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Energies 2010, 3 1508 3.1.2. Non-Precious Metal Catalysts One of the most attractive advantages of alkaline fuel cells is the possibility of using non-precious metal catalysts. Nickel has been used as an electro-catalyst for both anodic and cathodic reactions in organic synthesis and water electrolysis. It has been studied for the electro-oxidation of alcohols for decades [66]. Van Effen and Evans [67] studied the oxidation of ethanol in KOH solution on nickel. They discovered that the reaction involved the formation of a higher valence nickel oxide, which acted as a chemical oxidizing agent. This fact was confirmed [68] by cyclic voltammetry, which proved the presence of a mediation process involving the higher oxides and the organic molecules, and by alternating current impedance measurements. Taraszewska and Roslonek [19] found that a glassy carbon/Ni(OH)2 modified electrode was an effective catalyst for the oxidation of methanol. The use of Ni as a catalyst for the electro-oxidation of methanol in alkaline medium was studied using cyclic voltammetry by Abdel Rahim et al. [69]. Ni dispersed on graphite showed catalytic activity towards methanol oxidation but massive Ni did not. Ni was dispersed on graphite by the electro-deposition from acidic Ni2SO4 solution. The catalytic activity of the C/Ni electrodes towards methanol oxidation was found to vary with the amount of electro-deposited Ni. Methanol oxidation starts as Ni-oxide is formed on the electrode surface and indicates that the electro-oxidation of methanol is activation controlled, proceeding by direct chemical reaction with NiO(OH) for thin nickel oxides and by charge transfer with the electrode for thick oxides. The accumulation of NiO(OH) had an inhibiting effect on activity which can be counteracted by a period of re-activation in the hydrogen evolution potential region. A Ni zeolite has been reported with a superior methanol oxidation activity to Ni and Pt supported on graphite [70]. This performance was assigned to a lower blocking of active sites than Pt due to repeated utilization. Synthesis and characterisation of electrodeposited Ni–Pd alloy electrodes for methanol oxidation in alkaline electrolyte was studied by Kumar et al. [71]. Structural characterisation of the electrocatalysts showed that the Ni–Pd catalysts formed a complete solid solution in the alloy. The percentage shift in the d-spacing, calculated from X-ray diffraction, was in good agreement with the palladium percentages in the alloy. The catalysts were active for methanol oxidation in alkaline medium. A Co-W alloy prepared by electroplating was evaluated by Shobba et al. for methanol oxidation in alkaline media [72]. Heat treatment was shown to improve oxidation performance with open circuit potentials of 0.918 V obtained. P-M-C complex materials were prepared by polymer template coordination with metal-ions loaded with a carbon-reduction method. P stands for polymer; M = Fe, Co and Ni; C is carbon. The catalyst showed very high electrocatalytic activity and stability for ethanol oxidation in alkaline media [73]. Lanthanum, strontium oxides have been studied by several research groups: Raghuveer and Vishwanathan [74] investigated the electro-oxidation of methanol on bulk and nano crystalline La1.8Sr0.2CuO4 in 1 M KOH. Raghuveer et al. [75] investigated methanol oxidation on La1.8Sr0.2CuO4, La1.6Sr0.4CuO4 and La1.9Sr0.1Cu0.9Sb0.1O4 in 3.0 M KOH. Yu et al. [76] studied La0.75Sr0.25CuO3−δ and La0.75Sr0.25CoO3−δ in 1 M NaOH and 1 M CH3OH. All oxides gave reasonable oxidation currents in potential ranges appropriate to fuel cell operation.PDF Image | Aspects of Direct Alkaline Alcohol Fuel Cells
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