Li Yongjin, Wang Liming, Gao Yong, Yang Weijun, Li Yingying, Guo Cancheng
College of Chemistry and Chemical Engineering, Hunan University Changsha 410082 Hunan China
RSC Adv. 2018 Feb 15;8(14):7330-7339. doi: 10.1039/c7ra12701d. eCollection 2018 Feb 14.
Novel conjugated metalloporphyrin polymers (PP-EPMn and PX-EPMn) were synthesized by the Sonogashira coupling reaction with Mn(iii)5,10,15,20-tetraksi(4'-ethynylphenyl)porphyrin ([p-ethynyl]PMn) as building block, and with phenylene and xenyl groups as bridges, respectively. Fine nanospheres were obtained through control of the reaction conditions. The two polymer nanospheres were characterized in detailed by BET, FE-SEM, HR-TEM, FT-IR, UV-Vis and XPS, revealing that they were highly ordered, highly developed microporous and super-conjugated metalloporphyrin polymers with large surface areas and uniform pore sizes. Their electrochemical behaviors and hydrophilicity were also investigated. With the synergistic effects of porous nanosphere structure and conjugated covalent structure, PP-EPMn and PX-EPMn showed excellent catalytic activity and reusability in the catalytic degradation of methylene blue (3,7-bis(dimethylamino)-5-phenothiazinium chloride) in aqueous solution. The good hydrophilicity of the polymer nanospheres promoted the catalytic degradation. In particular, unlike Fenton degradation systems that require acidic conditions, PP-EPMn degraded methylene blue significantly better under alkaline conditions, which implied a good prospect in treating industrial methylene blue dye wastewater.
以5,10,15,20-四（4'-乙炔基苯基）锰卟啉（[对乙炔基]PMn）为结构单元，分别以亚苯基和联苯基为桥，通过Sonogashira偶联反应合成了新型共轭金属卟啉聚合物（PP-EPMn和PX-EPMn）。通过控制反应条件获得了精细纳米球。通过BET、FE-SEM、HR-TEM、FT-IR、UV-Vis和XPS对这两种聚合物纳米球进行了详细表征，结果表明它们是高度有序、高度发达的微孔和超共轭金属卟啉聚合物，具有大的表面积和均匀的孔径。还研究了它们的电化学行为和亲水性。在多孔纳米球结构和共轭共价结构的协同作用下，PP-EPMn和PX-EPMn在水溶液中催化降解亚甲基蓝（3,7-双（二甲基氨基）-5-吩噻嗪鎓氯化物）时表现出优异的催化活性和可重复使用性。聚合物纳米球良好的亲水性促进了催化降解。特别是，与需要酸性条件的芬顿降解系统不同，PP-EPMn在碱性条件下对亚甲基蓝的降解效果明显更好，这意味着在处理工业亚甲基蓝染料废水方面具有良好的前景。
