The influences Of Support (silica or titania) and loading of Fe promoter oil the activity and selectivity of Rh-based catalysts for the direct synthesis of ethanol from syngas were explored. The reaction was performed in a fixed-bed reactor system typically operating at 543 K, 20 atm, WHSV of 8000 cm(3) g(cat)(1) h(1) and H-2:CO ratio of 1:1. Characterization by H-2 chemisorption and electron microscopy indicated that rhodium was very highly dispersed oil the Supports and was in direct contact with the Fe promoter. Although little ethanol was produced over 2 wt% Rh on silica, a similar loading of Rh on titania was active for this reaction. Promotion of 2 wt% Rh/SiO2 by I wt% re produced a catalyst that exhibited a 22% selectivity to ethanol, with methane being the primary side-product. Addition of Fe to 2 wt% Rh/titania also improved the selectivity to ethanol with the highest selectivity being 37% for a sample with 5 wt% Fe. The effects of temperature, pressure and H-2:CO ratio oil the performance of 2 wt% Rh/TiO2 and 2 wt% Rh-2.5 wt% Fe/TiO2 were also studied. Although the influence of pressure and H-2:CO ratio was moderate, higher temperatures clearly increased methane production at the expense of ethanol and methanol. Adsorption and thermal desorption of CO in Ar or H-2 were also Studied by DRIFTS spectroscopy on 2 wt% Rh/TiO2 and 2 wt% Rh-2.5 wt% Fe/TiO2. The gem-dicarbonyl species that was the primary species on these catalysts at room temperature after exposure to CO was more thermally stable on the Fe-promoted catalyst. (C) 2008 Elsevier Inc. All rights reserved.