Effect of valence and spin state on ethane dehydrogenation in Fe-S-1 catalyst

Light alkanes non-oxidative dehydrogenation is an attractive non-oil route for olefins production.The alkane dehydrogenation reaction is limited by thermodynamic equilibrium,and the C-H bond cleavage is commonly considered as the rate-determined step.The valence state of metal sites in catalysts will influence the stabilization of the vital intermediate(i.e.,C_(x)H_(y)...M^(δ+)...H)during the C-H bond cleavage process,which in turn affects the catalytic reactivity.Herein,we explicitly investigated the effect of different valence states of framework-Fe in silicate-1 zeolite on ethane dehydrogenation reaction through the combination of experimental and theoretical study.Fe(Ⅱ)-S-1 and Fe(Ⅲ)-S-1 catalysts are successfully synthesized by ligand-assisted in situ crystallization method,In-situ C_(2)H_6-FTIR shows the higher coverage of hydrocarbon intermediates on Fe(Ⅱ)-S-1,Under the same evaluation co nditio n,Fe(Ⅱ)-S-1 exhibits a higher space time yield of ethylene.Density functional theory(DFT)results reveal that the more coordinate-unsaturated and electron-enriched Fe(Ⅱ)sites boost the first C-H bond activation by slight deformation and efficient electron donation with C_(2)H_(5)^(*)species.Remarkably,the second C-H bond cleavage on Fe(Ⅱ)-S-1 undergoes a spin-crossing process from quintet state to triplet state,which involves a two-electro n-two-orbital interaction,further promoting the formation of ethylene.Microkinetic analysis is consistent with the experimental and DFT results.This work could provide methodology for elucidating the effect of metal valence states on catalytic performance as well as offer guidance for designing more efficient Fe-zeolite catalysts.

Thermal stable Pt clusters anchored by K/TiO_(2)—Al_(2)O_(3)for efficient cycloalkane dehydrogenation

Catalytic dehydrogenation of cycloalkanes is considered a valuable endothermic process for alleviating the thermal barrier issue of hypersonic vehicles.However,conventional Pt-based catalysts often face the severe problem of metal sintering under high-temperature conditions.Herein,we develop an efficient K_(2)CO_(3)-modified Pt/TiO_(2)—Al_(2)O_(3)(K—Pt/TA)for cycloalkane dehydrogenation.The optimized K—Pt/TA showed a high specific activity above 27.9 mol·mol^(-1)·s^(-1)(H_(2)/Pt),with toluene selectivity above 90.0%at 600℃with a high weight hourly space velocity of 266.4 h^(-1).The introduction of alkali metal ions could generate titanate layers after high-temperature hydrogen reduction treatment,which promotes the generation of oxygen vacancy defects to anchored Pt clusters.In addition,the titanate layers could weaken the surface acidity of catalysts and inhibit side reactions,including pyrolysis,polymerization,and isomerization reactions.Thus,this work provides a modification method to develop efficient and stable dehydrogenation catalysts under high-temperature conditions.

Synthesizing active and durable cubic ceria catalysts(<6 nm)for fast dehydrogenation of bio-polyols to carboxylic acids coproducing green H_(2)

Dehydrogenation is considered as one of the most important industrial applications for renewable energy.Cubic ceria-based catalysts are known to display promising dehydrogenation performances in this area.Large particle size(>20 nm)and less surface defects,however,hinder further application of ceria materials.Herein,an alternative strategy involving lactic acid(LA)assisted hydrothermal method was developed to synthesize active,selective and durable cubic ceria of<6 nm for dehydrogenation reactions.Detailed studies of growth mechanism revealed that,the carboxyl and hydroxyl groups in LA molecule synergistically manipulate the morphological evolution of ceria precursors.Carboxyl groups determine the cubic shape and particle size,while hydroxyl groups promote compositional transformation of ceria precursors into CeO_(2) phases.Moreover,enhanced oxygen vacancies(Vo)on the surface of CeO_(2) were obtained owing to continuous removal of O species under reductive atmosphere.Cubic CeO_(2) catalysts synthesized by the LA-assisted method,immobilized with bimetallic PtCo clusters,exhibit a record high activity(TOF:29,241 h^(-1))and Vo-dependent synergism for dehydrogenation of bio-derived polyols at 200℃.We also found that quenching Vo defects at air atmosphere causes activity loss of PtCo/CeO_(2) catalysts.To regenerate Vo defects,a simple strategy was developed by irradiating deactivated catalysts using hernia lamp.The outcome of this work will provide new insights into manufacturing durable catalyst materials for aqueous phase dehydrogenation applications.

