The effect a 45 atom-thick overlayer of aluminum oxide, deposited by atomic layer deposition, was investigated on a 2.5 wt.% Pd/Al2O3 catalyst in which the Pd nanoparticles were encapsulated by the support consequent to the preparation method. The overlayer suppressed the activity for oxidative dehydrogenation of ethane, but it also effectively prevented metal sintering and suppressed coking for reactions at high temperatures. On the catalyst with the alumina overlayer, a steady activity was observed even at 600 degrees C and above when the gaseous oxygen was completely consumed, while attaining 70% selectivity for ethene at 38% conversion, versus 10% selectivity at comparable conversions without the overlayer. The overlayer preferentially deposited on edge Pd atoms, as indicated by preferentially suppression of the CO chemisorption peak at 2056 cm(-1), which are responsible for coking. The high ethene selectivity at 675 degrees C could be due to coupled homogeneous and heterogeneous reactions at the high temperature, together with phase change of PdO to Pd. (c) 2012 Elsevier Inc. All rights reserved.