Propylene oxide(PO),with its reactive three-membered epoxide functional group,exhibits remarkable functional versatility and serves as a crucial bridge connecting the gaps between fossil energy utilization and chemica...Propylene oxide(PO),with its reactive three-membered epoxide functional group,exhibits remarkable functional versatility and serves as a crucial bridge connecting the gaps between fossil energy utilization and chemical intermediate generation for new material innovation [1].For instance,PO's downstream derivatives,such as polyether polyols,carbonic esters,and polyurethanes,are widely utilized in wind power generation,battery electrolytes,solar cells,and CO_(2)-based degradable polymers,contributing to sustainable decarbonization in industry [2].展开更多
As an important chemical product,propylene(C_(3)H_(6))is widely used in production of many crucial chemical products such as polypropylene.Propane(C_(3)H_(8))is introduced as an inevitable gas impurity during the naph...As an important chemical product,propylene(C_(3)H_(6))is widely used in production of many crucial chemical products such as polypropylene.Propane(C_(3)H_(8))is introduced as an inevitable gas impurity during the naphtha cracking in propylene production.At present,thermal-driven energy-intensive cryogenic distillation is the most common purification method in industry.An energy-efficient,cost-effective and environmental-friendly separation technology is required to get polymer grade C_(3)H_(6)(higher than 99.5%).In face of the increasing demand of propylene,new separation technology based on porous adsorbents is expected to be a promising alternative.In recent years,metal-organic frameworks(MOFs)have obtained attention by their high porosity,regular adjustable pore shape and pore environment and keep making breakthroughs in separation and purification of many industrial gas mixtures,and are thus considered as one of the most potential types of adsorbents.The physical properties of C_(3)H_(6)and C_(3)H_(8),such as boiling point,size and kinetic diameter,are close to each other,making their separation a challenge.Most C_(3)H_(6)/C_(3)H_(8)sieving MOFs based on narrow sieving channels that restrict the access of molecules larger than their confined entrance purify mixtures at the cost of diffusion and capacity.To improve the adsorption of MOFs based on molecular sieving,a novel‘pearl-necklace’strategy was designed,which was named for its connected channel and molecular pocket vividly,but the diffusion limitation remains unsolved.展开更多
We report a robust pillar-layered metal-organic framework,Zn‑tfbdc‑dabco(tfbdc:tetrafluoroterephthal-ate,dabco:1,4-diazabicyclo[2.2.2]octane),featuring the fluorinated pore environment,for the preferential binding of ...We report a robust pillar-layered metal-organic framework,Zn‑tfbdc‑dabco(tfbdc:tetrafluoroterephthal-ate,dabco:1,4-diazabicyclo[2.2.2]octane),featuring the fluorinated pore environment,for the preferential binding of propane over propylene and thus highly inverse selective separation of propane/propylene mixture.The inverse propane-selective performance of Zn‑tfbdc‑dabco for the propane/propylene separation was validated by single-component gas adsorption isotherms,isosteric enthalpy of adsorption calculations,ideal adsorbed solution theory calculations,along with the breakthrough experiment.The customized fluorinated networks served as a propane-trap to form more interactions with the exposed hydrogen atoms of propane,as unveiled by the simulation studies at the molecular level.With the advantage of inverse propane-selective adsorption behavior,high adsorption capacity,good cycling stability,and low isosteric enthalpy of adsorption,Zn‑tfbdc‑dabco can be a promising candidate adsorbent for the challenging propane/propylene separation to realize one-step purification of the target propylene substance.展开更多
A novel environmentally benign biphasic system composed of propylene carbonate(PC) and aqueous solution of p-toluenesulfonic acid(p-TsOH aq) was designed for the efficient valorization of lignocellulosic bamboo residu...A novel environmentally benign biphasic system composed of propylene carbonate(PC) and aqueous solution of p-toluenesulfonic acid(p-TsOH aq) was designed for the efficient valorization of lignocellulosic bamboo residues, resulting in more than 95.5% of hemicellulose and 97.2% of lignin digested under mild conditions of 130°C for 1 h. Meanwhile, 91.9% of cellulose was retained with loose structure, followed by 95.8% enzyme hydrolysis yield and 347.9 mg g-1of glucose yield. Notably, the synergistic effect between PC and p-TsOH on efficiency and selectivity was proposed by a control group experiment and subsequently verified, which is believed to be responsible for the simultaneous degradation and separation of lignin and hemicelluloses into oligomeric phenols and pentose, also facilitating subsequent valorization.Furthermore, the novel PC/p-TsOH aq biphasic system demonstrated excellent retrievability and adaptability to different feedstocks, offering a promising green strategy for the efficient valorization of lignocellulosic biomass in industrial biorefineries.展开更多
