Silicate perovskites((Mg, Fe)SiO 3 and CaS iO 3) are believed to be the major constituent minerals in the lower mantle. The phase relation, solid solution, spin state of iron and water solubility related to the lo...Silicate perovskites((Mg, Fe)SiO 3 and CaS iO 3) are believed to be the major constituent minerals in the lower mantle. The phase relation, solid solution, spin state of iron and water solubility related to the lower mantle perovskite are of great effect on the geodynamics of the Earth's interior and on ore mineralization. Previous studies indicate that a large amount of iron coupled with aluminum can incorporate into magnesium perovskite, but this is discordant with the disproportionation of(Mg,Fe)SiO 3 perovskite into iron-free MgS i O3 perovskite and hexagonal phase(Mg0.6Fe0.4)SiO 3 in the Earth's lower mantle. MnS iO 3 is the first chemical component confirmed to form wide range solid solution with Ca SiO 3 perovskite and complete solid solution with MgS i O3 perovskite at the P-T conditions in the lower mantle, and addition of Mn Si O3 will strongly affects the mutual solubility between Mg Si O3 and CaS iO 3. The spin state of iron is deeply depends on the site occupation of the Fe3+or Fe2+, the synthesis and the annealing conditions of the sample. It seems that the spin state of Fe2+ in the lower mantle perovskite can be settled as high spin, however, the existence of intermediate spin or low spin state of Fe2+ in perovskite has not been clarified. Moreover, different results have also been reported for the spin state of Fe3+ in perovskite. The water solubility of the lower mantle perovskite is related with its composition. In pure Mg SiO 3 perovskite, only less than 500 ppm water was reported. Al–Mg Si O3 perovskite or Al–Fe–MgS iO 3 perovskite in the lower mantle accommodates water of 1100 to 1800 ppm. Further experiments are necessary to clarify the detailed conditions for perovskite solid solution, to reliably analyze the valence and spin states of iron in the coexisting iron-bearing phases, and to compare the water solubility of different phases at different layers for deeply understanding the geodynamics of the Earth's interior and ore mineralization.展开更多
Nanocrystals of Ce1-xMnxO2-δ(x=0.00,0.05,0.10,0.15,and 0.20) were synthesized by a hydrothermal reaction route.The solid solutions crystallized in a cubic fluorite structure with a particle size in the range of 11...Nanocrystals of Ce1-xMnxO2-δ(x=0.00,0.05,0.10,0.15,and 0.20) were synthesized by a hydrothermal reaction route.The solid solutions crystallized in a cubic fluorite structure with a particle size in the range of 11~15 nm.The incorporation of Mn ions in CeO2 resulted in a lattice volume reduction.Mn ions showed a mixed valence state of +2,+3 and +4 in CeO2 lattice.An obvious red-shift of the absorption threshold edge was observed from the UV-visible spectrum.Compared with the bulk CeO2,Ce1-xMnxO2-δ nanocrystals exhibited a lower releasing oxygen temperature as indicated by TPR technique.展开更多
基金partly supported by projects from JSPS KAKENHI (Grant No. 18340167)MEXT KAKENHI (Grant No. 20103002)+2 种基金NSFC (Grand No.90914002)China Geological Survey (Grant No. 1212011220926)the Ministry of Education of China (Grant No. 20130022110003)
文摘Silicate perovskites((Mg, Fe)SiO 3 and CaS iO 3) are believed to be the major constituent minerals in the lower mantle. The phase relation, solid solution, spin state of iron and water solubility related to the lower mantle perovskite are of great effect on the geodynamics of the Earth's interior and on ore mineralization. Previous studies indicate that a large amount of iron coupled with aluminum can incorporate into magnesium perovskite, but this is discordant with the disproportionation of(Mg,Fe)SiO 3 perovskite into iron-free MgS i O3 perovskite and hexagonal phase(Mg0.6Fe0.4)SiO 3 in the Earth's lower mantle. MnS iO 3 is the first chemical component confirmed to form wide range solid solution with Ca SiO 3 perovskite and complete solid solution with MgS i O3 perovskite at the P-T conditions in the lower mantle, and addition of Mn Si O3 will strongly affects the mutual solubility between Mg Si O3 and CaS iO 3. The spin state of iron is deeply depends on the site occupation of the Fe3+or Fe2+, the synthesis and the annealing conditions of the sample. It seems that the spin state of Fe2+ in the lower mantle perovskite can be settled as high spin, however, the existence of intermediate spin or low spin state of Fe2+ in perovskite has not been clarified. Moreover, different results have also been reported for the spin state of Fe3+ in perovskite. The water solubility of the lower mantle perovskite is related with its composition. In pure Mg SiO 3 perovskite, only less than 500 ppm water was reported. Al–Mg Si O3 perovskite or Al–Fe–MgS iO 3 perovskite in the lower mantle accommodates water of 1100 to 1800 ppm. Further experiments are necessary to clarify the detailed conditions for perovskite solid solution, to reliably analyze the valence and spin states of iron in the coexisting iron-bearing phases, and to compare the water solubility of different phases at different layers for deeply understanding the geodynamics of the Earth's interior and ore mineralization.
基金Supported by NNSFC (Nos 20671092, 20773132, 20771101)National Basic Research Program of China (No 2007BAE08B01, 2009 CB613306)
文摘Nanocrystals of Ce1-xMnxO2-δ(x=0.00,0.05,0.10,0.15,and 0.20) were synthesized by a hydrothermal reaction route.The solid solutions crystallized in a cubic fluorite structure with a particle size in the range of 11~15 nm.The incorporation of Mn ions in CeO2 resulted in a lattice volume reduction.Mn ions showed a mixed valence state of +2,+3 and +4 in CeO2 lattice.An obvious red-shift of the absorption threshold edge was observed from the UV-visible spectrum.Compared with the bulk CeO2,Ce1-xMnxO2-δ nanocrystals exhibited a lower releasing oxygen temperature as indicated by TPR technique.