本文選題：Kn(?)lker鐵 + 銅光敏劑��； 參考：《浙江工業(yè)大學》2016年碩士論文

【摘要】：利用太陽能直接分解水使其光能轉換成氫氣化學能,是當今新能源的研究前沿,也是全球關注的十大科學難題之一。高效、穩(wěn)定、價廉、無毒的光能轉換催化產(chǎn)氫體系是光解水系統(tǒng)中的核心部分,也是目前制約太陽能利用效率的關鍵問題。本文擬以銅-鐵組建的非貴金屬光解水制氫體系為研究對象,設計合成新型氮磷雜配銅基光敏劑和鐵基催化劑,探索其光催化性能及其作用機理。首先以鄰氨基苯甲醛或鄰氨基苯甲酰類衍生物和環(huán)己二酮為原料,進行Friedlander縮合反應合成菲咯啉衍生物—6,7-二氫苯并菲咯啉(A-C),然后以5,8-二苯基-6,7-二氫苯并菲咯啉(C)為原料,Pd/C催化脫氫芳構化得到5,8-二苯基-6,7-苯并菲咯啉(D)。以這些菲咯啉衍生物A-D為氮配體,以XantPhos(Ⅰ)和2,8-二甲基-4,6-雙(2,8-二甲基氧膦雜蒽-10基)氧硫雜蒽(Ⅱ)為膦配體,通過原位配位形成銅(Ⅰ)氮磷雜配絡合物,研究其在均相光解水制氫體系中的光敏性能。結果表明,以2,8-二甲基-4,6-雙(2,8-二甲基氧膦雜蒽-10基)氧硫雜蒽(Ⅱ)為膦配體,5,8-二苯基-6,7-二氫苯并菲咯啉(C)為氮配體合成的銅光敏劑具有最高光敏活性,制氫催化轉換數(shù)TON達441,穩(wěn)定性可達15h。通過光物理性質和電化學表征證實長壽命的銅光敏劑激發(fā)態(tài)有利于提高光敏制氫活性。理論計算研究結果指出這類銅配合物主要躍遷模式是配體到配體的躍遷,而且進一步證實了氮配體的6,7位C-C單鍵結構可以增大能力間隙和增加氮配體在HOMO軌道的電子云密度,從而提高了光敏活性。Kn(?)lker’s鐵已在各類還原反應中被證實是高效催化劑,然而尚未見其在光解水中的催化性能研究。以Cu(Xantphos)(4,7-二苯基-2,9-二甲基-1,10-菲咯啉)(CuPS G I)作為光敏劑,發(fā)現(xiàn)堿活化原位形成的Kn(?)lker’s鐵具有良好的光解水制氫催化性能,制氫的速度為常用的Fe_3(CO)_(12)催化劑的15倍。通過熒光淬滅、循環(huán)伏安和質譜跟蹤等實驗證實還原淬滅機理和Kn(?)lker’s鐵催化過程�？傊�,通過配體調(diào)控研究了銅鐵組建的均相光解水催化體系,獲得了其構效關系及作用機理,為深入理解和開發(fā)高效光解水體系提供一些理論研究支撐。
[Abstract]:Using solar energy to decompose water directly to convert its light energy into hydrogen chemical energy is the frontier of new energy research and one of the ten scientific problems that the world pays close attention to. Efficient, stable, inexpensive and non-toxic photo-energy conversion catalytic hydrogen production system is the core part of the photodissociation water system, and also the key problem that restricts the efficiency of solar energy utilization. In this paper, a new type of nitro-phosphorous heteropoly copper-based Guang Min and iron-based catalysts were designed and synthesized, and their photocatalytic properties and mechanism were explored. First of all, using o-aminobenzaldehyde or o-aminobenzoyl derivatives and cyclohexanedione as raw materials, Phenanthroline derivative -6- (7-dihydrobenzophenanthroline) was synthesized by Friedlander condensation reaction and then dehydroaromatization was carried out by catalytic dehydroaromatization of 5 ~ (8) -diphenyl-6-dihydrobenzophenanthroline (C) as a starting material for the synthesis of 5 ~ (8) -diphenyl-6- (benzophenanthroline) -diphenanthroline (DX) as a catalyst for the dehydroaromatization of 5 ~ (8) -diphenyl-6- (phenanthroline). These phenanthroline derivatives A-D were used as nitrogen ligands and XantPhos1 (鈪，

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