ITR zeolite could be potentially used as catalysts in methanol to propylene(MTP),where their performance is strongly related to its Al distribution.However,the control of Al distribution in ITR zeolite poses a signifi...ITR zeolite could be potentially used as catalysts in methanol to propylene(MTP),where their performance is strongly related to its Al distribution.However,the control of Al distribution in ITR zeolite poses a significant synthetic challenge.Herein,we demonstrate the possibility to control the Al distribution in ITR zeolites using zeolite A as an aluminum source(A-ITR).The A-ITR exhibited similar crystallinity,nanosheet morphology,textual parameters,and acidic concentration with those of conventional ITR made zeolites using aluminum isopropoxide as an aluminum source(C-ITR).Characterizations of the zeolite product with^(27)Al MQ.MAS NMR spectra,^(27)Al MAS NMR spectra,and 1-hexene cracking reveal that the A-ITR zeolites have more Al species distributed in T6 and T8 sites located in relatively smaller micropores of the framework than C-ITR.As a result,the A-ITR gave enhanced catalyst lifetime and propylene selectivity due to the suppression of the aromatic cycle in the MTP reaction,compared with the C-ITR.This work provides an alternative approach to prepare efficient ITR zeolites for MTP reaction.展开更多
Propylene,a readily accessible and economically viable light olefin,has garnered substantial interest for its potential conversion into valuable higher olefins through oligomerization processes.The distribution of pro...Propylene,a readily accessible and economically viable light olefin,has garnered substantial interest for its potential conversion into valuable higher olefins through oligomerization processes.The distribution of products is profoundly influenced by the catalyst structure.In this study,Fe_(2)O_(3)-doped NiSO_(4)/Al_(2)O_(3) catalysts have been meticulously developed to facilitate the selective trimerization of propylene under mild conditions.Significantly,the 0.25Fe_(2)O_(3)-NiSO_(4)/Al_(2)O_(3) catalyst demonstrates an enhanced reaction rate(48.5 mmol_(C3)/(g_(cat).·h)),alongside a high yield of C9(~32.2%),significantly surpassing the performance of the NiSO_(4)/Al_(2)O_(3) catalyst(C9:~24.1%).The incorporation of Fe_(2)O_(3) modifies the migration process of sulfate ions,altering the Lewis acidity of the electron-deficient Ni and Fe sites on the catalyst and resulting a shift in product distribution from a Schulz-Flory distribution to a Poisson distribution.This shift is primarily ascribed to the heightened energy barrier for theβ-H elimination reaction in the C6 alkyl intermediates on the doped catalyst,further promoting polymerization to yield a greater quantity of Type II C9.Furthermore,the validation of the Cossee-Arlman mechanism within the reaction pathway has been confirmed.It is noteworthy that the 0.25Fe_(2)O_(3)-NiSO_(4)/Al_(2)O_(3) catalyst exhibits remarkable stability exceeding 80 h in the selective trimerization of propylene.These research findings significantly enhance our understanding of the mechanisms underlying olefin oligomerization reactions and provide invaluable insights for the development of more effective catalysts.展开更多
Ethylene carbonate(EC)is an important electrolyte used in lithium-ion batteries due to its excellent electrochemical performance.However,propylene carbonate(PC)differs from EC by only one methyl substituent and exhibi...Ethylene carbonate(EC)is an important electrolyte used in lithium-ion batteries due to its excellent electrochemical performance.However,propylene carbonate(PC)differs from EC by only one methyl substituent and exhibits markedly poorproperties.The EC-PC disparity is still poorly understood at the molecular level.In this study,we demonstrated that femtosecond broadband sum frequency generation vibrational spectroscopy(SFG-VS)with simultaneous measurement of multiple polarization combinations provides a powerful probe for investigating the physicochemical processes at the electrode-electrolyte interface during the charge-discharge cycles of lithium batteries.Using monolayer graphene as the working electrode,we observed the distinct reaction outcomes of EC and PC on the electrode surface.The interfacial reaction of EC occurred only in the first charge-discharge cycle,while the interfacial reaction of PC was ongoing along with the charge-discharge cycles,which explains why EC is a better electrolyte choice than PC.This study provides direct experimental evidence in elucidating the differences in interfacial performance between EC and PC,facilitating a deeper understanding of battery interface reactions and guiding the design of high-performance lithium-ion batteries.展开更多
