Selenium Speciation in Aqueous Solutions Using a Hydride Generation Atomic Absorption Spectrophotometry Technique

A sensitive analytical technique for the determination of soluble selenium species [Se(IV), Se(VI), Se(0,-II), dimethyl selenide (DMSe), and oxidized methylated organo-Se compounds], using hydride generation atomic absorption spectrophotometry is described. Dimethyl selenide is purged out of a solution and trapped on a U-tube immersed in liquid N₂. After controlled heating of the sample trap, DMSe is quantified in a quartz flame-in-tube atomizer aligned in the optical path of an atomic absorption spectrophotometer. Selenite [Se(IV)] and oxidized methylated Se-compounds are reduced by NaBH₄ in 4 M HCl to H₂Se and DMSe, repectively. Entrained by a He carrier gas the H₂Se and DMSe are trapped in a liquid N₂ cooled U-tube. Their separation is accomplished by controlled heating of the sample trap.

Hydrogen selenide and DMSe carried out of the trap into the atomization cell are detected as two distinct and sharp absorption signals. Oxidative and/or reductive chemical digestions are used to quantitatively convert total soluble Se or Se(VI) to Se(IV), while the original Se(IV) stays unchanged. The digestions are analyzed for Se(IV). Selenate [Se(VI)] is calculated from the difference between the Se(IV) and [Se(VI)+Se(IV)] analysis. The difference between the total Se content and the [Se(VI)+Se(IV)] analysis represents the Se(0,-II) fraction. The technique has been applied for Se speciation in sediment-water extracts.     

Mössbauer,magnetic, and x-ray properties of the system (FeS)1−x(FeSe)x

Powders of (rmFeS)_1?x(FeSe)_x have been studied by Ms?sbauer, magnetic, and X-ray techniques. For our heat treatment of the samples the structure of the solid solutions is NiAs-like for 0≤x≤0.6, beyond which the structure is PbO-like. The samples contain also increasing amounts (with increasing x) of spurious “background” material which consists of metallic iron together with commensurate amounts of Fe₇S₈ and/or Fe₇Se₈. The tetragonal (PbO-like) FeSe shows no magnetic hyperfine structure and is thought to exhibit Pauli paramagnetism.     

Flow‐Injection Online Reduction Atomic Fluorescence Spectrometry Determination of Se(IV) and Se(VI) with Electrochemical Hydride Generation

Abstract

A new flow‐injection online reduction electrochemical hydride generation system for the determination of Se(IV) and Se(VI) by atomic fluorescence spectrometry (AFS) was developed. In the system, an electromagnetic induction oven was used as heating resource to reduce Se(VI) to Se(IV) and a homemade tubular electrolytic cell as hydride generator. All analytical procedures were automatically controlled by a computer. The conditions of online reduction, including temperature, HCl concentration, and reduction time, have been studied in detail. The detection limits (3σ) of Se(IV) and Se(VI) in aqueous solution were 0.26 µg L^?1 and 0.23 µg L^?1, respectively. The precision for 11 replicate measurements of 50 µg L^?1 Se(IV) and Se(VI) was 2.2% and 2.5%. This proposed method has been applied to the determination of Se(IV) and Se(VI) in springwater samples.     

Magnetic properties of the ternary alloy system (FexNi1−x)11Se8 for 0.042<x<0.23

The ternary alloy system (Fe_xNi_1?x)₁₁Se₈ for 0.04257Fe Mössbauer experiments at 4.2 K. A preliminary analysis of the spectra reveals that all samples are magnetically ordered at 4.2 K and the magnetic hyperfine field increases with increasing iron concentration. Temperature dependent Mössbauer spectra measured for x=0.22 indicate that the transition temperature is about 108±2 K. The results are discussed in terms of the magnetic and structural properties of the system.     

