Carburization of ferrochromium metals in chromium ore fines containing coal during voluminal reduction by microwave heating

Chromium ore fines containing coal (COFCC) can be rapidly heated by microwave to conduct the voluminal reduction, which lays a foundation of getting sponge ferrochromium powders with a lower content of C. Under the conditions of COFCC with n(O)-n(C) (molar ratio) as 1.00-0.84 and n(SiO2)-n(CaO) as 1.00-0.39, the samples were heated by 10 kW microwave power to reach the given temperatures and held for different times respectively. The results show that the low-C-Cr ferrochromium metal phase in the reduced materials forms before the high-C-Cr ferrochromium metal phase does. With increasing temperature the C content of ferrochromium metals is in a positive correlation with the content of Cr. The C content of ferrochromium metal in reduced materials is 0-10.07% with an average value of 4.68%. With the increase of holding time the Cr content in ferrochromium metals is in a negative correlation with the content of C, while the content of Fe changes in the contrary way. In the microwave field the kinetic conditions of carburization are closely related with the temperature of microwave heating, holding time and carbon fitting ratio.

Reduction and carburization of iron oxides for Fischer–Tropsch synthesis

The activation of iron oxide Fischer–Tropsch Synthesis(FTS) catalysts was investigated during pretreatment: reduction in hydrogen followed by carburization in either CO or syngas mixture, or simultaneously reduction and carburization in syngas. A combination of different complementary in situ techniques was used to gain insight into the behavior of Fe-based FTS catalysts during activation. In situ XRD was used to identify the crystalline structures present during both reduction in hydrogen and carburization. An increase in reduction rate was established when increasing the temperature. A complete reduction was demonstrated in the ETEM and a grain size dependency was proven, i.e. bigger grains need higher temperature in order to reduce. XPS and XAS both indicate the formation of a small amount of carbonaceous species at the surface of the bulk metallic iron during carburization.

PHASE TRANSITION OF W－Co OXIDE MIXTURE DURING DIRECT REDUCTION／CARBURIZATION BY H_2／CH_4

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Direct reduction of carburized pre-reduced pellets by microwave heating

A new iron-making process using carburized pre-reduced iron ore pellets and microwave heating is investigated. The pre-reduced pellets, with a porous structure, and fine particles are carburized homogeneously at 400-650 ℃ in a CO atmosphere. The carburized carbon not only acts reaction as a reduction agent, but also absorbs microwave in the reduction process. Hence, the carburized pre-reduced pellets can be rapidly reduced by microwave heating. There are three procedures involved in the process, namely, gas-based pre-reduction, low-temperatttre carburization and deep reduction by microwave heating. Carburized pre-reduced iron ore pellets show a rapid temperature rise that is twice as fast as the results for pre-reduced pellets in the laboratory. This not only improves the efficiency of the microwave heating, but also accelerates the reduction of iron oxides. The temperature of the pre-reduced pellets rises to 1050 ℃ in 45 min when the carburization rate is 2.02%, and the metallization rate and compressive strength reach 94.24% and 1725 N/pellet, respectively.

Electrocatalysts with atomic-level site for nitrate reduction to ammonia

Ammonia(NH_(3))is an important raw material for modern agriculture and industry,being widely demanded to sustain the sustainable development of modern society.Currently,the industrial production methods of NH_(3),such as the traditional Haber-Bosch process,have drawbacks including high energy consumption and significant carbon dioxide emissions.In recent years,the electrocatalytic nitrate reduction reaction(NO_(3)RR)powered by intermittent renewable energy sources has gradually become a multidisciplinary research hotspot,as it allows for the efficient synthesis of NH_(3)under mild conditions.In this review,we focus on the research of electrocatalysts with atomic-level site,which have attracted attention due to their extremely high atomic utilization efficiency and unique structural characteristics in the field of NO_(3)RR.Firstly,we introduce the mechanism of nitrate reduction for ammonia synthesis and discuss the in-situ characterization techniques related to the mechanism study.Secondly,we review the progress of the electrocatalysts with atomic-level site for nitrate reduction and explore the structure-activity relationship to guide the rational design of efficient catalysts.Lastly,the conclusions of this review and the challenges and prospective of this promising field are presented.

