Unsupported NiO and NiO-CuO nano-particles were prepared by a facile method and these nano-particles showed promising catalytic activity towards methane decomposition. The decomposition of fibrous nickel (or mixed) oxalate precursors led to the formation of porous oxide aggregates with small primary oxide particles of 8-20 nm. Similar to supported catalysts, nickel copper alloy particles showed steady catalytic activities even at high reaction temperatures (>700 degrees C). Unlike the supported catalysts, it was necessary to introduce methane to the reactor at lower temperatures to avoid catalyst particles sintering into bigger ones during the reaction. The initial carbon nano-fibres (CNFs) acted as living supports to take the catalyst particles away and prevent them from sintering with adjacent particles. The textural properties of the CNFs were characterized by transmission electron microscopy (TEM), X-ray diffraction (XRD) and N-2 adsorption. The textural and micro-structural properties depended on the composition of the catalyst and the reaction temperature. (c) 2012 Elsevier B.V. All rights reserved.