Catalytic performances of Pt based catalysts supported on (Al2O3)(x) (MgO)(1-x) oxides prepared by sot-gel techniques, with x varying from 0.25 to 0.75 were investigated for acetonitrile hydrogenation to check the influence of acid-base properties of the support. The results evidenced a correlation between these properties and the yield towards the primary amines, the most desired ones. Thus, the more basic the support is, the higher the production of primary amines will be. However, an optimal values for both activity and selectivity is obtained for 1% Pt/(Al2O3)(0.25)(MgO)(0.75). Then, hydrogenation of acetonitrile was studied by in situ FUR spectroscopy and the formation of an intermediate species that would lead to secondary and tertiary amines formation was observed on the catalysts. In accordance to previous reaction pathways, ketenimine (CH2=C=NH) was proposed as this species. (C) 2014 Elsevier B.V. All rights reserved.