Small Pt clusters within Na-[Fe]ZSM5-protected channels catalyze C3H8 and C2H6 dehydrogenation with unprecedented turnover rates and catalyst stability. Alkene selectivities are greater than 97% at near-equilibrium alkane conversions. Mild oxidative treatments fully restored initial catalytic rates and selectivities. Exchange sites in Na-[Fe]ZSM5 lead to well-dispersed Pt precursors and catalytic Pt clusters, which reside within ZSM5 channels that inhibit the formation of large unreactive organic residues. The weak acidity of residual OH groups in [Fe]ZSM5 minimizes beta-scission and oligomerization reactions, which lead to loss of alkene selectivity and to unreactive organic residues. Thermodynamic constraints were removed by selective combustion of H-2 using O-2 coreactants. More than 90% of the O-2 introduced was used to form H2O from H-2, even when hydrocarbons were the predominant available reactants. Equivalent O-2 amounts cofed with C3H8 reactants led instead to similar to 5% selectivity for H-2 combustion. Hydrocarbon combustion was the predominant reaction and the cofed O-2 was depleted before H-2 could be formed and dehydrogenation approached equilibrium. Alkene yield enhancements of similar to 1.6 above equilibrium were achieved by selective H-2 removal using O-2 staging. These yield enhancements exceed those achieved with previously reported three-stage reactor systems. The O-2 staging approach reported here requires only one reactor and one catalytic composition; thus, it decreases significantly process complexity and cost. H-2 removal by selective combustion using O-2 requires precise control of O-2 introduction and availability in order to avoid H-2 depletion and high CO selectivities, which can lead to unreactive deposits and to catalyst deactivation during alkane dehydrogenation. (C) 2003 Elsevier Inc. All rights reserved.