Stannum-(II) dopant effects on morphology evolution and upconversion performance of Yb3+/Er3+:NaGdF4 crystals

Hexagonal Yb³⁺/Er³⁺:NaGdF₄ nanocrystals codoped with Sn²⁺ ions were prepared via a modulated solvothermal method. Upon introducing 25mol% Sn²⁺ ions into the host lattice by substituting Gd³⁺ ions, a portion of Yb³⁺/Er³⁺:NaGdF₄ nanocrystals was converted into nanorods. Meanwhile, the upconversion (UC) luminescence intensity of 542 nm and 652 nm were intensified by 24 and 33 times respectively, when compared with samples without Sn²⁺ ions doping. The effect of Sn²⁺ ions doping content on the morphology and UC emission performances of Yb³⁺/Er³⁺:NaGdF₄ nanocrystals were discussed in detail. The enhancement of UC luminescence intensity could be attributed to the growth of UC nanocrystals and the low crystal local symmetry around Yb³⁺/Er³⁺ ion pairs. This study may be beneficial for fabricating high-performance UC materials and realizing their practical applications.     

Thermal stability of tin charge states in the structure of the (As<Subscript>2</Subscript>Se<Subscript>3</Subscript>)<Subscript>0.4</Subscript>(SnSe)<Subscript>0.3</Subscript>(GeSe)<Subscript>0.3</Subscript> glass

Two valence states of tin atoms (namely, the doubly charged Sn²⁺ and quadruply charged Sn⁴⁺ states) in the structure of the (As₂Se₃)_0.4(SnSe)_0.3(GeSe)_0.3 glasses are identified by ¹¹⁹Sn Mössbauer spectroscopy. It is demonstrated that the concentration ratio of the doubly charged Sn²⁺ and quadruply charged Sn⁴⁺ states in the glass of this composition depends on the rate of quenching of the melt and on the initial temperature of the melt before quenching. The optical band gap and the activation energy for electrical conduction of the studied glass do not depend on the concentration ratio of the Sn²⁺ and Sn⁴⁺ ions. This behavior of the optical band gap and the activation energy is explained within the model according to which the structure of the glasses under investigation is built up of the structural units AsS_3/2, As_2/2Se_4/4, GeSe_4/2, SnSe_4/2, and SnSe_3/3, which correspond to the compounds AsSe₃, AsSe, GeSe₂, SnSe₂, and SnSe, respectively.     

Chromatographic Separations of Metal Ions on Zirconium Tungstoarsenate Impregnated Ion-Exchange Papers

Abstract

A new heteropolyacid salt ion-exchanger, zirconium tungstoarsenate, has been used for preparing impregnated ion-exchange papers. Twenty-nine metal ions have been chromatographed and R_F values determined in seven different mixed solvent systems containing 1-propanol and HNO³ or HCl. On the basis of the difference in selectivities for different metal ions on impregnated papers, a large number of binary and ternary separations has been obtained. Some of the important separations achieved are Ag⁺–Tl⁺, Ag⁺–Pt(IV), Zn²⁺–Hg²⁺, Sb³⁺–Bi³⁺, Zn²⁺–UO₂ ²⁺, Fe²⁺–Fe³⁺, Sb³⁺–Bi³⁺–Hg²⁺, Ag⁺–Ba²⁺–UO₂ ²⁺, and Ag⁺–Zn²⁺–Cu²⁺–Sn²⁺. The results are compared with those obtained on plain papers.     

Application of a macromolecular Sn (II) complex to the preparation of 99mTc radiopharmaceuticals

To develop insoluble Sn²⁺ complexes for the preparation of ^99mTc radiopharmaceuticals, the adsorption of Sn²⁺ to macroreticular chelating ion exchange resins having various functional groups was investigated. Among them, a resin containing aminophosphonic acid groups showed a high adsorption capacity for Sn²⁺, which was bound strongly to the resin by chelation. This macromolecular Sn²⁺ complex was very stable against hydrolysis and oxidation, and could be applied satisfactorily for the reduction of ^99mTc.     

