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Effect of valence and spin state on ethane dehydrogenation in Fe-S-1 catalyst
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作者 Liusai Huang Yumeng Fo +6 位作者 Peng Zhang Shaojia Song Xinxin Zhang Xueqiu Wu Saeed Soltanali Jian Liu Weiyu Song 《Journal of Energy Chemistry》 SCIE EI CAS CSCD 2024年第10期677-686,I0014,共11页
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 consi... 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. 展开更多
关键词 IRON Ethane dehydrogenation Electron-enriched Spin crossover DFT
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Synthesizing active and durable cubic ceria catalysts(<6 nm)for fast dehydrogenation of bio-polyols to carboxylic acids coproducing green H_(2)
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作者 Mengyuan Liu Puhua Sun +3 位作者 Guangyu Zhang Xin Jin Chaohe Yang Honghong Shan 《Green Energy & Environment》 SCIE EI CAS CSCD 2024年第3期529-543,共15页
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 partic... 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. 展开更多
关键词 Cubic ceria Oxygen vacancy dehydrogenation C-H bond activation
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Effect of Fe Addition on Dehydrogenation Performance of Methylcyclohexance over Pt/Al_(2)O_(3)
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作者 Tong Fengya Tian Hao +2 位作者 Wang Hao Miao Changxi Song Lei 《China Petroleum Processing & Petrochemical Technology》 SCIE CAS CSCD 2024年第1期12-18,共7页
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 methylcycl... 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. 展开更多
关键词 methylcyclohexane dehydrogenation hydrogen storage DEACTIVATION Fe addition
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Mn-doped SrCoO_(3-δ) Perovskite Oxides for Ethylene Production via Chemical Looping Oxidative Dehydrogenation of Ethane
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作者 Li Zhi Liu Linjiao +4 位作者 Hao Daijun Ren Xiaohang Shen Fangxia Li Xin Yu Anping 《China Petroleum Processing & Petrochemical Technology》 SCIE CAS CSCD 2024年第3期53-62,共10页
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.... 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. 展开更多
关键词 ETHANE ETHYLENE PEROVSKITE chemical looping oxidative dehydrogenation
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Ethane Chemical Looping Oxidative Dehydrogenation to Ethylene over Co_(2)O_(3)(Fe_(2)O_(3),NiO)/LaCoO_(3) Oxygen Carriers
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作者 Liang Hao Meng Jinhong +1 位作者 Sun Jie Wei Dongkai 《China Petroleum Processing & Petrochemical Technology》 SCIE CAS CSCD 2024年第3期33-41,共9页
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 w... 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). 展开更多
关键词 chemical looping oxidative dehydrogenation ETHANE ETHYLENE oxygen carrier PEROVSKITE
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Thermal stable Pt clusters anchored by K/TiO_(2)—Al_(2)O_(3)for efficient cycloalkane dehydrogenation
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作者 Zhendong Wang Bofeng Zhang +1 位作者 Guozhu Liu Xiangwen Zhang 《Chinese Journal of Chemical Engineering》 SCIE EI CAS CSCD 2024年第8期187-198,共12页
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 pro... 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. 展开更多
关键词 Cycloalkane dehydrogenation Pt clusters Oxygen vacancy defects COKING Stability DEACTIVATION
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CO_(2)-assisted oxidation dehydrogenation of light alkanes over metal-based heterogeneous catalysts
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作者 Yingbin Zheng Xinbao Zhang +4 位作者 Junjie Li Jie An Longya Xu Xiujie Li Xiangxue Zhu 《Chinese Journal of Catalysis》 SCIE CAS CSCD 2024年第10期40-69,共30页
Light olefins are important platform feedstocks in the petrochemical industry,and the ongoing global economic development has driven sustained growth in demand for these compounds.The dehydrogenation of alkanes,derive... Light olefins are important platform feedstocks in the petrochemical industry,and the ongoing global economic development has driven sustained growth in demand for these compounds.The dehydrogenation of alkanes,derived from shale gas,serves as an alternative olefins production route.Concurrently,the target of realizing carbon neutrality promotes the comprehensive utilization of greenhouse gas.The integrated process of light alkanes dehydrogenation and carbon dioxide reduction(CO_(2)-ODH)can produce light olefins and realize resource utilization of CO_(2),which has gained wide popularity.With the introduction of CO_(2),coke deposition and metal reduction encountered in alkanes dehydrogenation reactions can be effectively suppressed.CO_(2)-assisted alkanes dehydrogenation can also reduce the risk of potential explosion hazard associated with O_(2)-oxidative dehydrogenation reactions.Recent investigations into various metal-based catalysts including mono-and bi-metallic alloys and oxides have displayed promising performances due to their unique properties.This paper provides the comprehensive review and critical analysis of advancements in the CO_(2)-assisted oxidative dehydrogenation of light alkanes(C2-C4)on metal-based catalysts developed in recent years.Moreover,it offers a comparative summary of the structural properties,catalytic activities,and reaction mechanisms over various active sites,providing valuable insights for the future design of dehydrogenation catalysts. 展开更多
