Sr(NO3)2·DCH18C6配合物晶体结构与辐射稳定性

二环己基-18-冠-6（DCH18C6）可以有效地从高放废液中分离⁹⁰Sr,对于减小放射性废物的危害和实现高放废物的减容有重要意义. 由于在实际应用中DCH18C6处于射线照射下,其结构可能会被破坏并引起络合能力的变化,因此有必要对该配合物的辐射稳定性进行研究. 本文合成了Sr（NO₃）₂·DCH18C6 配合物晶体,并通过单晶X射线衍射（XRD）与扩展X射线吸收精细结构谱（EXAFS）等方法进行了表征,确定Sr²⁺与周围氧原子的配位数为10,Sr―O平均键长约为0.268 nm/0.266 nm（XRD/EXAFS）. 配位原子来自DCH18C6 的六个氧原子以及两个作为双齿配体的硝酸根的四个氧原子. 对该配合物晶体在空气中进行γ辐照,EXAFS结果表明吸收剂量为400 kGy时,Sr―O键长及配位数没有发生变化,配位结构没有被破坏,具有很好的耐辐照稳定性. 显微红外光谱（Micro-FTIR）结果进一步证明辐照后冠醚环的部分C―H 键氧化为羟基或羰基,但并不影响DCH18C6与Sr²⁺的配位结构.     

X-ray absorption fine structure study of amorphous metal oxide thin films prepared by photochemical metalorganic deposition

The oxidation state and local geometry of the metal centers in amorphous thin films of Fe₂O₃ (Fe³⁺ oxidation state), CoFe₂O₄ (Co²⁺/Fe³⁺ oxidation states), and Cr₂O₃ (Cr³⁺ oxidation state) are determined using K edge X-ray absorption near-edge structure (XANES) spectroscopy and extended X-ray absorption fine structure (EXAFS) spectroscopy. The metal oxide thin films were prepared by the solid-state photochemical decomposition of the relevant metal 2-ethylhexanoates, spin cast as thin films. No peaks are observed in the X-ray diffraction patterns, indicating the metal oxides are X-ray amorphous. The oxidation state of the metals is determined from the edge position of the K absorption edges, and in the case of iron-containing samples, an analysis of the pre-edge peaks. In all cases, the EXAFS analysis indicates the first coordination shell consists of oxygen atoms in an octahedral geometry, with a second shell consisting of metals. No higher shells are observed beyond 3.5 Å for all samples, indicating the metal oxides are truly amorphous, consistent with X-ray diffraction results.     

Tunable luminescence and energy transfer process between Tb3+ and Eu3+ in GYAG:Bi3+, Tb3+, Eu3+ phosphors

A series of Eu³⁺ ions co-doped (Gd_0.9Y_0.1)₃Al₅O₁₂:Bi³⁺, Tb³⁺ (GYAG) phosphors have been synthesized by means of solvothermal reaction method. The XRD pattern of GYAG phosphor sintered at 1500 °C confirms their garnet phase. The luminescence properties of these phosphors have been explored by analyzing their excitation and emission spectra along with their decay curves. The excitation spectra of the GYAG:Bi³⁺, Tb³⁺, Eu³⁺ phosphors consists of broad bands in the shorter wavelength region due to 4f⁸ → 4f⁷5d¹ transition of Tb³⁺ ions overlapped with 6s² → 6s¹6p¹ (¹S₀ → ³P₁) transition of Bi³⁺ ions and the charge transfer band of Eu³⁺–O^2?. The present phosphors exhibit green and red colors due to ⁵D₄ → ⁷F₅ transition of Tb³⁺ ions and ⁵D₀ → ⁷F₁ transition of Eu³⁺ ions, respectively. The emission was shifted from green to red color by co-doping with Eu³⁺ ions, which indicate that the energy transfer probability from Tb³⁺ to Eu³⁺ ions are dependent strongly on the concentration of Eu³⁺ ions.     

Diffraction of X-rays and hydration phenomena in aqueous solutions of Mg(NO3)2

The ionic coordination of Mg(NO₃)₂ in aqueous solutions has been investigated by X-ray diffraction. The experimental correlation functions appear to be characterized by the hydration of the cation. Satisfactory agreement with the experimental data has been reached through a model in which: (i) the nitrate ions do not produce any structuring effect in their neighbourhood; (ii) the Mg²⁺ ions possess an inner hydration shell of six water molecules and a second coordination shell.     

