Review of Iron-Based Catalysts for Carbon Dioxide Fischer-Tropsch Synthesis

Capturing and utilizing CO_(2)from the production process is the key to solving the excessive CO_(2)emission problem. CO_(2)hydrogenation with green hydrogen to produce olefins is an effective and promising way to utilize CO_(2)and produce valuable chemicals. The olefins can be produced by CO_(2)hydrogenation through two routes, i.e., CO_(2)-FTS (carbon dioxide Fischer- Tropsch synthesis) and MeOH (methanol-mediated), among which CO_(2)-FTS has significant advantages over MeOH in practical applications due to its relatively high CO_(2)conversion and low energy consumption potentials. However, the CO_(2)-FTS faces challenges of difficult CO_(2)activation and low olefins selectivity. Iron-based catalysts are promising for CO_(2)-FTS due to their dual functionality of catalyzing RWGS and CO-FTS reactions. This review summarizes the recent progress on iron-based catalysts for CO_(2)hydrogenation via the FTS route and analyzes the catalyst optimization from the perspectives of additives, active sites, and reaction mechanisms. Furthermore, we also outline principles and challenges for rational design of high-performance CO_(2)-FTS catalysts.

A critical review towards the causes of the iron-based catalysts deactivation mechanisms in the selective oxidation of hydrogen sulfide to elemental sulfur from biogas

Hydrogen sulfide(H_(2)S) not only presents significant environmental concerns but also induces severe corrosion in industrial equipment,even at low concentrations.Among various technologies,the selective oxidation of hydrogen sulfide(SOH_(2)S) to elemental sulfur(S) has emerged as a sustainable and environmentally friendly solution.Due to its unique properties,iron oxide has been extensively investigated as a catalyst for SOH_(2)S;however,rapid deactivation has remained a significant drawback.The causes of iron oxide-based catalysts deactivation mechanisms in SOH_(2)S,including sulfur or sulfate deposition,the transformation of iron species,sintering and excessive oxygen vacancy formation,and active site loss,are thoroughly examined in this review.By focusing on the deactivation mechanisms,this review aims to provide valuable insights into enhancing the stability and efficiency of iron-based catalysts for SOH_(2)S.

Effect of Manganese Incorporation Manner on an Iron-Based Catalyst for Fischer-Tropsch Synthesis

A systematic study was undertaken to investigate the effects of the manganese incorporation manner on the textural properties, bulk and surface phase compositions, reduction/carburization behaviors, and surface basicity of an iron-based Fischer-Tropsch synthesis （FTS） catalyst. The catalyst samples were characterized by N2 physisorption, X-ray photoelectron spectroscopy （XPS）, H2 （or CO） temperature-programmed reduction （TPR）, CO2 temperature-programmed desorption （TPD）, and M5ssbauer spectroscopy. The FTS performance of the catalysts was studied in a slurry-phase continuously stirred tank reactor （CSTR）. The characterization results indicated that the manganese promoter incorporated by using the coprecipitation method could improve the dispersion of iron oxide, and decrease the size of the iron oxide crystallite. The manganese incorporated with the impregnation method is enriched on the catalyst＇s surface. The manganese promoter added with the impregnation method suppresses the reduction and carburization of the catalyst in H2, CO, and syngas because of the excessive enrichment of manganese on the catalyst surface. The catalyst added manganese using the coprecipitation method has the highest CO conversion （51.9%） and the lowest selectivity for heavy hydrocarbons （C12＋）.