Au sites supported on Ti-containing materials(Au/Ti-containing catalyst)are currently considered as a promising catalyst for the propylene epoxidation owing to the synergistic effect that hydrogen peroxide species for...Au sites supported on Ti-containing materials(Au/Ti-containing catalyst)are currently considered as a promising catalyst for the propylene epoxidation owing to the synergistic effect that hydrogen peroxide species formed on Au sites diffuses to the Ti sites to form the Ti-hydroperoxo intermedi-ates and contributes to the formation of propylene oxide(PO).In principle,thermal treatment will significantly affect the chemical and physical structures of Ti-containing materials.Consequently,the synergy between tailored Ti sites with different surface properties and Au sites is highly expected to enhance the catalytic performance for the reaction.Herein,we systematically studied the intrinsic effects of different microenvironments around Ti sites on the PO adsorption/desorption and conversion,and then effectively improved the catalytic performance by tailoring the number of surface hydroxyl groups.The Ti^(Ⅵ) material with fewer hydroxyls stimulates a remarkable enhancement in PO selectivity and H_(2) efficiency compared to the Ti^(Ⅵ) material that possessed more hydroxyls,offering a 7-fold and 4-fold increase,respectively.As expected,the Ti^(Ⅵ+Ⅳ) and Ti^(Ⅳ) materials also exhibit a similar phenomenon to the Ti^(Ⅵ) materials through the same thermal treatment,which strongly supports that the Ti sites microenvironment is an important factor in suppressing PO con-version and enhancing catalytic performance.These insights could provide guidance for the rational preparation and optimization of Ti-containing materials synergizing with Au catalysts for propylene epoxidation.展开更多
Herein,a layered chiral coordination polymer,[Cd2(D‑cam)_(2)(2,2′‑bipy)_(2)]_(n)(Cd‑CP),was synthesized using a solvothermal method with camphoric acid(D‑H_(2)cam),2,2′‑bipyridine(2,2′‑bipy)and Cd^(2+),and Tb^(3+)@...Herein,a layered chiral coordination polymer,[Cd2(D‑cam)_(2)(2,2′‑bipy)_(2)]_(n)(Cd‑CP),was synthesized using a solvothermal method with camphoric acid(D‑H_(2)cam),2,2′‑bipyridine(2,2′‑bipy)and Cd^(2+),and Tb^(3+)@Cd‑CP was in‑situ synthesized introducing Tb^(3+)ions.The fluorescence experiments revealed that compared to Cd‑CP,Tb^(3+)@Cd‑CP exhibited ultra‑high fluorescence performance.The luminescence sensing performance demonstrated that Tb^(3+)@Cd‑CP could distinguish R/S‑propylene glycol(R/S‑PG)by fluorescence responses,with fluorescence quenching constant of 5.3×10^(3)and 2.0×10^(3)L·mol^(-1)respectively and the enantioselectivity factor(α)of 2.65.Moreover,Tb^(3+)@Cd‑CP demonstrated limits of detection of 9.3 and 19.0μmol·L^(-1)for R‑PG and S‑PG,respectively,and showed good reproducibility.展开更多
The highly efficient method has been developed for the synthesis of NHC·VOCl_(3) containing symmetrical or unsymmetrical Nheterocyclic carbene(NHC) ligands by the transmetallation reaction of NHC·AgCl with V...The highly efficient method has been developed for the synthesis of NHC·VOCl_(3) containing symmetrical or unsymmetrical Nheterocyclic carbene(NHC) ligands by the transmetallation reaction of NHC·AgCl with VOCl_(3).The total isolated yield of VOCl_(3)[1,3-(2,4,6-Me_(3)C_(6)H_(2))_(2)(NCH=)_(2)C:](V4') reached 86% by transmetallation reaction,which is much higher than that(48%) by direct coordination method.This methodology has also been used to synthesize the novel vanadium complexes containing unsymmetrical NHC ligands of VOCl_(3)[PhCH_(2)NCH=CHNR)C:](V5',R=2,4,6-Me_(3)C_(6)H_(2);V6',R=2,4-Me_(2)-6-Ph-C_(6)H_(2);V7',R=2,6-^(i)Pr_(2)-C_(6)H_(3)) with high yield,which could not be obtained by direct coordination method.The catalytic activity and copolymerization ability would be improved by introducing unsymmetrical NHC ligands due to their less steric bulky effect.The vanadium complex V5' containing unsymmetrical NHC ligand exhibits higher catalytic activity(3.7×10^(5)g_(copolymer)·mol^(-1) of V·h^(-1)) than that of V4' containing symmetrical NHC ligand.Moreover,the higher propylene incorporation ratio(45.6 mol%) in the copolymers of ethylene with propylene could be obtained by using V5' than that(39.9%) by using V4'.The results would provide a highly efficient strategy for the synthesis of early transition metal complexes containing versitile NHC ligands,affording the catalyst with both high catalytic activity and copolymerization ability for the synthesis of high performance polyolefin elastomers.展开更多
The catalysis technology of propylene dimerization to form 4-methyl-1-pentene(4MP1)using a Cu-K/K_(2)CO_(3) solid base catalyst is a well-known heterogeneous catalytic reaction.In this study,the intrinsic kinetics of ...The catalysis technology of propylene dimerization to form 4-methyl-1-pentene(4MP1)using a Cu-K/K_(2)CO_(3) solid base catalyst is a well-known heterogeneous catalytic reaction.In this study,the intrinsic kinetics of propylene dimerization were studied in a fixed-bed continuous reactor.Internal and external diffusion during the dimerization reaction experiments were eliminated by adjusting the flow rate of the carrier gas and the particle size of the catalyst support.Then,the concentration changes of each substance at the outlet of the catalyst bed under different residence times were investigated.Moreover,the suitable reaction kinetics equations was derived using the Langmuir Hinshelwood-Hougen-Watson kinetic model.Finally,the activation energy for each reaction involved in the dimerization reaction was calculated.The activation energies of 4MP1,branched by-products,and 1-hexene were 115.0,150.8,and 177.4 kJ/mol,respectively.The effect of process conditions on propylene dimerization with solid base catalysts was studied through kinetic model simulation.By comparing the theoretical values obtained from the simulation with the experimental results,the applicability and accuracy of the kinetic model were verified.展开更多