Structure of two new borates YCa3(AlO)3(BO3)4 and YCa3(GaO)3(BO3)4

By replacing Mn in YCa₃(MnO)₃(BO₃)₄ with trivalent Al and Ga, two new borates with the compositions of YCa₃(MO)₃(BO₃)₄ (M=Al, Ga) were prepared by solid-state reaction. Structure refinements from X-ray powder diffraction data revealed that both of them are isostructural to gaudefroyite with a hexagonal space group P6₃/m. Cell parameters of a=10.38775(13)Å, c=5.69198(10)Å for the Al-containing compound and a=10.5167(3)Å, c=5.8146(2)Å for the Ga analog were obtained from the refinements. The structure is constituted of AlO₆ or GaO₆ octahedral chains interconnected by BO₃ groups in the ab plane to form a Kagomé-type lattice, leaving trigonal and apatite-like tunnels. It is found that most rare-earth and Cr, Mn ions can be substituted into the Y³⁺ and M³⁺ sites, respectively, and the preference of rare-earth ions to locate in the trigonal tunnel is correlated to the sizes of the M³⁺ ions.     

EXAFS, SAXS and Eu3+ Luminescence Spectroscopy of Sol-Gel Derived Siloxane-Polyethyleneoxide Hybrids

Hybrid Eu³⁺-doped silica-poliethyleneoxide (PEO) nanocomposites with covalent bonds between the inorganic (siloxane) and organic (PEO) phases have been obtained by sol-gel process. These materials are transparent, flexible and present high Eu³⁺ luminescence output. Their luminescence properties, local environment around europium ions and structure have been investigated as a function of europium content. EXAFS measurements indicate that the increase in Eu-doping induces a decrease in Eu³⁺ coordination number. An increase in symmetry degree around the metal ion is also observed for increasing Eu³⁺ concentration, while non radiative decay paths from the ⁵D₀ excited state become more important. SAXS results suggest the preferential interaction of europium ions with ether-type oxygens of the polymer chains. However, the existence of interactions between the cations and the carbonyl groups from urea bridges located at the siloxane-PEO interface can not be excluded.     

Fine tuning bifunctional properties of Y0.5Gd0.5BO3 by doping with Ce3+ and co-doping with Li+,Ca2+ and Al3+ following an epoxide mediated gel approach

Realizing the ubiquitous presence of rare-earth orthoborates in various applications involving their optical properties, the current investigation is directed towards the exploration of epoxide mediated rapid synthesis to make YBO₃. Highly crystalline orthoborate with disordered vaterite structure resulted on calcining xerogel from the reaction of yttrium chloride, boric acid and propylene oxide at 900 °C as verified from diffraction, vibration spectroscopic and microscopic techniques. Following this approach, orthoborate containing 50 mol% of Y and Gd was obtained and characterized. Dissolution limit of Ce³⁺ in Y_0.50Gd_0.50BO₃ has been determined. Cerium doping resulted in the reduction in the optical band gap of these samples and appended photocatalytic ability in terms of degradation of aqueous rhodamine-6G (Rh-6G) dye solution. The intensity of 4f → 5d transition of Ce³⁺ increased monotonously with increase in cerium content. The role of distortion on the blue emission from Ce³⁺ and photocatalytic properties of these samples were comprehended by characterizing Li⁺, Ca²⁺ and Al³⁺-doped samples (up to 10 mol%) for yttrium. The distortion of Y_0.50?xM_xGd_0.45Ce_0.05BO₃ lattice decreased in the order, R_Ca2+ > R_Y3+ > R_Li+ > R_Al3+, with the emission intensity (5d → 4f transitions) from Ce³⁺ increasing in the reverse order. Optical band gap was found to decrease for the Li⁺, Ca²⁺ and Al³⁺ doped samples as compared to undoped one. These doped samples retained their catalytic ability as verified from their use in the photo degradation of rhodamine-B (Rh-B) dye. An insight in to possible mechanism operative in the present photo catalytic degradation experiments has been attempted by carrying out trapping experiments.     

Properties and structure of NiO-Al2O3 catalysts

Summary It was shown by x-ray and magnetochemical methods that the formation of spinel from coprecipitated nickel and aluminum hydroxides by thermal treatment consists of the following stages: a) formation of a solid solution of nickel and aluminum hydroxides or nickel hydroaluminate by coprecipitation; b) decomposition of the gel and crystal formation in the range 100–250°, accompanied by a sharp decrease in the water content; c) rearrangement of the crystal lattice at 250–300° to a cubic, face-centered spinel-type lattice; d) ordering of the crystal lattice at 300–700° without noticeable redistribution of Ni²⁺ ions, accompanied by a gradual decrease in water content; and e) further ordering of the crystal lattice at 700–1200° with redistribution of Ni²⁺ ions in accordance with the reversibility coefficient of spinel NiAl₂O₄.     

