64413-48-5Relevant articles and documents
A series of highly stable porphyrinic metal-organic frameworks based on iron-oxo chain clusters: design, synthesis and biomimetic catalysis
Liu, Gang,Cui, Hao,Wang, Sujuan,Zhang, Li,Su, Cheng-Yong
supporting information, p. 8376 - 8382 (2020/05/16)
Iron-based porphyrinic metal-organic frameworks (PMOFs) are desirable for biomimetic applications, due to the low toxicity and high abundance of Fe as well as the rich biomimetic functions of metalloporphyrins. Besides, the uniform dispersion of porphyrin centers in PMOFs can effectively protect them from self-dimerization. Nevertheless, it remains a big challenge to synthesize iron-based PMOFs. In this study, a series of Fe-oxo chain-based PMOFs incorporating different metals in porphyrinic centers (namely M-PMOF-3(Fe), M = Fe, Co, Ni, Cu) are synthesized directly from the reaction of metalloporphyrin and iron salts with an improved modulating strategy using a pair of monocarboxylic acids and water as the three-component modulator. The prepared materials of M-PMOF-3(Fe) possess high stability to resist a broad pH range (0-11) and even 2 M HCl in aqueous solutions for 2 days, and their frameworks can be maintained up to 350 °C. Catalytic tests show that M-PMOF-3(Fe) are effective in the aerobic oxidation of C-H bonds using oxygen from the air as the oxidant.
Remote ion-pair interactions in Fe-porphyrin-based molecular catalysts for the hydrogen evolution reaction
Kasemthaveechok, Sitthichok,Fabre, Bruno,Loget, Gabriel,Gramage-Doria, Rafael
, p. 1301 - 1308 (2019/03/12)
The environmentally benign production of clean energy is extremely important for the sustainable progress of our society. In this respect, dihydrogen (H2) has been considered in the last decades as an efficient energy carrier and much effort has been directed to the hydrogen evolution reaction (HER). Herein, we report on the efficiency of iron-based 5,10,15,20-tetraphenylporphyrins containing carboxylate groups in different positions (ortho, meta and para of the meso-substituted aryl groups of the porphyrin backbone) as molecular catalysts for the HER. The iron-based porphyrin containing the carboxylic acids in the ortho position was found completely inactive in the HER. Furthermore, besides stereoelectronic control, the subtle differences observed in the cyclic voltammograms (CV) as well as those associated with the electrocatalytic activity might involve a previously neglected ion-pair interaction between the carboxylate groups of the porphyrin scaffold and the chloride anions belonging to the proton source, which highlights the relevance of ion-pair contacts remote from the active center for this type of catalytic system.
Iron-based metalloporphyrins as efficient catalysts for aerobic oxidation of biomass derived furfural into maleic acid
Xie, Yongdi,Huang, Yi,Wu, Chunyan,Yuan, Wenwen,Xia, Yongmei,Liu, Xiang,Wang, Haijun
, p. 20 - 27 (2018/04/05)
A series of porphyrin type catalysts with the metal active sites of Fe were prepared and investigated in aerobic oxidation of biomass-based furfural to maleic acid (MAD) in aqueous phase. The catalytic performance of meso-tetrakis(4-bromophenyl)porphyrin iron (III) chloride (FeT(p-Br)PPCl) immobilized on different supports was evaluated. It was interesting to find that the catalytic activity varied with the supports and followed the trend: FeT(p-Br)PPCl/SBA–15 > FeT(p-Br)PPCl/meso-ZSM–5 > FeT(p-Br)PPCl/MCM-41. The effect of reaction conditions were discussed in detail over FeT(p-Br)PPCl/SBA-15 catalyst, and 56.1% yield and 73.8% selectivity of MAD were obtained from renewable furfural under the optimal conditions. Moreover, the FeT(p-Br)PPCl/SBA-15 catalyst could be reused five times without a significant decrease of activity in recycling examinations.
