Effect of B sites on the catalytic activities for perovskite oxides La_(.6)Sr_(.4)Co_xFe_(1-x)O_(3-δ) as metal-air batteries catalysts

The effect of B sites on the catalytic activities of oxygen evolution reaction(OER)for perovskite oxides La_(0.6)Sr_(0.4)Co_xFe_(1-x)O_(3-δ)(x=0,0.2,0.4,0.6,0.8,1,denoted as LSF,LSCF-28,LSCF-46,LSCF-64,LSCF-82 and LSC,respectively)prepared by a convenient and simple method of electrospinning technique is reported.The prepared La_(0.6)Sr_(0.4)Co_xFe_(1-x)O_(3-δ)catalysts possess almost same crystal structures,similar morphologies(except for the LSC catalyst)and slightly different BET surface areas.Upon the optimization of the Co/Fe atomic ratio,the optimal LSCF-82 catalyst exhibits the OER performance with a low onset potential of 1.541 V,a small Tafel slope of 80.56 mV dec~(-1),a high charge-transfer rate and a large electrochemical surface area in 0.1 M KOH solution.LSCF-82 catalyst exhibits the long-term stability under the catalytic operation condition for 12 h.Such catalytic activity may mainly cause by the synergy of higher catalytic activity Co and lower catalytic activity Fe.Thus,the reasonable optimization of the transition metal composition in B sites for the perovskite oxides is in favor of the improvement of OER performance.     

Ethylene tetramerization with a highly active and long-lifetime trinuclear diphenylphosphinoamine/Cr（III）/MAO catalyst

The synthesis and characterization of a novel trinuclear diphosphinoamine ligand 2 are reported. The ligand combined with Cr(III), activated with methylaluminoxane, lead to highly active and long-lifetime catalytic systems for the tetramerization of ethylene to form 1-octene. The effects of reaction temperature, reaction pressure, molar ratio of Al/Cr and bis(diphenylphosphino)amine/Cr on the catalytic activity and product selectivity were studied. Compared with its mononuclear analogue 1, ligand 2 showed a higher catalytic activity and longer lifetime for ethylene tetramerization in the presence of methylaluminoxane as cocatalyst. High molecular weight polyethylene was generated as a by-product with extremely broad molecular weight distributions.     

Transition-metal-doped Fe2O3 nanoparticles for oxygen evolution reaction

Hematite(α-Fe_2O_3)has been extensively studied as a promising photocatalyst,with the capacity to split water under visible light.To tune its electronic structure and improve the performance for oxygen evolution reaction(OER),high-quality single crystals ofα-Fe_2O_3nanoparticles were synthesized and doped by various transition metals(M=V,Cr,Mn,Zn,Co,Ni,Cu,Nb,Mo,Ti)by a molten-salt flux method.Optical,electronic and catalytic properties of transition-metal-dopedα-Fe_2O_3(TM-dopedα-Fe_2O_3)have been systematically investigated.Cobalt has been identified as the best dopant forα-Fe_2O_3,reducing the OER overpotential by 0.16 V with respect to the undoped.     

Catalytic combustion properties of nanocomplex oxide for natural gas

The catalysts of copper oxide supported on cerium dioxide were prepared by different methods for methane catalytic combustion. The effects of copper content in the catalysts and calcination temperatures of the catalysts on the catalytic activity are investigated. Results show that the complex oxide catalyst exhibits high catalytic activity for methane combustion due to the synergistic effect of CuO and CeO₂. The catalyst prepared by impregnation is more active than that prepared by controlled coprecipitation even if CuO content is the same. When W(CuO)<13%, the light-off temperature and full conversion temperature for the CH₄ reaction decrease with the increasing of CuO content in the catalysts. However, when the copper content is above 13%, the excess CuO has a negative effect on the catalytic activity owing to the formation of bulk CuO particles. A proper calcinations temperature of 650 ℃ can lead to a high dispersion of CuO and accordingly can enhance the catalytic activity of the composites.     

