Facile preparation of Ag–Ag<Subscript>2</Subscript>S hetero-dendrites with high visible light photocatalytic activity

A stable and highly efficient Ag–Ag₂S hetero-dendrites (HDs) photocatalyst has been obtained via an extremely facile electrodeposition and subsequently in situ sulfuration route. The SEM and TEM show well-defined uniform dendrites morphology with an average diameter about 30 nm. In addition, the absorption spectra of Ag–Ag₂S HDs exhibit strong absorption in both visible and NIR regions. The EIS indicates that the low charge transfer resistance of Ag–Ag₂S HDs enhances the photocatalytic activity. The prepared HDs-4 photocatalyst with moderate degree of vulcanization shows excellent activity for degradation the methylene blue (MB) under the sunlight irradiation owing to the suitable ratios of Ag–Ag₂S. The enhanced photocatalytic activity could be attributed to the favorable synergistic effects between Ag and Ag₂S materials, such as huge extended absorption of solar light, low charge transfer resistance and high electron–hole separation efficiency. Moreover, radical scavenger experiments confirmed that superoxide radicals and holes were the main reactive species for MB degradation. Meanwhile, the Ag–Ag₂S HDs displays good photocatalytic stability after being recycled five times.     

Wide range magnetoresistance and high temperature coefficient of resistance in La<Subscript>0.7</Subscript>Sr<Subscript>0.3−x</Subscript>Ag<Subscript>x</Subscript>MnO<Subscript>3</Subscript> system

We report observation of composition and process parameter dependant wide range magnetoresistance and high temperature coefficient of resistance in La_0.7Sr_0.3−xAg_xMnO₃ (0 ≤ x ≤ 0.3) system. The polycrystalline samples synthesized through solid state reaction method exhibited rhombohedral structure with systematic change in lattice parameters. The samples with x ≤ 0.2 showed metallic behavior below room temperature. A broad metal-insulator transition is observed for x = 0.3, which becomes sharp for the samples sintered at high temperature. The broad transition resulted in magnetoresistance (MR) value around 35% over a wide temperature range whereas the sharp transition results in MR value as high as 85%. The temperature coefficient of resistance value of 11% is seen as a consequence of sharp transition. The magnetic transition was sharp for the samples sintered at high temperature.     

Synthesis and photocatalytic performance of TiO<Subscript>2</Subscript> nanospheres–graphene nanocomposite under visible and UV light irradiation

In this article, we present a fast and simple method to produce TiO₂ nanospheres–graphene nanocomposite with high photocatalytic activity under visible and UV light irradiation. TiO₂ nanospheres were adsorbed on graphene in sol–gel process. First, titanium (IV) butoxide underwent hydrolysis in graphene oxide (GO) ethanol solution resulting in TiO₂ nanospheres deposition on GO. Next, the material was calcinated to generate the phase transition of TiO₂ into anatase and reduce GO to graphene. The detailed characterization of the material was performed via transmission electron microscopy, energy dispersive X-rays spectrometer, Fourier-transformed infrared spectroscopy, X-ray diffraction, and Raman spectroscopy. Interestingly, the band-gap energy of the prepared photocatalyst was drastically decreased in comparison with the commercial photocatalyst P25 from 3.05 to 2.36 eV. This influenced in the activation of the material under visible light and resulted in high photocatalytic activity in the process of phenol decomposition in visible and UV irradiation.     

Characterization and electrical conductivity of La<Subscript>1−x</Subscript>Sr<Subscript>x</Subscript>CrO<Subscript>3</Subscript> NTC ceramics

The La_1?xSr_xCrO₃ (x?=?0–0.1) negative temperature coefficient (NTC) ceramics have been prepared by the traditional solid state reaction method. X-ray diffraction (XRD) analysis has revealed that the as-sintered ceramics crystallize in a single perovskite structure. Scanning Electron Microscope (SEM) images show that the doped Sr²⁺ contributes to in the decrease in porosity. X-ray photoelectron spectroscopy (XPS) analysis indicates the existence of Cr³⁺ and Cr⁶⁺ ions on lattice sites, which result in hopping conduction. The presence of the Cr⁶⁺ is one of the key factors that affect the electrical conductivity of La_1?xSr_xCrO₃. Resistance–temperature characteristics were studied in the range of ?80 to 10?°C for the ceramic samples, the electrical characterizations show that the electrical resistivity and material constant B decrease with the increase of the strontium content.     

