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1.
Fluorescence and spectral hole burning properties of Eu3+ ions were studied in nanocrystals-precipitated SnO2-SiO2 glasses. The glasses were prepared to contain various amount of Eu2O3 using the sol-gel method, in which SnO2 nanocrystals were precipitated by heating in air. In the glasses containing Eu2O3 less than 1%, the Eu3+ ions were preferentially doped in the SnO2 nanocrystals and their fluorescence intensities were enhanced by the energy transfer due to the recombination of electrons and holes excited in SnO2 crystals. The SnO2 nanocrystals-precipitated glasses exhibited the persistent spectral holes with the depth of ∼25% of the total fluorescence intensities of the Eu3+ ions. With the increasing Eu2O3 concentration, the amount of SnO2 nanocrystals decreased and the Sn4+ ions formed the random glass structure together with the silica network. This structure change induced the fluorescence intensities and the hole depth to decrease.  相似文献   

2.
Persistent spectral hole burning was studied in Eu3+ ions-doped Al2O3-SiO2 glass prepared by a sol-gel method. The gel synthesized by the hydrolysis of Si- and Al-alkoxides and EuCl3·6H2O was heated in air and hydrogen gas atmospheres. For the glass heated in air to contain OH bonds, the hole was formed by the photoinduced rearrangement of the OH bonds surrounding the Eu3+ ions, and was thermally refilled and erased above 200 K. On the other hand, the glass heated in hydrogen gas showed the hole spectrum above 200 K. It was found that the hole depth was independent of the temperature and was 7% of the total intensity at room temperature. The proposed mechanism was the electron transfer between the Eu3+ ions and the defect centers formed in glass matrix.  相似文献   

3.
Persistent spectral hole burning was investigated for the Eu3+ ions-doped glasses prepared by a sol-gel method. For the glasses containing OH bonds, persistent spectral hole is burned by the laser-induced rearrangement of the OH bonds surrounding the Eu3+ ions, which is thermally unstable to erase up to 200 K. On the other hand, the Eu3+-doped Al2O3-SiO2 glasses which are heated under H2 gas or irradiated with X-ray exhibit room temperature PSHB. The depth of the burnt hole increases as the Al2O3 content increases. The hole-formation could be explained by a model of the excitation of the Eu3+ ions and subsequent electron transfer with the excited [Eu3+] or oxygen-defect centers in the Al—O bonds. The burnt holes are more stable compared with those burned by the rearrangement of the OH bonds.  相似文献   

4.
The title complexes, K[SmIII(Edta)(H2O)3] · 2H2O(I)(H4Edta = ethylenediamine-N,N,N′,N′-tetraacetic acid) and K2[SmIII(Pdta)(H2O)2]2 · 4.5H2O (II) (H4Pdta = propylenediamine-N,N,N′,N′-tetraacetic acid), were prepared and their compositions and structures were determined by elemental analyses and single-crystal X-ray diffraction techniques, respectively. Complex I has a mononuclear structure, and the Sm3+ ion is nine-coordinated by an Edta ligand and three water molecules, yielding a pseudo-monocapped square antiprismatic conformation, and the complex crystallizes in the orthorhombic crystal system with space group Fdd2. The crystal data are as follows: a = 19.84(5), b = 35.58(9), c = 12.15(3) ?, V = 8580(38) ?3, Z = 16, ρ c = 1.925 g/cm3, μ = 3.010 mm−1, F(000) = 4976, R = 0.0252, and wR = 0.0560 for 3510 observed reflections with I ≥ 2σ(I). Complex II has a binuclear structure and the Sm3+ ion is ten-coordinated by a Pdta ligand, two oxygen atoms from a carboxylic group of adjacent Pdta ligand and two water molecules, yielding a distorted bicapped square antiprismatic prism. The complex crystallizes in the triclinic crystal system with space group P $ \bar 1 $ \bar 1 . The crystal data are as follows: a = 8.9523(15), b = 10.7106(15), c = 11.6900(19) ?, α = 80.613(5)°, β = 80.397(5)°, γ = 76.530(4)°, V = 1065.7(3) ?3, Z = 1, ρc = 1.970 g/cm3, μ = 2.532 mm−1, F(000) = 1620, R = 0.0332 and wR = 0.0924 for 5390 observed reflections with I ≥ 2σ(I).  相似文献   

