Total oxidation of volatile organic compounds on Au/Ce–Ti–O and Au/Ce–Ti–Zr–O mesoporous catalysts

Cerium–titanium mixed oxides and mesoporous cerium-modified titanium and cerium-modified titanium–zirconium mixed oxides were synthesized in order to obtain active support for gold volatile organic compound (VOC) oxidation catalysts. Ce–Ti mixed oxides were synthesized by sol–gel method. Mesoporous TiO₂ and Ti–Zr mixed oxides were prepared through the surfactant templating technique. Gold was loaded on supports by deposition-precipitation method. The catalysts were characterized by thermal analysis, XRD, N₂ analysis, TPR, DR/UV–vis and IR. The results evidenced the beneficial role of ceria modifying additive in decreasing the degree of crystallinity of mesoporous support and its particle size. A high degree of synergistic interaction between ceria and mesoporous oxide was observed. H₂-TPR revealed that the reducibility of the catalysts is greatly enhanced in the presence of gold. Considering the light off temperature, the activity of Au/mesoporous cerium-modified titanium oxide is particularly interesting for VOC oxidation comparatively to the same catalysts with a classical support. The gold particles would be more dispersed and stable. However, the sample Au/mesoporous cerium-modified titanium–zirconium mixed oxide is less interesting for VOC oxidation, particularly for toluene oxidation whose activity depends essentially on the adsorption of toluene molecule.     

介孔炭作为加氢脱硫催化剂载体材料的研究

以介孔硅SBA-15为模板,焦糖和呋喃醇为碳源,通过多种浇注法制备介孔炭材料.采用低温氮吸附、透射电镜和X射线小角衍射分析模板及介孔炭的织构.结果显示合成的介孔炭成功地复制了SBA-15的结构.以制备的介孔炭作载体担载钴钼合成了加氢脱硫催化剂,利用X射线能谱、透射电镜能量分布谱及一氧化氮化学吸附评估了催化剂的活性及活性点分布,结果表明介孔炭担载的催化剂活性高于活性炭担载的同类催化剂.     

Photocatalytic properties of the SBA-15 mesoporous silica molecular sieve modified with titanium

We describe three methods of post-synthesis modification of the SBA-15 mesoporous molecular sieve with titanium: impregnation with Ti(OEt)₄ in an ethanolic solution, grafting with titanocene dichloride, and modification with colloidal titania. The products were characterized using X-ray diffraction (XRD) and N₂ adsorption as well as Fourier-transform infrared and ²⁹Si NMR spectroscopies. All three methods yield materials containing 1.4--4.7 wt.% titanium and with high surface areas. The absorbance at 960 cm⁻¹ in SBA-15 modified with colloidal titania and SBA-15 grafted with titanocene indicates the formation of Ti–O bonds. All products showed significant activity towards the degradation of p-chlorophenol. UV-vis absorption spectra of SBA-15 samples modified with titanium indicate that the variation in the photocatalytic activity is governed by isolated titanium sites.     

Interaction of ZrFe<Subscript>2</Subscript> doped with Ti and Al with hydrogen

The influence of doping with Ti and Al on the structure and hydrogen sorption properties of ZrFe₂ was studied by XRD, XRSMA, and measurement of hydrogen absorption and desorption isotherms at pressure up to 300 MPa. The hydrogen capacity and equilibrium desorption pressures of hydrides decrease with increasing Al content at a constant ratio of Ti and Zr. The increase in the Ti content at a constant content of Al in alloys also leads to a decrease in hydrogen capacity; however, the equilibrium desorption pressures of hydrides increase considerably. Zr_1−x Ti _x (Fe_1−y Al _y )₂ (x= 0.2–0.8; y = 0.05–0.4) alloys were investigated.     

