苯酚选择性氧化制对苯二酚催化剂的合成及性能研究

实验室合成了吡啶类三支架配体（4-btapa），与镉离子自组装合成三维多孔金属有机骨架材料（Cd-MOF-cat），并对合成的催化剂进行表征。分析Cd-MOF-cat的三维通道结构以及通道内壁的化学环境，并以Cd-MOF-cat为催化剂、H₂O₂为氧化剂、水-乙醇为溶剂催化苯酚羟基化选择性制备对苯二酚。实验结果表明，Cd-MOF-cat为催化剂时，反应有较好的转化率和选择性，苯酚转化率为85%~86%，对苯二酚选择性（对苯二酚与邻苯二酚物质的量比）达到2.6~2.8，结合苯酚和1-萘酚羟基化催化实验结果，初步探讨了催化机理，推断该反应机理可能是催化剂对苯酚的尺寸和形状选择性催化。催化剂“滤去”实验说明该催化为异相催化。

Synthesis and catalytic properties of catalyst Cd-MOF-cat for selective oxidation of phenol to hydroquinone

A three coordinated ligand 4-btapa was synthesized. Using 4-btapa ligand, a 3 D porous metal- organic framework catalyst Cd-MOF-cat was synthesized by self-assembled method with Cd2＋, and was characterized by 1H-NMR,XRD and TGA. The structure and chemical environment of 3D channels of the catalyst Cd-MOF-cat were analyzed. Using hydrogen peroxide as the oxidant,H20-ethanol as the solvent, the hydroxylation of phenol and 1-naphthol to hydroquinone over catalyst Cd-MOF-cat was investigated. The results showed that catalyst Cd-MOF-cat exhibited good catalytic activity. The conversion of phenol was up to 85% - 86%, and the para/ortho-selectivity to hydroquinone was 2.6 - 2.8. The catalytic mech- anism was discussed initially based on the catalytic experimental results of hydroxylation of phenol and 1-naphthol over catalyst Cd-MOF-cat. These phenomena probably originated from the size and shape selective catalysis of phenol. The results of catalyst filtration experiment indicated that the catalytic reac- tion was heterogeneous catalysis.