The isolated hydrophilic black alder(Alnus glutinosa)bark extractives were characterized in terms of component and functional composition and converted at 150℃-170℃ into liquid green polyols using solvent-free and l...The isolated hydrophilic black alder(Alnus glutinosa)bark extractives were characterized in terms of component and functional composition and converted at 150℃-170℃ into liquid green polyols using solvent-free and lowtoxic base-catalyzed modification with propylene carbonate(PC).FTIR spectroscopy,HP-LC,GC,GPC,and wet chemistry methods were used to characterize the starting constituents,intermediate and final products of the reaction and to monitor the different pathways of PC conversion.The reaction of extractives as well as the model compounds,including catechol,xylose,PEG 400,and benzoic acid,with PC indicated the ability of OH groups of different origins present in the extractives to condense with equivalent amounts of PC.The polyols obtained consist of a copolymer fraction with one oxypropyl unit grafted per OH functionality of extractive components on average and oligo oxypropyl diols with a small number of carbonate linkages in the chain,obtained as a result of remaining PC homopolymerization.The domination of the oxypropylation mechanism vs.transcarbonation for PC ring opening was observed for both copolymerization and homopolymerization processes,making the process of oxypropylation with PC similar to that of conventional oxypropylation.At optimal reaction conditions,including a PC/OH ratio of 3.0 and a 24-h duration at 150°C,uniform polyols with low viscosity of~900 mPa·s^(-1),a biomass content of~27%,and an OHV of~500 mg KOH·g^(-1) were obtained.Increasing the temperature of modification allows shortening the process but drastically increases the polyol viscosity.At fixed temperature values,increasing the PC/OH ratio not only decreases the biomass content but also strongly prolongs the processing.The significantly increased duration of the process using PC as an alternative oxyalkylation agent compared to that of oxyalkylation with propylene oxide is a reasonable trade-off for using a safer and more environmentally friendly technology.展开更多
The catalytic cracking of light diesel oil （235–337 ＆#176;C） over gold‐modified ZSM‐5 was investigated in a small confined fluidized bed at 460 ＆#176;C and ambient pressure. Different Au/ZSM‐5 catalysts were p...The catalytic cracking of light diesel oil （235–337 ＆#176;C） over gold‐modified ZSM‐5 was investigated in a small confined fluidized bed at 460 ＆#176;C and ambient pressure. Different Au/ZSM‐5 catalysts were prepared by a modified deposition‐precipitation method by changing the preparation procedure and the amount of gold loading and were characterized by X‐ray diffraction, N2 adsorp‐tion‐desorption, temperature‐programmed desorption of NH3, transmission electron microscopy and inductively coupled plasma spectrometer. It was found that a small amount of gold had a posi‐tive effect on the catalytic cracking of light diesel oil and increased propylene production at a rela‐tively low temperature. The maintenance of the ZSM‐5 MFI structure, pore size distribution and the density of weak and strong acid sites of the Au/ZSM‐5 catalysts depended on the preparation pa‐rameters and the Au loading. Simultaneous enhancement of the micro‐activity and propylene pro‐duction relies on a synergy between the pore size distribution and the relative intensity of the weak and strong acid sites. A significant improvement in the micro‐activity index with an increase of 4.5 units and in the propylene selectivity with an increase of 23.2 units was obtained over the Au/ZSM‐5 catalyst with an actual Au loading of 0.17 wt%.展开更多
The elementary reactions of propylene polymerization catalyzed by conventional Ziegler-Natta catalysts was proposed according to the comprehensive view and without considering the effect of any impurity in the materia...The elementary reactions of propylene polymerization catalyzed by conventional Ziegler-Natta catalysts was proposed according to the comprehensive view and without considering the effect of any impurity in the material on propylene polymerization. The Monte Carlo simulation technique was employed to investigate the kinetics of propylene polymerization in order to determine the validity of the stationary state assumption and the effects of the polymerization temperature on the polymerization. The simulated total amount of active species, which only increases quickly at the beginning of the polymerization, indicates that the stationary state assumption in the studied system is valid. Moreover, significant effects of polymerization temperature on the polymerization conversion, and the molecular weight and its distribution were also analyzed. The simulated results show that the consumption rate of propylene increases with the increase of polymerization temperature; the maximum values of the number-average degree of polymerization are constant at different polymerization temperatures, however, the peak appears earlier with the higher temperature; as the polymerization temperature increases, the average molecular weight decreases and the molecular weight distribution changes greatly.展开更多
