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.

Synthesis of cation exchange resin-supported iron and magnesium oxides/hydroxides composite for nitrate removal in water

In this study,we reported on the concept and practical use of cation exchange resin(CER)for removing anions in water via pretreating the CER with metal salts.The cation exchange resinsupported iron and magnesium oxides/hydroxides composite(FeMg/CER)was synthesized and introduced as a new and potential adsorbent for selective removal of nitrate ion in the water environment.Characteristics of FeMg/CER were determined by techniques such as Fouriertransform infrared spectroscopy,scanning electron microscopy,and Xray diffraction.The results showed that FeMg/CER material had a high nitrate adsorption capacity of 200 mg NO_(3)^()·g^(1)with a fast equilibrium adsorption time of 30 min at pH 5.In addition,it had good durability of at least 10 times of regeneration,which could be applied to practical water and wastewater treatment.

复杂染料废水降解过程中生物炭对Aeromonas hydrophila菌的影响

生物降解复杂染料废水过程中细菌活性是有效降解的关键。本研究分离驯化出染料废水降解菌,并对其进行形态学特征和系统发育的分析鉴定,将生物炭及Fe_(2)O_(3)/生物炭(Fe-BC)分别与菌构建复合体系,研究降解过程中生物炭和Fe-BC对菌的影响。结果表明,该降解菌为Aeromonashydrophila(嗜水气单胞菌菌属),生物炭-菌和Fe-BC-菌体系中降解脱色率分别提高18%和75%,降解脱色过程符合准一级动力学模型。在Fe-BC-菌体系中,Fe-BC可以促进菌细胞的代谢和细胞间的物质传递,使得参与代谢的N、P、S、Ca、Na及Fe等元素含量增加,并促使细胞产生胞外分泌物。Fe^(2+)参与菌降解复杂有机物的过程,降解产物主要有N-2-(3,4-二羟苯基)-乙基甲胺、2,3-二氢-1,3-二氧-1H-异吲哚-5-羧酸(含C=O)及甲氧基乙酸甲酯(含C—O)。生物炭与Fe-BC可以提高嗜水气单胞菌的生物活性,完成对复杂染料废水的降解脱色.

Caveolin‑1 is critical for hepatic iron storage capacity in the development of nonalcoholic fatty liver disease

Background:Nonalcoholic fatty liver disease(NAFLD)is associated with disordered lipid and iron metabolism.Our previous study has substantiated the pivotal role of Caveolin-1(Cav-1)in protecting hepatocytes and mediating iron metabolism in the liver.This study aimed to explore the specific mechanisms underlying the regulation of iron metabolism by Cav-1 in NAFLD.Methods:Hepatocyte-specific Cav-1 overexpression mice and knockout mice were used in this study.Cav-1-knockdown of RAW264.7 cells and mouse primary hepatocytes were performed to verify the changes in vitro.Moreover,a high-fat diet and palmitic acid plus oleic acid treatment were utilized to construct a NAFLD model in vivo and in vitro,respectively,while a high-iron diet was used to construct an in vivo iron overload model.Besides,iron concentration,the expression of Cav-1 and iron metabolism-related proteins in liver tissue or serum were detected using iron assay kit,Prussian blue staining,Western blotting,immunofluorescence staining,immunohistochemical staining and ELISA.The related indicators of lipid metabolism and oxidative stress were evaluated by the corresponding reagent kit and staining.Results:Significant disorder of lipid and iron metabolism occurred in NAFLD.The expression of Cav-1 was decreased in NAFLD hepatocytes(P<0.05),accompanied by iron metabolism disorder.Cav-1 enhanced the iron storage capacity of hepatocytes by activating the ferritin light chain/ferritin heavy chain pathway in NAFLD,subsequently alleviating the oxidative stress induced by excess ferrous ions in the liver.Further,CD68^(+) CD163^(+) macrophages expressing Cav-1 were found to accelerate iron accumulation in the liver,which was contrary to the effect of Cav-1 in hepatocytes.Positive correlations were also observed between the serum Cav-1 concentration and the serum iron-related protein levels in NAFLD patients and healthy volunteers(P<0.05).Conclusions:These findings confirm that Cav-1 is an essential target protein that regulates iron and lipid metabolic homeostasis.It is a pivotal molecule for predicting and protecting against the development of NAFLD.