Structural,magnetic and photocatalytic characterization of Bi<Subscript>1−<Emphasis Type="Italic">x</Emphasis></Subscript>La<Subscript><Emphasis Type="Italic">x</Emphasis></Subscript>FeO<Subscript>3</Subscript> nanoparticles synthesized by thermal decomposition method

Single-phase La-substituted bismuth ferrite (Bi\(_{\boldsymbol {1-x}}\)La\(_{\boldsymbol {x}}\)FeO\(_{\mathbf {3}}\)) nanoparticles have been synthesized by thermal decomposition of a glyoxylate precursor. The crystal structure transition of BiFeO\(_{\mathbf {3}}\) from the rhombohedral (R3c) to the cubic \(\boldsymbol {Pm}\bar {\mathbf {3}}\boldsymbol {m}\) structure by La addition was confirmed by X-ray diffraction and infrared spectrometry methods. Furthermore, the Bi\(_{\boldsymbol {1-x}}\)La\(_{\boldsymbol {x}}\)FeO\(_{\mathbf {3}}\) nanoparticles showed a weak ferrimagnetism behaviour, while the magnetization increased from 0.18 to 0.48 emu g\(^{\mathbf {-1}}\) with La substitution. The Bi\(_{\boldsymbol {1-x}}\)La\(_{\boldsymbol {x}}\)FeO\(_{\mathbf {3}}\) nanoparticles exhibited strong absorption in the visible region with the optical band gap calculated from Tauc’s plot in the range of 2.19–2.15 eV. Furthermore, the effects of La substitution on the photodegradation of the methylene blue (MB) under visible light were also studied. The photodegradation of MB dye was enhanced from 64 to \(\sim \)99% with increasing La substitution from \(\boldsymbol {x =}\) 0 to 0.1 and then decreased to 8% for \(\boldsymbol {x =}\) 0.15.     

Magnetic properties and electron density distribution of La<Subscript><Emphasis Type="Italic">x</Emphasis></Subscript>Bi<Subscript>1−<Emphasis Type="Italic">x</Emphasis></Subscript>FeO<Subscript>3</Subscript>

La _x Bi_1?x FeO₃(x = 0, 0.03, 0.06, 0.1, 0.2, 0.3, 0.5, 1) powders and thin films have been prepared by a conventional ceramic processing technique, and their mass magnetization and magnetic susceptibility have been measured at temperatures from 77 to 1000 K. The electron density distribution in BiFeO₃ and antiferromagnetic La_0.5Bi_0.5FeO₃ has been determined using self-consistent FP LMTO calculations within the localdensity-functional approximation.     

Electrical properties of B site substituted (K<Subscript>0.48</Subscript>Na<Subscript>0.52</Subscript>)(W<Subscript>2/3</Subscript>Bi<Subscript>1/3</Subscript>)<Subscript>x</Subscript>Nb<Subscript>1−x</Subscript>O<Subscript>3</Subscript> piezoceramics

