Please use this identifier to cite or link to this item: http://hdl.handle.net/1959.13/919956

OpenURL Link
Title
Dissociative adsorption of molecular oxygen on the Cu(001) surface: a density functional theory study
Author/Creator
Suleiman, I. A.;  Radny, M. W.;  Gladys, M. J.;  Smith, P. V.;  Mackie, J. C.;  Kennedy, E. M.;  Dlugogorski, B. Z.
Institution
The University of Newcastle. Faculty of Engineering & Built Environment, School of Engineering
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.
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
Date
2009
Publisher
School of Mechanical and Mining Engineering, University of Queensland
Keyword(s)
DFT;  copper;  oxygen;  adsorption;  Deacon reaction;  transition state
Resource Type
conference paper
Identifier
http://hdl.handle.net/1959.13/919956
Identifier
ISBN:9781864999802
Reviewed
Reviewed
23 Visitors 25 Hits 0 Downloads
Save/E-mail Citation
Citation Format
E-mail Address
Subject
"Dissociative adsorption of molecular oxygen on the Cu(001) surface: a density functional theory study"
 
OR