H_6PMo_9V_3O_(40)/SiO_2催化剂催化酚类化合物选择性硝化  

Selective Nitration of Phenols via H_6PMo_9V_3O_(40)/SiO_2 Catalysts

作　　者：吴锦明[1] 施磊[1] 沈爱宝[1] 汤艳峰[1] 陆天虹[2,3] 

机构地区：[1]南通大学化学化工学院,南通226019 [2]江苏省新型动力电池重点实验室南京师范大学化学与材料科学学院,南京210097 [3]中国科学院长春应用化学研究所,长春130022

出　　处：《应用化学》2014年第4期437-443,共7页Chinese Journal of Applied Chemistry

基　　金：国家自然科学基金(21173122);江苏省高校自然科学基金(11KJD530001)资助项目~~

摘　　要：为创建洁净高效的酚类化合物硝化工艺，以杂多酸H6PMo9V3O40（PMAV3）为活性组分，硅胶为载体，浸渍法制备了负载型催化剂PMAV3／SiO2，采用红外光谱、X射线衍射谱、N2吸附-脱附法及TG-DSC分析等测试技术对该催化剂的结构及热稳定性进行了表征；考察了该催化剂对多种酚类化合物硝化反应的催化性能。结果显示，该催化剂对多种酚类化合物的硝化反应具有很强的催化活性和区域选择性，产率为83.7％。94.5％，其中苯酚、邻甲酚、邻氯苯酚和邻氟苯酚以邻位硝化产物居多，水杨酸的对位硝化产物占绝对优势；负载催化剂的织构性质与载体相近，但随负载量增加，比表面积逐渐降低；PMAV3／SiO2的热稳定性好于本体PMAV3。催化剂回收容易，重复使用5次，活性基本不变。To establish a clean and efficient nitration process of phenolic compounds, heteropolyacid H6PMo9V3O40（ PMAV3 ） and chromatographic silica gel were respectively chosen as active component and carrier for the preparation of a series of supported catalysts（ PMAV3/SiO2 ） via the conventional impregnation method. The catalysts were characterized by Fourier transform infrared spectroscopy（ FTIR）, X-ray diffraction （XRD）, N2 adsorption-desorption and thermogravimetry-differential scanning calorimetry （TG-DSC）. The catalytic performance of catalysts was evaluated for the nitration of phenols. The results reveals that PMAVJ SiO2 exhibits excellent catalytic activity and regioselectivity for the nitration of phenols, the nitration yield is in the range of 83.7% ～ 94. 5%. For salicylic acid, the para-selectivity is nearly 100%, but for phenol, 2-methylphenol, 2-chlorophenol and 2-fluorphenol, the ortho-selectivity is observed. The textural properties of PMAV3/SiO2 are close to that of PMAV3, but BET of the supported catalysts is decreased PMAV3 loading. PMAV3/SiO2 shows better thermal stability than PMAV3. The catalyst can be and reused for five times without noticeable drop in activity. with the rise of recovered easily.

关 键 词：催化剂 杂多酸 H6PMo9V3O40 硅胶 硝化 酚类化合物 

分 类 号：O625.6[理学—有机化学] O643.3[理学—化学]