CO_2 methanation over TiO_2–Al_2O_3 binary oxides supported Ru catalysts

TiO_2 modified Al_2O_3 binary oxide was prepared by a wet-impregnation method and used as the support for ruthenium catalyst. The catalytic performance of Ru/TiO_2–Al_2O_3catalyst in CO_2 methanation reaction was investigated. Compared with Ru/Al_2O_3 catalyst, the Ru/TiO_2–Al_2O_3catalytic system exhibited a much higher activity in CO_2 methanation reaction. The reaction rate over Ru/TiO_2–Al_2O_3 was 0.59 mol CO_2·(g Ru)1·h-1, 3.1 times higher than that on Ru/Al_2O_3[0.19 mol CO_2·(gRu)-1·h-1]. The effect of TiO_2 content and TiO_2–Al_2O_3calcination temperature on catalytic performance was addressed. The corresponding structures of each catalyst were characterized by means of H_2-TPR, XRD, and TEM. Results indicated that the averaged particle size of the Ru on TiO_2–Al_2O_3support is 2.8 nm, smaller than that on Al_2O_3 support of 4.3 nm. Therefore, we conclude that the improved activity over Ru/TiO_2–Al_2O_3catalyst is originated from the smaller particle size of ruthenium resulting from a strong interaction between Ru and the rutile-TiO_2 support, which hindered the aggregation of Ru nanoparticles.

Al_2O_3包覆LiCoO_2对4.35V锂离子电池性能的影响

用固相法对钴酸锂(LiCoO2)正极材料进行纳米三氧化二铝(Al2O3)表面包覆,在充电终止电压为4.35 V时分析制备的495060AR型锂离子电池的性能。在放电截止电压为3.00 V时,以0.5 C放电,包覆、未包覆LiCoO2的比容量分别为167.6 mAh/g、170.9 mAh/g,平均电压分别为3.763 V、3.776 V;常温下1.0 C循环200次,包覆、未包覆LiCoO2的容量保持率分别为94.46%、96.40%。在55℃、48 h储存测试中,包覆LiCoO2制备的电池表现出更好的环境适应性;包覆LiCoO2制备的电池在高温45℃下以0.5 C循环200次,容量保持率为93.50%。对电池进行过充、热冲击测试,均未起火、爆炸。

Enhanced CO oxidation over potassium-promoted Pt/Al_2O_3 catalysts:Kinetic and infrared spectroscopic study

A series of K-promoted Pt/Al2O3 catalysts were tested for CO oxidation. It was found that the addition of K significantly enhanced the activity. A detailed kinetic study showed that the activation energies of the K-containing catalysts were lower than those of the K-free ones, particularly for catalysts with high Pt contents （51.6 k）/mol for 0.42K-2.0Pt/Al2O3 and 6：3.6 kJ/mol for 2.0Pt/Al2O3 ）. The CO reaction orders were higher for the K-containing catalysts （about -0.2） than for the K-free ones （about -0.5）, with the former having much lower equilibrium constants for CO adsorption than the latter. In situ Fourier-transform infrared spectroscopy showed that surface CO desorption from the 0.42K-2.0Pt/Al2O3 catalyst was easier than from 2.0Pt/Al2O3. The promoting effect of K was therefore caused by weakening of the interactions between CO and surface Pt atoms. This decreased coverage of the catalyst with CO and facilitated competitive O2 chemisorption on the Pt surface, and significantly lowered the reaction barrier between chemisorbed CO and O2 species.

Fabrication of Pd-based metal-acid-alkali multifunctional catalysts for one-pot synthesis of MIBK

The one-pot synthesis of methyl isobutyl ketone（MIBK） from acetone using multifunctional catalysts is an important sustainable organic synthesis method with high atom and energy efficiency.Herein. we report a series of Pd supported on mixed metal oxide（MMO） catalysts with controllable acidic/basic/metallic sites on the surface. We study the relationship between the nature, synergy,and proximity of active sites and the catalytic performance of the multifunctional catalyst in the tandem reaction, in detail. In the existence of Lewis acid and base sites, the catalysts with medium-strength acidic/basic sites show preferred activity and/or MIBK selectivity. For multifunctional catalysts, the catalytic properties are more than just a collection of active sites, and the Pd/Mg_3Al-MMO catalyst possessing 0.1% Pd loading and ~0.4 acid/base molar ratio exhibits the optimal 42.1% acetone conversion and 37.2% MIBK yield, which is among the best reported so far for this tandem reaction under similar conditions. Moreover, the proximity test indicates that the intimate distance between acidic/basic/metallic sites can greatly shorten the diffusion time of the intermediate species from each active site, leading to an enhancement in the catalytic performance.