AgSbSe2 and AgSb(S,Se)2 thin films for photovoltaic applications

Silver antimony selenide (AgSbSe₂) thin films were prepared by heating sequentially deposited multilayers of antimony sulphide (Sb₂S₃), silver selenide (Ag₂Se), selenium (Se) and silver (Ag). Sb₂S₃ thin film was prepared from a chemical bath containing SbCl₃ and Na₂S₂O₃, Ag₂Se from a solution containing AgNO₃ and Na₂SeSO₃ and Se thin films from an acidified solution of Na₂SeSO₃, at room temperature on glass substrates. Ag thin film was deposited by thermal evaporation. The annealing temperature was 350 °C in vacuum (10⁻³ Torr) for 1 h. X-ray diffraction analysis showed that the thin films formed were polycrystalline AgSbSe₂ or AgSb(S,Se)₂ depending on selenium content in the precursor films. Morphology and elemental analysis of these films were done using scanning electron microscopy and energy dispersive X-ray spectroscopy. Optical band gap was evaluated from the UV-visible absorption spectra of these films. Electrical characterizations were done using Hall effect and photocurrent measurements. A photovoltaic structure: glass/ITO/CdS/AgSbSe₂/Al was formed, in which CdS was deposited by chemical bath deposition. J-V characteristics of this structure showed V_oc = 435 mV and J_sc = 0.08 mA/cm² under illumination using a tungsten halogen lamp. Preparation of a photovoltaic structure using AgSbSe₂ as an absorber material by a non-toxic selenization process is achieved.     

77Se NMR study of the pairing symmetry and the spin dynamics in K(y)Fe(2-x)Se2

We present a 77Se NMR study of the newly discovered iron selenide superconductor K(y)Fe(2-x)Se2, in which T(c) = 32 K. Below T(c), the Knight shift 77K drops sharply with temperature, providing strong evidence for singlet pairing. Above T(c), Korringa-type relaxation indicates Fermi-liquid behavior. Our experimental results set strict constraints on the nature of possible theories for the mechanism of high-T(c) superconductivity in this iron selenide system.     

Sorption of selenium(IV) and selenium(VI) onto magnetite

In this work, we have studied the sorption of selenium (⁷⁹Se is one of the main radionuclides in a spent nuclear fuel repository) on magnetite (Fe₃O₄), a mineral present in the near-field of a nuclear waste repository that might represent an important retardation factor for the mobility of many radionuclides.The sorption of both Se(IV) and Se(VI) onto magnetite has been fitted by a non-competitive Langmuir isotherm with Γ_max = (3.13 ± 0.07) × 10⁻⁶ mol m⁻² and K_L = (1.19 ± 0.07) × 10⁶ dm³ mol⁻¹ for Se(IV) and Γ_max = (3.5 ± 0.2) × 10⁻⁶ mol m⁻² and K_L = (3.0 ± 0.1) × 10⁵ dm³ mol⁻¹ for Se(VI).The variation of the sorption of selenium with pH has been modeled using the Triple Layer Surface Complexation Model and the equilibrium constants between selenium and magnetite have been obtained using the FITEQL program. For the case of Se(IV), the best fitting has been obtained using two inner-sphere complexes, FeOHSeO₃²⁻ and FeHSeO₃, while for Se(VI), the best fitting has been obtained considering only an outer-sphere complex, FeOH₂⁺SeO₄²⁻.The surface complexation reactions derived in this work are in agreement with those stated by other authors for sorption of Se(IV) and Se(VI) on hydrous iron oxides.     

77Se solid-state NMR investigations on As(x)Se(1-x) glasses using CPMG acquisition under MAS

⁷⁷Se (I=1/2) solid-state NMR is a very sensitive probe of the local structure of selenide glasses, which themselves are promising for optical applications. In this work, we show that although ⁷⁷Se has a low natural abundance (7.58%) and a wide spectral range, the sensitivity can be dramatically increased using Carr–Purcell–Meiboom–Gill (CPMG) trains of rotor-synchronized π pulses during the detection of ⁷⁷Se magnetization but may be affected by chemical shift anisotropy when the Magic Angle Spinning rate is not fast enough and by offset effects. The indirect dimension of the T₂^CPMG-resolved spectrum shows a strong influence of the J-couplings between naturally occurring ⁷⁷Se pairs. The resulting spectra show that the structural model known as “chains crossing model” is not entirely suitable to describe the glassy network of the Se-rich compositions.     