TLC of 48 Metal Ions on Silica Gel-G Plates in DMSO-HCI Systems

Abstract

The thin-layer chromatography of 48 metal ions has been performed in 29 DMSO-HCI solvent systems. The HC1 concentration varies from 1 to 6 M and the ratios of DMSO-HCI by volume are 1: 9, 3: 7, 5: 5,7: 3, and 9:1. A number of interesting separations have been achieved: e.g., Sn⁴⁺-Sn²⁺, Ti⁴⁺-Fe³⁺, Zr⁴⁺-UO₂ ²⁺, Zr⁴⁺-Th⁴⁺, Zr⁴⁺-La³⁺, Sn²⁺-Sb³⁺, and W⁶⁺ - MO⁶⁺-UO₂ ²⁺.     

Ba4R2Sn4Nb6O30 (R = La,Nd, Sm) lead-free relaxors with filled tungsten bronze structure

Ba₄R₂Sn₄Nb₆O₃₀ (R = La, Nd, Sm) lead-free relaxor ceramics were prepared by a standard solid-state reaction process. The B-site substitution effects of Sn⁴⁺ on crystal chemistry, dielectric, and ferroelectric nature were systematically discussed. Tetragonal tungsten bronze compound in space group P4/mbm was confirmed as the major phase for each composition. With decreasing temperature, a broad peak with strong frequency dispersion was observed for both the dielectric constant (ε′) and dielectric loss (tan δ), which could be well described by the Vogel-Fulcher relation. Raman analysis revealed the transformation of the internal vibration modes, demonstrating the modification effects of Sn⁴⁺ on the crystal chemical environment owing to its d¹⁰ electron configuration. The ferroelectrically inert Sn⁴⁺ in B sites acted as disturbing centers which weakened the dipole coupling and the long-range ferroelectric order, and subsequently led to the suppression of ferroelectric transition and the enhancement of relaxor behavior.     

Temperature dependent negative permittivity in solid solutions Sr2Mn1-xSnxO4 (x = 0, 0.3, 0.5)

A few compositions of the system Sr₂Mn_1-xSn_xO₄ (x = 0.0, 0.3, 0.5) were synthesized in the air by the solid-state ceramic route. A change in the sign (positive to negative) of the permittivity above a particular temperature (T_C) is observed at all the measured frequencies. The negative permittivity was analyzed by the Drude-Lorentz model. It was found that negative permittivity is caused by the plasma oscillations of thermally excited free charge carriers. Analysis of XPS spectra confirmed the presence of mixed-valence states of both Mn (Mn⁴⁺ and Mn³⁺) and Sn (Sn⁴⁺ and Sn²⁺) ions. The UV–vis.-IR spectroscopy results indicated generation of a large number of defect states in the forbidden bandgap region of Sr₂MnO₄ on the substitution of Sn at Mn site. Synthesized samples are promising metamaterials for radio frequency (10 Hz -2 MHz) region applications due to the high-temperature plasmonic behavior.     

Characterization of indium tin oxide (ITO) thin films prepared by a sol-gel spin coating process

Indium tin oxide (ITO) thin films were prepared by a sol-gel spin coating method, fired, and then annealed in the temperature range of 450-600°. The XRD patterns of the thin films indicated the main peak of the (2 2 2) plane and showed a higher degree of crystallinity with an increase in the annealing temperature. Upon annealing the films at 500 and 600°, two binding energy levels of Sn⁴⁺ ion of 486.9 eV and 486.6 eV, respectively, were measured in the XPS spectra. The ITO film that was annealed at 600° contained two oxidation states of Sn, Sn²⁺ and Sn⁴⁺, and it had a higher sheet resistance based on a rather low doping concentration of Sn⁴⁺. The film that was annealed at 500° and subsequently treated with 0.1 N HCl solution for 40 s showed a sheet resistance of 225 Ω/square. The surface treatment by the acidic solution diminished the RMS (root mean square) roughness value and the residual carbon content (XPS peak intensity of carbon) of the ITO films. It seems that the acid-cleaning of the ITO thin films led to a decrease of the surface roughness and sheet resistance.     

