【作者】 黄晓；

【导师】 吴海虹；

【作者基本信息】 华东师范大学 ， 有机化学， 2021， 硕士

【摘要】 二氧化碳（CO₂）是一种丰富、无毒的C1资源,将CO₂作为化学原料合成各种工业增值品是绿色化学中实现CO₂转化的重要途径。多相催化剂由于容易循环回收且对环境不会造成污染,因此被广泛应用于CO₂的固定与转化。有序介孔酚醛树脂材料因其高比表面积、可调节的孔道结构以及较大孔径等特点成为多相催化剂载体选择之一。本论文围绕氮掺杂功能化有序介孔酚醛树脂材料的制备及其催化相关CO₂反应的性能研究开展工作,研究具体内容如下:（1）以4-二甲胺基苯酚代替部分苯酚原料,与苯酚和甲醛在三嵌段共聚物F127作模板剂的条件下,通过溶剂挥发自组装作用一锅法合成二甲胺基功能化有序介孔聚合物（NMe₂-MPs）,并将其应用于催化邻苯二胺与CO₂生成苯并咪唑的反应。研究发现催化剂在CO₂压力为1MPa和120℃条件下反应12h便可以得到95%的产率。该催化剂对其他邻苯二胺类化合物也具有良好的普适性,且循环5次后仍有很好的催化效果。（2）以第一章得到的二甲胺基功能化有序介孔聚合物NMe₂-MPs为载体,原位吸附银离子并还原得到负载银纳米颗粒的介孔聚合物（NMe₂-MPs/Ag）,XRD、TEM和XPS等测试表明金属银纳米颗粒成功负载到材料上。将制备的催化剂用于催化炔丙醇、CO₂以及伯胺的环化反应中,在40℃和常压下便可以得到96%的催化产率;催化剂循环5次后活性并没有明显下降。（3）以酚醛树脂前驱体、TBD与模板F127通过溶剂挥发自组装得到TBD功能化的有序介孔聚合物材料（TBD-FDU）并将其应用于催化CO₂、N-苯腙与吡咯烷的偶联反应。在120℃以及2MPa压力条件下TBD-FDU便可催化该反应得到不错的产率,催化剂具有优异的底物普适性和良好的稳定性,循环5次活性未有下降。这是多相催化剂在CO₂、N-苯腙与吡咯烷的偶联反应中的首次报道。更多还原

【Abstract】 CO₂ is actually an abundant and non-toxic C1 resource.Conversion of CO₂ to value-added products is of great importance for green chemistry.Heterogeneous catalysts,which could be easily recycled and eco-friendly,are widely used in the fixation and conversion of CO₂.Ordered mesoporous phenolic resin materials,possessing high specific surface area,adjustable pore structure and large pore size,have been widely used as heterogeneous catalysts or catalyst carriers.Herein,series of N-doped ordered mesoporous phenolic resin materials were prepared and used for the catalytic conversion of the CO₂ related reactions.The detailed contents are as follows:1.Dimethylamino-functionalized ordered mesoporous phenolic polymers NMe₂-MPs were directly prepared via the evaporation-induced self-assembly by using 4-dimethylaminophenol,phenol,formaldehyde and F127.The prepared NMe₂-MPs were used to catalyze the reaction of o-phenylenediamine with carbon dioxide.An optimized yield of 95%could be obtained at 1 MPa and 120 ℃ after 12 hours.The prepared catalysts showed excellent substrate universality and recyclability.High product yield could still be obtained after five cycles.2.Mesoporous polymer supported silver nanoparticle catalysts NMe₂-MPs/Ag were prepared using the NMe₂-MPs prepared above as the carrier.The silver ions were adsorbed in-situ and reduced to silver nanoparticles.Characterizations such as XRD,TEM and XPS confirmed that the metallic silver nanoparticles were successfully loaded on NMe₂-MPs.The NMe₂-MPs/Ag exhibited excellent performance in the reaction of propargyl alcohol,carbon dioxide and primary amine,with the yield of 96%at 40°C and atmospheric pressure.No obvious decrease in the product yield could be observed after 5 catalytic cycles.3.The TBD-functionalized ordered mesoporous polymers（TBD-FDU）were prepared via the evaporation-induced self-assembly of resole,organic base TBD and template F127.The prepared materials were used to catalyze the coupling reaction of carbon dioxide,N-phenylhydrazone and pyrrolidine.Good product yield could be obtained at 120 ℃ and 2 MPa.TBD-FDU exhibited excellent substrate universality and recyclability,with no obvious decrease in the catalytic performance after 5 catalytic cycles.It should be mentioned that this is the first report on the reaction of carbon dioxide,N-phenylhydrazone and pyrrolidine catakyzed by the heterogeneous catalyst.更多还原