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.

Effects of Potassium and Manganese Promoters on Nitrogen-Doped Carbon Nanotube-Supported Iron Catalysts for CO_2 Hydrogenation

Nitrogen-doped carbon nanotubes （NCNTs） were used as a support for iron （Fe） nanoparticles applied in car- bon dioxide （CO_2） hydrogenation at 633 K and 25 bar （1 bar = 10-5 Pa）. The Fe/NCNT catalyst promoted with both potassium （K） and manganese （Mn） showed high performance in CO_2 hydrogenation, reaching 34.9% conversion with a gas hourly space velocity （GHSV） of 3.1 L-（g·h）-1. Product selectivities were high for olefin products and low for short-chain alkanes for the K-promoted catalysts. When Fe/NCNT catalyst was promot- ed with both K and Mn, the catalytic activity was stable for 60 h of reaction time. The structural effect of the Mn promoter was demonstrated by X-ray diffraction （XRD）, temperature-programmed reduction （TPR） with molecular hydrogen （H2）, and in situ X-ray absorption near-edge structure （XANES） analysis. The Mn pro- moter stabilized wtistite （FeO） as an intermediate and lowered the TPR onset temperature. Catalytic ammo- nia （NH_3） decomposition was used as an additional probe reaction for characterizing the promoter effects. The Fe/NCNT catalyst promoted with both K and Mn had the highest catalytic activity, and the Mn-promoted Fe/NCNT catalysts had the highest thermal stability under reducing conditions.

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.

Synthesis of alumina-nitrogen-doped carbon support for CoMo catalysts in hydrodesulfurization process

More stringent environmental legislation imposes severe requirements to reduce the sulfur content in diesel to ultra-low levels with high efficient catalysts.In this paper,a series of CoMo/NDC@alumina catalysts were synthesized by combination of the chemical vapor deposition of nitrogen-doped carbon(NDC)using 1,10-phenanthroline and co-impregnation of Mo and Co active components.The optimal catalyst with additive of 25%1,10-phenanthroline was screened by a series of property characterization and the hydrodesulfrization(HDS)active test.The amount of“CoMoS”active phase of the optimal CoMo/C3 catalyst increased 5.3%as compared with the CoMo/c-Al_(2)O_(3).The introduction of NDC improved the sulfidation degree of Mo by 21.8%as compared to the CoMo/c-Al_(2)O_(3) catalyst,which was beneficial to form more active sites.The HDS conversion of the NDC supported catalysts are higher than CoMo/c-Al_(2)O_(3) whether for the dibenzothiophene(DBT)or 4,6-dimethyl dibenzothiophene(4,6-DMDBT).Further hydroprocessing evaluation with Dagang diesel revealed that the CoMo/C3 catalyst possessed higher HDS property and the removal rate of DBTs in the diesel increased by 4%–11%as compared to the CoMo/c-Al_(2)O_(3) catalyst.

Heterogeneous single-cluster catalysts(Mn_(3),Fe_(3),Co_(3),and Mo_(3))supported on nitrogen-doped graphene for robust electrochemical nitrogen reduction

Electrochemical nitrogen reduction reaction(NRR)is one of the most promising alternatives to the traditional Haber-Bosch process.Designing efficient electrocatalysts is still challenging.Inspired by the recent experimental and theoretical advances on single-cluster catalysts(SCCs),we systematically investigated the catalytic performance of various triple-transition-metal-atom clusters anchored on nitrogen-doped graphene for NRR through density functional theory(DFT)calculation.Among them,Mn_(3)-N4,Fe_(3)-N4,Co_(3)-N4,and Mo_(3)-N4 were screened out as electrocatalysis systems composed of non-noble metal with high activity,selectivity,stability,and feasibility.Particularly,the Co_(3)-N4 possesses the highest activity with a limiting potential of-0.41 V through the enzymatic mechanism.The outstanding performance of Co_(3)-N4 can be attributed to the unique electronic structure leading to strong π backdonation,which is crucial in effective N_(2) activation.This work not only predicts four efficient non-noble metal electrocatalysts for NRR,but also suggest the SCCs can serve as potential candidates for other important electrochemical reactions.

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.

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 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＋）.

