3,4-dichlorotoluene ammoxidation to 3,4-dichlorobenzonitrile over VPO/SiO<Subscript>2</Subscript> catalyst

Ammoxidation of 3,4-dichlorotoluene (DCT) to prepare 3,4-dichlorobenzonitrile (DCBN) over silica supported vanadium phosphorus oxide catalysts has been studied. On the VPO/SiO₂ catalyst, the influence of the reaction temperature, the molar ratio of air/DCT, the molar ratio of NH₃/DCT in the feed gas and the space velocity (v ₁) on the conversion, yield and selectivity was observed. The most appropriate reaction condition is: reactionT=673 K,n(DCT):n(NH₃):n(air)=1:7:30 andv ₁=250 h⁻¹. At this optimum reaction condition, the conversion of DCT is 97.8%; the molar yield of DCBN is 67.4%. It was found that the addition of element phosphorus can improve the yield of DCBN compared with VO/SiO₂ catalyst. Foundation item: Supported by Youth Chen-Guang Project of the Committee of Science and Technology of Wuhan (20015005042) Biography: Huang Chi(1972-), male, Ph D, Lecture, research direction: ammoxidation.     

疏水性固体酸H3PW12O40/HZSM-5催化合成丙烯酸正丁酯

制备了负载型疏水性固体酸催化剂H₃PW₁₂O₄₀/HZSM-5，并将该疏水性固体酸催化剂用于丙烯酸（简称AA）与正丁醇的酯化反应中。结果表明，硅铝摩尔比为60的HZSM-5负载质量分数为40％的H₃PW₁₂O₄₀，180℃干燥2h，H₃PW₁₂O₄₀/HZS-5催化剂的活性最高，丙烯酸转化率可达96.44％。H₃PW₁₂O₄₀/HZSM-5催化剂循环使用4次，丙烯酸的转化率仍保持在71.98%。采用XRD、FTIR以及原位红外对催化剂的结构和酸性进行了表征，测试结果均表明H₃PW₁₂O₄₀较好的分散于HZSM的表面，在催化剂表面存在Lewis酸和Brnosted酸，且其负载型疏水性固体酸H₃PW₁₂O₄₀/HZSM-5的酸量、催化活性和疏水性能均高于单组分H₃PW₁₂O₄₀。     

An ultra-sensitive non-enzymatic hydrogen peroxide sensor based on SiO2-APTES supported Au nanoparticles modified glassy carbon electrode

A novel electrochemical sensor based on (3-aminopropyl)triethoxysilane (APTES) functionalized SiO₂ supported Au nanoparticles and Nafion (Nf) as the protective membrane was fabricated for the electrochemical determination of H₂O₂ in contact lens-cleaning solution. The modification steps of glassy carbon working electrode (GCE) were evaluated by electrochemical impedance spectroscopy (EIS) and cyclic voltammetry (CV). The amperometric results showed that Nf/[email protected]₂-APTES/GCE sensor can be used to determine H₂O₂ in contact lens solutions with the linear ranges of 14–180 μM and 0.18–7.15 mM, excellent sensitivities of 2514.6 and 894.2 μA mM cm^?2, and a low limit of detection (LOD) of 4.25 μM depending upon signal-to-noise ratio of 3. Nf/[email protected]₂-APTES/GCE exhibited excellent repeatability with relative standard deviation (RDS) of 2.66% and acceptable reproducibility with RSD of 3.35%. The sensor displayed reasonable selectivity in the presence of uric acid, dopamine, ascorbic acid, glucose, mannose, glycine, fructose, histidine, and arginine with RSD less than 2.5%. The fabricated Nf/[email protected]₂-APTES/GCE sensor has been successfully applied to detect H₂O₂ in contact lens cleaning solutions.     