Oxidative coupling of alcohols and amines to an imine over Mg-Al acid-base bifunctional oxide catalysts

A series of Mg‐Al mixed oxide catalysts are prepared and introduced as efficient irreducible catalysts for the oxidative coupling of alcohols and amines to imine.The structure and surface properties of Mg‐Al oxides are modulated by changing the Mg/Al ratios,calcination temperature and treatment with probe molecules.Detailed characterization,including X‐ray diffraction,27Al magic angle spinning nuclear magnetic resonance spectroscopy,N2‐adsorption,NH3‐temperature‐programmed desorption,CO2‐temperature‐programmed desorption and X‐ray photoelectron spectroscopy are carried out to determine the physicochemical properties of these catalysts.The Mg‐Al oxides with Mg/Al=3exhibit the highest activity in the reaction,which possess a large number of surface weak basic sites and a relatively small number of weak acidic sites.The role of the acidic and basic sites in the reaction process is systematically investigated,and are shown to serve as adsorption and activation sites for amines and alcohols,respectively.Under the synergistic effect of these acid‐base centers,the oxidative coupling process successfully occurs on the surface of Mg‐Al mixed oxides.Compared with the acidic sites,the weak basic sites play a more important role in the catalytic process.The acidic sites are the catalytic centers for the benzyl alcohol activation,which control the reaction rate of the oxidative coupling reaction.

Effect of Current Density on Al Alloy Microplasma Oxidation

The microplasma oxidation process of LY 12 Al alloy in Na2SiO3-KOH-NaAL2 system has been studied. The voltage-time curve of oxidation process is changed with the variation of current densities. The voltage breakdown and hardness of coating increase with increasing current density. The phase composition, morphologies, element and the distribution of ceramic coating are investigated by XRD, EPMA.

Synthesis and Characterization of Worm-shaped Tubular Lanthanum Aluminum Composite Mesoporous Materials

The lanthanum aluminum mesoporous materials were synthesized using sodium dodecyl sulfate as a template agent by ultrasonic hydrothermal method.The resulting samples were characterized by low angle X-ray diffraction（XRD）,N2 adsorption-desorption studies,transmission electron microscopy（TEM）and surface morphology analysis（SEM）,surface acid（NH3-TPD）,reducibility properties（TPR）,X-ray energy dispersive spectrometer（EDS）and thermogravimetric analysis（TG/DTG）.A l/La composite mesoporous material were synthesized with n（Al）︰n（La）=70︰1.0,80°C of reaction temperature,20 h of reaction time,12 h of crystallization time,650°C of calcination temperature.The specific surface area of the sample is 273.90 m 2 ·g ？1 ,with the average diameter 5.642 nm and pore volume 0.2354 cm 3 ·g ？1 .The samples have mesoporous structure and its particles are similar to a worm-shaped tubular structure.The influence of calcination temperature on the surface physical and chemical properties of Al/La composited mesoporous materials was examined,and the results showed that the acid strength was increased but the amount of acidic sites is decreased as the calcination temperature increased.It was found that the sample calcined at 650°C had appropriate acid content,acid strength and better reducibility.

Microstructure and abrasive wear behaviour of anodizing composite films containing Si C nanoparticles on Ti6Al4V alloy

Anodized composite films containing Si C nanoparticles were synthesized on Ti6Al4 V alloy by anodic oxidation procedure in C4O6H4Na2 electrolyte. Scanning electron microscopy(SEM), energy dispersive spectroscopy(EDS) and X-ray photoelectron spectroscopy(XPS) were employed to characterize the morphology and composition of the films fabricated in the electrolytes with and without addition of Si C nanoparticles. Results show that Si C particles can be successfully incorporated into the oxide film during the anodizing process and preferentially concentrate within internal cavities and micro-cracks. The ball-on-disk sliding tests indicate that Si C-containing oxide films register much lower wear rate than the oxide films without Si C under dry sliding condition. Si C particles are likely to melt and then are oxidized by frictional heat during sliding tests. Potentiodynamic polarization behavior reveals that the anodized alloy with Si C nanoparticles results in a reduction in passive current density to about 1.54×10-8 A/cm2, which is more than two times lower than that of the Ti O2 film(3.73×10-8 A/cm2). The synthesized composite film has good anti-wear and anti-corrosion properties and the growth mechanism of nanocomposite film is also discussed.