Hydrothermal growth of Sn-doped FeS2 cubes on FTO substrates and its photoelectrochemical properties

Sn⁴⁺-doped FeS₂ cubes with high yield thin films have been successfully synthesized on FTO glass through a simple hydrothermal process. The Sn⁴⁺-doped FeS₂ cubes are single crystalline in cubic structure with (2 0 0) facet as the main exposed surface. The formation process was investigated. Sn²⁺ was found to play an important role during the formation process of FeS₂ growing on FTO glass. The direct optical band gap value can be estimated to be 1.71 eV which is much larger than that of bulk FeS₂ due to the Sn⁴⁺ doping. The photoelectrochemical properties of the Sn⁴⁺-doped FeS₂ films were studied as well. There is a significant increase in photocurrent of Sn⁴⁺-doped FeS₂ electrode compared to that of undoped sample.     

Effect of Sn4+ doping on the photoactivity inhibition and near infrared reflectance property of mica-titania pigments for a solar reflective coating

The influence of Sn⁴⁺ doping on the photoactivity inhibition and near infrared reflectance property of mica-titania pigments was investigated. X-ray diffraction analysis confirmed that Sn⁴⁺doping promoted phase transformation from anatase to rutile. The rutile promoting effect of Sn⁴⁺ can be ascribed to the distortion of the crystal structure of anatase after the replacement of Ti⁴⁺ by Sn⁴⁺. Sn⁴⁺ doping had a great influence on the photoactivity of mica-titania pigments. The photoactivity of mica-titania pigments was enhanced at low dopant levels, whereas its photoactivity was inhibited at high dopant levels. Remarkably, the degradation rate constant of mica-titania pigments doped with 1.0 wt% of SnCl₄ was approximately 12.9% of that of the undoped sample. A possible mechanism for this effect was proposed. Moreover, the near-infrared solar reflectance of mica-titania pigments reached 0.97. An approximately 8.3 °C decrease in temperature was obtained for the inner surface of a calcium silicate board coated with mica-titania pigments. Furthermore, a solar reflective coating coloured with low photocatalytic mica-titania pigments exhibited high photostability against weathering conditions. Therefore, mica-titania pigments with high levels of the Sn⁴⁺dopant are excellent candidates for use in solar reflective coatings.     

Exploring the luminescence of tin-incorporated nickel-sensitized lithium gallate short-wave-infrared phosphors

A series of Ni²⁺-sensitized LiGa₅O₈ nanocrystals doped with varying amounts of Sn⁴⁺ were synthesized via a high-temperature solid-state method. X-ray diffraction and scanning electron microscopy were employed to investigate the microstructure of the LiGa₅O₈ host, and optical spectroscopy was used to examine the effects of Sn⁴⁺ addition on the emission spectra and persistent luminescence (PersL) properties, which indicated a homogeneous distribution of the constituent elements in the phosphor. The Sn⁴⁺ incorporation led to an approximately sixfold enhancement of photoluminescence intensity at room temperature and decrease in the energy transition of Ni²⁺(³T₂(³F)→³A₂(³F)), which resulted in ∼65 nm bathochromic shift in the photoluminescence emission maxima. However, the addition of Sn⁴⁺ dopant led to a decrease in the quantum yield of luminescence compared to that of the original phosphor. Temperature-dependent thermoluminescence measurements revealed that doping of LiGa₅O₈ with Sn⁴⁺ interfered with the Ni²⁺ trap centers. Moreover, Ni²⁺-sensitized Sn⁴⁺-doped LiGa₅O₈ nanocrystals exhibited an afterglow effect that persisted for up to 300 s.     

