Photocatalytic Oxidation of Isopropanol in Aqueous Solution Using Perovskite‐Structured La2Ti2O7

This study is focused on the application of a highly‐doped layered perovskite, La₂Ti₂O₇, as the photocatalyst for the photocatalytic decomposition of isopropanol (IPA). The La₂Ti₂O₇ powder prepared by solid state reaction was characterized by X‐ray diffraction (XRD), scanning electron microscopy (SEM), UV‐Vis diffuse reflectance spectrophotometry (UV‐DRS), X‐ray photoelectron spectroscopy (XPS), and zeta potential. The temporal behavior of the photocatalytic decomposition of IPA in aqueous solution by the UV/La₂Ti₂O₇, with a photoreactor operated in a recirculation mode, was studied under various conditions including solution pH, light intensity, and La₂Ti₂O₇ loading. The decomposition of IPA in aqueous solution by La₂Ti₂O₇ photocatalytic processes was found to be technically feasible. A kinetic equation was developed for modeling the photocatalytic decomposition of IPA by the UV/La₂Ti₂O₇ photocatalytic processes.     

Low Thermal Conductivity of Rare‐Earth Zirconate‐Stannate Solid Solutions (Yb2Zr2O7)1−x(Ln2Sn2O7)x (Ln = Nd,Sm)

Dense monoliths of rare‐earth zirconate‐stannate solid solutions (Yb₂Zr₂O₇)_1?x(Ln₂Sn₂O₇)_x (Ln = Nd, Sm) were prepared by solid‐state reaction. Characterized by XRD, Raman, SEM, and TEM, a double‐phase structure of Yb₂Zr₂O₇‐rich fluorite and Nd₂Sn₂O₇‐rich pyrochlore was observed in the specimens of x = 0.4 and 0.5 of (Yb₂Zr₂O₇)_1?x(Nd₂Sn₂O₇)_x series while complete solid solutions were formed within the whole composition range of (Yb₂Zr₂O₇)_1?x(Sm₂Sn₂O₇)_x series. Except for the defect phonon scattering, lattice softening caused by order–disorder phase transformation between pyrochlore and fluorite structures also plays an important role in minimizing the thermal conductivity. Low thermal conductivity with positive temperature dependence is achieved in both the series. Considering the structure stability and low thermal conductivity, rare‐earth zirconate‐stannate solid solutions may be promising materials for thermal insulating applications, such as thermal barrier coatings.     

Preparation,Structural Characterization,and Enhanced Electrical Conductivity of Pyrochlore‐type (Sm1–xEux)2Zr2O7 Ceramics

(Sm_1–xEu_x)₂Zr₂O₇ (0 ≤ x ≤ 1.0) samples are prepared by solid state reaction method using Sm₂O₃, Eu₂O₃, and ZrO₂ as starting materials. The phase composition and microstructure of (Sm_1–xEu_x)₂Zr₂O₇ ceramics are investigated by X‐ray diffraction (XRD), scanning electron microscopy, high‐resolution transmission electron microscopy (HRTEM) coupled with selected area electron diffraction and Raman spectroscopy. XRD and TEM show that all the samples exhibit a single pyrochlore‐type structure. HRTEM observation indicates that the whole grain interior of Sm₂Zr₂O₇ ceramic is a perfect crystal free of any dislocation. Raman spectroscopy reveals that the degree of structural disorder of (Sm_1–xEu_x)₂Zr₂O₇ ceramics increases gradually with increasing Eu content. The electrical conductivity of (Sm_1–xEu_x)₂Zr₂O₇ ceramics is investigated by impedance spectroscopy in the air and hydrogen atmospheres, respectively. The electrical conductivity of (Sm_1–xEu_x)₂Zr₂O₇ ceramics increases with increasing Eu content at identical temperature levels. Both the activation energy E_g and the pre‐exponential factor σ_0g for the grain conductivity gradually increase with increasing Eu content. As the ionic conductivity shows no obvious change in both air and hydrogen atmospheres, the conduction of (Sm_1–xEu_x)₂Zr₂O₇ is purely ionic with negligible electronic conduction.     

