Catalytic decomposition of liquid fuels (n-octane, iso-octane, 1-octene, toluene and methylcyclohexane) is achieved in a continuous tubular aerosol reactor as a model for the solar initiated production of hydrogen, and easily separable CO free carbonaceous aerosol product. The effects of fuel molecular structure and catalyst concentration on the overall hydrogen yield were studied. Iron aerosol particles used as the catalysts, were produced on-the-fly by thermal decomposition of iron pentacarbonyl. The addition of iron catalyst significantly decreases the onset temperature of hydrogen generation as well as improves the reaction kinetics by lowering the reaction activation energy. The activation energy without and with iron addition was 260 and 100 kJ/mol, respectively representing a decrease of over 60%. We find that with the addition of iron, toluene exhibits the highest hydrogen yield enhancement at 900 degrees C, with a 6 times yield increase over thermal decomposition. The highest H(2) yield obtained was 81% of the theoretical possible, for n-octane at 1050 degrees C. The general trend in hydrogen yield enhancement is that the higher the non-catalytic thermal decomposition yield, the weaker the catalytic enhancement. The gaseous decomposition products were characterized using a mass spectrometer. An XRD analysis was conducted on the wall deposit to determine the product composition and samples for electron-microscopic analysis were collected exiting the furnace by electrostatically precipitating the aerosol onto a TEM grid. (C) 2010 Professor T. Nejat Veziroglu. Published by Elsevier Ltd. All rights reserved.