Block antiferromagnetism and possible ferroelectricity in KFe2Se2

Superconductors and multiferroics are two of the hottest branches in condensed matter physics. The connections between those two fields are fundamentally meaningful to unify the physical rules of correlated electrons. Recently, BaFe₂Se₃, was predicted to be multiferroic [Phys. Rev. Lett. 113 , 187204 (2014)] due to its unique one‐dimensional block‐type antiferromagnetism. Here, another iron‐selenide KFe₂Se₂, a parent state of iron‐based superconductor, is predicted to be multiferroic. Its two‐dimensional block‐type antiferromagnetism can generate a moderate electric dipole for each Fe–Se layer via the Fe–Se–Fe exchange striction. Different stacking configurations of these magnetic blocks give closely proximate energies and thus the ground state of KFe₂Se₂ may be switchable between antiferroelectric and ferroelectric phases.

Crystal structure of KFe₂Se₂. (a) Purple: K; green: Se; brown: Fe. Two Fe sheets in a minimum unit cell are indicated as A and B. (b) One Fe–Se layer with magnetism. Brown: spin up; blue: spin down. (c) A side view of Fe–Se bonds. The ionic displacements driven by exchange striction are indicated by arrows.     

Common crystalline and magnetic structure of superconducting A2Fe4Se5 (A=K,Rb,Cs,Tl) single crystals measured using neutron diffraction

Single-crystal neutron diffraction studies on superconductors A(2)Fe(4)Se(5), where A=Rb, Cs, (Tl, Rb), and (Tl, K) (T(c) ～ 30 K), uncover the same Fe vacancy ordered crystal structure and the same block antiferromagnetic order as in K(2)Fe(4)Se(5). The Fe order-disorder transition occurs at T(S)=500-578 K, and the antiferromagnetic transition at T(N) = 471-559 K with an ordered magnetic moment ～3.3μ(B)/Fe at 10 K. Thus, all recently discovered A intercalated iron selenide superconductors share the common crystalline and magnetic structure, which are very different from previous families of Fe-based superconductors, and constitute a distinct new 245 family.     

Relationship between structural and magnetic properties in (Ti,Fe)O2 powders obtained by mechanical milling

Fe-doped TiO₂ samples with different Fe content were prepared by mechanical alloying starting from TiO₂ rutile and FeO. The samples were structurally and magnetically characterized by XRD, Mössbauer spectroscopy, X-ray absorption spectroscopy (XAS), AC-susceptibility and magnetization measurements. XAS results showed that Fe ions were incorporated into the rutile phase with oxygen coordination that was lower than that expected in this phase. The oxygen coordination number decreased with the increase of Fe²⁺ ions such as it was previously found in the milled samples of TiO₂ doped with hematite. The RT Mössbauer spectra were reproduced using two paramagnetic interactions, one corresponding to Fe²⁺ (δ∼0.87 mm/s) and the other to Fe³⁺ (δ∼0.31 mm/s). Magnetometry measurements showed the presence of paramagnetic and ferromagnetic-like interactions at room temperature. Although saturation and coercivity of the ferromagnetic phase increased with iron, the effective magnetic moment per iron atom decreased, probably due to the precipitation of Fe rich antiferromagnetic structures.     

