化学学报 ›› 2004, Vol. 62 ›› Issue (22): 2228-2232. 上一篇    下一篇

研究论文

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

张燕慧1, 佘远斌2, 钟儒刚1, 周贤太2, 纪红兵3   

  1. 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
  • 收稿日期:2004-03-25 修回日期:2004-07-09 出版日期:2004-11-28 发布日期:2014-02-17
  • 通讯作者: 佘远斌,E-mail:sheyb@bjut.edu.cn E-mail:sheyb@bjut.edu.cn
  • 基金资助:
    北京市自然科学基金(No.2002002)和北京市科技新星计划(No.953811200)资助项目.

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

ZHANG Yan-Hui1, SHE Yuan-Bin2, ZHONG Ru-Gang1, ZHOU Xian-Tai2, JI Hong-Bing3   

  1. 1. College of Life Science and Bio-engineering, Beijing 100022;
    2. Laboratory of Green Chemistry, Beijing University of Technology, Beijing 100022;
    3. School of Chemical and Energy Engineering, South China University of Technology, Guangzhou 510640
  • Received:2004-03-25 Revised:2004-07-09 Online:2004-11-28 Published:2014-02-17

设计并合成了12种钴卟啉催化剂,在温和反应条件(55℃, 2.0 MPa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,其催化活性越高.

关键词: 钴卟啉催化剂, 分子前线轨道能级, 催化活性, 相关性研究, PM3

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℃, 2.0 MPa). It was found that the 12 cobalt porphyrins had considerable 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 EHOMO and ΔEL-H. ΔEL-H had greater impact on catalytic activity than EHOMO, and the lower the EHOMO and ΔEL-H, the higher the catalytic activity.

Key words: cobalt porphyrin catalyst, molecular frontier orbital energy, catalytic activity, correlation, PM3