Double bonds of internal olefins can be efficiently migrated to the terminal carbons and regioselectively hydroesterified with formates in the presence of Pd(OAc)_(2) and 1,2-DTBPMB under mild reaction conditions,prov...Double bonds of internal olefins can be efficiently migrated to the terminal carbons and regioselectively hydroesterified with formates in the presence of Pd(OAc)_(2) and 1,2-DTBPMB under mild reaction conditions,providing a wide variety of corresponding linear carboxylic esters bearing various functional groups in good yields and>20:1 linear/branch ratios.The reaction is optionally simple and does not need to use CO gas and acid co-catalysts.展开更多
The concept of liquid-solid hybrid catalyst that featuring a truly homogeneous liquid microenvironment together with insoluble solid characteristics has been established recently by our group,which enables us to conve...The concept of liquid-solid hybrid catalyst that featuring a truly homogeneous liquid microenvironment together with insoluble solid characteristics has been established recently by our group,which enables us to conveniently bridge the gap between homo-and heterogeneous catalysis.In this study,we extend this general concept to the confinement of molecular rhodium phosphine complexes,including Rh-TPPTS,Rh-TPPMS and Rh-SXP,for olefin hydroformylation reactions.A series of hybrid catalyst materials consisting a modulated liquid interior([BMIM]NTf_(2),[BMIM]PF_(6),[BMIM]BF_(4) or H_(2)O)and a permeable silica crust were fabricated through our developed Pickering emulsion-based method,showing 9.4–24.2-fold activity enhancement and significantly improved aldehyde selectivity(from 72.2%,61.8%to 86.6%)compared to their biphasic counterparts or traditional supported liquid phase system in the hydroformylation of 1-dodecene.Interestingly,the catalytic efficiency was demonstrated to be tunable by rationally engineering the thickness of porous crust and dimensions of the liquid pool.The thus-attained hybrid catalyst could also successfully catalyze the hydroformylation of a variety of olefin substrates and be recycled without a significant loss of activity for at least seven times.展开更多
The design of low-cost and high-performance cyclic olefin copolymers remains challenging.Ethylene copolymers with dicyclopentadiene(DCPD)were prepared using Ph_(2)C(Cp)(Flu)ZrCl_(2)(Cat.1),rac-Et(Ind)_(2)ZrCl_(2)(Cat....The design of low-cost and high-performance cyclic olefin copolymers remains challenging.Ethylene copolymers with dicyclopentadiene(DCPD)were prepared using Ph_(2)C(Cp)(Flu)ZrCl_(2)(Cat.1),rac-Et(Ind)_(2)ZrCl_(2)(Cat.2),Me_(2)C(Cp)(Flu)ZrCl_(2)(Cat.3)andMe_(2)Si(Ind)_(2)ZrCl_(2)(Cat.4)combined with[Ph_(3)C][B(C_(6)F_(5))_(4)]/iBu_(3)Al.Ni(acac)_(2)/iBu_(3)Al was then used to catalyze the hydrogenation of the intracyclic double bonds of ethylene/DCPD copolymers.The results showed that compared to C_(2) symmetric catalysts(Cat.2 and Cat.4),Cs symmetric catalysts(Cat.1 and Cat.3)facilitated the incorporation of copolymers with higher DCPD.1H-and ^(13)C-NMR spectra indicated that ethylene/DCPD copolymerization occurred via enhancement of the norbornene ring.Additionally,measurement of the reactivity ratios provided further confirmation that the copolymers had random sequence distributions.All these samples demonstrated transmittance values above 90%in the visible wavelength range from 400 nm to 800 nm.By changing the fraction of monomers,the glass transition temperature,refractive index,Young's modulus,and tensile strength of the copolymer increased as the incorporation of DCPD increased,whereas the Abbe number and elongation at break decreased.Compared with ethylene/norbornene and ethylene/tetracyclicdodecene copolymers,ethylene/DCPD copolymers,with excellent optical and mechanical properties,are promising materials.展开更多
The design and synthesis of a novel π-conjugated fiuorescent framework by external ligand-assisted C-H olefination of heterocycles with excellent regioselectivity and broad substrate scope are reported herein.These n...The design and synthesis of a novel π-conjugated fiuorescent framework by external ligand-assisted C-H olefination of heterocycles with excellent regioselectivity and broad substrate scope are reported herein.These novel fiuorescent materials could present full-color-tunable emissions with large Stokes shifts. Furthermore, the protocol provides an opportunity to rapidly screen novel organic single-molecule whitelight materials with high fiuorescence quantum yields. The robust organic and low-cost white lightemitting diodes could rapidly be fabricated using the white-light-emitting material. Experimental data and theoretical calculations indicate that in the white-light dual emission the relatively short wavelength from high-lying singlet state emission and the relatively long wavelength from low-lying singlet state emission. The anti-Kasha dual-emission systems will provide a foundation for the development and application of organic single-molecule white light materials, effectively promoting the development and innovation of luminescent materials. In addition, this method demonstrated its potential application in the synthesis of new near-infrared(NIR) fiuorescence materials with large Stokes shifts based on the olefination of heterocycles.展开更多
Direct conversion of syngas to light olefins(STO)on bifunctional catalysts has garnered significant attention,yet a comprehensive understanding of the reaction pathway and reaction kinetics remains elusive.Herein,we t...Direct conversion of syngas to light olefins(STO)on bifunctional catalysts has garnered significant attention,yet a comprehensive understanding of the reaction pathway and reaction kinetics remains elusive.Herein,we theoretically addressed the kinetics of the direct STO reaction on typical ZnAl_(2)O_(4)/zeolite catalysts by establishing a complete reaction network,consisting of methanol synthesis and conversion,water gas shift(WGS)reaction,olefin hydrogenation,and other relevant steps.The WGS reaction occurs very readily on ZnAl_(2)O_(4) surface whereas which is less active towards alkane formation via olefin hydrogenation,and the latter can be attributed to the characteristics of the H_(2) heterolytic activation and the weak polarity of olefins.The driving effect of zeolite component towards CO conversion was demonstrated by microkinetic simulations,which is sensitive to reaction conditions like space velocity and reaction temperature.Under a fixed ratio of active sites between oxide and zeolite components,the concept of the“impossible trinity”of high CO conversion,high olefin selectivity,and high space velocity can thus be manifested.This work thus provides a comprehensive kinetic picture on the direct STO conversion,offering valuable insights for the design of each component of bifunctional catalysts and the optimization of reaction conditions.展开更多
