碳纳米管、碳化钨在直接法合成过氧化氢中的应用

选用新型纳米材料——碳纳米管（CNTs）作为催化剂载体,用沉积沉淀法制备负载型钯-铂合金催化剂。同时选用过渡金属碳化物材料（碳化钨）为催化剂,其具有类似于Pt的表面电子结构,有望替代贵金属催化剂。探讨了Pd-Pt/CNTs及碳化钨在氢氧直接合成过氧化氢反应中的催化性能。     

Local structure of the MgxNixCoxCuxZnxO(x=0.2) entropy‐stabilized oxide: An EXAFS study

Entropy‐stabilized oxides (ESOs) provide an alternative route to novel materials discovery and synthesis. It is, however, a challenge to demonstrate that the constituent elements in an entropy‐stabilized crystal are homogeneously and randomly dispersed among a particular sublattice, resulting in a true solid solution with no evidence of local order or clustering. In this work, we present the application and analysis of extended X‐ray absorption fine structure (EXAFS) on the prototype ESO composition Mg_xNi_xCo_xCu_xZn_xO (x=0.2). In so doing, we can quantify the local atomic structure on an element‐by‐element basis. We conclude that local bond lengths between metal and oxygen vary around each absorbing cation, with notable distortion around the Cu–O polyhedra. By the second near neighbor (i.e., the cation‐cation pair), interatomic distances are uniform to the extent that the collected data can resolve. Crystal models that best fit the experimental scattering data include cations that are distributed randomly on an FCC sublattice with minimal positional disorder, with an interleaved FCC anion sublattice with oxygen ions displaced from the ideal locations to accommodate the distortions in the cation polyhedra. Density functional theory calculations of the ESO system yield a significant broadening in the positional distribution for the oxygen sublattice compared to that for the cation sublattice for all peaks, showing consistency with the conclusion from the experimental data that the distortion from an ideal rock salt structure occurs primarily through disorder in the oxygen sublattice.     

Flame synthesis of tungsten-doped titanium-dioxide nanoparticles using novel precursor combination of liquid titanium tetra-isopropoxide and solid tungsten mesh

Tungsten-doped titanium-dioxide (W-TiO₂) nanoparticles are successfully synthesized using a multiple-diffusion-flame burner with a separate center tube. Vaporized titanium tetra-isopropoxide (TTIP) precursor issues from a center tube to produce TiO₂ nanoparticles, while a tungsten mesh, suspended above the surrounding multiple over-ventilated hydrogen diffusion flames, serves as the solid-phase metal doping source. At a lower tungsten loading rate, W-TiO₂ nanoparticles are generated, as indicated by an obvious angle shift of 0.15° for the entire x-ray diffraction spectrum. However, at a higher tungsten loading rate, homogenous nucleation of WO_x occurs before or concurrently with TiO₂ nucleation, producing mixed nanopowders, permitting fewer tungsten ions to be doped into TiO₂. Ultraviolet–visible spectroscopic characterization reveals that the as-synthesized W-TiO₂ nanoparticles possess augmented absorbing ability in the visible-light wavelength range, where the band gap is reduced from 3.20 to 3.05 eV, compared with that for the nondoped TiO₂ nanoparticles.     

Synthesis of hexagonal phases of WN and W2.25N3 by high‐pressure metathesis reaction

Hexagonal tungsten nitrides were synthesized by the metathesis reaction between WCl₆ and NaN₃ under high pressure and temperature. As well as tungsten mononitride (WN), which is isostructural with hexagonal tungsten carbide (WC), a nitrogen‐rich hexagonal compound was also confirmed in the product. The ratio of nitrogen to tungsten was determined to be 1.34 by the quantitative combustion method. The composition was estimated to be W_2.25N₃ by considering the crystal structure that is best explained by the X‐ray diffraction profile. Volume compression measurements under hydrostatic pressure revealed that the WC‐type WN has a higher bulk modulus (K₀ = 342 ± 1 GPa) than that of hexagonal W_2.25N₃ (K₀ = 291 ± 2 GPa).     

