具有电或光催化水分解性能的钴、铁和铜配合物的设计、合成与研究

发布时间：2017-12-31 10:30

本文关键词：具有电或光催化水分解性能的钴、铁和铜配合物的设计、合成与研究　出处：《华南理工大学》2016年硕士论文　论文类型：学位论文

【摘要】：21世纪,是信息的时代,也是技术的时代。伴随着科技的飞速发展,能源的需求量也是愈来愈大,但是全球的储备量却日渐减少,开发并利用新的能源成为当下的难题。氢能成为21世纪最理想的能源。水的裂解是由水的氧化和还原两部分构成,需要113.38 kcal/mol(4.92 eV)的自由能。所以从热力学的角度说,水是一个相对稳定的分子。电解水可以得到纯净的氢气和氧气,但是得消耗一部分电能。所以我们试图从化学角度上来降低电能的消耗,一个化学反应加入合适的催化剂可以降低反应所需的活化能。同理,寻找一种高效的催化剂,也可以减少电解水反应所需要的电能。我们知道,微生物可以通过光合作用,在氢化酶的作用下,催化裂解水生成氢气。虽然光合作用的生物环境是无法模拟的,但是这种现象使得科学家们对分子催化剂的研究有了更深层的思考:能否通过光催化的方法制取氢气,这样就可以减少电能的消耗。本研究旨在所以通过设计新型配体和不同类型过渡金属配合物,以寻找新的水裂解催化剂。本论文包括:1)三种有机配体的合成:1-[(2-甲氧基)苯]-3-[(2-苯并噻唑)苯]三氮烯(HLa)、(N,N-二甲基)乙二胺-N,N-二(2-叔丁基-4-甲基苯酚)(H2Lb)、(2-氨甲基吡啶)-N-(2-亚甲基-4-乙基-6-叔丁基苯酚),N-(2-亚甲基-4-甲基-6-叔丁基苯酚)(H2Lc)。2)五种新型分子催化剂配合物[Co2(La)4]1、配合物[LbCoCl]2、配合物[LbCo(H2O)]3、配合物[LcFeCl]4、配合物[CuMe2(oxpn)Cu(OH)2]5的制备、结构和光谱。3)一种新型配合物的电催化制氢和制氧性能研究:配合物[CuMe2(oxpn)Cu(OH)2]5同时具有水还原和水氧化的性能,水还原的TOF为654 h-1(pH 7.0),水氧化的TOF为2.56 s-1(pH 10.4)。4)两种新型配合物的电催化和光催化性能研究:配合物[Co2(La)4]1、配合物[LbCoCl]2同时具有电催化和光催化制氢的性能,电解制氢的TOF依次为为223 h-1(pH 7.0)、162h-1(pH 7.0),光催化制氢的TON为4360、4125。5)催化机理的初步研究。
[Abstract]:Twenty-first Century is the era of information technology, but also the era. With the rapid development of science and technology, the demand of energy is increasing, but the global reserves are gradually reducing, the development and use of new energy has become the current problems. Hydrogen has become the ideal twenty-first Century energy. Water is cracking by oxidation of water and the reduction of two parts, 113.38 kcal/mol (4.92 eV) of the free energy. So from the point of view of thermodynamics, water is a relatively stable molecule. The electrolysis of water can be pure hydrogen and oxygen, but a part of the electric power consumption. So we try to reduce the consumption of electrical energy from chemical angle a chemical reaction, adding suitable catalyst can lower the activation energy required for the reaction. In the same way, looking for a highly efficient catalyst, can also reduce the water electrolysis reaction power. As we know, by microorganisms Photosynthesis, in the role of the hydrogenase, hydrogen generation catalytic pyrolysis of water. Although the photosynthesis biological environment can not be simulated, but this phenomenon allows scientists to study the molecular catalysts have deeper thinking: whether through the method of photocatalytic preparation of hydrogen gas, which can reduce the power consumption in this research. So to through the design of new ligands and transition metal complexes of different types, in order to find new water cracking catalyst. This thesis includes: 1) the synthesis of three kinds of organic ligands: 1-[(2- methoxy benzene]-3-[(2-) benzothiazoles) phenyl] three azene (HLa), (N, N- two methyl) Ethylenediamine -N (2-, N- two -4- methyl phenol tert Ding Ji (H2Lb) (2-), -N- (aminomethyl pyridine) 2- methylene -4- ethyl -6- TERT phenol, N- (Ding Ji) 2- methylene -4- methyl -6- tert Ding Ji phenol) (H2Lc).2) five new molecular catalyst complexes [Co2 (La 4]1) [LbC complexes OCl]2, [LbCo (H2O)]3 complexes, [LcFeCl]4 complexes, complexes of [CuMe2 (oxpn) Cu (OH) 2]5 preparation, structure and spectral.3) on Electrocatalytic hydrogen and oxygen production performance of a new type of complexes: complexes of [CuMe2 (oxpn) Cu (OH) 2]5 with water and reduction water oxidation performance, water reduction of TOF 654 H-1 (pH 7), water oxidation of TOF was 2.56 S-1 (pH 10.4).4) electro catalytic and photocatalytic properties of two new complexes: complexes of [Co2 (La) 4]1, and has performance of electro catalytic and photocatalytic hydrogen production [LbCoCl]2 with the electrolytic hydrogen production of TOF were followed by 223 H-1 (pH 7), 162h-1 (pH 7), photocatalytic TON 43604125.5) preliminary study on catalytic mechanism.

【学位授予单位】：华南理工大学
【学位级别】：硕士
【学位授予年份】：2016
【分类号】：O641.4

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