ZnO nanoparticles supported on mesoporous MCM-41 and SBA-15: a comparative physicochemical and photocatalytic study

A simple solvothermal impregnation method was used to prepare ZnO nanoparticles supported on MCM-41 and SBA-15. X-ray powder diffraction, N₂ adsorption–desorption, Electron Probe Micro Analysis (EPMA), and UV–vis spectroscopy were used to characterize the prepared materials. The influence of the ZnO loading of different supports on the structural characteristics and the photocatalytic activity toward degradation of methylene blue in water under ultraviolet irradiation were investigated. Wide angle X-ray diffraction and UV–vis Diffuse Reflectance confirmed the existence of ZnO phase. A much smaller influence of impregnation with ethanolic zinc salt solution on the porosity was observed for SBA-15 compared with MCM-41. Finally, the adsorption and photocatalytic activity of the ZnO/mesoporous materials depend on porous characteristics of the support materials.     

Texture evolution during hot-rolling and recrystallization in B2-type FeAl, NiAl and CoTi intermetallic compounds

The texture evolution during the hot-rolling and the recrystallization of B2-type Fe–48Al, Ni–50Al and Co–50Ti (expressed by at.%) intermetallic compounds were investigated. By hot-rolling at 973 K, Fe–48Al showed a microstructure with coarse grains elongated along rolling direction, while Ni–50Al and Co–50Ti showed a deformed microstructure featured by the heavily distorted (elongated) grains and/or the deformation bands. The hot-rolling texture of Fe–48Al was composed of {111}<uvw>, while those of Ni–50Al and Co–50Ti were composed of {111}<110> and {111}<112>, respectively. After annealing, the recrystallized grains were preferentially nucleated at the grain boundaries for Fe–48Al, and in the heavily distorted regions or the deformation bands for Ni–50Al and Co–50Ti. The orientations of the recrystallized grains were similar with those of the deformed matrix, especially for Ni–50Al and Co–50Ti. The recrystallization textures were generally more dispersive than the hot-rolling texture. Based on these results, the texture evolution during the hot rolling and the recrystallization of the B2-type intermetallic compounds were discussed.     

Solid acid catalysts for dehydration of glycerol to acrolein in gas phase

The reaction of glycerol dehydration to acrolein was performed at temperatures 220–300 °C over Keggin-type heteropolyacid (H₃PW₁₂O₄₀·xH₂O), supported on alumina and W-modified SBA-15 (Si/W = 20). The supports and catalysts were characterized by nitrogen adsorption, XRD, IR, UV–Vis DRS, SEM, and TPD of NH₃. The acid sites strength, determined according to data from TPD of ammonia, follows the order: HPW/W-SBA-15 > W-SBA-15 > H₃PW₁₂O₄₀ > HPW/γ-Al₂O₃ > γ-Al₂O₃. It was found that this order well correlates with the catalytic activity of studied samples. The most active and selective sample, HPW/W-SBA-15, showed acrolein selectivity of about 75% at almost 100% conversion of glycerol in all studied temperature interval.     

Y2O3/(Cu–Me) systems (Me=Al, Ti): interface reactions and wetting

Wetting behavior and interface interaction between Y₂O₃ and Cu–alloys were investigated at 1,423 K. Pure copper does not wet yttria substrate but the wettability is significantly improved by additions of Al and Ti. Different interface structures were observed in the Y₂O₃/(Cu–Al) and Y₂O₃/(Cu–Ti) systems. Relatively deep crater was detected at the interface in the first system, while Cu alloying by Ti led to formation of a flat interface with a thin reaction layer. The results of the wetting experiments and the interface features were well accounted of by thermodynamic analysis of the Y₂O₃/(Cu–Me) systems.     

Influence of ultrasonic melt treatment on the formation of primary intermetallics and related grain refinement in aluminum alloys

Ultrasonic melt treatment (UST) is known to induce grain refining in aluminum alloys. Previous studies have clearly shown that in Al–Zr–Ti alloys, the primary Al₃Zr intermetallics were dramatically refined by cavitation-assisted fragmentation, and a good refinement effect was achieved. In this article, Al–Ti, Al–Ti–Zr alloys, and some commercial aluminum alloys are used to analyze the effect of UST on primary intermetallics and grain refinement. The addition of a small amount of Al–3Ti–B master alloy is also studied in order to compare with the addition of Ti and Zr in commercial aluminum alloys. Experimental results show that the ultrasonic grain refining effect is not only related to the size of particles which are refined and/or dispersed by UST, but also related to an undercooling available for activation of these particles in the solidification process. Athermal heterogeneous nucleation theory is considered to explain the effect of size and distribution of substrate particles on the grain structure with different undercoolings. The distribution of primary particle sizes results in the distribution of required undercoolings. Grain refining occurs when the undercooling is large enough to activate the refined primary intermetallics or dispersed inoculants.     