Syntheses and Characterization of Diorganotin Derivatives of 2-Mercapto-5-methyl-1,3,4-thiadiazole: X-ray Crystal Structure of Polymeric (C3H3S2N2) [(n-C4H9)6Sn3O(OH)2](C3H3S2N2)

Diorganotin derivatives of 2-mercapto-5-methyl-1,3,4 -thiadiazole, (R = Me 1, n-Bu 2, Ph 3, PhCH₂ 4), have been synthesized and characterized by IR, ¹H, ¹³C and ¹¹⁹Sn NMR spectroscopy. Among them, polymer 2 was also characterized by X-ray crystallography diffraction analysis. This revealed that 2 showed a unique tricyclic structure consisting of a fused five-membered Sn₂ON₂ ring and a four-membered Sn₂O₂ ring. These formed a planar N₂Sn₃O₂ skeleton, with distorted trigonal bipyramidal coordination at the two tin centers and a distorted octahedral coordination at the other tin center. The supramolecular structure of polymer 2 was a 1D zig-zag polymeric chain stabilized by intermolecular O–H...S hydrogen bonds. An erratum to this article can be found at     

Evolution of microstructure,optical, and magnetic properties in multiferroic CuFe1-xSnxO2 (x = 0–0.05)

Evolution of the microstructure, optical, and magnetic properties have been investigated systematically in multiferroic CuFe_1-xSn_xO₂ (x?=?0–0.05) ceramics. Substitution of Sn⁴⁺ for Fe³⁺ results in expansion of CuFeO₂ lattice, and reduces the density of the material, but the metal oxidation states are unchanged. Observation of the optical properties shows that the value of the direct optical band gap (E_g) decreases with increasing Sn doping level, and that the CuFe_1-xSn_xO₂ (x?=?0–0.04) series with values >?3.1?eV. Magnetic susceptibility measurements show that Sn⁴⁺ doping decreases the Curie-Weiss temperature, i.e. weakens the strength of the antiferromagnetic interaction between high-spin Fe³⁺ ions, but does not affect the stability of the antiferromagnetic phase, and all samples undergo successive magnetic transitions at about T_N1 =?15?K and T_N2 =?11?K. However, magnetization curves show that changes occur in the magnetic interactions and both ferromagnetism and antiferromagnetism co-exist in the Sn⁴⁺-doped samples. The maximum value of the saturation magnetization of 1.8?emu·g^?1 was observed for the x?=?0.03 sample in a 2.5?kOe field. The changes in the magnetic behavior are closely related to the lattice distortion and charge compensation, which are discussed in detail in this work.     

Electrochemical synthesis of Ni-Sn alloys in molten LiCl-KCl

The electrochemical formation of Ni-Sn was investigated in molten LiCl-KCl in the temperature range 380-580 °C. Before, an electrochemical study of the Ni²⁺/Ni⁰, Sn⁴⁺/Sn²⁺ and Sn²⁺/Sn⁰ redox couples was performed by cyclic voltametry and chronopotentiometry in a wide temperature range. It had been pointed out that in the case of the Sn⁴⁺/Sn²⁺ redox couple, an insoluble compound is probably formed for T < 460 °C. For higher temperature, this compound becomes soluble and then, the shape of the cyclic voltammogram is analogue to the one usually observed when a diffusion-controlled process is involved. The diffusion coefficient values of Ni²⁺ and Sn²⁺ ions were determined. For instance, D_Ni(II) and D_Sn(II) values deduced from chronopotentiometry were about 2.1 × 10⁻⁵ and 2.7 × 10⁻⁵ cm² s⁻¹ at 440 °C, respectively. Then, Ni-Sn alloys have been formed in potentiostatic mode. The electrochemical route proposed in this paper leads to the formation of crystallized alloys with a well-defined composition depending on the operating conditions.     

Microwave dielectric properties of (Zn1/3B2/3)0.5(Ti0.8M0.2)0.5O2 (B = Nb5+, Ta5+, M = Sn4+, Ge4+) ceramics

Dielectric properties of (Zn_1/3Nb_(2?x)/3Ta_x/3)_0.5(Ti_0.8Sn_0.1Ge_0.1)_0.5O₂ (x = 0, 1, 2) and/or (Zn_1/3Nb_1/3Ta_l/3)_0.5(Ti_0.8Sn_0.2(l?y)Ge_0.2y)_0.5O₂ (y = 0, 0.5, 1) were investigated at the microwave frequencies. For the compositions with single phase of rutile structure, the dielectric constant (K) of specimens was not only dependent on the dielectric polarizabilities, but also on the bond length ratio of apical bond (d_apical) to equatorial bond (d_equatorial) of oxygen octahedron in the unit cell. Temperature coefficients of the resonant frequencies (TCF) of the specimens with B = Nb⁵⁺ and/or M = Sn⁴⁺ was larger than those with B = Ta⁵⁺ and/or M = Ge⁴⁺. These results could be attributed to the changes of the degree of oxygen octahedral distortion. Quality factors (Qf) of the specimens with B = Ta⁵⁺ and/or M = Sn⁴⁺ were larger than those with B = Nb⁵⁺ and/or M = Ge⁴⁺.     