Photoluminescence characterization and heat treatment effect on luminescence behavior of BaTa2O6:Dy3+ phosphor

Undoped and Dy³⁺‐doped barium tantalate phosphors were synthesized by the solid‐state reaction method at 1425°C. Also, 10 mol% Dy³⁺‐doped BaTa₂O₆ was sintered between 1150 and 1425°C in order to determine temperature effect on structural and luminescence properties. Afterwards, they were characterized by XRD, SEM‐EDS and photoluminescence (PL) analyses. PL spectra exhibited the excitation peaks between 300 and 440 nm. Two typical emissions were observed at 486.2 nm (blue) and 577.7 nm (yellow) due to the ⁴F_9/2→⁶H_15/2 and ⁴F_9/2→⁶H_13/2 transitions, respectively. Emission intensities increased with increasing doping concentration of Dy³⁺ up to 10 mol% and then decreased due to the concentration quenching effect. Moreover, depending on the increase in heat treatment temperature, the intensity of emission reached maximum at 1425°C. The calculated CIE chromaticity coordinates of phosphors located in the white light region.     

X‐ray absorption spectroscopy study of synthetic cobalt blue pigments similar to Kangxi blue and white porcelain

A series of cobalt blue pigments, which were synthesized based on the chemical compositions of the blue pigments in Kangxi blue and white porcelain, were investigated by Co, Mn, and Fe K‐edge and L_2,3‐edge X‐ray absorption spectroscopy to determine the oxidation states and species of the elements and to discern their impact on the blue color. The results reveal that Co is bivalent and mainly located at tetrahedral sites, which is the main parameter controlling the blue color. Mn is mainly present as Mn²⁺, or Co_xZn_1‐xAl₂O₄ and Fe is mainly present as Fe³⁺. In particular, Fe³⁺ substitutes the Al in CoAl₂O₄ and occupies octahedral sites with a high Mn content. All the synthetic cobalt blue pigments can form a solid solution with various end‐members or an intermediate solution spinel. The spectroscopic determination of the oxidation states and speciation of Co, Mn, and Fe furthers understanding of the coloration of blue pigments in blue and white porcelain.     

Synthesis,structural characterization,and photoluminescence properties of TTB‐type PbTa2O6:Eu3+ phosphor

Undoped and Eu³⁺‐doped tetragonal tungsten bronze (TTB) PbTa₂O₆ phosphors were synthesized by using solid‐state reaction method. Synthesized samples were characterized by XRD, SEM‐EDS, and photoluminescence analyses. XRD results revealed TTB‐type crystal structure with single phase up to 10 mol% Eu³⁺ doping concentration. In SEM‐EDS analyses, elemental composition of Pb decreased with the increasing concentration of Eu³⁺. Emissions at the excitation wavelength of 398.5 nm were observed at 593.2 and 618.8 nm due to ⁵D₀→⁷F₁ transitions and ⁵D₀→⁷F₂ transitions, respectively. Emission increased with the increasing Eu³⁺ doping concentration up to 10 mol% and not observed concentration quenching.     

Mechanochemical Synthesis of Lanthanum Oxyfluoride from Lanthanum Oxide and Lanthanum Fluoride

A powder mixture of lanthanum oxide (La₂O₃) and lanthanum fluoride (LaF₃) was ground by a planetary ball-mill to investigate the mechanochemical reaction forming lanthanum oxyfluoride (LaOF) at room temperature. The grinding enables us to form LaOF monophase, and the reaction proceeds with an increase in grinding time, whereas the crystallite size of LaOF formed is about 15–20 nm irrespective of the grinding time. Other rare-earth oxyfluorides (R–OF, R = Pr, Nd, Sm, Gd) can be synthesized by grinding the constituent components (R₂O₃ and RF₃).     

Formation of sodium bismuth titanate—barium titanate during solid‐state synthesis

Phase formation of sodium bismuth titanate (Na_0.5Bi_0.5TiO₃ or NBT) and its solid solution with barium titanate (BaTiO₃ or BT) during the calcination process is studied using in situ high‐temperature diffraction. The reactant powders were mixed and heated to 1000°C, while X‐ray diffraction patterns were recorded continuously. Phase evolutions from starting materials to final perovskite products are observed, and different transient phases are identified. The formation mechanism of NBT and NBT–xBT perovskite structures is discussed, and a reaction sequence is suggested based on the observations. The in situ study leads to a new processing approach, which is the use of nano‐TiO₂, and gives insights to the particle size effect for solid‐state synthesis products. It was found that the use of nano‐TiO₂ as reactant powder accelerates the synthesis process, decreases the formation of transient phases, and helps to obtain phase‐pure products using a lower thermal budget.     