Fe-based catalysts are widely used for CO_(2)hydrogenation to light olefins(C_(2–4)=);however,precise regulation of active phases and the balance between intermediate reactions remain significant challenges.Herein,we...Fe-based catalysts are widely used for CO_(2)hydrogenation to light olefins(C_(2–4)=);however,precise regulation of active phases and the balance between intermediate reactions remain significant challenges.Herein,we find that the addition of moderate amounts of Ti forms a strong interaction with Fe compositions,modulating the Fe_(3)O_(4)and Fe_(5)C_(2)contents.Enhanced interaction leads to an increased Fe_(5)C_(2)/Fe_(3)O_(4)ratio,which in turn enhances the adsorption of reactants and intermediates,promoting CO hydrogenation to unsaturated alkyl groups and facilitating C–C coupling.Furthermore,the strong Fe-Ti interaction induces the preferential growth of Fe_(5)C_(2)into prismatic structures that expose the(020),(–112),and(311)facets,forming compact active interfacial sites with Fe_(3)O_(4)nanoparticles.These facet and interfacial effects significantly promote the synergistic coupling of the reverse water gas shift and Fischer-Tropsch reactions.The optimized 3K/FeTi catalyst with the highest Fe_(5)C_(2)/Fe_(3)O_(4)ratio of 3.6 achieves a 52.2%CO_(2)conversion rate,with 44.5%selectivity for C2–4=and 9.5%for CO,and the highest space-time yield of 412.0 mg gcat^(–1)h^(–1)for C_(2–4)=.展开更多
Non-metallocene catalysts have emerged as a promising alternative to traditional metallocene catalysts for olefin polymerization,offering unique advantages regarding polymer structure control and product diversity.Rec...Non-metallocene catalysts have emerged as a promising alternative to traditional metallocene catalysts for olefin polymerization,offering unique advantages regarding polymer structure control and product diversity.Recent advancements in ligand design and synthesis have led to the development of highly active and selective non-metallocene catalysts capable of producing polyolefins with tailored properties.These catalysts exhibit enhanced thermal stability,improved comonomer incorporation,and the ability to polymerize a wider range of monomers.Furthermore,nonmetallocene catalysts have shown potential as promising compounds for the production of novel polymer architectures,including hyperbranched and stereoblock polymers.This work provides an overview of the current state of non-metallocene catalysts for olefin polymerization,examining their advantages,challenges,and future prospects in the field of polymer synthesis.展开更多
Light olefins is the incredibly important materials in chemical industry.Methanol to olefins(MTO),which provides a non-oil route for light olefins production,received considerable attention in the past decades.However...Light olefins is the incredibly important materials in chemical industry.Methanol to olefins(MTO),which provides a non-oil route for light olefins production,received considerable attention in the past decades.However,the catalyst deactivation is an inevitable feature in MTO processes,and regeneration,therefore,is one of the key steps in industrial MTO processes.Traditionally the MTO catalyst is regenerated by removing the deposited coke via air combustion,which unavoidably transforms coke into carbon dioxide and reduces the carbon utilization efficiency.Recent study shows that the coke species over MTO catalyst can be regenerated via steam,which can promote the light olefins yield as the deactivated coke species can be essentially transferred to industrially useful synthesis gas,is a promising pathway for further MTO processes development.In this work,we modelled and analyzed these two MTO regeneration methods in terms of carbon utilization efficiency and technology economics.As shown,the steam regeneration could achieve a carbon utilization efficiency of 84.31%,compared to 74.74%for air combustion regeneration.The MTO processes using steam regeneration can essentially achieve the near-zero carbon emission.In addition,light olefins production of the MTO processes using steam regeneration is 12.81%higher than that using air combustion regeneration.In this regard,steam regeneration could be considered as a potential yet promising regeneration method for further MTO processes,showing not only great environmental benefits but also competitive economic performance.展开更多
Heavy oil millisecond gas-phase in-line catalytic dehydrogenation over bifunctional catalysts was adopted to produce low-carbon olefins.In this study,the effect of the uncatalyzed reaction composition and distribution...Heavy oil millisecond gas-phase in-line catalytic dehydrogenation over bifunctional catalysts was adopted to produce low-carbon olefins.In this study,the effect of the uncatalyzed reaction composition and distribution of atmosphere residue(AR)pyrolysis vapor at 650℃ was investigated for the first time.In the pyrolysis vapor,the yield of low-carbon olefins was only 15.2%.The yield of 1-olefin and n-alkanes,which are the primary products of rapid heavy oil pyrolysis,reached approximately 54.0%.To achieve further catalytic dehydrogenation,AR pyrolysis volatiles were catalyzed over single calcium aluminate(C_(12)A_(7)),ZSM-5,and C_(12)A_(7)-ZSM-5(CZ)catalysts at 650℃,which possess different pore structures,and acid-base properties.The ZSM-5 catalyst obtained the highest low-carbon olefin yield after catalytic dehydrogenation of pyrolysis volatiles.Finally,the C_(12)A_(7) and CZ stepwise coupling bifunctional catalysts increased the catalytic activity,and thus increased the higher low-carbon olefin yield but reduced the yields of alkanes and aromatics fraction.Notably,the yields of propylene and butane were important sources of the low-carbon olefins.Thus,heavy oil millisecond gas-phase in-line catalytic dehydrogenation could achieve the maximum conversion of these residues to produce low-carbon olefins.展开更多
