Electrocatalytic oxidation of coal on Ti-supported metal/metal oxides coupled with liquid catalysts is systematically investigated as a method of producing hydrogen at the cathode. The composition of the liquid catalyst was varied to determine its effect on the coal electrolysis. A spectrum of byproducts from the coal oxidation at the anode was analyzed. The Ti-supported metal oxide electrodes were prepared by thermal decomposition and characterized by scanning electron microscopy (SEM). X-ray diffraction results show that the composition of the electrodes was Ti/Pt, Ti/RuO2, Ti/IrO2 and Ti/IrO2-RuO2, Coal oxidation tests on these electrodes indicate that Ti/IrO2 has the best electrocatalytic activity. Polarization curves reveal that redox catalysts, such as Fe3+, K3Fe(CN)(6), KBr and V2O5, bridge the coal particles and the solid electrode surface, thus increasing the rates of coal oxidation. The dynamic transition of Fe3+/Fe2+ is proven by a KMnO4 titration experiment, and the possible catalytic mechanism is discussed. Product analysis shows that pure H-2 is generated at the cathode and that CO2 is the main product at the anode. (C) 2009 Elsevier Ltd. All rights reserved.