Synthesis,structure, and optical and photocatalytic properties of quasi-one-dimensional ZnO doped with Со<Subscript>3</Subscript>O<Subscript>4</Subscript> and carbon

One-dimensional nanocomposites Zn_1–x Co _x O_1–y С _у :nCo₃O₄ and solid solutions Zn_1–x Co _x O_1–y С _у , which are promising photocatalysts for the oxidation of toxic organic compounds in visible light, are obtained via the thermolysis of Zn_1–x Co _x (HCOO)(OCH₂CH₂O)_1/2 (0.1 ≤ x ≤ 0.5) precursor in a controlled gaseous atmosphere.     

Structural and magnetic properties of Fe<Subscript>m</Subscript>Y<Subscript>n</Subscript> (m + n = 7, Y = Ru,Rh, Pd,and Pt) nanoalloys

The structural and magnetic properties of the small binary clusters Fe _m Y _n (with m + n = 7, Y = Ru, Rh, Pd, Pt) were studied through extensive ab initio calculations, by means of the fully unconstrained version of the density-functional method, as implemented in the SIESTA code, within the generalized gradient approximation. The lowest energy state geometries, the chemical ordering, and the electronic and the magnetic structures were calculated. We found that the lowest energy geometrical structures for the pure Ru, Rh, Pd, Pt, and Fe heptamers, are a cube without an apex, a triangular prism capped on a square face, a decahedron, a side capped double square, and a decahedron, respectively. Starting from these geometries of the pure element heptamers, we followed the changes in the geometric structure as a function of the chemical composition. We analyzed all the different chemical arrangements, which depend on the particular geometry, and magnetic moment orientations, in the whole range of compositions. In general, there are important modifications to the magnetic moment of the Y atoms as soon as one of them is substituted by an Fe atom in the cluster. In contrast, under the same circumstances, the Fe magnetic moment takes values larger than 3 μ _B and keeps almost this value, insensitive to the structure, composition and chemical order of the system.     

Optical,electrochemical, and <Superscript>1</Superscript>H NMR characteristics of Mono-, Bi-, and tetranuclear cyclopalladated complexes with 4,4′-bipyridyl

The [Pd(C∧N)(4,4′-bpy)Cl], [Pd(C∧N)NO₃]₂(μ-4,4′-bpy) and [Pd(C∧N)(μ-4,4′-bpy)]₄(NO₃)₄ complexes (C∧N⁻ are deprotonated forms of 2-phenylpyridine (ppy), 2-(2′’-thienyl)pyridine (tpy), and 2-phenylbenzothiazole (bt); bpy is 4,4′ bipyridyl) are synthesized and characterized by ¹H NMR spectroscopy, electronic absorption and emission spectroscopy, and cyclic voltammetry. The upfield shifts of the chemical shift of a proton in the ortho-position to the donor carbon atom of the cyclopalladated ligand of complexes (Δδ = −(1.1–1.5) ppm) is assigned to the anisotropic effect of the circular current of the pyridine rings of 4,4′-bipyridyl orthogonal to the coordination plane. The characteristic long-wavelength absorption and phosphorescence bands of the complexes are assigned to the chromophore metal-complex fragment {M(C∧N)}. The quasi-reversible reduction waves of complexes are assigned to the ligand-centered processes of successive electron transfer to the π*-orbitals localized mainly on the coordinated pyridine components of 4,4′-bipyridyl.     

Vibrational properties of Cu<Subscript>3</Subscript>XY<Subscript>4</Subscript> sulvanites (X = Nb,Ta, and V; and Y = S,and Se) by ab initio molecular dynamics

In this work, we present a structural and dynamic characterisation of six different types of sulvanites Cu₃ X Y ₄ with X = Nb, V and Ta, and Y = S and Se. These materials have been the subject of intense study in recent times primarily as potential candidates for solar cell devices, as well as for their enhanced opto-electrical properties. Here, by means of first-principles calculations, we study the structural and dynamic behaviour of these materials at different temperatures, which is important for use of these materials in high-temperature conditions. In this work the dynamic and structural properties are studied using the Density Functional Theory technique. The simulations were performed at four different temperatures, ranging from room temperature to ~1500 K. By using first-principles molecular dynamics in the microcanonical ensemble, we are able to determine the vibrational spectra of these sulvanites. With this information we report for the first time the partial vibrational density of states of these structures at different temperatures. With these results we determine the vibrational properties of the basic building blocks of those sulvanites and their dynamic behaviour under temperature effects. We also show that the building blocks that which make up these structures, remain stable as the temperature increases.     