In this work, a conceptual DFT investigation is carried out to study the electrophilic aromatic substitution reaction (SEAr) of 1,2-dimethoxybenzene and 3-(p-nitrobenzoyloxy)-but-3-en-2-one (a captodative olefin). Her...In this work, a conceptual DFT investigation is carried out to study the electrophilic aromatic substitution reaction (SEAr) of 1,2-dimethoxybenzene and 3-(p-nitrobenzoyloxy)-but-3-en-2-one (a captodative olefin). Herein, we have studied the regioselectivity of such reactions considering the effect of solvents of different polarities and the presence of BF3 as the catalyst. Understanding the effect of the solvent and the role of the Lewis catalyst on the pathway of Friedel-Crafts reactions is important to further facilitate the introduction of side chains in aromatic rings with captodative olefins, and thus be able to synthesize compounds analogous to natural products, e.g., α-asarone. Global and local reactivity descriptors were obtained, finding a key role when these reactions take place in the presence of nonpolar solvents. In addition, the Intrinsic Reaction Coordinate diagrams (IRCs) were calculated. Such results of the free activation energy (ΔG‡) clearly show that this reaction is entirely regioselective, forming the unique product in the para position, in agreement with our predictions of the local reactivity descriptors obtained from the Parr functions, wherein the first reaction step, the carbon C4 of the aromatic compound 1,2-dimethoxybenzene is favored. Moreover, from the IRCs, we found that the reactivity of the para adduct increases in the presence of nonpolar solvents. Interestingly, considering a polar solvent (MeCN), the intermediate formed (σ-complex) is more stable since it presents a more significant charge transfer with the solvent than the intermediate in the presence of a nonpolar solvent, making a reaction more challenging to reach when the reaction is carried out in the presence of MeCN because of the increasing of the energetic barrier from σ-complex to the TS2 in the intrinsic reactive coordinate diagram. Therefore, the polarity of the solvent plays an important role, particularly in the activation energy of the TS2. Our computational results explained our experimental results quite well, confirming the importance of the solvent’s polarity to this SEAr reaction and explaining why, experimentally, the nonpolar solvent drove the reaction under catalyzed conditions.展开更多
Fe‐based catalysts for the production of light olefins via the Fischer‐Tropsch synthesis were modi‐fied by adding a Zn promoter using both microwave‐hydrothermal and impregnation methods. The physicochemical prope...Fe‐based catalysts for the production of light olefins via the Fischer‐Tropsch synthesis were modi‐fied by adding a Zn promoter using both microwave‐hydrothermal and impregnation methods. The physicochemical properties of the resulting catalysts were determined by scanning electron mi‐croscopy, the Brunauer‐Emmett‐Teller method, X‐ray diffraction, H2 temperature‐programed re‐duction and X‐ray photoelectron spectroscopy. The results demonstrate that the addition of a Zn promoter improves both the light olefin selectivity over the catalyst and the catalyst stability. The catalysts prepared via the impregnation method, which contain greater quantities of surface ZnO, exhibit severe carbon deposition following activity trials. In contrast, those materials synthesized using the microwave‐hydrothermal approach show improved dispersion of Zn and Fe phases and decreased carbon deposition, and so exhibit better CO conversion and stability.展开更多
The ZSM-5 zeolite with an unusual snowflake-shaped morphology was hydrothermally synthesized for the first time,and compared with common ellipsoidal and boat-like shaped samples.These samples were characterized by N2 ...The ZSM-5 zeolite with an unusual snowflake-shaped morphology was hydrothermally synthesized for the first time,and compared with common ellipsoidal and boat-like shaped samples.These samples were characterized by N2 adsorption-desorption,X-ray fluorescence spectroscopy,scanning electron microscopy,X-ray diffraction,magic angle spinning nuclear magnetic resonance,temperature-programmed desorption of ammonia,and infrared spectroscopy of pyridine adsorption.The results suggest that the BET surface area and SiO2/Al2O3 ratio of these samples are similar,while the snowflake-shaped ZSM-5 zeolite possesses more of the（101） face,and distortion,dislocation,and asymmetry in the framework,resulting in a larger number of acid sites than the conventional samples.Catalysts for the methanol to olefin（MTO） reaction were prepared by loading Ca on the samples.The snowflake-shaped Ca/ZSM-5 zeolite exhibited excellent selectivity for total light olefin（72%） and propene（39%） in MTO.The catalytic performance influenced by the morphology can be mainly attributed to the snowflake-shaped ZSM-5 zeolite possessing distortion,dislocation,and asymmetry in the framework,and lower diffusion limitation than the conventional samples.展开更多
The density functional theory on the level of B3LYP/6-31G was empolyed to study the chain growth mechanism in polymerization process of α-linear olefin in TiCl3/AlEt2Cl catalytic system to synthesize drag reduction a...The density functional theory on the level of B3LYP/6-31G was empolyed to study the chain growth mechanism in polymerization process of α-linear olefin in TiCl3/AlEt2Cl catalytic system to synthesize drag reduction agent. Full parameter optimization without symmetry restrictions for reactants, products, the possible transition states, and intermediates was calculated. Vibration frequency was analyzed for all of stagnation points on the potential energy surface at the same theoretical level. The internal reaction coordinate was calculated from the transition states to reactants and products respectively. The results showed as flloes： （i） Coordination compounds were formed on the optimum configuration of TiCl3/AlEt2Cl.（ii） The transition states were formed. The energy di？erence between transition states and the coordination compounds was 40.687 kJ/mol. （iii） Double bond opened and Ti-C（4） bond fractured, and the polymerization was completed. The calculation results also showed that the chain growth mechanism did not essentially change with the increase of carbon atom number of α-linear olefin. From the relationship between polymerization activation energy and carbon atom number of the α-linear olefin, it can be seen that the α-linear olefin monomers with 6-10 carbon atoms had low activation energy and wide range. It was optimum to synthesize drag reduction agent by polymerization.展开更多