Syntheses and proton conductivity of mesoporous Nd<Subscript>2</Subscript>O<Subscript>3</Subscript>–SiO<Subscript>2</Subscript> and NdOCl–SiO<Subscript>2</Subscript> composites

Two mesoporous oxide composites of Nd₂O₃–SiO₂ and NdOCl–SiO₂ were synthesized using SBA-15 as a template and neodymium nitrate or neodymium chloride as a precursor. The porous Nd₂O₃–SiO₂ with a SBA-15-like structure has amorphous walls and the porous NdOCl–SiO₂ with a replicated structure of SBA-15 has crystalline walls. These porous materials were characterized by X-ray diffraction, transmission electron microscopy and nitrogen adsorption/desorption. They exhibited significant proton conductivities in the presence of moisture at low temperatures and the highest conductivity observed was 4.55 × 10⁻⁴ S/cm at 47 °C in wet air (RH = 28.6%).     

Foaming behavior of Ti6Al4V particle-added aluminum powder compacts

The foaming behavior of 5 wt.% Ti6Al4V (Ti64) particle (30–200 μm)-added Al powder compacts was investigated in order to assess the particle-addition effects on the foaming behavior. Al compacts without particle addition were also prepared with the same method and foamed. The expansions of Ti64 particle-added compacts were measured to be relatively low at small particle sizes and increased with increasing particle size. At highest particle size range (160–200 μm), particle-added compacts showed expansion behavior similar to that of Al compacts without particle addition, but with lower expansion values. Expansions studies on 30–45 μm size Ti64-added compacts with varying weight percentages showed that the expansion behavior of the compacts became very similar to that of Al compact when the particle content was lower than 2 wt.%. However, Ti64 addition reduced the extent of drainage. Ti64 particles and TiAl₃ particles formed during foaming increased the apparent viscosity of the liquid foam and hence reduced the flow of liquid metal from cell walls to plateau borders. The reduced foamability in the compacts with the smaller size Ti64 addition was attributed to the relatively high viscosities, due to the higher cumulative surface area of the particles and higher rate of TiAl₃ formation between liquid Al and Ti64 particles.     

An investigation of the effect of Ti, Pd and Zr on the dehydriding kinetics of MgH2

The effect of additives Ti, Pd and Zr on the rate of hydrogen desorption from MgH₂ is investigated using high-pressure differential scanning calorimetry. Van’t Hoff analysis as well as X-ray powder diffraction measurements confirm that no new intermetallic phases are formed in these systems but enhanced dehydriding kinetics are obtained in the presence of Pd and Zr. For the Mg–Zr composite, Zr precipitates are formed throughout the material on heating to 500 °C but these do not grow with further thermal cycling. The desorption rate for all the composites was found to increase with temperature as well as pressure difference between experimental and equilibrium pressures. A value of 114 ± 4 kJ mol⁻¹ was obtained for the activation energy for dehydriding of the Mg–Ti–Pd composite.     

Comparisons of immersion and electrochemical properties of highly biocompatible Ti–15Zr–4Nb–4Ta alloy and other implantable metals for orthopedic implants

Abstract

Metal release from implantable metals and the properties of oxide films formed on alloy surfaces were analyzed, focusing on the highly biocompatible Ti–15Zr–4Nb–4Ta alloy. The thickness and electrical resistance (R_p) of the oxide film on such an alloy were compared with those of other implantable metals. The quantity of metal released during a 1-week immersion test was considerably smaller for the Ti–15Zr–4Nb–4Ta than the Ti–6Al–4V alloy. The potential (E₁₀) indicating a current density of 10 μA cm^?2 estimated from the anodic polarization curve was significantly higher for the Ti–15Zr–4Nb–4Ta than the Ti–6Al–4V alloy and other metals. Moreover, the oxide film (4–7 nm thickness) formed on the Ti–15Zr–4Nb–4Ta surface is electrochemically robust. The oxide film mainly consisted of TiO₂ with small amounts of ZrO₂, Nb₂O₅ and Ta₂O₅ that made the film electrochemically stable. The R_p of Ti–15Zr–4Nb–4Ta was higher than that of Ti–6Al–4V, i.e. 0.9 Ω cm² in 0.9% NaCl and 1.3 Ω cm² in Eagle's medium. This R_p was approximately five-fold higher than that of stainless steel, which has a history of more than 40 years of clinical use in the human body. Ti–15Zr–4Nb–4Ta is a potential implant material for long-term clinical use. Moreover, E₁₀ and R_p were found to be useful parameters for assessing biological safety.     

