Hydrochlorination of Acetylene Using SiC Foam Supported Structured C/Au Catalysts

AuCl3 loaded structured catalysts were prepared on SiC foam supported with pre-coated activated carbon layers. The catalytic properties of the structured catalysts towards hydrochlorination of acetylene were tested in a fixed- bed reactor with the AuCl3 loaded on activated carbon pellets as a reference. For isopyknic catalysts, the structured catalyst with only one fifth of the Au amount as that was used on the reference catalyst exhibited even a little higher acetylene conversion and much better stability than the latter no matter what the gas hourly space velocities of acetylene were used. The results indicated that the more homogeneous distribution of AuCl3 particles and better heat transfer along the fixed-bed reactor originated from the low pressure drop and high thermal conductivity of the SiC foam supported structured catalysts might be able to account for their improved efficiency and stability. It is befieved that these novel structured C/Au catalysts can be potentially applied in VCM industrialization in view of their greatly reduced cost and much prolonged life.     

Effect of Oxide Assisted Metal Nanoparticles on Microstructure and Morphology of Gallium oxide Nanowires

Several researches have been reported about the characteristic of β-Ga2O3 nanowires which was synthesized on nickel oxide particle. But indeed, recent researches about synthesis of β-Ga2O3 nanowires on oxide-assisted transition metal are limited to nickel or cobalt oxide catalyst. In this work, Gallium oxide (β-Ga2O3 ) nanowires were synthesized by a simple thermal evaporation method from gallium powder in the range of 700 - 1000℃ using the iron, nickel, copper, cobalt and zinc oxide as a catalyst, respectively. The β-Ga2O3 nanowires with single crystalline without defects were successfully synthesized at the reaction temperature of 850, 900 and 950℃ in all the catalysts. But optimum experimental condition in synthesis of nanowires varied with the kind of catalyst. As increasing synthesis temperature,the morphology of gallium oxide nanowires changed from nanowires to nanorods, and its diameter increased. From these results, we could be proposed that the growth mechanism of β-Ga2O3 nanowires was changed with synthesis temperature of nanowires. Microstructure and morphology of Synthesized nanowire was characterized by HR-TEM, FE-SEM, EDX and XRD.     

Synthesis of High Purity SiC Powder for High-resistivity SiC Single Crystals Growth

High purity silicon carbide （SIC） powder was synthesized in-situ by chemical reaction between silicon and carbon powder. In order to ensure that the impurity concentration of the resulting SiC powder is suitable for high-resistivity SiC single crystal growth, the preparation technology of SiC powder is different from that of SiC ceramic. The influence of the shape and size of carbon particles on the morphology and phase composition of the obtained SiC powder were discussed. The phase composition and morphology of the products were investigated by X-ray diffraction, Raman microspectroscopy and scanning electron microscopy. The results show that the composition of resulting SiC by in-situ synthesis from Si/C mixture strongly depends on the nature of the carbon source, which corresponds to the particle size and shape, as well as the preparation temperature. In the experimental conditions, flake graphite is more suitable for the synthesis of SiC powder than activated carbon because of its relatively smaller particle size and flake shape, which make the conversion more complete. The major phase composition of the full conversion products is β-SiC, with traces of α-SiC. Glow discharge mass spectroscopy measurements indicated that SiC powder synthesized with this chemical reaction method can meet the purity demand for the growth of high-resistivity SiC single crystals.     

A Prussian blue route to nitrogen-doped graphene aerogels as efficient electrocatalysts for oxygen reduction with enhanced active site accessibility

Developing high-performance nonpredous-metal electrocatalysts for the oxygen reduction reaction (ORR) is crudal for a variety of renewable energy conversion and storage systems.Toward that end,rational catalyst design principles that lead to highly active catalytic centers and enhanced active site accessibility are undoubtedly of paramount importance.Here,we used Prussian blue nanoparticles to anchor Fe/Fe3C species to nitrogen-doped reduced graphene oxide aerogels as ORR catalysts.The strong interaction between nanosized Fe3C and the graphitic carbon shell led to synergistic effects in the ORR,and the protection of the carbon shell guaranteed stability of the catalyst.As a result,the aerogel electrocatalyst displayed outstanding activity in the ORR on par with the state-of-the-art Pt/C catalyst at the same mass loading in alkaline media,good performance in acidic media,and excellent stability and crossover tolerance that rivaled that of the best nonprecious-metal ORR electrocatalysts reported to date.     