Effect of Al_2O_3 Binder on the Precipitated Iron-Based Catalysts for Fischer-Tropsch Synthesis

A series of iron-based Fischer-Tropsch synthesis （FTS） catalysts incorporated with Al2O3 binder were prepared by the combination of co-precipitation and spray drying technology. The catalyst samples were characterized by using N2 physical adsorption, temperature-programmed reduction/desorption （TPR/TPD） and MSssbauer effect spectroscopy （MES） methods. The characterization results indicated that the BET surface area increases with increasing Al2O3 content and passes through a maximum at the Al2O3/Fe ratio of 10/100 （weight basis）. After the point, it decreases with further increase in Al2O3 content. The incorporation of Al2O3 binder was found to weaken the surface basicity and suppress the reduction and carburization of iron-based catalysts probably due to the strong K-Al2O3 and Fe-Al2O3 interactions. Furthermore, the H2 adsorption ability of the catalysts is enhanced with increasing Al2O3 content. The FTS performances of the catalysts were tested in a slurry-phase continuously stirred tank reactor （CSTR） under the reaction conditions of 260 ℃, 1.5 MPa, 1000 h^-1 and molar ratio of H2/CO 0.67 for 200 h. The results showed that the addition of small amounts of Al2O3 affects the activity of iron-based catalysts to a little extent. However, with further increase of Al2O3 content, the FTS activity and water gas shift reaction （WGS） activity are decreased severely. The addition of appropriate Al2O3 do not affect the product selectivity, but the catalysts incorporated with large amounts of Al2O3 have higher selectivity for light hydrocarbons and lower selectivity for heavy hydrocarbons.

Promoter effect on the CO_2-H_2O formation during Fischer-Tropsch synthesis on iron-based catalysts

The effects of Mg,La and Ca promoters on primary and secondary CO2 and H2O formation pathways during Fischer-Tropsch synthesis on precipitated Fe/Cu/SiO2 catalysts are investigated.The chemisorbed oxygen atoms in the primary pathway formed in the CO dissociation steps reacted with co-adsorbed hydrogen or carbon monoxide to produce H2O and CO2,respectively.The secondary pathway was the water-gas shift reaction.The results indicated that the CO2 production led to an increase in both primary and secondary pathways,and H2O production decreased when surface basicity of the catalyst increased in the order Ca 〉 Mg 〉 La.

Effect of Addition Sequence during Neutralization and Precipitation on Iron-based Catalysts for High Temperature Shift Reaction

The preparation of the iron-based catalysts promoted by cobalt with a small amount of copper and aluminum for the high temperature shift reaction （HTS） with different sequences of adding catalyst raw materials during neutralization and precipitation was investigated. XRD, BET and particle size distribution （PSD） were used to characterize the prepared catalysts. It was found that the catalyst crystals were all γ-Fe2O3, and the intermediate of the catalyst after aging was Fe3O4. The crystallographic form of the catalyst and its intermediate was not affected by the addition sequence in the neutralization and precipitation process. The results showed that the specific surface area and the particle size of the catalysts depended on the addition sequence to the mother liquor. Cobalt with a small amount of copper and aluminum could increase the specific surface area and decrease the particle size of catalysts.

KINETICS OF IRON-BASED CATALYST IN TEMPERATURE-PROGRAMMED REDUCTION

In this work, Temperature-Programmed Reduction Processes of iron oxide and 12 other kinds of promoted iron oxides were investigated. It is suggested that the reduction activation energy can be expressed as a normal distribution. The distribution parameters were obtained by kinetic data fitting, which depends on the chemical and geometric characteristics of both the iron oxide and the promoter.

Towards advanced removal of organics in persulfate solution by heterogeneous iron-based catalyst:A review

Heterogeneous iron-based catalysts have drawn increasing attention in the advanced oxidation of persulfates due to their abundance in nature,the lack of secondary pollution to the environment,and their low cost over the last a few years.In this paper,the latest progress in the research on the activation of persulfate by heterogeneous iron-based catalysts is reviewed from two aspects,in terms of synthesized catalysts(Fe0,Fe_(2)O_(3),Fe_(3)O_(4),FeOOH)and natural iron ore catalysts(pyrite,magnetite,hematite,siderite,goethite,ferrohydrite,ilmenite and lepidocrocite)focusing on efforts made to improve the performance of catalysts.The advantages and disadvantages of the synthesized catalysts and natural iron ore were summarized.Particular interests were paid to the activation mechanisms in the catalyst/PS/pollutant system for removal of organic pollutants.Future research challenges in the context of field application were also discussed.

