Simulated temperature programmed desorption experiments for nanoceria powders
| Autor: | Jolla Kullgren, Dou Du, Peter Broqvist, Kersti Hermansson, Bojana Kocmaruk |
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| Rok vydání: | 2020 |
| Předmět: |
Solid-state chemistry
010405 organic chemistry Thermal desorption spectroscopy Coordination number chemistry.chemical_element Nanoparticle 010402 general chemistry 01 natural sciences Oxygen Catalysis 0104 chemical sciences Adsorption chemistry Physical chemistry Molecule Density functional theory Physical and Theoretical Chemistry |
| Zdroj: | Journal of Catalysis. 384:252-259 |
| ISSN: | 0021-9517 |
| Popis: | Density functional theory calculations (DFT), coupled with microkinetic modelling, have been used to simulate Temperature Programmed Desorption (TPD) experiments for calcined ceria nanopowders with the aim to gain insight into the chemistry governing their high redox activity. Our simulations consider two main nanoparticle models. One is a perfect ceria octahedron supercharged with adsorbed oxygen molecules turned into superoxide ions, as has previously been used to explain the enhanced oxygen storage capacity (OSC) in nanoceria. The other model is a variant where we have introduced oxygen vacancies under ridge Ce ions, thereby reducing their coordination numbers to five. The results from our microkinetic modelling suggest that including such five-coordinated Ce adsorption sites results in a TPD spectrum that better matches the experimental counterpart in terms of both peak position and width. In addition, this new structural model allows for the co-existence of Ce 3 + ions, superoxide ions and O2 molecules, as seen in experiments in the literature. |
| Databáze: | OpenAIRE |
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