MCM-4 1固载异双核金属配合物的合成表征及催化性能

石油化工高等学校学报 ›› 2007, Vol. 20 ›› Issue (1): 42-47.

MCM-4 1固载异双核金属配合物的合成表征及催化性能

高丽娟, 李瑞丰

太原理工大学精细化工研究所, 山西太原0 3 0 0 2 4

收稿日期:2006-06-09 出版日期:2007-03-20 发布日期:2017-06-28
作者简介:高丽娟( 1 9 6 8-) , 女, 山西太原市, 副教授, 在读博士。

Synthesis and Catalytic Properties in Cyclohexane Oxidation of Macrocyclic Heterodinuclear Complexes Encapsulated in MCM-41

GAO Li-juan, LI Rui-feng

Institute of Special Chemicals, Taiyuan University of Technology, Taiyuan Shanxi 030024,P.R.China

Received:2006-06-09 Published:2007-03-20 Online:2017-06-28

摘要/Abstract

摘要： 合成了9个具有混合价态的大环d-f异双核配合物[ M 1M 2 L] ( NO ₃) ( H₂O) n( M, L分别代表金属和配体) 。采用浸渍法将d-f异双核配合物分别固载在中孔分子筛 MCM-4 1上制得负载催化材料。I R, UV-V i s ,XR D, I C P-AE S和 TG / DTA表征表明异双核配合物被固载后, 配合物结构仍保持完整。以环己烷氧化为探针反应,考察了负载催化材料的催化性能。结果表明该系列催化剂具有较高的活性, 其 TOF值分别为2 0. 4~4 9. 2h-1。当选用冰醋酸做溶剂时, 环己烷的转化率高达7 2. 1%。此外, 分别考察了反应时间、反应温度、氧化剂加入量及催化剂的加入量对环己烷催化氧化的影响。该系列催化剂在环己烷液相反应中的最佳反应条件为: 反应时间1 0~1 2h,反应温度在3 4 3~3 9 3K, 双氧水的最佳加入量为5~1 5mL, 催化剂的最佳加入量0. 5~1. 0g。

关键词: 异双核配合物, MCM-4 1, 催化氧化反应, 固载

Abstract:

Nine macrocyclic d-f heterodinuclear complexes ［M1M2L］(NO ₃)(H₂O)n(M,L stand for metal and ligand) were synthesized. Nine d-f heterodinuclear complexes were immobilized on MCM-41 mesoporous materials to prepare encapsulated catalyst by impregnation. The samples were characterized by using IR and UV-Vis, XRD, ICP-AES and TG/DTA techniques. The results show that the structures of heterodinuclear complexes in MCM-41 are unchanged. The catalytic properties of the prepared catalysts were studied by cyclohexane oxidation. The results show that they have better activity in cyclohexane oxidation; TOF values of these encapsulated catalysts are in the range of 20.4~49.2 h-1; the conversion of cyclohexane is the highest (72.1%) when acetic acid is used as solvent. The influence of time, temperature and the amounts of the oxidant and catalyst on cyclohexane oxidation was also investigated. The best reactive conditions are reaction time of 10~12 h, reaction temperature of 343~393 K, H2O2 amount of 5~15 mL and catalyst content of 0.5~1.0 g respectively.

Key words:

Heterodinuclear complexes, MCM-41, Oxidation reaction, Encapsulation

高丽娟, 李瑞丰. MCM-4 1固载异双核金属配合物的合成表征及催化性能[J]. 石油化工高等学校学报, 2007, 20(1): 42-47.

GAO Li-juan, LI Rui-feng .

Synthesis and Catalytic Properties in Cyclohexane Oxidation of Macrocyclic Heterodinuclear Complexes Encapsulated in MCM-41

[J]. Journal of Petrochemical Universities, 2007, 20(1): 42-47.