In-situ self-templated preparation of porous core-shell Fe_(1-x)S@N,S co-doped carbon architecture for highly efficient oxygen reduction reaction

Transition metal compound(TMC)/carbon hybrids,as prospering electrocatalyst,have attracted great attention in the field of oxygen reduction reaction(ORR).Their morphology,structure and composition often play a crucial role in determining the ORR performance.In this work,we for the first time report the successful fabrication of porous core-shell Fe_(1-x)S@N,S co-doped carbon(Fe_(1-x)S@NSC-t,t represents etching time)by a novel in-situ self-template induced strategy using Fe3O4 nanospheres and pyrrole as sacrificial self-template.The post-polymerization of pyrrole can be accomplished by the Fe^(3+)released through the etching of Fe_(3)O_(4) by HCl acid.Thus,the etching time has a significant effect on the morphology,structure,composition a nd ORR performance of Fe_(1-x)S@NSC-t.Based on the cha racterizations,we find Fe_(1-x)S@NSC-24 can realize effective and balanced combination of Fe_(1-x)S and NSC,possessing porous core-shell architecture,optimized structure defect,specific surface area and doped heteroatoms configurations(especially for pyridinic N,graphitic N and Fe-N structure).These features thus lead to outstanding catalytic activity and cycling stability towards ORR.Our work provides a good guidance on the design of TMC/carbon-based electrodes with unique stable morphology and optimized structure and composition.

Preparation of Phenolic Resin/Silver Nanocomposites via in-situ Reduction

Resol type phenolic resin/silver nanocomposite was prepared by in-situ reduction method, in which the curing of phenolic resin and the formation of silver nano-particles took place simultaneously. The silver ions were reduced completely to silver nanoparticles, which were dispersed homogeneously in the resin matrix with narrow size distribution.

Evaluation of In-situ Sludge Reduction and Enhanced Nutrient Removal in an Integrated Repeatedly Coupling Aerobic and Anaerobic and Oxic-setting-anaerobic System

Aiming to achieve simultaneous good performances of in-situ sludge reduction and effluent quality,an integrated repeatedly coupling aerobic and anaerobic and oxic-setting-anaerobic system( r CAA + OSA) is developed to reduce sludge production and enhance nutrient removal. Considering the mechanism of in-situ sludge reduction in this r CAA +OSA system,the combined effect of energy uncoupling metabolism and sludge cryptic growth maybe attributed to the higher reduction of biomass. Results show that the maximal sludge reduction in this r CAA + OSA system is obtained when the hydraulic retention time( HRT) is controlled at6. 5 h,which an increase in 16. 67% reduction in excess sludge is achieved compared with OSA system( HRT of 6. 5 h). When compared the performances of effluent qualities,the enhanced nutrient removal efficiencies also can be observed in this r CAA + OSA system. Three-dimensional excitation emission matrix( 3D-EEM)fluorescence spectroscopy is applied to characterize the effluent organic matters( Ef OM) under different HRTs in the OSA and the r CAA+OSA systems. Analyses of 3D-EEM spectra show that more refractory humic-like and fulvic-like components are observed in the effluent of the OSA system. On the basis of these results,simultaneous enhanced in-situ sludge reduction and improved nutrient removal can be obtained in the r CAA +OSA systems.

Sulphur-doped ordered mesoporous carbon with enhanced electrocatalytic activity for the oxygen reduction reaction

Metal-free, heteroatom functionalized carbon-based catalysts have made remarkable progress in recent years in a wide range of applications related to energy storage and energy generation. In this study, high surface area mesoporous ordered sulphur doped carbon materials are obtained via one-pot hydrothermal synthesis of carbon/SBA-15 composite after removal of in-situ synthesized hard template SiO2. 2-thiophenecarboxy acid as sulphur source gives rise to sulphur doping level of 5.5 wt%. Comparing with pristine carbon, the sulphur doped mesoporous ordered carbon demonstrates improved electro-catalytic activity in the oxygen reduction reaction in alkaline solution. (C) 2016 Science Press and Dalian Institute of Chemical Physics, Chinese Academy of Sciences. Published by Elsevier B.V. and Science Press. All rights reserved.