Mn-doped SrCoO_(3-δ) Perovskite Oxides for Ethylene Production via Chemical Looping Oxidative Dehydrogenation of Ethane

Chemical looping oxidative dehydrogenation (CL-ODH) is an economically promising method for convertingethane into higher value-added ethylene utilizing lattice oxygen in redox catalysts, also known as oxygen carriers. Inthis study, perovskite-type oxide SrCoO_(3-δ) and B-site Mn ion-doped oxygen carriers (SrCo_(1-x)MnxO_(3-δ), x=0.1, 0.2, 0.3)were prepared and tested for the CL-ODH of ethane. The oxygen-deficient perovskite SrCoO_(3-δ) exhibited high ethyleneselectivity of up to 96.7% due to its unique oxygen vacancies and lattice oxygen migration rates. However, its low ethyleneyield limits its application in the CL-ODH of ethane. Mn doping promoted the reducibility of SrCoO_(3-δ) oxygen carriers,thereby improving ethane conversion and ethylene yield, as demonstrated by characterization and evaluation experiments.X-ray diffraction results confirmed the doping of Mn into the lattice of SrCoO_(3-δ), while X-ray photoelectron spectroscopy(XPS) indicated an increase in lattice oxygen ratio upon incorporation of Mn into the SrCoO_(3-δ) lattice. Additionally, H2temperature-programmed reduction (H2-TPR) tests revealed more peaks at lower temperature reduction zones and a declinein peak positions at higher temperatures. Among the four tested oxygen carriers, SrCo0.8Mn0.2O_(3-δ) exhibited satisfactoryperformance with an ethylene yield of 50% at 710 °C and good stability over 20 redox cycles. The synergistic effect of Mnplays a key role in increasing ethylene yields of SrCoO_(3-δ) oxygen carriers. Accordingly, SrCo0.8Mn0.2O_(3-δ) shows promisingpotential for the efficient production of ethylene from ethane via CL-ODH.

Ethane Chemical Looping Oxidative Dehydrogenation to Ethylene over Co_(2)O_(3)(Fe_(2)O_(3),NiO)/LaCoO_(3) Oxygen Carriers

Ethane chemical looping oxidative dehydrogenation(CL-ODH)to ethylene is a new technology for converting ethane to ethylene.In the current study MeO/LaCoO_(3)(MeO=Fe_(2)O_(3),NiO or Co_(2)O_(3))composite metal oxides were prepared via citrate gel and impregnation methods,and used as oxygen carriers for CL-ODH.X-ray diffraction results indicated that all oxygen carriers had a perovskite structure even after eight redox cycles.Under a reaction temperature of 650°C,a reaction pressure of 0.1 MPa,and a weight hourly space velocity(WHSV)of 7500 mL/(g·h),ethane conversion over Co_(2)O_(3)/LaCoO_(3) reached 100%and ethylene selectivity reached 60%,both of which were better than corresponding values attained over Fe_(2)O_(3)/LaCoO_(3) and NiO/LaCoO_(3).Ethylene selectivity remained stable for 80 cycles over Co_(2)O_(3)/LaCoO_(3),then decreased gradually after 80 cycles.X-ray photoelectron spectroscopy results and evaluation results indicated that lattice oxygen and O_(2)2-had a direct relationship with ethane conversion and ethylene selectivity.Co_(2)O_(3)/LaCoO_(3) exhibited a strong capacity to release and absorb oxygen,mainly due to interaction between Co_(2)O_(3) and LaCoO_(3).

