The addition of 0.10 wt% Li to Rh/TiO(2) more than doubled the CO conversion for CO hydrogenation while increasing ethanol selectivity. The addition of Li also increases formation Of C(2) oxygenates at the expense of C(1) species, methanol and methane. This is attributed to enhanced dispersion of Rh by Li that appears to reduce dissociation of CO, which previous studies have shown requires large ensembles of Rh atoms on the surface. Li promotion appears to increase the associatively adsorbed CO, allowing for increased H(2) chemisorption on the surface compared to the dissociative adsorption of the same number of CO atoms This increases selectivity to ethanol compared to the unpromoted catalysts. CO-TPD shows more reactive adsorbed CO species on the Li-promoted catalyst. FTIR results suggest that Li promotion alters CO bonding at bridged or interfacial sites and its effect is more structural than electronic. (C) 2009 Elsevier B V. All rights reserved.