A Review of In‑Situ Techniques for Probing Active Sites and Mechanisms of Electrocatalytic Oxygen Reduction Reactions

Electrocatalytic oxygen reduction reaction(ORR)is one of the most important reactions in electrochemical energy technologies such as fuel cells and metal–O2/air batteries,etc.However,the essential catalysts to overcome its slow reaction kinetic always undergo a complex dynamic evolution in the actual catalytic process,and the concomitant intermediates and catalytic products also occur continuous conversion and reconstruction.This makes them difficult to be accurately captured,making the identification of ORR active sites and the elucidation of ORR mechanisms difficult.Thus,it is necessary to use extensive in-situ characterization techniques to proceed the real-time monitoring of the catalyst structure and the evolution state of intermediates and products during ORR.This work reviews the major advances in the use of various in-situ techniques to characterize the catalytic processes of various catalysts.Specifically,the catalyst structure evolutions revealed directly by in-situ techniques are systematically summarized,such as phase,valence,electronic transfer,coordination,and spin states varies.In-situ revelation of intermediate adsorption/desorption behavior,and the real-time monitoring of the product nucleation,growth,and reconstruction evolution are equally emphasized in the discussion.Other interference factors,as well as in-situ signal assignment with the aid of theoretical calculations,are also covered.Finally,some major challenges and prospects of in-situ techniques for future catalysts research in the ORR process are proposed.

Mechanistic insight into N_2O formation during NO reduction by NH_3 over Pd/CeO_2 catalyst in the absence of O_2

N2O is a major by-product emitted during low-temperature selective catalytic reduction of NO with NH3(NH3-SCR), which causes a series of serious environmental problems. A full understanding of the N2O formation mechanism is essential to suppress the N2O emission during the low-temperature NH3-SCR, and requires an intensive study of this heterogeneous catalysis process. In this study, we investigated the reaction between NH3 and NO over a Pd/CeO2 catalyst in the absence of O2, using X-ray photoelectron spectroscopy, NH3-temperature-programmed desorption, NO-temperature-programmed desorption, and in-situ Fourier-transform infrared spectroscopy. Our results indicate that the N2O formation mechanism is reaction-temperature-dependent. At temperatures below 250 ℃, the dissociation of HON, which is produced from the reaction between surface H· adatoms and adsorbed NO, is the key process for N2O formation. At temperatures above 250 ℃,the reaction between NO and surface N·, which is produced by NO dissociation, is the only route for N2O formation, and the dissociation of NO is the rate-determining step. Under optimal reaction conditions, a high performance with nearly 100% NO conversion and 100% N2 selectivity could be achieved. These results provide important information to clarify the mechanism of N2O formation and possible suppression of N2 O emission during low-temperature NH3-SCR.

Slope analysis based on local strength reduction method and variable-modulus elasto-plastic model

Employing an ideal elasto-plastic model,the typically used strength reduction method reduced the strength of all soil elements of a slope.Therefore,this method was called the global strength reduction method(GSRM).However,the deformation field obtained by GSRM could not reflect the real deformation of a slope when the slope became unstable.For most slopes,failure occurs once the strength of some regional soil is sufficiently weakened; thus,the local strength reduction method(LSRM)was proposed to analyze slope stability.In contrast with GSRM,LSRM only reduces the strength of local soil,while the strength of other soil remains unchanged.Therefore,deformation by LSRM is more reasonable than that by GSRM.In addition,the accuracy of the slope's deformation depends on the constitutive model to a large degree,and the variable-modulus elasto-plastic model was thus adopted.This constitutive model was an improvement of the Duncan–Chang model,which modified soil's deformation modulus according to stress level,and it thus better reflected the plastic feature of soil.Most importantly,the parameters of the variable-modulus elasto-plastic model could be determined through in-situ tests,and parameters determination by plate loading test and pressuremeter test were introduced.Therefore,it is easy to put this model into practice.Finally,LSRM and the variable-modulus elasto-plastic model were used to analyze Egongdai ancient landslide.Safety factor,deformation field,and optimal reinforcement measures for Egongdai ancient landslide were obtained based on the proposed method.

Preparation of ultrafine WC-10Co composite powders by reduction and carbonization

A solid state synthesis of ultrafine/nanocrystalline WC-10Co composite powders was reported from WO3 , Co3O4 and carbon powders after reduction and carburization at relatively low temperatures in a short time under pure H2 atmosphere. The effects of ball milling time and reaction temperature on the preparation of ultrafine/nanocrystalline WC-Co composite powders were studied using X-ray diffraction and scanning electron microscope (SEM). The results show that fine mixed oxide powders (WO3 , Co3O4 and carbon powders) can be obtained by long time ball milling. Increasing the reaction temperature can decrease the formation of Co3W3C and graphite phases and increase the WC crystallite size. Long-time ball milling and high reaction temperature are favorable to obtain fine and pure composite powders consisting of nanocrystalline WC from WO3 , Co3O4 and carbon powders.

