Graphdiyne-hybridized N-doped TiO<Subscript>2</Subscript> nanosheets for enhanced visible light photocatalytic activity

In this study, graphdiyne (GD)-hybridized nitrogen-doped TiO₂ nanosheets with exposed (001) facets (GD-NTNS) have been prepared via a hydrothermal reaction and utilized as photocatalyst for the photodegradation of rhodamine B (RhB) under visible light illumination. The resultant GD-NTNS composites exhibit superior visible light photocatalytic activity than that of the bare TiO₂ nanosheets (TNS) and nitrogen-doped TiO₂ nanosheets (NTNS). The enhanced photoactivity can be attributed to the synergistic effects of GD and nitrogen doping with efficient electron transfer and strong visible light absorption. It has been revealed that ^·O^2? and h⁺ are the major species for the enhanced photoactivity under visible light. Our work will facilitate the potential for future design of hybrid materials for practical applications beyond photocatalysts.     

High-temperature phase transition of Tm<Subscript>2</Subscript>Ti<Subscript>2</Subscript>O<Subscript>7</Subscript>

The high-temperature (>1600°C) order—disorder phase transition of Tm₂Ti₂O₇ is shown to be irreversible. The 740°C ionic conductivity of nanocrystalline Tm₂Ti₂O₇ ceramics synthesized at 1670°C is 2 × 10^-3 S/cm and remains unchanged upon heat treatment in air at 860°C for 240 h. The conductivity of the high-temperature (disordered pyrochlore) phase of Tm₂Ti₂O₇ is independent of grain size in the range 20–30 nm.Translated from Neorganicheskie Materialy, Vol. 40, No. 12, 2004, pp. 1495–1500.Original Russian Text Copyright © 2004 by Shlyakhtina, Knotko, Larina, Borichev, Shcherbakova.     

Visible photocatalytic degradation of methylene blue on magnetic semiconducting La<Subscript>0.2</Subscript>Sr<Subscript>0.7</Subscript>Fe<Subscript>12</Subscript>O<Subscript>19</Subscript>

Methylene blue (MB) is a representative of a class of dyestuffs resistant to biodegradation. This paper presents a novel photocatalytic degradation of MB by La_0.2Sr_0.7Fe₁₂O₁₉ compound, which is a traditional permanent magnet and displays a large magnetic hysteresis (M–H) loop. The remnant magnetic moment and coercive field are determined to be 52 emu/g and 5876 Oe, respectively. UV–Visible optical spectroscopy reveals that La_0.2Sr_0.7Fe₁₂O₁₉ is simultaneously a semiconductor, whose direct and indirect band gap energies are determined to be 1.47 and 0.88 eV, respectively. The near infrared band gap makes it a good candidate to harvest sunlight for photocatalytic reaction or solar cell devices. This magnetic compound demonstrates excellent photocatalytic activity on degradation of MB under visible illumination. The colour of MB dispersion solution changes from deep blue to pale white and the absorbance decreases rapidly from 1.8 down to zero when the illumination duration extends to 6 h. Five absorption bands did not make any blue shifts along with the reaction time, suggesting a one-stepwise degradation process of MB, which makes La_0.2Sr_0.7Fe₁₂O₁₉ a unique magnetic catalyst and differs from TiO₂ and other conventional catalysts.     

Synthesis and high-temperature electrical conductivity of Ln<Subscript>2</Subscript>Ti<Subscript>2</Subscript>O<Subscript>7</Subscript> and LnYTi<Subscript>2</Subscript>O<Subscript>7</Subscript> (Ln = Dy,Ho)

Ho₂Ti₂O₇ and LnYTi₂O₇ (Ln = Dy, Ho) pyrochlores have been synthesized using hydroxide coprecipitation, mechanical activation, and firing at 1600°C. The bulk and grain-boundary components of their conductivity have been determined for the first time by impedance spectroscopy. The 740°C bulk conductivity of Ho₂Ti₂O₇ is 4 × 10^?4 S/cm, and that of HoYTi₂O₇ is 1 × 10^?3 S/cm, with activation energies E _a = 1.01 and 1.17 eV, respectively, suggesting that these materials are new oxygen-ion conductors. The bulk conductivity of DyYTi₂O₇ (3 × 10^?4 S/cm at 740°C, E _a = 1.09 eV) is almost one order of magnitude lower than that of HoYTi₂O₇ (1 × 10^?3 S/cm at 740°C, E _a = 1.17 eV).     