Striking Stabilization Effect of Spinel Cobalt Oxide Oxygen Evolution Electrocatalysts in Neutral pH by Dual-Sites Iron Incorporation

Developing stable and efficient nonprecious-metal-based oxygen evolution catalysts in the neutral electrolyte is a challenging but essential goal for various electrochemical systems.Particularly,cobalt-based spinels have drawn a considerable amount of attention but most of them operate in alkali solutions.However,the frequently studied Co-Fe spinel system never exhibits appreciable stability in nonbasic conditions,not to mention attract further investigation on its key structural motif and transition states for activity loss.Herein,we report exceptional stable Co-Fe spinel oxygen evolution catalysts(~30%Fe is optimal)in a neutral electrolyte,owing to its unique metal ion arrangements in the crystal lattice.The introduced iron content enters both the octahedral and tetrahedral sites of the spinel as Fe^(2+)and Fe^(3+)(with Co ions having mixed distribution as well).Combining density functional theory calculations,we find that the introduction of Fe to Co_(3)O_(4)lowers the covalency of metal-oxygen bonds and can help suppress the oxidation of Co^(2+/3+)and 0^(2-).It implies that the Co-Fe spinel will have minor surface reconstruction and less lattice oxygen loss during the oxygen evolution reaction process in comparison with Co_(3)O_(4)and hence show much better stability.These findings suggest that there is still much chance for the spinel structures,especially using reasonable sublattices engineering via multimetal doping to develop advanced oxygen evolution catalysts.

Carbon Monoxide Modulates Auxin Transport and Nitric Oxide Signaling in Plants under Iron Deficiency Stress

Carbon monoxide(CO)and nitric oxide(NO)are signal molecules that enhance plant adaptation to environmental stimuli.Auxin is an essential phytohormone for plant growth and development.CO and NO play crucial roles in modulating the plant’s response to iron deficiency.Iron deficiency leads to an increase in the activity of heme oxygenase(HO)and the subsequent generation of CO.Additionally,it alters the polar subcellular distribution of Pin-Formed 1(PIN1)proteins,resulting in enhanced auxin transport.This alteration,in turn,leads to an increase in NO accumulation.Furthermore,iron deficiency enhances the activity of ferric chelate reductase(FCR),as well as the expression of the Fer-like iron deficiency-induced transcription factor 1(FIT)and the ferric reduction oxidase 2(FRO2)genes in plant roots.Overexpression of the long hypocotyl 1(HY1)gene,which encodes heme oxygenase,or the CO donor treatment resulted in enhanced basipetal auxin transport,higher FCR activity,and the expression of FIT and FRO2 genes under Fe deficiency.Here,a potential mechanism is proposed:CO and NO interact with auxin to address iron deficiency stress.CO alters auxin transport,enhancing its accumulation in roots and up-regulating key iron-related genes like FRO2 and IRT1.Elevated auxin levels affect NO signaling,leading to greater sensitivity in root development.This interplay promotes FCR activity,which is crucial for iron absorption.Together,these molecules enhance iron uptake and root growth,revealing a novel aspect of plant physiology in adapting to environmental stress.

High temperature oxidation of inoculated high Si/SiMo ductile cast irons in air and combustion atmospheres

The present work aims to investigate the effect of heating temperature(400,600 and 800°C)and inoculating elements(Ca,Ca-Ba,Ca-RE)on oxidation behavior of ductile irons containing 5.25%Si and 4.8%Si-2.3%Mo in dry air and combustion gas containing water vapour(natural gas burning).The oxidation is influenced by the gas atmosphere type,the iron alloying system,and the inoculating elements depending on the heating temperature.The weight gain increases from 0.001%-0.1%(400°C)to 0.05%-0.70%(600°C)and up to 0.10%-2.15%(800°C).No particular effects of the considered influencing factors are found when heating at 400°C,while at 600°C,mainly the oxidation gas atmosphere type shows a visible influence.At the highest heating temperature of 800°C,a limited increase of the weight gain is found for dry air atmosphere(up to 0.25%),but it drastically increases for combustion atmospheres(0.65%-2.15%).The water vapour presence in the combustion atmosphere is an important oxidising factor at 600-800°C.The alloying system appears to influence the oxidation behavior mainly at a heating temperature of 800°C in the combustion atmosphere,as evidenced by the lower weight gain in 5.25%silicon cast iron.Positive effects of inoculating elements increase with the heating temperature,with Ca and Ba-FeSi inoculation generally showing better performance.Irons inoculated with CaRE-FeSi exhibit a higher degree of oxidation.These results are in good relationship with the previous reported data:Ca-Ba-inoculation system appears to be better than simple Ca for improving the graphite parameters,while RE-bearing inoculant negatively affects the compactness degree of graphite particles in high-Si ductile irons.As the lower compactness degree is typical for graphite nodules in high-Si ductile irons,which negatively affects the oxidation resistance,it is necessary to employ specific metallurgical treatments to improve nodule quality.Inoculation,in particular,is a potential method to achieve this improvement.

