Single-Site Vanadyl Species Isolated within Molybdenum Oxide Monolayers in Propane Oxidation

The cooperation of metal oxide subunits in complex mixed metal oxide catalysts for selective oxidation of alkanes still needs deeper understanding to allow for a rational tuning of catalyst performance. Herein we analyze the interaction between vanadium and molybdenum oxide species in a monolayer supported on mesoporous silica SBA-15. Catalysts with variable Mo/V ratio between 10 and 1 were studied in the oxidation of propane and characterized by FTIR, Raman, and EPR spectroscopies, temperature-programmed reduction, UV/vis spectroscopy in combination with DFT calculations, and time-resolved experiments to analyze the redox properties of the catalysts. Molybdenum oxide (sub)­monolayers on silica contain mainly dioxo (Si–O−)₂Mo­(O)₂ species. Dilution of silica-supported vanadium oxide species by (Si–O−)₂Mo­(O)₂ prevents the formation of V–O–V bonds, which are abundant in the pure vanadium oxide catalyst that predominantly contains two-dimensional vanadium oxide oligomers. Existing single vanadyl (Si–O−)₃V­(O) sites and neighboring (Si–O−)₂Mo­(O)₂ sites do not strongly interact. The rates of reduction in propane and of oxidation in oxygen are lower for single metal oxide sites compared to those for oligomers. The rate of propane oxidation correlates with the overall redox rates of the catalysts but not linearly with the chemical composition. Retarded redox behavior facilitates selectivity toward acrolein on single-site catalysts. The abundance of M–O–M bonds is more important in terms of activity and selectivity compared to the nature of the central atom (molybdenum versus vanadium).