Inner-pore reduction nucleation of palladium nanoparticles in highly conductive wurster-type covalent organic frameworks for efficient oxygen reduction electrocatalysis

Covalent organic frameworks(COFs)have emerged as a class of promising supports for electrocatalysis because of their advantages including good crystallinity,highly ordered pores,and structural diversity.However,their poor conductivity represents the main obstruction to their practical application.Here,we reported a novel synthesis strategy for synergistically endowing a triphenylamine-based COFs with improved electrical conductivity and excellent catalytic activity for oxygen reduction,via the in-situ redox deposition and confined growth of palladium nanoparticles inside the porous structure of COFs using reductive triphenylamine frameworks as reducing agent;meanwhile,the triphenylamine unit was oxidized to radical cation structure and affords radical cation COFs with conductivity as high as3.2*10^(-1) S m^(-1).Such a uniform confine palladium nanoparticle on highly conductive COFs makes it an efficient electrocatalyst for four-electron oxygen reduction reaction(4e-ORR),showing excellent activities and fast kinetics with a remarkable half-wave potential(E_(1/2))of 0.865 V and an ultralow Tafel slope of 39.7 mV dec^(-1) in alkaline media even in the absence of extra commercial conductive fillers.The generality of this strategy was proved by preparing the different metal and metal alloy nanoparticles supported on COFs(Au@COF,Pt@COF,AuPd@COF,AgPd@COF,and PtPd@COF)using reductive triphenylamine frameworks as reducing agent.This work not only provides a facile strategy for the fabrication of highly conductive COF supported ORR electrocatalysts,but also sheds new light on the practical application of Zn-air battery.

Research progress of precise structural regulation of single atom catalyst for accelerating electrocatalytic oxygen reduction reaction

The development and utilization of renewable clean energy can effectively solve the two major problems of energy and environment. As an efficient power generation device that converts hydrogen energy into electric energy, fuel cell has attracted more and more attention. For fuel cells, the oxygen reduction reaction(ORR) at the cathode is the core reaction, and the design and development of high-performance ORR catalysts remain quite challenging. Since the microenvironment of the active center of single atom catalysts(SACs) has an important influence on its catalytic performance, it has been a research focus to improve the ORR activity and stability of electrocatalysts by adjusting the structure of the active center through reasonable structural regulation methods. In this review, we reviewed the preparation and structure–activity relationship of SACs for ORR. Then, the structural precision regulation methods for improving the activity and stability of ORR electrocatalysts are discussed. And the advanced in-situ characterization techniques for revealing the changes of active sites in the electrocatalytic ORR process are summarized. Finally, the challenges and future design directions of SACs for ORR are discussed. This work will provide important reference value for the design and synthesis of SACs with high activity and stability for ORR.

Zeolite-mediated hybrid Cu^(+)/Cu~0 interface for electrochemical nitrate reduction to ammonia

The electrocatalytic conversion of reactive nitrogen species to ammonia is a promising strategy for efficient NH_(3) synthesis.In this study,we reveal that the hybrid Cu^(+)/Cu~0 interface is catalytically active for electrochemical ammonia synthesis from nitrate reduction.To maintain the hybrid Cu^(+)/Cu~0 state at negative reaction potentials,hydrophilic zeolite is used to modify Cu/Cu_(2)O electrocatalyst,which demonstrates an impressive NH_(3) production rate of 41.65 mg h^(-1) cm^(-2)with ~100% Faradaic efficiency of ammonia synthesis at-0.6 V vs.RHE.In-situ Raman spectroscopy unveil the high activity originates from the zeolite reconstruction at the electrode–electrolyte interface,which protects the valence state of Cu~0/Cu^(+) site under negative potential and promotes electrochemical activity towards NH_(3) synthesis.

Enhancing the electrocatalytic performance of nitrate reduction to ammonia by in-situ nitrogen leaching

