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Title
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How oxygen vacancies activate dissociation on anatase (001)
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Author
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Abstract
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| The adsorption, dissociation, and diffusion of CO2 on the anatase (001) surface was studied using DFT by means of the generalized gradient approximation using the PerdewBurckeErnzerhof (PBE)-functional and applying corrections for long-range dispersion interactions. Different stable adsorption configurations were identified for the fully oxidized surface. The most stable adsorption configuration is the monodentated carbonate-like structure. Small energy barriers were identified for the conversion of a physisorbed to a chemisorbed configuration. CO2 dissociation is found to be unfeasible on the stoichiometric surface. The introduction of oxygen vacancy defects gives rise to new highly stable adsorption configurations with a stronger activation of the CO bonds. This leads to the possibility of exothermic dissociation of CO2 with barriers up to 22.2 kcal/mol, corresponding to chemical lifetimes of less than 4 s at 300 K. These reactions cause a CO molecule to be formed, which will easily desorb, and the reduced surface to become oxidized. It is clear that oxygen vacancy defects play a key role in the catalytic activity of an anatase (001) surface. Oxygen vacancies play an important role in the dissociation of CO2 on the anatase (001) surface, and will play a significant role in complex problems, such as the catalytic conversion of CO2 to value-added chemicals. |
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Language
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English
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Source (journal)
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The journal of physical chemistry: C : nanomaterials and interfaces. - Washington, D.C., 2007, currens
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Publication
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Washington, D.C.
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2016
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ISSN
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1932-7447
[print]
1932-7455
[online]
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DOI
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10.1021/ACS.JPCC.6B07459
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Volume/pages
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120
:38
(2016)
, p. 21659-21669
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ISI
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000384626800055
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Full text (Publisher's DOI)
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Full text (open access)
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Full text (publisher's version - intranet only)
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