A 0.5 wt% Pd/LaCoO3, prepared by flame-spray pyrolysis (FP), was tested as catalyst for the low-temperature selective reduction of NO by H-2 in the presence of excess O-2. In particular, the effect of the precalcination and prereduction temperature on catalytic activity was compared with that of a similar Pd/LaCoO3 sample prepared by impregnation with a Pd solution of FP-prepared LaCoO3. The FP-made catalyst allowed full NO conversion at 150 degrees C, with 78% selectivity to N-2, thus outperforming the catalytic behavior of the corresponding sample prepared by impregnation. The higher activity of the FP-made catalyst has been attributed to the formation of segregated Co metal particles, not present in the impregnated sample, formed during the precalcination at 800 degrees C, followed by reduction at 300 degrees C. Two reaction mechanisms can be deduced from the temperature-programmed experiments. The first of these, occurring at lower temperatures, indicates cooperation between the Pd and Co metal particles, with formation of active nitrates on cobalt, successively reduced by hydrogen spillover from Pd. The second, occurring at higher temperature, allows 50% conversion of NO, with >90% selectivity to N-2, and involves N adatoms formed by dissociative NO adsorption over Pd. Prereduction at 600 degrees C led to a slight increase in catalytic activity, due to the formation of a Pd-Co alloy, which is more stable on reoxidization compared with Pd alone. Moreover, the cooperative reaction mechanism seems to be favored by the proximity of Co and Pd in metal particles. (C) 2007 Elsevier Inc. All rights reserved.