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The Role of Non‐Reactive Binding Sites in the AlVO 4 + +CO/AlVO 3 + +N 2 O Catalytic Cycle
Author(s) -
Sweeny Brendan C.,
Ard Shaun G.,
Shuman Nicholas S.,
Viggiano Albert A.
Publication year - 2018
Publication title -
chemphyschem
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.016
H-Index - 140
eISSN - 1439-7641
pISSN - 1439-4235
DOI - 10.1002/cphc.201800714
Subject(s) - chemistry , catalysis , isomerization , ion , reaction rate constant , reactivity (psychology) , analytical chemistry (journal) , kinetics , chromatography , organic chemistry , medicine , physics , alternative medicine , pathology , quantum mechanics
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.