Plasma preparation of highly reactive Ag-Cu NPs anchored in N-PC as catalysts for Aluminum-air battery

Efficient,stable and economical catalysts play a crucial role in enhancing the kinetics of slow oxygen reduction reactions(ORR)in Aluminum-air batteries.Among the potential next-generation candidates,Ag catalysts are promising due to their high activity and low cost,but weaker oxygen adsorption has hindered industrialization.To address this bottleneck,Ag-alloying has emerged as a principal strategy.In this work,we successfully prepared Ag-Cu nanoparticles(NPs)with a rich eutectic phase and uniform dispersion structure using plasma evaporation.The increased solid solution of Ag and Cu led to changes in the electronic structure,resulting in an upward shift of the d-band center,which significantly improved oxygen adsorption.The combination of Ag and Cu in the NPs synergistically enhanced the adsorption of Ag and the desorption of Cu.Density functional theory(DFT)calculations revealed that Ag-Cu25 NPs exhibited the smallest limiting reaction barrier,leading to increased ORR activity.To further optimize the catalyst’s performance,we utilized N-doped porous nanocarbon(N-PC)with high electrical conductivity and abundant mesoporous channels as the support for the Ag-Cu NPs.The N-PC support provided optimal mass transfer carriers for the highly active Ag-Cu25 NPs.As a result,the Ag-Cu25/NPC catalyst displayed excellent ORR activity in alkaline media,with a half-wave potential(E_(1/2))of 0.82 V.Furthermore,the Al-air battery incorporating the Ag-Cu25/NPC catalyst exhibited outstanding electrochemical performance.It demonstrated high open-circuit voltages of 1.89 V and remarkable power densities of 193 m W cm^(-2).The battery also sustained a high current output and maintained a stable high voltage for 120 hours under mechanical charging,showcasing its significant potential for practical applications.

Nitrogen-Doped Carbon Nanotube-Supported Pd Catalyst for Improved Electrocatalytic Performance toward Ethanol Electrooxidation

In this study, hydrothermal carbonization(HTC)was applied for surface functionalization of carbon nanotubes(CNTs) in the presence of glucose and urea. The HTC process allowed the deposition of thin nitrogen-doped carbon layers on the surface of the CNTs. By controlling the ratio of glucose to urea, nitrogen contents of up to 1.7 wt%were achieved. The nitrogen-doped carbon nanotube-supported Pd catalysts exhibited superior electrochemical activity for ethanol oxidation relative to the pristine CNTs.Importantly, a 1.5-fold increase in the specific activity was observed for the Pd/HTC-N1.67%CNTs relative to the catalyst without nitrogen doping(Pd/HTC-CNTs). Furtherexperiments indicated that the introduction of nitrogen species on the surface of the CNTs improved the Pd(0)loading and increased the binding energy.

A correlation between structural changes in a Ni-Cu catalyst during decomposition of ethylene/ammonia mixture and properties of nitrogen-doped carbon nanofibers

Changes of a 65Ni25Cu10A1203 catalyst consisting of Ni-enriched and Cu-enriched alloys were investigated in the bulk and on the surface during the growth of nitrogen-doped carbon nanofibers （N-CNFs） by decomposition of a 50%C2I-I4/50%NH3 mixture using in situ X-ray diffraction （XRD） analysis, ex situ X-ray photoelectron spectroscopy （XPS） and transmission electron microscopy （TEM） techniques. It was shown that N-CNF growth at 450-650 ℃is accompanied by dissolution of carbon and nitrogen in the Ni-enriched alloy, whereas Cu-enriched alloy remains inactive. A correlation between nickel and copper surface concentrations and properties of N-CNFs in relation to the nitrogen content was found. It was demonstrated that phase composition of the catalyst during N-CNF growth determines the type of N-CNFs structure.

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.

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.

Fischer–Tropsch synthesis over iron catalysts with corncob-derived promoters

A sustainable strategy for Fischer–Tropsch iron catalysts is successfully achieved by embedding of synergistic promoters from a renewable resource, corncob. The iron-based catalysts, named as 'corncob-driven'catalysts, are composed of iron species supported on carbon as primary active components and various minerals(K, Mg, Ca, and Si, etc.) as promoters. The corncob-driven catalysts are facilely synthesized by a one-pot hydrothermal treatment under mild conditions. The characterization results indicate that the formation of iron carbides from humboldtine is clearly enhanced and the morphology of catalyst particles tends to be more regular microspheres after adding corncob. It is observed that the optimized corncob-driven catalyst exhibits a higher conversion than without promoters' catalyst in Fischer–Tropsch synthesis(ca. 73% vs. ca. 49%). More importantly, a synergistic effect exists in multiple promoters from corncob that can enhance heavy hydrocarbons selectivity and lower CO_2 selectivity, obviously different from the catalyst with promoters from chemicals. The proposed synthesis route of corncob-driven catalysts provides new strategies for the utilization of renewable resources and elimination of environmental pollutants from chemical promoters.