Conductivity of Sm<Subscript>2</Subscript>TiO<Subscript>5</Subscript> and Sm<Subscript>2</Subscript>Ti<Subscript>2</Subscript>O<Subscript>7</Subscript>

The oxygen-ion conductivity of porous materials, the coarse-grained pyrochlore-like Sm₂Ti₂O₇ and fine-grained Sm₂TiO₅ compounds, produced by mechanical activation of initial oxides is studied at 400–1000 °C. The Sm₂TiO₅ samples contain ～15 wt % of the nanosized pyrochlore-like Sm₂TiO₅ phase in addition to the rhombic phase. As determined by impedance spectroscopy, the ionic conductivities of Sm₂TiO₅ and Sm₂Ti₂O₇ at 1000°C are 1.3 × 10^?3 and 1.8 × 10^?4 S cm^?1, and the activation energies of the bulk and grainboundary conductivities of the materials are 1.04 and 1.24 eV for Sm₂TiO₅ and 1.69 and 1.80 eV for Sm₂Ti₂O₇.     

Phase equilibria in the La<Subscript>2</Subscript>O<Subscript>3</Subscript>-Nb<Subscript>2</Subscript>O<Subscript>5</Subscript>-Nb system and thermal stability of LaNb<Subscript>7</Subscript>O<Subscript>12</Subscript>

The phase equilibria in the ternary system La₂O₃-Nb₂O₅-Nb have been studied at subsolidus temperatures in vacuum (6.65 × 10^?3 Pa), and the temperature stability limits of LaNb₇O₁₂ have been determined in vacuum and during heating in air.     

Assembly of WO<Subscript>3</Subscript> nanosheets/Bi<Subscript>24</Subscript>O<Subscript>31</Subscript>Br<Subscript>10</Subscript> nanosheets composites with superior photocatalytic activity for degradation of tetracycline hydrochloride

In this work, a high-performance composite photocatalyst composed of WO₃ nanosheets and Bi₂₄O₃₁Br₁₀ nanosheets was successfully synthesized. The photocatalytic activity of the obtained samples was studied by the degradation of tetracycline hydrochloride under visible light irradiation. The results showed that Bi₂₄O₃₁Br₁₀ modified with the appropriate amount of WO₃ nanosheet exhibits higher catalytic activity and stability during the photocatalytic processes, and the holes (h⁺) is involved in the photolysis reaction as the main active species. The crystallization, morphology, optical and electrochemical properties of the as-prepared composite photocatalyst were characterized, and the mechanism of high photocatalytic activity was also explored. The optimal sample (10%-WO₃/Bi₂₄O₃₁Br₁₀) exhibited the best performance for tetracycline hydrochloride (TC) degradation, and more than 80% of the TC was degraded after 60 min under light irradiation. The degradation rate constant k was about 3.34-fold and 1.54-fold higher than pure WO₃ and Bi₂₄O₃₁Br₁₀, respectively. Its high photocatalytic performance can be attributed to the following reasons: the appropriate conduction band and valence band positions between WO₃ and Bi₂₄O₃₁Br₁₀, the close contact between the two visible light-driven photocatalysts, and the effective separation of the spatial charge. Our work may help to further expand the potential application of oxygen-rich bismuth oxyhalides photocatalyst in wastewater treatment, and provide a new strategy for the modification of nanostructured photocatalysts.     

