Surface chemistry of phase-pure M1 MoVTeNb oxide during operation in selective oxidation of propane to acrylic acid

The surface of a highly crystalline MoVTeNb oxide catalyst for selective oxidation of propane to acrylic acid composed of the M1 phase has been studied by infrared spectroscopy, microcalorimetry, and in situ photoelectron spectroscopy. The acid–base properties of the catalyst have been probed by NH₃ adsorption showing mainly Brønsted acidity that is weak with respect to concentration and strength of sites. Adsorption of propane on the activated catalyst reveals the presence of a high number of energetically homogeneous propane adsorption sites, which is evidenced by constant differential heat of propane adsorption qdᵢff,ᵢₙᵢₜᵢₐₗ=57kJmol⁻¹ until the monolayer coverage is reached that corresponds to a surface density of approximately 3 propane molecules per nm² at 313K. The decrease of the heat to qdᵢff,ᵢₙᵢₜᵢₐₗ=40kJmol⁻¹ after catalysis implies that the surface is restructured under reaction conditions. The changes have been analyzed with high-pressure in situ XPS while the catalyst was working applying reaction temperatures between 323 and 693K, different feed compositions containing 0mol.% and 40mol.% steam and prolonged reaction times. The catalytic performance during the XPS experiments measured by mass spectrometry is in good agreement with studies in fixed-bed reactors at atmospheric pressure demonstrating that the XPS results taken under operation show the relevant active surface state. The experiments confirm that the surface composition of the M1 phase differs significantly from the bulk implying that the catalytically active sites are no part of the M1 crystal structure and occur on all terminating planes. Acrylic acid formation correlates with surface depletion in Mo⁶⁺ and enrichment in V⁵⁺ sites. In the presence of steam in the feed, the active ensemble for acrylic acid formation appears to consist of V⁵⁺ oxo-species in close vicinity to Te⁴⁺ sites in a Te/V ratio of 1.4. The active sites are formed under propane oxidation conditions and are embedded in a thin layer enriched in V, Te, and Nb on the surface of the structural stable self-supporting M1 phase.