In order to further study the postpartum care technology of dairy cows,the effects of oral administration of propylene glycol or Ca-P-Mg mixture and compound oral rehydration salts on milk quality and SCC of dairy cow...In order to further study the postpartum care technology of dairy cows,the effects of oral administration of propylene glycol or Ca-P-Mg mixture and compound oral rehydration salts on milk quality and SCC of dairy cows after birth were investigated. The results showed that the milk fat and dry matter contents in the dairy cows administered with Ca-P-Mg mixture and compound oral rehydration salts were higher than those in the dairy cows administered with propylene glycol（P 〈0.05）. However, there were no significant differences in milk sugar and protein contents and SCC between the two administration groups.展开更多
The unsupported Cu and Ag catalysts with different oxidation states were prepared, and their catalytic performances for propylene epoxidation were investigated.The metallic Cu catalyst exhibits much higher catalytic a...The unsupported Cu and Ag catalysts with different oxidation states were prepared, and their catalytic performances for propylene epoxidation were investigated.The metallic Cu catalyst exhibits much higher catalytic activity and propylene oxide(PO) selectivity than Cu2 O and Cu O catalysts.The Cu0 species are the main active sites for propylene epoxidation, but Cu2 O and Cu O species are in favor of CO2 and acrolein production.The PO selectivity of 54.2 % and propylene conversion of 2.6 % can be achieved over the metallic Cu catalyst at 160 °C in initial stage, but metallic Cu catalyst would be oxidized to Cu2 O during propylene epoxidation, resulting in a sharp decrease in the PO selectivity and propylene conversion.Nanosize Ag Cuxbimetallic catalysts were prepared.It is found that adding Ag to the metallic Cu catalysts can prevent the oxidation of Cu and make Ag Cuxbimetallic catalysts more stable under the condition of propylene epoxidation.The Ag/Cu molar ratio can remarkably affect the catalytic performance of Ag Cuxcatalyst and the selectivity to PO and acrolein.After Ag Cuxwas supported on MOx-modified a-Al2O3, its catalytic performance can be improved and has a close relationship with the acid–base property of support.展开更多
Ag‐Cu‐Cl/BaCO3 catalysts with different Cl and Cu loadings, prepared by the reduction deposition impregnation method, were investigated for gas‐phase epoxidation of propylene by molecular oxygen and characterized b...Ag‐Cu‐Cl/BaCO3 catalysts with different Cl and Cu loadings, prepared by the reduction deposition impregnation method, were investigated for gas‐phase epoxidation of propylene by molecular oxygen and characterized by X‐ray diffraction, X‐ray photoelectron spectroscopy and O2 temperatureprogrammed desorption. Ag‐Cu‐Cl/BaCO3 catalyst with 0.036 wt% Cu and 0.060 wt% Cl exhibitedthe highest catalytic performance for gas‐phase epoxidation of propylene by molecular oxygen. Apropylene oxide selectivity of 83.7% and propylene conversion of 1.2% were achieved under thereaction conditions of 20% C3H6‐10% O2‐70% N2, 200 °C, 0.1 MPa and 3000 h?1. Increasing the Clloading allowed Ag to ensemble easier, whereas changing the Cu loading showed little effect on Agcrystallite size. The appropriate Cl loading of Ag‐Cu‐Cl/BaCO3 catalyst can reduce the dissociationadsorption of oxygen to atomic oxygen species leading to the combustion of propylene to CO2, whichbenefits epoxidation of propylene by molecular oxygen. Excessive Cl loading of Ag‐Cu‐Cl/BaCO3catalyst decreases propylene conversion and propylene oxide selectivity remarkably because of Clpoisoning. The appropriate Cu loading of Ag‐Cu‐Cl/BaCO3 catalyst is efficient for the epoxidation ofpropylene by molecular oxygen, and an excess Cu loading decreases propylene oxide selectivitybecause the aggregation of Cu species increases the exposed surfaces of Ag nanoparticles, whichwas shown by slight increases in atomic oxygen species adsorbed. The appropriate loadings of Cu and Cl of Ag‐Cu‐Cl/BaCO3 catalyst are important to strike the balance between molecular oxygen and atomic oxygen species to create a favorable epoxidation of propylene by molecular oxygen.展开更多
Ansa-Cyclohexyl-bis（4,5,6,7-tertrahydro-l-indenyl） zirconium dichloride （5） was used as catalyst for propylene and ethylene polymerization together with methyl aluminoxane （MAO） as the cocatalyst. Isotactic poly...Ansa-Cyclohexyl-bis（4,5,6,7-tertrahydro-l-indenyl） zirconium dichloride （5） was used as catalyst for propylene and ethylene polymerization together with methyl aluminoxane （MAO） as the cocatalyst. Isotactic polypropylene （PP） was obtained with the highest activity of 6.37× 107g PP （molZr）^-1h^-1. The mesomeso （mmmmm） pentads sequence content of PP was determined by 13C NMR spectroscopy. The dependence of the microstructure on the reaction temperature and the AI/Zr molar ratio was examined and the catalytic activity of complex 5 was compared with that of the similar ansa-zirconocene 3. The high activity of the new zirconocene 5 for propylene isospectic polymerization at high temperature （60℃） is the result of its unique bridged-group structure. Complex 5/MAO displays also high catalytic activity of 0.46× 10^6 to 9.87× 10^6g PE（molZr）^-h^-in the homo-polymerization of ethylene, The visometric molecular weight of PE ranges from 0.97×10^4 to 11.16×10^4 g.mol^- under the given conditions.^13C NMR spectroscopy analysis proves the PE to be linear polyethylene （LPE）.展开更多