关键词 Light alkanes dehydrogenation CO_(2)utilization Metal-based catalysts Light olefins Coupling reaction
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Ab initio molecular dynamics simulation reveals the influence of entropy effect on Co@BEA zeolite-catalyzed dehydrogenation of ethane
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作者 Yumeng Fo Shaojia Song +8 位作者 Kun Yang Xiangyang Ji Luyuan Yang Liusai Huang Xinyu Chen Xueqiu Wu Jian Liu Zhen Zhao Weiyu Song 《Chinese Journal of Catalysis》 SCIE CAS CSCD 2024年第10期195-205,共11页
The C–H bond activation in alkane dehydrogenation reactions is a key step in determining the reaction rate.To understand the impact of entropy,we performed ab initio static and molecular dynamics free energy simulati... The C–H bond activation in alkane dehydrogenation reactions is a key step in determining the reaction rate.To understand the impact of entropy,we performed ab initio static and molecular dynamics free energy simulations of ethane dehydrogenation over Co@BEA zeolite at different temperatures.AIMD simulations showed that a sharp decrease in free energy barrier as temperature increased.Our analysis of the temperature dependence of activation free energies uncovered an unusual entropic effect accompanying the reaction.The unique spatial structures around the Co active site at different temperatures influenced both the extent of charge transfer in the transition state and the arrangement of 3d orbital energy levels.We provided explanations consistent with the principles of thermodynamics and statistical physics.The insights gained at the atomic level have offered a fresh interpretation of the intricate long-range interplay between local chemical reactions and extensive chemical environments. 展开更多
关键词 Ethane dehydrogenation C-H bond activation Ab initio molecular dynamics simulation ENTROPY Heterogeneous catalysis
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NiO-Doped Fe_(2)O_(3)/MgO Properties for the Chemical Looping Oxidative Dehydrogenation of Ethane
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作者 Liang Hao Chen Junjie +1 位作者 Sun Jie Sun Hui 《China Petroleum Processing & Petrochemical Technology》 SCIE CAS CSCD 2024年第1期27-33,共7页
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 Ni... 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). 展开更多
关键词 chemical looping oxidative dehydrogenation oxygen carrier Fe_(2)O_(3)/MgO NIO
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Small molecule inhibitor DDQ-treated hippocampal neuronal cells show improved neurite outgrowth and synaptic branching
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作者 Jangampalli Adi Pradeepkiran Priyanka Rawat +2 位作者 Arubala P.Reddy Erika Orlov PHemachandra Reddy 《Neural Regeneration Research》 SCIE CAS 2025年第9期2624-2632,共9页
The process of neurite outgrowth and branching is a crucial aspect of neuronal development and regeneration.Axons and dendrites,sometimes referred to as neurites,are extensions of a neuron's cellular body that are... The process of neurite outgrowth and branching is a crucial aspect of neuronal development and regeneration.Axons and dendrites,sometimes referred to as neurites,are extensions of a neuron's cellular body that are used to start networks.Here we explored the effects of diethyl(3,4-dihydroxyphenethylamino)(quinolin-4-yl)methylphosphonate(DDQ)on neurite developmental features in HT22 neuronal cells.In this work,we examined the protective effects of DDQ on neuronal processes and synaptic outgrowth in differentiated HT22cells expressing mutant Tau(mTau)cDNA.To investigate DDQ chara cteristics,cell viability,biochemical,molecular,western blotting,and immunocytochemistry were used.Neurite outgrowth is evaluated through the segmentation and measurement of neural processes.These neural processes can be seen and measured with a fluorescence microscope by manually tracing and measuring the length of the neurite growth.These neuronal processes can be observed and quantified with a fluorescent microscope by manually tracing and measuring the length of the neuronal HT22.DDQ-treated mTau-HT22 cells(HT22 cells transfected with cDNA mutant Tau)were seen to display increased levels of synaptophysin,MAP-2,andβ-tubulin.Additionally,we confirmed and noted reduced levels of both total and p-Tau,as well as elevated levels of microtubule-associated protein 2,β-tubulin,synaptophysin,vesicular acetylcholine transporter,and the mitochondrial biogenesis protein-pe roxisome prolife rator-activated receptor-gamma coactivator-1α.In mTa u-expressed HT22 neurons,we observed DDQ enhanced the neurite characteristics and improved neurite development through increased synaptic outgrowth.Our findings conclude that mTa u-HT22(Alzheimer's disease)cells treated with DDQ have functional neurite developmental chara cteristics.The key finding is that,in mTa u-HT22 cells,DDQ preserves neuronal structure and may even enhance nerve development function with mTa u inhibition. 展开更多
关键词 diethyl(3 4-dihydroxyphenethylamino)(quinolin-4-yl)methylphosphonate(ddq) hippocampal neuronal cells HT22 neurite outgrowth neuronal development small molecule
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Ca_(2)MnO_(4)-layered perovskite modified by NaNO_(3)for chemical-looping oxidative dehydrogenation of ethane to ethylene
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作者 Weixiao Ding Kun Zhao +2 位作者 Shican Jiang Zhen Huang Fang He 《Chinese Journal of Chemical Engineering》 SCIE EI CAS CSCD 2024年第4期53-64,共12页