Research progress of alkaline earth metal iron-based oxides as anodes for lithium-ion batteries

Anode materials are an essential part of lithium-ion batteries(LIBs),which determine the performance and safety of LIBs.Currently,graphite,as the anode material of commercial LIBs,is limited by its low theoretical capacity of 372 mA·h·g^(−1),thus hindering further development toward high-capacity and large-scale applications.Alkaline earth metal iron-based oxides are considered a promising candidate to replace graphite because of their low preparation cost,good thermal stability,superior stability,and high electrochemical performance.Nonetheless,many issues and challenges remain to be addressed.Herein,we systematically summarize the research progress of alkaline earth metal iron-based oxides as LIB anodes.Meanwhile,the material and structural properties,synthesis methods,electrochemical reaction mechanisms,and improvement strategies are introduced.Finally,existing challenges and future research directions are discussed to accelerate their practical application in commercial LIBs.

Electronic Structure Investigation of 12442 Iron-Based Superconductors Based on Block-Layer Model

Superconducting transition temperature(Tc),as a crucial parameter,exploring its relationship with various macroscopic and microscopic factors helps to understand the mechanism of high-temperature superconductivity from multiple perspectives,aiding in a multidimensional comprehension of high-temperature superconductivity mechanisms.Drawing inspiration from the block-layer structure models of cuprate superconductors,we computationally investigated the interlayer interaction energies in the 12442-type iron-based superconducting materials AkCa_(2)Fe_(4)As_(4)F_(2)(Ak=K,Rb,Cs)systems based on the block-layer model and explored their relationship with Tc.We observed that an increase in interlayer combinative energy leads to a decrease in Tc,while conversely,a decrease in interlayer combination energy results in an increase in Tc.Further,we found that the contribution of the Fe 3d band structure,especially the 3dz2 orbital,to charge transfer is significant.

Physico-chemical structure evolution characteristics of coal char during gasification in the presence of iron-based waste catalyst

The present study aims to explore the physico-chemical structure evolution characteristic during Yangchangwan bituminous coal(YCW)gasification in the presence of iron-based waste catalyst(IWC).The catalytic gasification reactivity of YCW was measured by thermogravimetric analyzer.Scanning electron microscope–energy dispersive system,nitrogen adsorption analyzer and laser Raman spectroscopy were employed to analyze the char physico-chemical properties.The results show that the optimal IWC loading ratio was 5 wt%at 1000°C.The distribution of IWC on char was uneven and Fe catalyst concentrated on the surface of some chars.The specific surface area of YCW gasified semi-char decreased significantly with the increase of gasification time.i.e.,the specific surface area reduced from 382 m2/g(0 min)to 192 m2/g(3 min),meanwhile,the number of micropores and mesopores decreased sharply at the late gasification stage.The carbon microcrystalline structure of YCW gasified semi-char was gradually destroyed with the increase of gasification time,and the microcrystalline structure with small size was gradually generated,resulting in the decreasing order degree of carbon microcrystalline structure.IWC can catalyze YCW gasification which could provide theoretical guidance for industrial solid waste recycling.

Direct decomposition of nitric oxide in low temperature over iron-based perovskite-type catalyst modified by Ru

Iron-based perovskite-type compounds modified by Ru were prepared through sol-gel process to study its catalytic activity of NOx direct decomposition at low temperature and evaluate the conversion of NO under the experimental conditions. The catalytic activity of La 0.9Ce 0.1Fe 0.8-nCo 0.2RunO3 （n=0.01,0.03,0.05,0.07,0.09）series for the NO, NO-CO two components, CO-HC-NO three components were also analyzed. The catalytic investigation evidenced that the presence of Ru is necessary for making highly activity in decomposition of nitric oxide even at low temperature（400 ℃）and La 0.9Ce 0.9Fe 0.75Co 0.2Ru 0.05O3 （n=0.05） has better activity in all the samples, the conversion of it is 58.5%. With the reducing gas（CO,C3H6）added into the gas, the catalyst displayed very high activity in decomposition of NO and the conversion of it is 80% and 92.5% separately.