Effect of competing solutes on arsenic(Ⅴ) adsorption using iron and aluminum oxides

The study focused on the effect of several typical competing solutes on removal of arsenic with Fe2O3 and Al2O3. The test results indicate that chloride, nitrate and sulfate did not have detectable effects, and that selenium（Ⅳ） （Se（Ⅳ）） and vanadium（Ⅴ） （V（Ⅴ）） showed slight effects on the adsorption of As（Ⅴ） with Fe2O3. The results also showed that adsorption of As（Ⅴ） on A12O3 was not affected by chloride and nitrate anions, but slightly by Se（Ⅳ） and V（Ⅴ） ions. Unlike the adsorption of As（Ⅴ） with Fe2O3, that with Fe2O3 was affected by the presence of sulfate in water solutions. Both phosphate and silica have significant adverse effects on the adsorption of As（Ⅴ） adsorption with Fe2O3 and Al2O3. Compared to the other tested anions, phosphate anion was found to be the most prominent solute affecting the As（Ⅴ） adsorption with Fe2O3 and Al2O3. In general, Fe2O3 has a better performance than Al2O3 in removal of As（Ⅴ） within a water environment where multi competing solutes are present.

Selective catalytic oxidation of NO over iron and manganese oxides supported on mesoporous silica

The selective catalytic oxidation （SCO） of NO was studied on a catalyst consisting of iron-manganese oxide supported on mesoporous silica （MPS） with different Mn/Fe ratios. Effects of the amount of manganese and iron, oxygen, and calcination temperature on NO conversion were also investigated. It was found that the Mn-Fe/MPS catalyst with a Mn/Fe molar ratio of 1 showed the highest activity at the calcination temperature of 400 °C. The results showed that over this catalyst, NO conversion reached 70% under the condition of 280 °C and a space velocity of 5000 h-1. SO2 and H2O had no adverse impact on the reaction activity when the SCO reaction temperature was above 240 °C. In addition, the SCO activity was suppressed gradually in the presence of SO2 and H2O below 240 °C, and such an effect was reversible after heating treatment.

Study on Kinetics of Iron Oxide Reduction by Hydrogen

Kinetics parameters of iron oxide reduction by hydrogen were evaluated by the isothermal method in a differential micro-packed bed. Influence of external diffusion, internal diffusion and heat transfer on the intrinsic reaction rate was investigated and the conditions free of internal and external diffusion resistance have been determined. In the experiments, in order to correctly evaluate the intrinsic kinetics parameters for reducing Fe203 to Fe3O4, the reaction temperatures were set between 440 ℃ and 490 ℃. However, in order to distinguish the reduction of Fe304 to FeO from that of FeO to Fe, the reaction temperature in the experiment was set to be greater than 570 ℃. Intrinsic kinetics of iron oxide reduction by hydrogen was established and the newly established kinetic models were validated by the experimental data.

Dissolution kinetics of iron oxides in clay in oxalic acid solutions

Clay samples containing 8.15% iron oxides and 27.49% alumina were leached in oxalic acid. Leaching experiments were per-formed in aqueous solutions of oxalic acid of 0.2-2 mol/L at 40-80 C for up to 90 min. The mixed kinetic mechanism, i.e., t/τ=[（1 2X/3） （1 X）2/3 ]＋b[ 1 （1 X）1/3], seemed to be the most appropriate one to fit the kinetic data of leaching iron oxides contained in clay in the aqueous oxalic acid solutions. The Arrhenius activation energy for leaching in the 1.8 mol/L oxalic acid was found to be 41.035 kJ/mol.