A series of acetate ionic liquids were synthesized using a typical two‐step method.The ionic liquids were used as environmentally benign catalysts in the production of propylene glycol ethers from propylene oxide and...A series of acetate ionic liquids were synthesized using a typical two‐step method.The ionic liquids were used as environmentally benign catalysts in the production of propylene glycol ethers from propylene oxide and alcohols under mild conditions.The basic strengths of the ionic liquids were evaluated by determination of their Hammett functions,obtained using ultraviolet‐visible spectroscopy,and the relationship between their catalytic activities and basicities was established.The catalytic efficiencies of the ionic liquids were higher than that of the traditional basic catalyst NaOH.This can be attributed to the involvement of a novel reaction mechanism when these ionic liquids are used.A possible electrophilic‐nucleophilic dual activation mechanism was proposed and confirmed using electrospray ionization quadrupole time‐of‐flight mass spectrometry.In addition,the effects of significant reaction parameters such as concentration of catalyst,molar ratio of alcohol to propylene oxide,reaction temperature,and steric hindrance of the alcohol were investigated in detail.展开更多
Selective propylene epoxidation to propylene oxide(PO) with hydrogen peroxide(H_2O_2) was carried out in a catalytic semi-batch reactor.High propylene epoxidation activity(44 h^(-1)) was observed over Nb based mesopor...Selective propylene epoxidation to propylene oxide(PO) with hydrogen peroxide(H_2O_2) was carried out in a catalytic semi-batch reactor.High propylene epoxidation activity(44 h^(-1)) was observed over Nb based mesoporous silicate materials Nb-TUD-1 under mild operating conditions.The physical and chemical properties of the Nb based silicates characterized using BET,FTIR,TPD,TEM and UV–Vis revealed that the site isolation and surface acidity are crucial for PO production.Catalyst synthesis methods were investigated for their effects on PO productivity,PO selectivity and H_2O_2 utilization efficiency.It is found that Nb-TUD-1 material synthesized by the sol–gel method is more active and selective than impregnated materials for liquid phase propylene epoxidation.Surface characterization confirms that thus synthesized Nb-TUD-1 catalysts have more Lewis acidity and less Bronsted acidity compared to the catalysts by impregnation.展开更多
基金supported by the National Natural Science Foundation of China (29792072, 22278441, 22478452)National Key Research and Development Program of China (937) (2006CB202508)the SINOPEC Project (419019-2, 413108)。
文摘Propylene oxide(PO),with its reactive three-membered epoxide functional group,exhibits remarkable functional versatility and serves as a crucial bridge connecting the gaps between fossil energy utilization and chemical intermediate generation for new material innovation [1].For instance,PO's downstream derivatives,such as polyether polyols,carbonic esters,and polyurethanes,are widely utilized in wind power generation,battery electrolytes,solar cells,and CO_(2)-based degradable polymers,contributing to sustainable decarbonization in industry [2].
基金support of the National Natural Science Foundation of China(Nos.22378369 and 22205207)Major Project of Natural Science Foundation of Zhejiang Province(LD24B060001).
文摘As an important chemical product,propylene(C_(3)H_(6))is widely used in production of many crucial chemical products such as polypropylene.Propane(C_(3)H_(8))is introduced as an inevitable gas impurity during the naphtha cracking in propylene production.At present,thermal-driven energy-intensive cryogenic distillation is the most common purification method in industry.An energy-efficient,cost-effective and environmental-friendly separation technology is required to get polymer grade C_(3)H_(6)(higher than 99.5%).In face of the increasing demand of propylene,new separation technology based on porous adsorbents is expected to be a promising alternative.In recent years,metal-organic frameworks(MOFs)have obtained attention by their high porosity,regular adjustable pore shape and pore environment and keep making breakthroughs in separation and purification of many industrial gas mixtures,and are thus considered as one of the most potential types of adsorbents.The physical properties of C_(3)H_(6)and C_(3)H_(8),such as boiling point,size and kinetic diameter,are close to each other,making their separation a challenge.Most C_(3)H_(6)/C_(3)H_(8)sieving MOFs based on narrow sieving channels that restrict the access of molecules larger than their confined entrance purify mixtures at the cost of diffusion and capacity.To improve the adsorption of MOFs based on molecular sieving,a novel‘pearl-necklace’strategy was designed,which was named for its connected channel and molecular pocket vividly,but the diffusion limitation remains unsolved.
