The effects of using fumed SiO2, MCM-41, and SBA-15 as supports for Ru and Ni catalysts oil ammonia decomposition were investigated. It was found that the supported catalysts on these siliceous materials are more active than those supported on ordinary silica. In general, the supported Ru catalysts are more active than the Ni catalysts, and MCM-41 is the best support material for Ru and Ni. Significant enhancement in activity was observed when the supported Ru catalysts were modified by KOH, but such effect was minimal in the cases of supported Ni catalysts. The results of N-2 adsorption and transmission electron microscopy studies revealed that the Ni particles of Ni/MCM-41 (TIE) prepared by template-ion exchange (TIE) method are largely located inside the pores of MCM-41. Compared with the Ni/MCM-41 (IMP) catalyst prepared by impregnation method, the Ni/MCM-41 (TIE) catalyst exhibited appropriate Ni dispersion and weaker Ni/support interaction, and consequently higher catalytic activity. In terms of the remarkable changes in turnover frequency (TOF) with Ni dispersion oil different catalysts. it was demonstrated that NH3 decomposition over Ni is significantly structure sensitive. Some unique metal clusters similar to B5 active sites should be responsible for the catalytic activities. Preparation methodology has a substantial influence on metal dispersion. For the supported Ni catalysts prepared by the TIE method, the generated metal particles are very small and the constitution of unique active sites becomes unfavorable, which accounts for the apparently lower TOF values. (c) 2005 Elsevier Inc. All rights reserved.