5.
A 3D infinitely extended structural rare earth coordination compound with a formula of K3{[Sm(H2O)7]2Na[α-SiW11O39Sm(H2O)4]2}·14H2O has been synthesized by reaction of Sm2O3, HClO4, NaOH with α-K8SiW11O39·nH2O, and characterized by IR, UV spectra, ICP, TG-DTA, cyclic voltammetry, variable-temperature magnetic susceptibility and X-ray single-crystal diffraction. X-ray single-crystal diffraction indicates that the title compound crystallizes in a triclinic lattice, Pī space group, with a = 1.2462(3) nm, b = 1.2652(3) nm, c = 1.8420(4) nm, α = 87.45(3)°, β = 79.91(3)°, γ= 82.57(3)°, Z = 1, R1 = 0.0778, wR2 = 0.1610. Structural analysis reveals that Sm3+(1) coordination cation has incorporated into the vacant site of [α-SiW11O39]8− entity, forming the [α- SiW11O39Sm(H2O)4]5− subunit. The two adjacent [α-SiW11O39Sm(H2O)4]5− subunits are combined with each other through two Sm(1)-O-W bridges accompanying the formation of dimmer structural unit [α-SiW11O39Sm(H2O)4]2 10− of the title compound. The neighboring dimmer structural units [α-SiW11O39Sm(H2O)4]2 10− are linked to form the 1D chainlike structure by means of two Sm3+(2) and a Na+(1) coordination cations. The K+(1) cations connect the 1D packing chains constructing the 2D netlike structure, and adjacent netlike layers are also grafted by K+(2) cations to build the novel 3D infinitely extended structure. The result of TG-DTA curves manifests that the decomposition temperature of the title polyanionic framework is 554°C. The cyclic voltammetry measurements show that the title polyanion has the two-step redox processes in aqueous solution with pH = 3.1. Variable temperature magnetic susceptibility indicates the title compound obeys the Cruie-Weiss Law in the higher temperature range from 110 to 300 K, while in the lower temperature range from 2 to 110 K the comparatively strong antiferromagnetism interactions can be observed.  相似文献   

6.
pH potentiometric and spectrophotometric investigations on the complex formation equilibria of CuII with iminodiacetate (ida2−) and heterocyclic N-bases, viz. imidazole and benzimidazole (B), in aqueous solution in binary and ternary systems using different molar ratios of the reactants indicated the formation of complexes of the types, Cu(ida), Cu(ida)(OH), (ida)Cu(OH)Cu(ida), Cu(B)2+, Cu(H-1B)+, Cu(ida)(H−1B), (ida)Cu(B)Cu(ida) and (ida)Cu(H−1B)Cu(ida). Formation constants of the complexes at 25 ±1° at a fixed ionic strength,I = 0.1 mol dm−3 (NaNO3) in aqueous solution were evaluated and the complex formation equilibria were elucidated with the aid of speciation curves. Departure of the experimental values of the reproportionation constants(ΔlogK cu) of ternary Cu(ida)(H−1B) complexes from the statistically expected values, despite their formation in appreciable amounts at equilibrium, were assigned tofac(f)-mer(m) equilibria of the ida2− ligand coordinated to CuII, as the N-heterocyclic donors, (H−1B), coordinatetrans- to the N-(ida2−) atom in the binary Cu(ida) f complex to form the ternary Cu(ida) m (H−1B) complexes  相似文献   

7.
A method is described for construction of an amperometric xanthine biosensor based on graphite rod modified through adsorption of xanthine oxidase. Enzymatically produced H2O2 from xanthine was split into 2H+ + O2 + 2e− at 0.6 V and the current was measured, which was directly proportional to xanthine concentration ranging from 1 ° 10−7 to 6 ° 10−7 M with a detection limit of 1 ° 10−7 M. The biosensor exhibited optimum response within 35 sec at pH 7.0 and 35°C. It was employed for determination of xanthine in tea leaves (0.9 ° 10−5−2.5 ° 10−5 mmol/g), coffee powder (3.2 μmol/g) and fish meat (90 mmol/g). The content of xanthine in fish meat increased 6.5 times with its storage at room temperature during 15 days. The enzyme electrode could be reused 200 times during the span of 30 days, when stored in reaction buffer at 4°C.  相似文献   

8.
RbAlO2-based solid solutions are synthesized in the systems Rb2 − x Al2 − x A x O4 (A = P, V). Temperature and concentration dependences of their conductance are studied; the rubidium-cationic character of the conductance is corroborated. The high ionic conductivity of the synthesized phases (∼5 × 10−3 S cm−1 at 300°C, ∼2 × 10−2 S cm−1 at 700°C) is caused by (a) formation of rubidium vacancies as a result of the replacing of Al3+ ions by fivefold-charged cations of phosphorus or vanadium and (b) disordered crystal structure of γ-KAlO2 type. The obtained data are compared with the results of the studying of similar systems. Original Russian Text ? G.Sh. Shekhtman, E.I. Volegova, E.I. Burmakin, 2009, published in Elektrokhimiya, 2009, Vol. 45, No. 4, pp. 495–499.  相似文献   

