具有电催化产氢性能镍、铜、钴和钼配合物的设计、合成与研究

发布时间：2018-05-14 18:40

本文选题：配合物 + 分子结构　；参考：《华南理工大学》2015年硕士论文

【摘要】：在环境污染日益严重、能源紧缺的21世纪,人们开始努力寻找具有可再生的清洁能源来替代石油、煤炭、天然气等化石能源。氢气由于其热值高、清洁、安全、运输方便、可再生等优越的性能,成为人们关注的焦点。如何通过简单、高效的途径获取氢气已成为全球科学家们的研究目标。自然界中,氢化酶能高效催化水还原生成氢气,但是这种生物环境是不可模拟的,不过这种启示拉开了科学家对分子催化剂研究的序幕。本工作致力于通过设计新型配位体和组装不同类型过渡金属配合物,寻找新的还原水产氢催化剂。本论文工作包括:1)四种有机配体的合成:2,3-二(2-羟基苯二胺)-2,3-丁二氰(H2LA),2-吡啶氨基-N,N-二(2-亚甲基-4,6-二氟苯酚)(H2LB),2-吡啶氨基-N,N-二(2-亚甲基-4-甲氧基-6-叔丁基酚)(H2LC),(N,N-二甲基)乙二胺-N,N-二(2,4-二氟苯酚)(H2LD)。2)六种新型配合物的制备和表征:[NiIILA]1,[CuIILA]2,[CoIL’(py)3][CoIIL’2]3[LBMoVI(O)2]4,[LCMoVI(O)2]5,[LDMoVI(O)2]6。3)六种新型配合物的电催化性能研究:六种配合物都具有良好的电催化制氢性能,它们的TOF(turnover frequency)值分别为574(1,p H=6.0),1258(2,p H=5.0),3855(3,p H=7.0),756(4,p H=6.0),493(5,p H=7.0)和88 h-1(6,DMF)。4)催化机理的初步推论。研究结果表明,不同金属离子和不同配体都明显影响着电催化产氢效率,可以通过有机配体的设计和配合物的组装来提高分子催化剂的电催化产氢效率。特别指出,含有拉电子取代的配体能够提高配合物的催化制氢效率,推电子取代基配体则会有相反的效果。长时间的控制电位电解实验数据和电解前后的紫外电子光谱数据表明6个配合物的催化能力都具有稳定性、耐久性。
[Abstract]:In the 21st century, when environmental pollution is increasingly serious and energy is scarce, people are trying to find renewable clean energy to replace fossil energy such as oil, coal, natural gas and so on. Because of its high calorific value, clean, safe, convenient transportation, renewable and other superior performance, hydrogen has become the focus of attention. How to obtain hydrogen by simple and efficient way has become the research goal of scientists all over the world. In nature, hydrogenase can efficiently catalyze water reduction to produce hydrogen, but this biological environment can not be simulated. However, this revelation opens up the prelude to the study of molecular catalysts. The aim of this work is to find new hydrogen-reducing catalysts by designing new ligands and assembling different types of transition metal complexes. The work of this thesis includes the synthesis of four kinds of organic ligands: 2 ~ (2 +) ~ (3) -dimethylidene-2-hydroxy phenylenediamine (H _ (2) C ~ (2) -N ~ (2) -butyldicyanodioxy (H _ (2) -pyridylamino ~ (2) -N _ (2) -difluorophenol (N ~ (2) -difluorophenol (H _ (2) LBX) -pyridylamino -N (N) -dimethylene _ 2-methyl-4-methoxy -6- tert Ding Ji phenol (H _ 2LC ~ (2) C ~ (2) -N _ (2) -dimethyl) Preparation and characterization of six novel complexes: [NiIILA] 1, [CuIILA] 2, [CoIL'(py)3] [CoIIL'2] 3 [LBMoVI(O)2] 4, [LCMoVI(O)2] 5, [LDMoVI(O)2] 6.3). The TOF(turnover frequency values of them are 574g / h 6.0 / 1258m / 2H ~ (5.0) ~ 3855 / h ~ (7. 0) ~ (756 / H) ~ (6. 0) and 88h-16 ~ (6) DMF 路4) respectively. The results show that the catalytic mechanism of these two compounds is very important and the effect of the activity of the catalyst on the catalytic mechanism is better than that of the control group (P & lt; 0.05) and the catalytic mechanism of the catalyst is 88 h ~ (16) DMF 路4). The results show that different metal ions and different ligands have a significant effect on the efficiency of electrocatalytic hydrogen production, which can be improved by the design of organic ligands and the assembly of complexes. It is pointed out in particular that ligands containing electron-pulling substituents can improve the catalytic hydrogen production efficiency of the complexes, while the push-electron substituted ligands have the opposite effect. The experimental data of controlled potential electrolysis for a long time and the UV electron spectrum data before and after electrolysis show that the catalytic ability of the six complexes is stable and durable.
【学位授予单位】：华南理工大学
【学位级别】：硕士
【学位授予年份】：2015
【分类号】：O641.4;TQ116.2

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