The present work is focused on the sal-gel synthesis, characterization and catalytic performance evaluation of novel Mg-Ce-Zr-O-based mixed oxides supported Rh catalysts for the purification of H-2-rich gas streams from phenol through steam reforming in the 575-730 degrees C range. Phenol is used as a model compound of tars, the former being one of the main constituents of tars formed during steam gasification and pyrolysis of biomass. Novel Rh catalysts (0.1 wt%) supported on Mg-Ce-Zr-O-based mixed oxides modified by alkaline-earth, rare earth, and transition metal ions, having the general formula Mg-Ce-Zr-X-O (where X stands for La, Sr, Ba, Ca and Zn) were systematically studied. The physicochemical properties of the catalysts were evaluated using complementary bulk and surface characterization techniques, such as BET, XPS, in situ XRD, TEM/SAED and SEM/EDX. Transient techniques including H-2-TPR,TPD-CO2 and TPD-NH3 were employed in order to characterize redox behavior, surface basicity, and surface acidity of support, respectively. Among the catalysts examined, a 0.1 wt% Rh/40Mg-20Ce-20Zr-20La-O was found to exhibit the highest hydrogen product yield, specific H-2 production rate (mu mol H-2/m(2) min), and the lowest CO/CO2 product ratio (575-730 degrees C), even when compared to a Ni-based commercial steam reforming of tars catalyst. At 655 degrees C, a H-2 yield of similar to 95% and a specific reaction rate of 100 mu mol H-2/m(2) min were obtained for a feed containing 0.5 vol% phenol and 40 vol% H2O at a gas hourly space velocity of similar to 80,000 h(-1). This activity behavior is correlated with the largest concentration of basic sites and labile oxygen species (mu mol/m(2)), and also with the largest acid/base site ratio present in the 40Mg-20Ce-20Zr-20La-O support composition. Steam was also found to be an efficient reagent for the removal of carbonaceous deposits (e.g., CxHy) formed on the catalyst surface during phenol steam reforming. The H/C atom compositional ratio of the carbonaceous deposits was found to depend on reaction temperature. (C) 2011 Elsevier B.V. All rights