本文選題：光催化產(chǎn)氫 + 光敏劑�。� 參考：《重慶工商大學》2015年碩士論文

【摘要】：近100年來,化石燃料的開采和消耗帶來了日益嚴重的環(huán)境問題,如溫室效應、霧霾、大氣污染等。將取之不盡的太陽能轉化為潔凈無污染的氫能是從根本上解決環(huán)境污染及能源危機的理想途徑之一。自然界中一些藻類由于體內(nèi)存在氫化酶,可通過光合作用產(chǎn)生氫氣。受此啟發(fā),模擬自然界光合作用開發(fā)高效的人工光合作用體系,驅(qū)動能量貧乏的水分子分解生成能量豐富的氫分子受到國內(nèi)外科學家的高度關注。開發(fā)活性高、穩(wěn)定性好的光敏劑是光催化產(chǎn)氫體系研究的關鍵。本論文中,我們基于非貴金屬鈷肟配合物作為催化劑,三乙醇胺(TEOA)作為電子供體,設計合成了兩類有機染料作為光敏劑,構建均相光催化產(chǎn)氫體系,該體系完全不含貴重金屬。首先,我們以間溴苯胺為原料,通過四步反應合成了三種氧雜蒽醌類有機染料,分別為Si、Ge、Sn取代吡羅紅框架結構中的氧原子而得到的衍生物,并通過質(zhì)譜和核磁共振對這三種吡羅紅衍生物進行結構鑒定。構建使用合成的三種氧雜蒽醌類有機染料作為光敏劑、鈷肟配合物Co1作為催化劑、TEOA作為電子供體的均相光催化產(chǎn)氫體系,對體系的產(chǎn)氫條件進行了一系列的優(yōu)化,優(yōu)化結果為體積比為1:1的乙腈水溶液作為反應溶劑,TEOA(6%)為電子供體,p H值為7。該體系在最優(yōu)條件下,產(chǎn)氫壽命為18 h,產(chǎn)氫周轉數(shù)(TON)分別為203、228、258。隨后,我們以N,N-二甲基間溴苯胺為原料,通過四步反應合成了七種新型的含氮雜環(huán)吖啶鹽類有機染料,并通過質(zhì)譜和氫核磁共振對其進行結構鑒定。構建以合成的含氮雜環(huán)吖啶鹽染料作為光敏劑、鈷肟配合物Co1作為催化劑、TEOA作為電子供體的三元光催化產(chǎn)氫體系。對體系產(chǎn)氫條件進行一系列的優(yōu)化,優(yōu)化結果為體積比為1:1的乙腈水溶液作為反應溶劑,TEOA(6%)為電子供體,p H值為7。在最優(yōu)條件下,以含氮雜環(huán)吖啶鹽12和15為光敏劑時,體系具有最高的產(chǎn)氫活性和最長的產(chǎn)氫壽命,產(chǎn)氫時間長達50 h,相對于光敏劑的TON分別為1100和1280。以有機染料作為光敏劑具有結構易變、種類繁多、成本低等優(yōu)點,對于構建光催化產(chǎn)氫體系有很大的潛力,本文的研究為有機染料光敏劑的設計提供了有用的思路。
[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.
【學位授予單位】：重慶工商大學
【學位級別】：碩士
【學位授予年份】：2015
【分類號】：TQ116.2

【共引文獻】

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本文編號：1785295