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Dimethyl ether (DME) reacts to form formaldehyde with high selectivity at 500−600 K on MoOx−ZrO2 catalysts with a wide range of MoOx surface density (0.5−50.1 Mo/nm2) and local structure (monomers, oligomers, MoO3 crystallites, and ZrMo2O8). Reaction rates (per Mo-atom) increased markedly as MoOx surface density increased from 2.2 to 6.4 Mo/nm2 and two-dimensional polymolybdates and MoO3 clusters became the prevalent active species. The rate of incipient stoichiometric reduction of MoOx−ZrO2 samples in H2 also increased with increasing MoOx surface density, suggesting that catalytic turnovers involve redox cycles that become faster as the size and dimensionality of MoOx domains increase. DME reaction rates (per Mo-atom) decreased as MoOx surface densities increased above 6.4 Mo/nm2, as MoO3 and ZrMo2O8 clusters with increasingly inaccessible MoOx species form. On MoOx and ZrMo2O8, areal reaction rates reach a constant value at MoOx surface densities above 10 Mo/nm2, as the exposed surfaces become covered ...

the journal of physical chemistry b

Zirconia-Supported MoO<i><sub>x</sub></i> Catalysts for the Selective Oxidation of Dimethyl Ether to Formaldehyde: Structure, Redox Properties, and Reaction Pathways

Zirconia-Supported MoOx Catalysts for the Selective Oxidation of Dimethyl Ether to Formaldehyde: Structure, Redox Properties, and Reaction Pathways

Zirconia-Supported MoO_x Catalysts for the Selective Oxidation of Dimethyl Ether to Formaldehyde: Structure, Redox Properties, and Reaction Pathways