Long-range chemical interactions in solid-state reactions: effect of an inert Ag interlayer on the formation of L10-FePd in epitaxial Pd(0 0 1)/Ag(0 0 1)/Fe(0 0 1) and Fe(0 0 1)/Ag(0 0 1)/Pd(0 0 1) trilayers

The effect of 0, 0.5, and 1?μm-thick Ag interlayers on the chemical interaction between Pd and Fe in epitaxial Pd(0?0?1)/Ag(0?0?1)/Fe(0?0?1)/MgO(0?0?1) and Fe(0?0?1)/Ag(0?0?1)/Pd(0?0?1)/MgO(0?0?1) trilayers has been studied using X-ray diffraction, ⁵⁷Fe Mössbauer spectroscopy, X-ray photoelectron spectroscopy, and magnetic structural measurements. No mixing of Pd and Fe occurs via the chemically inert Ag layer at annealing temperatures up to 400?°C. As the annealing temperature is increased above 400?°C, a solid-state synthesis of an ordered L1₀-FePd phase begins in the Pd(0?0?1)/Ag(0?0?1)/Fe(0?0?1) and Fe(0?0?1)/Ag(0?0?1)/Pd(0?0?1) film trilayers regardless of the thickness of the buffer Ag layer. In all samples, annealing above 500?°C leads to the formation of a disordered Fe_xPd_1?x(0?0?1) phase; however, in samples lacking the Ag layer, the synthesis of Fe_xPd_1?x is preceded by the formation of an ordered L1₂-FePd₃ phase. An analysis of the X-ray photoelectron spectroscopy results shows that Pd is the dominant moving species in the reaction between Pd and Fe. According to the preliminary results, the 2.2?μm-thick Ag film does not prevent the synthesis of the L1₀-FePd phase and only slightly increases the phase’s initiation temperature. Data showing the ultra-fast transport of Pd atoms via thick inert Ag layers are interpreted as direct evidence of the long-range character of the chemical interaction between Pd and Fe. Thus, in the reaction state, Pd and Fe interact chemically even though the distance between them is about 10⁴ times greater than an ordinary chemical bond length.     

Enhanced superconducting properties in epitaxial FeSe thin films with self-assembled Fe3O4 nanoparticles

In this paper we report epitaxial tetragonal iron selenide thin films grown on single crystal SrTiO₃ (STO) (0 0 1) and MgO (0 0 1) substrates by a pulsed laser deposition (PLD) technique. Deposition temperature and annealing process are found to be critical for achieving the tetragonal phase and the optimum superconducting properties of the films. The critical transition temperature of the thin films ranges from 2 K to 11.5 K depending on the deposition temperature and annealing condition. The samples with higher critical transition temperatures show better film crystallinity along with self-assembled Fe₃O₄ nanoparticles (～15 nm in average particle size) in the films according to both X-ray diffraction (XRD) and transmission electron microscopy (TEM) analysis. Besides the better crystallinity achieved in the films, the formation of Fe₃O₄ nanoparticles could assist the formation of the tetragonal FeSe phase and thus lead to the enhanced superconducting properties.     

Investigations of Sm6(Mn1-xFex)23 system

The new Sm₆(Mn_1-xFe_x)₂₃(0?x?1.0) system hasbeen synthesized and investigated in a wide temperature range by the X-ray, magnetometric and Mössbauer effect methods. The X-ray studies show that the system forms solid solutions which are isostructural with the Th₆Mn₂₃ type crystal structure throughout the entire compositional range. Both Fe-rich and Mn-rich regions of the system are magnetically ordered and are separated from each other by the non-magnetically ordered 0.22?x?0.33 region. The substitution of Fe atoms for Mn atoms in the Mn-rivh region and similarly of Mn atoms for Fe atoms in the Fe-rich region decreases both the Curie temperature and the value of the magnetic moment per molecule. The temperature dependence of the reciprocal susceptibility obeys the Néel law. The Mössbauer absorption spectra reflect wide distributions of the ⁵⁷Fe hyperfine interaction parameters, and disappearance of long range magnetic coupling of Fe atoms in the magnetically ordered x=0 to 0.22 composition range.     