反应介质对氢氧直接合成过氧化氢的影响研究

以超声浸渍法制备的PdO／γ-Al2O3-U为催化剂,考察不同无机酸、不同硫酸浓度对氢氧直接合成过氧化氢的影响。结果表明：酸性介质有利于氢氧直接合成过氧化氢,当反应介质为H2SO4溶液时,氢氧直接合成过氧化氢收率好于其他,其最佳浓度为0．35mol／L。     

氢氧直接合成过氧化氢贵金属催化剂的研究

采用浸渍法制备了一系列负载型钯催化剂，用于催化氢气和氧气直接合成过氧化氢的反应。分别考察了钯负载节、溶剂、载体预处理对反应的影响；结合XPS分析推断了催化剂活性组分价态。结果发现钯最佳负载量为1．88％（质量分数）；氢气在溶剂中的溶解度越大其反应转化率也越高，其中甲醇和丙酮都是良好的溶剂；载体经过卤化铵预处理可大幅度地提高催化剂的选择性；金属态钯为具有催化活性的价态。     

Insight into the Growth Reaction Mechanism of Ceramic Co3TeO6: Synchrotron Structural and Thermal Analysis

A two‐step solid‐state reaction is proposed to synthesize monophasic cobalt tellurate Co₃TeO₆ (CTO), a type II multiferroic, using Co₃O₄ and TeO₂ as the starting reagents. First step of the reaction results in the secondary monoclinic (P2₁/c) CoTeO₄ compound, which on further calcination (second step) leads to the primary monoclinic (C2/c) Co₃TeO₆ phase. High‐resolution synchrotron X‐ray diffraction and the subsequent Rietveld analysis are used to probe different phases present in the synthesized CTO and to achieve its single phase. X‐ray absorption near‐edge structure studies at Co K and Te L edges reveal mixed oxidation states (Co^2+/3+) of Co and hexavalent Te, respectively. Charge imbalance due to mixed valence Co ions has been attributed to cations vacancies. Enhanced multiferroic properties, such as effective magnetic moment, spin phonon coupling, etc., have been attributed to the aforementioned observations in grown ceramic CTO via proposed synthesis route.     

Rapid synthesis of nanocrystalline YAG via microwave‐assisted solvothermal process

A rapid synthesis procedure for the preparation of nanocrystalline yttrium aluminium garnet (nYAG) particles has been developed, for the first time, using the combination of subcritical conditions and microwave irradiation. It is believed that the use of butanediol delayed the onset of pressure rise due to its low partial pressure, while the microwaves facilitated a selective crystallization of nanocrystalline YAG particles in the solvent medium. This methodology was found to encourage rapid bulk nucleation with minimal particle growth or agglomeration of nYAG particles. The resultant powder characteristics, examined using XRD and TEM analyses, revealed that a narrow window of pressure and temperature conditions needed to be maintained to achieve spherical particles in the size range 60‐80 nm without any intermediate phases being formed. The STEM/EDX and FTIR results obtained suggested that the nucleated YAG particles were masked by carbon clouds until they were completely crystallized into single phase YAG particles; this allowed them to be dispersed in water with little agglomeration.     

Direct synthesis of hydrogen peroxide from hydrogen and oxygen over a Pd core-silica shell catalyst

Pd core–silica shell particles (Pd@SiO₂) were prepared by encapsulating Pd colloids with a silica shell through the Stöber method. The palladium core particles were well dispersed (Dispersion = 43%) and had uniform size (4 nm) and shape inside the porous silica shell. Pd@SiO₂ showed good catalytic activity (554 mmol H₂O₂/g Pd·h) for the direct synthesis of H₂O₂, which was better than those of impregnated Pd catalysts (Pd/SiO₂ and Pd/Al₂O₃). It is expected that the stabilization of less coordinated Pd crystals in a highly dispersed state by core-shell formation is effective for the improvement of H₂O₂ production.     

Oxygen permeation characteristics of sol‐gel derived barium‐substituted strontium ferrite membranes

The pervoskite‐type oxides have received attention due to their potential applications in catalysis, solid oxide fuel cells, gas sensors, and gas separable membranes. In view of their importance in oxygen separation from air, Ba_xSr_1?xFeO_3?δ (0≤x≤1.0) samples have been synthesized by sol‐gel process and investigated with regard to phase(s), oxygen permeation, and electrical conductivity. These compounds possess at room temperature, a perovskite‐type cubic, mixture of rhombohedral and hexagonal, and hexagonal phase(s) depending upon the composition 0≤x≤0.94, x=0.96‐0.98, and x=1.0, respectively. The barium incorporation causes initially enhancement but decrease in electrical conductivity above x=0.94. Above 800°C, all the compositions exhibit a stable cubic phase. The compacts made in the form of discs serve as stable oxygen permeable membranes displaying flux density () of ~2.45‐3.58 mL/cm².min at 1000°C. A good correlation has been demonstrated between the oxygen permeation and the electrical conductivity data. The maximum values of and conductivity correspond to Ba_xSr_1?xFeO_3?δ (x=0.94) with a perovskite‐type cubic structure. Hence, this membrane is quite suitable for oxygen separation technology.     

