Robust Nitrogen-Doped Microporous Carbon via Crown Ether-Functionalized Benzoxazine-Linked Porous Organic Polymers...

Nitrogen-doped carbon materials, characterized by abundant microporous and nitrogen functionalities, exhibit significant potential for carbon dioxide capture and supercapacitors. In this study, a class of porous organic polymer (POP) were successfully synthesized by linking Cr-TPA-4BZ-Br₄ and tetraethynylpyrene (Py-T). The model benzoxazine monomers of Cr-TPA-4BZ and Cr-TPA-4BZ-Br₄ were synthesized using the traditional three-step method [involving CH═N formation, reduction by NaBH₄, and Mannich condensation]. Subsequently, the Sonogashira coupling reaction connected the Cr-TPA-4BZ-Br₄ and Py-T monomers, forming Cr-TPA-4BZ-Py-POP. The successful synthesis of Cr-TPA-4BZ-Br₄ and Cr-TPA-4BZ-Py-POP was confirmed through various analytical techniques. After verifying the successful synthesis of Cr-TPA-4BZ-Py-POP, carbonization and KOH activation procedures were conducted. These crucial steps led to the formation of poly(Cr-TPA-4BZ-Py-POP)-800, a carbon material with a structure akin to graphite. In practical applications, poly(Cr-TPA-4BZ-Py-POP)-800 exhibited a noteworthy CO₂ adsorption capacity of 4.4 mmol/g, along with specific capacitance values of 397.2 and 159.2 F g^-1 at 0.5 A g^-1 (measured in a three-electrode cell) and 1 A g^-1 (measured in a symmetric coin cell), respectively. These exceptional dual capabilities stem from the optimal ratio of heteroatom doping. The outstanding performance of poly(Cr-TPA-4BZ-Py-POP)-800 microporous carbon holds significant promise for addressing contemporary energy and environmental challenges, making substantial contributions to both sectors.