NbSiMCM-41 and PUNbSiMCM-41 samples were characterised from the structural and morphological point of view. FT-IR studies allowed to evidence Water Gas Shift and reforming phenomena, taking place after CO introduction in the presence of an hydrated surface. The reactivity of the system and the role of the support towards hydrogen production were discussed on the base of infrared and TOF-SIMS results. (c) 2006 Elsevier B.V. All rights reserved.