Lead-free (K_0.48Na_0.52)(W_2/3Bi_1/3)_xNb_1−xO₃ (KNN-WBi) piezoceramics with x ranging from 0.004 to 0.010 were synthesized by conventional ceramic processing. The sintered KNN-WBi ceramics showed perovskite structure without detectable secondary phase containing W and Bi. With increasing x, the orthorhombic-tetragonal phase transition temperature (T _O-T) decreased from 200 to 184 °C whereas, the tetragonal-cubic phase transition temperature (T _C) decreased slightly. With the doping of (W_2/3Bi_1/3), the piezoelectric properties were greatly improved and the piezoelectric constants d ₃₃, k _p, Q _m exhibited maximum values of 136 pC/N, 43.3% and 175, respectively at x = 0.008. The KNN-WBi ceramics also exhibited good ferroelectric properties with remnant polarizations P _r higher than 25 μC/cm² and coercive fields E _c lower than 1,000 V/mm. The results strongly suggest that the B site doping of constructed quinquevalent element is an effective method for the investigation of potassium sodium niobate system.     

Synthesis and photocatalytic behaviors of Cr<Subscript>2</Subscript>O<Subscript>3</Subscript>–CNT/TiO<Subscript>2</Subscript> composite materials under visible light

Cr₂O₃–CNT/TiO₂ composites derived from chromium acetylacetonate, multi-walled carbon nanotubes (MWCNT) and titanium n-butoxide (TNB) were prepared, and the photocatalytic activity of the Cr₂O₃–CNT and CNT/TiO₂ composites was examined. The Cr₂O₃–CNT/TiO₂ composites were characterized by BET surface area measurement, X-ray diffraction, transmission electron microscopy, and energy dispersive X-ray analysis. The photocatalytic activity was determined from the decomposition of methylene blue (MB) under visible light irradiation. Methylene blue was photodegraded successfully in the presence of the Cr₂O₃–CNT/TiO₂ composite under visible light irradiation.     

A facile Pechini method to synthesize novel Bi<Subscript>12</Subscript>SiO<Subscript>20</Subscript>–Bi<Subscript>2</Subscript>SiO<Subscript>5</Subscript> heterostructure photocatalysts with enhanced visible light photocatalytic activity

Novel Bi₁₂SiO₂₀–Bi₂SiO₅ heterostructure photocatalysts were prepared by controlling the molar ratio of Bi/Si in the reactants via Pechini method. With the increasement of the molar ratio of Bi/Si, the samples tend to be well-crystallized Bi₁₂SiO₂₀ and the content of Bi₂SiO₅ decreases in composites. Experiments reveal that the heterojunction shows higher visible light photocatalytic activity than pure Bi₁₂SiO₂₀ and Bi₂SiO₅ due to an increase in light harvesting efficiency and an efficient electron–hole separation. And the heterostructure photocatalyst is stable in the photocatalytic reaction process. The influence of some trapping agents on the photodegradation of Rhodamine B was investigated, and h⁺ and ·O₂ ^? were verified to play more important roles than ·OH^?.     

Influence of Dy-doping on ferroelectric and dielectric properties in Bi<Subscript>1.05−x</Subscript>Dy<Subscript>x</Subscript>FeO<Subscript>3</Subscript> ceramics

Bi_1.05−xDy_xFeO₃ (BDFO) (x = 0−0.2) ceramics were synthesized by solid-state reaction method. The influence of Dy dopant on crystal structural, dielectric and ferroelectric properties was investigated. The lattice parameter and the Curie temperature of BDFO were degraded continuously with increasing contents of Dy³⁺ cations. Leakage current density, ferroelectric polarization and dielectric loss were improved by appropriate Dy doping. When x = 0.1, BDFO showed the best electric properties. At applied electric field of 53 kV/cm, the remnant polarization (2P _r ) was 12.2 μC/cm².These improvements in electric properties in BDFO ceramics could have resulted from the relatively low oxygen vacancy concentration and structural distortion.     