NiSAPO-34 and NiSAPO-34/HZSM-5 were prepared and evaluated for the performance of dimethyl ether （DME） conversion to light olefins （DTO）. The processes of two-stage light olefin production, DME synthesis and the f...NiSAPO-34 and NiSAPO-34/HZSM-5 were prepared and evaluated for the performance of dimethyl ether （DME） conversion to light olefins （DTO）. The processes of two-stage light olefin production, DME synthesis and the following DTO, were also investigated using biosyngas as feed gas over Cu/Zn/A1/HZSM-5 and the optimized 2%NiSAPO-34/HZSM- 5. The results indicated that adding 2%Ni to SAPO-34 did not change its topology structure, but resulted in the forming of the moderately strong acidity with decreasing acid amounts, which slightly enhanced DME conversion activity and C2=-C3= selectiw ity. Mechanically mixing 2%NiSAPO-34 with HZSM-5 at the weight ratio of 3.0 further prolonged DME conversion activity to be more than 3 h, which was due to the stable acid sites from HZSM-5. The highest selectivity to light olefins of 90.8% was achieved at 2 h time on stream. The application of the optimized 2%NiSAPO-34/HZSM-5 in the second-stage reactor for DTO reaction showed that the catalytic activity was steady for more than 5 h and light olefin yield was as high as 84.6 g/m3syngas when the biosyngas （H2/CO/CO2/N2/CH4=41.5/26.9/14.2/14.6/2.89, vol%） with low H/C ratio of 1.0 was used as feed gas.展开更多
The catalytic epoxidation of olefin was investigated on two copper complex-modified molybdenum oxides with a 3D supramolecular structure, [Cu（bipy）]4[Mo15O47].2H2O （1） and [Cu1（bix）][（Cu1bix） （δ-MoVl8O26）0....The catalytic epoxidation of olefin was investigated on two copper complex-modified molybdenum oxides with a 3D supramolecular structure, [Cu（bipy）]4[Mo15O47].2H2O （1） and [Cu1（bix）][（Cu1bix） （δ-MoVl8O26）0.5] （2） （bipy = 4,4＇-bipyridine, bix = 1,4-bis（imidazole-1-ylmethyl）benzene）. Both compounds were catalytically active and stable for the epoxidation of cyclooctene, 1-octene, and styrene with tert-butyl hydroperoxide （t-BuOOH） as oxidant. The excellent catalytic performance was attributed to the presence of stable coordination bonds between the molybdenum oxide and copper complex, which resulted in the formation of easily accessible Mo species with high electropositivity. In addition, the copper complex also acted as an active site for the activation of t-BuOOH, thus im- proving these copper complex-modified polyoxometalates.展开更多
Co2C‐based catalysts with SiO2,γ‐Al2O3,and carbon nanotubes(CNTs)as support materials were prepared and evaluated for the Fischer‐Tropsch to olefin(FTO)reaction.The combination of catalytic performance and structu...Co2C‐based catalysts with SiO2,γ‐Al2O3,and carbon nanotubes(CNTs)as support materials were prepared and evaluated for the Fischer‐Tropsch to olefin(FTO)reaction.The combination of catalytic performance and structure characterization indicates that the cobalt‐support interaction has a great influence on the Co2C morphology and catalytic performance.The CNT support facilitates the formation of a CoMn composite oxide during calcination,and Co2C nanoprisms were observed in the spent catalysts,resulting in a product distribution that greatly deviates from the classical Anderson‐Schulz‐Flory(ASF)distribution,where only 2.4 C%methane was generated.The Co3O4 phase for SiO2‐andγ‐Al2O3‐supported catalysts was observed in the calcined sample.After reduction,CoO,MnO,and low‐valence CoMn composite oxide were generated in theγ‐Al2O3‐supported sample,and both Co2C nanospheres and nanoprisms were identified in the corresponding spent catalyst.However,only separated phases of CoO and MnO were found in the reduced sample supported by SiO2,and Co2C nanospheres were detected in the spent catalyst without the evidence of any Co2C nanoprisms.The Co2C nanospheres led to a relatively high methane selectivity of 5.8 C%and 12.0 C%of theγ‐Al2O3‐and SiO2‐supported catalysts,respectively.These results suggest that a relatively weak cobalt‐support interaction is necessary for the formation of the CoMn composite oxide during calcination,which benefits the formation of Co2C nanoprisms with promising catalytic performance for the sustainable production of olefins via syngas.展开更多
The Fischer–Tropsch to olefins（FTO） process is a method for the direct conversion of synthesis gas to lower C–Colefins. Carbon-supported iron carbide nanoparticles are attractive catalysts for this reaction.The ca...The Fischer–Tropsch to olefins（FTO） process is a method for the direct conversion of synthesis gas to lower C–Colefins. Carbon-supported iron carbide nanoparticles are attractive catalysts for this reaction.The catalytic activity can be improved and undesired formation of alkanes can be suppressed by the addition of sodium and sulfur as promoters but the influence of their content and ratio remains poorly understood and the promoted catalysts often suffer from rapid deactivation due to particle growth. A series of carbon black-supported iron catalysts with similar iron content and nominal sodium/sulfur loadings of 1–30/0.5–5 wt% with respect to iron are prepared and characterized under FTO conditions at 1and 10 bar syngas pressure to illuminate the influence of the promoter level on the catalytic properties.Iron particles and promoters undergo significant reorganization during FTO operation under industrially relevant conditions. Low sodium content（1–3 wt%） leads to a delay in iron carbide formation. Sodium contents of 15–30 wt% lead to rapid loss of catalytic activity due to the covering of the iron surface with promoters during particle growth under FTO operation. Higher activity and slower loss of activity are observed at low promoter contents（1–3 wt% sodium and 0.5–1 wt% sulfur） but a minimum amount of alkali is required to effectively suppress methane and C–Cparaffin formation. A reference catalyst support（carbide-derived carbon aerogel） shows that the optimum promoter level depends on iron particle size and support pore structure.展开更多
Low-carbon light olefins are the basic feedstocks for the petrochemical industry. Catalytic cracking of crude bio-oil and its model compounds （including methanol, ethanol, acetic acid, acetone, and phenol） to light ...Low-carbon light olefins are the basic feedstocks for the petrochemical industry. Catalytic cracking of crude bio-oil and its model compounds （including methanol, ethanol, acetic acid, acetone, and phenol） to light olefins were performed by using the La/HZSM-5 catalyst. The highest olefins yield from crude bio-oil reached 0.19 kg/（kg crude bio-oil）. The reaction conditions including temperature, weight hourly space velocity, and addition of La into the HZSM-5 zeolite can be used to control both olefins yield and selectivity. Moderate adjusting the acidity with a suitable ratio between the strong acid and weak acid sites through adding La to the zeolite effectively enhanced the olefins selectivity and improved the catalyst stability. The production of light olefins from crude bio-oil is closely associated with the chemical composition and hydrogen to carbon effective ratios of feedstock. The comparison between the catalytic cracking and pyrolysis of bio-oil was studied. The mechanism of the bio-oil conversion to light olefins was also discussed.展开更多
基金financial support from the National Natural Science Foundation of China(Nos.22271024,21632005)Changzhou University.