Metal-doped(Cu,Zn)Fe_2O_4 from integral utilization of toxic Zn-containing electric arc furnace dust: An environment-friendly heterogeneous Fenton-like catalyst

Pure metal-doped(Cu,Zn)Fe_2O_4 was synthesized from Zn-containing electric arc furnace dust(EAFD) by solid-state reaction using copper salt as additive. The effects of pretreated EAFD-to-Cu_2(OH)_2CO_3·6H_2O mass ratio, calcination time, and calcination temperature on the structure and catalytic ability were systematically studied. Under the optimum conditions, the decolorization efficiency and total organic carbon(TOC) removal efficiency of the as-prepared ferrite for treating a Rhodamine B solution were approximately 90.0% and 45.0%, respectively, and the decolorization efficiency remained 83.0% after five recycles, suggesting that the as-prepared(Cu,Zn)Fe_2O_4 was an efficient heterogeneous Fenton-like catalyst with high stability. The high catalytic activity mainly depended on the synergistic effect of iron and copper ions occupying octahedral positions. More importantly, the toxicity characteristic leaching procedure(TCLP) analysis illustrated that the toxic Zncontaining EAFD was transformed into harmless(Cu,Zn)Fe_2O_4 and that the concentrations of toxic ions in the degraded solution were all lower than the national emission standard(GB/31574—2015), further confirming that the as obtained sample is an environment-friendly heterogeneous Fenton-like catalyst.     

Development and progress on hydrogen metallurgy

Hydrogen metallurgy is a technology that applies hydrogen instead of carbon as a reduction agent to reduce CO_2 emission, and the use of hydrogen is beneficial to promoting the sustainable development of the steel industry. Hydrogen metallurgy has numerous applications,such as H_2reduction ironmaking in Japan, ULCORED and hydrogen-based steelmaking in Europe; hydrogen flash ironmaking technology in the US; HYBRIT in the Nordics; Midrex H_2TM by Midrex Technologies, Inc.(United States); H_2FUTURE by Voestalpine(Austria); and SALCOS by Salzgitter AG(Germany). Hydrogen-rich blast furnaces(BFs) with COG injection are common in China. Running BFs have been industrially tested by AnSteel, XuSteel, and BenSteel. In a currently under construction pilot plant of a coal gasification–gas-based shaft furnace with an annual output of 10000 t direct reduction iron(DRI), a reducing gas composed of 57 vol% H_2 and 38 vol% CO is prepared via the Ende method. The life cycle of the coal gasification–gas-based shaft furnace–electric furnace short process(30 wt% DRI + 70 wt% scrap) is assessed with 1 t of molten steel as a functional unit. This plant has a total energy consumption per ton of steel of 263.67 kg standard coal and a CO_2 emission per ton of steel of 829.89 kg, which are superior to those of a traditional BF converter process. Considering domestic materials and fuels, hydrogen production and storage, and hydrogen reduction characteristics, we believe that a hydrogen-rich shaft furnace will be suitable in China. Hydrogen production and storage with an economic and large-scale industrialization will promote the further development of a full hydrogen shaft furnace.     

Highly effective La-deficient La_(1-x)Ce_xMnO_3 mixed oxides for the complete oxidation of methane

La-deficient La_(1-x)Ce_xMnO_3 mixed oxides, obtained by selective dissolution in 1 M nitric acid, were employed in methane complete oxidation. The majority of the La cations in these perovskites were removed, resulting in increased specific surface areas, better reducibility and greater activity. Incorporation of a small amount of Ce stabilized the structure and a perovskite phase persisted in La-deficient La_(1-x)Ce_xMnO_3 mixed oxides after 12 h of acid dissolution. La_(0.95)Ce_(0.05)MnO_3 after the acid treatment exhibited satisfactory catalytic activity, with T50 and T90 values of 365 and 459℃, respectively, which was even comparable to that previously reported 1% Pd/Al_2O_3 catalysts. And it showed excellent long-term activity even in the presence of CO_2 and H_2O.     

含钛高炉炉渣微波合成碳化钛及其介电性能测定

The preparation of functional material titanium carbide by the carbothermal reduction of Ti-bearing blast furnace slag with microwave heating is an effective method for valuable metals recovery; it can alleviate the environmental pressure caused by slag stocking. The dynamic dielectric parameters of Ti-bearing blast furnace slag/pulverized coal mixture under high-temperature heating are measured by the cylindrical resonant cavity perturbation method. Combining the transient dipole and large π bond delocalization polarization phenomena, the interaction mechanism of the microwave macroscopic non-thermal effect on the titanium carbide synthesis reaction was revealed. The material thickness range during microwave heating was optimized by the joint analysis of penetration depth and reflection loss, which is of great significance to the design of the microwave reactor for the carbothermal reduction of Ti-bearing blast furnace slag.     