Catalytic oxidation of phenol in wastewater-A new application of the amorphous Fe78Si9B13 alloy

The amorphous Fe78Si9B13 alloy was used as a heterogeneous Fenton catalyst in the process of phenol degradation.The influences of main operating parameters such as reaction temperature,catalyst amount,hydrogen peroxide dosage and initial pH of solution on phenol degradation rate were investigated.The maximum mineralization of phenol was achieved at 60°C,6 g/L Fe78Si9B13, 0.31 mol/L hydrogen peroxide,with an initial pH of 2.5.More than 99%of phenol was completely removed under the optimum conditions within 10 min for a solution containing 1000 mg/L of phenol.Batch experiments for solutions containing phenol con- centrations ranging from 50 to 2000 mg/L were investigated under the above conditions and the same excellent degradation rate was obtained.The Fe78Si9B13 showed better catalytic activity than iron powder and Fe 2+ .Addition of n-butannol(hydroxyl radical scavenger)decreased the degradation rate of phenol,which demonstrates that hydroxyl radicals were mainly responsible for the removal of phenol.We demonstrated that phenol may be degraded by hydroxyl radicals decomposed by hydrogen peroxide on the surface of Fe78Si9B13 and illustrated the reaction mechanism for this process.This amorphous alloy exhibited high stability in recycling experiments and showed excellent reuse performance even after continuous operations of 8 cycles.     

Dissolution of Al<Subscript>2</Subscript>TiO<Subscript>5</Subscript> inclusions in CaO-SiO<Subscript>2</Subscript>-Al<Subscript>2</Subscript>O<Subscript>3</Subscript> slags at 1823 K

Al-Ti-O inclusions always clog submerged nozzles in Ti-bearing Al-killed steel. A typical synthesized Al₂TiO₅ inclusion was immersed in a CaO-SiO₂-Al₂O₃ molten slag for different durations at 1823 K. The Al₂TiO₅ dissolution paths and mechanism were revealed by scanning electron microscopy (SEM) and energy dispersive spectroscopy (EDS). Decreased amounts of Ti and Al and increased amounts of Si and Ca at the dissolution boundary prove that inclusion dissolution and slag penetration simultaneously occur. SiO₂ diffuses or penetrates the inclusion more quickly than CaO, as indicated by the w(CaO)/w(SiO₂) value in the reaction region. A liquid product (containing 0.7–1.2 w(CaO)/w(SiO₂), 15wt%–20wt% Al₂O₃, and 5wt%–15wt% TiO₂) forms on the inclusion surface when Al₂TiO₅ is dissolved in the slag. Al₂TiO₅ initially dissolves faster than the diffusion rate of the liquid product toward the bulk slag. With increasing reaction time, the boundary reaches its largest distance, the Al₂TiO₅ dissolution rate equals the liquid product diffusion rate, and the dissolution process remains stable until the inclusion is completely dissolved.     

Activity coefficients of NiO and CoO in CaO-Al2O3-SiO2 slag and their application to the recycling of Ni-Co-Fe-based end-of-life superalloys via remelting

To design optimal pyrometallurgical processes for nickel and cobalt recycling, and more particularly for the end-of-life process of Ni-Co-Fe-based end-of-life (EoL) superalloys, knowledge of their activity coefficients in slags is essential. In this study, the activity coefficients of NiO and CoO in CaO-Al₂O₃-SiO₂ slag, a candidate slag used for the EoL superalloy remelting process, were measured using gas/slag/metal equilibrium experiments. These activity coefficients were then used to consider the recycling efficiency of nickel and cobalt by remelting EoL superalloys using CaO-Al₂O₃-SiO₂ slag. The activity coefficients of NiO and CoO in CaO-Al₂O₃-SiO₂ slag both show a positive deviation from Raoult's law, with values that vary from 1 to 5 depending on the change in basicity. The activity coefficients of NiO and CoO peak in the slag with a composition near B=(%CaO)/(%SiO₂)=1, where B is the basicity. We observed that controlling the slag composition at approximately B=1 effectively reduces the cobalt and nickel oxidation losses and promotes the oxidation removal of iron during the remelting process of EoL superalloys.     

Effect of SiO<Subscript>2</Subscript> addition on the microstructure and electrical properties of ZnO-based varistors

The microstructure and electrical properties of ZnO-based varistors with the SiO₂ content in the range of 0–1.00mol% were prepared by a solid reaction route. The varistors were characterized by scanning electron microscopy, X-ray diffraction, energy-dispersive X-ray spectrometry, inductively coupled plasma-atomic emission spectrometry, and X-ray photoelectron spectroscopy. The results indicate that the average grain size of ZnO decreases with the SiO₂ content increasing. A new second phase (Zn₂SiO₄) and a glass phase (Bi₂SiO₅) are found. Element Si mainly exists in the grain boundary and plays an important role in controlling the Bi₂O₃ vaporization. The electric measurement shows that the incorporation of SiO₂ can significantly improve the nonlinear properties of ZnO-based varistors, and the nonlinear coefficients of the varistors with SiO₂ are in the range of 36.8–69.5. The varistor voltage reaches the maximum value of 463 V/mm and the leakage current reaches the minimum value of 0.11 μA at the SiO₂ content of 0.75mol%.     