Recent advances in iron-based sulfides electrocatalysts for oxygen and hydrogen evolution reaction

Increasing environmental pollution and shortage of conventional fossil fuels have made it urgent to develop renewable and clean energy sources. Electrocatalytic water splitting, with its abundant raw materials, simple process, and zero carbon emission, is considered one of the most promising processes for producing carbon-neutral hydrogen which has excellent energy conversion efficiency and high gravimetric energy density. Among them, oxygen evolution reaction (OER) electrocatalysts and hydrogen evolution reaction (HER) electrocatalysts are critical to decreasing the intrinsic reaction energy barrier and boosting the hydrogen evolution efficiency. Therefore, it is imperative to develop and design low-cost, highly active, and stable OER and HER electrocatalysts to lower the overpotential and drive the electrocatalytic reactions. Transition metal sulfides, especially iron-based sulfides, have attracted extensive exploration by researchers as a result of its high abundance in the Earth's crust and near-metallic conductivity. Consequently, in this review, we systematically and comprehensively summarize the progress in the application of iron-based sulfides and their composites as OER and HER electrocatalysts in electrocatalysis. Detailed descriptions and illustrations of the special relationships among their composition, structure, and electrocatalytic performance are presented. Finally, this review points out the challenges and future prospects of iron-based sulfides in practical applications for designing and fabricating more promising iron-based sulfide OER and HER electrocatalysts. We believe that iron-based sulfide materials will have a wide range of application prospects as OER and HER electrocatalysts in the future.

New Iron-based SiC Spherical Composite Magnetic Abrasive for Magnetic Abrasive Finishing

SiC magnetic abrasive is used to polish surfaces of precise, complex parts which are hard, brittle and highly corrosion-resistant in magnetic abrasive finishing（MAF）. Various techniques are employed to produce this magnetic abrasive, but few can meet production demands because they are usually time-consuming, complex with high cost, and the magnetic abrasives made by these techniques have irregular shape and low bonding strength that result in low processing efficiency and shorter service life. Therefore, an attempt is made by combining gas atomization and rapid solidification to fabricate a new iron-based SiC spherical composite magnetic abrasive. The experimental system to prepare this new magnetic abrasive is constructed according to the characteristics of gas atomization and rapid solidification process and the performance requirements of magnetic abrasive. The new iron-based SiC spherical composite magnetic abrasive is prepared successfully when the machining parameters and the composition proportion of the raw materials are controlled properly. Its morphology, microstructure, phase composition are characterized by scanning electron microscope（SEM） and X-ray diffraction（XRD） analysis. The MAF tests on plate of mold steel S136 are carried out without grinding lubricant to assess the finishing performance and service life of this new SiC magnetic abrasive. The surface roughness（Ra） of the plate worked is rapidly reduced to 0.051 μm from an initial value of 0.372 μm within 5 min. The MAF test is carried on to find that the service life of this new SiC magnetic abrasive reaches to 155 min. The results indicate that this process presented is feasible to prepare the new SiC magnetic abrasive; and compared with previous magnetic abrasives, the new SiC spherical composite magnetic abrasive has excellent finishing performance, high processing efficiency and longer service life. The presented method to fabricate magnetic abrasive through gas atomization and rapid solidification presented can significantly improve the finishing performance and service life of magnetic abrasive, and provide a more practical approach for large-scale industrial production of magnetic abrasive.

Signal Detection of Carbon in Iron-Based Alloy by Double-Pulse Laser-Induced Breakdown Spectroscopy

Although single-pulse lasers are often used in traditional laser-induced breakdown spectroscopy （LIBS） measurements, their measurement outcomes are generally undesirable because of the low sensitivity of carbon in iron-based alloys. In this article, a double-pulse laser was applied to improve the signal intensity of carbon. Both the inter-pulse delay and the combination of laser wavelengths in double-pulse laser-induced breakdown spectroscopy （DP-LIBS） were optimized in our experiment. At the optimized inter-pulse delay, the combination of a first laser of 532 nm and a second laser of 1,064 nm achieved the highest signal enhancement. The properties of the target also played a role in determining the mass ablation enhancement in DP-LIBS configuration.

