CO₂ Adsorption on N-Doped Porous Biocarbon Synthesized from Biomass Corncobs in Simulated Flue Gas

This study was to develop a low-cost N-doped porous biocarbon adsorbent that can directly adsorb CO₂ in high-temperature flue gas from fossil fuel combustion. The porous biocarbon was prepared by nitrogen doping and nitrogen-oxygen codoping through K₂CO₃ activation. Results showed that these samples exhibited a high specific surface area of 1209-2307 m²/g with a pore volume of 0.492-0.868 cm³/g and a nitrogen content of 0.41-3.3 wt %. The optimized sample CNNK-1 exhibited a high adsorption capacity of 1.30 and 0.27 mmol/g in the simulated flue gas (14.4 vol % CO₂ + 85.6 vol % N₂) and a high CO₂/N₂ selectivity of 80 and 20 at 25 and 100 °C and 1 bar, respectively. Studies revealed that too many microporous pores could hinder CO₂ diffusion and adsorption due to the decrease of CO₂ partial pressure and thermodynamic driving force in the simulated flue gas. The CO₂ adsorption of the samples was mainly chemical adsorption at 100 °C, which depended on the surface nitrogen functional groups. Nitrogen functional groups (pyridinic-N and primary and secondary amines) reacted chemically with CO₂ to produce graphitic-N, pyrrolic-like structures, and carboxyl functional groups (-N-COOH). Nitrogen and oxygen codoping increased the amount of nitrogen doping content in the sample, but acidic oxygen functional groups (carboxyl groups, lactones, and phenols) were introduced, which weakened the acid-base interactions between the sample and CO₂ molecules. It was demonstrated that SO₂ and water vapor had inhibition effects on CO₂ adsorption, while NO nearly has no effect on the complex flue gas. Cyclic regenerative adsorption showed that CNNK-1 possessed excellent regeneration and stabilization ability in complex flue gases, indicating that corncob-derived biocarbon had excellent CO₂ adsorption in high-temperature flue gas.