Here we show that the introduction of N into a carbon surface facilitates the hydrogen-bonding interactions between the carbon surface and CO2 molecules, which accounts for the superior CO2 uptake of the N-doped activated carbons. This new finding challenges the long-held viewpoint that acid–base interactions between N-containing basic functional groups and acidic CO2 gas are responsible for the enhanced CO2 capture capacity of N-doped carbons.
Microporous carbon materials with extremely small pore size are prepared by employing polyaniline as a carbon precursor and KOH as an activating agent. CO2 sorption performance of the materials is systematically investigated at the temperatures of 0, 25 and 75 °C. The prepared carbons show very high CO2 uptake of up to 1.86 and 1.39 mmol g−1 under 1 bar, 75 °C and 0.15 bar, 25 °C, respectively. These values are amongst the highest CO2 capture amounts of the known carbon materials. The relation between CO2 uptake and pore size at different temperatures is studied. An interesting and innovative point that the micropores with pore size smaller than a critical value play a crucial role in CO2 adsorption at different temperatures is demonstrated. It is found that the higher the sorption temperature is, the smaller this critical value of pore size is. Pores smaller than 0.54 nm are manifested to determine CO2 capture capacity at high sorption temperature, e.g. 75 °C. This research proposes a basic principle for designing highly efficient CO2 carbon adsorbents; that is, the adsorbents should be primarily rich in extremely small micropores.