A bulk gamma-Al2O3 catalyst shows high selectivity for propane dehydrogenation upon pretreatment and co-feeding with H2S. The reaction kinetics, deactivation rates, and active sites for propane dehydrogenation on this catalyst were characterized using fixed bed conversion studies, NH3-TPD, O-2-TPO, XPS, and density functional theory (DFT). Specifically, we observe that the selectivity to propylene was 94% at ca. 16% propane conversion at 560 degrees C for a C3H8:H-2:H2S ratio of 1.1:1:0.1 on gamma-Al2O3. Our results indicate that H2S can irreversibly modify the active sites of gamma-Al2O3, postulated to be defect sites on the 110 facet comprised of a tri-coordinated Al atom, such that the modified site was more active and selective towards propylene and less inhibited by co-fed H2S. Along with XPS and O-2-TPO, the dehydrogenation-regeneration experiments suggest the formation of sulfurous coke and strong adsorption of reaction products result in a less active catalyst. This study shows the potential of alumina/metal-sulfide as an earth-abundant and relatively benign class of catalysts for alkane activation, especially in the context of sour natural gas upgrading. (C) 2020 Elsevier Inc. All rights reserved.