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研究了MPc(M=CO、Fe)在异丙苯液相氧化中的催化作用,并考察了Py、bPy和菲绕啉等含N配体对MPc催化性能的影响.发现反应遵循配位-链锁反应机理.反应速度对异丙苯为1.5级,对催化剂为0.5级.反应活化能分别为53.1kJ/mol.(CoPe)和43.9 kJ/mol.(FePc).在所选择的反应条件下,异丙苯转化率较低(小于35%),生成过氧化氢异丙苯选择性约为100%.加入第五配体可使诱导期消失.电子光谱和反应动力学结果同时表明,反应是由O_2的配位活化引发的,ESR结果证明酞菁环的电子可和金属离子进行交换.
The catalytic effect of MPc (M = CO, Fe) in the liquid phase oxidation of cumene was studied, and the effect of the ligands containing Py, bpy and phenanthroline on the catalytic properties of MPc was investigated. Chain reaction mechanism.The reaction rate for the cumene 1.5, 0.5 for the catalyst.The activation energy was 53.1kJ / mol (CoPe) and 43.9 kJ / mol (FePc) .In the selected reaction conditions , The conversion of cumene is lower (less than 35%), the selectivity to cumene hydroperoxide is about 100% .The addition of the fifth ligand can disappear the induction period.The results of electron spectroscopy and reaction kinetics also show that, The reaction is triggered by the coordination of O 2, and ESR results show that the phthalocyanine ring can be exchanged with metal ions.