Effect of Fe Addition on Dehydrogenation Performance of Methylcyclohexance over Pt/Al_(2)O_(3)

Catalysts with varying Fe contents were prepared using a sequential impregnation method to investigate the effects of Fe addition on the physicochemical properties of Pt/Al_(2)O_(3) and their performance in methylcyclohexane(MCH)dehydrogenation.The results demonstrated that the addition of Fe to Pt/Al_(2)O_(3) enhanced the electron density of Pt and improved catalytic activity,while exhibiting negligible influence on the catalytic selectivity for toluene.When the Fe content was 0.057%,the catalyst exhibited the highest MCH consumption rate,which was approximately two times higher than that of the catalyst without Fe.Additionally,the incorporation of Fe inhibited the formation of coke and reduced the quantity of coke deposits on the catalyst,thereby improving its catalytic durability.Overall,Fe shows promise as a prospective secondary element for Pt/Al_(2)O_(3) to enhance the MCH dehydrogenation performance.

Ca_(2)MnO_(4)-layered perovskite modified by NaNO_(3)for chemical-looping oxidative dehydrogenation of ethane to ethylene

Chemical-looping oxidative dehydrogenation(CL-ODH)is a process designed for the conversion of alkanes into olefins through cyclic redox reactions,eliminating the need for gaseous O_(2).In this work,we investigated the use of Ca_(2)MnO_(4)-layered perovskites modified with NaNO_(3) dopants,serving as redox catalysts(also known as oxygen carriers),for the CL-ODH of ethane within a temperature range of 700-780℃.Our findings revealed that the incorporation of NaNO_(3) as a modifier significantly-nhanced the selectivity for-thylene generation from Ca_(2)MnO_(4).At 750℃and a gas hourly space velocity of 1300 h^(-1),we achieved an-thane conversion up to 68.17%,accompanied by a corresponding-thylene yield of 57.39%.X-ray photoelectron spectroscopy analysis unveiled that the doping NaNO_(3) onto Ca_(2)MnO_(4) not only played a role in reducing the oxidation state of Mn ions but also increased the lattice oxygen content of the redox catalyst.Furthermore,formation of NaNO_(3) shell on the surface of Ca_(2)MnO_(4) led to a reduction in the concentration of manganese sites and modulated the oxygen-releasing behavior in a step-wise manner.This modulation contributed significantly to the enhanced selectivity for ethylene of the NaNO_(3)-doped Ca_(2)MnO_(4) catalyst.These findings provide compelling evidence for the potential of Ca_(2)MnO_(4)-layered perovskites as promising redox catalysts in the context of CL-ODH reactions.

NiO-Doped Fe_(2)O_(3)/MgO Properties for the Chemical Looping Oxidative Dehydrogenation of Ethane

Ethane chemical looping oxidative dehydrogenation(CL-ODH)to ethylene is a new technology for ethylene preparation.Fe_(2)O_(3)/MgO oxygen carrier was prepared using the co-precipitation method.The influence of added NiO and its different loadings on Fe_(2)O_(3)/MgO were investigated.Then,a series of oxygen carriers were applied in the CL-ODH of the ethane cycle system.Brunauer-Emmett-Teller(BET),X-ray diffractometry(XRD),X-ray photoelection spectroscopy(XPS),and H2-temperature programmed reduction(TPR)were used to characterize the physicochemical properties of these oxygen carriers.It was confirmed that an interaction between NiO and Fe_(2)O_(3) occurred based on the XPS and H2-TPR results.Based on the CL-ODH activity performance tests conducted in a fixed-bed reactor,it was revealed that ethylene selectivity was significantly improved after NiO addition.Fe_(2)O_(3)-10%NiO/MgO showed the best activity performance with 93%ethane conversion and 50%ethylene selectivity at a reaction temperature of 650℃,atmospheric pressure,and space velocity of 7500 mL/(g·h).

Influence of carbonization temperature on cobalt-based nitrogendoped carbon nanopolyhedra derived from ZIF-67 for nonoxidative propane dehydrogenation

Propylene is a significant basic material for petrochemicals such as polypropylene,propylene oxide,etc.With abundant propane supply from shale gas,propane dehydrogenation(PDH)becomes extensively attractive as an on-purpose propylene production route in recent years.Nitrogen-doped carbon(NC)nanopolyhedra supported cobalt catalysts were synthesized in one-step of ZIF-67 pyrolysis and investigated further in PDH.XPS,TEM and N_(2) adsorption-desorption were used to study the influence of carbonization temperature on as-prepared NC supported cobalt catalysts.The temperature is found to affect the cobalt phase and nitrogen species of the catalysts.And the positive correlation was established between Co0 proportion and space time yield of propylene,indicating that the modulation of carbonization temperature could be important for catalytic performance.