Preparation and luminescence characteristics of Sr3SiO5：Eu^2＋ phosphor for white LED

The Sr3SiO5：Eu^2＋ phosphor was synthesized by high temperature solid-state reaction. The emission spectrum of Sr3SiO5：Eu^2＋ shows two bands centered at 487 and 575 nm, which well agree with the theoretic values of emission spectrum. The excitation spectrum for 575 nm emission center has several excitation bands at 365, 418, 458 and 473 nm. And the results show that the emission spectrum of Sr3SiO5：Eu^2＋ is influenced by the Eu^2＋ concentration. The relative emission spectra of the white-emitting InGaN-based YAG：Ce^3＋ LED and Sr3SiO5：Eu^2＋ LED were investigated. The results show that the color development of InGaN-based Sr3SiO5：Eu^2＋ is better than that of InGaN-based YAG：Ce^3＋, and the CIE chromaticity of InGaN-based Sr3SiO5：Eu^2＋ is （x=0.348, y=0.326）.     

Preparation of BST nanocrystals embedded in SiO<Subscript>2</Subscript> film by magnetron sputtering for nonvolatile memory applications

We develop a method that uses magnetron sputtering to fabricate barium strontium titanate (BST) nanocrystals embedded in dielectric SiO2 films.Transmission electron microscope images show that the BST nanocrystals have an average diameter of 5 nm and are well distributed in the SiO2 film.In addition,we also analyze the BST nanocrystals composition deviation during the sputtering process by electron dispersive spectroscopy.     

以空心SiO2为载体的蛋壳型贵金属Pd催化剂的制备及表征

以空心SiO₂为载体采用浸渍法制备了一系列蛋壳型贵金属Pd催化剂和Ca-Pd 催化剂，应用TEM，XRD和EDS方法表征催化剂。结果表明，贵金属Pd不仅能够负载到空心SiO₂载体上，分散也比较均匀，且粒径较小，Pd/SiO₂催化剂上Pd的粒径约为7 nm，Ca-Pd/SiO₂催化剂上Pd的粒径约为5 nm。在蛋壳型催化剂Pd/SiO₂ 中加入助催化剂Ca能够形成蛋壳型Ca-Pd复合催化剂。空心SiO₂可以作为蛋壳型贵金属Pd催化剂载体。催化活性评价结果表明，蛋壳型复合催化剂Ca-Pd/SiO₂的催化活性和甲醇的选择性较纯Pd催化剂有了较大幅度的提高，其中催化活性提高了7倍。     

Microwave absorption properties of SiC@SiO2@Fe3O4 hybrids in the 2-18 GHz range

To enhance the microwave absorption performance of silicon carbide nanowires (SiCNWs), SiO₂ nanoshells with a thickness of approximately 2 nm and Fe₃O₄ nanoparticles were grown on the surface of SiCNWs to form SiC@SiO₂@Fe₃O₄ hybrids. The microwave absorption performance of the SiC@SiO₂@Fe₃O₄ hybrids with different thicknesses was investigated in the frequency range from 2 to 18 GHz using a free-space antenna-based system. The results indicate that SiC@SiO₂@Fe₃O₄ hybrids exhibit improved microwave absorption. In particular, in the case of an SiC@SiO₂ to iron(Ⅲ) acetylacetonate mass ratio of 1:3, the microwave absorption with an absorber of 2-mm thickness exhibited a minimum reflection loss of -39.58 dB at 12.24 GHz. With respect to the enhanced microwave absorption mechanism, the Fe₃O₄ nanoparticles coated on SiC@SiO₂ nanowires are proposed to balance the permeability and permittivity of the materials, contributing to the microwave attenuation.     