Determination of dielectric properties of titanium carbide fabricated by microwave synthesis with Ti-bearing blast furnace slag

The preparation of functional material titanium carbide by the carbothermal reduction of Ti-bearing blast furnace slag with microwave heating is an effective method for valuable metals recovery; it can alleviate the environmental pressure caused by slag stocking.The dynamic dielectric parameters of Ti-bearing blast furnace slag/pulverized coal mixture under high-temperature heating are measured by the cylindrical resonant cavity perturbation method.Combining the transient dipole and large π bond delocalization polarization phenomena, the interaction mechanism of the microwave macroscopic non-thermal effect on the titanium carbide synthesis reaction was revealed.The material thickness range during microwave heating was optimized by the joint analysis of penetration depth and reflection loss, which is of great significance to the design of the microwave reactor for the carbothermal reduction of Ti-bearing blast furnace slag.     

Natural Mg silicates with different structures and morphologies: Reaction with K to produce K_2MgSiO_4 catalyst for biodiesel production

In this work, different magnesium silicate mineral samples based on antigorite, lizardite, chrysotile(which have the same general formula Mg_3Si_2O_5(OH)_4), and talc(Mg_3Si_4O_(10)(OH)_2) were reacted with KOH to prepare catalysts for biodiesel production. Simple impregnation with 20 wt% K and treatment at 700–900°C led to a solid-state reaction to mainly form the K_2MgSiO_4 phase in all samples. These results indicate that the K ion can diffuse into the different Mg silicate structures and textures, likely through intercalation in the interlayer space of the different mineral samples followed by dehydroxylation and K_2MgSiO_4 formation. All the materials showed catalytic activity for the transesterification of soybean oil(1:6 of oil : methanol molar ratio, 5 wt% of catalyst, 60°C). However, the best results were obtained for the antigorite and chrysotile precursors, which are discussed in terms of mineral structure and the more efficient formation of the active phase K_2MgSiO_4.     

Effect of chemical activation process on adsorption of As(Ⅴ) ion from aqueous solution by mechano-thermally synthesized zinc ferrite nanopowder

Nanostructured Zn Fe_2O_4 was synthesized by the heat treatment of a mechanically activated mixture of Zn O/α-Fe_2O_3. X-ray diffraction(XRD) and differential thermal analysis(DTA) results demonstrated that, after 5 h of the mechanical activation of the mixture, Zn Fe_2O_4 was formed by heat treatment at 750°C for 2 h. To improve the characteristics of Zn Fe_2O_4 for adsorption applications, the chemical activation process was performed. The 2 h chemical activation with 1 mol·L~(-1) HNO_3 and co-precipitation of 52%-57% dissolved Zn Fe_2O_4 led to an increase in the saturated magnetization from 2.0 to 7.5 emu·g~(-1) and in the specific surface area from 5 to 198 m~2·g~(-1). In addition, the observed particle size reduction of chemically activated Zn Fe_2O_4 in field emission scanning electron microscopy(FESEM) micrographs was in agreement with the specific surface area increase. These improvements in Zn Fe_2O_4 characteristics considerably affected the adsorption performance of this adsorbent. Adsorption results revealed that mechano-thermally synthesized Zn Fe_2O_4 had the maximum arsenic adsorption of 38% with the adsorption capacity of 0.995 mg·g~(-1) in a 130 mg·L~(-1) solution of As(V) after 30 min of agitation. However, chemically activated Zn Fe_2O_4 showed the maximum arsenic adsorption of approximately 99% with the adsorption capacity of 21.460 mg·g~(-1) under the same conditions.These results showed that the weak adsorption performance of mechano-thermally synthesized Zn Fe_2O_4 was improved by the chemical activation process.     

Enhanced microwave absorption properties of rod-shaped Fe2O3/Fe3O4/ MWCNTs composites

A novel type of composite absorber,i.e.Fe_2O_3/Fe_3O_4/MWCNTs composites(0%,1.7%and 5%MWCNTs),with microwave absorption properties was successfully fabricated by a facile hydrothermal method.The preparedα-Fe_2O_3/Fe_3O_4nanoparticles displayed rod-shaped morphology.The complex permittivity and permeability of the Fe_2O_3/Fe_3O_4/MWCNTs composites distinctly increased,furthermore,with the introduction of MWCNTs,the Fe_2O_3/Fe_3O_4/MWCNTs composites exhibited fine microwave absorption performance with strong absorption and wide absorption band.In particular,for Fe_2O_3/Fe_3O_4/1.7%MWCNTs composite with an absorber thickness of 2.5 mm,the reflection loss(RL)reached a minimum of-44.1 d B at 10.4 GHz and the effective absorption bandwidth(RL-10 d B)covered 3.3 GHz.The enhanced microwave absorption performance of the Fe_2O_3/Fe_3O_4/MWCNTs composites was attributed to the high dielectric loss and improved impedance matching which was closely related to the rod-shaped morphology of Fe_2O_3,Fe_3O_4and the introduction of MWCNTs.     