Co-substitution effect on the structural,electrical, and electrochemical properties of nanostructured Co<Subscript>x</Subscript>Ni<Subscript>1-x</Subscript>MnP<Subscript>2</Subscript>O<Subscript>7</Subscript> (x = 0, 0.25, 0.5, and 0.75)

Cobalt-nickel-manganese pyrophosphate nanostructures with formula Co_xNi_1-xMnP₂O₇ were prepared via the hydrothermal method at 150 °C, with further calcinations at 500 °C. A structural analysis of Co_xNi_1-xMnP₂O₇ samples was carried out using X-ray diffraction (XRD). The effect of Co substitution on the structural, electrical, and electrochemical properties of Co_xNi_1-xMnP₂O₇ is reported. The electrochemical results show that the specific capacity increases from 59 to 205 mAh/g with increasing Co content. This study demonstrates the Co substitution effect on the mixed electrical conductivity. The temperature dependence of the dc electrical conductivity, for both pure and Co²⁺-doped samples, obeys the Arrhenius law. The frequency dependence of ac conductivity for the materials exhibited a Jonscher’s universal power law. The plots of pre-exponent (n) versus temperature suggested that the conduction mechanism can be described using correlated barrier hopping model. The improved electrical conductivity and electrochemical proprieties of Co_xNi_1-xMnP₂O₇ nanomaterials could be ascribed to the synergistic effect of nickel and cobalt ions. The best results have been obtained for the composition x(Co) = 0.75, where the electrical conductivity is maximum, and the Co_0.75Ni_0.25MnP₂O₇ demonstrates the highest specific capacity, implying their promising potential applications in the energy storage.     

Baryon masses,chiral extrapolations,and all that<Superscript>⋆</Superscript>

We calculate the baryon octet masses to fourth order in chiral perturbation theory employing dimensional and cut-off regularization. We analyze the pion and kaon mass dependences of the baryon masses based on the MILC data. We show that chiral perturbation theory gives stable chiral extrapolation functions for pion (kaon) masses below 550 (600) MeV. For the pion-nucleon sigma term we find (0) = 39.5...46.7MeV.     

Ab initio study of structural,electronic, and elastic properties of M<Subscript>2</Subscript>SbP (M = Ti,Zr, and Hf)

This study predicts the structural behaviour of selected M₂SbP compounds with the same structure as MAX phases. Zero pressure results of the lattice parameters, equilibrium volume, and the internal parameter Z_M are calculated with an error less than 3%. Band structure, total and partial density of states were calculated and show the metallic character of these phases. Moreover we observed strong hybridising states; M d–P p, and M d–Sb p. The pressure dependence of the volume, and the lattice parameters were studied. The stiffness of M–P, and M–Sb bonds was discussed in term of relative length change under hydrostatic pressure. Hf₂SbP present the highest bulk modulus and the unidirectional elastic modulus C₃₃ is slightly greater than C₁₁.     

Magnetoinduced structural,Jahn–Teller,dielectric, and transport effects in La<Subscript>0.875</Subscript>Sr<Subscript>0.125</Subscript>MnO<Subscript>3</Subscript>

The temperature and magnetic field dependences of elastic moduli and resistance are studied in a La_0.875Sr_0.125MnO₃ single crystal. In addition to the metal–insulator transition, the structural transition from the cooperative J–T strongly distorted orthorhombic phase to the charge ordering phase is studied at T _J–T = 150 K in magnetic fields of up to 2 T. Results show it is possible to control the acoustic parameters in the vicinity of T _J–T via magnetic fields.     

