Solar H2 production by the two-step water splitting process with thermochemical reaction has been proposed to convert solar energy into chemical energy. We succeeded in repeating the cyclic two-step water splitting process composed of the O2-releasing and H2-generation reactions with metal (Fe, Ni) doped ceria. The metal doped ceria with low content of metal ion (Fe3+, Ni2+) formed a solid solution with fluorite-type structure between ceria (CeO2) and metal oxide (Fe2O3, NiO). The empirical formula of the solid solution was Ce1-αMαO2−δ (M = Fe, Ni), and it was assumed that the high reactivity on the two-step water splitting process was due to an oxygen deficiency in the solid solution. The metal doped ceria with different Ce:M mole ratio (Ce:M = 0.97:0.03–0.7:0.3) was prepared through the combustion method. The two-step water-splitting process with metal doped ceria proceeded at 1673K for the O2-releasing reaction and at 1273K for the H2-generation reaction by irradiation of an infrared imaging lamp for a solar simulator. The amounts of H2 gas evolved in the H2-generation reaction with Fe-doped ceria and Ni-doped ceria with different Ce:M (M = Fe, Ni) mole ratio were 0.97–1.8 and 1.7–2.5 cm3/g, respectively, and the evolved H2/O2 ratios were approximately equaled to 2 of the stoichiometric value. The amounts of H2 and O2 gases evolved in the two-step water splitting process varied with the Ce:M mole ratio in the metal doped ceria. It was suggested that the O2-releasing and H2-generation reactions with metal doped ceria was repeated with the reduction and oxidation of Ce4+-Ce3+ enhanced by the presence of Fe or Ni ions. Furthermore, the O2-releasing reaction with Ni-doped ceria proceeded under a high O2 partial pressure atmosphere (pO2 = 0.05 atm) and at the temperature of 1773K. The progress of the O2-releasing reaction under a high pO2 indicates that metal doped ceria can be applicable for the rotary-type solar reactor developed by Tokyo Tech group for solar H2 production.

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