)兩個Cu(Ⅱ)離子。2.在醋酸鈉-氫氧化鈉的緩沖溶液中,以過硫酸氫鉀作為氧化劑,測定了雙核銅配合物在不同pH值、不同濃度條件下的水氧化催化活性。其中,(1)在pH=12.50的緩沖溶液中催化活性較好,轉(zhuǎn)化數(shù)(TON)為2.4。(2)在pH=12.50的緩沖溶液中催化活性較好,轉(zhuǎn)化數(shù)為3.8。 (1)和(2)的電催化活性研究表明,在pH=12.50的醋酸鈉-氫氧化鈉的緩沖溶液中,(1)和(2)催化水氧化的起始電壓約為0.8 V。3.合成了三個雙核鐵的配合物[Fe2O(C12H8N2)4](H2O)2(ClO4)4(3) (C12H8N2= 1,10-鄰菲羅啉)、[Fe20(CioH8N2)4](H20)2(C104)4 (4) (C10H8N2=2,2’-聯(lián)吡啶)、[Fe2O(Ci2Hi2N2)4](H2O)2(ClO4)4 (5) (C12H12N2=4,4'-二甲基-2,2'-聯(lián)吡啶),并研究了它們的水氧化催化性能。在醋酸鈉-醋酸的緩沖溶液中,以過硫酸氫鉀作為氧化劑,測定配合物(3)-(5)在不同pH值、不同濃度條件下的催化活性。其中,(3)在pH=4.50的緩沖溶液中催化活性較好,TON為3.8；(4)在pH=3.45的緩沖溶液中催化活性較好,TON為7.7；(5)在pH=7.00的緩沖溶液中催化活性較好,TON為12.3。(3)、(4)和(5)的電催化活性研究表明,在pH=7.50的醋酸鈉-醋酸的緩沖溶液中,(3)、(4)和(5)的催化水氧化起始電壓約為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..

【學(xué)位授予單位】：廣西大學(xué)
【學(xué)位級別】：碩士
【學(xué)位授予年份】：2016
【分類號】：O641.4

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