Adsorption of 2-chlorophenol on Cu2O(111)-Cu-CUS: A first-principles density functional study

作者：Altarawneh Mohammednoor; Radny Marian W^*; Smith Phillip V; Mackie John C; Kennedy Eric M; Dlugogorski Bogdan Z; Soon Aloysius; Stampfl Catherine

来源：Applied Surface Science, 2010, 256(15): 4764-4770.

DOI：10.1016/j.apsusc.2010.01.101

• 2-Chlorophenol
• PCDD/F
• Polychlorodibenzo-p-dioxins
• Polychlorodibenzofurans
• CuO
• DFT calculations

First-principles density functional theory and a periodic-slab model have been utilized to investigate the adsorption of a 2-chlorophenol molecule on a CuO(1 1 1) surface with a vacant Cu surface site, namely Cu2O(1 1 1)-Cu-CUS. Several vertical and flat orientations have been studied. All of these molecular configurations interact very weakly with the Cu2O(1 1 1)-Cu-CUS surface, an observation which also holds for clean copper surfaces and the Cu2O(1 1 0): CuO surface. Hydroxyl-bond dissociation assisted by the surface was found to be endoergic by 0.42-1.72 eV, depending predominantly on the position of the isolated H on the surface. In addition, the corresponding adsorbed 2-chlorophenoxy moiety was found to be more stable than a vacuum 2-chlorophenoxy radical by about 0.76 eV. Despite these predicted endoergicities, however, we would predict the formation of 2-chlorophenoxy radicals from gaseous 2-chlorophenol over the copper (I) oxide Cu2O(1 1 1)-Cu-CUS surface to be a feasible and important process in the formation of PCDD/Fs in the post-flame region where gas-phase routes are negligible.

• 出版日期2010-5-15