Micro-structural,dielectric, ferroelectric and piezoelectric properties of mechanically processed (Pb<Subscript>1−x</Subscript>La<Subscript>x</Subscript>)(Zr<Subscript>0.60</Subscript>Ti<Subscript>0.40</Subscript>)O<Subscript>3</Subscript> ceramics

In this work, (Pb_1?xLa_x)(Zr_0.60Ti_0.40)O₃ (PLZT x/60/40, x?=?at.%) ceramics were prepared by using high energy mechanical ball milling followed by cold isostatic pressing (CIP), investigated for their micro-structural, dielectirc, ferroelectric and piezoelectric properties. Mechanical activation results in the highly reactive nature of the nano size milled PLZT powders, which enables the partial perovskite phase formation, confirmed by room temperature XRD patterns. CIP leads to a higher density with a closely packed dense microstructure of sintered PLZT ceramics shown in SEM images. The grain size of PLZT x/60/40 ceramics was found to be decreasing with increasing La³⁺ content. The highest relative density of ~?97% was found to be for PLZT 8/60/40 ceramics with grain size of ~?1.35 µm. The PLZT 8/60/40 system also shows the highest dielectric constant of ~?1976, remnant polarization of 29.1 µC/cm², piezoelectric coefficients (d₃₃?\(~ \cong ~\)?570 pC/N, g₃₃?\(~ \cong ~\)?28.03?×?10^?3 Vm/N) and electromechanical coupling factors (k_p?=?k₃₃?=?64.1% and k₃₁?=?54%). The elastic compliances for the PLZT x/60/40 ceramics were also obtained.     

Novel g-C<Subscript>3</Subscript>N<Subscript>4</Subscript> wrapped γ-Al<Subscript>2</Subscript>O<Subscript>3</Subscript> microspheres heterojunction for efficient photocatalytic application under visible light irradiation

The novel g-C₃N₄ wrapped γ-Al₂O₃ microspheres heterojunction was successfully prepared by a simple hydrothermal process followed by calcination. The photocatalytic performances of the composite were evaluated by the degradation of methyl orange (MO) and rhodamine B (RhB) under visible light irradiation. The obtained Al₂O₃/g-C₃N₄ heterojunction exhibited much higher photocatalytic activity compared to pure g-C₃N₄. The enhanced performance may be mainly attributed to the tight contact between the components of the heterostructure as well as the efficient transfer of photoinduced electrons from the valence band (VB) of g-C₃N₄ to the defect sites of γ-Al₂O₃. The trapping experiment results indicated that the ·O₂ ^? radicals and holes (h⁺) are main active species in the decomposition of MO. This work will provide new ideas for manipulation of high-performance heterojunction for practical photocatalysis applications in water pollution controls.     

Electrical conduction in La<Subscript>0.9</Subscript>Ba<Subscript>0.1</Subscript>Er<Subscript>1−<Emphasis Type="Italic">x</Emphasis></Subscript>Mg<Subscript><Emphasis Type="Italic">x</Emphasis></Subscript>O<Subscript>3−α</Subscript> ceramics

Doubly doped LaErO₃ ceramics, La_0.9Ba_0.1Er_1−x Mg _x O_3−α (x = 0.05, 0.10, 0.15, 0.20), were synthesized by solid-state reaction method and characterized by X-ray diffraction (XRD). The samples have a single orthorhombic perovskite-type structure. The conduction behavior was investigated using various electrochemical methods including AC impedance spectroscopy, gas concentration cell, isotope effect of hydrogen, and hydrogen electrochemical permeation (pumping) in the temperature range of 500–1000 °C. The results indicated that specimens were pure ionic conductors under low oxygen partial pressure (about 10⁻⁷–10⁻²⁰ atm) and mixed conductors of proton, oxide ion, and electron hole under high oxygen partial pressure (about 10⁻⁵–1 atm). The pure ion conduction of the ceramics in hydrogen atmosphere was confirmed by electromotive force method of hydrogen concentration cell, and the observed emf values coincided well with the theoretical ones. The conductivity in H₂O–Ar atmosphere was higher than that in D₂O–Ar atmosphere, exhibiting an obvious isotope effect and proton conduction in water vapor containing atmosphere. It has been confirmed by electrochemical hydrogen permeation (hydrogen pumping) experiment that the ceramics were mainly proton conductors in hydrogen containing atmosphere. Whereas in dry oxygen-containing atmosphere, observed emf values of the oxygen concentration cell were far lower than the theoretical ones, indicating that the ceramics were mixed conductors of electron hole and oxide ion.     

