In this work, we reported the rational design and synthesis of two pyrene-4,5,9,10-tetraone (PT)-linked conjugated microporous polymers (PT-CMPs) as organic electrode precursors in energy storage applications, which were prepared through the Sonogashira polycondensation reaction of ethynyl pyrene (Py-T)/tetraphenylethene (TPE-T) as common units with brominated pyrene tetraene (PT-Br2) as a redox-active unit. We employed microscopic, spectroscopic, and N2 adsorption/desorption isotherm analyses to investigate the thermal stability, molecular structure, and porosity properties of both newly obtained PT-CMPs. Thermogravimetric analysis (TGA) revealed that both synthesized PT-CMPs feature moderate thermal stability. TheP-PT-CMP exhibited a high BET surface area of up to 300 m2 g–1 and a total pore volume was 0.34 cm3 g–1, based on N2 sorption analyses. Notably, the P-PT-CMP framework displayed a very high capacitance up to 400 F g–1 with superior capacitance stability up to 80% over 5000 cycles at 10 A g–1 according to the supercapacitor performance. In addition, we have evaluated the electrochemical performance of a symmetric coin supercapacitor, showing great potential for real-life applications in electrical energy storage (EES).

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We synthesized two hybrid organic–inorganic porous polymers (HPP) through the Heck reaction of 9,10 dibromoanthracene (A-Br2) or 1,3,6,8-tetrabromopyrene (P-Br4)/A-Br2 as co-monomers with octavinylsilsesquioxane (OVS), in order to afford OVS-A HPP and OVS-P-A HPP, respectively. The chemical structures of these two hybrid porous polymers were validated through FTIR and solid-state 13C and 29Si NMR spectroscopy. The thermal stability and porosity of these materials were measured by TGA and N2 adsorption/desorption analyses, demonstrating that OVS-A HPP has higher thermal stability (Td10: 579 °C) and surface area (433 m2 g−1) than OVS-P-A HPP (Td10: 377 °C and 98 m2 g−1) due to its higher cross-linking density. Furthermore, the electrochemical analysis showed that OVS-P-A HPP has a higher specific capacitance (177 F g −1 at 0.5 A F g−1) when compared to OVS-A HPP (120 F g −1 at 0.5 A F g−1). The electron-rich phenyl rings and Faradaic reaction between the π-conjugated network and anthracene moiety may be attributed to their excellent electrochemical performance of OVS-P-A HPP.

In this study, we synthesized three hybrid microporous polymers through Heck couplings of octavinylsilsesquioxane (OVS) with 2,5-bis(4-bromophenyl)-1,3,4-oxadiazole (OXD-Br2), tetrabromothiophene (Th-Br4), and 2,5-bis(4-bromophenyl)-3,4-diphenylthiophene (TPTh-Br2), obtaining the porous organic–inorganic polymers (POIPs) POSS-OXD, POSS-Th, and POSS-TPTh, respectively. Fourier transform infrared spectroscopy and solid state 13C and 29Si NMR spectroscopy confirmed their chemical structures. Thermogravimetric analysis revealed that, among these three systems, the POSS-Th POIP possessed the highest thermal stability (T5: 586 °C; T10: 785 °C; char yield: 90 wt%), presumably because of a strongly crosslinked network formed between its OVS and Th moieties. Furthermore, the specific capacity of the POSS-TPTh POIP (354 F g−1) at 0.5 A g−1 was higher than those of the POSS-Th (213 F g−1) and POSS-OXD (119 F g−1) POIPs. We attribute the superior electrochemical properties of the POSS-TPTh POIP to its high surface area and the presence of electron-rich phenyl groups within its structure.

We have successfully synthesized two types of two-dimensional conjugated microporous polymers (CMPs), Py-BSU and TBN-BSU CMPs, by using the Sonogashira cross-coupling reaction of BSU-Br2 (2,8-Dibromothianthrene-5,5′,10,10′-Tetraoxide) with Py-T (1,3,6,8-Tetraethynylpyrene) and TBN-T (2,7,10,15-Tetraethynyldibenzo[g,p]chrysene), respectively. We characterized the chemical structure, morphology, physical properties, and potential applications of these materials using various analytical instruments. Both Py-BSU and TBN-BSU CMPs showed high thermal stability with thermal decomposition temperatures (Td10) up to 371 °C and char yields close to 48 wt%, as determined by thermogravimetric analysis (TGA). TBN-BSU CMPs exhibited a higher specific surface area and porosity of 391 m2 g−1 and 0.30 cm3 g−1, respectively, due to their large micropore and mesopore structure. These CMPs with extended π-conjugated frameworks and high surface areas are promising organic electroactive materials that can be used as electrode materials for supercapacitors (SCs) and gas adsorption. Our experimental results demonstrated that the TBN-BSU CMP electrode had better electrochemical characteristics with a longer discharge time course and a specific capacitance of 70 F g−1. Additionally, the electrode exhibited an excellent capacitance retention rate of 99.9% in the 2000-cycle stability test. The CO2 uptake capacity of TBN-BSU CMP and Py-BSU CMP were 1.60 and 1.45 mmol g−1, respectively, at 298 K and 1 bar. These results indicate that the BSU-based CMPs synthesized in this study have potential applications in electrical testing and CO2 capture.