The Role of Non‐Reactive Binding Sites in the AlVO4++CO/AlVO3++N2O Catalytic Cycle
Abstract
The mechanisms involved in catalytic oxidation of CO by N2O promoted by the AlVO3+ and AlVO4+ 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 N2O by AlVO3+ 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 AlVO3+(N2O) complex resulted from approach on the V site, it did not block the reactive Al site and was observed to further react with N2O to form AlVO4+(N2O). The oxidation of CO by AlVO4+ 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.
Document Details
- Document Type
- Pub Defense Publication
- Publication Date
- Sep 19, 2018
- Source ID
- 10.1002/cphc.201800714
Entities
People
- Albert A Viggiano
- Brendan C Sweeny
- Nicholas S Shuman
- Shaun G Ard
Organizations
- Air Force Office of Scientific Research
- Air Force Research Laboratory
- Boston College
- National Academy of Sciences