Structural Stability of SrCo<Subscript>1 − <Emphasis Type="Italic">x</Emphasis></Subscript>Fe<Subscript>x</Subscript>O<Subscript>3 − δ</Subscript> Solid Solutions

SrCo_{1 − x} Fe_xO_{3 − δ} solid solutions with 0.3 ≤ x ≤ 0.9 are shown to have the cubic perovskite structure. The unit-cell parameter and volume of the solid solutions are nonmonotonic functions of Fe content, with a minimum at x = 0.4. Dilatometric data are used to determine the thermal expansion coefficients of the solid solutions. At low oxygen partial pressures ( ≤ 40 Pa), the high-temperature, disordered perovskite phase exists between 850 and 1000°C, which is the optimal temperature range for the effective use of SrCo_{1 − x} F_xO_{3 − δ} ceramics as oxygen membranes in oxygen partial pressure gradients of 10⁴–10⁵/10–100 Pa.__________Translated from Neorganicheskie Materialy, Vol. 41, No. 8, 2005, pp. 998–1004.Original Russian Text Copyright © 2005 by Kokhanovskii, Zonov, Ol’shevskaya, Pan’kov.     

Conductivity of La<Subscript>0.7</Subscript>Sr<Subscript>0.3</Subscript>MnO<Subscript>3 − δ</Subscript> films with small deviations from stoichiometry with respect to oxygen

We have studied the dynamics of the transport and optical characteristics of epitaxial La_0.7Sr_0.3MnO_{3 − δ} (LSMO) films with oxygen deficiency varied in the course of a multistage annealing. A hierarchical scheme for evaluating the defectness of the film material is proposed, which is based on the results of measurements of the minimum dc conductivity (σ_dc(T)) and the range of its variation with the temperature. It is established that the optical conductivity (σ_opt) at a radiation quantum energy of 2 eV corresponds to the limiting value of minimum σ_dc(T) in LSMO films without oxygen deficiency. This result does not contradict previously reported optical data and is consistent with the existing notions about the mechanisms of conductivity operative in the system under consideration.     

Electrical and oxygen sensing properties of Nd<Subscript>1−x</Subscript>Ba<Subscript>x</Subscript>CoO<Subscript>3</Subscript> ceramics

Nd_1?xBa_xCoO₃ (0?≤?x?≤?0.2) ceramics was synthesized by solid state reaction. All the samples have an orthorhombic perovskite structure (Space group P n m a). The electrical transport property indicates that Ba doped NdCoO₃ ceramics goes through semiconductor–metal phase transition. The electrical resistivity of Nd_1?xBa_xCoO₃ (0?≤?x?≤?0.15) ceramics decreases, while the electrical resistivity of Nd_0.8Ba_0.2CoO₃ ceramics increases with the increase of temperature. The chemical-sensing property shows that Nd_1?xBa_xCoO₃ ceramics is very sensitive to oxygen. Also, increasing Ba²⁺ doping concentration can reduce the oxygen desorption rate and increase the sensitivity of resistivity. These results indicate that Ba²⁺ doped NdCoO₃ ceramics is not only the good candidate of the cathode materials of solid fuel cells but also the good materials of gas sensor devices.     

