In this study, we prepared a series of conjugated microporous polymers (CMPs) through Sonogashira–Hagihara cross-couplings of a tetrabenzonaphthalene (TBN) monomer with pyrene (Py), tetraphenylethylene (TPE), and carbazole (Car) units and examined their chemical structures, thermal stabilities, morphologies, crystallinities, and porosities. TBN–TPE-CMP possessed a high surface area (1150 m2 g–1) and thermal stability (T d10 = 505 °C; char yield = 68 wt %) superior to those of TBN–Py-CMP and TBN–Car-CMP. To improve the conductivity of the TBN-CMP materials, we blended them with highly conductive single-walled carbon nanotubes (SWCNTs). Electrochemical measurements revealed that the TBN–Py-CMP/SWCNT nanocomposite had high capacitance (430 F g–1) at a current density of 0.5 A g–1 and outstanding capacitance retention (99.18%) over 2000 cycles; these characteristics were superior to those of the TBN–TPE-CMP/SWCNT and TBN–Car-CMP/SWCNT nanocomposites.

In this paper we report the construction of a hollow microtubular triazine‐ and benzobisoxazole‐based covalent organic framework (COF) presenting a sponge‐like shell through a template‐free [3+2] condensation of the planar molecules 2,4,6‐tris(4‐formylphenyl)triazine (TPT‐3CHO) and 2,5‐diaminohydroquinone dihydrochloride (DAHQ‐2HCl). The synthesized COF exhibited extremely high crystallinity, a high surface area (ca. 1855 m2 g−1), and ultrahigh thermal stability. Interestingly, a time‐dependent study of the formation of the hollow microtubular COF having a sponge‐like shell revealed a transformation from initial ribbon‐like crystallites into a hollow tubular structure, and confirmed that the hollow nature of the synthesized COF was controlled by inside‐out Ostwald ripening, while the non‐interaction of the crystallites on the outer surface was responsible for the sponge‐like surface of the tubules. This COF exhibited significant supercapacitor performance: a high specific capacitance of 256 F g−1 at a current density of 0.5 A g−1, excellent cycling stability (98.8 % capacitance retention over 1850 cycles), and a high energy density of 43 Wh kg−1. Such hollow structural COFs with sponge‐like shells appear to have great potential for use as high‐performance supercapacitors in energy storage applications.

There is currently a pursuit of synthetic approaches for designing porous carbon materials with selective CO2 capture and/or excellent energy storage performance that significantly impacts the environment and the sustainable development of circular economy. In this study we prepared a new bio-based benzoxazine (AP-BZ) in high yield through Mannich condensation of apigenin, a naturally occurring phenol, with 4-bromoaniline and paraformaldehyde. We then prepared a PA-BZ porous organic polymer (POP) through Sonogashira coupling of AP-BZ with 1,3,6,8-tetraethynylpyrene (P-T) in the presence of Pd(PPh3)4. In situ Fourier transform infrared spectroscopy and differential scanning calorimetry revealed details of the thermal polymerization of the oxazine rings in the AP-BZ monomer and in the PA-BZ POP. Next, we prepared a microporous carbon/metal composite (PCMC) in three steps: Sonogashira coupling of AP-BZ with P-T in the presence of a zeolitic imidazolate framework (ZIF-67) as a directing hard template, affording a PA-BZ POP/ZIF-67 composite; etching in acetic acid; and pyrolysis of the resulting PA-BZ POP/metal composite at 500 °C. Powder X-ray diffraction, thermogravimetric analysis, scanning electron microscopy, transmission electron microscopy, and Brunauer–Emmett–Teller (BET) measurements revealed the properties of the as-prepared PCMC. The PCMC material exhibited outstanding thermal stability (Td10 = 660 °C and char yield = 75 wt%), a high BET surface area (1110 m2 g–1), high CO2 adsorption (5.40 mmol g–1 at 273 K), excellent capacitance (735 F g–1), and a capacitance retention of up to 95% after 2000 galvanostatic charge–discharge (GCD) cycles; these characteristics were excellent when compared with those of the corresponding microporous carbon (MPC) prepared through pyrolysis of the PA-BZ POP precursors with a ZIF-67 template at 500 °C.

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In this study we synthesized two tetraphenyl-p-phenylenediamine-based covalent organic frameworks (TPPDA-TPPyr and TPPDA-TPTPE COFs) for potential use in high-performance electrochemical supercapacitors.