Crystal chemistry and structural design of iron-based superconductors

The second class of high-temperature superconductors （HTSCs）, iron-based pnictides and chalcogenides, necessarily contain Fe2X2 （＂X＂ refers to a pnictogen or a chalcogen element） layers, just like the first class of HTSCs which possess the essential CuO2 sheets. So far, dozens of iron-based HTSCs, classified into nine groups, have been discovered. In this article, the crystal-chemistry aspects of the known iron-based superconductors are reviewed and summarized by employing ＂hard and soft acids and bases （HSAB）＂ concept. Based on these understandings, we propose an alternative route to exploring new iron-based superconductors via rational structural design.

Angle-resolved photoemission spectroscopy study on iron-based superconductors

Angle-resolved photoemission spectroscopy （ARPES） has played an important role in determining the band structure and the superconducting gap structure of iron-based superconductors. In this paper, from the ARPES perspective, we briefly review the main results from our group in recent years on the iron-based superconductors and their parent compounds, and depict our current understanding on the antiferromagnetism and superconductivity in these materials.

Corrosion properties of high silicon iron-based alloys in nitric acid

The effect of copper and rare-earth elements on corrosion behavior of high silicon iron-based alloys in nitric acid was studied by means of static and loading current corrosion experiments.The anodic polarization curve was also made to discuss the corrosion mechanism.The examination on alloy microstructure and SEM corrosion pattern showed that when silicon content reached 14.5%,the Fe3Si phase appeared and the primary structure of the iron-base alloy was ferrite.When adding 4.57% copper in the iron alloy,its corrosion resistance in static diluted sulfuric acid was improved while its corrosion resistance and electrochemical corrosion properties in the nitric acid were decreased.In contrast,the addition of rare earth elements could improve the corrosion properties in all above conditions including in static diluted sulfuric acid and in nitric acid.

Electronic structure and spatial inhomogeneity of iron-based superconductor FeS

Iron-based superconductor family FeX(X=S,Se,Te)has been one of the research foci in physics and material science due to their record-breaking superconducting temperature(FeSe film)and rich physical phenomena.Recently,FeS,the least studied Fe X compound(due to the difficulty in synthesizing high quality macroscopic crystals)attracted much attention because of its puzzling superconducting pairing symmetry.In this work,combining scanning tunneling microscopy and angle resolved photoemission spectroscopy(ARPES)with sub-micron spatial resolution,we investigate the intrinsic electronic structures of superconducting FeS from individual single crystalline domains.Unlike FeTe or FeSe,FeS remains identical tetragonal structure from room temperature down to 5 K,and the band structures observed can be well reproduced by our ab-initio calculations.Remarkably,mixed with the 1×1 tetragonal metallic phase,we also observe the coexistence of √5×√5 reconstructed insulating phase in the crystal,which not only helps explain the unusual properties of FeS,but also demonstrates the importance of using spatially resolved experimental tools in the study of this compound.

Application and mechanism of Fenton-like iron-based functional materials for arsenite removal

Between the two major arsenic-containing salts in natural water, arsenite(As(Ⅲ)) is far more harmful to human and the environment than arsenate(As(V)) due to its high toxicity and transportability. Therefore, preoxidation of As(Ⅲ) to As(V) is considered to be an effective means to reduce the toxicity of arsenic and to promote the removal efficiency of arsenic. Due to their high catalytic activity and arsenic affinity, iron-based functional materials can quickly oxidize As(Ⅲ) to As(V) in heterogeneous Fenton-like systems, and then remove As(V) from water through adsorption and surface coprecipitation. In this review, the effects of different iron-based functional materials such as zero-valent iron and iron(hydroxy) oxides on arsenic removal are compared, and the catalytic oxidation mechanism of As(Ⅲ) in heterogeneous Fenton process is further clarified. Finally, the main challenges and opportunities faced by iron-based As(Ⅲ) oxidation functional materials are prospected.