Crab shell-based hierarchical micro/meso-porous carbon as an efficient nano-adsorbent for CO/CH separation: experiments and DFT modeling.

In this study, we prepared a range of nanoporous carbon nano-adsorbents from crab shells (CSs) using KOH activation and evaluated their suitability for selective adsorption of CO/CH gas mixtures. We employed various characterization techniques, including XRD, FT-IR, SEM, Raman, TGA, and BET analysis, to assess the properties of these nano-adsorbents. Our investigation includes the systematic study of various parameters, such as activation time, activation temperature, and the KOH to CS activating agent ratio. The nanoporous carbons were evaluated for their CO adsorption capabilities at 1-10 bar and 25 ℃ condition. The results demonstrated that the CS-2-2-900 sample, activated for 1 h at 900 ℃ with a 2:1 ratio of KOH to CS, exhibited the highest gas adsorption capacity, reaching 7.217 mmol/g at a pressure of 10 bar under room temperature conditions. Additionally, the synthesized CS-2-2-900 sample displayed excellent surface area (914.85 m/g), a pore volume of 1.1 cm/g, and an average pore diameter of 4.82 nm. Furthermore, we functionalized the CSs to enhance their selectivity for ammonia adsorption. Using the Myers and Pravnitz theory, we calculated that the FCS-2-2-900 sample exhibited the highest selectivity, reaching 18.99 at 25 ℃ under pressures of up to 10 bar. To gain a more comprehensive understanding of the interactions between the adsorbents and the adsorbed molecules, as well as to identify the active sites involved in the adsorption process, we employed density functional theory (DFT). Our DFT calculations revealed that pyrrolic nitrogen and carboxylic sites played a significant role in enhancing the separation of CO in binary mixtures. In summary, nanoporous carbons derived from crab shells outperformed those derived from other waste materials. These functionalized porous nanocarbons represent promising adsorbents for the selective adsorption of CO gas in CO/CH mixtures due to their nitrogen content, high porosity, stability, and economic efficiency.