【作者】 马艳丽；

【导师】 方桂珍；

【作者基本信息】 东北林业大学 ， 林产化学加工工程， 2011， 博士

【摘要】 本研究是哈尔滨市科技局科技创新人才研究专项资金(RC2009QN01705-3)和林业公益性行业科研专项经费(20090472)的部分内容。针对工业木质素具有甲氧基含量高、化学反应活性低的缺点,依据光电转化原理提高TiO2可见光催化性能,本论文制备了可以响应可见光激发的喹啉方酸菁/TiO2复合催化剂。与一般的可见光响应/TiO2复合催化剂比较,喹啉方酸菁/TiO2复合催化剂具有催化条件温和、可见光响应范围广、负载方法简单、成本低的优点。在可见光激发条件下,喹啉方酸菁/TiO2增加了碱木质素的羟基、羰基和羧基等活性基团并保留碱木质素的苯环结构。本文研究了喹啉方酸菁/TiO2催化剂的制备方法及表征、喹啉方酸菁/TiO2催化剂的性能评价及其对碱木质素的活化机制。合成了二羟基-喹啉方酸菁和二甲醚-喹啉方酸菁2种可见光敏化剂。结果表明,二羟基-喹啉方酸菁易溶于水,得率87.05%、纯度为98.6%；分子量为1063.2(三聚体),化学式为C72H50N6O4。二甲醚-喹啉方酸菁难溶于水,得率66.07%,纯度为99.6%；分子量为394.5,化学式为C26H22N2O2。在380nm～800nm响应区间,2种喹啉方酸菁可见光的吸收性能显著高于TiO2。制备了响应可见光激发的喹啉方酸菁/TiO2复合催化剂。以浸渍法和烧结法分别将二羟基-喹啉方酸菁和二甲醚-喹啉方酸菁负载于纳米TiO2表面制备了2种喹啉方酸菁/TiO2催化剂；结果表明,二羟基-喹啉方酸菁催化剂对气体苯的催化呈一级反应。二甲醚-喹啉方酸菁/TiO2在反应初期对气体苯的催化呈一级反应。喹啉方酸菁/TiO2在活化过程中可生成具有催化活性的超氧自由基、单线态氧、羟基自由基,证实光电转化原理可以应用于提高TiO2可见光催化性能的研究。研究了喹啉方酸菁/TiO2-可见光催化剂对碱木质素的活化作用和活化机制。考察了活化碱木质素的抗氧化性和吸附性能；探讨了喹啉方酸菁/TiO2-可见光协同技术对碱木质素的活化机制。结果表明,活化后的碱木质素总羟基含量为9.4%,较碱木质素提高18%。在酸性环境下pH=5时活化碱木质素的溶解度是碱木质素的16.32倍。活化碱木质素降解液对[DPPH"]和[O2-·]的清除率均能达到常见抗氧化剂BHT自由基清除率的80%以上。活化木质素进行Cu2+的吸附性能测定优于碱木质素,吸附量为6.65mg/g,碱木质素对Cu2+的吸附量为3.28mg/g。综上,本论文证实光电转化原理可以应用于提高TiO2可见光催化性能的研究。喹啉方酸菁/TiO2-可见光协同技术对碱木质素的活化效果较好。喹啉方酸菁/TiO2活化碱木质素的研究为提高碱木质素反应活性提供了一种新方法。更多还原

【Abstract】 The study was supported by forestry industry research special funds for public welfare projects(No.20090472) and special Fund Project for Science and Technology Innovation of Harbin (No. RC2009QN01705-3).For industrial lignin have shortcomings of methoxyl content and lower chemical reactivity,, the aim of paper was looking after a way which could increased the quantity of hydroxyl, carbonyl, carboxyl and kept benzene-ring of alkali lignin. Based on principles of photoelectric conversion, two kinds of quinoline squarylium cyanine/TiO2were prepared. The composite catalysts were increased the quantity of above groups of alkali lignin in visible lilght. There are four sections in the paper that included preparation, characterization, performance evaluation of quinoline squarylium cyanine/TiO2and activation mechanism to alkali lignin.Two kinds of quinoline squarylium cyanine were synthesized. QSC-(OH)2squarylium cyanine is soluble in water, yield87.05%, purity98.6%, molecular weight of1063.2(trimer) and chemical formula C72H50N6O4. QSC-(OCH3)2squarylium cyanine is difficulty soluble in water, yield66.07%, a purity of99.6%, molecular weight394.5and chemical formula C26H22N2O2. Response in the380nm-800nm, absorbance capacity of QSC-(OH)2/TiO2is significantly higher than QSC-(OCH3)2/TiO2.Two kinds of quinoline squarylium cyanine/TiO2were prepared. Results show that catalyst reaction of QSC-(OH)2/TiO2was order reaction for gas benzene in the whole. But catalyst reaction of QSC-(OCH3)2/TiO2was order reaction for gas benzene in the initial, quinoline squarylium cyanine/TiO2also can generate the superoxide radical, singlet oxygen and hydroxyl radicals. The work confirmed photosensitization/TiO2in gas and liquid systems can improve catalytic properties of TiO2in visible light.The activation mechanism of quinoline squarylium cyanine/TiO2to alkali lignin was researched. Anti-oxidation and adsorption properties of activated alkali lignin were investigated. Results show that the total hydroxyl content of activated alkali lignin is9.4%, higher18%than alkali lignin. At pH=5, the solubility of activated alkali lignin was16.32times that of alkali lignin.. The [DPPH·] and[O2-·] radical-scavenging rate of activated alkali lignin and its supernatant liquid could be80%of anti-oxidant BHT. Cu2+adsorption of activated alkali lignin better than alkali lignin, adsorption was6.65mg/g.In summary, Photosensitive/TiO2were confirmed to increase the response to visible light of TiO2. Activated technology of visible light assisted quinoline squarylium cyanine/TiO2has better activation. The paper provided a novel approach to improve the reactivity of alkali lignin.更多还原