Oxidation Behaviour of Sputtered Ni-3Cr-20Al Alloy

The oxidation behavior of sputtered Ni-3Cr-20Al coating at 900℃ in air was investigated. A dense Al2O3 layer was formed on the sputtered Ni-3Cr-20AI coating after 200 h oxidation. However, owing to the segregation of Ni3Al during oxidation process at high temperature, the spinel NiAI2O4 was also formed in the Al2O3 layer. It was found that the formation of NiAI204 had no detrimental effect on the oxidation resistance of the sputtered N?3O-20AI coating due to the excellent adhesion shown by the Al2O3 and NiAl2O4complex oxide scale.

Influence of surface etching pretreatment on PEO process of eutectic Al–Si alloy

To solve the problems generally encountered during the plasma electrolytic oxidation(PEO) of Al alloys with high Si content, a pretreatment of chemical etching was applied before the process. The influence of such pretreatment was studied by SEM, EDS and XRD. The pretreatment presents a significant effect on positive voltage at the beginning stage of PEO, leading to higher voltage over the whole process. The difference between the positive voltages of non-etched and etched specimens decreases gradually with the increase of processing time. The pretreatment exhibits much less influence on the negative voltage. For the sample with surface pretreatment, the average growth rate of PEO coating is increased from 0.50 to 0.84 μm·min-1and the energy consumption is decreased from 6.30 to 4.36 k W·h·μm-1·m-2. At the same time, both mullite and amorphous Si O2 contents are decreased in the coating.

Preparation of Hydroxyapatite-titanium Dioxide Coating on Ti6Al4V Substrates using Hydrothermal-electrochemical Method

Ti6Al4V substrates were anodized in a 0.5 mol/L H_2SO_4 solution at applied voltages of 90-140 V.A hydroxyapatite-titanium oxide（HA-TiO2）coating was then deposited on the anodized Ti6Al4 V substrates via a hydrothermal-electrochemicalmethod at a constant current.The obtained films and coatings were characterized by X-ray diffraction,scanning electron microscopy,energy-dispersive X-ray spectroscopy,and Fourier-transform infrared spectrometry.The microstructures of the porous films on the Ti6Al4 V substrates were studied to investigate the effect of the anodizing voltage on the phase and morphology of the HATiO_2 coating.The results indicated that both the phase composition and the morphology of the coatings were significantly influenced by changes in the anodizing voltage.HA-TiO_2 was directly precipitated onto the surface of the substrate when the applied voltage was between 110 and 140 V.The coatings had a gradient structure and the HA exhibited both needle-like and cotton-like structures.The amount of cotton-like HA structures decreased with an increase in voltage from 90 to 120 V,and then increased slightly when the voltage was higher than 120 V.The orientation index of the（002）plane of the coating was at a minimum when the Ti6Al4 V substrate was pretreated at 120 V.

NITRIC OXIDE DECOMPOSITION ON ALKALI-PROMOTED Pd/AL_2o_3 CATALYSTS

Alkali-promoted Pd/Al2O3 catalysts exhibit much higher activities in NO decomposition than Pd/Al2O3. FTIR study shows that on the alkali promoted catalyst.nitric oxide exists on the surface mainly in negatively charged form(NO-)at high temperatures.which is consistent with the activity improvement.

Memory Behaviors Based on ITO/Graphene Oxide/Al Structure

We investigate the memory properties of the ITO/graphene oxide/Al diodes. It is found that the devices show different memory behaviors with the diverse geometry and thickness of Al. When the thickness of the Al electrode is relatively thick, the device of the cross-point Al electrode shows a three-level memory effect, and the counterpart device of the cross-bar Al electrode exhibits a volatile static random access memory effect. When the thickness of the AI electrode is thinner, the above devices demonstrate a flash memory effect. The different memory behaviors of ITO/GO/AI diodes are ascribed to the mode and degree of reduction and oxidation of GO.