Anomalous metastable hcp Ni nanocatalyst induced by non-metal N doping enables promoted ammonia borane dehydrogenation

Developing high-performing non-noble transition metal catalysts for H_(2) evolution from chemical hydrogen storage materials is of great significance for the hydrogen economy system, yet challenging. Herein,we present for the first time that anomalous metastable hexagonal close-packed Ni nanoparticles induced by heteroatom N doping encapsulated in carbon(N-hcp-Ni/C) can exhibit admirable catalytic performance for ammonia borane(AB) dehydrogenation, prominently outperforming conventional fcc Ni counterpart with similar morphology and favorably presenting the state-of-the-art level.Comprehensive experimental and theoretical studies unravel that unusual hcp phase engineering of Ni together with N doping could induce charge redistribution and modulate electronic structure, thereby facilitating H_(2)O adsorption and expediting H_(2)O dissociation(rate-determining step). As a result, AB dehydrogenation can be substantially boosted with the assistance of N-hcp-Ni/C. Our proposed strategy highlights that unconventional crystal phase engineering coupled with non-metal heteroatom doping is a promising avenue to construct advanced transition metal catalysts for future renewable energy technologies.

Effect of boron species on carbon surface on oxidative dehydrogenation of propane

Carbon catalysts for propane oxidative dehydrogenation(PODH)can potentially replace metal oxide catalysts due to their environmental friendliness(greenness)and excellent catalytic performance.Biomass carbon materials have the advantages of being abundant in variety,inexpensive,and easily available,but their catalytic selectivity is relatively poor in PODH.Therefore,we report here on a boron-doped sisal fiber carbon catalyst,which showed excellent selectivity of propylene in PODH,excluding the effect of surface-covered B2O3 on the catalytic performance by hot water washing.The carbon material exhibited the best catalytic performance with a load of 2%(mass)and a calcination temperature of 1100℃.At a reaction temperature of 400℃,the conversion rate of propane was 2.0%,and the selectivity toward propylene reached 88.6%.The new chemical bonds formed by boron on the surface of the carbon materials had an important effect on the catalytic performance,as determined by XPS characterization.The BAO groups affected the catalytic activity by inhibiting the generation of electrophilic oxygen species,while the BAC content improved the selectivity toward propylene by changing the electron cloud density.

A mini review on oxidative dehydrogenation of propane over boron nitride catalysts

Oxidative dehydrogenation of propane is an attractive route for the synthesis of propylene due to its favorable thermodynamic and kinetic characteristics, however, it is challenging to realize high selectivity towards propylene. Recently, it has been discovered that boron nitride (BN) is a promising catalyst that affords superior selectivity towards propylene in oxidative dehydrogenation of propane. Summarizing the progress and unravelling the reaction mechanism of BN in oxidative dehydrogenation of propane are of great significance for the rational design of efficient catalysts in the future. Herein, in this review, the underlying reaction mechanisms of oxidative dehydrogenation of propane over BN are extracted;the developed BN catalysts are classified into pristine BN, functionalized BN, supported BN and others, and the applications of each category of BN catalysts in oxidative dehydrogenation of propane are summarized;the challenges and opportunities on oxidative dehydrogenation of propane over BN are pointed out, aiming to inspire more studies and advance this research field.

