The Potential of MN4-GPs (M = Mn, Fe, Co, Ni, Cu, Mo) as Adsorbents for the Efficient Separation of CH4 from CO2 and H2S

Carbon dioxide (CO₂) and hydrogen sulfide (H₂S) as harmful gases are always associated with methane (CH₄) in natural gas, biogas, and landfill gas. Given that chemisorption and physisorption are the key gas separation technologies in industry, selecting appropriate adsorbents is crucial to eliminate these harmful gases. The adsorption of CH₄, CO₂, and H₂S has been studied based on the density functional theory (DFT) in this work to evaluate the feasibility of transition metal (M = Mn, Fe, Co, Ni, Cu, Mo) porphyrin-like moieties embedded in graphene sheets (MN₄-GPs) as adsorbents. It was found that the interactions between gas molecules and MN₄-GPs (M = Mn, Fe, Co, Ni, Cu, Mo) are different. The weaker interactions between CH₄ and MN₄-GPs (M = Co, Ni, Cu, Mo) than those between CO₂ and MN₄-GPs or between H₂S and MN₄-GPs are beneficial to the separation of CH₄ from CO₂ and H₂S. The maximum difference in the interactions between gas molecules and MoN₄-GPs means that MoN₄-GPs have the greatest potential to become adsorbents. The different interfacial interactions are related to the amount of charge transfer, which could promote the formation of bonds between gas molecules and MN₄-GPs to effectively enhance the interfacial interactions.