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... 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. 展开更多
关键词 Chemical-looping oxidative dehydrogenation ETHANE ETHYLENE NaNO_(3)-doped Ca_(2)MnO_(4)redox catalyst Layered perovskites
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Influence of carbonization temperature on cobalt-based nitrogendoped carbon nanopolyhedra derived from ZIF-67 for nonoxidative propane dehydrogenation 被引量:1
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作者 Yu-Ming Li Zi-Ye Liu +5 位作者 Qi-Yang Zhang Ya-Jun Wang Guo-Qing Cui Zhen Zhao Chun-Ming Xu Gui-Yuan Jiang 《Petroleum Science》 SCIE EI CAS CSCD 2023年第1期559-568,共10页
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-pu... 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. 展开更多
关键词 Propane dehydrogenation ZIF-67 Nitrogen-doped carbon COBALT
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Anomalous metastable hcp Ni nanocatalyst induced by non-metal N doping enables promoted ammonia borane dehydrogenation 被引量:1
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作者 Ping Li Yuqi Huang +3 位作者 Quhua Huang Ran Chen Jixin Li Shuanghong Tian 《Journal of Energy Chemistry》 SCIE EI CAS CSCD 2023年第4期72-82,共11页
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... 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. 展开更多
关键词 Hcp Ni Non-metal doping Phase engineering Electronic regulation Ammonia borane dehydrogenation
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Effect of boron species on carbon surface on oxidative dehydrogenation of propane
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作者 Tingcong Wang Mingyuan Zhu 《Chinese Journal of Chemical Engineering》 SCIE EI CAS CSCD 2023年第10期310-317,共8页
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 ... 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. 展开更多
关键词 BORON-DOPED Oxidative dehydrogenation PROPANE SELECTIVITY
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A mini review on oxidative dehydrogenation of propane over boron nitride catalysts
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作者 Zhu Fu De-Zheng Li +5 位作者 Li-Dai Zhou Yu-Ming Li Jia-Wen Guo Yu-Qiao Li Hui-Min Liu Qi-Jian Zhang 《Petroleum Science》 SCIE EI CAS CSCD 2023年第4期2488-2498,共11页
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... 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. 展开更多
关键词 Oxidative dehydrogenation of propane Boron nitride PROPYLENE Reaction mechanism
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Progress in Processes and Catalysts for Dehydrogenation of Cyclohexanol to Cyclohexanone
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作者 Jing Gong Shixin Hou +1 位作者 Yue Wang Xinbin Ma 《Transactions of Tianjin University》 EI CAS 2023年第3期196-208,共13页
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 re... 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. 展开更多
关键词 CYCLOHEXANOL dehydrogenation CYCLOHEXANONE Copper-based catalyst Reaction coupling processes
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Finned Zn-MFI zeolite encapsulated noble metal nanoparticle catalysts for the oxidative dehydrogenation of propane with carbon dioxide
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作者 En-Hui Yuan Yiming Niu +7 位作者 Xing Huang Meng Li Jun Bao Yong-Hong Song Bingsen Zhang Zhao-Tie Liu Marc-Georg Willinger Zhong-Wen Liu 《Journal of Energy Chemistry》 SCIE EI CAS CSCD 2023年第5期479-491,I0011,共14页
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 existin... 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. 展开更多
关键词 Oxidative dehydrogenation PROPANE Carbon dioxide Finned Zn-MFI zeolite Encapsulated noble metal nanoparticles
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Unravelling the role of boron dopant in borocarbonitirde catalytic dehydrogenation reaction
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作者 Xuefei Zhang Yanbing Lu +2 位作者 Yingyi Han Runping Feng Zailai Xie 《Journal of Energy Chemistry》 SCIE EI CAS CSCD 2023年第10期137-143,I0006,共8页
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)... 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. 展开更多
关键词 Borocarbonitride Oxidative dehydrogenation Intrinsic activity CO_(2)selectivity
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Sub-nanometer Pt_(2)In_(3) intermetallics as ultra-stable catalyst for propane dehydrogenation
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作者 Yanan Xing Guiyue Bi +11 位作者 Xiaoli Pan Qike Jiang Yuanlong Tan Yang Su Leilei Kang Bonan Li Lin Li Aiqin Wang Jingyuan Ma Xiaofeng Yang Xiao Yan Liu Tao Zhang 《Journal of Energy Chemistry》 SCIE EI CAS CSCD 2023年第8期304-312,I0009,共10页
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 ... 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. 展开更多
关键词 Propane dehydrogenation PROPYLENE Pt-In catalyst Intermetallic compounds Pt_(2)ln_(3)
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Plasma treated M1 MoVNbTeO_(x)-CeO_(2) composite catalyst for improved performance of oxidative dehydrogenation of ethane
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作者 Shuairen Qian Yuxin Chen +1 位作者 Binhang Yan Yi Cheng 《Green Energy & Environment》 SCIE EI CAS CSCD 2023年第3期904-914,共11页
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... 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. 展开更多
关键词 Oxidative dehydrogenation of ethane(ODHE) MoVNbTeO_(x) Composite catalyst Oxygen plasma Energy conversion
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