表面活性剂调节高矫顽力FePt纳米颗粒的合成

在表面活性剂聚乙烯吡咯烷酮(PVP)存在的体系中,通过NaBH4还原前驱体Fe(acac)3和H2PtCl6·6H2O,制备出了单分散的尺寸在3.0 nm左右的FePt纳米颗粒。XRD和TEM表征结果显示,表面活性剂PVP的用量影响FePt纳米颗粒相变,但对颗粒的尺寸无明显作用。由此推测,PVP对FePt纳米颗粒的相变起"催化"作用,适量的PVP诱导纳米颗粒的相变,可以通过改变表面活性剂的用量来调节FePt纳米颗粒的磁性能,当表面活性剂PVP单体与FePt前驱体的摩尔比(PVP/FePt)为7时,制得的FePt纳米颗粒经过500℃保温30 min热处理后,矫顽力高达5.2 kOe。     

Measurement of O and Ti atom displacements in TiO2 during flash sintering experiments

In‐situ flash experiments on rutile TiO₂ were performed at the synchrotron at the Brookhaven National Laboratory. Pair distribution function analysis of total X‐ray scattering measurements yielded mean‐square atomic displacements of oxygen and titanium atoms during the progression of the 3 stages of flash. The displacements are measured to be far greater for oxygen atoms than for titanium atoms. These large displacements may signal an “elastic softening” of the lattice, which, recently, has been predicted as a precursor to the onset of flash.     

Valence state and ionic conduction in Mn‐doped MgO partially stabilized zirconia

The mechanism of the enhancement in the ionic conductivity resulting from cubic phase stabilization in MgO partially stabilized zirconia (MgPSZ) by Mn doping was studied by examining the local Zr‐O structure. Cubic phase (14 vol%) in MgPSZ was increased with the addition of MnO₂, and 10 mol% Mn‐doped MgPSZ exhibited the highest cubic phase fraction (98.72%), which was analyzed by Rietveld refinement. In addition, only the cubic phase, not the monoclinic and tetragonal phases, was observed in the TEM‐SAED pattern of 10 mol% Mn‐doped MgPSZ. Doped Mn exhibited a high Mn²⁺/Mn⁴⁺ ratio, which was identified by X‐ray photoelectron spectroscopy (XPS). In addition, it indicates that oxygen vacancy formation by substitution of Mn²⁺ in the Zr⁴⁺ site in MgPSZ increased cubic phase fraction. Ionic conductivity of MgPSZ was improved by the cubic phase increase attributed to Mn doping, and 10 mol% Mn‐doped MgPSZ exhibited higher ionic conductivity than MgPSZ. To investigate the mechanism of the ionic conductivity improvement, Zr‐O local structure in Mn‐doped MgPSZ was analyzed by Zr K‐edge EXAFS of MgPSZ, and the number of bonding of the Zr‐O first shell decreased with increased Mn substitution. Therefore, it was considered that the oxygen vacancy generation led to an increase in the cubic phase and the number of ionic conduction sites.     

氢氧直接合成过氧化氢用催化剂的研究进展

过氧化氢（H₂O₂）是一种高效的绿色氧化剂,广泛应用于化学品合成、印染纺织、污水处理等领域。近年来,氢氧直接合成过氧化氢作为一种简单、环保、原子效率高的合成方法,成为一大研究热点。本文系统性地介绍了近年来氢氧直接合成过氧化氢催化剂的催化反应机理,负载金属的不同结构和性质对直接合成过氧化氢的催化性能与作用机理,重点讨论了与催化剂载体相关的载体结构、载体酸性、载体添加物、载体与金属相互作用等方面对反应活性和选择性的影响。最后对比了近年来直接合成过氧化氢用催化剂的催化性能,认为合成高选择性、高产率的催化剂仍是未来直接合成过氧化氢工业化应用的发展方向。     

直接合成过氧化氢Pd/TiO2催化剂的制备

常温和常压下,氢氧直接合成过氧化氢过程中,采用浸渍沉淀法制备Pd/TiO₂催化剂。考察了pH、搅拌时间t₁、静置时间t₂及焙烧温度等制备条件对催化剂活性的影响。正交实验结果表明,影响催化剂活性的顺序为：pH＞搅拌时间＞焙烧温度＞静置时间。在pH=8、t₁=0、t₂=0和（250～300）　℃焙烧3 h的条件下,制备的催化剂活性最好。