MCF, NbMCF and TaMCF Mesostructured Cellular Foams were used as supports for platinum and silver (1 wt%). Metallic and bimetallic catalysts were prepared by grafting of metal species on APTMS (3-amino propyltrimethoxysilane) and MPTMS (2-mercaptopropyltrimethoxysilane) functionalized supports. Characterizations by X-ray diffraction (XRD), ultraviolet-visible (UV-Vis) spectroscopy, X-ray photoelectron spectroscopy (XPS), X-ray fluorescence (XRF) spectroscopy, and in situ Fourier Transform Infrared (FTIR) spectroscopy allowed to monitor the oxidation state of metals and surface properties of the catalysts, in particular the formation of bimetallic phases and the strong metal-support interactions. It was evidenced that the functionalization agent (APTMS or MPTMS) influenced the metals dispersion, the type of bimetallic species and Nb/Ta interaction with Pt/Ag. Strong Nb-Ag interaction led to the reduction of niobium in the support and oxidation of silver. MPTMS interacted at first with Pt to form Pt-Ag ensembles highly active in CH3OH oxidation. The effect of Pt particle size and platinum-silver interaction on methanol oxidation was also considered. The nature of the functionalization agent strongly influenced the species formed on the surface during reaction with methanol and determined the catalytic activity and selectivity. (C) 2016 Elsevier Inc. All rights reserved.