Drying and calcining effects on 16-19 wt% Co/SiO2 Fischer-Tropsch (FT) catalysts, prepared by impregnation with cobalt nitrate, have been examined using ultrahigh vacuum (UHV) surface analysis and conventional catalyst characterization techniques. Drying in air at 110 degrees C or under vacuum at 100 degrees C and then calcining in air at 400 degrees C causes large Co3O4 particles to form, which easily reduce under hydrogen at 300 degrees C. In contrast, dried samples annealed under UHV prior to calcining exhibit dramatically different characteristics. The decomposition of cobalt nitrate during drying initiates the formation of a surface cobalt silicate. Prolonged air drying eventually converts the surface silicate into Co3O4, while vacuum drying disperses the nitrate precursor on the support, forming cobalt silicate islands. Annealing air-dried samples in UHV stabilizes the surface silicate against reduction or oxidation through the migration of Co2+ ions into the support to form a well-ordered bulk cobalt silicate. Annealing of vacuum-dried samples to 200 degrees C in UHV produces a continuous, conductive surface silicate that sinters upon heating to temperatures above 250 degrees C. Analysis of species generated during the decomposition of the Co(NO3)(2) . 6H(2)O precursor indicates that the concentration of gas phase NOx near the surface determines the nature of the cobalt surface phase. The formation of an intermediate surface cobalt silicate under specific activation conditions maximizes the amount of reducible cobalt surface area available for FT reactions.