Synthesis and Luminescence of Eu3+-Doped Narsarsukite Prepared by the Sol-Gel Process

The sol-gel synthesis and structural characterisation of narsarsukite powders are reported. Samples doped with different Eu³⁺ amounts (Ti/Eu = 20 and 200), calcined at 800°C, have been characterised by powder XRD, ²³Na, ²⁹Si MAS NMR, Raman and luminescence spectroscopies. Eu³⁺-doped narsarsukite displays a high and stable room-temperature luminescence. The presence in narsarsukite of two different Eu³⁺ local environments is inferred based both on the distinct ⁵D₀ ⁷F₀ lines observed and on the local field splitting of the ⁷F_1,2 levels. For low lanthanide contents, the Eu³⁺ ions are essentially localised in a centrosymmetric environment characterized by a low-energy ⁵D₀ ⁷F₀ line and a relatively long ⁵D₀ lifetime (3.56–3.96 ms). In contrast, at high lanthanide contents the Eu³⁺ ions are also present in a second local site with a less covalent first coordination shell. This corresponds to a high-energy ⁵D₀ ⁷F₀ line and a short ⁵D₀ lifetime (0.84–0.99 ms). Therefore, it is likely that Eu³⁺ ions substitute for both Ti⁴⁺ and Na⁺, although the former ions are preferentially replaced at low Eu³⁺ content.     

Luminescent properties of SrBPO5:Dy3+ and effect of Co-doping with Tm3+

A series of phosphors SrBPO₅:Dy³⁺ and SrBPO₅:Dy³⁺,Tm³⁺ was synthesized by traditional solid-state high-temperature method and was characterized by X-ray diffraction (XRD) and fluorescence spectrophotometry. For SrBPO₅:Dy³⁺ material, the f-f transitions of Dy³⁺ ions were assigned and discussed, and the optimal doping concentration of Dy³⁺ was found. As a result of co-doping SrBPO₅:Dy³⁺ with Tm³⁺, the phosphors SrBPO₅:Dy³⁺,Tm³⁺ can be effectively excited by 360 nm ultraviolet (UV), and exhibit color-tunable emission from blue to yellowish-white region with different doping concentration. The present study can pave the way for the creation of efficient UV phosphors using Dy³⁺,Tm³⁺ co-doped systems for near-UV InGaN-based light emitting diodes (LEDs).     

Effect of Ce<Superscript>3+</Superscript> on spectral characteristic of D1/D2/Cytb559 complex from spinach

It was studied by spectroscopy that PSII reaction center complex consisting of three polypeptides, D₁, D₂ and Cytb559, were purified from PSII particle of CeCl₃ treated spinach. The results of the experiment show that Ce³⁺ could improve the growth of spinach, and accelerate electron transport of PSII particles. Of chl-a of UV-Vis spectrum of D1/D2/Cytb559 complex, Soret band was blue-shifted by 3 nm and Q band by 2 nm, respectively, and the fluorescence emission peak was blue-shifted by 5 nm in CeCl₃-treated spinach compared with the one in control. By the extended X-ray absorption fine structure (EXAFS) spectroscopy methods, it has been found that Ce³⁺ is coordinated with 8 nitrogen atoms in the first coordination shell with Ce-N bond length of 0.253 nm, and Ce³⁺ with 6 oxygen atoms in the second coordination shell with Ce-O bond length of 0.32 nm. However, the secondary structure of D1/D2/Cytb559 complex by circular dichroism (CD) spectroscopy has no significant change after CeCl₃ treated. It might be that Ce³⁺ binds to porphyrin rings of chlorophyll and oxygen of amino acid residue of polypeptide in D1/D2/Cytb559 complex, and then accelerates the primary reaction of PSII, intensifies function of P680⁺ primary electron donor of D1/D2/Cytb559, but there is little change in conformation of PSII reaction center complex.     