Low‐Temperature Synthesis of CoNb2O6 Microwave Dielectric Ceramics

Low‐fired cobalt niobate (CoNb₂O₆) microwave dielectric ceramics were prepared through a developed sol–gel process using Nb₂O₅·nH₂O as starting source. A metal‐dioxo‐bridged complex precursor was described on the basis of FT‐IR spectrum. The crystalline phases of calcined powders were characterized by X‐ray diffraction. Nanosized CoNb₂O₆ particles with orthorhombic α‐PbO₂‐type structure were obtained above 750°C. There was no subsequent phase change upon sintering, and all compounds sintered to at least 94% of theoretical density. At 1000°C/4 h, CoNb₂O₆ ceramics exhibited ε_r ~ 21.9, Q × f ~ 66 140 GHz (at 8.9 GHz) and τ_f ~ ?39.7 ppm/°C, having a good potential for low‐temperature cofired ceramic applications.     

Direct Formation and Luminescence of Nanocrystals in the System Eu2Sn2O7–Gd2Sn2O7 Complete Solid Solutions

Nanocrystals with orange‐reddish luminescence based on the pyrochlore‐type complete solid solutions with cube‐like morphology in the Eu₂Sn₂O₇–Gd₂Sn₂O₇ system were directly formed from the precursor solutions of SnCl₄, GdCl₃, and EuCl₃ under weakly basic hydrothermal conditions at temperatures higher than 180°C for 5 h. The crystallite of Gd₂Sn₂O₇ pyrochlore gradually grew from 10 to 37 nm as the hydrothermal treatment temperature rose from 180°C to 240°C. The lattice parameter of cubic phase linearly increased with increased europium concentration according to the Vegard's law. The characteristic orange‐reddish photoluminescence spectra of Gd₂Sn₂O₇:Eu³⁺ cubelike nanocrystals with crystallite size from 34 to 37 nm that were formed at 240°C for 5 h were attributed to the most sharp orange (586 nm) luminescence with high intensity and quite broad red (610–630 nm) emission with weak intensity, according to the ⁵D₀→⁷F₁ and ⁵D₀→⁷F₂ transitions of Eu³⁺, respectively. At a composition of (Eu_0.09Gd_0.91)₂Sn₂O₇, the intensity of orange emission reached the maximum. The Red‐to‐Orange (⁵D₀→⁷F₂/⁵D₀→⁷F₁) (R/O) emission intensity ratio was in the low range from 0.10 to 0.14, which was a characteristic of Gd₂Sn₂O₇:Eu³⁺.     

Synthesis of Si–C–O Bulk Ceramics with Various Chemical Compositions from Polycarbosilane

Si-C-O bulk ceramics with various atomic ratios were produced by pyrolysis and high-temperature treatment (HTT) of a polycarbosilane (PCS) precursor with a given amount of oxygen. The oxygen introduction within the PCS molecular structure makes the compact infusible during the pyrolysis step, and supports sintering. The derived chemical compositions are mapped on a Si-C-O constitution diagram, with their transition behaviors due to HTT described. Upon heating between 1500° and 1700°C, the chemical compositions of the as-pyrolyzed specimens were as follows: PCS-6 (SiC_1.36O_0.26), PCS-8 (SiC_1.25O_0.45), and PCS-10 (SiC_1.02O_0.68), moving toward C/Si = 1.2, 1.0, and 0.8 with a reduction of the oxygen content, respectively. It is also shown that there are influences of the initial oxygen content on the resulting microstructure of both as-pyrolyzed and heat-treated specimens.     

Bi2Sn2O7粉体微波水热法制备及其吸附-可见光催化性能研究

以物质的量比为1∶1的Bi(NO3)3.5H2O和Na2SnO3.3H2O为原料,采用微波水热法合成Bi2Sn2O7粉体。采用XRD、SEM对粉体的晶相和形貌进行了表征,并以甲基橙为目标污染物,测试粉体的光催化性能。研究了合成时间、合成温度等因素对样品催化性能的影响,同时以KI、NBT及乙腈作为抑制剂,检测光催化过程产生的活性物质。结果表明:200℃、30 min微波水热合成的2 g/L Bi2Sn2O7粉体在暗光条件下搅拌2 h,对20 mg/L甲基橙溶液的吸附率为40%,将其置于250 W的卤素灯下光照2 h,甲基橙溶液的脱色率达95%以上。活性物种的检测表明光催化过程产生的主要活性物种为·OH和·O2-。     