文摘Double bonds of internal olefins can be efficiently migrated to the terminal carbons and regioselectively hydroesterified with formates in the presence of Pd(OAc)_(2) and 1,2-DTBPMB under mild reaction conditions,providing a wide variety of corresponding linear carboxylic esters bearing various functional groups in good yields and>20:1 linear/branch ratios.The reaction is optionally simple and does not need to use CO gas and acid co-catalysts.
文摘The concept of liquid-solid hybrid catalyst that featuring a truly homogeneous liquid microenvironment together with insoluble solid characteristics has been established recently by our group,which enables us to conveniently bridge the gap between homo-and heterogeneous catalysis.In this study,we extend this general concept to the confinement of molecular rhodium phosphine complexes,including Rh-TPPTS,Rh-TPPMS and Rh-SXP,for olefin hydroformylation reactions.A series of hybrid catalyst materials consisting a modulated liquid interior([BMIM]NTf_(2),[BMIM]PF_(6),[BMIM]BF_(4) or H_(2)O)and a permeable silica crust were fabricated through our developed Pickering emulsion-based method,showing 9.4–24.2-fold activity enhancement and significantly improved aldehyde selectivity(from 72.2%,61.8%to 86.6%)compared to their biphasic counterparts or traditional supported liquid phase system in the hydroformylation of 1-dodecene.Interestingly,the catalytic efficiency was demonstrated to be tunable by rationally engineering the thickness of porous crust and dimensions of the liquid pool.The thus-attained hybrid catalyst could also successfully catalyze the hydroformylation of a variety of olefin substrates and be recycled without a significant loss of activity for at least seven times.
基金supported by the National Natural Science Foundation of China(Nos.52130307 and 5240031453).
文摘The design of low-cost and high-performance cyclic olefin copolymers remains challenging.Ethylene copolymers with dicyclopentadiene(DCPD)were prepared using Ph_(2)C(Cp)(Flu)ZrCl_(2)(Cat.1),rac-Et(Ind)_(2)ZrCl_(2)(Cat.2),Me_(2)C(Cp)(Flu)ZrCl_(2)(Cat.3)andMe_(2)Si(Ind)_(2)ZrCl_(2)(Cat.4)combined with[Ph_(3)C][B(C_(6)F_(5))_(4)]/iBu_(3)Al.Ni(acac)_(2)/iBu_(3)Al was then used to catalyze the hydrogenation of the intracyclic double bonds of ethylene/DCPD copolymers.The results showed that compared to C_(2) symmetric catalysts(Cat.2 and Cat.4),Cs symmetric catalysts(Cat.1 and Cat.3)facilitated the incorporation of copolymers with higher DCPD.1H-and ^(13)C-NMR spectra indicated that ethylene/DCPD copolymerization occurred via enhancement of the norbornene ring.Additionally,measurement of the reactivity ratios provided further confirmation that the copolymers had random sequence distributions.All these samples demonstrated transmittance values above 90%in the visible wavelength range from 400 nm to 800 nm.By changing the fraction of monomers,the glass transition temperature,refractive index,Young's modulus,and tensile strength of the copolymer increased as the incorporation of DCPD increased,whereas the Abbe number and elongation at break decreased.Compared with ethylene/norbornene and ethylene/tetracyclicdodecene copolymers,ethylene/DCPD copolymers,with excellent optical and mechanical properties,are promising materials.
基金the Fundamental Research Funds for the Central Universities (Nos. 2024CDJXY0022023CDJYGRH-YB17+4 种基金2022CDJXY-025)the Venture & Innovation Support Program for Chongqing Overseas Returnees (No. cx2022061)the Natural Science Foundation of Chongqing (No. CSTB2022NSCQ-MSX1123)the Chongqing Talents: Exceptional Young Talents Project (No. cstc2021ycjh-bgzxm0067)the Hongshen Young Scholars Program from Chongqing University (No. 0247001104426) for financial support。
文摘The design and synthesis of a novel π-conjugated fiuorescent framework by external ligand-assisted C-H olefination of heterocycles with excellent regioselectivity and broad substrate scope are reported herein.These novel fiuorescent materials could present full-color-tunable emissions with large Stokes shifts. Furthermore, the protocol provides an opportunity to rapidly screen novel organic single-molecule whitelight materials with high fiuorescence quantum yields. The robust organic and low-cost white lightemitting diodes could rapidly be fabricated using the white-light-emitting material. Experimental data and theoretical calculations indicate that in the white-light dual emission the relatively short wavelength from high-lying singlet state emission and the relatively long wavelength from low-lying singlet state emission. The anti-Kasha dual-emission systems will provide a foundation for the development and application of organic single-molecule white light materials, effectively promoting the development and innovation of luminescent materials. In addition, this method demonstrated its potential application in the synthesis of new near-infrared(NIR) fiuorescence materials with large Stokes shifts based on the olefination of heterocycles.