Column adsorption of Cu(Ⅱ) by polymer-supported nano-iron oxides in the presence of sulfate: Experimental and mathematical modeling

Polymer-supported hydrous iron oxides(HFOs) are promising for heavy metals removal from aqueous systems.The ubiquitous inorganic ligands, e.g., sulfate, are expected to exert considerable impacts on pollutants removal by these hybrid sorbents. Herein, we obtained a hybrid sorbent HFO-PS by encapsulating nanosized HFO into macroporous polystyrene(PS) resin. Both batch and column sorption experiments of Cu(Ⅱ) by HFO-PS were carried out in the presence of sulfate. Obviously, the presence of sulfate is favorable for Cu(Ⅱ) sorption onto HFO-PS.The performances of column Cu(Ⅱ) removal were fitted and predicted with Adams–Bohart, Clark, Thomas and BDST models. Thomas model is suggested best-fit to predict the breakthrough curves. Besides, a linear correlation is observed between breakthrough time and column length based on BDST model, which might be useful for predicting the breakthrough time for Cu(Ⅱ) removal by HFO-PS.

Catalytic performance of cerium iron complex oxides for partial oxidation of methane to synthesis gas

The cerium iron complex oxides oxygen carrier was prepared by the co-precipitation method. The reactions between methane and lattice oxygen from the complex oxides were investigated in a fixed micro-reactor system. The reduced oxygen carder could be re-oxidized by air and its initial state could be restored. The characterizations of the oxygen carders were studied using XRD, O2-TPD, and H2-TPR. The results showed that the bulk lattice oxygen of CeO2-Fe2O3 was found to be suitable for the partial oxidation of methane to synthesis gas. There were two kinds of oxygen species on the oxygen carrier： the stronger oxygen species that was responsible for the complete oxidation of methane, and the weaker oxygen species （bulk lattice oxygen） that was responsible for the selective oxidation of methane to CO and H2 at a higher temperature. Then, the lost bulk lattice oxygen could be selectively supplemented by air re-oxidation at an appropriate reaction condition. CeFeO3 appeared on the oxygen carrier after 10 successive redox cycles, however, it was not bad for the selectivity of CO and H2.

Annealing temperature dependent catalytic water oxidation activity of iron oxyhydroxide thin films

Nanostructured iron oxyhydroxide（Fe OOH） thin films have been synthesized using an electrodeposition method on a nickel foam（NF） substrate and effect of air annealing temperature on the catalytic performance is studied. The as-deposited and annealed thin films were characterized by X-ray diffraction（XRD）,X-ray photoelectron spectroscopy（XPS）, field emission scanning electron microscopy（FE-SEM） and linear sweep voltammetry（LSV） to determine their structural, morphological, compositional and electrochemical properties, respectively. The as-deposited nanostructured amorphous Fe OOH thin film is converted into a polycrystalline Fe;O;with hematite crystal structure at a high temperature. The Fe OOH thin film acts as an efficient electrocatalyst for the oxygen evolution reaction（OER） in an alkaline 1 M KOH electrolyte. The film annealed at 200 °C shows high catalytic activity with an onset overpotential of 240 m V with a smaller Tafel slope of 48 m V/dec. Additionally, it needs an overpotential of 290 mV to the drive the current density of 10 m A/cm;and shows good stability in the 1 M KOH electrolyte solution.

Morphology, chemical compositions and size distribution of rare earth oxides in pure iron

The pure iron was melted and deoxidized by metallic Al and rare earth elements La, Ce and Y respectively at 1600℃ in a vertical resistance furnace. The morphology, chemical composition and size distribution of the inclusions in deoxidized liquid iron have been investigated by using of SEM and image-analysis techniques. The investigated results show that the deoxidation products in molten iron are complex inclusions of rare earth oxide or A12O3 combined with FeO finely distributed. The proper holding time and rapid cooling rate can make inclusions finer. La, Y and Al are more effective than Ce for obtaining finely distributed inclusions.

Relationship Between Iron Oxides and Surface Charge Characteristics in Soils

The relationship between iron oxides and surface charge characteristics in variable charge soils ( latosol and red earth ) was studied in following three ways. ( 1 ) Remove free iron oxides ( Fed ) and amorphous iron oxides ( Feo ) from the soils with sodium dithionite and acid ammonium oxalate solution respectively. ( 2 ) Add 2% glucose ( on the basis of air-dry soil weight ) to soils and incubate under submerged condition to activate iron oxides, and then the mixtures are dehydrated and air-dried to age iron oxides. ( 3 ) Precipitate various crystalline forms of iron oxides onto kaolinite. The results showed that free iron oxides ( Fed ) were the chief carrier of variable positive charges. Of which crystalline iron oxides ( Fed-Feo ) presented mainly as discrete particles in the soils and could only play a role of the carrier of positive charges, and did little influence on negative charges. Whereas the amorphous iron oxides ( Feo ) , which presented mainly as a coating with a large specific surface area, not only had positive charges, but also blocked the negative charge sites in soils. Submerged incubation activated iron oxides in the soils, and increased the amount of amorphous iron oxides and the degree of activation of iron oxide, which resulted in the increase of positive and negative charges of soils. Dehydration and air-dry aged iron oxides in soils and decreased the amount of amorphous iron oxides and the degree of activation of iron oxide, and also led to the decrease of positive and negative charges. Both the submerged incubation and the dehydration and air-dry had no significant influence on net charges. Precipitation of iron oxides onto kaolinite markedly increased positive charges and decreased negative charges. Amorphous iron oxide having a larger surface area contributed more positive charge sites and blocked more negative charge sites in kaolinite than crystalline goethite.