The dependence of lattice thermal conductivity on phonon modes in pyrochlore-related Ln2Sn2O7 (Ln = La,Gd)

Rare-earth pyrochlore materials are promising thermal barrier coatings materials and fundamental understanding of their thermal transport is crucial for further improving its performance. In this work, using density functional theory (DFT) method, we calculated the intrinsic lattice thermal conductivities of Ln₂Sn₂O₇ (Ln = La, Gd) and conducted a comprehensive analysis on the mode thermal conductivity, relaxation time, Grüneisen parameters, group velocity, and specific heat, respectively. It is shown that in pyrochlore-type materials the number of the optical phonons is much larger than that of the acoustic phonon, and the thermal conductivity of acoustic phonons are suppressed, both of which increase the contribution ratio of optical phonons. Especially, through cumulative analysis, we found that the contribution of optical phonons is significant: the ratio of optical contribution is more than 50% and 64% in La₂Sn₂O₇ and Gd₂Sn₂O₇. This work provides a comprehensive picture illustrating the significant role of the optical phonons in the lattice thermal conduction in rare-earth pyrochlore materials, and points out an avenue to obtain low thermal conductivity in complex structural thermal insulation materials.     

Facile Synthesis of BiOBr/Bi2Sn2O7 Heterojunction Photocatalysts with Improved Photocatalytic Activities

BiOBr/Bi₂Sn₂O₇ heterojunction photocatalysts were successfully synthesized by treating hydrothermal as‐prepared Bi₂Sn₂O₇ nanoparticles with hydrobromic acid (HBr). Partial Bi₂Sn₂O₇ nanoparticles reacted with HBr to form the sheet‐like BiOBr, and Bi₂Sn₂O₇ nanoparticles distributed evenly on BiOBr sheets. BiOBr/Bi₂Sn₂O₇ photocatalysts treated with different concentrations of HBr solution were successfully obtained, and their structures, morphologies, optical, and visible light photocatalytic properties were characterized by XRD, DRS, PL, SEM, and TEM. The experimental results showed that the BiOBr/Bi₂Sn₂O₇ photocatalysts showed improved photocatalytic activity under visible light irradiation than pure Bi₂Sn₂O₇. The sample treated with 0.08 mol/L HBr solution shows the best visible light photodegradation performance of rhodamine B. In addition, the active species and photocatalytic mechanism were discussed in detail.     

Synthesis and thermophysical performances of complex Ca3Ln3Ti7Ta2O26.5 (Ln=Dy and Er) oxides

Ca₃Dy₃Ti₇Ta₂O_26.5 and Ca₃Er₃Ti₇Ta₂O_26.5 oxides were synthesized using a high-temperature solid-state fritting technique, and the thermophysical performances of these two oxides were investigated. Both Ca₃Dy₃Ti₇Ta₂O_26.5 and Ca₃Er₃Ti₇Ta₂O_26.5 show a monophasic pyrochlore-type lattice. The thermal conductivity of Ca₃Er₃Ti₇Ta₂O_26.5 is lower than that of Ca₃Dy₃Ti₇Ta₂O_26.5. The oxides exhibit lower thermal conductivities than YSZ owing to their complex elemental compositions, large number of ions, and high oxygen vacancy concentrations. The thermal expansion coefficients of the obtained oxides are similar to that of YSZ.     

Pyrochlore‐Free Ferroelectric 0.64Pb(Ni1/3Nb2/3)O3–0.36PbTiO3 Ceramics Synthesized by the Combustion Method

By adopting Nb₂O₅, HNO₃ and coordination agents EDTA as raw materials, pyrochlore‐free 0.64Pb(Ni_1/3Nb_2/3)O₃–0.36PbTiO₃(0.64PNN–0.36PT) powders were successfully synthesized via a combustion route. Free of pyrochlore phase was realized by the chelation formation of EDTA‐metal ions which isolate niobium and lead oxides and then prevent the formation of pyrochlore phases, therein generate the desired perovskite phases. Comparing the results with similar samples synthesized by the Columbite method, the new 0.64PNN–0.36PT ceramics here shown much better dielectric and ferroelectric performances: a maximum dielectric constant of 22 856 at 1 kHz and a remnant polarization of 21.6 μC/cm² at 40 kV/cm.     

