硫化铅固载四(五氟苯基)锰卟啉催化氧化环己烷  

Catalytic oxidation of cyclohexane over manganese tetra(pentafluorophenyl) porphyrin supported on lead sulfide

作　　者：王培[1] 黄冠[1] 刘垚[1] 王未来[1] 郭勇安[1] 

机构地区：[1]广西大学化学化工学院,广西南宁530004

出　　处：《广西大学学报（自然科学版）》2017年第5期1835-1842,共8页Journal of Guangxi University（Natural Science Edition）

基　　金：国家自然科学基金资助项目(51363001);广西自然科学基金资助项目(2014GXNSFDA118009);广西科技攻关项目(桂科攻12118008-12-3)

摘　　要：为模拟细胞色素P-450酶中轴向配体活性调节作用,通过离子键和配位键作用将四(五氟苯基)锰卟啉固载到硫化铅晶体上,以此获得仿生催化材料[Mn TPFPP/Pb S]。该催化材料形态与结构的表征采用UV-Vis、FT-IR、XRD、TG、BET、SEM和XPS等技术进行解析。同时在无任何溶剂和还原剂的条件下,对[Mn TPFPP/Pb S]催化氧化环己烷的性能进行研究。结果表明:在较优的催化条件下(145℃,0.8 MPa),用仅含0.94×10-6mol Mn TPFPP Cl的催化材料[Mn TPFPP/Pb S]可重复催化氧气氧化环己烷6次,催化效能平均值为环己烷转化率24.61%,酮醇产率16.25%,选择性66.21%,转化数5.40×105,相比Mn TPFPP Cl具有更好的催化活性和重复使用性。由此说明载体硫化铅对四(五氟苯基)锰卟啉[Mn TPFPP Cl]具有促进其催化作用能力和保护金属卟啉免遭氧化破坏的作用。Manganese tetra （pentafluorophenyl） porphyrin was supported on lead sufide（PbS） via the coordination and the electrostatic interaction between the sulfide and the metal porphyrin, for mimicking the activity regulation by cysteinate axial ligand in cytochrome P450 enzyme and achieving a highly efficient catalysis for cyclohexane oxidation under mild conditions. The supported catalyst was characterized by UV-Vis spectra, FF-IR spectra, X-ray diffraction （XRD） pattern, thermogravimetric analysis（ TG）, BET method, transmission electron microscope （SEM） and X-ray Photoelectron Spectroscopy（XPS）. The catalyst was used to catalyze cyclohexane oxidation in the absence of any solvents or co-reductants. The results showed that a quantity of catalyst, containing only 0.94×10-6 mol of Mn TPFPPC1 could be efficiently reused 6 times for cyclohexane oxidation, on average, with 24. 61% cyclohexane conversion rate, 16. 25 % of yields and 66. 21% selectivity for ketone and alcohol, and a catalyst turnover number of 5.40 × 105 under the optimal reaction conditions of 145 ℃ and 0. 8 MPa. It was more effective and reusable for cyclohexane oxidation than the unsupported catalyst. The research results confirmed that PbS had a promotion for the catalysis of Mn TPFPPC1 for the cyclohexane oxidation and a protection of Mn TPFPPC1 from oxidation destruction by 02.

关 键 词：硫化铅 四(五氟苯基)锰卟啉 氧化 环己烷 

分 类 号：O643.3[理学—物理化学]