纳米孔壳聚糖固载四(五氟苯基)铁卟啉催化氧化环己烷作用  

Catalysis of iron tetrakis(pentafluorophenyl) porphyrin immobilized on nanoporous-chitosan for cyclohexane oxidation

作　　者：莫林强 黄冠[1] 郭勇安[1] 覃欢 卫炎勋 刘垚[1] 赵树凯[1] 邵珊 梁荣华 MO Lin-qiang;HUANG Guan;GUO Yong-an;QIN Huan;WEI Yan-xun;LIU Yao;ZHAO Shu-kai;SHAO Shan;LIANG Rong-hua(School of Chemistry and Chemical Engineering,Guangxi University,Nanning 530004,China)

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）》2018年第2期740-751,共12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);广西科技项目(12118008-12-3);广西大学创新计划基金资助项目(201610593032)

摘　　要：为模拟细胞色素P-450酶的键联作用、轴向配位作用以及空腔的功能,实现温和条件下环己烷氧化的高效催化作用,采用微波辅助法制备纳米孔壳聚糖(np-CTS)共价接枝与轴向配位固载四(五氟苯基)铁卟啉(Fe TPFPP),即Fe TPFPP/np-CTS。应用扫描电镜(SEM),氮气物理吸/脱附(BET,BJH),紫外—可见光谱(UV-Vis),热重分析(TG-DSC),红外光谱(FT-IR)和X射线光电子能谱技术(XPS)研究其结构。在温和氧化反应条件下,用此催化剂催化氧气氧化环己烷。Fe TPFPP/np-CTS表现出较好的催化性能,其催化氧化环己烷的转化率和KA油产率分别为38.2%和24.5%,比未固载的和无孔壳聚糖固载的铁卟啉分别提高28%和66%,以及18%和74%。其中壳聚糖对铁卟啉的接枝,轴向配位及其空腔都起着重要的作用。To mimic the functions of cysteinate-axial ligand and cavity in cytochrome P-450 enzyme and achieve a highly efficient catalysis for cyclohexane oxidation under mild conditions,iron tetrakis(pentafluorophenyl)porphyrin(Fe TPFPP)was immobilized on nanoporous-chitosan(np-CTS),forming Fe TPFPP/np-CTS catalyst material.The immobilized catalyst material was characterized by scanning electron microscopy(SEM),N 2 adsorption/desorption isotherm(BET,BJH),UV-vis spectroscopy(UV-Vis),thermogravimetric and differential scanning calorimetry(TG-DSC),Fourier-transform infrared spectroscopy(FT-IR)and X-ray photoelectron spectroscopy(XPS).The oxidation of cyclohexane over Fe TPFPP/np-CTS under mild oxidation reaction conditions was investigated.The immobilized catalyst material could be reused more than two times and it showed a good catalytic performance.The cyclohexane conversion,and yields(ketone+alcohol)reached 38.2%and 24.5%respectively,which were higher than those obtained from Fe TPFPP and Fe TPFPP/nonp-CTS.The grafted immobilization,axial coordination and cavity of np-CTS all contributed the improvements of the catalytic activity of iron porphyrin.It was because the grafted immobilization of Fe TPFPP on np-CTS and the coordination of amino groups in np-CTS to Fe TPFPP increased the positive charge of Fe ion,and the cavity of np-CTS could offer more chances for reacting iron porphyrin with O 2 and cyclohexane.

关 键 词：轴向配位 四(五氟苯基)铁卟啉 纳米孔壳聚糖 催化作用 环己烷 

分 类 号：O643.3[理学—物理化学]