Selective Dinitrogen Capture from Coalbed Methane Using 2D Porphyrin-based Sheet with 3d Transition Metal Ion Sites: A First-principles Computational Study

Abstract

Selective dinitrogen (N₂) capture from coalbed methane (CBM) is significant in chemical industries, but it remains a challenge because of similar physicochemical properties of N₂ and CH₄. Herein, the adsorption of them on the 2D porphyrin sheets doped with various 3d transition metal ions (marked as MPor, M=Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn) were comparatively investigated by using density functional theory to screen a suitable adsorbent for CBM separation. Though systematical comparison of adsorption energies of gas molecules and Gibbs free energy change the N₂ desorption process on all MPor surfaces, FePor is confirmed to be a promising adsorbent because of its undemanding regeneration conditions and modest chemical bonding state with N₂ molecule. Further mechanism analysis reveals that the charge transferred from lone pair of N₂ molecule to d_z2 orbital of Fe ion and back-donated from d_xz and d_yz orbitals of Fe ion to the unoccupied π* orbital of N₂ molecule. Such hybridization of orbitals improves the selective adsorption of N₂ from CBM.

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