As the rate-determining half reaction (OER) in the overall CO2 photoreduction, the four-electron-involving OER on S-vacancy sites was favored, therefore facilitating the hole-elimination/proton release and unleashing the CO2 reduction half reaction.
A quantum-mechanical potential barrier model for estimating the number ratio between different valence cations in multiatom compounds is proposed. It is supposed that there is a potential barrier between a cation-anion pair. The height of the potential barrier is proportional to the ionization energy of the cation, and the width of the potential barrier is related to the distance between neighboring cations and anions. As examples for using this model, the distribution of cations with different valences in some ABO3 lanthanum manganites is explained satisfactorily.
The effects of lanthanum deficiency on the structural and magnetic properties of manganites with normal composition La0.7−xSr0.3MnO3 prepared by the sol-gel method with the highest heat treatment temperature at 800 °C have been investigated. X-ray diffraction (XRD) spectra indicate that the materials possess a single phase with the R3¯c perovskite structure for x≤0.05, and that they possess two phases with the R3¯c perovskite being the dominant phase and Mn3O4 being the second phase for x≥0.10. Using XRD analysis, these materials can be expressed as La0.7−xSr0.3Mn1−yO3−1.5(x+y)/(Mn3O4)y/3. On the basis of the thermal equilibrium theory of crystal defects, the ion ratios at the A, B, and O sites in the ABO3 perovskite phase were calculated. Those ion ratios were used in Rietveld fitting of the XRD spectra. It was found that the dependence of the Curie temperature TC on the content ratio RM4 of Mn4+ ions at B site is similar to that of the typical perovskite La1−xSrxMnO3.
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