Ni and Co supported on SiO2 and Al2O3 Silica Cloth Thin Layer Catalysts (TLC) were investigated in the Catalytic Decomposition of Natural Gas (CDNG) reaction using a Multilayer Catalytic Reactor (MCR). The influence of support and reaction temperature was evaluated with the aim to design a novel catalyst suitable to develop a dual-step process to produce pure hydrogen for fuel cell. Ni and Co silica supported catalyst, due to the low metal supported interaction (MSI) characterizing such systems, were not found suitable to efficiently perform CDNG reaction. On the contrary in case alumina was used as support both metals strongly interact with surface becoming so more resistant to sintering. In addition in case the metals (both Ni and Co) strongly interact with support surface, the formation of encapsulating carbon is depressed and only filamentous carbon forms. Using Ni and Co TLC supported on Al2O3 samples it has been possible to realize a cyclic dual-step process based on reaction and regeneration in oxygen stream without any catalyst detriment. A deactivation modelling to discriminate the role of sintering and coking on the deactivation pattern is proposed. (C) 2011 Elsevier B. V. All rights reserved.