Role of Ti diffusion on the formation of phases in the Al<Subscript>2</Subscript>O<Subscript>3</Subscript>–Al<Subscript>2</Subscript>O<Subscript>3</Subscript> brazed interface

Diffusivities of Ti, Cu, Al and Ag in the interface of Al₂O₃–Al₂O₃ braze joints using Ag–Cu–Ti active filler alloy, have been calculated by Matano–Boltzman method. The Matano plane has been identified for each elemental diffusion at various brazing temperatures. The diffusivities of Ag, Cu and Al are almost insignificant on formation of interface during brazing, whereas the diffusivity of Ti changes significantly with the brazing temperature and controls the formation of different reaction product in the interface. Presence of TiO and Ti₃Cu₃O phases in the interface has been confirmed by transmission electron microscopy (TEM).     

Interface microstructure and shear strength in the diffusion brazing joint of TiC–Al<Subscript>2</Subscript>O<Subscript>3</Subscript> ceramic composite with W18Cr4V tool steel

The diffusion brazing of TiC–Al₂O₃ ceramic composite with W18Cr4V tool steel is realized by using Ti and Cu filler metals at 1500°K for 1 h under a pressure of 15 MPa in a vacuum of 10^–5 Pa. Thus, a brazed TiC–Al₂O₃/W18Cr4V joint was obtained with an interface shear strength of up to 105 MPa. The microstructural characteristics of the TiC–Al₂O₃/ W18Cr4V joint are studied by using a scanning electron microscope (SEM) with energy-dispersion spectroscopy (EDS) and X-ray diffractometer (XRD). The results indicated that the interface layer with a thickness of 90 μm was formed between TiC–Al₂O₃ and W18Cr4V steel. The Ti and Cu filler metals were completely fused and diffused to react with Al and C from the substrates, whereas Ti₃Al, Ti₃AlC₂, TiC, and CuTi₂ were produced in the TiC–Al₂O₃/W18Cr4V joint.     

Characterization and catalytic performance of Co/SBA-15 supported gold catalysts for CO oxidation

Cobalt-containing SBA-15 supported gold catalysts for low-temperature CO oxidation were prepared and characterized by N₂ adsorption/desorption, X-ray diffraction, transmission electron microscopy, inductively coupled plasma-atom emission spectroscopy and X-ray photoelectron spectroscopy techniques. The effects of cobalt and gold content on the catalyst activity were investigated in detail. Among them, 2% Au/40% Co/SBA-15 shows the highest activity, its complete conversion temperature for CO is at 273 K. It was believed that both the dispersion of Co₃O₄ and the high surface areas caused by SBA-15 contribute to the good activities of cobalt-containing SBA-15 supported gold catalysts. Furthermore, the strong metal-support interaction between gold and cobalt oxides is greatly related to the catalytic performance.     

Al2O3基石油加氢脱硫催化剂研究现状与进展

综述了以三氧化二铝(Al_2O_3)为载体,负载Mo、Ni单一组元和Mo-Ni-W等复合组元,用于炼制石油加氢脱硫的催化剂的国内外研究现状与进展。全面总结了传统的浸渍法、混捏法、共沉淀法、离子交换法以及新型的微波-超声波法等催化剂合成方法,对Al_2O_3基催化剂的加氢脱硫性能进行了讨论,着重对催化剂合成过程中载体、活性组分、助剂(P、F、B等)和pH值对催化剂性能的影响进行了概述,在此基础上总结了Al_2O_3基加氢脱硫催化剂的不足之处,并展望了此类催化剂的发展方向与研究前景。     