Shear-thinning behavior of the CaO-SiO2-CaF2-Si3N4 system mold flux and its practical application

Satisfying the mold-flux performance requirements for high-speed continuous casting necessitates the development of a new non-Newtonian-fluid mold flux with shear-thinning behavior, i.e., a mold flux whose viscosity is relatively high under lower shear rates and relatively low under higher shear rates. In this work, a mold flux that exhibits shear-thinning behavior was developed by adding different amounts of Si₃N₄ to the CaO-SiO₂-CaF₂ mold flux. The shear-thinning behavior was investigated using a rotational viscometer. In addition, the microstructure of the newly prepared slags was studied by high-temperature Raman spectroscopy and X-ray photoelectron spectroscopy. The results showed that the mechanism of shear-thinning was attributable to a temporary viscosity loss caused by the one-way shear stress, whereas the corresponding magnitude of shear-thinning was closely related to the degree of polymerization (DP). Finally, the non-Newtonian fluid mold flux was used for laboratory casting tests, which revealed that the mold flux could reduce slag entrapment and positively affect the continuous casting optimization.     

Electrochemical properties of LiNi<Subscript>0.5</Subscript>Mn<Subscript>1.3</Subscript>Ti<Subscript>0.2</Subscript>O<Subscript>4</Subscript>/Li<Subscript>4</Subscript>Ti<Subscript>5</Subscript>O<Subscript>12</Subscript> cells

Spinel compounds LiNi_0.5Mn_1.3Ti_0.2O₄ (LNMTO) and Li₄Ti₅O₁₂ (LTO) were synthesized by different methods. The particle sizes of LNMTO and LTO are 0.5–2 and 0.5–0.8 μm, respectively. The LNMTO/LTO cell exhibits better electrochemical properties at both a low current rate of 0.2C and a high current rate of 1C. When the specific capacity was determined based on the mass of the LNMTO cathode, the LNMTO/LTO cell delivered 137 mA·h·g⁻¹ at 0.2C and 118.2 mA·h·g⁻¹ at 1C, and the corresponding capacity retentions after 30 cycles are 88.5% and 92.4%, respectively.     

铬取代磷钒杂多酸催化合成苹果酯

以乙酰乙酸乙酯和乙二醇为原料,环己烷为带水剂,用自制的Bi-capped Keggin型铬钒磷杂多酸为催化剂,合成了苹果酯.探讨了催化剂用量、原料配比、带水剂用量和反应时间对产品收率的影响,并用多种手段对产品做了检测分析.得到合成该酯的最佳工艺条件为:n(乙酰乙酸乙酯)/n(乙二醇)=1∶2,催化剂用量为反应物料总质量的1.0%,环己烷做带水剂,在反应温度80～104　℃回流反应60　min,酯收率可达98.54%.在此条件下,酯收率可达98.54%.     

Corrosion-wear behavior of nanocrystalline Fe88Si12 alloy in acid and alkaline solutions

The corrosion-wear behavior of a nanocrystalline Fe₈₈Si₁₂ alloy disc coupled with a Si₃N₄ ball was investigated in acid (pH 3) and alkaline (pH 9) aqueous solutions. The dry wear was also measured for reference. The average friction coefficient of Fe₈₈Si₁₂ alloy in the pH 9 solution was approximately 0.2, which was lower than those observed for Fe₈₈Si₁₂ alloy in the pH 3 solution and in the case of dry wear. The fluctuation of the friction coefficient of samples subjected to the pH 9 solution also showed similar characteristics. The wear rate in the pH 9 solution slightly increased with increasing applied load. The wear rate was approximately one order of magnitude less than that in the pH 3 solution and was far lower than that in the case of dry wear, especially at high applied load. The wear traces of Fe₈₈Si₁₂ alloy under different wear conditions were examined and analyzed by scanning electron microscopy, energy-dispersive X-ray spectroscopy, and X-ray photoelectron spectroscopy. The results indicated that the tribo-chemical reactions that involve oxidation of the worn surface and hydrolysis of the Si₃N₄ ball in the acid solution were restricted in the pH 9 aqueous solution. Thus, water lubrication can effectively improve the wear resistance of nanocrystalline Fe₈₈Si₁₂ alloy in the pH 9 aqueous solution.     

In situ time-resolved FTIR investigation on the reaction mechanism of partial oxidation of methane to syngas over supported Rh and Ru catalysts

In situ time-resolved FTIR spectroscopy was used to study the reaction mechanism of partial oxidation of methane (POM) to synthesis gas and the reaction of CH₄/O₂/He (2/1/45, molar ratio) gas mixture with adsorbed CO species over Rh/SiO₂, Ru/γ-Al₂O₃ and Ru/SiO₂ catalysts at 500—600℃. It was found that CO is the primary product of POM reaction over reduced and working state Rh/SiO₂ catalysts. Direct oxidation of CH₄ is the main pathway of synthesis gas formation over Rh/SiO₂ catalyst. CO₂ is the primary product of POM over Ru/γ-Al₂O₃ and Ru/SiO₂ catalysts. The dominant reaction pathway for synthesis gas formation over Ru/γ-Al₂O₃ catalyst is via the reforming reactions of CH₄ with CO₂ and H₂O. For the POM reaction over Rh/SiO₂ and Ru/γ-Al₂O₃ catalysts, consecutive oxidation of surface CO species is an important pathway of CO₂ formation.     