EFFECTS OF NEODYMIUM ON OXIDATION BEHAVIOUR OF Ti-11Al ALLOY

The oxidation behaviours of pure 77,Ti-11 at% Al and Ti-11 at% Al-Nd alloys in air at the tempera- ture range 800～1000℃ have been investigated in the present paper.Their oxidation kinetics follows substantially the parabolic rate law.The activation energies of oxidation processes are 103 and 91 kcal/mole for Ti-11 Al and Ti-11 Al-Nd alloys,respectively.The platinum wire tagging tests have shown that oxygen atoms diffuse into the substrate during oxidation of pure Ti and that Ti,Al and Nd atoms diffuse across a scale of oxides outwards during oxidations of these alloys.Nd addition promotes the selective oxidation of aluminium.The addition of Al and Nd decreases the extent of penetration of oxygen atoms into the Ti substrate.The X-ray diffraction analysis confirms that the oxide scales of the alloys consist of TiO_2 and α-Al_2O_3,or TiO_2,α-Al_2O_3 and a small amount of Nd_2O_3 for Ti-11 Al and Ti-11 Al-Nd alloys, respectively.

Formation of Ultrafine Metal Particles and Metal Oxide Precursor on Anodized Al by Electrolysis Deposition

Nickel was deposited by ac electrolysis deposition in the pores of the porous oxide film of Al produced by anodizing in phosphoric acid. Ultrafine rod-shaped Ni particles were formed in the pores. At the same time a film of Ni oxide precursor was developed on the surface of the porous oxide film. The Ni particles and the Ni oxide precursor were examined by SEM, TEM and X-ray diffraction. The thickness of the barrier layer of the porous oxide film was thin and it attributed to the formation of the metal particles, while the formation of the oxide precursor was associated with the surface pits which were developed in the pretreatment of Al.

Preparation of SiC_p/Al_2O_3-Al Composites by Directed Metal Oxidation

SiCp/Al2O3-Al composites were synthesized by means of direct metal oxidation method. The composition and microstructures of the composites were investigated using X-ray diffraction （XRD）, scanning electron microscopy （SEM） and metallurgical microscope. The effects of technical parameters on the properties of the product were analyzed. The results indicate that the composite possesses a dense microstructure, composed of three interpenetrated phases. Of them, SiO2 layer prohibits the powdering of the composites; Mg promotes the wetting and infiltration of the system and Si restricts the interfacial reaction while improving the wetting ability between reinforcement and matrix.

Structure and properties of brazed joints on dispersion-strengthened copper

Development of the technological process for brazing of heat-resistant copper alloy strengthened with Al2O3 oxide particles is an important task of fabrication of high-temperature application structures. As mechanical properties of the brazed joints directly depend on the structural factor and morphological peculiarities of the brazed seams, the latter are of technological interest in terms of making of permanent joints. This study gives results of X-ray spectral microanalysis of the brazed joints on dispersion-strengthened copper alloy （ Gridcop Al-25 ） produced by using the Ti-Cu system adhesion-active brazing filler alloy, different heat sources and temperature-time parameters of the brazing process. Shown are differences in formation of structure of the seams made by vacuum brazing using radiation and high-frequency heating. Vacuum brazing with radiation heating provides the homogeneous seams with crystallisation of the phases based on the CuTi and CuTi2 compounds in the form of discrete faceted particles 2 - 9μm in size against the background of the copper matrix. Based on investigation of structural peculiarities of the brazed seams, the temperature-time conditions of vacuum brazing with radiation heating were selected for manufacture of specimens for mechanical tests. Analysis of the results of strength tests of the butt brazed specimens proved the expediency of preliminary heat treatment of the base material, providing strength of the joints at a level of about 92% of that of the base material.