Visible light irradiated photocatalytic and magnetic properties of Fe-doped SnS<Subscript>2</Subscript> nanopowders

Fe-doped SnS₂ (SnS₂:Fe) nanopowders were synthesized by cost effective chemical method and characterized by thermo gravimetric-differential thermal analysis, X-ray diffraction, scanning electron microscopy, transmission electron microscopy, X-ray photoelectron spectroscopy and vibrating sample magnetometer techniques. The photocatalytic activity was evaluated for the degradation of congo red dye under visible light irradiation. XRD studies indicate that both the undoped and doped SnS₂ nanopowders exhibit hexagonal crystal structure with a strong (1 0 1) preferential growth. Nanosized grains are evinced from the TEM images. XPS spectra confirmed the presence of Fe in the doped samples. Photodegradation efficiency increased with increase in Fe doping concentration and the SnS₂:Fe nanopowder with 10 wt% Fe doping concentration exhibits a maximum efficiency of 93.94% after 180 min light irradiation. Ferromagnetic ordering of pure SnS₂ improved with Fe doping. The outcome of the results indicated that Fe-doped SnS₂ nanopowders are well suited as diluted magnetic semiconductor and also can be used as an efficient photocatalyst.     

Synthesis and high-temperature heat capacity of Yb<Subscript>2</Subscript>Sn<Subscript>2</Subscript>O<Subscript>7</Subscript> and Lu<Subscript>2</Subscript>Sn<Subscript>2</Subscript>O<Subscript>7</Subscript>

Yb₂Sn₂O₇ and Lu₂Sn₂O₇ have been prepared by solid-state reactions, by firing mixtures of Yb₂O₃ or Lu₂O₃ and SnO₂ at 1473 K, and the molar heat capacity of these compounds (pyrochlore structure) has been determined by differential scanning calorimetry. The C _p (T) data have been used to evaluate the thermodynamic properties of the stannates: enthalpy increment, entropy change, and reduced Gibbs energy.     

Electroluminescence of (Pb<Subscript>0.91</Subscript>La<Subscript>0.09</Subscript>)(Zr<Subscript>0.65</Subscript>Ti<Subscript>0.35</Subscript>)O<Subscript>3</Subscript> ceramics with nanopolar structure

Lanthanum-doped lead zirconate titanate (PLZT) relaxor ceramics with (Pb_0.91La_0.09)(Zr_0.65Ti_0.35)O₃ composition exhibits a repolarization-induced electroluminescence (EL) with a pronounced discrete character of emission. It is established that this behavior is related to the reorientation of nanodimensional polar regions in a strong pulsed electric field in the vicinity of a smeared phase transition. The temporal and temperature dependences of the EL intensity have been studied.     

Synthesis and High-Temperature Heat Capacity of Dy<Subscript>2</Subscript>Ge<Subscript>2</Subscript>O<Subscript>7</Subscript> and Ho<Subscript>2</Subscript>Ge<Subscript>2</Subscript>O<Subscript>7</Subscript>

The Dy₂Ge₂O₇ and Ho₂Ge₂O₇ pyrogermanates have been prepared by solid-state reactions in several sequential firing steps in the temperature range 1237–1473 K using stoichiometric mixtures of Dy₂O₃ (or Ho₂O₃) and GeO₂. The heat capacity of the synthesized germanates has been determined as a function of temperature by differential scanning calorimetry in the range 350–1000 K. The experimentally determined C _p (T) curves of the dysprosium and holmium germanates have no anomalies and are well represented by the Maier–Kelley equation. The experimental C _p (T) data have been used to evaluate the thermodynamic functions of the Dy₂Ge₂O₇ and Ho₂Ge₂O₇ pyrogermanates: enthalpy increment H°(T)–H°(350 K), entropy change S°(T)–S°(350 K), and reduced Gibbs energy Ф°(T).     