Transformation of Fe(II)-Fe(III) Hydroxysulphite into Hydroxysulphate Green Rusts

Fe(II)-Fe(III) hydroxysulphite Green Rust 1, GR1(SO₃ ^2?), can be obtained by oxidation of Fe(OH)₂ precipitates in aqueous solution and characterised by X-ray diffraction and Mössbauer spectroscopy. In contrast to other Green Rusts (GRs) which then oxidise directly into ferric oxyhydroxides and magnetite, GR1(SO₃ ^2?) first oxidises into a Green Rust two compound, as identified by X-ray diffraction. Mössbauer analysis reveals that this GR2 is the Fe(II)-Fe(III) hydroxysulphate, GR2(SO₄ ^2?). Such an oxidation process, GR1(SO₃ ^2?) → GR2(SO₄ ^2?) confirms that the average oxidation number of Fe increases according to the chemical formulae previously proposed, [Fe^II ₆Fe^III ₂(OH)₁₆]²⁺[SO₃ · mH₂O]^2?, and [Fe^II ₄Fe^III ₂(OH)₁₂]²⁺[SO₄ · nH₂O]^2? for GR1(SO₃ ^2?) and GR2(SO₄ ^2?) with oxidation numbers of 2.25 and 2.33, respectively. The process implies likely the presence of sulphate ions inherent to the oxidation of sulphite in the solution.     

Formation,Structure and Magnetic Properties of Polymer Matrix Nanocomposites Processed by Thermal Decomposition of the Fe(III)Co(II) Acrylate Complex

Structure and magnetic properties of polymer matrix nanocomposites, processed by pyrolysis of the Fe(III)Co(II) acrylate complex, were investigated. It was shown that thermal transformation of the complex studied consisted of three macrostages: dehydration, solid state polymerisation and decarboxylation of a metallopolymer form. The main products of the decomposition were nanoparticles stabilised by polymeric matrix. The crystalline phases, which were found in the fully processed material, were Fe₃O₄, CoFe₂O₄ and CoO. The mean crystallite size was 10nm. In the intermediate stages of the thermolysis iron was present in the forms of Fe^III (trivalent low – spin iron), Fe²⁺(divalent high – spin iron) and Fe₃O₄. The hysteresis loops measured at temperatures below 200K were opened and shifted towards negative field. The coercivity and remanence showed room temperature values of 0.18T and 15.5mT, respectively.     

Photooxidation of different organic dyes (RB, MO, TB, and BG) using Fe(III)-doped TiO2 nanophotocatalyst prepared by novel chemical method

The nano-structured Fe(III)-doped TiO₂ photocatalysts with anatase phase have been developed for the oxidation of non-biodegradable different organic dyes like methyl orange (MO), rhodamine B (RB), thymol blue (TB) and bromocresol green (BG) using UV-Hg-lamp. The different compositions of Fe_xTi_1−xO₂ (x = 0.005, 0.01, 0.05, and 0.1) nanocatalysts synthesized by chemical method (CM), have been characterized by X-ray diffraction (XRD), UV-vis diffuse reflectance spectra, specific surface area (BET), transmission electronic microscopy (TEM) analysis, XPS, ESR and zeta potential. From XRD analysis, the results indicate that all the compositions of Fe(III) doped in TiO₂ catalysts gives only anatase phase not rutile phase. For complete degradation of all the solutions of the dyes (MO, RB, TB, and BG), the composition with x = 0.005 is more photoactive compared all other compositions of Fe_xTi_1−xO₂, and degussa P25. The decolorization rate of different dyes decreases as Fe(III) concentration in TiO₂ increases. The energy band gap of Fe(III)-doped TiO₂ is found to be 2.38 eV. The oxidation state of iron has been found to be 3+ from XPS and ESR show that Fe³⁺ is in low spin state.     