Ni-doped hibonite (CaAl12O19): A new turquoise blue ceramic pigment

A new structure for ceramic pigments was synthesized by a conventional solid state reaction process. It is based on Ni-doped hibonite, CaAl₁₂O₁₉, which assumes a turquoise-like blue colour similar to that of V-doped zircon. Hibonite is associated with anorthite, CaAl₂Si₂O₈, acting like a fluxing agent in order to lower the synthesis temperature, and with cassiterite, SnO₂, acting as a tin buffer to promote coupled Ni²⁺ + Sn⁴⁺ → Al³⁺ + Al³⁺ substitutions, in order to ensure the electric neutrality of the hibonite lattice. Since relatively low chromophore contents are required, this new system constitutes an interesting alternative to the common blue ceramic pigments based on cobalt aluminate spinel or vanadium-doped zircon, implying lower cost and environmental advantages. The pigments characterization was performed by X-ray powder diffraction, diffuse reflectance spectroscopy, CIELAB colorimetric analysis, and testing in ceramic glazes and bodies. The substitution of Al³⁺ by bigger ions, like Ni²⁺ and Sn⁴⁺, increases the cell volume compared to undoped hibonite and is responsible for the turquoise blue colour, as verified by UV–vis analysis. The chromatic mechanism is due to incorporation of Ni²⁺ in tetrahedral coordination, likely occurring at the site M3 of the hibonite lattice, where it partially substitutes the Al³⁺ ion. While this product shows a strong hue as a pigment, it is not stable after severe testing in glazes and attempts to improve its colouring performance are now under development.     

Model study of pyrite demineralization by hydrogen peroxide oxidation at 30 °C in the presence of metal ions (Ni2+, Co2+ and Sn2+)

Dissolution of pyrite involving oxidation by hydrogen peroxide (H₂O₂) in the presence of metal ions (Ni²⁺, Co²⁺ and Sn²⁺) has been investigated. Before oxidation, pure and well crystalline structure of the acid washed pyrite sample, used in the present investigation, was confirmed by X-ray diffraction and chemical analysis. Oxidation of pyrite was examined by the determination of soluble sulfur. The rate of oxidation of pyrite with H₂O₂ is best represented by determining the rates of total soluble sulfur production. Each experiment was carried out for short (1–4 h) and extended (24 h) time periods. Pyrite is oxidized by H₂O₂ (1:1) up to the extent of 31.3% at short time period, which however remained the same even at extended time period. Increased amount of soluble sulfur has been observed when pyrite was oxidized by H₂O₂ (1:1) in the presence of Ni²⁺ or Co²⁺ or Sn²⁺ ion at short time period. The effectiveness of these metal ions in relation to pyrite oxidation at short time period decreases in the order Co²⁺>Sn²⁺>Ni²⁺, while at extended time period the order is Co²⁺>Ni²⁺>Sn²⁺. With Co²⁺ ion, the highest pyrite oxidation is obtained both at short (34.0%) and extended (35.0%) time period, while it is the lowest 31.3% with Ni²⁺ ion at short time and 25.3% with Sn²⁺ ion at extended time period. The effect of chloride ion on the rate of oxidation of pyrite is not pronounced in the metal ion containing systems. Substantial depletion in the concentration of externally added metal ions is in good agreement with the level of oxidation and infers certain adsorption or precipitation of metal ions on pyrite surface. The results of this study throw a new light of the influence of metal ions in the dissolution of pyrite in oxidation systems and has considerable applications in fields of demineralization, desulfurization and environmental science.     

