Abstract
Through metal-free protocol, hypercrosslinked porous polyporphyrin with permanent porosity was obatined via the Friedel–Crafts alkylation of tetracarbazolylporphyrin using formaldehyde dimethyl acetal as an external cross-linker. Its chemical structure and porosity was well characterized and confirmed. The BET specific surface area value of HCP-TCPP is 1050 m2 g−1 and related dominant pore size is centered at 0.63 nm. The adsorption amount of methanol by HCP-TCPP is high up to 800 mg g−1 (about 25.0 mmol g−1) at its saturated vapor pressure, which is higher than that of toluene (600 mg g−1, 6.5 mmol g−1). Further study indicates that polymer HCP-TCPP, possessing the high BET specific surface area and total pore volume, exhibits good hydrogen uptake of 3.44 wt % (77 K) and high carbon dioxide uptake of 41.1 wt % (298 K) at 18.0 bar. Besides, the obtained porous polymer can also be used as an effective heterogeneous catalyst for the Knoevenagel condensation between various aldehydes and malononitrile.
Highlights
As one of intrinsic nanoporous polymers, hypercrosslinked porous polymer represent a type of porous organic networks with high specific surface area and good thermal/ chemical stability, which have been used for the adsorption of gas and organic vapors, the removal of organic compounds from water,[1] and the heterogeneous catalyst of organic transformation.[2]
Compared with metalloporphyrin based porous materials, the porous polymer based on free-base porphyrin obtained with lower cost can display special properties and function derived from the basic pyrrole containing macrocyclic cavity with large p-conjugated system
Owing to the basic pyrrole containing macrocyclic cavities, the obtained porous polymer can be used as a heterogeneous catalyst for the Knoevenagel condensation between various aldehydes and malononitrile
Summary
As one of intrinsic nanoporous polymers, hypercrosslinked porous polymer represent a type of porous organic networks with high specific surface area and good thermal/ chemical stability, which have been used for the adsorption of gas and organic vapors, the removal of organic compounds from water,[1] and the heterogeneous catalyst of organic transformation.[2]. Porous organic polymers based on porphyrin have drawn great attentions due to the rigid structure and special function of porphyrin.[8,9,10,11,12,13,14,15] It is reported that metalloporphyrin-based porous materials can promote some important chemical transformation such as photosynthesis, oxygen transport, and catalytic oxidations.[8,9,11,12] porphyrin-based porous organic polymers without built-in metal sites in the skeleton have been reported rarely until now.[16,17] Compared with metalloporphyrin based porous materials, the porous polymer based on free-base porphyrin obtained with lower cost can display special properties and function derived from the basic pyrrole containing macrocyclic cavity with large p-conjugated system. Its adsorption performance can be comparable with some conjugated porous polymers we reported before.[20,21] Owing to the basic pyrrole containing macrocyclic cavities, the obtained porous polymer can be used as a heterogeneous catalyst for the Knoevenagel condensation between various aldehydes and malononitrile
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