A great number of C-C polymerization has been applied in the synthesis of nanoporous polymers. By us-ing these polymerization techniques, however, introducing a large aromatic subunit such as graphene na-noribbons into a 3D polymer has remained a challenge due to the low solubility of monomers and its high affinity to restack to form graphite. In this sense, bottom-up synthetic approach is an attractive method to incorporate GNRs into polymers, for example by introducing a permanent ‘spacer’ such as porosity be-tween GNRs. In this thesis, I present a new polymerization strategy, that is catalyst-free Diels-Alder cy-cloaddition polymerization and subsequent $FeCl_3-catalyzed$ intramolecular cyclodehydrogenation reac-tion, to introduce graphene nanoribbons up to 2 nm in length and 1.1 nm in width into a graphene nano-ribbon framework (GNF). The first graphene nanoribbon framework showed high thermal stability up to $400^\circ C$ in air with relatively narrow pore size distribution and exhibited BET surface area of $679 m^2 g^{-1}$. GNF possesses high affinity for $H_2$ (Qst 7.7 kJ $mol^{-1}$, 1.03 wt% at 77 K, 1 bar), $CO_2$ (Qst = 28.7 kJ $mol^{-1}$, $94.6 mg g^{-1}$ at 273 K, 1 bar), and $CH_4$ (Qst = 24. 1 kJ $mol^{-1}$, $11.5 mg g^{-1}$ at 273 K, 1 bar). The enhance-ment in gas affinities was attributed to the unique combination of large $\pi$-surface area arising from gra-phene nanoribbons and small pores (~5.8 A) from $\pi - \pi$ stacking interactions in GNF. The application of GNF can also be extended to natural gas purification process with remarkable $CO_2/CH_4$ (5:95) selectivity of 62.7, which is being the highest value reported to date at 298 K. While previous studies focus mostly on increasing the affinity of $CO_2$ in order to increase $CO_2/CH_4$ selectivity, our approach utilized molecu-lar sieving effect, considering relatively larger kinetic diameter of $CH_4 (3.8 \AA)$ compared to that of $CO_2 (3.30 \AA)$, thus offering low-cost efficient alternative for natural gas purification process.
대부분의 그래핀 나노리본은 용해도가 낮아 3차원의 고분자 형태로 만들기엔 한계가 있다. 또한 방향족화의 $\pi- \pi$ 결합으로 인해 흑연의 형태로 돌아가려는 성질 때문에 현재까지는 3차원의 그래핀 나노리본 연구가 극히 제한적이었다. 이에 상기문제점을 해결하기 위하여 그래핀 나노리본 사이에 ‘spacer’를 달아서 흑연의 형태로는 돌아가지 않으면서 3차원 구조체의 특성을 가지는 물질로 합성하였다. 두 단계의 합성을 통하여 그래핀 나노리본을 3차원 형태의 다공성 고분자에 결합시켜 다공성의 흡착제를 제조하는 방법을 완성하였다. 그래핀 나노리본 구조체의 수소, 이산화탄소, 메탄가스 흡착 실험에서 본 구조체는 각각의 기체에서 높은 흡착열을 보였다. 뿐만 아니라 그래핀 나노리본의 $\pi- \pi$ 결합으로 인해 분자체(molecular sieve)의 특성을 가지고 있으면서 메탄가스/이산화탄소의 혼합기체에서 이산화탄소의 선택도가 높은 것으로 보였다.