Multifunctional Ir–Ru alloy catalysts for reversal-tolerant anodes of polymer electrolyte membrane fuel cells

To address the problem of fuel starvation in fuel-cell electric vehicles,which causes cell voltage reversal and results in cell failure when repeated continuously,we developed a reversal-tolerant anode(RTA) to promote water oxidation in preference to carbon corrosion.Graphitized carbon-supported Ir-Ru alloys with different compositions are employed as RTA catalysts in an acidic polyol solution and are shown to exhibit composition-dependent average crystallite sizes of <5.33 nm.The adopted approach allows the generation of relatively well-dispersed Ir-Ru alloy nanoparticles on the carbon support without severe agglomeration.The activity of IrRu₂/C for the hydrogen oxidation reaction is 1.10 times that of the stateof-the-art Pt/C catalyst.Cell reversal testing by simulation of fuel starvation reveals that the durability of IrRu₂/C(~7 h) significantly exceeds that of the conventional Pt/C catalyst(~10 min) and is the highest value reported so far.Thus,the developed Ir-Ru alloy catalyst can be used to fabricate practical RTAs and replace Pt catalysts in the anodes of polymer electrolyte membrane fuel cells.     

Bridging localized electron states of pyrite-type C0S2 cocatalyst for activated solar H2 evolution

The development of low-cost and high-active cocatalysts is one of the most significant links for photocatalytic water splitting.Herein,a novel strategy of electron delocalization modulation for transition metal sulfides has been developed by anion hybridization.P-modified CoS₂(CoS₂|P)nanocrystals were firstly fabricated via a gas-solid reaction and coupled with CdS nanorods to construct a composite catalyst for solar H2 evolution reaction(HER).The CdS/CoS₂|P catalyst shows an HER rate of 57.8 pmol h-1,which is 18 times that of the bare CdS,8 times that of the CdS/CoS2,and twice that of Pt/CdS.The reduced energy barrier and suppressed reverse reaction for HER on the catalyst have been predicted and explained by density functional theory(DFT)calculation.The underlying design strategy of novel cocatalysts by electron delocalization modulation may shed light on the rational development of other advanced catalysts for energy conversion.     

Effects of Pressure on the Performance of CNTs-Supported Catalyst in a Fischer-Tropsch Reaction

Fischer-Tropsch （FT） reaction involves conversion of syngas （a mixture of carbon monoxide and hydrogen） into higher hydrocarbons in the presence of an active catalyst. The syngas can be derived from non-petroleum feedstocks such as coal, biomass and natural gas, thus the FT reaction provides an alternative route for production of clean fuels. The FT process has received growing interest in recent years due to uncertainty in the Middle East, fast depletion of fossil fuel and environmental concern. This paper reports the synthesis, physicochemical properties and catalytic performance of cobalt-based catalyst in the FT reaction. The catalysts comprised metal nanoparticles supported on carbon nanotubes （CNTs） which were synthesized via a wet impregnation method. The catalysts were characterized using transmission electron microscopy （TEM）, temperature-programmed reduction/desorption （TPR/TPD） and X-ray photoelectron spectroscopy （XPS）. The performance of the cobalt-based catalyts in a FT reaction was evaluated in a fixed bed microreactor equipped with an on-line gas chromatograph for analyses of hydrocarbon products. The catalysts investigated in this work were Co/CNTs, 70Co30Mn/CNTs, 0.06%K/70Co30Fe/CNTs and 0.04%Nb/70Co30Fe/CNTs. TEM analyses revealed that the average sizes of the metal nanoparticles were 4-5 nm. Based on TPD analyses, the dispersion of these nanoparticles on CNTs were greater than 90%. The presence of both Co2＋ and Co3＋ ions were confirmed by XPS analysis. The 0.04% Nb/70Co30Fe/CNTs catalyst performed better than other catalysts in the FT reaction where it resulted in CO conversion of 35% and 16% C5＋ selectivity at pressure of 1 bar, 220 ~C and H2：CO of 2：1. Using the same catalyst, the CO conversion and C5＋ selectivity increased to 60% and 57%, respectively when the pressure was increased to 20 bar.     

