Neodymium oxyfluoride has received much attention in the fields of anionic solid electrolytes.luminescent,catalytic and magnetic materials because of its structure combined advantages of rareearth cations with F^(-)an...Neodymium oxyfluoride has received much attention in the fields of anionic solid electrolytes.luminescent,catalytic and magnetic materials because of its structure combined advantages of rareearth cations with F^(-)and O_(2)^(-)anions.In this work,neodynium oxyfluoride was synthesized by the reaction between neodymium oxide and four fluoride media with different fluoride ion activities.The synthesis processes in molten LiF-CaF_(2)-NdF_(3),LiF-NdF_(3),NaF-CaF_(2)-NdF_(3)and NaF-KF-NdF_(3)are observed in situ by a confocal scanning laser microscope.The expansion of neodymium oxide particle is observed in the LiF-CaF_(2)-NdF_(3),LiF-NdF_(3),and NaF-KF-NdF_(3)melts,and the growth of needle crystals on neodymium oxide particle is clearly observed in molten NaF-CaF_(2)-NdF_(3).Based on scanning electron microscopy(SEM)-energy dispersive X-ray spectroscopy(EDS)and X-ray diffraction(XRD)analyses of products,neodynium oxyfluoride was successfully synthesized in the four fluoride media.The neodynium oxyfluoride generated in the LiF-CaF_(2)-NdF_(3),LiF-NdF_(3),and NaF-KF-NdF_(3)melts is a tetragonal structure.However,in molten NaF-CaF_(2)-NdF_(3),neodynium oxyfluoride with a rhombohedral structure is formed.It is suggested that the substitution of Na(Ⅰ)and Ca(Ⅱ)for Nd(Ⅲ)can transform NdOF from tetragonal structure to rhombohedral structure.The growth rate of needle crystals generated in molten NaF-CaF_(2)-NdF_(3)was calculated based on the result of a confocal scanning laser microscope,and it is found that the reaction kinetics of crystal formation is zero-order reaction.The effect of fluoride media on the structure and morphology of formed NdOF were evaluated by XRD,X-ray photoelectron spectroscopy(XPS)and SEM.The neodymium oxyfluoride prepared in the fluoride media with high fluoride ion activity has low binding energy of F 1 s.The ratio of adsorbed oxygen to lattice oxygen for neodymium oxyfluoride prepared in molten LiF-NdF_(3)is larger than those in the other three fluoride media,so it can have better catalytic performance.展开更多
基金Project supported by National Key Research and Development Program of China(2020YFC1909102)Natural Science Foundation of Inner Mongolia(2020BS05033)+1 种基金Inner Mongolia Major Basic Research Open Project(0406091701)Major Projects of Natural Science Foundation of Inner Mongolia of China(2018ZD07)。
文摘Neodymium oxyfluoride has received much attention in the fields of anionic solid electrolytes.luminescent,catalytic and magnetic materials because of its structure combined advantages of rareearth cations with F^(-)and O_(2)^(-)anions.In this work,neodynium oxyfluoride was synthesized by the reaction between neodymium oxide and four fluoride media with different fluoride ion activities.The synthesis processes in molten LiF-CaF_(2)-NdF_(3),LiF-NdF_(3),NaF-CaF_(2)-NdF_(3)and NaF-KF-NdF_(3)are observed in situ by a confocal scanning laser microscope.The expansion of neodymium oxide particle is observed in the LiF-CaF_(2)-NdF_(3),LiF-NdF_(3),and NaF-KF-NdF_(3)melts,and the growth of needle crystals on neodymium oxide particle is clearly observed in molten NaF-CaF_(2)-NdF_(3).Based on scanning electron microscopy(SEM)-energy dispersive X-ray spectroscopy(EDS)and X-ray diffraction(XRD)analyses of products,neodynium oxyfluoride was successfully synthesized in the four fluoride media.The neodynium oxyfluoride generated in the LiF-CaF_(2)-NdF_(3),LiF-NdF_(3),and NaF-KF-NdF_(3)melts is a tetragonal structure.However,in molten NaF-CaF_(2)-NdF_(3),neodynium oxyfluoride with a rhombohedral structure is formed.It is suggested that the substitution of Na(Ⅰ)and Ca(Ⅱ)for Nd(Ⅲ)can transform NdOF from tetragonal structure to rhombohedral structure.The growth rate of needle crystals generated in molten NaF-CaF_(2)-NdF_(3)was calculated based on the result of a confocal scanning laser microscope,and it is found that the reaction kinetics of crystal formation is zero-order reaction.The effect of fluoride media on the structure and morphology of formed NdOF were evaluated by XRD,X-ray photoelectron spectroscopy(XPS)and SEM.The neodymium oxyfluoride prepared in the fluoride media with high fluoride ion activity has low binding energy of F 1 s.The ratio of adsorbed oxygen to lattice oxygen for neodymium oxyfluoride prepared in molten LiF-NdF_(3)is larger than those in the other three fluoride media,so it can have better catalytic performance.