Structure,stability, and thermomechanical properties of Ca-substituted Pr<Subscript>2</Subscript>NiO<Subscript>4 + δ</Subscript>

Ca-substituted layered nickelates with a general Pr_2–x Ca _x NiO_{4 + δ} composition (x = 0–0.7, Δx = 0.1) were prepared in the present work and their structural and physic-chemical properties were investigated in order to select the most optimal materials, which can be used as cathodes for solid oxide fuel cells. With an increase in Ca content in Pr_2–x Ca _x NiO_{4 + δ} the following tendencies were observed: (i) a decrease in the concentration of nonstoichiometric oxygen (δ), (ii) a decrease in the unit cell parameters and volume, (iii) stabilization of the tetragonal structure, (iv) a decrease of the thermal expansion coefficients, and (v) enchancement of thermodynamic stability and compatibility with selected oxygen- and proton-conducting electrolytes. The Pr_1.9Ca_0.1NiO_{4 + δ} material, having highest δ value, departs from the general “properties–composition” dependences ascertained. This indicates that oxygen non-stoichiometry has determining influence on the functional properties of layered nickelates.     

Synthesizing and investigating the structure and phase transitions in A<Subscript>3</Subscript>TeO<Subscript>6</Subscript> (A—Mn,Co, Ni) oxides

Single-phase samples of A₃TeO₆ (A—Mn, Co, Ni) oxides and solid solutions in a (Mn_1-xB_x)₃TeO₆, B—Co, Cd system belonging to the structural series of magnesium orthotellurate were obtained by solid-phase synthesis. The temperature behavior of the ceramics’ magnetization, thermal capacity, and dielectric properties were studied.     

Conductance studies of NaCl,KCl, NaBr,KBr, NaI,Bu<Subscript>4</Subscript>NI,and NaBPh<Subscript>4</Subscript> in water + 2-propoxyethanol mixtures at 298.15 K

The molar conductances of sodium chloride (NaCl), potassium chloride (KCl), sodium bromide (NaBr), sodium iodide (NaI), tetrabutylammonium iodide (Bu₄NI), and sodium tetraphenylborate (NaBPh₄) in water?+?2-propoxyethanol binary mixtures at T?=?298.15 K were determined. Conductance values were analyzed using a low-concentration chemical model (lcCM). The ionic conductivities of Na⁺, K⁺, Bu₄N⁺, Cl^?, I^?, Br^?, and BPh₄ ^? ions were determined using Fuoss–Hirsch’s assumption. The dependencies of the values of limiting molar conductance (Λ _o), limiting ionic conductance of the individual anions (λ _o ^± ), and Walden products (Λ _o???η and λ _o ^± ???η) as a function of the composition of water?+?2-propoxyethanol binary mixtures were discussed.

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Graphical abstract Limiting molar conductances Λ _o [S·cm²·mol^?1] of NaCl, NaBr, NaI, KCl, NaBPh₄, and NBu₄I as a function of the mole fraction, x ₂, in water (1)?+?2-propoxyethanol (2) mixtures at 298.15 K: empty diamonds NaCl, empty squares NaBr, empty triangles NaI, filled triangles KCl, filled squares NaBPh₄, and filled diamonds NBu₄I

     

Preparation and characterization of LiNi<Subscript>0.495</Subscript>M<Subscript>0.01</Subscript>Mn<Subscript>0.495</Subscript>O<Subscript>2</Subscript> (M = Zn,Co, and Y) for lithium ion batteries

Layered structured LiNi_0.5Mn_0.5O₂ and LiNi_0.495M_0.01Mn_0.495O₂ (M = Zn, Co, and Y) compounds were prepared by PVP (poly(vinyl pyrrolidone))-assisted sol-gel method, and their structural, morphological, vibrational, transport, and electrochemical properties were characterized by XRD, SEM, FTIR, Raman, AC impedance, and galvanostatic charge and discharge analysis. XRD patterns reveal that doping does not change the crystal structure of the LiNi_0.5Mn_0.5O₂ compound. SEM images show that the average size of the particle is in sub-micron ranges. The AC impedance studies shows an electrical conductivity of ～2.5 × 10^?7 S/cm for the parent compound. The introduction of Zn/Co/Y at equivalent sites increased the electrical conductivity by one order ～10^?6 S/cm. The compound LiNi_0.495Co_0.01Mn_0.495O₂ shows the highest electrical conductivity of 2.85 × 10^?6 S/cm and delivers a specific discharge capacity of 110 mAh/g at the end of the 25th cycle in the voltage window of 2.5–4.4 V for a current density of 30 mA/g.     