Microstructure and properties of the Ba<Subscript>0.75−x</Subscript>Ca<Subscript>x</Subscript>La<Subscript>0.25</Subscript>Fe<Subscript>11.6</Subscript>Co<Subscript>0.25</Subscript>Ti<Subscript>0.15</Subscript>O<Subscript>19</Subscript> hexaferrites

In the case of Ti⁴⁺ remain unchanged, the Ca²⁺ substituted Ba_0.75?xCa_xLa_0.25Fe_11.6Co_0.25Ti_0.15O₁₉ (0?≤?x?≤?0.05) were prepared by conventional solid-state reaction method at temperature of 1280 °C. A ball-to-power weight ratio of 10:1. Their crystal structure and magnetic properties were mainly investigated. The results show that the single magnetoplumbite phase structure transformed into the multiphase structure. Meanwhile, the small amount of α-Fe₂O₃ phase existed in M-type phase. The micrographs were observed by a field emission scanning electron microscopy (SEM). Vibrating sample magnetometer (VSM) was used to analyze the magnetic properties. The saturation magnetization (M _s ) first increases then decreases when x from 0 to 0.03. But, when x from 0.03 to 0.05, the saturation magnetization (M _s ) first increases then decreases too. The maximum value is at x?=?0.04 (M _s ?=?70.73 emu/g). The value of coercivity (H _c ) first increases then decreases when x from 0 to 0.04. But, the value increased when x from 0.04 to 0.05. The maximum value is at x?=?0.02 (H _c ?=?1691 Oe).     

Structural,magnetic and magnetocaloric investigation of La<Subscript>0.67</Subscript>Ba<Subscript>0.33</Subscript>Mn<Subscript>1−x</Subscript>Ni<Subscript>x</Subscript>O<Subscript>3</Subscript> (x = 0, 0.025 and 0.075) manganite

In this paper, we report the structural, magnetic and magnetocaloric properties of Ni-doped La_0.67Ba_0.33Mn_1?xNi_xO₃ (x?=?0, 0.025 and 0.075) manganites. Our compounds were synthesized using the sol–gel method. The structural analysis using Rietveld refinement shows that Ni-doped LaBaMnO₃ system crystallizes in the rhombohedral symmetry with \({\text{R}}\bar {3}{\text{c}}\) space group. Magnetization measurements versus temperature in a magnetic applied field of 0.05 T reveal that all the compositions exhibit a transition from a ferromagnetic to paramagnetic phase with increasing temperature. A systematic decrease in the transition temperature is clearly observed upon Ni doping and a near room temperature T_C (302 K) is achieved with x?=?0.075 composition. The maximum magnetic entropy change \(\left( { - ~\Delta {\text{S}}_{{\text{M}}}^{{\hbox{max} }}} \right)\) in a magnetic field change of 5 T is found to be 2.12, 2.78 and 1.78 J/kg K for x?=?0, 0.025 and 0.075, respectively. At this value of magnetic field, large relative cooling power values are obtained in our samples, especially for x?=?0.075 (271 J/kg) making it a promising candidate for magnetic refrigeration near room temperature.     

Laser and electromagnetic loss properties of Perovskite SmNi<Subscript>x</Subscript>Fe<Subscript>1−x</Subscript>O<Subscript>3</Subscript>

SmNi_xFe_1?xO₃ (0?≤?x?≤?0.5) with perovskite-type structure has been successfully prepared by conventional solid-state reaction as a microwave and laser multi-functional material. The optimized synthesis temperature and the effects of Ni doping on the reflectivity, electromagnetic loss properties were investigated in details. XRD results shown that synthesis temperature did not change the perovskite structure of SmFeO₃. The reflectivity at 1.06 μm was about 0.33% at 1200–1300?°C. Doping Ni did not cause the change of perovskite structure. The incorporation of Ni in SmFeO₃ contributed to the decrease of reflectivity at a wider wavelength, SmNi_0.3Fe_0.7O₃ possessed the lowest reflectivity at 1.06 μm. Moreover, electromagnetic property was very sensitive to Ni content. The real and imaginary parts of complex permeability were enhanced remarkably at a certain frequency. The changes in magnetic performance provided possibility of choosing specific frequency of magnetic loss. The difference in electric and magnetic losses caused by Ni concentration could result in microwave absorption at different frequency. In a word, SmNi_xFe_1?xO₃ could be a promising candidate for a multi-functional material with compatible camouflage capability for radar and laser waveband.