Use of a water-soluble niobium peroxo complex allowed the preparation of niobium-modified aluminas containing up to 90% of the theoretical niobia monolayer in one impregnation step. There was a maximum in the density of surface Lewis acid sites at 45% of the theoretical monolayer. FTIR of adsorbed pyridine and adsorbed CO2 suggest the vertical growth of the Nb2O5 layer for the largest niobium contents. The addition of 22.5% of the theoretical monolayer eliminated about 80% of the basic surface hydroxyls, inhibiting the adsorption of gas phase CO2 by the samples. The niobia/alumina catalysts suffered less inhibition by CO2 than the pure alumina in the methanol dehydration reaction, confirming that Nb2O5 is mainly deposited on sites where the CO2 adsorption is stronger, leaving free sites that are active in catalytic dehydration and less inhibited by CO2, however none of the niobia/aluminas was more active than the pure alumina. Nevertheless, in the direct syngas to DME conversion using a mixed catalyst system comprised of a CuZnAl methanol synthesis catalyst and a methanol dehydration component, the activity was significantly larger with a niobia/alumina as a dehydrating component than with the pure alumina. (c) 2012 Elsevier B.V. All rights reserved.