Controlled flame synthesis of αFe<Subscript>2</Subscript>O<Subscript>3</Subscript> and Fe<Subscript>3</Subscript>O<Subscript>4</Subscript> nanoparticles: effect of flame configuration,flame temperature,and additive loading

Superparamagnetic iron oxide nanoparticles are used in diverse applications, including optical magnetic recording, catalysts, gas sensors, targeted drug delivery, magnetic resonance imaging, and hyperthermic malignant cell therapy. Combustion synthesis of nanoparticles has significant advantages, including improved nanoparticle property control and commercial production rate capability with minimal post-processing. In the current study, superparamagnetic iron oxide nanoparticles were produced by flame synthesis using a coflow flame. The effect of flame configuration (diffusion and inverse diffusion), flame temperature, and additive loading on the final iron oxide nanoparticle morphology, elemental composition, and particle size were analyzed by transmission electron microscopy (TEM), high-resolution TEM (HR-TEM), energy dispersive spectroscopy (EDS), and Raman spectroscopy. The synthesized nanoparticles were primarily composed of two well known forms of iron oxide, namely hematite αFe₂O₃ and magnetite Fe₃O₄. We found that the synthesized nanoparticles were smaller (6–12 nm) for an inverse diffusion flame as compared to a diffusion flame configuration (50–60 nm) when CH₄, O₂, Ar, and N₂ gas flow rates were kept constant. In order to investigate the effect of flame temperature, CH₄, O₂, Ar gas flow rates were kept constant, and N₂ gas was added as a coolant to the system. TEM analysis of iron oxide nanoparticles synthesized using an inverse diffusion flame configuration with N₂ cooling demonstrated that particles no larger than 50–60 nm in diameter can be grown, indicating that nanoparticles did not coalesce in the cooler flame. Raman spectroscopy showed that these nanoparticles were primarily magnetite, as opposed to the primarily hematite nanoparticles produced in the hot flame configuration. In order to understand the effect of additive loading on iron oxide nanoparticle morphology, an Ar stream carrying titanium-tetra-isopropoxide (TTIP) was flowed through the outer annulus along with the CH₄ in the inverse diffusion flame configuration. When particles were synthesized in the presence of the TTIP additive, larger monodispersed individual particles (50–90 nm) were synthesized as observed by TEM. In this article, we show that iron oxide nanoparticles of varied morphology, composition, and size can be synthesized and controlled by varying flame configuration, flame temperature, and additive loading.     

Physicochemical,dielectric, and piezoelectric properties and conductivity of LiNbO<Subscript>3</Subscript>: ZnO crystals (4.02–8.91 mol %)

The physicochemical characteristics of the crystal–melt system during the growth of LiNbO₃: ZnO crystals have been investigated in the range of impurity concentration [ZnO] in the melt of 4.02–8.91 mol %. The threshold impurity concentration corresponding to a significant change in the formation conditions and structure of LiNbO₃: ZnO crystals is refined ([ZnO] = 6.76 mol % in the melt). The dielectric and piezoelectric properties and conductivity of multidomain LiNbO₃: ZnO crystals have been analyzed. The occurrence of a significant spontaneous increase in the unipolarity upon high-temperature annealing has only been shown to be typical of LiNbO₃: ZnO crystals grown from melts in the near-threshold concentration range (~5.4 < [ZnO] ≤ 6.76 mol % in the melt). This effect is accompanied by a large and reproducible increase in the static piezoelectric coefficient d ₃₃₃. The value of the piezoelectric-coefficient jump Δd ₃₃₃ linearly increases with an increase in the specific-conductivity jump Δσ near the temperature T* ≈ 800 K.     

