A series of 2.5% Rh/M@Al(2)O(3) model catalysts were prepared by supporting Rh on high-area gamma-Al(2)O(3), resulting in a surface covered by a monolayer (4.5-7 atoms/nm(2)) of MO promoter oxides (M = Fe, V. Nb, Ta, Ti, Y, Pr, Nd, Sm). The catalysts were extensively characterized and evaluated for the conversion of synthesis gas to oxygenates at 553 K, 5.0 MPa, H(2)/CO = 1, and space velocity adjusted to attain CO conversion around 15%. The broad range of products formed depending on the specific promoter were, for the first time, quantitatively described using the selectivity parameter (Phi) defined here, which indicates, for a given reaction product, the contribution of carbon atoms derived from dissociative (C(dis)) and nondissociative (C(ins)) activation of CO. Both the catalytic activity and, more interestingly, the selectivity pattern given by the Phi parameter were correlated with the electronic properties of the MO(x) promoters (i.e., electron-donating/electron-withdrawing capacity) for an extensive series of catalysts. Low-temperature and at-work CO-FTIR experiments suggested that the high activity and hydrocarbon selectivity displayed by catalysts promoted by more electron-withdrawing (acidic) oxide promoters (e.g., TaO(x)) were related to a higher proportion of bridged Rh(2)(CO)(B) adsorption sites and to a higher electron density (i.e., a higher electron back-donation ability) of the Rh(0) surface sites, both factors promoting CO dissociation events. In contrast, linear CO adsorption on Rh(0) sites displaying decreased electron back-donation in catalysts promoted by electron-donating (basic) oxides (e.g., PrO(x), SmO(x)) was likely related to nondissociative CO activation and thus to the selective formation of oxygenates. TEM. XPS, and CO-FTIR results pointed to differences in morphology, rather than size or partial electronic charge, of the nano-sized Rh(0) crystallites as the likely cause for the different proportions of CO adsorption sites. The Rh NP morphology, both as-reduced and at-work, is a function of the electronic properties of the underlying promoter oxide. (C) 2011 Elsevier Inc. All rights reserved.