A hydrated amorphous iron oxide nanoparticle as active water oxidation catalyst

Developing efficient water oxidation catalysts(WOCs)with earth‐abundant elements still remains a challenging task for artificial photosynthesis.Iron‐based WOC is a promising candidate because it is economically cheap,little toxic and environmentally friendly.In this study,we found that the catalytic water oxidation activity on amorphous iron‐based oxide/hydroxide(FeOx)can be decreased by an order of magnitude after the dehydration process at room temperature.Thermogravimetric analysis,XRD and Raman results indicated that the dehydration process of FeOx at room temperature causes the almost completely loss of water molecule with no bulk structural changes.Based on this finding,we prepared hydrated ultrasmall(ca.2.2 nm)FeOx nanoparticles of amorphous feature,which turns out to be extremely active as WOC with turnover frequency(TOF)up to 9.3 s^-1 in the photocatalytic Ru(bpy)3^2+‐Na2S2O8 system.Our findings suggest that future design of active iron‐based oxides as WOCs requires the consideration of their hydration status.

Synergism of Pt nanoparticles and iron oxide support for chemoselective hydrogenation of nitroarenes under mild conditions

An efficient and low-cost supported Pt catalyst for hydrogenation of niroarenes was prepared with colloid Pt precursors andα-Fe2O3 as a support.The catalyst with Pt content as low as 0.2 wt%exhibits high activities,chemoselectivities and stability in the hydrogenation of nitrobenzene and a variety of niroarenes.The conversion of nitrobenzene can reach 3170 molconv h^–1 molPt^–1 under mild conditions(30°C,5 bar),which is much higher than that of commercial Pt/C catalyst and many reported catalysts under similar reaction conditions.The spatial separation of the active sites for H2 dissociation and hydrogenation should be responsible for the high chemoselectivity,which decreases the contact possibility between the reducible groups of nitroarenes and Pt nanoparticles.The unique surface properties ofα-Fe2O3 play an important role in the reaction process.It provides active sites for hydrogen spillover and reactant adsorption,and ultimately completes the hydrogenation of the nitro group on the catalyst surface.

Fluidization behavior and reduction kinetics of pre-oxidized magnetite-based iron ore in a hydrogen-induced fluidized bed

The influence of different pre-oxidation temperatures and pre-oxidation degrees on the reduction and fluidization behaviors of magnetite-based iron ore was investigated in a hydrogen-induced fluidized bed.The raw magnetite-based iron ore was pre-oxidized at 800 and1000℃ for a certain time to reach a partly oxidation and deeply oxidation state.The structure and morphology of the reduced particles were analyzed via optical microscope and scanning electron microscopy(SEM).The reaction kinetic mechanism was determined based on the double-logarithm analysis.The results indicate that the materials with higher oxidation temperature and wider particle size range show better fluidization behaviors.The lower oxidation temperature is more beneficial for the reduction rate,especially in the later reduction stage.The pre-oxidation degree shows no obvious influence on the fluidization and reduction behaviors.Based on the kinetic analysis,the reduction progress can be divided into three stages.The reduction mechanism was discussed combing the surface morphology and phase structure.

A model for estimating the rate constant between CO_2-CO gas and molten slag containing iron oxides using optical basicity

A simple model for estimating the rate constant between CO2-CO gas and molten slag containing iron oxides was developed using optical basicity only. In this model, the temperature dependence of the rate constant can be described by the Arrhenius law, and the activation energy can be expressed with a linear function of the slag＇s optical basicity. The model was applied to some molten slag systems, such as FeO, FeO-CaO, FeO-SiO2, FeO-Na2O, FeO-CaO-SiO2, FeO-SiO2-P2O5, FeO-SiOE-Na2O, and FeO-CaO-SiOE-P2O5. A comparison between the predicted results and measured data showed that the model worked well.