Aberration-corrected high-angle annular dark-field scanning transmission electron microscopy (HAADF-STEM) has been used to image the basal {001} plane of the catalytically relevant M1 phase in MoVTeNb complex oxides. Facets {010}, {120}, and {210} are identified as the most frequent lateral termination planes of the crystals. Combination of STEM with He ion microscopy (HIM) images, Rietveld analysis, and kinetic tests reveals that the activation of ethane is correlated to the availability of facets {001}, {120}, and {210} at the surface of M1 crystals. The lateral facets {120} and {210} expose crystalline positions related to the typical active centers described for propane oxidation. Conversely, the low activity of the facet {010} is attributed to its configuration, consisting of only stable M6 O21 units connected by a single octahedron. Thus, we quantitatively demonstrated that differences in catalytic activity among M1 samples of equal chemical composition depend primarily on the morphology of the particles, which determines the predominant terminating facets.

A novel pathway of increasing the surface density of catalytically active oxygen radical sites on a MoVTeNb oxide (M1 phase) catalyst during alkane oxidative dehydrogenation is reported. The novel sites form when a fraction of Te is reduced and emitted from the M1 crystals under catalytic operating conditions, without compromising structural integrity of the catalyst framework. Density functional theory calculations show this Te reduction induces multiple inter-related electron transfers, and the associated cooperative effects lead to the formation of O radicals. The in situ observations identify complex dynamic changes in the catalyst on an atomistic level, highlighting a new way to tailor structure and dynamics for highly active catalysts.

Ethane oxidative dehydrogenation (ODH) is an alternative route for ethene production. Crystalline M1 phase of Mo-V mixed metal oxide is an excellent catalyst for this reaction. Here we show a hydrothermal synthesis method that generates M1 phases with high surface areas starting from poorly soluble metal oxides. Use of organic additives allows control of the concentration of metals in aqueous suspension. Reactions leading to crystalline M1 take place at 190 °C, i.e., approximately 400 °C lower than under current synthesis conditions. The evolution of solvated polyoxometalate ions and crystalline phases in the solid is monitored by spectroscopies. Catalysts prepared by this route show higher ODH activity compared to conventionally prepared catalysts. The higher activity is due not only to the high specific surface area but also to the corrugated lateral termination of the M1 crystals, as seen by atomic resolution electron microscopy, exposing a high concentration of catalytically active sites.

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