Fine tailoring the steric configuration of initial building blocks to construct ultramicroporous polycarbazole networks with high CO2 uptake and selectivity of CO2 over N2

Abstract

a b s t r a c tThree carbazole based building blocks with similar propeller-like steric configuration are designed and synthesized. The polycarbazole networks P-4, 4 0 -biscarbazolyl-phenyl (P-BCz), P-tetracarbazolyl-pdifluorobenzene (P-TCz) and P-hexacarbazolyl-phenyl (P-HCz) are obtained with high surface areas and uniform ultramicropores. The aggregation morphologies of networks vary from regular spherical particles, ribbon-like structure to large lamellar structure as the number of carbazole increased around the benzene ring. The networks P-TCz, with four carbazole decorating on the benzene ring, have the largest surface area and highest gas uptake ability among the three networks. However, the CO 2 and CH 4 isosteric enthalpies increased linearly with increasing the number of carbazole. The networks P-HCz with six carbazole show the excellent CO 2 /N 2 separative capacity (107 at 273 K, and 127 at 298 K), which is among the highest reported about CO 2 separation using organic pore networks. Fine designing and tailoring the topological structure of monomer can control the adsorption properties and optimize the gas uptake performance.

Carbazolic Porous Framework with Tetrahedral Core for Gas Uptake and Tandem Detection of Iodide and Mercury

“…The desorption branches are close to adsorption, indicating that the CO 2 sorption is reversible. As can be seen, the CO 2 uptake of Cz-TPM is higher than that of many reported carbazolic MOPs, such as Cz-POF-2 (7.7 wt %, 273 K/1 bar), CPOP-2,3,4 (7.8–9.0 wt %, 273 K/1 bar), P-TPATCz (2.9 wt %, 273 K/1.1 bar), and P-BCz (9.27 wt %, 273 K/1.1 bar) . However, it is still moderate compared with other carbazolic MOPs with good CO 2 uptake capacities, such as CPOPs-5-19 (10.3–18.2 wt %, 273 K/1 bar), ,,, MFCMP-1 (16.2 wt %, 273 K/1 bar), C-SP (10.7 wt %, 273 K/1 bar), and P-CzPTCz (17.0 wt %, 273 K/1.1 bar) .…”

“…Cz-TPM exhibited an uptake of 149.3 (1.34 wt %) and 102.3 cm 3 g -1 (0.92 wt %), respectively. Its capacity is lower than that of some reported porous polymers, such as polycarbazole CPOP-8 (H 2 uptake, 1.92 wt % at 77 K/1.0 bar) 17 and Cz-POF-1( 2.24 wt % at 77 K/1.0 bar) 18 but exceeds that of Cz-POF-2 (0.97 wt % at 77 K/1.0 bar), 18 P-BCz (1.14 wt % at 77 K/1.0 bar), 26 and CP-CMP3 (0.93 wt % at 77 K/1.0 bar). 33 The isosteric heat for H 2 was calculated from the data measured at 77 and 87 K. Figure 4b shows that Cz-TPM has an isosteric enthalpy value, Q st , of 12.5 kJ mol −1 at low loading.…”

“…The apparent surface areas (Brunauer−Emmett− Teller (BET)) were calculated using N 2 adsorption under relative pressures between 0.01 and 0.2 on the basis of the BET model. The BET surface area of Cz-TPM is 713 m 2 g −1 , which surpassed some carbazolic porous polymers, such as Cz-POF-2 (671 m 2 g −1 ), 18 P-BCz (640 m 2 g −1 ), 26 P-TPATCz (337 m 2 g −1 ), 19 and CPOP-2,3,4 (510−660 m 2 g −1 ). 16 However, it is lower than other porous polymer analogues, such as porous polycarbazole CPOPs (980−2440 m 2 g −1 ), 15,16,22 Cz-POF-1 (2065 m 2 g −1 ), 18 and MFCMP-1(840 m 2 g −1 ).…”

“…As can be seen, the CO 2 uptake of Cz-TPM is higher than that of many reported carbazolic MOPs, such as Cz-POF-2 (7.7 wt %, 273 K/1 bar), 18 CPOP-2,3,4 (7.8−9.0 wt %, 273 K/1 bar), 16 P-TPATCz (2.9 wt %, 273 K/ 1.1 bar), 19 and P-BCz (9.27 wt %, 273 K/1.1 bar). 26 However, it is still moderate compared with other carbazolic MOPs with good CO 2 uptake capacities, such as CPOPs-5-19 (10.3−18.2 wt %, 273 K/1 bar), 16,22,28,29 MFCMP-1 (16.2 wt %, 273 K/1 bar), 27 C-SP (10.7 wt %, 273 K/1 bar), 20 and P-CzPTCz (17.0 wt %, 273 K/1.1 bar). 19 The high CO 2 uptake capacity may be ascribed to the strong interaction between the polycarbazole network and CO 2 molecules.…”

Carbazole-based porous organic polymers for carbon dioxide capture and catalytic conversion

“…阳仁强课题组 [27] 设计出含有芴酮结构的咔唑单体(图2, 6), 并经由噻吩 [28] . 同时, 阳仁强课题组 [29] 通过改变一 . 除材料的结构外, 聚合物的元素组成也是影 响CO 2 吸附性能的重要因素 [33] .…”