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.

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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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