Preparation and Microstructural Characterization of Activated Carbon-Metal Oxide Hybrid Catalysts:New Insights into Reaction Paths

In catalysis processes,activated carbon(AC) and metal oxides(MOs) are widely used either as catalysts or as catalyst supports because of their unique properties.A combination of AC and MO nanoparticles in a single hybrid material usually entails both chemical and microstructural changes,which may largely influence the potential catalytic suitability and performance of the resulting product.Here,the preparation of a wide series of AC-MO hybrid catalysts is studied.Three series of such catalysts are prepared by support first of MO(Al_2O_3,Fe_2O_3,SnO_2,TiO_2,WO_3,and ZnO) precursors on a granular AC by wet impregnation and oven-drying at 120 ℃,and by subsequent heat treatment at 200 or 850 ℃ in inert atmosphere.Both the chemical composition and microstructure are mainly investigated by powder X-ray diffraction.Yield and ash content are often strongly dependent on the MO precursor and heat treatment temperature,in particular for the Sn catalysts.With the temperature rise,trends are towards the transformation of metal hydroxides into metal oxides,crystallinity improvement,and occurrence of drastic composition changes,ultimately leading to the formation of metals in elemental state and even metal carbides.Reaction paths during the preparation are explored for various hybrid catalysts and new insights into them are provided.     

Relationship of particle stimulated nucleation,recrystallization and mechanical properties responding to Fe and Si contents in hot-extruded 7055 aluminum alloys

The variations of coarse intermetallic particles in hot-extruded 7055 aluminum alloys with 0.041 wt%Fe and 0.024 wt% Si increasing to 0.272 wt% Fe and 0.134 wt% Si were investigated.The particle stimulated nucleation(PSN) behaviors for different kind of coarse particles were detailly analyzed by EBSD.Moreover,the effect of PSN responding to Fe and Si contents on recrystallization and tensile properties of 7055 alloys was evaluated.With increasing Fe and Si contents,the size and number density of coarseη/S particles are reduced,while the number densities of coarse Al_7Cu_2 Fe and Mg_2Si particles are both increased and the coarse Al_7Cu_2 Fe particles transform from rod-like to irregular.More PSN recrystallized grains with predominant orientations deviated from the extruded fiber textures are stimulated by the irregular Al_7Cu_2 Fe and Mg_2Si particles,because a higher degree of local non-uniform deformation is produced.The rod-like Al_7Cu_2 Fe particles cause the greatest degree of local non-uniform deformation owing to the largest aspect ratio,but the shape also restricts the area of particle deformation zone(PDZ) resulting in fewer PSN recrystallized grains.The irregular η/S particles give rise to the lowest degree of local non-uniform deformation and fewest PSN recrystallized grains with the major orientations close to the extruded fiber textures.Consequently,despite the number and size of coarse η/S particles are reduced,the proportion of high angle grain boundaries(HAGBs) is increased and the extruded fiber textures are weakened with Fe and Si contents increasing,because of the increased Al_7Cu_2 Fe and Mg_2Si particles.The strength is slightly declined by the weakened 111//ED(extrusion direction) fiber texture,while the elongation is reduced for a larger number of coarse particles and more HAGBs with higher Fe and Si contents.     

