Zirconium Tin Research Articles

Synthesis and physical characteristics of narrow bandgap chalcogenide SnZrSe 3.

Background: The development of organic/inorganic metal halide perovskites has seen unprecedent growth since their first recognition for applications in optoelectronic devices. However, their thermodynamic stability and toxicity remains a challenge considering wide-scale deployment in the future. This spurred an interest in search of perovskite-inspired materials which are expected to retain the advantageous material characteristics of halide perovskites, but with high thermodynamic stability and composed of earth-abundant and low toxicity elements. ABX 3 chalcogenides (A, B=metals, X=Se, S) have been identified as potential class of materials meeting the aforementioned criteria. Methods: In this work, we focus on studying tin zirconium selenide (SnZrSe 3) relevant physical properties with an aim to evaluate its prospects for application in optoelectronics. SnZrSe 3 powder and monocrystals were synthesized via solid state reaction in 600 - 800 °C temperature range. Crystalline structure was determined using single crystal and powder X-ray diffraction methods. The bandgap was estimated from diffused reflectance measurements on powder samples and electrical properties of crystals were analysed from temperature dependent I-V measurements. Results: We found that SnZrSe 3 crystals have a needle-like structure (space group - Pnma) with following unit cell parameters: a=9.5862(4) Å, b=3.84427(10) Å, c=14.3959(5) Å. The origin of the low symmetry crystalline structure was associated with stereochemical active electron lone pair of Sn cation. Estimated bandgap was around 1.15 eV which was higher than measured previously and predicted theoretically. Additionally, it was found that resistivity and conductivity type depended on the compound chemical composition. Conclusions: Absorption edge in the infrared region and bipolar dopability makes SnZrSe 3 an interesting material candidate for application in earth-abundant and non-toxic single/multi-junction solar cells or other infrared based optoelectronic devices.

Studies on Electrochemical Properties of Polycarbazole Prepared Via Self-Support Polymerization and Self-Doping

Mixed glassy zirconium-tin phosphate, g-Zr0.64.Sn.0.36(HPO4)2.3H2O(g-ZrSnP), nano fibrous cerium phosphate, Ce(HPO4)2 2,9H2O(nCePf), and mixed glassy zirconium-tin phosphate / fibrous cerium phosphate nanocomposite membrane, [g-Zr0.64 Sn0.36 (HPO4)2]0.25 [Ce(HPO4)2]0.75 ..4.43H2O, were prepared and characterized. By chemical , x-ray diffraction (XRD), thermogravimetric analysis (TGA), and Fourier transform spectroscopy (FTIR), Zirconium tin mole ratio were estimated using (EDAX). Novel [g-Zr0.64 Sn0.36 (HPO4)2]0.25 [Ce(HPO4)2]0.75 / polycarbazole nanocomposite membrane was prepared via self-support polymerization of carbazole, which was promoted by the reduction of Ce(iv) phosphate present in the inorganic matrix. Possible explanation is nCePf present on the surface of the nanocomposite is attacked by carbazole, converted to cerium (III) orthophosphate(CePO4). The resultant polycarbazole was characterized by C,H,N analysis, SEM ,FT-IR. UV-Vis and electrical conductance measurements. From elemental (C,H,N) analysis, the amount of polycarbazole present in the composite found to be (2.15 % in wt.). Polycarbazole is considered as one of modern material used in solar cells, furthermore it has become an important material for optoelectronic applications in recent years. The dc conductivity of polycarbazole nanocomposite membrane at 280C (using RC-Circuit) found to be equal to 3x10-5 Scm-1, range of semi-conductors. We suggest self-doping occurred on polymerization, which is due to H+ present in (O3POH)2 groups of [g-Zr0.64 Sn0.36 (HPO4)2]0.25. The electrochemistry of resultant polycarbazole in acetonitrile solution for a range of concentrations from 1.06 x10-4 to 2.19 x 10–3 mol dm-3 was carried out using CV techniques. Investigation of its electrochemical properties affords insight into the mechanisms for their oxidation and reduction, therefore provides the basis for evaluating the stabilities of the material and for designing novel polycarbazole-derived materials with desired properties as well as new devices. That will be discussed.