Magnetic,electrical, magnetoelectrical,and magnetoelastic properties of La<Subscript>0.9</Subscript>Sr<Subscript>0.1</Subscript>MnO<Subscript>3 − <Emphasis Type="Italic">y</Emphasis></Subscript> manganites

This paper reports on a study of the influence of oxygen deficiency on the magnetization, paramagnetic susceptibility, electrical resistivity, magnetoresistance, and volume magnetostriction of the La_0.9Sr_0.1MnO_{3 − y} manganite with y = 0.03, 0.10, and 0.15. The magnetization M(T) behaves in a complex way with temperature; for T < 80 K, it only weakly depends on T, and at 80 ≤ T ≤ 300 K, the M(T) curve shows a falloff. Within the interval 240 K ≤ T ≤ 300 K, the long-range magnetic order breaks up into superparamagnetic clusters. For T < 80 K, the magnetic moment per formula unit is about one-fourth that which should be expected for complete ferromagnetic alignment of Mn ion moments. Although the composition with y = 0.03, in which part of acceptor centers is compensated by donors (oxygen vacancies), the negative magnetoresistance Δρ/ρ and volume magnetostriction ω are observed to pass through maxima near the Curie point, their values are one to two orders of magnitude smaller than those for the y = 0 composition. In compositions with y = 0.10 and 0.15 with electronic doping, the values of Δρ/ρ and ω are smaller by one to two orders of magnitude than those observed for the y = 0.03 composition. They do not display giant magnetoresistance and volume magnetostriction effects, which evidences the absence of ferrons near unionized oxygen vacancies. This allows the conclusion that the part played by both compensated and uncompensated doubly charged donors consists in forming dangling Mn-O-Mn bonds, which lead to a decrease in the Curie temperature with increasing y and to the formation above it of superparamagnetic clusters of the nonferron type.     

Synthesis of rod and lath-shaped CuSe and tremella-shaped Cu<Subscript>2−<Emphasis Type="Italic">x</Emphasis></Subscript>Se nanostructures at room temperature,and their optical properties

The research for tunable synthesis and characterization techniques is important for the investigation of nanomaterials. Herein we developed old precipitation reaction for the morphology- and phase-tunable synthesis of copper selenides nanostructures at room temperature, avoiding tedious preparation of selenium precursors, such as selenite or selenosulfate. The molar ratio of Cu²⁺ and Se sources served the function of a switch for selectively synthesis of stoichiometric CuSe and non-stoichiometric Cu_2−x Se. Nanorod and lath-like CuSe formed with excess of selenium source, while tremella-shaped Cu_2−x Se responded to the 1:1 of Cu²⁺/Se or excess of copper source. The structures of nanocrystals, especially the lifelike surface, were characterized in detail by electron microscopy techniques, such as STEM. Novel nanostructures put up the excellent absorption properties in the visible light region, respectively, and could bear potential applications in solar cell devices in the future. This strategy offered a convenient, mild and energy-efficient route for the preparation of other mental chalcogenides nanocrystals with different morphologies or tunable phases.     

Voice Training and Changing Weight—Are They Reflected in Speaking Fundamental Frequency, Voice Range, and Pitch Breaks of 13-Year-Old Girls? A Longitudinal Study

Objective

Assessment of the voice-change progress of 20 girls (12–13 years) over 1 year by observing changes in speaking fundamental frequency (SFo), voice range, and register pitch breaks in the context of weight, height, voice training, and self-perception.

Study Design

One-year longitudinal collective case study.

Method

Twenty girls were recorded at the beginning and end of a year; nine girls were recorded another three times. SFo, vocal range, and characteristics were analyzed and interactions between these data assessed against weight and height to indicate pubertal development, and to test the hypothesis that changes in weight, height, SFo, and pitch breaks were related. Effects of training and the girls' self-perception of their voice use were also assessed.

Results

Vocal characteristics changed as the girls passed through different weight ranges. During 47.5–52.4 kg (called band 2) and 52.4–57.5 kg (band 3), there was progressive contraction of vocal range and in some girls a slight rise in SFo between recording times 1 and 5. Both high- and low-pitch breaks were present in 45% of girls' voices. Girls in band 4 (<57.5 kg) had an increased vocal range, and pitch breaks in vocal-range areas that indicated the development of adult vocal registers. In this study, voice-trained girls were heavier, had higher SFo, used wider speech-range inflection, had a higher vocal range, and greater voice-use confidence; all girls lost confidence in their voice use over the year.

