The Role of Non‐Reactive Binding Sites in the AlVO 4 + +CO/AlVO 3 + +N 2 O Catalytic Cycle

The mechanisms involved in catalytic oxidation of CO by N 2 O promoted by the AlVO 3 + and AlVO 4 + ions are evaluated using temperature‐dependent rate constants and statistical modeling. Reactions were studied from 300–600 K using a selected ion flow tube (SIFT) apparatus, and the data compared to statistical modeling of proposed mechanisms previously identified by density functional theory (DFT) calculations. Reduction of N 2 O by AlVO 3 + was found to take place only by complexation to the Al site; however, attack on the V site also occurred and led to stable association complexes, reducing the overall efficiency of the reaction. As the AlVO 3 + (N 2 O) complex resulted from approach on the V site, it did not block the reactive Al site and was observed to further react with N 2 O to form AlVO 4 + (N 2 O). The oxidation of CO by AlVO 4 + was found to proceed solely by activation on the Al−O site; however, isomerization of complexes formed with CO initially complexed to the V site were found to add to the reactivity, especially at lower temperatures.