Probing the Positions of TeO Moieties in the Channels of the MoVNbTeO M1 Catalyst: A Density Functional Theory Model Study

With hybrid DFT calculations applied to periodic models of the bulk MoVNbTeO M1 catalyst, we examined how [TeO] 2+ species in the hexagonal channels of this material stabilize nearby reduced metal centers. In particular, an S2(Mo) site, with adjacent [TeO] 2+ moieties at both sides, is calculated to be reduced to Mo 5+ . The modeling study presented offers insight into how the redox behavior of V and Mo centers, a crucial aspect of the M1 catalyst for the selective partial oxidation of small hydrocarbons, may be fine-tuned via TeO moieties at various distances from the metal centers. Graphic Abstract TeO moieties in hexagonal channels, adjacent on either side of an S2(Mo) center, stabilize a gap state at the Mo center, facilitating its reduction to Mo 5+ .