Micromesoporous Nitrogen-Doped Carbon Materials Derived from Direct Carbonization of Metal-Organic Complexes for...

Metal-organic complexes (MOCs) are considered as excellent precursors to prepare carbon materials, due to the fact that heteroatoms and functional groups can be naturally reserved in the resulting carbon materials through the carbonization. Herein, micromesoporous nitrogen-doped carbons MPNC-1 and MPNC-2 are successfully obtained by direct carbonization (800 °C, KOH activation) of metal-organic complexes DQA-1 and DQA-2. MPNC-1 and MPNC-2 exhibit high BET surface area (2368.9 and 2327.6 m² g^-1), pore volume (1.95 and 1.89 cm³ g^-1), and N contents (17.2% and 12.3%). At 25 °C and 1 bar, MPNC-1 and MPNC-2 show high CO₂ adsorption of 7.53 and 6.58 mmol g^-1, the estimated CO₂/N₂ selectivity are 20.5 and 22.6, indicating excellent promise for practical CO₂ adsorption and separation applications. Theoretical calculation indicates carbon surfaces with pyridinic-N, pyrrolic-N, and graphitic-N coexistence could strongly change the local electronic distribution and electrostatic surface potential, enhancing the CO₂ adsorption with adsorption energy of -58.96 kJ mol g^-1. Theoretical calculation also highlights that CO₂ adsorption mechanism is electrostatic interaction with a large green isosurface between CO₂ molecules and the carbon surface.