Mineral-phase evolution and sintering behavior of MO-SiO2-Al2O3-B2O3 (M=Ca,Ba) glass-ceramics by low-temperature liquid-phase sintering

In this work, network former SiO₂ and network intermediate Al₂O₃ were introduced into typical low-melting binary compositions CaO·B₂O₃, CaO·2B₂O₃, and BaO·B₂O₃ via an aqueous solid-state suspension milling route. Accordingly, multiple-phase aluminosilicate glass-ceramics were directly obtained via liquid-phase sintering at temperatures below 950℃. On the basis of liquid-phase sintering theory, mineral-phase evolutions and glass-phase formations were systematically investigated in a wide MO-SiO₂-Al₂O₃-B₂O₃ (M=Ca, Ba) composition range. The results indicate that major mineral phases of the aluminosilicate glass-ceramics are Al₂₀B₄O₃₆, CaAl₂Si₂O₈, and BaAl₂Si₂O₈ and that the glass-ceramic materials are characterized by dense microstructures and excellent dielectric properties.     

活性炭负载磷钨杂多酸催化合成丁酮乙二醇缩酮

研究了负载型催化剂H3PW12O40／C催化合成丁酮乙二醇缩酮的催化行为．结果表明，该催化剂在丁酮和乙二醇的缩合反应中表现出较高的催化活性，经纯化后，丁酮乙二醇缩酮的最终收率可达67．3％，优于纯H3PW12O4。作催化剂时的收率．     

Preparation of In<Subscript>2</Subscript>S<Subscript>3</Subscript> and Cu-Doped In<Subscript>2</Subscript>S<Subscript>3</Subscript> 2D Ultrathin Nanoflakes with Tunable Absorption and Intense Photocurrent Response

We reported an effective method to synthesize In₂S₃ and Cu-doped In₂S₃ two-dimensional ultrathin nanoflakes by the hydrothermal method through tuning the Cu/In molar ratio. The transmission electron microscope images showed that the products had ultrathin flake-like shape with wrinkling and rolling. The X-ray diffraction patterns indicated the crystal phase of nanoflakes was varied from β-In₂S₃ to tetragonal-CuInS₂ as the Cu/In molar ratio was increased. The In₂S₃ nanoflakes exhibited absorption band at 450 nm, while new absorption peaks in turn appeared at 550 nm and 670 nm as the Cu/In molar ratio was increased. In addition, the two-dimensional ultrathin nanoflakes exhibited intense photocurrent response.     

Phase transformation and crystal growth behavior of 8mol% (SmO<Subscript>1.5</Subscript>, GdO<Subscript>1.5</Subscript>, and YO<Subscript>1.5</Subscript>) stabilized ZrO<Subscript>2</Subscript> powders

Nanocrystalline powders of ZrO₂-8mol%SmO_1.5(8SmSZ), ZrO₂-8mol%GdO_1.5 (8GdSZ), and ZrO₂-8mol%YO_1.5(8YSZ) were prepared by a simple reverse-coprecipitation technique. Differential thermal analysis/thermogravimetry (DTA/TG), Fourier transform infrared spectroscopy (FTIR), X-ray diffraction (XRD), Raman spectroscopy, and high-resolution transmission electron microscopy (HRTEM) were used to study the phase transformation and crystal growth behavior. The DTA results showed that the ZrO₂ freeze-dried precipitates crystallized at 529, 465, and 467℃ in the case of 8SmSZ, 8GdSZ, and 8YSZ, respectively. The XRD and Raman results confirmed the presence of tetragonal ZrO₂ when the dried precipitates were calcined in the temperature range from 600 to 1000℃ for 2 h. The crystallite size increased with increasing calcination temperature. The activation energies were calculated as 12.39, 12.45, and 16.59 kJ/mol for 8SmSZ, 8GdSZ, and 8YSZ respectively.