Nitrogen and sulfur Co-doped microporous activated carbon macro-spheres for CO₂ capture

Millimeter-sized nitrogen and sulfur co-doped microporous activated carbon spheres (NSCSs) were first synthesized from poly(styrene-vinylimidazole-divinylbenzene) resin spheres through concentrated H₂SO₄ sulfonation, carbonization and KOH activation. Styrene (ST) and N-vinylimidazole (VIM) were carbon and nitrogen sources, while the sulfonic acid functional groups introduced by the simple concentrated sulfuric acid sulfonation worked simultaneously as cross-linking agent and sulfur source during the following thermal treatments. It was found that the surface chemistries, textural structures, and CO₂ adsorption performances of the NSCSs were significantly affected by the addition of VIM. The NSCS-4-700 sample with a molar ratio of ST: VIM = 1: 0.75 showed the best CO₂ uptake at different temperatures and pressures. An exhaustive adsorption evaluation indicated that CO₂ sorption at low pressures originated from the synergistic effect of surface chemistry and micropores below 8.04 Å, while at the moderate pressure of 8.0 bar, CO₂ uptake was dominated by the volume of micropores. The thermodynamics suggested the exothermic and orderly nature of the adsorption process, which was dominated by a physisorption mechanism. The high CO₂ adsorption capacity, fast kinetic adsorption rate, and great regeneration stability of the nitrogen and sulfur co-doped activated carbon spheres indicated that the as-prepared carbon adsorbents were good candidates for large-scale CO₂ capture.