Electrochemical nitrate reduction reaction (NITRR) is regarded as a “two birds-one stone” method for the treatment of nitrate contaminant in polluted water and the synthesis of valuable ammonia, which is retarded by the lack of highly reactive and selective electrocatalysts .Herein, for the first time, nickel foam supported Co_(4) N was designed as a high-performance NITRR catalyst by an in-situ nonmetal leaching-induced strategy.At the optimal potential, the Co_(4) N/NF catalyst achieves ultra-high Faraday efficiency and NH_(3) selectivity of 95.4% and 99.4%, respectively.Ex situ X-ray absorption spectroscopy (XAS), together with other experiments powerfully reveal that the nitrogen vacancies produced by nitrogen leaching are stable and play a key role in boosting nitrate reduction to ammonia.Theoretical calculations confirm that Co_(4) N with abundant nitrogen vacancies can optimize the adsorption energies of NO_(3)^(-) and intermediates, lower the free energy (Δ G ) of the potential-determining step (*NH_(3) to NH_(3) ) and inhibit the formation of N-containing byproducts.In addition, we also conclude that the nitrogen vacancies can stabilize the adsorbed hydrogen, making H_(2) quite difficult to produce, and lowering ΔG from *NO to *NOH, which facilitates the selective reduction of nitrate.This study reveals significant insights about the in-situ nonmetal leaching to enhance the NITRR activity.

Recovery and in-situ reduction of precious metals by graphdiyne and graphdiyne oxide for antibacterial use

Based on the in-situ self-reduction and chemical stability,graphdiyne(GDY)and graphdiyne oxide(GDYO)are used as trapping agents to investigate the ability for recovering Au^(3+),Ag^+,and Pd^(2+)under different pH values and interfering ions.Under strong acidity at pH=1,these two agents demonstrate high select recovery towards the three precious metal ions,which could be insitu reduced to nanoparticles(NPs).In addition,superparamagnetic Fe_(3)O_(4)NPs are deposited on the surfaces of GDY and GDYO.The magnetic responses enable GDYFe_(3)O_(4)to recover precious metals conveniently and efficiently by the aid of an external magnetic field.This study also confirms the antibacterial activity of the as-recovered NPs deposited on GDY and GDYO against Escherichia coli and Staphylococcus aureus(1×10^(5)colony-forming unit(CFU)·mL^(-1)),and the antibacterial rates are 100%.This strategy of recovering precious metals and subsequently reusing to combat pathogens will be of great significance for environmental remediation and biomedical applications.

In-situ sludge reduction based on Mn^(2+)-catalytic ozonation conditioning:Feasibility study and microbial mechanisms

To improve the sludge conditioning efficiency without increasing the ozone dose,an in-situ sludge reduction process based on Mn^(2+)-catalytic ozonation conditioning was proposed.Using ozone conditioning alone as a control,a lab-scale sequencing batch reactor coupled with ozonated sludge recycle was evaluated for its operating performance at an ozone dose of 75 mg O_(3)/g VSS and 1.5 mmol/L Mn^(2+)addition.The results showed a 39.4%reduction in MLSS and an observed sludge yield of 0.236 kg MLSS/kg COD for the O_(3)+Mn^(2+)group compared to the O_(3)group (15.3%and 0.292 kg MLSS/kg COD),accompanied by better COD,NH_(4)^(+)-N,TN and TP removal,improved effluent SS and limited impact on excess sludge properties.Subsequently,activity tests,BIOLOG ECO microplates and 16S rRNA sequencing were applied to elucidate the changing mechanisms of Mn^(2+)-catalytic ozonation related to microbial action:(1) Dehydrogenase activity reached a higher peak.(2) Microbial utilization of total carbon sources had an elevated effect,up to approximately 18%,and metabolic levels of six carbon sources were also increased,especially for sugars and amino acids most pronounced.(3) The abundance of Defluviicoccus under the phylum Proteobacteria was enhanced to 12.0%and dominated in the sludge,they had strong hydrolytic activity and metabolic capacity.Denitrifying bacteria of the genus Ferruginibacter also showed an abundance of 7.6%,they contributed to the solubilization and reduction of sludge biomass.These results could guide researchers to further reduce ozonation conditioning costs,improve sludge management and provide theoretical support.

Propane dehydrogenation catalyzed by in-situ partially reduced zinc cations confined in zeolites

Propane dehydrogenation(PDH), employing Pt-or Cr-based catalysts, represents an emerging industrial route for propylene production. Due to the scarcity of platinum and the toxicity of chromium, alternative PDH catalysts are being pursued. Herein, we report the construction of Zn-containing zeolite catalysts,namely Zn@S-1, for PDH reaction. Well-isolated zinc cations are successfully trapped and stabilized by the Si-OH groups in S-1 zeolites via in-situ hydrothermal synthesis. The as-prepared Zn@S-1 catalysts exhibit good dehydrogenation activity, high propylene selectivity, and regeneration capability in PDH reaction under employed conditions. The in-situ partial reduction of zinc species is observed and the partially reduced zinc cations are definitely identified as the active sites for PDH reaction.