High Na‐ion conducting Na1+x[SnxGe2−x(PO4)3] glass‐ceramic electrolytes: Structural and electrochemical impedance studies

Na‐ion conducting Na_1+x[Sn_xGe_2?x(PO₄)₃] (x = 0, 0.25, 0.5, and 0.75 mol%) glass samples with NASICON‐type phase were synthesized by the melt quenching method and glass‐ceramics were formed by heat treating the precursor glasses at their crystallization temperatures. XRD traces exhibit formation of most stable crystalline phase NaGe₂(PO₄)₃ (ICSD‐164019) with trigonal structure. Structural illustration of sodium germanium phosphate [NaGe₂(PO₄)₃] displays that each germanium is surrounded by 6 oxygen atom showing octahedral symmetry (GeO₆) and phosphorous with 4 oxygen atoms showing tetrahedral symmetry (PO₄). The highest bulk Na⁺ ion conductivities and lowest activation energy for conduction were achieved to be 8.39 × 10^?05 S/cm and 0.52 eV for the optimum substitution levels (x = 0.5 mol%, Na_1.5[Sn_0.5Ge_1.5(PO₄)₃]) of tetrahedral Ge⁴⁺ ions by Sn⁴⁺ on Na–Ge–P network. CV studies of the best conducting Na_1.5[Sn_0.5Ge_1.5(PO₄)₃] glass‐ceramic electrolyte possesses a wide electrochemical window of 6 V. The structural and EIS studies of these glass‐ceramic electrolyte samples were monitored in light of the substitution of Ge by its larger homologue Sn.     

Novel Supramolecular Square Grid-Like Structure: Synthesis and Characterization of [(Me3Sn)2CrO4]

Reactions of K₂Cr₂O₇ and K₂CrO₄ with Me₃SnCl yielded [(Me₃Sn)₂CrO₄] (1) and [(Me₃Sn)₂CrO₄(Me₃SnOH)] (2), respectively, which were characterized by elemental analysis, ¹H-NMR spectroscopy, and an X-ray diffraction study. Compound 1 shows a novel square grid-like structure consisting of CrO₄ ^2– and Me₃Sn⁺ ions, whereas 2 exhibits a three-dimensional structure composed of CrO₄ ^2–, Me₃Sn⁺, and [(Me₃Sn)₂SnOH]⁺ ions.     

Reaction mechanism of tin nitride (de)lithiation reaction studied by means of Sn Mössbauer spectroscopy

Tin nitride thin films have been reported as promising negative electrode materials for lithium-ion solid-state microbatteries. However, the reaction mechanism of this material is not yet fully understood. Results on thin film electrodes pointed out that the conversion mechanism of tin nitride most likely differs from the conversion mechanism usually observed for other oxide and nitride conversion electrode materials. The electrochemical data showed that more than six Li per Sn atom can be reversibly exchanged by this material while about four are expected. In order to investigate in more detail the reaction mechanism of tin nitride, thick film electrodes of two compositions (1:1 and 3:4) have been studied. The as-prepared materials were characterized by means of X-ray diffraction, scanning electron microscopy, transmission electron microscopy and ¹¹⁹Sn Mössbauer spectroscopy. Moreover, films (de)lithiated to various extents were analyzed ex situ with Mössbauer spectroscopy. The corresponding results indicate that a more complex reaction mechanism than that generally accepted takes place. During Li-ion insertion, the disappearance of Sn⁴⁺ environments is correlated with the formation of Li-Sn phases, and most likely also of Li₃N. In the case of the SnN_x 1:1 composition films, the formation of various Li-Sn phases is evidenced while only the signature of ‘Li₂₂Sn₅’ is clearly measured for the 3:4 composition. Upon Li-ion extraction, the Li-Sn phases and Li₃N recombine to form octahedrally and tetrahedrally coordinated Sn⁴⁺. The extraction is not fully reversible and the end product consists of a mixture of a tin nitride structure plus a Li_ySn product having the same isomer shift as LiSn but a much higher quadrupole splitting, and most likely some Li₃N.