Microstructure and mechanical properties at elevated temperature of Mg-Al-Ni alloys prepared through powder metallurgy

Mg-Al-Ni alloys were prepared by powder metallurgy, and their microstructure and elevated temperature mechanical properties were investigated. Results indicate that, in addition to α-Mg matrix, both coarse Al_3Ni_2 particles and fine Al Ni nano-particles exist in the Mg-Al-Ni alloys. The strength at 150?C is improved with the increase in Ni content. Mg-18.3Al-8Ni alloy possesses a compressive strength of234.7 MPa and a yield strength of 146.5 MPa. Plasticity is also improved with a low concentration of Ni. Mg-11.3Al-2Ni alloy possesses a compression ratio of 17.3%. The phases of Al_3Ni_2 and Al Ni in the alloys block the movements of grain boundaries and dislocations during the deformation at elevated temperature. The existence of Al Ni phase provides a non-basal slip system, leading to the improvement in plasticity. Finally, the formation mechanism of Al-Ni phases in the process is discussed with thermodynamics and kinetics.     

Tribological Behavior of Ti3SiC2—based Material

The wear and friction properties of Ti3SiC2-based materials were studied using the pin-on-disc method. The friction coefficient of Ti3SiC2-based material was not very sensitive to normal load, the steady state value, μ, increased from 0.4 to 0.5 when the normal load increased from 7.7 N to 14.7 N. The wear volume for Ti3SiC2 disc increased with increasing normal load or sliding distance in the tests. The average wear rate of Ti3SiC2-based material was 9.9×10-5 mm3/Nm. The debris on the Ti3SiC2 disc was essentially made up of Ti3SiC2 and steel pin materials, while the debris on the steel sliders was generally pin material. The wear mechanism was concluded as the fracture and delamination of Ti3SiC2-based materials followed by adhesive wear of steel sliders.     

Tuning the coordination environment of single-atom catalyst M-N-C towards selective hydrogenation of functionalized nitroarenes

Fine-tuning of the coordination environment of single-atom catalysts(SACs)is effective to optimize their catalytic performances,yet it remains challenging due to the vulnerability of SACs.Herein,we report a new approach to engineering the coordination environment of M-N-C(M=Fe,Co,and Ni)SACs by using glutamic acid as the N/C source and pyrolysis atmosphere as a regulator.Compared with that in N2,NH3 was able to promote the doping of N at 7<700℃yet etch the N-species at higher temperatures,by which the M-N coordination number(CN)and the electronic structure were delicately tuned.It was found that the electron density of Ni single atoms increased with the decrease of Ni-N CN.As a consequence,the capability of Ni-N-C to dissociate H2 was greatly enhanced and a higher catalytic activity in chemoselective hydrogenation of functionalized nitroarenes was achieved.Moreover,this modulation method could be applied to other transition metals including Fe and Co.In particular,the as-synthesized Co-N-C SAC afforded a turnover frequency of 152.3 h~1 with 99%selectivity to 3-vinylaniline in the hydrogenation of 3-nitrostyrene,which was the highest ever reported thus far and was at least one order of magnitude more active than state-of-the-art noble-metal-free M-N-C catalysts,demonstrating the great potential of engineering the coordination environment of SACs.     

A Coprecipitation Coating Synthesis of SiC/YAG Composites

The α-SiC in 0.5μm size powders were coated with Al_2O_3 and Y_2O_3 by a coprecipitation coating (CPC) method forfabrication of SiC/YAG composites. The same powder preparation was carried out by conventional mechanical mixing(MM) method for comparison. Two kinds of SiC/YAG composites were manufactured by pressureless sintering usingthe different powders, named CPC composite and MM composite thereafter respectively. It is shown that the CPCcomposite has the advantages of homogeneous distribution of YAG phase and of being sintered to high density ata low temperature, 100℃ lower than that of MM composite. The strength (573 MPa) and hardness (23.3 GPa) ofthe CPC composite are significantly higher than those (323 MPa and 13.5 GPa) of the MM composite, respectively.     