Synthesis and physical characteristics of narrow bandgap chalcogenide SnZrSe3

Background: The development of organic/inorganic metal halide perovskites has seen unprecedent growth since their first recognition for applications in optoelectronic devices. However, their thermodynamic stability and toxicity remains a challenge considering wide-scale deployment in the future. This spurred an interest in search of perovskite-inspired materials which are expected to retain the advantageous material characteristics of halide perovskites, but with high thermodynamic stability and composed of earth-abundant and low toxicity elements. ABX3 chalcogenides (A, B=metals, X=Se, S) have been identified as potential class of materials meeting the aforementioned criteria. Methods: In this work, we focus on studying tin zirconium selenide (SnZrSe3) relevant physical properties with an aim to evaluate its prospects for application in optoelectronics. SnZrSe3 powder and monocrystals were synthesized via solid state reaction in 600 – 750 °C temperature range. Crystalline structure was determined using single crystal and powder X-ray diffraction methods. The bandgap was estimated from diffused reflectance measurements on powder samples and electrical properties of crystals were analysed from temperature dependent I-V measurements. Results: We found that SnZrSe3 crystals have a needle-like structure (space group – Pnma) with following unit cell parameters: a=9.5862(4) Å, b=3.84427(10) Å, c=14.3959(5) Å. The origin of the low symmetry crystalline structure was associated with stereochemical active electron lone pair of Sn cation. Estimated bandgap was around 1.15 eV which was higher than measured previously and predicted theoretically. Additionally, it was found that resistivity and conductivity type depended on the compound chemical composition. Conclusions: Absorption edge in the infrared region and bipolar dopability makes SnZrSe3 an interesting material candidate for application in earth-abundant and non-toxic single/multi-junction solar cells or other infrared based optoelectronic devices.

Adsorptive features of cesium and strontium ions on zirconium tin(IV) phosphate nanocomposite from aqueous solutions

ABSTRACT In this study, the sorption of Cs(I) and Sr(II) onto zirconium tin(IV) phosphate (ZrSnP) nanocomposite was achieved using the batch technique. ZrSnP has been prepared by the sol–gel technique and characterised using different analytical tools such as FT-IR, XRF, XRD, TGA & DTA, SEM, and TEM. The data obtained from this study showed that the sorption process was a fast equilibrium time (120 min). The distribution coefficients have sequence order; Cs(I) ˃ Sr(II). Reaction kinetic obeys the pseudo-second-order model. The capacity has the values 50.0, and 29.8 mg/g for Cs(I) and Sr(II), respectively. Sorption isotherms are more relevant to a Langmuir isotherm. Negative Gibbs energy values proved that the sorption process was spontaneous with high feasibility. Positive enthalpy values reveal that this process was endothermic. Positive entropy values showed that disorder between the solid–liquid phase increased during adsorption. The real sample study reveals that ZrSnP is a promising sorbent for the removal of 134Cs and 85Sr from low-level radioactive waste. The investigation proved that the ZrSnP is suitable for the removal of Cs(I) and Sr(II) from radioactive waste and could be considered potential material for purification of effluent polluted with these ions.

Nano Sized Tin Zirconium Phosphate Ion Exchanger as Copper Scavenger

A new four component nano sized tin zirconium molybdophosphate, an inorganic ion exchanger of the class of tetravalent metal acid (TMA) salts has been synthesized by co-precipitation method and its ion exchange behaviour was studied. Characterization of the exchanger was done by ICP-AES method and structural studies were carried out using TGA, XRD and FTIR. From the XRD pattern studies, the synthesized ion exchanger was found to be size of 70- 75 nm. The sodium exchange capacity of material was found to be 3.92meq/g. The chemical resistivity of the material has been assessed in various acids, bases and organic solvents like 1M HNO3, IM H2SO4, acetic acid etc. The effects of temperature on capacity, effect of electrolyte concentration and analytical applications also were studied. The protons of hydroxyl groups were found to be the active site. The distribution coefficients of different metal ions like Pb2+, Cu2+, Co2+, Cd2+, Mn2+, Zn2+, Mg2+, Bi3+, Hg2+, Ni2+, Th4+, Ca2+ were studied. On the basis of distribution studies, it was found that the exchanger has high affinity towards Pb2+ and Cu2+ compared with other metal ions. Due to its high affinity towards copper metal ion, it can be used as copper scavenger for waste water treatment and its binary separation of Cu2+ from Mn2+, Mg2+, Cd2+ and Ni2+ was carried out. The UV- Visible Spectrophotometer model JASCO V660 with diffuse reflectance accessories is used to study the absorption of the copper ion on the ion exchange.