CHARACTERIZATION ON DOPING POLYPYRROLE FILMS

The conductivity of polypyrrole films has been enhanced by electrochemical post-deposition doping with various anions. The change of conductivity was found to depend on the type and concentration of the anion. Results for the polypyrrole films doped with anions of H_2SO_4,,(C_2H_5)_4, N(O_3 SC_6H_4CH_3), KI,CH_3 C_6H_4 SO_3 H·H_2O(p-Toluene Sulfonic acid Monohydydrate), AlCl_3, KBrO_3 and HNO_3 showed that in the case of H_2 SO_4, (C_2H_5)_4 N(O_3SC_6 H_4 CH_3)and CH_3C_6H_4SO_3H·H_2O the conductivity can be enhanced by up to a factor of two, from a value of 67 sem~(-1) up to 165, 102 and 95 s cm~(-1), respectively. Doping with I~- had a negligible effect on the conductivity which was about 71 s cm~(-1), while in the case of AlCl_3, KBrO_3 and HNO_3 the conductivity of the polypyrrole decreased significantly for certain anion concentrations.     

ZrO_2-supported α-MnO_2:Improving low-temperature activity and stability for catalytic oxidation of methane

The single phaseα-Mn O_2and in-situ supportedα-Mn O_2/Zr O_2with different ratios of Mn/Zr were synthesized by one-pot hydrothermal method.They showed superior activity for catalytic oxidation of methane and even better than that of 1%Pt/Al_2O_3.The T_(50)of Mn O_2/Zr O_2catalysts with different ratios of Mn/Zr were located in the range of 315–335°C at a WHSV of 90 L g~(-1)h~(-1),whereas that of Pt/Al_2O_3was 380°C.After sulfur ageing,the Mn O_2/Zr O_2catalysts with Mn/Zr ratio of 2:1(2Mn O_2/1Zr O_2)and 1:1(1Mn O_2/1Zr O_2)exhibited satisfying sulfur resistance in comparison to the pure Mn O_2.The 2Mn O_2/1Zr O_2catalyst also showed acceptable catalytic stability,and the addition of 10 vol%CO_2had no obvious negative effect on its stability,whereas the addition of2.6 vol%H_2O caused slight but reversible decreasing methane oxidative activity.     

Analysis of Co3O4 /Mildly Oxidized Graphite Oxide (mGO) Nanocomposites of Mild Oxidation Degree for the Removal of Acid Orange 7

In this study,a series of Co_3O_4/ mildly oxidized graphite oxide(mGO) nanocatalysts(Co_3O_4/ mGO-l,Co_3O_4/ mGO-2 and Co_3O_4/mGO-3) were synthesized through solvothermal method and used as a mediator for the heterogeneous peroxymonosulfate(PMS)activation.The performance of CO_3O_4 / mGO/PMS system was investigated using acid orange 7(AO7).Results showed that Co_3O_4/mGO-3 had the best degradation efficiency of AO7 and the removal rate was above 90%in about 6 min.The phenomenon indicated the catalytic activity of Co_3O_4/mGO composites was related to the oxidation degree of graphite oxide(GO).In addition,experiments showed the content of Co_3O_4 had an effect on the catalytic activity.The composites were characterized with X-ray powder diffraction(XRD),FTIR,Raman,X-ray photoelectron spectroscopy(XPS) and transmission electron microscopy(TEM).According to the charactrization and synergistic catalytic mechanism,the generation of Co—OH complexes found to be the initial step to activate PMS in the heterogeneous system of Co_3O_4/mGO hybrid.     

