首页 | 官方网站   微博 | 高级检索  
     

铁卟啉催化剂前线轨道能量与其催化活性的关系
引用本文:王兰芝,佘远斌,钟儒刚,张燕慧,纪红兵.铁卟啉催化剂前线轨道能量与其催化活性的关系[J].化工学报,2006,57(6):1339-1345.
作者姓名:王兰芝  佘远斌  钟儒刚  张燕慧  纪红兵
作者单位:北京工业大学环能学院化学化工系,绿色化学与精细化工研究所,北京 100022;北京工业大学生命科学与生物工程学院,北京 100022;华南理工大学化工与能源学院,广东 广州 510640 ;
基金项目:国家高技术研究发展计划(863计划) , 北京市自然科学基金
摘    要:采用量化计算和分子模拟方法,设计、合成了9种不同结构的氯化金属卟啉铁催化剂,并对其前线轨道能量进行了计算,将计算结果与其催化氧气液相氧化对硝基甲苯制取对硝基苯甲酸反应的活性数据相结合,研究了不同结构的五配位金属卟啉铁催化剂的微观结构(EHOMO和ΔEL-H)与催化活性(产物收率)之间的关系,建立了相应的定量构效关系(QSAR)式.经统计检验量检验,发现五配位金属铁卟啉的EHOMO对催化活性的影响大于ΔEL-H对催化活性的影响.根据拟合的定量关系,对环外取代基为甲基的2种五配位金属铁卟啉催化剂的活性进行了预测,并经实验验证,证明所预测的活性与实测的活性相符.

关 键 词:金属卟啉  催化剂  量化计算  催化活性  
文章编号:0438-1157(2006)06-1339-07
收稿时间:05 30 2005 12:00AM
修稿时间:2005-05-302005-10-25

Relationship between structure and catalytic activity of chloro-iron tetraphenylporphyrin compounds
WANG Lanzhi,SHE Yuanbin,ZHONG Rugang,ZHANG Yanhui,JI Hongbing.Relationship between structure and catalytic activity of chloro-iron tetraphenylporphyrin compounds[J].Journal of Chemical Industry and Engineering(China),2006,57(6):1339-1345.
Authors:WANG Lanzhi  SHE Yuanbin  ZHONG Rugang  ZHANG Yanhui  JI Hongbing
Affiliation:1 Institute of Green Chemistry and Fine Chemicals, Department of Chemistry and Chemical Engineering, Beijing University of Technology, Beijing 100022, China ;2 School of Life Science and Bio-engineering, Beijing University of Technology, Beijing 100022, China; 3 School of Chemical and Energy Engineering, South China University of Technology, Guangzhou 510640, Guangdong, China
Abstract:Nine chloro-iron tetraphenylporphyrin (RTPPFeCl) compounds were designed and synthesized, and their catalytic activities were characterized by using dioxygen liquid-phase oxidation of p-nitrotoluene (PNT) to p-nitrobenzoic acid (PNBA) as model reaction, and their molecular frontier orbital energies EHOMO, ELUMO, ΔEL-H etc were calculated by using the PM3 semi-empirical molecular orbital method.The QSAR(quantitative relationship between structure and catalytic activity)of chloro-iron tetraphenylporphyrin (RTPPFeCl) was investigated by combining activity (yield of PNBA) with EHOMO and ΔEL-H of 9 catalysts.It was found that there was excellent linear correlation between catalytic activity and frontier orbital energy.Through linear regression the following equations were obtained: that is, for T(o-R)PPFeCl, Y=71.766-8.166EHOMO-10.701ΔEL-H, and correlation coefficient R=0.964.For T(p-R)PPFeCl: Y=80.031-9.297EHOMO-14.288ΔEL-H, and correlation coefficient R=0.998.It was also concluded that the effect of EHOMO on catalytic activity was larger than that of ΔEL-H for 5-coordinate of iron porphyrins.EHOMO was the main structure parameter influencing catalytic activities of 5-coordinate of iron-porphyrin compounds.Moreover the catalytic activities of two iron-porphyrin compounds with substituted methyl group were predicted according to this relationship.The results showed that the catalytic activity of metalloporphyrin was consistent with that predicted.The results made it possible to use the model of structure-activity relationship to predict unknown catalysts.Finally, the same correlation between the catalytic activities and electronic structure parameters of the Co, Mn and Fe metal porphyrins were obtained according to the authors’ research work published in three papers.These results will help not only to enrich biomimetic catalytic theory, but also to design excellent biomimetic catalysts from molecular levels.
Keywords:metalloporphyrin  catalyst  quantum chemical calculation  catalytic activity
本文献已被 CNKI 维普 万方数据 等数据库收录!
点击此处可从《化工学报》浏览原始摘要信息
点击此处可从《化工学报》下载全文
设为首页 | 免责声明 | 关于勤云 | 加入收藏

Copyright©北京勤云科技发展有限公司    京ICP备09084417号-23

京公网安备 11010802026262号