基于多吡啶钌化合物的光驱动水氧化研究

发布时间：2018-04-28 21:02

  本文选题：人工光合作用 + 光敏剂　； 参考：《大连理工大学》2015年硕士论文

【摘要】：随着社会的不断发展,煤、石油等能源的消耗逐年增加。传统化石能源的日益枯竭和环境污染的日益严重,使得人类不得不寻求更加清洁的可持续能源。自然光系统II能通过分解水将太阳能转化为化学能储存起来,因此人工模拟光合作用是解决能源危机的有效方法。其中光解水制氢被认为是一条非常具有前景的途径,而光解水制氢过程中的关键步骤是光解水产生氧气和质子。光驱动水氧化反应体系中存在的技术难题是如何设计和合成具有较长激发态寿命、较好的电荷分离态、较高氧化电位的光敏剂,从而构建高效的光驱动水氧化反应体系。本论文针对上述科学难题,尝试做了两部分工作。通过对[Ru(bpy)3]2+母体进行修饰,设计合成了基于四吡啶吩嗪配体的单核钌光敏剂[RuⅡ(bpy)2(tpphz)](PF6)2(PS1)和双核钌光敏剂[RuⅡ(bpy)2(tpphz) RuⅡ(bpy)2] (PF6)4(PS2)(bpy=2,2’-联吡啶,tpphz=四吡啶吩嗪)。在含10%乙腈的pH=6.8的磷酸缓冲溶液中,以PS 1或PS 2作为光敏剂,以Ru(bda)(pic)2(Ru 1; H2bda=2,2’-联吡啶-6,6’-二羧酸,pic=4-甲基吡啶)作为催化剂,以Na2S2O8作为电子受体组成三组分体系。研究结果表明,以PS 1为光敏剂时三组分体系的光驱动水氧化反应的活性比以PS 2和[RuⅡ(bpy)3] (PF6)2为光敏剂时体系的光驱动水氧化反应的活性都有较为显著的提高。在光敏剂PS 1的基础上设计合成了超分子催化剂RuⅡ(bpy)2(tpphz)RuⅡL(bpy)(pic)] (PF6)4 (SM; L=2,6-吡啶二甲酸)。研究结果表明,在相同条件下,含有超分子催化剂SM的超分子体系的光驱动催化水氧化反应的活性是三组分体系的两倍,其原因可能是超分子体系有利于电子在光敏剂和催化剂之间的传递。
[Abstract]:With the continuous development of society, the consumption of coal, petroleum and other energy sources is increasing year by year. With the depletion of traditional fossil energy and the increasingly serious environmental pollution, human beings have to seek cleaner and more sustainable energy. Natural light system II can convert solar energy into chemical energy by decomposing water, so artificial simulation of photosynthesis is an effective method to solve energy crisis. The photolysis of water to produce hydrogen is considered to be a promising approach, and the key step in the process of photolysis is the production of oxygen and protons by photolysis of water. The technical problem in dynamic water oxidation reaction system of optical drive is how to design and synthesize Guang Min agent with long excited state life, better charge separation state and higher oxidation potential, so as to construct an efficient photo-driven water oxidation reaction system. In view of the above scientific problems, this paper tries to do two parts of the work. Based on the modification of [Ru(bpy)3] 2 matrix, the mononuclear ruthenium Guang Min (Ru 鈪，

本文编号：1816849