Multiple potential active sites on the surface of γ-Al 2 O 3 have led to debate about the role of Lewis and/or Brønsted acidity in reactions of ethanol, while mechanistic insights into competitive production of ethylene and diethyl ether are scarce. In this study, elementary adsorption and reaction mechanisms for ethanol dehydration and etherification are studied on the γ-Al 2 O 3 (100) surface using density functional theory calculations. The O atom of adsorbed ethanol interacts strongly with surface Al (Lewis acid) sites, while adsorption is weak on Brønsted (surface H) and surface O sites. Water, a byproduct of both ethylene and diethyl ether formation, competes with ethanol for adsorption sites. Multiple pathways for ethylene formation from ethanol are explored, and a concerted Lewis-catalyzed elimination (E2) mechanism is found to be the energetically preferred pathway, with a barrier of E a = 37 kcal/mol at the most stable site. Diethyl ether formation mechanisms presented for the first time on γ-Al 2 O 3 indicate that the most favorable pathways involve Lewis-catalyzed S N 2 reactions (E a = 35 kcal/mol). Additional novel mechanisms for diethyl ether decomposition to ethylene are reported. Brønsted-catalyzed mechanisms for ethylene and ether formation are not favorable on the (100) facet because of weak adsorption on Brønsted sites. These results explain multiple experimental observations, including the competition between ethylene and diethyl ether formation on alumina surfaces.

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We examine the heterogeneity of the Lewis acidity on the (100) and (110) facets of γ-Al2O3 by computing the binding energies of various oxygenates, in addition to the reaction barriers of dehydration and etherification reactions of ethanol. We show that the ethanol dehydration barrier is moderately affected by site heterogeneity (barriers between 1.2 and 1.6 eV); in contrast, a nearly 3-fold change in the ethanol etherification barrier is found among the various Al3+ sites. In order to rationalize these results, the s-conduction band mean of the Al3+ sites is introduced as a descriptor to characterize the ability to transfer electron charge from the adsorbate to the Lewis acid site. It is shown for the first time that this descriptor quantitatively correlates the oxygenate binding energies and the ethanol dehydration reaction barriers. However, for the ethanol etherification reactions the s-conduction band mean of the Al3+ sites describes barriers only qualitatively due to the bimolecular nature of this reaction, which results in a change in the nucleophilicity of the ethoxy species by a nearby adsorbed ethanol. As a result, the strength of the Lewis acid sites is not the only descriptor for etherification chemistry. Hydration of the (110) facet indicates an increase in Lewis acidity strength as described by the s-conduction band mean that results in stronger binding. However, this increase in Lewis acidity results in either a negligible change of the ethanol dehydration reaction barriers on some sites or an increase due to a reduction in the basicity of the adjacent oxygen by the dissociated water. Similarly, ethanol etherification is slowed down by the presence of water due primarily to the change in nucleophilicity of the ethoxy species. Overall, our results clearly indicate that while the binding energy is an excellent descriptor of Lewis acidity strength and dehydration chemistry on the clean alumina surfaces, cooperative phenomena (i.e., modulation of the nucleophilicity of the ethoxy by the nearby oxygen or water and the basicity of oxygen in the presence of water) are key issues that lead to a breakdown in the correlation between Lewis acid strength in terms of the binding energy or the s-conduction band mean and the reaction barriers.

Catalyst deactivation mechanisms on MgO-supported Au(6) clusters are studied for the CO oxidation reaction via first-principle kinetic Monte Carlo simulations and shown to depend on support vacancies. In defect-poor MgO or in the presence of a Mg vacancy, O(2) does not bind to the clusters and the catalyst is poisoned by CO. On Au clusters interacting with O vacancies of the support, O(2) can be chemisorbed and transient activity is observed. In this case, an unexpected catalyst "breathing" mechanism (restructuring) leads to carbonate formation and catalyst deactivation, rationalizing several experimental observations. Our study underscores the importance of the cluster's charge state and dynamics on catalytic activity.