The catalytic conversion of ethanol was studied on a metallic Ni2P/SiO2 catalyst, and comparison was made with an acidic HZSM-5 catalyst. Chemisorption probes indicated that the Ni2P had substantial CO adsorption sites (134 mu mol g(-1)), while the HZSM-5 catalyst had large quantities of NH3 adsorption sites (565 mu mol g(-1)). The catalytic activity in ethanol deoxygenation of the Ni2P/SiO2 was higher than that of the HZSM-5 catalyst on the basis of these chemisorptions sites. In steady-state catalysis, contact time experiments indicated that for Ni2P, acetaldehyde was a primary product and ethylene was a secondary product. However, this was not the result of a sequential oxidation reaction followed by a reduction process, but rather, it was due to the formation of a surface intermediate that could desorb as acetaldehyde or react further to produce ethylene. This rake-type mechanism was supported by a simulation of the reaction sequence that produced good agreement with the experimentally determined acetaldehyde and ethylene yields. The mechanism was also supported by in situ Fourier transform infrared measurements, which revealed the presence of signals compatible with adsorbed acetaldehyde, the likely surface intermediate species involved in the reaction. The present studies indicate that the reactions of alcohols on metallic catalysts like Ni2P involve dehydrogenation/hydrogenation steps, rather than simple acid/base-catalyzed dehydration steps as occur in HZSM-5. (c) 2012 Elsevier Inc. All rights reserved.