9.
Substitution inertcis-diaqua CrIII complexes: cis-[(Lx−)CrIII(H2O)2](3−x)+ derived from N-donor ligands (Lx−) viz., bipyridine and 1,10-phenanthroline (x = 0) and N,O-donor ligands viz., nitrilotriacetate and anthranilate N,N-diacetate (x = 3) titrate as diprotic acids in aqueous solution and enhance the acidity of otherwise weakly acidic boric acid (H3BO3) producing mononuclear and binuclear mixed ligand CrIII-borate complexes: [(L)Cr(H2BO4)]x− and [(L)Cr(BO4)Cr(L)](1−2x)+ respectively through coordination of the H2O and/or OH ligands, cis-coordinated in the CrIII-complexes on the electron deficient BIII-atom in H3BO3 with release of protons. Deprotonation of the parent CrIII-complexes and their reactions with H3BO3 have been investigated by potentiometric method in aqueous solution,I = 0.1 mol dm−3 (NaNO3) at 25 ±0.1°C. The equilibrium constants have been evaluated by computerized methods and the tentative stoichiometry of the reactions have been worked out on the basis of the speciation curves  相似文献   

10.
The Na[SmIII(edta)(H2O)3] · 5H2O (H4edta = ethylenediamine-N,N,N′,N′-tetraacetic acid) and {[SmIII(Hpdta)(H2O)] · 2H2O} n (H4pdta = propylenediamine-N,N,N′,N′-tetraacetic acid) complexes were prepared with heat-refluxing and acidity-adjusting methods, respectively. And their composition and structures were determined by elemental analyses and single-crystal X-ray diffraction techniques. The Na[SmIII(edta)(H2O)3] · 5H2O complex shapes a mononuclear structure, and crystallizes in the orthorhombic crystal system with space group Fdd2. The central SmIII ion is nine-coordinated by one hexadentate edta ligand and three water molecules. The crystal data are as follows: a = 19.139(10) ?, b = 35.00(2) ?, c = 11.928(10) ?, V = 7989(9) ?3, Z = 16, D c = 2.014 g/cm3, μ = 3.046 mm−1, F(000) = 4848, R = 0.0439, and wR = 0.0941 for 3434 observed reflections with I ≥ 2σ(I). The SmN2O7 part in [SmIII(edta)(H2O)3] complex anion forms a pseudo-monocapped square antiprismatic polyhedron. The {[SmIII(Hpdta)(H2O)] · 2H2O} n complex is prepared with protonated pdta ligand firstly, which forms one dimensional unlimited ladderlike eight-coordinated structure, and crystallizes in the monoclinic crystal system with space group P21/n. The central SmIII ion, in one construction unit, is coordinated by two nitrogen atoms from one hexadentate pdta ligand and six oxygens from the same pdta ligand, one water molecule and one carboxylic group of neighbour pdta ligand, respectively. The crystal data are as follows: a = 12.720(3) ?, b = 9.3800(19) ?, c = 14.420(3) ?, β = 96.11(3)°, V = 1710.7(6) ?3, Z = 2, D c = 1.971 g/cm3, μ = 3.492 mm−1, F(000) = 1004, R = 0.0225 and wR = 0.0607 for 3182 observed reflections with I ≥ 2σ(I). Otherwise, each part of SmN2O6 in {[SmIII(Hpdta)(H2O)] · 2H2O} complex segment adopts a pseudo-square antiprismatic polyhedron.  相似文献   

11.
The Er3+-doped Al2O3 nanopowders have been prepared by the sol-gel method, using the aluminium isopropoxide [Al(OC3H7)3]-derived γ-AlOOH sols with addition of the erbium nitrate [Er(NO3)3·5H2O]. The five phases of γ-(Al,Er)2O3, θ-(Al,Er)2O3, α-(Al,Er)2O3, ErAlO3, and Al10Er6O24 were detected with the 0–20 mol% Er3+-doped Al2O3 nanopowders at the different sintering temperature of 600–1200°C. The average grain size was increased from about 5 to 62 nm for phase transformation of undoped γ-Al2O3→α-Al2O3 at the sintering temperature from 600 to 1200°C. At the same sintering temperature, average grain size was decreased with increase of the Er3+ doping concentration. Infrared absorption spectra of γ-Al2O3 and θ-Al2O3 nanopowders showed the two broad bands of 830–870 and 550–600 cm−1, the three broad bands of 830–870, 750–760, and 550–600 cm−1, respectively. The infrared absorption spectra for the α-Al2O3 nanopowder showed three characteristic bands, 640, 602, and 453 cm−1. The two characteristic bands of 669 and 418 cm−1 for Er2O3 clusters were observed for the Er3+-doped Al2O3 nanopowders when Er3+ doping concentration was increased up to 2 mol%. The 796, 788, 725, 692, 688, 669, 586, 509, 459, and 418 cm−1 are the characteristic bands of Al10Er6O24 phase.  相似文献   