Synthesis and High-Temperature Heat Capacity of Sm<Subscript>2</Subscript>Ge<Subscript>2</Subscript>O<Subscript>7</Subscript> and Eu<Subscript>2</Subscript>Ge<Subscript>2</Subscript>O<Subscript>7</Subscript>

The Sm₂Ge₂O₇ and Eu₂Ge₂O₇ germanates have been prepared by solid-state reactions via multistep firing of stoichiometric mixtures of Sm₂O₃ (Eu₂O₃) and GeO₂ in air at temperatures from 1273 to 1473 K. The molar heat capacity of the samarium and europium germanates has been determined by differential scanning calorimetry in the range 350–1000 K and the C _p (T) data have been used to evaluate their thermodynamic properties.     

Synthesis,microstructure and microwave dielectric properties of Ca<Subscript>4-x</Subscript>Mg<Subscript>x</Subscript>La<Subscript>2</Subscript>Ti<Subscript>5</Subscript>O<Subscript>17</Subscript> ceramics

Ca_4-xMg_xLa₂Ti₅O₁₇ ceramics were prepared by a solid state ceramic route for x = 0, 0.5, 1, 2, 3 and 4. The structure and microstructure of the ceramics were investigated using X-ray diffraction, scanning electron microscopy and energy dispersive X-ray spectroscopy. X-ray diffraction results show that the Ca_4-x Mg _x La₂Ti₅O₁₇ adopts an orthorhombic crystal structure with no secondary phase observed for x from 0 to 0.5. Secondary phase, MgTiO₃ occurs with further increasing doping level (1 ≤ x ≤ 3). When x = 4, mixture phases La_0.66TiO_2.993, MgTiO₃ and a trace of unknown phase coexist. Ca₄La₂Ti₅O₁₇ ceramic exhibits a relative permittivity (ε_r) ~ 65, quality factor (Q × f) ~13,338 GHz (at ~4.75 GHz), and temperature coefficient of resonant frequency (τ _f ) ~ 165 ppm/°C. The sintering temperature was distinctly reduced from 1,580 °C for x = 0 to 1,350 °C for x = 4. With increasing Mg content, ε_r and τ_f obviously decrease, while Q × f value initially decreases and then increases. The ceramic for x = 2 shows ε_r ~ 50, Q × f ~ 9,451 and τ _f  ~ 62.5 ppm/°C. By the complete replacement of Ca with Mg, Mg₄La₂Ti₅O₁₇ ceramic sintered at 1,350 °C for 4 h combines a high dielectric permittivity (ε _r  = 31), high quality factor (Q × f ~ 15,021) and near-zero temperature coefficient of resonant frequency (τ _f  ~ 4.0 ppm/°C). The materials are suitable for microwave applications.     

Highly textured La<Subscript>2</Subscript>Zr<Subscript>2</Subscript>O<Subscript>7</Subscript> and CeO<Subscript>2</Subscript> buffer layers by ink jet printing for coated conductors

The objective of this paper is to prove the possibility to produce single side buffered substrates for coated conductors. We report for the first time the production of highly textured NiW/La₂Zr₂O₇/CeO₂ system by all-chemical solution deposition means using an in-house built drop-on-demand ink-jet printer. Lanthanum zirconate precursor ink was produced using lanthanum acetate and zirconium n-propoxide modified with propionic and acetic acid, respectively, and diluted with methanol. Cerium oxide precursor ink was prepared using cerium acetylacetonate dissolved in acetylacetone and diluted in methanol. Optimized ink jet control parameters (inter-droplet distance, nozzle opening time and pressure in the chamber) allowed the deposition of homogeneous highly textured films with a thickness of approximately 150–200 nm at speeds as high as 27 cm/min. La₂Zr₂O₇ film showed in plane and out of plane misalignment of 6.6° and 7.4°, respectively, whereas values obtained for CeO₂ were 7.8° and 8.1°, respectively. This study represents a step forward in the production of reel-to-reel coated conductors in an efficient and economic way.     