Active Fischer-Tropsch synthesis Fe-Cu-K/SiO_2 catalysts prepared by autocombustion method without a reduction step

The purpose of this study was to prepare iron-based catalysts supported on silica by autocombustion method for directly using for Fischer-Tropsch synthesis（FTS） without a reduction step. The effect of different citric acid（CA）：iron nitrate（N） molar ratios and acid types on the FTS performance of catalysts were investigated. The CA：N molar ratios had an important influence on the formation of iron active phases and FTS activity. The iron carbide（FexC）, which is known to be one of the iron active phases, was demonstrated by the X-ray diffraction and X-ray photoelectron spectroscopy. Increasing the CA：N molar ratios up to 0.1 increased CO conversion of catalyst to 86.5%, which was then decreased markedly at higher CA：N molar ratios. An excess of CA resulted in carbon residues covering the catalyst surface and declined FTS activity. The optimal catalyst（CA：N molar ratio = 0.1） achieved the highest CO conversion when compared with other autocombustion catalysts as well as reference catalyst prepared by impregnation method, followed by a reduction step. The autocombustion method had the advantage to synthesize more efficient catalysts without a reduction step. More interestingly, iron-based FTS catalysts need induction duration at the initial stage of FTS reaction even after reduction, because metallic iron species need time to be transformed to FexC. But here, even if without reduction, FexC was formed directly by autocombustion and induction period was eliminated during FTS reaction.

Effect of operating conditions and potassium content on Fischer-Tropsch liquid products produced by potassium-promoted iron catalysts

The dependencies of Fischer-Tropsch synthesis liquid hydrocarbon product distribution on operating pressure and temperature have been studied over three potassium-promoted iron catalysts with increasing potassium molar content. The study followed an experimental planning and the results were analyzed based on surface response methodology. The effects of different operating conditions and potassium contents on the liquid product distribution were compared based on number average carbon number and dispersion. Results showed that high pressures （25 to 30 arm） favored the production of waxes that could be converted into liquid fuels through hydrocracking, while greater direct selectivity towards diesel was favored by low pressure （20 arm） using catalysts with low potassium to iron molar ratios. The liquid product distribution produced using an iron catalyst with high potassium content presented higher number-average number of carbons when compared to the distribution obtained using an iron catalyst with low potassium content.

Effect of incorporation manner of Zr promoter on precipitated ironbased catalysts for Fischer-Tropsch synthesis

The promotional effects of Zr on the structure, reduction, carburization and catalytic behavior of precipitated iron-based Fischer-Tropsch synthesis （FTS） catalysts were investigated. The catalysts were characterized by N2 physisorption, temperature-programmed reduction （TPR）, and M6ssbauer effect spectroscopy （MES） techniques. As revealed by N2 physisorption, Zr decreased the BET surface area and pore volume of the catalyst. The results of TPR and MES show that Zr suppresses the reduction and carburization of Fe catalysts because of the interaction between Fe and Zr. The FTS reaction results indicate that Zr decreases the FTS activity of Fe catalysts but improves the catalysts＇ stability. In addition, Zr promoter restraines the formation of light hydrocarbons （methane and C2-C4） and shifts the production distribution to the heavy hydrocarbons.

Size dependence of carbon-encapsulated iron-based nanocatalysts for Fischer–Trposch synthesis

The conversion from syngas derived from non-petroleum recourses to liquid fuels and chemicals via Fischer–Tropsch synthesis(FTS)is regarded as an alternative and potential route.Developing catalyst with controllable particle size and clarifying size effect are of significance to promote the process.Herein,we engineered carbon-encapsulation structure to restrict particle growth but avoid strong metal–support interactions.The prepared carbon-encapsulated nanoparticles(Fe@C)showed a superior catalytic activity compared with conventional carbon-supported nanoparticles(Fe/C).By tuning particle size from 3.0 to 9.1 nm,a volcano-like trend of iron time yield(FTY)peaked at 2659μmol·gFe^(−1)·s^(−1)is obtained with an optimum particle size of 5.3 nm.According to temperature-programmed reduction and desorption results,a linear relationship between apparent turnover frequency and CO dissociation capacity was established.The enhanced CO dissociative adsorption along with weakened H_(2)activation on larger nanoparticles resulted in higher C_(5+)selectivity.This study provides a strategy to synthesize carbon supported metal catalysts with controllable particle size and insight into size effect on Fe-based catalytic FTS.