文摘Direct conversion of syngas to light olefins(STO)on bifunctional catalysts has garnered significant attention,yet a comprehensive understanding of the reaction pathway and reaction kinetics remains elusive.Herein,we theoretically addressed the kinetics of the direct STO reaction on typical ZnAl_(2)O_(4)/zeolite catalysts by establishing a complete reaction network,consisting of methanol synthesis and conversion,water gas shift(WGS)reaction,olefin hydrogenation,and other relevant steps.The WGS reaction occurs very readily on ZnAl_(2)O_(4) surface whereas which is less active towards alkane formation via olefin hydrogenation,and the latter can be attributed to the characteristics of the H_(2) heterolytic activation and the weak polarity of olefins.The driving effect of zeolite component towards CO conversion was demonstrated by microkinetic simulations,which is sensitive to reaction conditions like space velocity and reaction temperature.Under a fixed ratio of active sites between oxide and zeolite components,the concept of the“impossible trinity”of high CO conversion,high olefin selectivity,and high space velocity can thus be manifested.This work thus provides a comprehensive kinetic picture on the direct STO conversion,offering valuable insights for the design of each component of bifunctional catalysts and the optimization of reaction conditions.
文摘Fe-based catalysts are widely used for CO_(2)hydrogenation to light olefins(C_(2–4)=);however,precise regulation of active phases and the balance between intermediate reactions remain significant challenges.Herein,we find that the addition of moderate amounts of Ti forms a strong interaction with Fe compositions,modulating the Fe_(3)O_(4)and Fe_(5)C_(2)contents.Enhanced interaction leads to an increased Fe_(5)C_(2)/Fe_(3)O_(4)ratio,which in turn enhances the adsorption of reactants and intermediates,promoting CO hydrogenation to unsaturated alkyl groups and facilitating C–C coupling.Furthermore,the strong Fe-Ti interaction induces the preferential growth of Fe_(5)C_(2)into prismatic structures that expose the(020),(–112),and(311)facets,forming compact active interfacial sites with Fe_(3)O_(4)nanoparticles.These facet and interfacial effects significantly promote the synergistic coupling of the reverse water gas shift and Fischer-Tropsch reactions.The optimized 3K/FeTi catalyst with the highest Fe_(5)C_(2)/Fe_(3)O_(4)ratio of 3.6 achieves a 52.2%CO_(2)conversion rate,with 44.5%selectivity for C2–4=and 9.5%for CO,and the highest space-time yield of 412.0 mg gcat^(–1)h^(–1)for C_(2–4)=.
文摘Non-metallocene catalysts have emerged as a promising alternative to traditional metallocene catalysts for olefin polymerization,offering unique advantages regarding polymer structure control and product diversity.Recent advancements in ligand design and synthesis have led to the development of highly active and selective non-metallocene catalysts capable of producing polyolefins with tailored properties.These catalysts exhibit enhanced thermal stability,improved comonomer incorporation,and the ability to polymerize a wider range of monomers.Furthermore,nonmetallocene catalysts have shown potential as promising compounds for the production of novel polymer architectures,including hyperbranched and stereoblock polymers.This work provides an overview of the current state of non-metallocene catalysts for olefin polymerization,examining their advantages,challenges,and future prospects in the field of polymer synthesis.
基金the financial support from the Strategic Priority Research Program of Chinese Academy of Sciences(XDA21010100)。
文摘Light olefins is the incredibly important materials in chemical industry.Methanol to olefins(MTO),which provides a non-oil route for light olefins production,received considerable attention in the past decades.However,the catalyst deactivation is an inevitable feature in MTO processes,and regeneration,therefore,is one of the key steps in industrial MTO processes.Traditionally the MTO catalyst is regenerated by removing the deposited coke via air combustion,which unavoidably transforms coke into carbon dioxide and reduces the carbon utilization efficiency.Recent study shows that the coke species over MTO catalyst can be regenerated via steam,which can promote the light olefins yield as the deactivated coke species can be essentially transferred to industrially useful synthesis gas,is a promising pathway for further MTO processes development.In this work,we modelled and analyzed these two MTO regeneration methods in terms of carbon utilization efficiency and technology economics.As shown,the steam regeneration could achieve a carbon utilization efficiency of 84.31%,compared to 74.74%for air combustion regeneration.The MTO processes using steam regeneration can essentially achieve the near-zero carbon emission.In addition,light olefins production of the MTO processes using steam regeneration is 12.81%higher than that using air combustion regeneration.In this regard,steam regeneration could be considered as a potential yet promising regeneration method for further MTO processes,showing not only great environmental benefits but also competitive economic performance.
基金the financial sponsored by the CNPC Innovation Found(No.2022DQ02-0402)the Natural Science Basic Research Program of Shaanxi(No.2024JC-YBMS-085)+2 种基金Shandong Provincial Postdoctoral Science Foundation(No.SDCX-ZG-202303044)the State Key Laboratory of Heavy Oil Processing(No.SKLHOP202201004,No.SKLHOP202403001)the Graduate Student Innovation and Practical Ability Training Program of Xi'an Shiyou University(No.YCS23213078).
文摘Heavy oil millisecond gas-phase in-line catalytic dehydrogenation over bifunctional catalysts was adopted to produce low-carbon olefins.In this study,the effect of the uncatalyzed reaction composition and distribution of atmosphere residue(AR)pyrolysis vapor at 650℃ was investigated for the first time.In the pyrolysis vapor,the yield of low-carbon olefins was only 15.2%.The yield of 1-olefin and n-alkanes,which are the primary products of rapid heavy oil pyrolysis,reached approximately 54.0%.To achieve further catalytic dehydrogenation,AR pyrolysis volatiles were catalyzed over single calcium aluminate(C_(12)A_(7)),ZSM-5,and C_(12)A_(7)-ZSM-5(CZ)catalysts at 650℃,which possess different pore structures,and acid-base properties.The ZSM-5 catalyst obtained the highest low-carbon olefin yield after catalytic dehydrogenation of pyrolysis volatiles.Finally,the C_(12)A_(7) and CZ stepwise coupling bifunctional catalysts increased the catalytic activity,and thus increased the higher low-carbon olefin yield but reduced the yields of alkanes and aromatics fraction.Notably,the yields of propylene and butane were important sources of the low-carbon olefins.Thus,heavy oil millisecond gas-phase in-line catalytic dehydrogenation could achieve the maximum conversion of these residues to produce low-carbon olefins.