Synthesis and characterization of nanoporous NaYF4:Yb3+, Tm3+@SiO2 nanocomposites

Novel upconversion nanocomposites with nanoporous structure were presented in this paper. Silica-coated cubic NaYF₄:Yb³⁺, Tm³⁺ nanoparticles were first prepared. After annealing, monodisperse cubic/hexagonal mixed phases NaYF₄:Yb³⁺, Tm³⁺@SiO₂ nanoparticles were obtained, and the NaYF₄:Yb³⁺, Tm³⁺ cores became nanoporous. To the best of our knowledge, the nanoporous structure in NaYF₄:Yb³⁺, Tm³⁺@SiO₂ nanocomposites was observed for the first time. They demonstrate increased upconversion emission compared with unannealed dense NaYF₄:Yb³⁺, Tm³⁺ nanoparticles due to the appearance of the hexagonal NaYF₄:Yb³⁺, Tm³⁺. The silica shell not only makes the nanocomposites possess bio-affinity but also protects the NaYF₄:Yb³⁺, Tm³⁺ cores from aggregating and growing up. Thus the upconversion, nanoporous and bio-affinity properties were combined into one single nanoparticle. The nanocomposites have been characterized by X-ray diffraction (XRD), field-emission scanning electron microscopy (FE-SEM), transmission electron microscopy (TEM), small angle X-ray diffraction (SAXRD) and emission spectroscopy. These multifunctional nanocomposites are expected to find applications in biological fields, such as biolabels, drug storage and delivery.     

Structure of Nano‐sized CeO2 Materials: Combined Scattering and Spectroscopic Investigations

The structure of several nano‐sized ceria, CeO₂, systems was investigated using neutron and X‐ray diffraction and X‐ray absorption spectroscopy. Whilst both diffraction and total pair distribution functions (PDFs) revealed that in all of the samples the occupancy of both Ce⁴⁺ and O^2? are very close to the ideal stoichiometry, the analysis using Reverse Monte Carlo technique revealed significant disorder around oxygen atoms in the nano‐sized ceria samples in comparison to the highly crystalline NIST standard. In addition, the analysis revealed that the main differences observed in the pair correlations from various X‐ray and neutron diffraction techniques were attributable to the particle size of the CeO₂ prepared by the reported three methods. Furthermore, detailed analysis of the Ce L₃‐ and K‐edge EXAFS data support this finding; in particular the decrease in higher shell coordination numbers with respect to the NIST standard, is attributed to differences in particle size.     

Sol–gel preparation and white up-conversion luminescence in rare-earth doped PbF<Subscript>2</Subscript> nanocrystals dissolved in silica glass

89.5(SiO₂)10(PbF₂)0.5(REF₃) silicate glasses have been prepared using room temperature sol–gel processing of Si(OCH₂CH₃)₄, Pb(CH₃COO)₂·3H₂O, RE(CH₃COO)₃·nH₂O and trifluoroacetic acid as a fluorinating agent, where RE stands for rare-earth ions, such as Yb³⁺, Er³⁺, Ho³⁺, Tm³⁺, or combinations of those ions. On heat treatment of these glasses at about 300–400 °C, the rare-earth doped spherical PbF₂ nanocrystals precipitate within SiO₂ glass matrix providing transparent nano-structured glass–ceramics, while the diameter of the nanocrystals can be set in the range from 5 to 25 nm by varying time and temperature of the heat treatment. The structural and photoluminescence studies confirm the incorporation of rare-earth ions into the PbF₂ nanocrystals and white and tuneable colour up-conversion luminescence has been detected in case of Yb³⁺-Er³⁺-Tm³⁺ and Yb³⁺-Ho³⁺-Tm³⁺ co-doped nanocrystals by varying dopant ratio and pump power.     

Energy Transfer Between Eu3+ Ions and CdS Quantum Dots in Sol-Gel Derived CdS/SiO2 : Eu3+ Gel

We have investigated the energetic correlation between rare-earth ions and semiconductor nanocrystals, using europium ion (Eu³⁺) doped silica (SiO₂) gel with adsorbed cadmium sulfide (CdS) particles. Samples were prepared by a sol-gel technique, in which several methods for the precipitation of CdS colloids were attempted. The fluorescence intensities were compared for different gels, with and without CdS particles. The intrinsic emission lines due to ⁵D₀ ⁷F_J(J = 0–4) transitions of Eu³⁺ were observed, which were enhanced for 24 h-immersed gel (dried at 50°C). From the results on the decay dynamics of fluorescence, we proposed the model that surface-trapped electrons on CdS particles nonradiatively excited 4f electrons in Eu³⁺ ions due to an energy transfer process.     