文摘We report a robust pillar-layered metal-organic framework,Zn‑tfbdc‑dabco(tfbdc:tetrafluoroterephthal-ate,dabco:1,4-diazabicyclo[2.2.2]octane),featuring the fluorinated pore environment,for the preferential binding of propane over propylene and thus highly inverse selective separation of propane/propylene mixture.The inverse propane-selective performance of Zn‑tfbdc‑dabco for the propane/propylene separation was validated by single-component gas adsorption isotherms,isosteric enthalpy of adsorption calculations,ideal adsorbed solution theory calculations,along with the breakthrough experiment.The customized fluorinated networks served as a propane-trap to form more interactions with the exposed hydrogen atoms of propane,as unveiled by the simulation studies at the molecular level.With the advantage of inverse propane-selective adsorption behavior,high adsorption capacity,good cycling stability,and low isosteric enthalpy of adsorption,Zn‑tfbdc‑dabco can be a promising candidate adsorbent for the challenging propane/propylene separation to realize one-step purification of the target propylene substance.
基金the Fundamental Research Foundation of CAF(CAFYBB2022QB001)National Nature Science Foundation of China(32222058)for financial support.
文摘A novel environmentally benign biphasic system composed of propylene carbonate(PC) and aqueous solution of p-toluenesulfonic acid(p-TsOH aq) was designed for the efficient valorization of lignocellulosic bamboo residues, resulting in more than 95.5% of hemicellulose and 97.2% of lignin digested under mild conditions of 130°C for 1 h. Meanwhile, 91.9% of cellulose was retained with loose structure, followed by 95.8% enzyme hydrolysis yield and 347.9 mg g-1of glucose yield. Notably, the synergistic effect between PC and p-TsOH on efficiency and selectivity was proposed by a control group experiment and subsequently verified, which is believed to be responsible for the simultaneous degradation and separation of lignin and hemicelluloses into oligomeric phenols and pentose, also facilitating subsequent valorization.Furthermore, the novel PC/p-TsOH aq biphasic system demonstrated excellent retrievability and adaptability to different feedstocks, offering a promising green strategy for the efficient valorization of lignocellulosic biomass in industrial biorefineries.
基金supported by the National Key Research and Development Program of China(2022YFA1503602)the National Natural Science Foundation of China(22288101,U21B20101 and 22172141)+1 种基金the BASF International Network of Centers of Excellence projectthe Zhejiang Provincial Natural Science Foundation of China(LR24B030001)。
文摘ITR zeolite could be potentially used as catalysts in methanol to propylene(MTP),where their performance is strongly related to its Al distribution.However,the control of Al distribution in ITR zeolite poses a significant synthetic challenge.Herein,we demonstrate the possibility to control the Al distribution in ITR zeolites using zeolite A as an aluminum source(A-ITR).The A-ITR exhibited similar crystallinity,nanosheet morphology,textual parameters,and acidic concentration with those of conventional ITR made zeolites using aluminum isopropoxide as an aluminum source(C-ITR).Characterizations of the zeolite product with^(27)Al MQ.MAS NMR spectra,^(27)Al MAS NMR spectra,and 1-hexene cracking reveal that the A-ITR zeolites have more Al species distributed in T6 and T8 sites located in relatively smaller micropores of the framework than C-ITR.As a result,the A-ITR gave enhanced catalyst lifetime and propylene selectivity due to the suppression of the aromatic cycle in the MTP reaction,compared with the C-ITR.This work provides an alternative approach to prepare efficient ITR zeolites for MTP reaction.
文摘Propylene,a readily accessible and economically viable light olefin,has garnered substantial interest for its potential conversion into valuable higher olefins through oligomerization processes.The distribution of products is profoundly influenced by the catalyst structure.In this study,Fe_(2)O_(3)-doped NiSO_(4)/Al_(2)O_(3) catalysts have been meticulously developed to facilitate the selective trimerization of propylene under mild conditions.Significantly,the 0.25Fe_(2)O_(3)-NiSO_(4)/Al_(2)O_(3) catalyst demonstrates an enhanced reaction rate(48.5 mmol_(C3)/(g_(cat).·h)),alongside a high yield of C9(~32.2%),significantly surpassing the performance of the NiSO_(4)/Al_(2)O_(3) catalyst(C9:~24.1%).The incorporation of Fe_(2)O_(3) modifies the migration process of sulfate ions,altering the Lewis acidity of the electron-deficient Ni and Fe sites on the catalyst and resulting a shift in product distribution from a Schulz-Flory distribution to a Poisson distribution.This shift is primarily ascribed to the heightened energy barrier for theβ-H elimination reaction in the C6 alkyl intermediates on the doped catalyst,further promoting polymerization to yield a greater quantity of Type II C9.Furthermore,the validation of the Cossee-Arlman mechanism within the reaction pathway has been confirmed.It is noteworthy that the 0.25Fe_(2)O_(3)-NiSO_(4)/Al_(2)O_(3) catalyst exhibits remarkable stability exceeding 80 h in the selective trimerization of propylene.These research findings significantly enhance our understanding of the mechanisms underlying olefin oligomerization reactions and provide invaluable insights for the development of more effective catalysts.