Photocatalytic Activities of TiO2 Coated on Different Semiconductive SiC Foam Supports

Different semiconductive SiC foam supports were prepared by varying the sintering temperature and atmosphere, and with or without alkaline solution treatment and high temperature oxidation following a macromolecule pyrogenation combined with reaction bonding method. Nano-TiO2 particles were immobilized onto these SiC foam supports by a composite sol-gel method. The phase, surface morphology, the type of conduction and the photocatalytic activity of the TiO2-SiC composite photocatalysts were studied. The TiO2 coated on p-type Si-free SiC support showed the highest photocatalytic efficiency in degradation of 4- aminobenzenesulfonic acid （4-ABS） in aqueous solution as compared to that coated on n-type SiC support and p-type SiC supports with residual Si or Si02 on the surface. The result showed that the TiO2 coatings immobilized on p-type semiconductive SiC foam supports exhibited obviously higher photocatalytic activity in comparison to that coated on n-type SiC foam support. The p-n heterojunctions formed between the p-type SiC supports and n-type TiO2 coatings might be able to account for the better charge separation and transfer as well as the photocatalytic activity of the TiO2-SiC composite photocatalyst.     

Effect of Primary and Eutectic Mg_2Si Crystal Modifications on the Mechanical Properties and Sliding Wear Behaviour of an Al–20Mg_2Si–2Cu–xBi Composite

This work investigated the microstructure evolution, tensile, impact, hardness, and sliding wear properties of an Al–20Mg_2Si–2Cu in situ composite treated with different Bi contents. The desired modification of primary Mg_2 Si particles was achieved with the addition of 0.4 wt% Bi. Increasing Bi beyond 0.4 wt%resulted in a loss of modification, possibly due to the formation of Al_8 MgB iS i4 compound before the precipitation of the primary Mg_2 Si. Additionally, the structure of the pseudo-eutectic Mg_2 Si was transformed from plate to fibrous, which was consistent with decrease of growth temperature extracted from the cooling curve thermal analysis. Addition of Bi had an effect on the morphology of Al_5 Fe Si(β), Al_2Cu(θ) and Al_5Cu_2Mg_8Si_6(Q) intermetallic compounds. The tensile strength, elongation percentage, impact toughness, and hardness increased by 6%, 13%, 75%, and 23%, respectively, due to modification of both the primary and eutectic Mg_2 Si crystals. The tensile and impact fracture surfaces showed fewer decohered particles in the Bi-treated composite. The enhancement in wear resistance of the Bi-treated composite could be attributed to solid lubricant function of insoluble soft Bi phase and modification effects on Mg_2 Si particles.     

Defect-rich MoS<Subscript>2</Subscript> nanowall catalyst for efficient hydrogen evolution reaction

Designing efficient electrocatalysts for the hydrogen evolution reaction (HER) has attracted substantial attention owing to the urgent demand for clean energy to face the energy crisis and subsequent environmental issues in the near future.Among the large variety of HER catalysts,molybdenum disulfide (MoS2) has been regarded as the most famous catalyst owing to its abundance,low price,high efficiency,and definite catalytic mechanism.In this study,defect-engineered MoS2 nanowall (NW) catalysts with controllable thickness were fabricated and exhibited a significantly enhanced HER performance.Benefiting from the highly exposed active edge sites and the rough surface accompanied by the robust NW structure,the defect-rich MoS2 NW catalyst with an optimized thickness showed an ultralow onset overpotential of 85 mV,a high current density of 310.6 mA·cm-2 at η =300 mV,and a low potential of 95 mV to drive a 10 mA.cm-2 cathodic current.Additionally,excellent electrochemical stability was realized,making this freestanding NW catalyst a promising candidate for practical water splitting and hydrogen production.     