Electrochemical properties of Li<Subscript>4</Subscript>Ti<Subscript>5</Subscript>O<Subscript>12</Subscript>/C and Li<Subscript>4</Subscript>Ti<Subscript>5</Subscript>O<Subscript>12</Subscript>/C/Ag nanomaterials

We have prepared and characterized lithium titanate-based anode materials, Li₄Ti₅O₁₂/C and Li₄Ti₅O₁₂/C/Ag, using polyvinylidene fluoride as a carbon source. The formation of such materials has been shown to be accompanied by fluorination of the lithium titanate surface and the formation of a highly conductive carbon coating. The highest electrochemical capacity (175 mAh/g at a current density of 20 mA/g) is offered by the Li₄Ti₅O₁₂-based anode materials prepared using 5% polyvinylidene fluoride. The addition of silver nanoparticles ensures a further increase in electrical conductivity and better cycling stability of the materials at high current densities.     

The shock properties of a La<Subscript>2</Subscript>O<Subscript>3</Subscript> filled silicate glass

A survey of the shock properties of the silicate glass, LACA has been carried out using manganin stress gauges. The principal Hugoniot has been measured and found to have significantly higher values than for other common silicate glasses. Gauges mounted on the rear of the target (supported with a block of polymethylmethacrylate) show reloading signals superimposed on the main compressive shock pulse. This has been interpreted as evidence of dynamic compressive failure (the failure wave or front). Manganin gauges mounted so as to be sensitive to the lateral component of stress support this hypothesis. Finally, failure front velocities, measured using known lateral gauge separations increase with increasing shock stress, tending towards the shear wave speed.     

Dielectric properties of B<Subscript>2</Subscript>O<Subscript>3</Subscript> doped Sm(Co<Subscript>1/2</Subscript>Ti<Subscript>1/2</Subscript>)O<Subscript>3</Subscript> ceramics at microwave frequency

The microwave dielectric properties and the microstructures of Sm(Co_1/2Ti_1/2)O₃ ceramics with B₂O₃ additions (0.25 and 0.5 wt%) prepared by conventional solid-state route have been investigated. The prepared Sm(Co_1/2Ti_1/2)O₃ exhibited a mixture of Co and Ti showing 1:1 order in the B-site. Doping with B₂O₃ (up to 0.5 wt%) can effectively promote the densification of Sm(Co_1/2Ti_1/2)O₃ ceramics with low sintering temperature. It is found that Sm(Co_1/2Ti_1/2)O₃ ceramics can be sintered at 1,260 °C due to the grain boundary phase effect of B₂O₃ addition. At 1,290 °C, Sm(Co_1/2Ti_1/2)O₃ ceramics with 0.5 wt% B₂O₃ addition possess a dielectric constant (ε _r) of 27.7, a Q × f value of 33,600 (at 9 GHz) and a temperature coefficient of resonant frequency (τ_f) of −11.4 ppm/ °C. The B₂O₃-doped Sm(Co_1/2Ti_1/2)O₃ ceramics can find applications in microwave devices requiring low sintering temperature.     

Confined growth of Li<Subscript>4</Subscript>Ti<Subscript>5</Subscript>O<Subscript>12</Subscript> nanoparticles in nitrogen-doped mesoporous graphene fibers for high-performance lithium-ion battery anodes

Nanomaterials with electrochemical activity are always suffering from aggregations, particularly during the high-temperature synthesis processes, which will lead to decreased energy-storage performance. Here, hierarchically structured lithium titanate/nitrogen-doped porous graphene fiber nanocomposites were synthesized by using confined growth of Li₄Ti₅O₁₂ (LTO) nanoparticles in nitrogen-doped mesoporous graphene fibers (NPGF). NPGFs with uniform pore structure are used as templates for hosting LTO precursors, followed by high-temperature treatment at 800 °C under argon (Ar). LTO nanoparticles with size of several nanometers are successfully synthesized in the mesopores of NPGFs, forming nanostructured LTO/NPGF composite fibers. As an anode material for lithium-ion batteries, such nanocomposite architecture offers effective electron and ion transport, and robust structure. Such nanocomposites in the electrodes delivered a high reversible capacity (164 mAh·g^–1 at 0.3 C), excellent rate capability (102 mAh·g^–1 at 10 C), and long cycling stability.

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