Novel SnZr oxides nanomaterials synthesized by ultrasonic-assisted co-precipitation method: Application in biodiesel production and DFT study

Novel solids as Sn2O3-ZrSnO4 nanoparticles were prepared by ultrasonic- assisted co-precipitation method and were characterized by several techniques. The catalytic efficiency of the sonicated SnZr oxide catalysts was evaluated by biodiesel production through a stearic acid esterification reaction with methanol. Also, the optimization conditions and the kinetic study for the esterification reaction were practically implemented. The optimized catalyst (SnZr15m) gave stearic acid conversion of 88.5% at the optimum conditions with pseudo- first order kinetic reaction and the thermodynamic parameters of the esterification reaction were inspected theoretically and compared with the practical data. Furthermore, the recycling experimental results and the theoretically DFT data proved that the stability of the SnZr15m catalyst in the esterification process was reasonable and possess useful quality. The different phases for tin zirconium oxides have been studied using density functional theory (DFT) calculations at the DFT/B3LYP level of theory, using the GENECP basis set in the gas phase. DFT modeling indicated that the stability of the Sn2O3-ZrSnO4 (Sn3ZrO7) phase is higher than the other phases of SnZr oxide which catalyzed the esterification process. The electronic parameters; dipole moment of these compounds in the ground state theoretically were analyzed by computing HOMO and LUMO pictures. Using frontier molecular orbital (FMO) analysis, non-linear optical (NLO) properties and quantum chemical parameters were evaluated. The charge transfer of the electron density in the studied compounds was characterized by natural bond orbital analysis (NBO). For understanding of the reactivity points, the molecular electrostatic potential surfaces (MEPS) plots have been computed. Finally, Illustration for the proposed interaction between stearic acid, the catalyst (Sn3ZrO7), and methanol to produce the biodiesel was proposed.

Preparation, characterization and application of novel surface-modified ZrSnO4 as Sn-based TMOs catalysts for the stearic acid esterification with methanol to biodiesel

Tin zirconium oxide catalysts (Sn-based TMOs) were successfully prepared with three different methods, ultrasonic-assisted hydrothermal, sol-gel, and traditional precipitation method, and applied for biodiesel production. The physicochemical and the catalytic efficiency by the esterification of stearic acid of the as-synthesized catalysts were investigated by different techniques. The production of biodiesel (as methyl stearate) has emerged as a greener and renewable substitute for petro based diesel fuel. The optimization of the esterification conditions for maximum yield of biodiesel was performed by studying different factors as the catalyst preparation method, reaction time, molar ratio of alcohol to stearic acid, reaction temperature, and the catalyst concentration. The preferred catalyst (SnZrh) was optimized as the reaction temperature of 120 °C, 150 M ratio of methanol to stearic acid, 0.2 g catalyst amount and reaction time of 60 min. The SnZrh catalyst exhibited 74% yield of methyl stearate. Also, the kinetic and thermodynamic studies of stearic acid esterification reaction were inspected. The reusability of the optimized tin zirconium oxide catalyst for seventh runs was professionally studied. The computational chemistry study showed that the interaction mechanism between the optimized catalyst and stearic acid was preferable between SnO2 active sites and carbonic group of stearic acid.

MWCNTs/SnZrMoP nano-composite as Ba (II)-selective electrode and heterogeneous catalyst for esterification of primary alcohols

The present investigation covers the synthesis, characterization and applications of a novel nano-composite of multiwalled carbon nanotubes–tin zirconium molybdophosphate (MWCNTs–SnZrMoP) ion exchanger. The synthesized material was characterized by various instrumental techniques viz. Fourier transform infrared spectroscopy (FT-IR), field emission scanning electron microscopy (FE-SEM), high-resolution transmission electron microscopy (HR-TEM), X-ray diffraction (XRD), and thermogravimetric/ differential thermal analysis (TGA/DTA). The nano-composite exhibited an ion exchange capacity of 2.56 meq g−1, which is higher than its inorganic counterpart SnZrMoP (1.95 meq g−1). The distribution studies confirmed that the as-synthesized nano-composite was selective for barium ions. The nano-composite was employed to fabricate an ion-selective electrode which showed a sub-Nernstian response for barium ions in the concentration range 1 × 10−7 M—1 × 10−1 M, with a response time of 11 s. The average slope of the calibration curve was observed to be 23.3 mV/decade with 1.78 × 10−8 M as limit of detection (LOD). The synthesized material was also used as a heterogeneous catalyst in esterification reactions of some primary alcohols due to its high mechanical, thermal and chemical stability. The esters produced were characterized by nuclear magnetic resonance (1H-NMR) and FT-IR techniques.

