A new stripping agent N,N-dimethyl-3-oxa-glutaramic Acid (DOGA) was used in TRPO process to simplify the TRPO process. The structures of the complexes of the DOGA with Eu(Ⅲ), Nd(Ⅲ), La(Ⅲ) were characterized with ex...A new stripping agent N,N-dimethyl-3-oxa-glutaramic Acid (DOGA) was used in TRPO process to simplify the TRPO process. The structures of the complexes of the DOGA with Eu(Ⅲ), Nd(Ⅲ), La(Ⅲ) were characterized with extended X-ray absorption fine structure spectroscopy (EXAFS), infrared spectra (IR) and mass spectra (MS). The molecular formula of the complexes of Eu(Ⅲ) and Nd(Ⅲ) is deduced to be M(DOGA)_3, and only La(Ⅲ) can form the complex HM(DOGA)_4 under condition of high consistency of the DOGA. The coordination number of Ln(Ⅲ) in the complexes is 8, and all of coordinated donor atoms are O atoms. For Eu(Ⅲ), Nd(Ⅲ), the coordination numbers of O atom in the first coordination shell is 6 and the average coordination bond lengths of Ln-O are 0 240 nm, 0 244 nm respectively, while the numbers of the second O shell are 2.4, and the average coordination bond lengths of Ln-O are 0 260 nm, 0 262 nm. For La(Ⅲ), the coordination numbers of O atom in the first coordination shell is 6 and the average coordination bond lengths of La-O are 0 258 nm, while the number of O atom in the second coordination shell is 4.4, and the average coordination bond length of La-O is 0 28 nm. The results of IR and MS show that there is no water coordinating with Ln(Ⅲ) in the complexes.展开更多
The coordination number of the gadolinium atom and bond distances in the crystal of inonomeric porphyrinate,[Gd(TPP)acac-8H2O 3TCB] (TCB: 1,2,4-trichlorobenzene,acac: anion of acetylacetone),were determined by EXAFS m...The coordination number of the gadolinium atom and bond distances in the crystal of inonomeric porphyrinate,[Gd(TPP)acac-8H2O 3TCB] (TCB: 1,2,4-trichlorobenzene,acac: anion of acetylacetone),were determined by EXAFS method.The Gd atom is eight-coordinated to the four nitrogen atoms of a tetraphenylporphyrin ring,to the two oxygen atoms of one acetylacetonato anion and to two water molecules with Gd-N=0.232 nm,Gd-O=0.243 nm.展开更多
Nanosized terbium doped Lu2O3 phosphors were synthesized via a modified co-precipitation processing. The as-prepared Tb:Lu2O3 phosphors was consisted of well crystallized nanosized sphere particles with a diameter of ...Nanosized terbium doped Lu2O3 phosphors were synthesized via a modified co-precipitation processing. The as-prepared Tb:Lu2O3 phosphors was consisted of well crystallized nanosized sphere particles with a diameter of about 30 nm. Local structure of Tb ions in Lu2O3 lattice was investigated by an analytical approach based on Fourier transformation of the extended X-ray absorption fine structure (EXAFS) data. X-ray near edge structure (XANES) spectra suggested that all Tb ions doped were tervalence. EXAFS results indicated that Tb ions have entered the Lu2O3 cubic lattice by means of solid solution. The coordination number and first shell Tb-O distance dropped with the increasing of Tb concentration. Emission spectra of the phosphors was shown to be typical for Tb3+ with main components at 542, 550 and 490 nm, derived from irradiative relaxation of 5D4 level. The emission intensity decreased severely with the increasing of Tb concentration from 1 mol.% to 15 mol.%, suggesting a significant concentration quenching above 1 mol.% Tb. The reduction of emission intensity was interpreted by higher distortion derived relaxation among the surface state resident Tb3+ ions.展开更多
基金Project supported by the China National"863"Program
文摘A new stripping agent N,N-dimethyl-3-oxa-glutaramic Acid (DOGA) was used in TRPO process to simplify the TRPO process. The structures of the complexes of the DOGA with Eu(Ⅲ), Nd(Ⅲ), La(Ⅲ) were characterized with extended X-ray absorption fine structure spectroscopy (EXAFS), infrared spectra (IR) and mass spectra (MS). The molecular formula of the complexes of Eu(Ⅲ) and Nd(Ⅲ) is deduced to be M(DOGA)_3, and only La(Ⅲ) can form the complex HM(DOGA)_4 under condition of high consistency of the DOGA. The coordination number of Ln(Ⅲ) in the complexes is 8, and all of coordinated donor atoms are O atoms. For Eu(Ⅲ), Nd(Ⅲ), the coordination numbers of O atom in the first coordination shell is 6 and the average coordination bond lengths of Ln-O are 0 240 nm, 0 244 nm respectively, while the numbers of the second O shell are 2.4, and the average coordination bond lengths of Ln-O are 0 260 nm, 0 262 nm. For La(Ⅲ), the coordination numbers of O atom in the first coordination shell is 6 and the average coordination bond lengths of La-O are 0 258 nm, while the number of O atom in the second coordination shell is 4.4, and the average coordination bond length of La-O is 0 28 nm. The results of IR and MS show that there is no water coordinating with Ln(Ⅲ) in the complexes.
基金Project supported by the National Natural Science Foundation of China (No. 29701002)the Sate Educational Committee of ChinaShandong University of China
文摘The coordination number of the gadolinium atom and bond distances in the crystal of inonomeric porphyrinate,[Gd(TPP)acac-8H2O 3TCB] (TCB: 1,2,4-trichlorobenzene,acac: anion of acetylacetone),were determined by EXAFS method.The Gd atom is eight-coordinated to the four nitrogen atoms of a tetraphenylporphyrin ring,to the two oxygen atoms of one acetylacetonato anion and to two water molecules with Gd-N=0.232 nm,Gd-O=0.243 nm.
基金Project supported by the National Natural Science Foundation of China (11079026)the Basic Research Key Project of Shanghai Municipal (09JC1406500)+1 种基金Shanghai leading Academic Disciplines (S30107)the Postgraduate Innovation Fund of Shanghai University (SHUCX102237)
文摘Nanosized terbium doped Lu2O3 phosphors were synthesized via a modified co-precipitation processing. The as-prepared Tb:Lu2O3 phosphors was consisted of well crystallized nanosized sphere particles with a diameter of about 30 nm. Local structure of Tb ions in Lu2O3 lattice was investigated by an analytical approach based on Fourier transformation of the extended X-ray absorption fine structure (EXAFS) data. X-ray near edge structure (XANES) spectra suggested that all Tb ions doped were tervalence. EXAFS results indicated that Tb ions have entered the Lu2O3 cubic lattice by means of solid solution. The coordination number and first shell Tb-O distance dropped with the increasing of Tb concentration. Emission spectra of the phosphors was shown to be typical for Tb3+ with main components at 542, 550 and 490 nm, derived from irradiative relaxation of 5D4 level. The emission intensity decreased severely with the increasing of Tb concentration from 1 mol.% to 15 mol.%, suggesting a significant concentration quenching above 1 mol.% Tb. The reduction of emission intensity was interpreted by higher distortion derived relaxation among the surface state resident Tb3+ ions.