Finned Zn-MFI zeolite encapsulated noble metal nanoparticle catalysts for the oxidative dehydrogenation of propane with carbon dioxide

Oxidative dehydrogenation of propane with carbon dioxide(CO_(2)-ODP)characterizes the tandem dehydrogenation of propane to propylene with the reduction of the greenhouse gas of CO_(2)to valuable CO.However,the existing catalyst is limited due to the poor activity and stability,which hinders its industrialization.Herein,we design the finned Zn-MFI zeolite encapsulated noble metal nanoparticles(NPs)as bifunctional catalysts(NPs@Zn-MFI)for CO_(2)-ODP.Characterization results reveal that the Zn2+species are coordinated with the MFI zeolite matrix as isolated cations and the NPs of Pt,Rh,or Rh Pt are highly dispersed in the zeolite crystals.The isolated Zn2+cations are very effective for activating the propane and the small NPs are favorable for activating the CO_(2),which synergistically promote the selective transformation of propane and CO_(2)to propylene and CO.As a result,the optimal 0.25%Rh0.50%Pt@Zn-MFI catalyst shows the best propylene yield,satisfactory CO_(2)conversion,and long-term stability.Moreover,considering the tunable synergetic effects between the isolated cations and NPs,the developed approach offers a general guideline to design more efficient CO_(2)-ODP catalysts,which is validated by the improved performance of the bifunctional catalysts via simply substituting Sn4+cations for Zn2+cations in the MFI zeolite matrix.

Progress in Processes and Catalysts for Dehydrogenation of Cyclohexanol to Cyclohexanone

The dehydrogenation of cyclohexanol to cyclohexanone is a crucial industrial process in the production of caprolactam and adipic acid, both of which serve as important precursors in nylon textiles. This endothermic reaction is constrained by thermodynamic equilibrium and involves a complex reaction network, leading to a heightened focus on catalysts and process design. Copper-based catalysts have been extensively studied and exhibit exceptional low-temperature catalytic performance in cyclohexanol dehydrogenation, with some being commercially used in the industry. This paper specifically concentrates on research advancement concerning active species, reaction mechanisms, factors influencing product selectivity, and the deactivation behaviors of copper-based catalysts. Moreover, a brief introduction to the new processes that break thermodynamic equilibrium via reaction coupling and their corresponding catalysts is summarized here as well. These reviews may off er guidance and potential avenues for further investigations into catalysts and processes for cyclohexanol dehydrogenation.

Unravelling the role of boron dopant in borocarbonitirde catalytic dehydrogenation reaction

Borocarbonitride(BCN) materials are newly developed metal-free catalytic materials exhibiting high selectivity in oxidative dehydrogenation(ODH) of alkanes. However, the in-depth understandings on the role of boron(B) dopants and the intrinsic activities of –C=O and –B–OH still remain unknown.Herein, we report a series of BCN materials with regulable B content and surface oxygen functional groups via self-assembly and pyrolysis of guanine and boric acid. We found that the B/C ratio is the key parameter to determine the activity of ODH and product distribution. Among them, the high ethylbenzene conversion(~57%) and styrene selectivity(~83%) are achieved in ODH for B_(1)CN. The styrene selectivity can be improved by increasing of B/C ratio and this value reaches near 100% for B_5CN.Structural characterizations and kinetic measurements indicate that –C=O and –B–OH dual sites on BCN are real active sites of ODH reaction. The intrinsic activity of –C=O(5.556 × 10^(-4)s^(-1)) is found to be 23.7 times higher than –B–OH(0.234 × 10^(-4)s^(-1)) site. More importantly, we reveal that the deep oxidation to undesirable CO_(2) occurs on –C=O rather than –B–OH site, and B dopant in BCN materials can reduce the nucleophilicity of –C=O site to eliminate the CO_(2) emission. Overall, the present work provides a new insight on the structure–function relationship of the BCN catalytic systems.

Sub-nanometer Pt_(2)In_(3) intermetallics as ultra-stable catalyst for propane dehydrogenation

Pt-based catalysts are the typical industrial catalysts for propane dehydrogenation(PDH),which still suffer from insufficient lo ng-term durability due to the structu ral instability and coke deposition.A commercial γ-Al_(2)O_(3) supported thermally robust sub-nanometer Pt2In3intermetallic catalyst with atomically ordered structure and rigorously separated Pt single atoms was fabricated,which showed outstanding robustness in 240 h long-term operation at 600℃ with the deactivation rate constant kdas low as0.00078 h^(-1), ranking among the lowest reported values.Based on various in situ characterizations and theoretical calculations,it was proved that the catalyst stability not only resulted from the separated Pt single-atom sites but also significantly affected by the distance of adjacent Pt atoms.An increasing distance to 3.25 A in the Pt_(2)In_(3)could induce a weak π-adsorption configuration of propylene on Pt sites,which facilitated the desorption of propylene and restrained the side reactions like coking.

