钴卟啉催化剂的前线轨道能级与其催化活性的相关性研究  

Study on the Correlation between Molecular Frontier Orbital Energy and Catalytic Activity of Cobalt Porphyrins

作　　者：张燕慧[1] 佘远斌[2] 钟儒刚[1] 周贤太[2] 纪红兵[3] 

机构地区：[1]北京工业大学生命科学与生物工程学院,北京100022 [2]北京工业大学绿色化学研究室,北京100022 [3]华南理工大学化工与能源学院,广州510640

出　　处：《化学学报》2004年第22期2228-2232,共5页Acta Chimica Sinica

基　　金：北京市自然科学基金 (No.2 0 0 2 0 0 2 );北京市科技新星计划 (No.95381 1 2 0 0 )资助项目

摘　　要：设计并合成了 12种钴卟啉催化剂 ,在温和反应条件 ( 5 5℃ ,2 .0MPa氧压 )下考察其催化氧气液相氧化对硝基甲苯制取对硝基苯甲酸的催化活性 ,发现其对上述反应均有显著的催化活性 .采用PM3半经验分子轨道法对所设计的钴卟啉化合物模型体系进行了计算 ,将计算结果与实验结果相结合 ,探讨了钴卟啉分子前线轨道能级与其催化活性之间的关系 .经研究发现 ,四配位或五配位钴卟啉催化剂的催化活性与EHOMO和ΔEL H均有一定的相关性 ,且ΔEL H对催化活性的影响大于EHOMO对催化活性的影响 ;EHOMO值越低、ΔEL H越小 。12 cobalt porphyrin catalysts were designed and synthesized, and their catalytic activities for oxidation of p-nitrotoluene (PNT) to p-nitrobenzoic acid (PNBA) were investigated in the presence of molecular oxygen under mild conditions (55 degreesC, 2.0 MPa). It was found that the 12 cobalt porphyrins had consider-able catalytic activity for the reaction. The correlation between molecular frontier orbital energies of all the cobalt porphyrins. and their catalytic activities was investigated by means of the PM3 semi-empirical molecular orbital method, and the result presented that the catalytic activity of 4-coordination or 5-coordination of cobalt porphyrins was related with E-HOMO and DeltaE(L-H), had greater impact on catalytic activity than E-HOMO and the lower the E-HOMO and DeltaE(L-H), the higher the catalytic activity.

关 键 词：钴卟啉催化剂 分子前线轨道能级 催化活性 相关性 对硝基甲苯 对硝基苯甲酸 

分 类 号：O643.3[理学—物理化学]