Visible Light Transparency for Polycrystalline Ceramics of MgO·2Al2O3 and MgO·2.5Al2O3 Spinel Solid Solutions

Magnesium aluminate spinel solid solutions with the alumina‐rich compositions MgO·2Al₂O₃ and MgO·2.5Al₂O₃ have been prepared as polycrystalline ceramics with average in‐line transmissions at 550 nm of 85.5 ± 0.3% and 80.9 ± 0.4%, respectively. Starting powders are prepared from combinations of high purity Mg(OH)₂ and γ‐Al₂O₃ thoroughly mixed in an aqueous slurry, and the solids are collected, dried, calcined, mixed with LiF sintering aid, and sieved. The optimum amount of LiF added varies with the alumina composition of the spinel solid solution. The powders are sintered into dense ceramics by hot pressing at 1600°C under vacuum and 20 MPa uniaxial load followed by hot isostatic pressing at 1850°C under 200 MPa in Ar. Both compositions exhibit exaggerated grain growth with average sizes well over 500 μm. Knoop hardness measurements are 11.2 ± 0.3 GPa for MgO·2Al₂O₃ and 11.0 ± 0.4 GPa for MgO·2.5Al₂O₃.     

Electrophoretic Deposition of Aqueous Nano‐Cr2O3 Suspension

The coating of nano‐Cr₂O₃ was successfully fabricated via aqueous electrophoretic deposition (EPD). The deposition behavior aqueous nano‐Cr₂O₃ suspension was affected by the added amount of nitric acid. The morphology of electrophoretic Cr₂O₃ coating was significantly influenced by the deposition voltage. For a suitable EPD, stable aqueous nano‐Cr₂O₃ suspension could be obtained by the addition of 0.0025 M nitric acid, and the suitable deposition voltage was 5 V. For the purpose of increasing deposition rate which was limited by lower deposition voltage, it was suggested to employ higher suspension concentration of Cr₂O₃.     

Aqueous Combustion Synthesis of Strontium-Doped Lanthanum Chromite Ceramics

An aqueous combustion synthesis is used to produce powders of La_0.8Sr_0.2CrO₃ perovskite. It is shown that interaction between chromium nitrate and glycine controls the process. In addition, it is suggested that glycine reacts with products of nitrate decomposition to yield an intermediate compound, which decomposes exothermically providing high-temperature conditions for complex oxide formation. It is remarkable that although reaction temperature is high (up to 800°C) and characteristic time is small (∼1 s) for synthesis under the self-propagating high-temperature mode, the produced perovskites have high specific surface area (∼40 m²/g) and well-defined crystalline structure. As a result, ceramics sintered by using these powders are dense (∼96% of theoretical) and possess high electronic and low ionic conductivities, important for interconnect applications in solid oxide fuel cells.     

Synthesis of Single‐Phase β‐Yb2Si2O7 and Properties of Its Sintered Bulk

Single‐phase β‐Yb₂Si₂O₇ was synthesized by solid‐state reaction using Yb₂O₃ and SiO₂ gel. SiO₂ gel significantly decreased the synthesis temperature and shortened the holding time. Bulk Yb₂Si₂O₇ was obtained by pressureless sintering. Grain size, relative density (92.9%), and flexural strength [(182.3 ± 2.0) MPa] were enhanced as the sintering temperature increased and equiaxed grains were obtained with an average grain size of approximately 3 μm. Bulk Yb₂Si₂O₇ possessed a suitable thermal expansion coefficient [(4.64 ± 0.01) × 10^?6/K] between 473 and 1573 K, and the thermal conductivities at 300 and 1400 K were 4.31 and 2.27 W/m·K, respectively.     

Phase Transformation Behavior of a Pyrochlore‐Type CeO2–ZrO2 Binary Compound

The phase transformation behavior of the superlattice structure of a CeO₂–ZrO₂ pyrochlore‐type binary compound (CP) was investigated so as to better understand how to improve the thermal stability of such a system. CP was synthesized through high‐temperature reduction of a conventional CeO₂–ZrO₂ solid solution with a 1:1 molar ratio of Ce and Zr. High‐resolution transmission electron microscopy and selected‐area electron diffraction clearly revealed that the pyrochlore structure of CP transformed to the standard disordered cubic fluorite or tetragonal zirconia structure after having been subjected to a high‐temperature durability test; moreover, it was determined that this phase transformation moves inward from the crystallite surface. This discovery suggests a new method by which to improve upon this material for practical applications.     