Selective reduction of carbon dioxide into amorphous carbon over activated natural magnetite

Natural magnetite formed by the isomorphism substitutions of transition metals, including Fe, Ti, Co, etc., was activated by mechanical grinding followed by H_2 reduction. The temperature-programmed reduction of hydrogen(H_2-TPR) and temperature-programmed surface reaction of carbon dioxide(CO_2-TPSR) were carried out to investigate the processes of oxygen loss and CO_2 reduction. The samples were characterized by X-ray diffraction(XRD), field emission scanning electron microscopy(FE-SEM), and energy-dispersive X-ray spectroscopy(EDS). The results showed that the stability of spinel phases and oxygen-deficient degree significantly increased after natural magnetite was mechanically milled and reduced in H_2 atmosphere. Meanwhile, the activity and selectivity of CO_2 reduction into carbon were enhanced. The deposited carbon on the activated natural magnetite was confirmed as amorphous. The amount of carbon after CO_2 reduction at 300°C for 90 min over the activated natural magnetite was 2.87 wt% higher than that over the natural magnetite.     

The catalytic behavior of La-Mn-O nanoparticle perovskite-type oxide catalysts for the combustion of the soot particle from the diesel engine

The La1-xMx MnO3（M=Li, Na, K, Rb, x=0, 0.10,0.25） perovskite-type oxides whose sizes are nanoparticle have been prepared by the citric acid-ligated method. The characters of the catalysts were characterized by means of XRD, IR, SEM and BET surface area measurement. The catalytic activity for the combustion of soot particulate was evaluated by a technique of the temperature-programmed reaction. In the LaMnO3 catalyst, the partial substitution of alkali metal （Li, Na, K, Rb） into A-site enhanced the catalytic activity for the combustion of soot particle. The La0.75K0.25MnO3 oxides are good candidate catalysts for the soot particle removal reaction, and the combustion temperatures of soot particle are between 285℃ and 430℃ when the contact of catalysts and soot is loose, and their catalytic activities for the combustion of soot particle are as good as supported Pt catalysts, which is the best catalyst system so far reported for soot combustion under loose contact conditions.     

Activity coefficients of NiO and CoO in CaO–Al_2O_3–SiO_2 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–Al_2O_3–SiO_2 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–Al_2O_3–SiO_2 slag. The activity coefficients of NiO and CoO in CaO–Al_2O_3–SiO_2 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)/(%SiO_2) = 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.     

Development of non-shrinkable ceramic composites for use in high-power microwave tubes

Al_2O_3–CaO–SiC-based ceramic composites with four different compositions were sintered at 1700℃ for 3 h in an air furnace. The phase analysis, microstructural characterization, and elemental composition determination of the developed composites were performed by X-ray diffraction(XRD), field-emission scanning electron microscopy(FESEM), and energy-dispersive X-ray(EDAX) analysis, respectively. The shrinkage, thermal properties, and electrical resistivity of the composites were also studied. The experimental results showed the effects of adding silicon carbide and calcia to alumina on the thermal, electrical, and shrinkage properties of the resultant composites. Among the four investigated ceramic composites, the one composed of 99 wt% alumina, 0.5 wt% CaO, and 0.5 wt% SiC exhibited the best characteristics for use as a potting material in a dispenser cathode of a microwave tube. The material exhibited slight expansion instead of shrinkage during drying or firing. Other properties of the composite powder, such as its thermal properties and electrical resistivity, were comparable to those of a commercial alumina powder.     

2-Steps Preparation Activated Carbon from Solidago Canadensis: Carbonized by Electrial heating and Activated by Microwave Radiation

The activated carbon(AC)was prepared from Solidago Canadensis(SC),an alien invasive plant.The plant was firstly carbonized under nitrogen at 400 ℃ for 90 min in an electrical furnace,and then the carbonized product was activated with KOH through microwave radiation.Effects of KOH/C ratio,microwave power,microwave radiation time on the adsorption capacities and yield of AC were evaluated.It indicated that the optimum conditions were KOH/C ratio 2 g/g,microwave power 700 W,and microwave radiation time 6 min.The carbonation process of SC was analyzed by thermogravimetry(TG).The pore structural parameters and surface functional groups of the AC were characterized by nitrogen adsorption-desorption and Fourier Transformed Infrared Spectroscopy(FTIR),respectively.The activation yield,the surface area,the average pore size,and the average micropore size of AC prepared from optimum conditions were 53.75%,1 888 m2/g,0.567 nm,and 0.488 nm,respectively.The adsorption amounts of AC were 302.4 mg/g for methylene blue and 1 470.27 mg/g for iodine.