Noble metal-free MgAl2O4 supported multicomponent catalysts for steam reforming of ethanol have been designed by means of combinatorial tools and high-throughput approaches. Additionally, the catalysts have been investigated using high-throughput temperature programmed technique. MgAl2O4 supported Ni-based catalysts have been found to be the most effective in hydrogen production. It has been revealed that practically no noble metal is required in order to achieve high hydrogen yield. At 500 degrees C a four-component catalyst containing Ni, Co, Ce and Mo has resulted in 4.4 mol hydrogen per mole of ethanol. In this system Ni is considered as the active metal, while Co, Ce and Mo are promoters. The results revealed strong synergism between Ni and Co leading to high activity in hydrogen production. In the temperature range between 320 and 370 degrees C pronounced coke formation via the Boudouard reaction was observed over the two-component Ni-Co catalyst. The addition of Ce to NiCo/MgAl2O4 system proved to be advantageous, resulting in further improvement in hydrogen yield and suppression of coke formation. The presence of Mo as the fourth component hindered all reactions of CO in the temperature range between 320 and 370 degrees C. Thus, the contribution of reactions, such as WGRS, CO methanation and coke formation were reduced as well. The four-component catalyst has been proved to be highly effective in hydrogen production at higher temperatures. Its advantage is the strong suppression of the formation of carbonaceous deposition. The analysis of results shows also that some of the catalysts compositions can be promising for ethanol pre-reforming producing both hydrogen and methane from ethanol for Molten Carbonate Fuel Cells. (C) 2010 Elsevier B.V. All rights reserved.