Highly Efficient Photoelectrocatalytic Reduction of CO2 to Methanol by a p–n Heterojunction CeO2/CuO/Cu Catalyst

Photoelectrocatalytic reduction of CO2 to fuels has great potential for reducing anthropogenic CO2 emissions and also lessening our dependence on fossil fuel energy.Herein,we report the successful development of a novel photoelectrocatalytic catalyst for the selective reduction of CO2 to methanol,comprising a copper catalyst modified with flower-like cerium oxide nanoparticles(CeO2 NPs)(a n-type semiconductor)and copper oxide nanoparticles(CuO NPs)(a p-type semiconductor).At an applied potential of−1.0 V(vs SCE)under visible light irradiation,the CeO2 NPs/CuO NPs/Cu catalyst yielded methanol at a rate of 3.44μmol cm^−2 h^−1,which was approximately five times higher than that of a CuO NPs/Cu catalyst(0.67μmol cm^−2 h^−1).The carrier concentration increased by^108 times when the flower-like CeO2 NPs were deposited on the CuO NPs/Cu catalyst,due to synergistic transfer of photoexcited electrons from the conduction band of CuO to that of CeO2,which enhanced both photocatalytic and photoelectrocatalytic CO2 reduction on the CeO2 NPs.The facile migration of photoexcited electrons and holes across the p–n heterojunction that formed between the CeO2 and CuO components was thus critical to excellent light-induced CO2 reduction properties of the CeO2 NPs/CuO NPs/Cu catalyst.Results encourage the wider application of composite semiconductor electrodes in carbon dioxide reduction.     

Microstructural Study of the Intermetallic Bonding Between AI Foam and Low Carbon Steel

Bonding between a metal foam core and a metallic skin is a pre requisite for the technological application of aluminum foam as filling reinforcement material to improve energy absorption and vibration damping of hollow components. This work is a preliminary study for the microstructural characterization of the interface layer formed between a commercial powder metallurgy （PM） precursor and a steel mould during foaming. The microstructure of the intermetallic layer was characterized by scanning electron microscopy, electron probe microanalysis and nanohardness measurements on the cross section. X-ray diffraction measurements, performed on the foam/substrate surface after stepwise material removal, allow the identification of the intermetallic phases. Two intermetallic layers, identified as Fe2Als and FeAI3, characterize the low Si foam/substrate while the AISiI0 foam/substrate interface evidences the presence of three Fe（Si, AI） intermetallic layers with different composition. Two and three different phases of increasing hardness could be distinguished going from the foam to the steel substrate for AIMglSi0.6 and AISiI0 precursors respectively. The results suggest the importance of elemental diffusion from steel substrate in the molten aluminum matrix （foam）. The possibility to control and tailor the microstructural properties of the interface between foam and steel skin is of fundamental importance in the technological process of foam filled structures manufacturing.     

High Strength Silicon Carbide Foams and Their Deformation Behavior

Silicon carbide （SIC） foams with a continuously connected open-cell structure were prepared and characterized for their mechanical performance. The apparent densities of SiC foams were controlled between about 0.4 and 2.3 g/cm^3, with corresponding compressive strengths ranging from about 23 to 60 MPa and flexural strengths from about 8 to 30 MPa. Compressive testing of the SiC foams yielded stress-strain curves with only one linear-elastic region, which is different from those reported on ceramic foams in literature. This can possibly be attributed to the existence of filaments with fine, dense and high strength microstructures. The SiC and the filaments respond homogeneously to applied loading.     

Al2O3—Coated Nano—SiC Particles Reinforced Al2O3 Matrix Composites

Properties of Al2O3-coated nano-SiC have been compared with those of as-received SiC.The isoelectric point(IEP) of SiC changed from pH3.4 to pH7.3 after coating with the alumina precursor,which is close to that of alumina.Because both surfaces of coated SiC and Al2O3 possess higher positive charge at pH=4.5-5.0 ,they are uniformly dispersed in the two-phase aqueous suspensions.Then a mixed powder containing nano-SiC dispersed homogeneously into the Al2O3 matrix was achieved from flocculating the two-phase suspension.Finally,Al2O3/SiC nanocomposited were obtained by coating nano-SiC with Al2O3 ,in which the majority of SiC particles were located within the Al2O3 grains.The observation by transmission electron microscopy(TEM) and the analysis by the X-ray photoelectron spectroscopy(XPS) showed that cracks propagated towards the intragranular SiC rather than along prain boundaries.