Er3+-Tm3+-Yb3+ tri-doped CaMoO4 upconverting phosphors in optical devices applications

The structural and optical properties of the Er³⁺-Tm³⁺-Yb³⁺codoped CaMoO₄ phosphors prepared by chemical route have been explored. The crystalline structures of the prepared phosphors have been investigated with the help of X-ray diffraction analysis. The presence of different vibrational modes and absorption bands arising due to the transitions from the ground state to different excited states of rare earth ions have been identified using the Raman and UV-VIS-NIR absorption spectra of the developed phosphor, respectively. The concentration quenching effect on the luminescence property of the prepared materials has been explained in detail. The upconversion luminescence property of the Er³⁺-Tm³⁺-Yb³⁺codoped CaMoO₄ phosphor annealed at different temperatures under 980 nm and 808 nm excitations have been reported. The energy transfer Er³⁺ → Tm³⁺, Yb³⁺ → Er³⁺ and Tm³⁺ has been found to be responsible for efficient UC emission. The dipole-dipole interaction is observed to be responsible for the concentration quenching of the luminescence intensity. The effect of annealing temperature on the upconversion luminescence property has been explained in detail. The results suggest that the developed tri-doped phosphor may be suitable in making the efficient NIR to visible upconverter and lighting based optical devices.     

钙钛矿结构荧光材料MZrO3:Eu3+,A (M=Ca2+, Ba2+; A=Li+, Na+, K+)的制备及其发光性质

Calcium and barium zirconate powders based upon CaZrO₃:Eu³⁺,A and BaZrO₃:Eu³⁺,A (A=Li⁺, Na⁺, K⁺) were prepared by combustion synthesis method and heating to ~1000℃ to improve crystallinity.The structure and morphology of materials were examined by X-ray diffraction (XRD) and scanningelectron microscopy (SEM). XRD results showed that CaZrO₃:Eu³⁺,A and BaZrO₃:Eu³⁺,A (A=Li⁺, Na⁺, K⁺) perovskites possessed orthorhombic and cubic structures, respectively. The morphologies of all powderswere very similar consisting of small, coagulated, cubical particles with narrow size distributions andsmooth and regular surfaces. The characteristic luminescences of Eu³⁺ ions in CaZrO₃:Eu³⁺,A (A=Li⁺, Na⁺, K⁺) lattices were present with strong emissions at 614 and 625 nm for ⁵D₀→⁷F₂ transitions with other weakeremissions observed at 575, 592, 655, and 701 nm corresponding to ⁵D₀→⁷F_n transitions (where n=0, 1, 3, 4 respectively). In BaZrO₃:Eu³⁺ both the ⁵D₀→⁷F₁ and ⁵D₀→⁷F₂ transitions at 595 and 613 nm were strong.Photoluminescence intensities of CaZrO₃:Eu³⁺ samples were higher than those of BaZrO₃:Eu³⁺ lattices. Thisremarkable increase of photoluminescence intensity (corresponding to ⁵D₀→⁷F_n transitions) was observedin CaZrO₃:Eu³⁺ and BaZrO₃:Eu³⁺ if co-doped with Li⁺ ions. An additional broad band composed of manypeaks between 440 to 575 nm was observed in BaZrO₃:Eu³⁺,,A samples. The intensity of this band wasgreatest in Li⁺ co-doped samples and lowest for K⁺ doped samples.     

Spin-Hamiltonian parameters and angular distortion for the trigonal Nd3+ center in congruent LiNbO3

The 52 × 52 energy matrix related to the ground multiplet ⁴I_9/2 and the first to third excited multiplets ⁴I_11/2, ⁴I_13/2 and ⁴I_15/2 for 4f³ ions in trigonal crystal field under an external magnetic field is established. By diagonalizing the energy matrix, the spin-Hamiltonian parameters (g factor g_//, g_⊥ and hyperfine structure constants ¹⁴³A_//, ¹⁴³A_⊥, ¹⁴⁵A_//, ¹⁴⁵A_⊥) of the trigonal Nd³⁺ center in congruent LiNbO₃ crystal are calculated. The calculated results are in reasonable agreement with the experimental values. From the calculations, the negative signs of hyperfine structure constants are suggested and the angular distortion of the trigonal Nd³⁺ center in LiNbO₃, which is unable to be determined by EXAFS measurement, is obtained. The results are discussed.     

H NMR study of interparticle interactions in the system rare-earth element-acetic acid-diamagnetic salt

Complexation of acetic acid in 5.0 M NaNO₃ at 298 K with yttrium-group rare-earth ions (Dy³⁺, Er³⁺, Tm³⁺, Yb³⁺) in the absence and in the presence of Mg²⁺ ions was studied by ¹H NMR spectroscopy in combination with mathematical simulation of complex equilibria. In the presence of Mg²⁺, the stability constants of monoacetate complexes of rare-earth ions decrease relative to the Mg-free systems.