Mesoporous Conjugated Polycarbazole with High Porosity via Structure Tuning

Abstract

Monomer building units play a key role in the porosity and adsorption performance of porous conjugated polymers. Three tetracarbazolyl-substituted monomers (Cz-8–10) with similar molecular structures were designed and prepared in order to tune the porosity and pore size distribution of the obtained porous conjugated polycarbazoles (CPOP-8–10) via FeCl3-promoted carbazole-based oxidative coupling polymerization. Polymers CPOP-8 and CPOP-10 exhibit microporous nature similar to most of reported conjugated microporous polymers. Porosity analysis and adsorption performance indicate that CPOP-9 is predominantly mesoporous. The Brunauer–Emmett–Teller specific surface area of CPOP-9 is up to 2440 m2 g–1, which is the highest specific surface area among the reported porous conjugated polycarbazoles by the same method. Mesoporous CPOP-9 shows higher water vapor uptake capacity (804 mg g–1) than microporous polymers CPOP-8 (208 mg g–1) and CPOP-10 (181 mg g–1) at water saturated vapor pressure and 298 K, which might imply that pore size has a key effect on wettability of the porous polymers. With high specific surface area and pore volume, CPOP-9 exhibits high hydrogen uptake of 5.22 wt % (77 K) and carbon dioxide uptake of 70.0 wt % (298 K) at 18.0 bar. Additionally, the uptake capacity of CPOP-9 for toluene is high up to 1355 mg g–1 at the saturated vapor pressure (298 K). The adsorption performance of CPOP-9 can be comparable with that of the known porous organic polymers with ultrahigh specific surface area, such as PAF-1 and PNN-4, under the same conditions.

Facile Carbonization of Microporous Organic Polymers into Hierarchically Porous Carbons Targeted for Effective CO2 Uptake at Low Pressures

“…This may be attributed to the combination of the improved micropore volume (up to 0.68 cm 3 g -1 ) and the hierarchically porous structure, which 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60 makes that ultramicropores more efficient for the kinetic CO 2 molecules in the adsorption process. Notably, at 273 K and 1 bar, MOP-8C presents a high CO 2 uptake up to 214 mg g -1 , which surpasses most of the known porous organic polymers and the porous carbon materials, such as CPOPs (182 mg g -1 ), [45][46] HCPs (181 mg g -1 ), [47][48] CTFs (143 mg g -1 ), 49 CMPs (122 mg g -1 ), 50 nitrogen-doped graphene (114 mg g -1 ), 51 HPNCs (207 mg g -1 ). 52 Moreover, this value could also be comparable with those of the porous carbon materials with high pore volume and nitrogen content, for example microporous carbon TPC-1 (216 mg g -1 ) 53 with a pore volume of 1.23 cm 3 g -1 and a nitrogen content of 20.87 wt%, and mesoporous carbon OMC (132 mg g -1 at 278K) 54 with a pore volume of 2.17 cm 3 g -1 .…”

Four Simple Structure Carbazole‐Based Conjugated Microporous Polymers with Different Soft Connected Chains

“…These results demonstrated that such carbazole‐functionalized MOPs have great potential to increase the gas capture capacity. It has been showed that the porous properties of CMPs mainly depend on the length of the rigid connecting strut and topological structure design . However, until now the carbazole‐based CMPs with soft connecting chain have been never investigated.…”

Thermo-processable covalent scaffolds with reticular hierarchical porosity and their high efficiency capture of carbon dioxide

“…[1][2][3][4][5] These materials, with their pore size approaching molecular dimensions, have the potential to be used for molecular storage and separation, [6][7][8][9][10][11] catalysts or catalyst supports, [12][13][14][15][16][17][18] and sensors. [21][22][23][24][25][26][27] One of the main issues concerning the porous network of covalently bonded building blocks (referred to as a "covalent network") is to fabricate a hierarchical pore structure, i.e., a network consisting of interconnected pores of different sizes. [21][22][23][24][25][26][27] One of the main issues concerning the porous network of covalently bonded building blocks (referred to as a "covalent network") is to fabricate a hierarchical pore structure, i.e., a network consisting of interconnected pores of different sizes.…”