硫化镉固载四(4-羧基苯基)锰卟啉催化氧化环己烷  

Catalytic oxidation of cyclohexane with manganese tetrakis (4-carboxylphenyl) porphyrin supported on cadmium sulphide

作　　者：刘垚 黄冠 国文馨 郭勇安 赵树凯 危素娟 

机构地区：[1]广西大学化学化工学院,广西高校应用化学技术与资源开发重点实验室,广西南宁530004

出　　处：《广西大学学报（自然科学版）》2017年第6期2264-2273,共10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);广西大学“大学生创新创业训练计划”(201610593032)

摘　　要：为了模拟细胞色素P-450酶中巯基的轴向配位作用功能,将四(4-羧基苯基)锰卟啉(Mn TCPPCl)固载到载体硫化镉上,得到硫化镉固载四(4-羧基苯基)锰卟啉(Mn TCPP/Cd S)催化材料。用电感耦合等离子体发射光谱法(ICP-AES)、紫外—可见光谱(UV-Vis)、红外光谱(FT-IR)、热重分析(TG)、扫描电镜(SEM)、比表面积测试法(BET)、X-射线光电子能谱(XPS)对催化材料的形态和结构进行表征,并考察其催化氧气氧化环己烷的性能。实验结果表明:在最佳反应条件(155℃,0.8 MPa,1 mg Mn TCPPCl)下,固载催化材料(Mn TCPP/Cd S)可以循环催化氧化环己烷9次,环己烷转化率22.04%,醇酮产率13.94%。与未固载的Mn TCPPCl相比,环己烷的转化率和酮醇产率分别提高9.16%和8.31%,表现出良好的催化性能和重复使用性,具有较高的工业应用价值。To mimic the activity regulated by a thiolate ligand in cytochrome P450 enzymes,manganese tetrakis（ 4-carboxphenyl） porphyrin（ Mn TCPP） was immobiled on cadmium sulphide（ Cd S）, forming Mn TCPP/Cd S catalyst. The immobilized catalyst（ Mn TCPP/Cd S） was characterized by inductively coupled plasma atomic emission spectroscopy（ ICP-AES）,ultravioletvisible（ UV-Vis） spectra,Fourier transform infrared（ FT-IR） spectra,thermogravimetric analysis（ TG）,scanning electron microscopic（ SEM）,BET surface area analysis（ BET） and X-ray photoelectron spectrometer（ XPS） techniques. The performance of the catalyst in the aerobic oxidation of cyclohexane was investigated. The experimental results indicated that under optimal conditions of 155°C,0. 8 MPa and 1 mg of manganese porphyrin,the catalyst can be used 9 times for cyclohexane oxidation,and resultedin 22. 04 % of cyclohexane conversion and 13. 94 % yields of ketone and alcohol on average. The cyclohexane conversion rate and yields of ketone and alcohol offered by Mn TCPP/Cd S were 9. 16% and 8. 31% respectively,which were greater than those obtained by Mn TCPPCl. The Mn TCPP/Cd S catalyst present a better catalytic performance and reusability for cyclohexane oxidation,which were better than those of unimmobilized catalyst. It would be a catalyst possessing higher industrial values in practical application.

关 键 词：硫化镉 四(4-羧基苯基)锰卟啉 氧化 环己烷 

分 类 号：O643.3[理学—物理化学]