Effect of NASICON-type LiSnZr(PO4)3 ceramic filler on the ionic conductivity and electrochemical behavior of PVDF based composite electrolyte

Replacement of liquid electrolytes with polymer-based solid electrolytes is considered as the key to the realization of high-energy lithium metal anode in rechargeable batteries. However, the polymer electrolytes suffer from poor lithium-ion conductivity and low lithium-ion transference number. Poly(vinylidene difluoride) (PVDF) based polymer-ceramic composite electrolytes were fabricated at room temperature via the solution casting method. The effect of NASICON-type lithium tin zirconium phosphate (LiSnZr(PO4)3) particles added as the ceramic filler to the PVDF + LiTFSI polymer-salt matrix on the structure, ionic conductivity, transference number, and electrochemical behaviour was studied. The x-ray diffraction (XRD) and fourier transform infrared (FTIR) absorption studies confirmed the structure of the fabricated polymer as the mixed (α+β) phases of PVDF. The addition of LiSnZr(PO4)3 ceramic filler resulted in the enhancement in Li+ conductivity of the polymer composite and the sample with 15 wt% ceramic filler (CPE-15) showed the highest lithium-ion conductivity of 5.76 × 10−5 Scm−1 at 300 K. The addition of 15 wt% LSZP improved the stability window up to 4.73 V as confirmed by linear sweep voltammetry (LSV). A significant improvement in (tLi+) resulted from the addition of ceramic filler. The reversibility of Li+ transport across the composite ceramic-polymer electrolyte (15 wt% CPE) was confirmed by galvanostatic charging-discharging of symmetric lithium (Li||CPE||Li) cell at various current density for 100 h. Li||CPE||LTO cells with Li4Ti5O15 (LTO) as the working electrode, CPE-15 as the Li+ conducting separator, and Li foil as the counter electrode were fabricated to demonstrate the application of the CPE-15 as the electrolyte in all-solid-state batteries. Li||CPE||LTO cell delivered a specific discharge capacity of 133 mAhg−1 and 88% capacity retention after 20 cycles at 0.1C rate.

Biogenic synthesis of a silver nanoparticle–SnZrMoP nanocomposite and its application for the disinfection and detoxification of water

A silver nanoparticle (AgNP)–tin zirconium(iv) molybdophosphate (SnZrMoP) nano-composite was synthesized by a superficial and green synthetic approach using mulberry leaf extract, with the plant extract playing the role of a reducing agent as well as a capping agent.

Corrosion behavior in simulated environments of ITZO films prepared by two targets co-sputtering

Indium tin zirconium oxide (ITZO) films were deposited by a co-sputtering technique with ITO and zirconium targets. The stability and corrosion behavior of films in simulated environments were studied on account of microstructure and optical–electrical properties. The results show that ITZO films possess a better crystalline structure and optical–electrical properties. Zirconium-doping changes the preferred orientation of ITO films, and ITZO films under the optimum parameters have sheet resistance of 10Ω/sq and transmittance of above 85%. According to the polarization measurements and the relative resistance change of the films in simulated environments such as acidic climate, oceanic climate and industrial climate, the doping films show better chemical and thermal stabilities than ITO films. Besides the influence of crystal structure, the better stability of zirconium oxide can improve the chemical and thermal stabilities. ITZO films have better electrical stability and chemical antcaustic properties, and the films could find more extensive applications.

Electrical and Optical Properties of Indium Tin Zirconium Oxide Films at Different Annealing Treatment Temperatures

Indium tin oxide (ITO) and indium tin zirconium oxide (ITZO) films were deposited on glass substrates at room temperature by magnetron sputtering technology with one or two targets. Electrical and optical properties of ITO and ITZO films by air-annealing treatment were contrastively studied. ITZO films provided with the preferential crystalline orientation change from (222) to (400) plane, as well as the increase in grain size and the decrease in surface roughness. As result, zirconium -doping remarkably improved the optical-electrical properties of the films deposited at room temperature. The resistivity of ITO and ITZO films showed the trend which includes first dropping and then rising, which was closely related with the variations of carrier concentration and mobility. ITZO films had high optical transmittance of above 80% at lower annealing temperature. ITZO films prepared by co-sputtering reveal better optical-electrical properties.

