Triple Templates Directed Synthesis of Nitrogen‐Doped Hierarchically Porous Carbons from Pyridine Rich Monomer as Efficient and Reversible SO2 Adsorbents

Herein, a variety of 2,6-diaminopyridine (DAP) derived nitrogen-doped hierarchically porous carbon (DAP-NHPC-T) prepared from carbonization-induced structure transformation of DAP-Zn-SiO₂-P123 nanocomposites are reported, which are facilely prepared from solvent-free co-assembly of block copolymer templates P123 with pyridine-rich monomer of DAP, Zn(NO₃)₂ and tetramethoxysilane. In the pyrolysis process, P123 and SiO₂ templates promote the formation of mesoporous and supermicroporous structures in the DAP-NHPC-T, while high-temperature volatilization of Zn contributed to generation of micropores. The DAP-NHPC-T possess large BET surface areas (≈956-1126 m² g^-1), hierarchical porosity with micro-supermicro-mesoporous feature and high nitrogen contents (≈10.44-5.99 at%) with tunable density of pyridine-based nitrogen sites (≈5.99-3.32 at%), exhibiting good accessibility and reinforced interaction with SO₂. Consequently, the DAP-NHPC-T show high SO₂ capacity (14.7 mmol g^-1, 25 °C and 1.0 bar) and SO₂/CO₂/N₂ IAST selectivities, extraordinary dynamic breakthrough separation efficiency and cycling stability, far beyond any other reported nitrogen-doped metal-free carbon. As verified by in situ spectroscopy and theoretical calculations, the pyridine-based nitrogen sites of the DAP-NHPC-T boost SO₂ adsorption via the unique charge transfer, the adsorption mechanism and reaction model have been finally clarified.