钒席夫碱官能化PMOs的制备及在环己烷氧化中的点击催化作用  

Preparation and Cyclohexane Oxidation Click Catalysis of Periodic Mesoporous Organosilicas Functionalized with V-Schiff-base

作　　者：史秀锋[1] 胡晓虹[1] 范彬彬[2] 李瑞丰[1] 

机构地区：[1]太原理工大学化学化工学院,山西太原030024 [2]太原理工大学精细化工研究所,山西太原030024

出　　处：《分子催化》2015年第2期126-134,共9页Journal of Molecular Catalysis(China)

基　　金：国家自然科学基金(NO.20971095);山西省回国留学人员科研资助项目(NO.2013-047)

摘　　要：以周期性介孔有机硅(periodic mesoporous organosilicas,PMOs)中的有机桥联基团亚苯基为反应位对其进行氯甲基化反应,得到氯甲基官能化的PMOs-CH2Cl,然后再通过-CH2Cl和V-Saldien配合物中的-NH-进行反应得到钒席夫碱配合物官能化的杂化材料V-PMOs催化剂.采用XRD、N2吸附、FTIR、UV-vis、ICP和催化反应等手段对所制杂化材料的物化和催化性能进行了较为详细的研究,结果表明采用该法可将钒席夫碱配合物成功键联到PMOs上,且所制杂化材料同采用类似方法制备的V-SBA-15催化材料相对比,在无溶剂以叔丁基过氧化氢为引发剂,氧气为氧化剂的环己烷氧化反应中表现出定向转化为环己酮和环己醇的总选择性,具有点击反应的特性.PMOs-CH2Cl was synthesized by chloromethylation of phenylene moieties in the framework of periodic mesoporous organosilicas( PMOs). Then V-PMOs catalysts were obtained by grafting vanadium-Saldien on PMOsCH2Cl. The physicochemical properties and catalytic performance of the samples were characterized by XRD,N2 adsorption,FTIR,UV-vis,ICP and cyclohexane oxidation reaction. The results showed that vanadium-Saldien complexes can be successfully immobilized on the PMOs by that route. For comparison,vanadium-Saldien complexes functionalized SBA-15( V-SBA-15) was prepared by the similar method. In the solvent-free aerobic cyclohexane oxidation reaction system,V-PMOs showed the total selectivity to cyclohexanone and cyclohexanol with the characteristic of click reaction.

关 键 词：PMOS 氯甲基化 钒席夫碱 环己烷氧化 

分 类 号：O643.36[理学—物理化学]