Niobium Insertion into αII-VOPO4: Tuning the Catalytic Properties for Selective Oxidation

A holistic understanding of the key catalytic features of vanadyl(IV) pyrophosphate enabling high maleic anhydride (MAN) yields in n-butane oxidation has fostered a debate which has continued since the finding of the catalyst. Under reaction conditions, vanadium(V) orthophosphate structure fragments were detected on the surface of the catalyst. However, single-phase αII- and β-VVOPO4 reveal a much lower catalytic performance. This study shows that introducing Nb into αII-VOPO4 forming a solid solution (V1-xNbx)OPO4 yields a bulk material with tunable catalytic properties. Selectivities of SMAN = 48% at a conversion of Xn‑butane = 30% on (V0.1Nb0.9)OPO4 are shown to be related to the isolation of surface V-sites, which surpass known VOPO4 catalysts by far. A boost in the overall n-butane consumption and MAN selectivity under alkane-rich feed conditions is shown to be another characteristic of (V1-xNbx)OPO4, leading to a highly increased MAN productivity. XPS studies reveal that a progressive replacement of V by Nb induces a reduction of the averaged oxidation state of near-surface V from +4.7 to +4.3, a finding that correlates linearly with an elevated MAN selectivity. This study experimentally confirms site isolation and electronic environment of the near-surface V-species as the key catalytic properties, from which catalyst design rules are derived to optimize partial oxidation reactions.