Formation of reactive oxygen by N2O decomposition over binuclear cationic sites of Fe-ferrierite zeolite: Periodic DFT + U study

Abstract The electronic nature of sites over Fe-ferrierite zeolite stabilizing active α-oxygen is analyzed by the periodic DFT + U approach. It is shown that two antiferromagnetically coupled Fe 2+ cations with bridging OH-bonds form a stable bi-nuclear site of the [Fe 2+ Fe 2+ ] doped FER complex. Frontier orbitals of this complex populated by two electrons with minority spins are localized in the bandgap. As a result, [Fe 2+ Fe 2+ ] unit acquires the properties of a binuclear Lewis acid dipolarophile for 1,3-dipole N 2 O. First reaction step of N 2 O decomposition follows the Huisgen′s concept of the 1,3-dipolar cycloaddition concept followed by the formation of reactive oxygen species Fe O.