This work presents for the first time the development of a selective catalyst to enable selective hydrocarbon detection when coupled with a microcalorimetric sensor. Specifically, the application of VOx/Al2O3 and Fe-2(MoO4)(3)-MoO3 catalysts as selective sensor substrates for thermal microsensor detection of ethanol in automotive fuel is described. At 453K, 8VO(x)/Al2O3 (monolayer surface density of similar to 8V/nm(2)) and Fe-2(MoO4)(3)-MoO3 (Mo:Fe = 1.9) catalysts convert ethanol towards one highly exothermic oxidative dehydrogenation product, acetaldehyde, with selectivities of 95% and 98%, respectively. For 8VO(x)/Al2O3 and Fe-2(MoO4)(3)-MoO3, rates at 453 K are 1.3 x 10(-G) and 3.4 x 10(-G) mol ethanol converted/gs, respectively, and they are independent of ethanol concentration from 0.2 to 2.0 kPa ethanol. At 453 K, these catalysts provide excellent reaction selectivity towards all classes of hydrocarbons present in automotive fuels. No reaction is observed for common constituents of gasoline such as benzene, toluene, 1-pentene, 1-hexene, 2-methyl butane, butyraldehyde, and 2-methyl pentane at 453 K in binary or ternary mixtures with ethanol. All of these non-target hydrocarbons except butyraldehyde also have no impact on the ethanol partial oxidation rate or selectivity. MTBE proves to be active at 453 K over both 8VO(x)/Al2O3 and Fe-2(MoO4)(3)-MoO3. Both MTBE and butyraldehyde decrease the ethanol reaction rate due to competitive surface adsorption on active sites but have no impact on the selectivity of the ethanol partial oxidation reaction. (C) 2010 Elsevier B.V. All rights reserved.