文摘In this work, a conceptual DFT investigation is carried out to study the electrophilic aromatic substitution reaction (SEAr) of 1,2-dimethoxybenzene and 3-(p-nitrobenzoyloxy)-but-3-en-2-one (a captodative olefin). Herein, we have studied the regioselectivity of such reactions considering the effect of solvents of different polarities and the presence of BF3 as the catalyst. Understanding the effect of the solvent and the role of the Lewis catalyst on the pathway of Friedel-Crafts reactions is important to further facilitate the introduction of side chains in aromatic rings with captodative olefins, and thus be able to synthesize compounds analogous to natural products, e.g., α-asarone. Global and local reactivity descriptors were obtained, finding a key role when these reactions take place in the presence of nonpolar solvents. In addition, the Intrinsic Reaction Coordinate diagrams (IRCs) were calculated. Such results of the free activation energy (ΔG‡) clearly show that this reaction is entirely regioselective, forming the unique product in the para position, in agreement with our predictions of the local reactivity descriptors obtained from the Parr functions, wherein the first reaction step, the carbon C4 of the aromatic compound 1,2-dimethoxybenzene is favored. Moreover, from the IRCs, we found that the reactivity of the para adduct increases in the presence of nonpolar solvents. Interestingly, considering a polar solvent (MeCN), the intermediate formed (σ-complex) is more stable since it presents a more significant charge transfer with the solvent than the intermediate in the presence of a nonpolar solvent, making a reaction more challenging to reach when the reaction is carried out in the presence of MeCN because of the increasing of the energetic barrier from σ-complex to the TS2 in the intrinsic reactive coordinate diagram. Therefore, the polarity of the solvent plays an important role, particularly in the activation energy of the TS2. Our computational results explained our experimental results quite well, confirming the importance of the solvent’s polarity to this SEAr reaction and explaining why, experimentally, the nonpolar solvent drove the reaction under catalyzed conditions.
基金supported by the Key Project of Natural Science Foundation of Ningxia(NZ13010)the National Natural Science Foundation of China(21366025)~~
文摘Fe‐based catalysts for the production of light olefins via the Fischer‐Tropsch synthesis were modi‐fied by adding a Zn promoter using both microwave‐hydrothermal and impregnation methods. The physicochemical properties of the resulting catalysts were determined by scanning electron mi‐croscopy, the Brunauer‐Emmett‐Teller method, X‐ray diffraction, H2 temperature‐programed re‐duction and X‐ray photoelectron spectroscopy. The results demonstrate that the addition of a Zn promoter improves both the light olefin selectivity over the catalyst and the catalyst stability. The catalysts prepared via the impregnation method, which contain greater quantities of surface ZnO, exhibit severe carbon deposition following activity trials. In contrast, those materials synthesized using the microwave‐hydrothermal approach show improved dispersion of Zn and Fe phases and decreased carbon deposition, and so exhibit better CO conversion and stability.
基金Synfuels China Co.Ltd.for the financial and equipments support
文摘The ZSM-5 zeolite with an unusual snowflake-shaped morphology was hydrothermally synthesized for the first time,and compared with common ellipsoidal and boat-like shaped samples.These samples were characterized by N2 adsorption-desorption,X-ray fluorescence spectroscopy,scanning electron microscopy,X-ray diffraction,magic angle spinning nuclear magnetic resonance,temperature-programmed desorption of ammonia,and infrared spectroscopy of pyridine adsorption.The results suggest that the BET surface area and SiO2/Al2O3 ratio of these samples are similar,while the snowflake-shaped ZSM-5 zeolite possesses more of the（101） face,and distortion,dislocation,and asymmetry in the framework,resulting in a larger number of acid sites than the conventional samples.Catalysts for the methanol to olefin（MTO） reaction were prepared by loading Ca on the samples.The snowflake-shaped Ca/ZSM-5 zeolite exhibited excellent selectivity for total light olefin（72%） and propene（39%） in MTO.The catalytic performance influenced by the morphology can be mainly attributed to the snowflake-shaped ZSM-5 zeolite possessing distortion,dislocation,and asymmetry in the framework,and lower diffusion limitation than the conventional samples.
文摘The density functional theory on the level of B3LYP/6-31G was empolyed to study the chain growth mechanism in polymerization process of α-linear olefin in TiCl3/AlEt2Cl catalytic system to synthesize drag reduction agent. Full parameter optimization without symmetry restrictions for reactants, products, the possible transition states, and intermediates was calculated. Vibration frequency was analyzed for all of stagnation points on the potential energy surface at the same theoretical level. The internal reaction coordinate was calculated from the transition states to reactants and products respectively. The results showed as flloes： （i） Coordination compounds were formed on the optimum configuration of TiCl3/AlEt2Cl.（ii） The transition states were formed. The energy di？erence between transition states and the coordination compounds was 40.687 kJ/mol. （iii） Double bond opened and Ti-C（4） bond fractured, and the polymerization was completed. The calculation results also showed that the chain growth mechanism did not essentially change with the increase of carbon atom number of α-linear olefin. From the relationship between polymerization activation energy and carbon atom number of the α-linear olefin, it can be seen that the α-linear olefin monomers with 6-10 carbon atoms had low activation energy and wide range. It was optimum to synthesize drag reduction agent by polymerization.
基金ACKNOWLEDGM ENTS This work was supported by the National Natural Science Foundation of China （No.51006110, No.51276183, and No.51036006）, the National Natural Research Foundation of China/Japan Science and Technology Agency （No.51161140331）, and National Key Basic Research Program 973 Project Founded by MOST of China （No.2013CB228105）.
