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Three-dimensional porphyrin-based covalent organic frameworks with tetrahedral building blocks for single-site catalysis

Abstract

Two three-dimensional (3D) porphyrin covalent organic frameworks, PCOF-1 and PCOF-2, were synthesized via imine condensation of planar porphyrin tetraamine (TAPP or TABPP) and rigid tetrahedral aldehyde based on steric hindrance of 3,3’,5,5’-tetrakis(4-formylphenyl)bimesityl (TFBM). The structures of PCOF-1 and PCOF-2 were studied by FT-IR, and 13C CP-MAS solid state NMR. Powder X-ray diffraction revealed obvious crystallinity with two intense peaks at 3.28o and 3.75o for PCOF-1, and 2.63o and 2.98o for PCOF-2. Structural simulation confirmed their 3D rutile type (pts) topological structures with two different pore sizes. X-ray single crystal diffraction indicated a distorted tetrahedral structure for the building block TFBM with two dihedral angles of 119° and 107.8°, and a planar square structure for model compound (MC) with a outspread angle of 176.5°. PCOF-1 and PCOF-2 present Brunauer-Emmett-Teller (BET) surface areas of 316 and 234 m2/g, respectively. The morphologies of PCOF-1 and PCOF-2 were investigated by scanning electron microscopy and transmission electron microscopy methods. PCOF-1 and PCOF-2 showed high thermal stability up to 420 °C without decomposition through thermogravimetric analysis (TGA), and high chemical stability with no obvious mass loss after three days of immersion in various solutions. Due to the large surface area and appropriate pore size, PCOF-Fe exhibited excellent biocatalytic catalytic performance, while PCOF-Co exhibited good electrocatalytic activity towards oxygen evolution reaction. These results indicate that 3D porphyrin-based COFs constructed from tetrahedral building block with steric hindrance are promising candidates for single-site catalysis.

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Supplementary files

Publication details

The article was received on 02 Aug 2019, accepted on 01 Oct 2019 and first published on 02 Oct 2019


Article type: Paper
DOI: 10.1039/C9NJ04017J
New J. Chem., 2019, Accepted Manuscript

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    Three-dimensional porphyrin-based covalent organic frameworks with tetrahedral building blocks for single-site catalysis

    Y. Liu, X. Yan, T. Li, W. Zhang, Q. Fu, H. Lu, X. Wang and Z. Gu, New J. Chem., 2019, Accepted Manuscript , DOI: 10.1039/C9NJ04017J

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