Selective production of hydrogen by partial oxidation of methanol (CH(3)oH -> (1/2)O-2 -> 2H(2) + CO2) over Au/TiO2 catalysts, prepared by a deposition-precipitation method, was studied. The catalysts were characterized by XRD, TEM, and XPS analyses. TEM observations show that the Au/TiO2 catalysts exhibit hemispherical gold particles, which are strongly attached to the metal oxide support at their flat planes. The size of the gold particles decreases from 3.5 to 1.9 nm during preparation of the catalysts with the rise in pH from 6 to 9 and increases from 2.9 to 4.3 nm with the rise in calcination temperature up to 673 K. XPS analyses demonstrate that in uncalcined catalysts gold existed in three different states: i.e., metallic gold (Au-0), non-metallic gold (Audelta+) and AU(2)O(3), and in catalysts calcined at 573 K only in metallic state. The catalytic activity is strongly dependent on the gold particle size. The catalyst precipitated at pH 8 and uncalcined catalysts show the highest activity for hydrogen generation. The partial pressure of oxygen plays an important role in determining the product distribution. There is no carbon monoxide detected when the O-2/CH3OH molar ratio in the feed is 0.3. Both hydrogen selectivity and methanol conversion increase with increasing the reaction temperature. The reaction pathway is suggested to consist of consecutive methanol combustion, partial oxidation and steam reforming. (c) 2005 Elsevier B.V. All rights reserved.