The effect of zirconia phase on the activity and selectivity of Cu/ZrO2, for the hydrogenation of CO was investigated. Relatively pure t-ZrO2 and m-ZrO2 were prepared with high Surface areas (similar to 145 m(2)/g). Copper was then deposited on the surface of these materials by either incipient-wetness impregnation or deposition-precipitation. For a fixed Cu surface area, Cu/m-ZrO2 was ten time, more active for methanol synthesis than Cu-ZrO2 from a feed of 3:1 H2/CO at 3.0 MPa and temperatures between 473 and 523 K. Cu/m-ZrO2 also exhibited it higher selectivity for methanol. Increasing the Cu surface area on m-ZrO2 resulted in further improvement in activity with minimal change in selectivity. Methanol productivity increased linearly for both Cu/t-ZrO2, and Cu/m-ZrO2, with increasing Cu surface area, The difference in inherent activity of each phase paralleled the stronger and larger CO adsorption capacity of the Cu/m-ZrO2 as quantified by CO-TPD. The higher CO adsorption capacity of Cu/m-ZrO2 is attributed to the presence of a high concentration of anionic vacancies on the surface of m-ZrO2. Such vacancies expose cus-Zr4+ cations, which act as Lewis acid centers and enhance the Bronsted acidity of adjacent Zr-OH groups. The presence of cus-Zr4+ sites and adjacent Bronsted acidic Zr-OH groups contributes to the adsorption of CO as IICOO-Zr groups, which are the initial precursors to methanol. (c) 2005 Elsevier Inc. All rights reserved.