Is [FeO]²⁺ the Active Center Also in Iron Containing Zeolites? A Density Functional Theory Study of Methane Hydroxylation Catalysis by Fe-ZSM-5 Zeolite

Arguments are put forward that the active alpha-oxygen site in the Fe-ZSM-5 catalyst consists of the FeO(2+) moiety. It is demonstrated that this zeolite site for FeO(2+) indeed obeys the design principles for high reactivity of the FeO(2+) moiety proposed earlier: a ligand environment consisting of weak equatorial donors (rather oxygen based than nitrogen based) and very weak or absent trans axial donor. The alpha-oxygen site would then owe its high reactivity to the same electronic structure features that lends FeO(2+) its high activity in biological systems, as well as in the classical Fenton chemistry.