Phosphorus speciation and colloidal phosphorus responses to short-term cessation of fertilization in a lime concretion black soil

Long-term excessive application of mineral fertilizer has led to soil acidification and phosphorus(P) accumulation, increasing the risk of P loss and environmental pollution, and cessation of fertilization is widely considered as a cost-effective management strategy to relieve this situation;however, how such cessation influences P speciation and concentrations in a bulk soil and colloidal fractions and whether decreasing P concentration might maintain soil fertility remain unclear. In this study, the effects of long-term fertilization(ca. 40 years) and short-term cessation of fertilization(ca. 16 months) on inorganic, organic,and colloidal P in lime concretion black soil were investigated using P sequential fractionation and31P nuclear magnetic resonance spectroscopy. After long-term fertilization, available P, dicalcium phosphate, iron-bound P, orthophosphate monoesters, and orthophosphate diesters increased significantly, but soil p H decreased by ca. 2.8 units, indicating that long-term fertilization caused soil acidification and P accumulation and changed P speciation markedly. In contrast, short-term fertilization cessation increased soil p H by ca. 0.8 units and slightly reduced available and inorganic P. Available P after fertilization cessation was 22.9–29.8 mg kg-1, which was still sufficient to satisfy crop growth requirements. Additionally, fertilization cessation increased the proportions of fine colloids(100–450 nm, including nontronite and some amorphous iron oxides) and drove a significant release of iron/aluminum oxide nanoparticles(1–100 nm) and associated P with orthophosphate and pyrophosphate species. In summary, short-term fertilization cessation effectively alleviated soil acidification and inorganic P accumulation, while concomitantly maintaining soil P fertility and improving the potential mobilization of P associated with microparticles.

Effects of Ionic Strength and Sesquioxides on Adsorption of Toxin of Bacillus thuringiensis subsp.kurstaki on Soils

Chemical reactions and fate of the toxins of Bacillus thuringiensis （Bt） in the soil environment are causing increasing concerns due to the large-scale cultivation of transgenic Bt plants. In this study, the effect of ionic strength （0-1 000 mmol kg-1） adjusted by NaCl or CaCl2 on adsorption of Bt toxin by a lateritic red soil, a paddy soil and these soils after chemical removal of organic-bound or free Fe and Al oxides, as well as by pure minerals （goethite, hematite and gibbsite） which are widespread in these soils, were studied. The results indicated that when the supporting electrolyte was NaCl, the adsorption of Bt toxin by the lateritic red soil and paddy soil increased rapidly until the ionic strength reached 250 mmol kg-1 and then gradually slowed down with the increase of ionic strength; while in ease the supporting electrolyte was CaCl2, the adsorption of Bt toxin enhanced significantly at low ionic strength （〈 10 mmol kg-1） and then decreased as the ionic strength increased. The adsorption of Bt toxin by the tested minerals and soils after the removal of organic-bound or free Fe and Al oxides also increased with increasing ionic strength controlled by NaCl. Removing organic-bound Fe and Al oxides obviously increased the adsorption of Bt toxin in the tested soils. Differently, removing free Fe and Al oxides increased the Bt adsorption by the paddy soil, but decreased the adsorption by the lateritic red soil. The study indicated that the varieties of ionic strength and the presence of Ve and Al oxides affected the adsorption of Bt toxin by the soils, which would contribute to the further understanding of the fate of Bt toxin in the soil environment and provide references for the ecological risk assessment of transgenic Bt plants.

Improving tribological and corrosion resistance of Ti6Al4V alloy by hybrid microarc oxidation/enameling treatments

A promising duplex coating was prepared by microarc oxidation（MAO） and enameling processes onto polished Ti6A14V alloy. The TiO2 ceramic coating deposited by MAO was characterized and then combined with an enameling treatment in order to improve the tribological and corrosion resistance of Ti6A14V alloy. The morphology, phase composition, and hardness of MAO and MAO/enameling-coated Ti6A14V alloy were evaluated by scanning electron microscopy（SEM）, X-ray diffraction（XRD）, and Vickers microhardness tester, respectively.The tribological performance was investigated using a ballon-disk tribometer. The corrosion resistance was studied using immersion tests and potentiodynamic polarization.Wear tests show that the enamel coating on the MAOcoated surface causes a reduction in the friction coefficient.Immersion tests demonstrate that the duplex coating is more effective in improving the corrosion resistance of Ti6A14V than the MAO coating especially at high temperature（80 ℃）. Potentiodynamic polarization curves reveal that the corrosion potential of the duplex coating increases by about 250 mV and the corrosion current density is slightly lower than that of the MAO coating. The duplex coating is superior to the stand-alone MAO coating in improving the tribological and corrosion behavior of Ti6A14V.