School of Environment and Civil Engineering, Dongguan University of Technology, Dongguan 523808, China.
Dalian National Laboratory for Clean Energy, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian, 116023, China.
Dalton Trans. 2018 Oct 7;47(37):13135-13141. doi: 10.1039/c8dt02913j. Epub 2018 Aug 31.
A series of Mg-porphyrin complex doped divinylbenzene (DVB) based porous organic polymers (POPs) were systematically afforded through the method of free radical polymerization under solvothermal conditions. These POP catalysts have physical advantages of high surface areas, hierarchical pore structures, high thermal stability and spatially separated active Mg-porphyrin sites, which lead to very high efficiency in the conversion of CO to cyclic carbonates with the aid of tetra-n-butyl ammonium bromide (TBAB) as a nucleophile. The effect of the doping ratio (Mg-porphyrin complex to DVB) on catalytic efficiency was studied and discussed, and the detrimental embedding effect was found. The effects of reaction temperature and pressure on catalytic activity as well as other epoxide substrates were also examined fully. More importantly, under very mild conditions (30 °C, 0.1 MPa CO), a considerable turnover number (TON) value of 1800 was obtained. The heterogeneous POP catalyst can be easily recovered and reused 10 times without loss of activity.
通过自由基聚合在溶剂热条件下，系统地制备了一系列镁卟啉配合物掺杂的二乙烯基苯（DVB）基多孔有机聚合物（POP）。这些 POP 催化剂具有高比表面积、分级孔结构、高热稳定性和空间分离的活性镁卟啉位等物理优势，在四丁基溴化铵（TBAB）作为亲核试剂的帮助下，可非常有效地将 CO 转化为环状碳酸酯。研究并讨论了掺杂比（镁卟啉配合物与 DVB）对催化效率的影响，发现存在有害的嵌入效应。还充分研究了反应温度和压力对催化活性以及其他环氧化物底物的影响。更重要的是，在非常温和的条件（30°C，0.1 MPa CO）下，得到了相当高的转化率（TON）值 1800。多相 POP 催化剂可在不损失活性的情况下，10 次重复回收和再使用。