Plasma treated M1 MoVNbTeO_(x)-CeO_(2) composite catalyst for improved performance of oxidative dehydrogenation of ethane

High activity and productivity of MoVNbTeO_(x) catalyst are challenging tasks in oxidative dehydrogenation of ethane(ODHE)for industrial application.In this work,phase-pure M1 with 30 wt%CeO_(2) composite catalyst was treated by oxygen plasma to further enhance catalyst performance.The results show that the oxygen vacancies generated by the solid-state redox reaction between M1 and CeO_(2) capture active oxygen species in gas and transform V^(4+)to V^(5+)without damage to M1 structure.The space-time yield of ethylene of the plasma-treated catalyst was significantly increased,in which the catalyst shows an enhancement near~100% than that of phase-pure M1 at 400℃ for ODHE process.Plasma treatment for catalysts demonstrates an effective way to convert electrical energy into chemical energy in catalyst materials.Energy conversion is achieved by using the catalyst as a medium.

Selective oxidative dehydrogenation of ethane to ethylene over a hydroxylated boron nitride catalyst

Boron nitride containing hydroxyl groups efficiently catalysed oxidative dehydrogenation of ethane to ethylene,offering rather high selectivity（95%） but only small amount of CO2 formation（0.4%） at a given ethane conversion of 11%.Even at high conversion level of 63%,the selectivity of ethylene retained at 80%,which is competitive with the energy-demanding industrialized steam cracking route.A long-term test for 200 h resulted in stable conversion and product selectivity,showing the excellent catalytic stability.Both experimental and computational studies have identified that the hydrogen abstraction of B-OH groups by molecular oxygen dynamically generated the active sites and triggered ethane dehydrogenation.

Modulating the microstructure and surface chemistry of carbocatalysts for oxidative and direct dehydrogenation: A review

The catalytic performance of solid catalysts depends on the properties of the catalytically active sites and their accessibility to reactants, which are significantly affected by the microstructure（morphology, shape, size, texture, and surface structure） and surface chemistry（elemental components and chemical states）. The development of facile and efficient methods for tailoring the microstructure and surface chemistry is a hot topic in catalysis. This contribution reviews the state of the art in modulating the microstructure and surface chemistry of carbocatalysts by both bottom‐up and top‐down strategies and their use in the oxidative dehydrogenation（ODH） and direct dehydrogenation（DDH） of hydrocarbons including light alkanes and ethylbenzene to their corresponding olefins, important building blocks and chemicals like oxygenates. A concept of microstructure and surface chemistry tuning of the carbocatalyst for optimized catalytic performance and also for the fundamental understanding of the structure‐performance relationship is discussed. We also highlight the importance and challenges in modulating the microstructure and surface chemistry of carbocatalysts in ODH and DDH reactions of hydrocarbons for the highly‐efficient, energy‐saving,and clean production of their corresponding olefins.

Oxidative Dehydrogenation of Alkanes using Oxygen-Permeable Membrane Reactor

The oxidative dehydrogenation （ODH） reactions of ethane and propane were investigated in a catalytic membrane reactor, incorporating oxygen-permeable membranes based upon La2Ni0.9V0.1O4＋δor Ba0.5Sr0.5Co0.8Fe0.2O3-δ. As a compromise between the occurrence of a measureable oxygen flux and excessive homogenous gas phase reactions, the measurements were conducted at an intermediate temperature, either at 550 or 650 oC. The results show the dominating role of the oxygen flux across the membrane and available sites at the membrane surface in primary activation of the alkane and, hence, in achieving high alkane conversions. The experimental data of ODH of propane and ethane on both membrane materials can be reconciled on the basis of Mars-van Krevelen mechanism, in which the alkane reacts with lattice oxygen on the membrane surface to produce the corresponding olefin. It is further demonstrated that the oxygen concentration in the gas phase and on the membrane surface is crucial for determining the olefin selectivity.