Hydrothermal synthesis and structural characterization of framework microporous mixed tin–zirconium silicates with the structure of umbite

A novel framework mixed tin–zirconium silicate, K2Sn0.25Zr0.75Si3O9·H2O (1), was synthesized under mild hydrothermal conditions. The unit cell is orthorhombic, a=10.260(2) Å, b=13.272(2) Å, c=7.174(1) Å, space group P212121, Z=4. Isotypic with the mineral umbite, the structural formula may be written as K2(Sn,Zr){uB,1∞1}[3Si3O9]. In a topotactical process, the K+ ions in compound 1 were replaced by Na+ ions, thus obtaining compound 2: Na2Sn0.25Zr0.75Si3O9·H2O (2), a=10.500(1) Å, b=13.354(2) Å, c=7.2731(9) Å.

Transparent conducting films of In 2O 3–ZrO 2, SnO 2–ZrO 2 and ZnO–ZrO 2

The optical transparencies and electrical conductivities of thin films of In 2O 3, SnO 2 and ZnO mixed with ZrO 2 have been investigated. These films were deposited on glass substrates at room temperature using pulsed-laser deposition. Indium–zirconium oxide films with a ZrO 2 content up to 15 wt.% were conducting and more than 80% transparent from 450–700 nm. As the ZrO 2 content increased from 0 to 15 wt.%, the electrical resistivities increased from 1.28×10 −3 to 6.48×10 −2 Ω cm; the carrier densities decreased from 2.14×10 20 to 1.0×10 18 cm −3; and the Hall mobilities decreased from 21 to 5 cm 2 V −1 s −1, all monotonically. The electrical resistivities of tin–zirconium oxide increased from 1.65×10 −2 to 7.33×10 −2 Ω cm as the ZrO 2 content varied between 0 and 5 wt.%, whereas the resistivities of the zinc–zirconium oxide varied from 3×10 −2 to 3.5×10 −1 Ω cm for ZrO 2 contents between 0 and 10 wt.%.

Structure determination of SnZrS3

The structure of tin zirconium trisulfide is of the NH4CdCl3 type with double columns of edge-sharing Zr octahedra. These columns are linked together by Sn atoms. Sn is coordinated to three S atoms at 2 x 2.619 (2) and 2.765 (2) angstrom; a fourth S atom is at 3.065 (2) angstrom. The zirconium coordination is approximately octahedral with six S atoms at 2.524 (2), 2 x 2.545 (2), 2.582 (2) and 2 x 2.592 (2) angstrom. Powder diffraction data were also collected; the JCPDS rue No. for tin zirconium sulfide is 44-1494.

On the Sorption of d-Metal Ions on Mixed Phosphates of the 4-th Group Elements

Abstract Mixed titanium–zirconium, tin–zirconium, and tin–titanium phosphates containing different amounts of the 4-th group elements were synthesized and their ion-exchange properties towards Cu2+, Co2+, Ni2+, and Cr3+ ions were studied. The values of the equilibrium costants of the ion-exchange reactions of the d-metal sorptions from acetate and chloride solutions were calculated. It was found that the sorbents affinity to the transitional metal ions greatly depended on their chemical composition; enriching of tin-containing samples with Zr and, especially, with Ti increases the affinity to Co2+ ions; enrichment of titanium-zirconium containing ionites with Zr increases their affinity to Cu2+ ions, etc. It is suggested that the observed changes in the selectivity of the inorganic ion-exchangers are connected with the possibility of creating in their structure adsorption centers with different geometrical parameters depending on the dimensions of the 4-th group elements.

Optical metallography of zinc, zirconium, and zirconiumtin with a laser beam

Some observations of the surface of polycrystalline zinc, zirconium, and zirconiumtin, with the use of an optical microscope illuminated with a laser beam, are reported. Both normal and oblique incidence of the laser beam on the surface of the specimen were employed and the micrographs obtained are compared with those produced under normal (white) light. Finally, it is shown that by illuminating with a laser beam, it is possible to reveal grain boundaries at an earlier stage of the specimen etching than by illuminating with white light.