【作者】 王佳；

【导师】 张海全；

【作者基本信息】 燕山大学 ， 材料物理与化学， 2015， 硕士

【摘要】 酞菁(phthalocyanines,Pcs)因其独特的光物理性质,较高的化学稳定性和热稳定性,以及在可将光区具有较强的吸收等特性,在可见光催化领域具有较高的应有价值。本论文制备出了具有独特结构的酞菁铁、酞菁铁/碳化钛复合物和聚酞菁铁,研究内容具体包括:(1)利用亲核取代(Nucleophilic substitution)原理成功将4-硝基邻苯二甲腈与对溴苯酚反应生成酞菁前驱体4-对溴苯氧基邻苯二甲腈,通过传统DBU液相催化法合成出β-对溴苯氧基酞菁铁(PBP-Fe Pc),运用红外光谱、紫外-可见光谱、热分析测试和场发射扫描电镜等测试对产物进行了表征。用300 W氙灯模拟可见光源,PBP-FePc在黑暗条件下吸附能力达到饱和状态时吸附罗丹明B(RhB)10%,光照5 h催化降解RhB 70%,反应动力学呈一级线性关系,催化反应速率常数为0.003 min-1。(2)采用4-硝基邻苯二甲腈为原料,通过亲核取代、DBU液相催化法等反应合成出可见光响应型酞菁铁/碳化钛复合物。通过紫外-可见吸收谱图、红外谱图、X射线衍射仪、扫描电镜等途径对合成的催化剂材料进行表征。该类材料是以酞菁物质作为电子给体,碳化钛作为电子受体,碳化钛良好的导电性有效提高了传输过程中电子的寿命,酞菁铁/碳化钛复合物在黑暗条件下吸附能力达到饱和状态时吸附RhB 10%,光照6 h催化降解RhB 80%,反应动力学呈一级线性关系,催化反应速率常数为0.004 min-1。(3)以4-硝基邻苯二甲腈和对苯二酚为原料,制备出聚酞菁前体四腈基苯,再通过DUB液相催化法制备出大平面的多核酞菁铁。多核酞菁铁在黑暗条件下吸附能力达到饱和状态时吸附RhB 12%,光照6 h催化降解RhB 62%,反应动力学呈一级线性关系,催化反应速率常数为0.003 min-1。更多还原

【Abstract】 Phthalocyanines(Pcs) have received considerable attentions due to their unique photophysical properties, high chemical stability and thermal stability. They absorb well in the visible and near infrared spectrum which give rise to the application of Pcs in various domains, such as visible-light responded photocatalyst. In this paper, we have prepared phthalocyanine iron, phthalocyanine iron/carbon composites and poly iron phthalocyanine with unique structures. The research contents including:(1) The functionalized monomer 4-the bromine phenoxy phthalicnitrile was successfully synthesized via nucleophilic substitution useing 4-Nitrophthalonitrile and P-Bromophenol. The targeted β-the bromine phenoxy phthalocyanine iron(PBP-Fe Pc) has been synthesized at the existence of a liquid alkali catalysis-DBU. PBP-Fe Pc was characterized by FT-IR, UV-vis, TGA analysis and field emission scanning electron microscopy. 300 W xenon lamp was used to simulate the visible light, and the results show that the concentration of Rh B was reduced nearly 10% in the dark reaching adsorption saturation, and then the concentration of Rh B was reduced nearly 70% by 5 hours’ with the light. Reaction kinetics is first-order linear relationship, catalytic reaction rate constant was 0.003 min-1.(2) The visible light response phthalocyanine iron/carbon composites were synthesized from 4-Nitrophthalonitrile by a series of reactions including nucleophilic substitution and catalysis-DBU reaction. Phthalocyanine iron/carbon composites were characterized by FT-IR, UV-vis, XRD and field emission scanning electron microscopy.Pcs as electron donor materials and titanium carbide as electron acceptor materials. The good effectively conductivity of titanium carbide improved the service life of transmission in the process of electronic. The results show that the concentration of Rh B was reduced nearly 10% in the dark reaching adsorption saturation, and then the concentration of Rh B was reduced nearly 80% by 6 hours’ with the light. Reaction kinetics is first-order linear relationship, catalytic reaction rate constant was 0.004 min-1.(3) Polyphthalocyanine iron precursor-four nitrile benzene were synthesized4-Nitrophthalonitrile and 1,4-Dihydroxybenzene. And then polyphthalocyanine with large flat structure were synthesized though catalysis-DBU reaction. The results show that the concentration of Rh B was reduced nearly 12% in the dark reaching adsorption saturation,and then the concentration of Rh B was reduced nearly 62 % by 6 hours’ with the light.Reaction kinetics is first-order linear relationship, catalytic reaction rate constant was0.003 min-1.更多还原