Rhodium catalysts loaded on silica modified by various transition metal oxides were investigated for the conversion of syngas to ethanol. Iron oxide was found to be an efficient promoter for ethanol formation. The increase in iron content up to 5 wt% significantly increased CO conversion and ethanol selectivity. The preparation method used for introducing FeO(x) was found to affect both the conversion and the selectivity significantly. The catalyst prepared by the impregnation of a FeO(x)-SiO(2) composite, which was synthesized by a sol-gel technique preliminarily, with Rh(NO(3))(3) aqueous solution provided better ethanol formation activity than those prepared by co-impregnation and co-sol-gel methods. An ethanol selectivity of 42% was achieved at CO conversion of 12% over a 5 wt% Rh/(5 wt% FeO(x)-SiO(2)) catalyst prepared by this method. Larger interfaces between Rh and FeO(x) species were proposed to be a crucial factor for obtaining higher ethanol selectivity. The co-existence of Rh(3+) with Rh(0) and the size of Rh particles also played key roles in ethanol formation. (C) 2011 Elsevier B.V. All rights reserved. ; National Natural Science Foundation of China[20873110, 20923004, 21033006]; National Basic Program of China[2010CB732303]; Research Fund for the Doctoral Program of Higher Education[20090121110007]; Key Scientific Project of Fujian Province[2009HZ0002-1]