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)–CuCUS. Several vertical and flat orientations have been studied. All of these molecular configurations interact very weakly with the Cu₂O(1 1 1)–CuCUS 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)–CuCUS 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.
Applied Surface Science Vol. 256, Issue 15, p. 4764-4770