文摘NiSAPO-34 and NiSAPO-34/HZSM-5 were prepared and evaluated for the performance of dimethyl ether （DME） conversion to light olefins （DTO）. The processes of two-stage light olefin production, DME synthesis and the following DTO, were also investigated using biosyngas as feed gas over Cu/Zn/A1/HZSM-5 and the optimized 2%NiSAPO-34/HZSM- 5. The results indicated that adding 2%Ni to SAPO-34 did not change its topology structure, but resulted in the forming of the moderately strong acidity with decreasing acid amounts, which slightly enhanced DME conversion activity and C2=-C3= selectiw ity. Mechanically mixing 2%NiSAPO-34 with HZSM-5 at the weight ratio of 3.0 further prolonged DME conversion activity to be more than 3 h, which was due to the stable acid sites from HZSM-5. The highest selectivity to light olefins of 90.8% was achieved at 2 h time on stream. The application of the optimized 2%NiSAPO-34/HZSM-5 in the second-stage reactor for DTO reaction showed that the catalytic activity was steady for more than 5 h and light olefin yield was as high as 84.6 g/m3syngas when the biosyngas （H2/CO/CO2/N2/CH4=41.5/26.9/14.2/14.6/2.89, vol%） with low H/C ratio of 1.0 was used as feed gas.
基金supported by the National Natural Science Foundation of China(21173100 and 21320102001)~~
文摘The catalytic epoxidation of olefin was investigated on two copper complex-modified molybdenum oxides with a 3D supramolecular structure, [Cu（bipy）]4[Mo15O47].2H2O （1） and [Cu1（bix）][（Cu1bix） （δ-MoVl8O26）0.5] （2） （bipy = 4,4＇-bipyridine, bix = 1,4-bis（imidazole-1-ylmethyl）benzene）. Both compounds were catalytically active and stable for the epoxidation of cyclooctene, 1-octene, and styrene with tert-butyl hydroperoxide （t-BuOOH） as oxidant. The excellent catalytic performance was attributed to the presence of stable coordination bonds between the molybdenum oxide and copper complex, which resulted in the formation of easily accessible Mo species with high electropositivity. In addition, the copper complex also acted as an active site for the activation of t-BuOOH, thus im- proving these copper complex-modified polyoxometalates.
文摘Co2C‐based catalysts with SiO2,γ‐Al2O3,and carbon nanotubes(CNTs)as support materials were prepared and evaluated for the Fischer‐Tropsch to olefin(FTO)reaction.The combination of catalytic performance and structure characterization indicates that the cobalt‐support interaction has a great influence on the Co2C morphology and catalytic performance.The CNT support facilitates the formation of a CoMn composite oxide during calcination,and Co2C nanoprisms were observed in the spent catalysts,resulting in a product distribution that greatly deviates from the classical Anderson‐Schulz‐Flory(ASF)distribution,where only 2.4 C%methane was generated.The Co3O4 phase for SiO2‐andγ‐Al2O3‐supported catalysts was observed in the calcined sample.After reduction,CoO,MnO,and low‐valence CoMn composite oxide were generated in theγ‐Al2O3‐supported sample,and both Co2C nanospheres and nanoprisms were identified in the corresponding spent catalyst.However,only separated phases of CoO and MnO were found in the reduced sample supported by SiO2,and Co2C nanospheres were detected in the spent catalyst without the evidence of any Co2C nanoprisms.The Co2C nanospheres led to a relatively high methane selectivity of 5.8 C%and 12.0 C%of theγ‐Al2O3‐and SiO2‐supported catalysts,respectively.These results suggest that a relatively weak cobalt‐support interaction is necessary for the formation of the CoMn composite oxide during calcination,which benefits the formation of Co2C nanoprisms with promising catalytic performance for the sustainable production of olefins via syngas.
基金supported by a Post Doc grant of the German Academic Exchange Service(Deutscher Akademischer Austauschdienst,DAAD grant no.91552012)by the European Research Council(EU FP7 ERC advanced grant no.338846)
文摘The Fischer–Tropsch to olefins（FTO） process is a method for the direct conversion of synthesis gas to lower C–Colefins. Carbon-supported iron carbide nanoparticles are attractive catalysts for this reaction.The catalytic activity can be improved and undesired formation of alkanes can be suppressed by the addition of sodium and sulfur as promoters but the influence of their content and ratio remains poorly understood and the promoted catalysts often suffer from rapid deactivation due to particle growth. A series of carbon black-supported iron catalysts with similar iron content and nominal sodium/sulfur loadings of 1–30/0.5–5 wt% with respect to iron are prepared and characterized under FTO conditions at 1and 10 bar syngas pressure to illuminate the influence of the promoter level on the catalytic properties.Iron particles and promoters undergo significant reorganization during FTO operation under industrially relevant conditions. Low sodium content（1–3 wt%） leads to a delay in iron carbide formation. Sodium contents of 15–30 wt% lead to rapid loss of catalytic activity due to the covering of the iron surface with promoters during particle growth under FTO operation. Higher activity and slower loss of activity are observed at low promoter contents（1–3 wt% sodium and 0.5–1 wt% sulfur） but a minimum amount of alkali is required to effectively suppress methane and C–Cparaffin formation. A reference catalyst support（carbide-derived carbon aerogel） shows that the optimum promoter level depends on iron particle size and support pore structure.
基金This work is supported by the National Key Basic Program of China （No.2013CB228105） and the National Natural Science Foundation of China （No.51161140331）.
文摘Low-carbon light olefins are the basic feedstocks for the petrochemical industry. Catalytic cracking of crude bio-oil and its model compounds （including methanol, ethanol, acetic acid, acetone, and phenol） to light olefins were performed by using the La/HZSM-5 catalyst. The highest olefins yield from crude bio-oil reached 0.19 kg/（kg crude bio-oil）. The reaction conditions including temperature, weight hourly space velocity, and addition of La into the HZSM-5 zeolite can be used to control both olefins yield and selectivity. Moderate adjusting the acidity with a suitable ratio between the strong acid and weak acid sites through adding La to the zeolite effectively enhanced the olefins selectivity and improved the catalyst stability. The production of light olefins from crude bio-oil is closely associated with the chemical composition and hydrogen to carbon effective ratios of feedstock. The comparison between the catalytic cracking and pyrolysis of bio-oil was studied. The mechanism of the bio-oil conversion to light olefins was also discussed.