Effect of different catalyst supports on the (n,m) selective growth of single-walled carbon nanotube from Co–Mo catalyst

Co–Mo catalysts supported on four different high surface area oxides (SiO₂, Al₂O₃, MgO, and TiO₂) were evaluated to investigate the (n,m) selectivity control in single-walled carbon nanotube (SWCNT) synthesis. Results from Raman spectroscopy and thermogravimetric analysis showed that Co–Mo catalysts supported on SiO₂ and MgO possessed good selectivity toward SWCNTs, while photoluminescence and ultraviolet–visible–near-infrared spectroscopy results indicated that these two catalyst supports induced the same (n,m) selectivity to near-armchair tubes, such as (6,5) and (7,5) tubes. Catalysts supported on TiO₂ produced a mixture of multi-walled carbon nanotubes (MWCNTs) and SWCNTs, whereas catalysts supported on Al₂O₃ mainly grew MWCNTs. Characterization of catalysts by ultraviolet–visible diffuse reflectance spectroscopy suggested that the surface morphology of metal clusters over different supports was not directly responsible for the (n,m) selectivity. Analysis of monometallic (Co or Mo) and bimetallic (Co–Mo) catalysts using temperature program reduction demonstrated that catalyst supports changed the reducibility of metal species. The interaction between supports and Co/Mo metals perturbed the synergistic effect between Co and Mo, leading to the formation of different metal species that are responsible for the observed distinction in SWCNT synthesis.     

Microstructure and mechanical properties of Al–Si cast alloy with additions of Zr–V–Ti

The microstructure and tensile properties at temperatures up to 300 °C of an experimental Al–7Si–1Cu–0.5Mg (wt.%) cast alloy with additions of Ti, V and Zr were assessed and compared with those of the commercial A380 grade. The microstructure of both alloys consisted of Al dendrites surrounded by Al–Si eutectic containing, within its structure, the ternary Al–Al₂Cu–Si phase. Whereas the Al₁₅(FeCrMn)₃Si₂ phases were present in the A380 alloy, Ti/Zr/V together with Al and Si phases, Al(ZrTiV)Si, were identified in the experimental alloy. As a result of chemistry modification the experimental alloy achieved from 20% to 40% higher strength and from 1.5 to 5 times higher ductility than the A380 reference grade. The role of chemistry in improving the alloy thermal stability is discussed.     

Synthesis, characterization, and enhanced luminescence of CaWO4:Eu3+/SBA-15 composites

Considering the combination of lanthanide-doped CaWO₄ nanophosphor and mesoporous matrix may contribute to superior luminescent properties, CaWO₄:Eu³⁺/SBA-15 composites were successfully synthesized in a mild condition. The physicochemical properties of the resultant composites were carefully characterized by X-ray diffraction, high-resolution transmission electron microscopy, inductive coupled plasma optical emission spectroscopy (ICP), N₂ adsorption–desorption, Fourier transform infrared spectroscopy, and luminescence spectra. It’s found that the incorporation of CaWO₄:Eu³⁺ showed no obvious impact on the ordered mesostructure of the host matrix SBA-15, which, however, led to a decrease of BET surface area from 836 to 187 m² g⁻¹ for pure SBA-15 and CES (0.5), respectively. ICP results indicated that the real loaded amount of CaWO₄:Eu³⁺ in SBA-15 host was lower than the initial molar ratios (x) of CaWO₄:Eu³⁺ to SBA-15 for all samples. The maximum loaded level of CaWO₄:Eu³⁺ in SBA-15 is about 27.3 %. Moreover, the real Eu³⁺ dopant concentration increased with the initial molar ratios (x), which showed a maximum of about 6.51 % at x = 0.25. The resultant CaWO₄:Eu³⁺/SBA-15 composites exhibited enhanced-luminescent properties than that of pure CaWO₄:Eu³⁺ nanoparticles, which can be mainly attributed to the variation of Eu³⁺ dopant concentration and the host-protect effect through interaction between guest molecules and host matrix. The available large surface area, pore volume, and superior luminescent properties would facilitate future applications for the composites.