【作者】 沈启慧；

【导师】 裘式纶；

【作者基本信息】 吉林大学 ， 无机化学， 2008， 博士

【摘要】 由于环境污染以及能源问题越来越严重,以减少污染物排放、降低能源消耗以及处理污染物为主要目的的“绿色化学”得到了快速发展,而实现绿色化学的一条重要途径就是从源头上减少污染,即使用更先进、利用率更高的合成工艺以及对环境毒害更小的原料来合成低污染或消除污染的产品。本论文从绿色化学的角度出发,分别讨论了羟基磷酸铜、碲化镉纳米晶体、金属/二氧化钛核壳结构光催化剂的新合成方法和应用,使其具有低污染、低能耗、低成本的特点。首先,在不使用乙二胺的情况下用磷酸和乙酸铜直接合成了羟基磷酸铜晶体,并研究了合成条件对合成过程和结构的影响,结合在催化苯酚羟化中的实际应用,提出了最佳合成路线,另外将这种催化剂应用到光催化氧化降解罗丹明B,拓展了羟基磷酸铜的应用领域。其次,在常温常压的条件下,于水相中合成高质量的CdTe纳米晶体,其量子产率接近60%,并将合成的CdTe纳米晶体用于为微生物的活体标记和隐性指纹的显现,取得比较好的效果。最后,将金属/二氧化钛核壳型光催化剂的合成拓展到普通金属,降低了合成成本并减少了对环境的污染。更多还原

【Abstract】 Because the questions of environment pollution and energy crisis were outstanding,“Green Chemistry”developed rapidly and aimed at low pollution, energy saving and less cost. We improved the synthesized methods of copper hydroxyphosphate （Cu₂OHPO₄）, cadmium telluride nanocrystals （CdTe NCs）, metal / titania （TiO₂） photocatalysts towards Green Chemistry.Firstly, we discovered a new way to synthesis Cu₂OHPO₄ and extended the scope of applications. In this way, the Cu₂OHPO₄ was prepared from phosphoric acid and cupric acetate dihydrate directly and optimized the reaction conditions. We found that : a) the different kinds of cupric salt did not changed the quality of Cu₂OHPO₄; b) the quantity of phosphoric acid and pH would affect on crystal plane in a certain extent; c) the crystalline perfection and the time of hydrothermal crystallization would fluctuates according to temperature. Furthermore, the ultrasonic wave and microwave were applied to assist in synthesis of Cu₂OHPO₄. And these technologies would save a great deal of time in hydrothermal crystallization. We optimized the process according to the phenol hydroxylation. Compared with the old courses, the new route improved the utilization coefficient of raw materials from 17% to more than 90%, curtail the time of hydrothermal crystallization from 3 days to about 4 hours, and the Cu₂OHPO₄ show a significant activities on the hydroxylation of phenol. Moreover, we applied the Cu₂OHPO₄ to photocatalytic degradation of Rhodamine B （RhB）.Secondly, we synthesized CdTe semiconductor NCs at room temperature and accelerated by one reagent, hydrazine hydrate. Compared with the organometallic routes, aqueous synthesis is more reproducible, cheaper, and less toxic, and the as-prepared samples have aqueous stability and biological compatibility. But the temperature of aqueous synthesis was so high; as a result, the mercapto stabilizer was destroyed and brought the low quantum yield and less stability. According to the Ostwald ripping, the emission spectra were broadening with the growth of CdTe NCs. In the new route, we could receive CdTe NCs with high quantum yield （～60%）, and full width at half maximum of emissions located in 30～50 nm, and the solution could kept at room temperature for more than three years. In conclusion, there were no extra energy consumption and it adapt to mass production.Finally, we prepared a core-shell photocatalyst Cu/TiO₂, and the core was Cu particle and the shell was TiO₂. Because metal particles had a favorable Fermi level, metal particles could improve the activity of photocatalysts by stabilized photo-induced electron when contacted with TiO₂. Most of the researcher chose the Au and Ag as the core, due to the poor stability of most of metal particles. We chose the Cu nanoparticles as the core; it was low cost and less environmental toxicity. Moreover, the photocatalytic activity of Cu/TiO₂ was well than P25 （a commercial photocatalyst） when degradation of RhB in aqueous.更多还原