有机染料光敏剂的合成及其在光催化产氢体系中的应用

发布时间：2018-04-22 03:03

本文选题：光催化产氢 + 光敏剂　；参考：《重庆工商大学》2015年硕士论文

【摘要】：近100年来,化石燃料的开采和消耗带来了日益严重的环境问题,如温室效应、雾霾、大气污染等。将取之不尽的太阳能转化为洁净无污染的氢能是从根本上解决环境污染及能源危机的理想途径之一。自然界中一些藻类由于体内存在氢化酶,可通过光合作用产生氢气。受此启发,模拟自然界光合作用开发高效的人工光合作用体系,驱动能量贫乏的水分子分解生成能量丰富的氢分子受到国内外科学家的高度关注。开发活性高、稳定性好的光敏剂是光催化产氢体系研究的关键。本论文中,我们基于非贵金属钴肟配合物作为催化剂,三乙醇胺(TEOA)作为电子供体,设计合成了两类有机染料作为光敏剂,构建均相光催化产氢体系,该体系完全不含贵重金属。首先,我们以间溴苯胺为原料,通过四步反应合成了三种氧杂蒽醌类有机染料,分别为Si、Ge、Sn取代吡罗红框架结构中的氧原子而得到的衍生物,并通过质谱和核磁共振对这三种吡罗红衍生物进行结构鉴定。构建使用合成的三种氧杂蒽醌类有机染料作为光敏剂、钴肟配合物Co1作为催化剂、TEOA作为电子供体的均相光催化产氢体系,对体系的产氢条件进行了一系列的优化,优化结果为体积比为1:1的乙腈水溶液作为反应溶剂,TEOA(6%)为电子供体,p H值为7。该体系在最优条件下,产氢寿命为18 h,产氢周转数(TON)分别为203、228、258。随后,我们以N,N-二甲基间溴苯胺为原料,通过四步反应合成了七种新型的含氮杂环吖啶盐类有机染料,并通过质谱和氢核磁共振对其进行结构鉴定。构建以合成的含氮杂环吖啶盐染料作为光敏剂、钴肟配合物Co1作为催化剂、TEOA作为电子供体的三元光催化产氢体系。对体系产氢条件进行一系列的优化,优化结果为体积比为1:1的乙腈水溶液作为反应溶剂,TEOA(6%)为电子供体,p H值为7。在最优条件下,以含氮杂环吖啶盐12和15为光敏剂时,体系具有最高的产氢活性和最长的产氢寿命,产氢时间长达50 h,相对于光敏剂的TON分别为1100和1280。以有机染料作为光敏剂具有结构易变、种类繁多、成本低等优点,对于构建光催化产氢体系有很大的潜力,本文的研究为有机染料光敏剂的设计提供了有用的思路。
[Abstract]:In recent 100 years, fossil fuel exploitation and consumption have brought more and more serious environmental problems, such as Greenhouse Effect, haze, air pollution and so on. Converting inexhaustible solar energy into clean and clean hydrogen energy is one of the ideal ways to solve the environmental pollution and energy crisis. Some algae in nature can produce hydrogen through photosynthesis because of the existence of hydrogenase. Inspired by this, the simulation of photosynthesis in nature to develop an efficient artificial photosynthesis system, driving the decomposition of energy-poor water molecules to generate energy-rich hydrogen molecules has attracted great attention from scientists at home and abroad. The development of Guang Min with high activity and good stability is the key to the study of photocatalytic hydrogen production system. In this thesis, we designed and synthesized two kinds of organic dyes as Guang Min based on non-precious metal cobalt oxime complex as catalyst and triethanolamine (TEOAA) as electron donor to construct homogeneous photocatalytic hydrogen production system, which contains no precious metals at all. Firstly, three oxyanthracene quinone organic dyes were synthesized from m-bromoaniline by four-step reaction. The structures of these three derivatives were identified by MS and NMR. In this paper, three synthetic oxyanthracene quinone organic dyes were used as Guang Min and cobalt oxime complex Co1 as catalyst for homogeneous photocatalytic hydrogen production. The hydrogen production conditions of the system were optimized. The optimized result is that acetonitrile aqueous solution with a volume ratio of 1:1 as the reaction solvent is the electron donor and its pH value is 7. Under the optimum conditions, the hydrogen production life is 18 h and the hydrogen production turnover number is 203228258. Seven novel azacridine organic dyes were synthesized by four-step reaction from NN- dimethyl-m-bromoaniline and their structures were identified by mass spectrometry and hydrogen nuclear magnetic resonance spectroscopy (HNMR). A ternary photocatalytic hydrogen production system was constructed using azo-containing acridine dyes as Guang Min and cobalt oxime complex Co1 as catalyst and TeOA as electron donor. A series of optimization was carried out on the hydrogen production conditions of the system. The optimized results showed that the molar ratio of acetonitrile aqueous solution to 1:1 as the reaction solvent TEOAA 6) was 7. Under the optimum conditions, the system has the highest hydrogen production activity and the longest hydrogen production life when the azo acridine salt (12 and 15) is used as Guang Min. The hydrogen production time is 50 h, and the TON of the system is 1100 and 1280, respectively. The use of organic dyes as Guang Min has many advantages, such as easy structure, variety and low cost, which has great potential for the construction of photocatalytic hydrogen production system. The research in this paper provides a useful idea for the design of the organic dye Guang Min agent.
【学位授予单位】：重庆工商大学
【学位级别】：硕士
【学位授予年份】：2015
【分类号】：TQ116.2

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