12.
The kinetics of nucleophilic substitution of pyridine in bis-cationic [Pt(L)(py)]2+ complexes (L=SNS, NNN, NSN) [SNS=bis(methylthiomethyl)pyridine, NNN=bis(2-pyridylmethyl)amine, NSN=bis(2-pyridylmethyl)sulphide] by a series of nucleophiles (Cl, Br, I, N3, (C2H5)2S, NH3, thiourea (tu), NO2, C5H10NH, SeCN, SCN, CN when L=SNS; Cl, Br, I, N3, (C2H5)2S, SCN, NH3, NO2 when L=NNN; Br, N3, NO2, NH3, C5H10NH when L=NSN) have been measured in MeOH at 25 °C, μ =0.1 mol dm−3 (LiClO4 or LiCF3SO3). The logarithms of the second-order rate constants calculated at μ=0, log k° 2, do not follow the dependence upon the n° Pt scale. In particular, the reactivity of the biphilic reagents tu, SeCN, SCN and, to a lesser extent, NO 2, towards these doubly charged substrates is largely lower than expected on the basis of the n° Ptscale. There are good linear relationships between logk° 2 for the bis-cationic substrate [Pt(SNS)(py)]2+, chosen as the standard, and log k° 2 for the same reactions with [Pt(NNN)(py)]2+, [Pt(NSN)(py)]2+ and other double charged complexes previously studied. A new wide nucleophilicity scale based on [Pt(SNS)(py)]2+, that is appropriate to all the bis-cationic substrates, is here proposed  相似文献   

13.
Ge nanocrystal-embedded SiO2 glasses were prepared by a sol-gel process. The glasses synthesized through the hydrolysis of Si(OC2H5)4 and GeCl4 were heated in H2 gas atmosphere at 500 to 800°C, in which Ge4+ ions were reduced to precipitate nanosized Ge crystals with the size smaller than 10 nm diameter. Glasses doped with Ge nanocrystals of diameter of ≈5 nm showed the optical absorption edge at ≈2.8 eV and a broad photoluminescence exhibiting the peak at around 2.2 eV. Large Ge crystals precipitated by heating above 800°C showed no photoluminescence.  相似文献   

14.
γ-Zirconium phosphate-phosphite, γ-Zr·PO4·H2PO3·2H2O, (γ-ZrPP), was prepared and characterized. Direct treatment of γ-zirconium phosphate-phosphite with an ethanol solution of 0.1M 1,10-phenanthrolin and 2,2'-bipyridyl gave the well defined composites, γ-Zr·PO4·H2PO3(phen)0.15·H2O and γ-Zr·PO4·H2PO3(bipy)0.18·0.6H2O respectively.K d values of a mixture of lanthanide ions: La3+, Sm3+, Eu3+ and Yb3+ for the intercalated products and for γ-ZrPP in HNO3 solution at room temperature and at pH 2 and 4 were determined by a radiotracer technique.140La,152mEu,153Sm and175Yb radioisotopes were used for the equilibration experiment using 500 μl (4.0·10−5 mmole) each of the solutions of the tracers as a mixture in 7.5 M HNO3 solution at the desired pH with 0.1 g of γ-ZrPP and of the intercalated products. The selectivity order was found to be dependent on the nature of the ligand and on the pH. The 2,2'-bipyridyl product posseses, at pH 2 in general, a highK d value, specially for Sm3+ (9815.9) compared to that of the 1,10-phenanthrolin product (3375.5) and to γ-ZrPP (419.8). This could be attributed to partial deintercalation of the 2,2'-bipyridyl at pH 2 and increasing of ionogenic groups.  相似文献   

