- Title
- Dissociative adsorption of molecular oxygen on the Cu(001) surface: a density functional theory study
- Creator
- Suleiman, I. A.; Radny, M. W.; Gladys, M. J.; Smith, P. V.; Mackie, J. C.; Kennedy, E. M.; Dlugogorski, B. Z.
- Relation
- Australian Combustion Symposium 2009. Proceedings of the Australian Combustion Symposium 2009 (Brisbane, Qld 2-4 December, 2009) p. 103-106
- Relation
- http://www.mech.uq.edu.au/conferences/ACS2009
- Publisher
- School of Mechanical and Mining Engineering, University of Queensland
- Resource Type
- conference paper
- Date
- 2009
- Description
- The presence of atomic oxygen on catalytic surfaces is essential for initiating the oxidation of hydrogen chloride to produce chlorine via the so-called Deacon process. This process provides molecular chlorine for the formation of polychlorinated dibenzo-p-dioxins and polychlorinated dibenzofurans (PCDD/F) in combustion. In this paper, the dissociative adsorption of molecular oxygen on the Cu(001) surface has been studied using density functional theory. A periodic p(3X2) 4 layer slab was adopted to simulate the adsorption of both molecular and atomic oxygen at a number of adsorption sites. We have found that a bridge-bridge configuration is the most stable structure on Cu(001) with the O₂ molecule adsorbed horizontally. The activation barrier for the dissociative adsorption of O₂ resulting from this configuration was calculated to be 5.1 kcal/mol, with an equivalent transition temperature of ~66 K. This is in good agreement with the experimental value of 40 K obtained under ultra high vacuum conditions. We have also found that a less energetically favourable, vertically oriented, physisorbed structure leads to an almost negligible reaction barrier for the dissociative adsorption of O₂ on Cu(001) (1.5 kcal/mol), with an equivalent transition temperature of ~20 K.
- Subject
- DFT; copper; oxygen; adsorption; Deacon reaction; transition state
- Identifier
- http://hdl.handle.net/1959.13/919956
- Identifier
- uon:9034
- Identifier
- ISBN:9781864999802
- Language
- eng
- Full Text
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