Conclusions

In this longitudinal study of twenty 13-year-old girls, voice changes in SFo, vocal range, and pitch-break frequency were synchronous with certain weight ranges. Girls with training registered higher maximum phonational frequency and were more confident in their voice use than girls without training.     

Structure,Ferroelectric, and Magnetoelectric Properties of Bulk PZT–NiFe<Subscript>1.9</Subscript>Co<Subscript>0.02</Subscript>О<Subscript>4 – δ</Subscript> Composites

The phase composition, microstructure, and dielectric, ferroelectric, magnetic, and magnetoelectric properties of bulk ceramic (1 – x)PZT–xNiFe_1.9Co_0.02О_{4 – δ} composites with 3–0 connectivity have been studied. Using X-ray diffraction and electron microscopy, it has been established that the ferrimagnetic (spinel- like) and ferroelectric (tetragonal perovskite-like) phases separately exist in the composites of all compositions. The simultaneous existence of ferroelectric and ferrimagnetic properties in the composites is confirmed by measuring their P(E) and σ(B) hysteresis loops and studying the temperature dependences of dielectric and magnetic properties. The synthesized composites have high magnetoelectric characteristics: their voltage coefficient at x = 0.4 is 215 mV/A at a frequency of 1 kHz and 130 V/A at an electromechanical resonance frequency of 380 kHz.     

Gd-doped SrTi<Subscript>0.5</Subscript>Fe<Subscript>0.5</Subscript>O<Subscript>3–δ</Subscript> mixed ionic-electronic conductors: structural,thermal, and electrical properties

The effect of Sr by Gd substitution on the structural, thermomechanical, electrical, and electrochemical properties of SrTi_0.5Fe_0.5O_3–δ was investigated in the present work. The powders were synthesized by a solid-state reaction method at 1150 °C with following sintering of the ceramic samples at 1350 °C. The unit cell parameters of the sintered Sr_1–x Gd _x Ti_0.5Fe_0.5O_3–δ (x = 0–0.4) ceramics were found to decrease with a gradual increase in Gd content, and a change in the crystal symmetry from cubic to tetragonal at x ≥ 0.1 was observed. It was found that the Gd doping enhanced the stability of the ceramic samples in a reducing atmosphere and reduced the thermal expansion coefficient value. Gd doping in the amount of 5 mol% can be used for long-term stabilization of the SrTi_0.5Fe_0.5O_3–δ material’s conductivity in reducing atmospheres with no significant alteration to the transport properties and oxygen permeability.     

Structural,electrical conductivity,and transport analysis of PAN–NH<Subscript>4</Subscript>Cl polymer electrolyte system

Poly (acrylonitrile) (PAN) and ammonium chloride (NH₄Cl)-based proton conducting polymer electrolytes with different compositions have been prepared by solution casting technique. The amorphous nature of the polymer electrolytes has been confirmed by XRD analysis. The FTIR analysis confirms the complex formation of the host polymer (PAN) with the salt (NH₄Cl). DSC measurements show a decrease in T_g with the increase in salt concentration. The conductivity analysis shows that the 25 mol% ammonium chloride doped polymer electrolyte has a maximum ionic conductivity, and it has been found to be 6.4 × 10^?3 Scm^?1, at room temperature. The temperature dependence of conductivity of the polymer electrolyte complexes appears to obey the Arrhenius nature. The activation energy (E_a = 0.23 eV) has been found to be low for 25 mol% salt doped polymer electrolyte. The dielectric behavior has been analyzed using dielectric permittivity (ε*), and the relaxation frequency (τ) has been calculated from the loss tangent spectra (tan δ). Using this maximum ionic conducting polymer electrolyte, the primary proton conducting battery with configuration Zn + ZnSO₄·7H₂O/75 PAN:25 NH₄Cl/PbO₂ + V₂O₅ has been fabricated and their discharge characteristics have been studied.