15.
Usually, Sm2+ ions could be reduced by heating the materials in reducing atmospheres. Exposure to ionizing radiations is also known to cause Sm3+→Sm2+ conversion. In this work, BaBPO5 doped with the samarium ion was prepared by high temperature solid-state reaction. Sm2+ ions were obtained by two different reduction methods, i.e., heating in H2 reduced atmosphere and X-ray irradiation. The measurements of X-ray diffraction (XRD), and scanning electron microscope (SEM) were investigated. It is found that the conversion of Sm3+→Sm2+ is very efficient in BaBPO5 hosts after X-ray irradiation. Sm2+ ions under these two reduction methods exhibit different characteristics that were studied by measurements of luminescence and decay. The results showed that the luminescence properties of Sm2+ ions in BaBPO5 were highly dependent on the sample preparation conditions.  相似文献   

16.
The phase and chemical compositions of the precipitates forming in the Sr(VO3)2-VOCl2-H2O system in the V4+/V5+ = 0.11–9 range at 80–90°C are reported. At pH 1–3 and V4+/V5+ = 0.25−9, the general formula of the precipitated compounds is Sr x V y 4+ V12−y 5+O31−δ·nH2)(0.37 ≤ x ≤ 1.0, 1.7 ≤ y ≤ 3.0, 0.95 ≤ δ ≤ 2.1). Polyvanadates containing the largest amount of vanadium(IV) are obtained at an initial V4+/V5+ ratio of 9 and pH 1.9. Precipitation from solutions at pH 3 takes place only in the presence of the VO2+ ion, and the highest precipitation rate is observed at V4+/V5+ = 0.11. The process is controlled by a second-order reaction on the polyvanadate surface. Under hydrothermal conditions at 180°C, Sr0.25V2O5·1.5H2O nanorods are obtained from solutions with a V4+/V5+ molar ratio of 0.1 at pH 3. The nanorods, 30–100 nm in diameter and up to 2–3 μm in length, have a layered structure with an interlayer spacing of 10.53 ± 0.08 ?.  相似文献   

17.
 The diagram of the ternary system Mg2+/Cl, SO4 2−–H2O was established at 15°C by means of analytical and conductimetric measurements. Three compounds were found in this diagram, which are MgSO4·6H2O, MgSO4·7H2O, and MgCl2·6H2O. The solubility field of MgSO4·7H2O is important whereas those of MgSO4·6H2O and MgCl2·6H2O are small. The compositions (mass-%) of the two invariant points determined by the two methods are: MgSO4:MgCl2=2.73:33.80 and MgSO4: MgCl2=3.38:28.91. Both the measured and the calculated isotherm at 15°C have been used for modelling of the diagram Mg2+/Cl, SO4 2−–H2O between 0 and 35°C. The polythermal invariant point was approximately located between 15 and 10°C.  相似文献   

18.
The kinetics of the acid hydrolysis of chromatopenta-amminecobalt(III) ion has been studied using a stopped-flow method over the acidity range 0.01≤[H+]<-1.0 mol dm−3 and 20.0°C<-ϕ<-30.0°C at ionic strengths 0.5 and 1.0 mol dm−3 (LiNO3). These studies reveal that the complex is first protonated and subsequently hydrolysed to the aquapentaammine cobalt(III) ion. The rate constants for the hydrolysis of the mono and diprotonated species at 25°C are 0.83±0.01 s−1 and (1.60±0.02)×104 mol−1 dm−3 s−1, respectively. TMC 2664  相似文献   

19.
128Xe is produced by one-day irradiation of potassium iodide at a neutron flux of 1013 n·cm−2·s−1 at a rate of 0.9 mm3 TPN for one gram of iodine. Xe is separated from the matrix by melting or hydrolysis. The main part of water is removed from the gas by cooling. Xenon (∼99%) thus obtained is freed from H2, O2, N2, CH4 and the last traces of water by gas chromatography and used for isotopic analysis.   相似文献   

20.
New high-conductance potassium-cation solid electrolytes based on potassium aluminate are synthesized by means of partial substitution of five-charged phosphorus cations for three-charged aluminum cations and investigated. The maximum conductivity in the system K2 − 2x Al2 − x P x O4 is found to equal 5 × 10−3 S cm−1 at 200°C and ∼1 S cm−1 at 700°C, which is one of the best values for potassium solid electrolytes. The principal factors responsible for the high conductance are the stabilization of a high-temperature form of potassium aluminate and the formation of additional vacancies in the potassium sublattice, which occurs during the substitution process Al3+ → P5+ + 2V K . __________ Translated from Elektrokhimiya, Vol. 41, No. 12, 2005, pp. 1501–1504. Original Russian Text Copyright ? 2005 by Burmakin, Shekhtman.  相似文献   

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