High temperature ferromagnetism of the vacuum-annealed (In1−xFex)2O3 powders

(In_1−xFe_x)₂O₃ (x = 0.02, 0.05, 0.2) powders were prepared by a solid state reaction method and a vacuum annealing process. A systematic study was done on the structural and magnetic properties of (In_1−xFe_x)₂O₃ powders as a function of Fe concentration and annealing temperature. The X-ray diffraction and high-resolution transmission electron microscopy results confirmed that there were not any Fe or Fe oxide secondary phases in vacuum-annealed (In_1−xFe_x)₂O₃ samples and the Fe element was incorporated into the indium oxide lattice by substituting the position of indium atoms. The X-ray photoelectron spectroscopy revealed that both Fe²⁺ and Fe³⁺ ions existed in the samples. Magnetic measurements indicated that all samples were ferromagnetic with the magnetic moment of 0.49-1.73 μ_B/Fe and the Curie temperature around 783 K. The appearance of ferromagnetism was attributed to the ferromagnetic coupling of Fe²⁺ and Fe³⁺ ions via an electron trapped in a bridging oxygen vacancy.     

Effect of the Calcination Atmosphere on the Structural Properties of the Reduced Fe/SiO2 System

Iron supported systems are frequently used as catalysts in the Fischer–Tropsch synthesis being the Fe⁰ the active phase for the reaction. We have studied the influence of the calcination atmosphere (air or nitrogen) on the iron oxide reducibility and the metallic iron particle size obtained in Fe/SiO₂ system. We have impregnated a silicagel with Fe(NO₃)₃·9H₂O aqueous solution and the solid obtained was calcinated in air or N₂ stream. These precursors, with 5% (wt/wt) of Fe, were characterized by Mössbauer Spectroscopy at 298 and 15 K. Amorphous Fe₂O₃ species with 3 nm diameter in the former, and α-Fe₂O₃ crystals of 48 nm diameter were detected in the last one. Both precursors were reduced in H₂ stream. Two catalysts were obtained and characterized by Mössbauer spectroscopy in controlled atmosphere at 298 and 15 K, CO chemisorption and volumetric oxidation. α-Fe⁰, Fe₃O₄ and Fe²⁺ were identified in the catalyst calcined in air. Instead, only α-Fe⁰ was detected in the catalyst calcined in N₂. The iron metallic crystal sizes were estimated as ≈2 nm for the former and ≈29 nm for the last one. The different oxide crystal sizes, obtained from the diverse calcination atmospheres, have led to different structural properties of the reduced solids. It has been possible to reduce totally the existing iron in an Fe/SiO₂ system with iron loading lower than 10% (wt/wt).     

Preparation and characterization of TiO2 photocatalysts co-doped with iron (III) and lanthanum for the degradation of organic pollutants

Titanium dioxide photocatalysts co-doped with iron (III) and lanthanum were prepared by a facile sol-gel method. The structure of catalysts was characterized by X-ray diffraction (XRD), Raman spectroscopy, UV-vis diffuse reflectance spectroscopy and X-ray photoelectron spectroscopy (XPS). The photocatalytic activities of the samples were evaluated by the degradation of methylene blue in aqueous solutions under visible light (λ > 420 nm) and UV light irradiation. Doping with Fe³⁺ results in a lower anatase to rutile (A-R) phase transformation temperature for TiO₂ particles, while doping with La³⁺ inhibits the A-R phase transformation, and co-doping samples indicate that Fe³⁺ partly counteracts the effect of La³⁺ on the A-R transformation property of TiO₂. Fe-TiO₂ has a long tail extending up the absorption edges to 600 nm, whereas La-TiO₂ results in a red shift of the absorption. However, Fe and La have synergistic effect in the absorption of TiO₂. Compared with Fe³⁺ and La³⁺ singly doped TiO₂, the co-doped simple exhibits excellent visible light and UV light activity and the synergistic effect of Fe³⁺ and La³⁺ is responsible for improving the photocatalytic activity.