The sulfurization mechanism of H2S on the ZnO(10 (1) over bar0) surface during the desulfurization of coal gas was investigated by using periodic density functional theory (DFT) calculations. The adsorption of H2S, SH, atomic S, and atomic H, as well as the coadsorption of SH and an H atom, and the coadsorption of S and two H atoms, were initially examined to identify energetically favorable intermediates. Potential energy profiles for three paths of H2S-ZnO(10 (1) over bar0) interactions producing H-2 and H2O were obtained, respectively. Our results show that H2S is preferred to dissociatively adsorb on the ZnO(10 (1) over bar0) surface, followed by dehydrogenation process to form sulfur species. Molecular-level calculations demonstrate that H2O formation via the H2S-ZnO interaction is the most probable reaction pathway both kinetically and thermodynamically. ZnO has double functions during the desulfurization of H2S. One is as a catalyst to accelerate the dissociation of H2S, while the other is as the reactant participating in the reaction of H2S with ZnO to form H2O. (C) 2012 Elsevier B.V. All rights reserved.