Roles of bulk γ(L)-Bi₂MoO₆ and surface β-Bi₂Mo₂O₉ in the selective catalytic oxidation of C₃H₆

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γ(L)-Bi₂MoO₆ (L: low temperature phase) catalysts, whose surface compositions have a Mo/Bi ratio above = 0.5, exhibited high selectivity in the partial oxidation of C₃H₆, while catalysts with Mo/Bi surface ratios near or below = 0.5 exhibited low selectivity. γ(L)-phase catalysts which have Mo/Bi surface ratios greater than = 0.5, were demonstrated to form β-Bi₂Mo₂O₉ on their surface. An interaction between the β- and γ(L)-phases was observed in these catalysts’ UV–vis spectra at 430 nm. The new β-phase material seems to grow along b-axis of γ(L)-phase, i.e., perpendicular to MoO₂–Bi₂O₂ layers. Structure visualizations revealed that the α-Bi₂Mo₃O₁₂, β-, and γ(H)-phases, which are selective catalysts, contain twin Mo tetrahedral structures, and that their Mo and Bi ions lie on the same plane. The pure γ(L)-phase does not contain this structure. A model for the very rapid transfer of oxygen between the γ(L)- and β-phases is discussed in relation to the kinetics of C₃H₆ oxidation.
2010-03-01