Crystal structure of rare-earth silicon-oxynitride J-phases,Ln4Si2O7N2

Rare-earth silicon-oxynitride J-phases, Ln₄Si₂O₇N₂ (Ln=Y, La, Pr, Nd, Sm, Gd, Tb, Dy, Ho, Er, Tm, Yb, and Lu), were prepared by the N₂ gas-pressured sintering method at 1 MPa of N₂ and 1500–1700 °C. The Rietveld analysis was carried out for X-ray powder diffraction data measured at room temperature. The crystal structures of Ln₄Si₂O₇N₂ were refined with the structure model of La₄Si₂O₇N₂ for Ln=La, Pr, Nd, and Sm, and with that of Lu₄Si₂O₇N₂ for Ln=Y, Gd, Tb, Dy, Ho, Er, Tm, Yb, and Lu. The refined monoclinic unit-cell parameters (lengths a, b, c, angles β, and volume V) increased linearly in their two series of Ln with increasing ionic radii of rare-earth atoms. Discontinuities of the unit-cell parameters were found between the two Ln series.     

Structured Porous Millireactors for Liquid‐Liquid Chemical Reactions

Milli‐scale reactors with an integrated microstructure offer a promising scale‐up approach for conventional microreactors. This study applies 3D‐printed structured porous millireactors to industrially relevant liquid‐liquid reactions. The underlying transport mechanisms are identified by quantifying interfacial heat and mass transfer. The structured reactors perform limited in Taylor flow compared to a packed‐bed reactor due to limited interfacial mass transfer. However, in stratified flow, their productivity increases significantly at a fraction of the pressure drop of a packed bed.     

Chemical Synthesis,Sintering and Piezoelectric Properties of Ba0.85Ca0.15 Zr0.1Ti0.9O3 Lead‐Free Ceramics

The preparation of Ba_0.85Ca_0.15 Zr_0.1Ti_0.9O₃ (BCZT) powders by wet chemical methods has been investigated, and the powders used to explore relationships between the microstructure and piezoelectric properties (d₃₃ coefficient) of sintered BCZT ceramics. Sol–gel synthesis has been shown to be a successful method for the preparation of BCZT nanopowders with a pure tetragonal perovskite phase structure, specific surface area up to 21.8 m²/g and a mean particle size of 48 nm. These powders were suitable for the fabrication of dense BCZT ceramics with fine‐grain microstructures. The ceramics with the highest density of 95% theoretical density (TD) and grain size of 1.3 μm were prepared by uniaxial pressing followed by a two‐step sintering approach which contributed to the refinement of the BCTZ microstructure. A decrease in the grain size to 0.8–0.9 μm was achieved when samples were prepared using cold isostatic pressing. Using various sintering schedules, BCZT ceramics with broad range of grain sizes (0.8–60.5 μm) were prepared. The highest d₃₃ = 410.8 ± 13.2 pC/N was exhibited by ceramics prepared from sol–gel powder sintered at 1425°C, with the relative density of 89.6%TD and grain size of 36 μm.     

High‐pressure synthesis of a 12CaO·7Al2O3–12SrO·7Al2O3 solid solution

Solid solutions of 12CaO·7Al₂O₃ (C12A7) and 12SrO·7Al₂O₃ (S12A7) crystals were synthesized under high pressure. X‐ray diffraction patterns revealed that the lattice constants of the synthesized samples depend linearly on the compositional ratio of C12A7 and S12A7. Electron‐probe X‐ray microanalyses show that the chemical compositions of the crystals are represented by xC12A7·(1?x)S12A7 (0<x<1). These results indicate that the variation in the lattice constants is originated from a difference in the ionic radii of Ca²⁺ and Sr²⁺ ions. From impedance measurements, it was found that S12A7 has the highest conductivity (~1 × 10^?3 Scm^?1 at 550°C) among the solid solutions in the C12A7–S12A7 system.