基金supported by the National Natural Science Foundation of China(No.21925302)the Strategic Priority Research Program of the Chinese Academy of Sciences(XDB0450202).
文摘Ethylene carbonate(EC)is an important electrolyte used in lithium-ion batteries due to its excellent electrochemical performance.However,propylene carbonate(PC)differs from EC by only one methyl substituent and exhibits markedly poorproperties.The EC-PC disparity is still poorly understood at the molecular level.In this study,we demonstrated that femtosecond broadband sum frequency generation vibrational spectroscopy(SFG-VS)with simultaneous measurement of multiple polarization combinations provides a powerful probe for investigating the physicochemical processes at the electrode-electrolyte interface during the charge-discharge cycles of lithium batteries.Using monolayer graphene as the working electrode,we observed the distinct reaction outcomes of EC and PC on the electrode surface.The interfacial reaction of EC occurred only in the first charge-discharge cycle,while the interfacial reaction of PC was ongoing along with the charge-discharge cycles,which explains why EC is a better electrolyte choice than PC.This study provides direct experimental evidence in elucidating the differences in interfacial performance between EC and PC,facilitating a deeper understanding of battery interface reactions and guiding the design of high-performance lithium-ion batteries.
文摘Au sites supported on Ti-containing materials(Au/Ti-containing catalyst)are currently considered as a promising catalyst for the propylene epoxidation owing to the synergistic effect that hydrogen peroxide species formed on Au sites diffuses to the Ti sites to form the Ti-hydroperoxo intermedi-ates and contributes to the formation of propylene oxide(PO).In principle,thermal treatment will significantly affect the chemical and physical structures of Ti-containing materials.Consequently,the synergy between tailored Ti sites with different surface properties and Au sites is highly expected to enhance the catalytic performance for the reaction.Herein,we systematically studied the intrinsic effects of different microenvironments around Ti sites on the PO adsorption/desorption and conversion,and then effectively improved the catalytic performance by tailoring the number of surface hydroxyl groups.The Ti^(Ⅵ) material with fewer hydroxyls stimulates a remarkable enhancement in PO selectivity and H_(2) efficiency compared to the Ti^(Ⅵ) material that possessed more hydroxyls,offering a 7-fold and 4-fold increase,respectively.As expected,the Ti^(Ⅵ+Ⅳ) and Ti^(Ⅳ) materials also exhibit a similar phenomenon to the Ti^(Ⅵ) materials through the same thermal treatment,which strongly supports that the Ti sites microenvironment is an important factor in suppressing PO con-version and enhancing catalytic performance.These insights could provide guidance for the rational preparation and optimization of Ti-containing materials synergizing with Au catalysts for propylene epoxidation.
文摘Herein,a layered chiral coordination polymer,[Cd2(D‑cam)_(2)(2,2′‑bipy)_(2)]_(n)(Cd‑CP),was synthesized using a solvothermal method with camphoric acid(D‑H_(2)cam),2,2′‑bipyridine(2,2′‑bipy)and Cd^(2+),and Tb^(3+)@Cd‑CP was in‑situ synthesized introducing Tb^(3+)ions.The fluorescence experiments revealed that compared to Cd‑CP,Tb^(3+)@Cd‑CP exhibited ultra‑high fluorescence performance.The luminescence sensing performance demonstrated that Tb^(3+)@Cd‑CP could distinguish R/S‑propylene glycol(R/S‑PG)by fluorescence responses,with fluorescence quenching constant of 5.3×10^(3)and 2.0×10^(3)L·mol^(-1)respectively and the enantioselectivity factor(α)of 2.65.Moreover,Tb^(3+)@Cd‑CP demonstrated limits of detection of 9.3 and 19.0μmol·L^(-1)for R‑PG and S‑PG,respectively,and showed good reproducibility.
基金financially supported by the National Natural Science Foundation of China (Nos.21774006 and 21634002)。
文摘The highly efficient method has been developed for the synthesis of NHC·VOCl_(3) containing symmetrical or unsymmetrical Nheterocyclic carbene(NHC) ligands by the transmetallation reaction of NHC·AgCl with VOCl_(3).The total isolated yield of VOCl_(3)[1,3-(2,4,6-Me_(3)C_(6)H_(2))_(2)(NCH=)_(2)C:](V4') reached 86% by transmetallation reaction,which is much higher than that(48%) by direct coordination method.This methodology has also been used to synthesize the novel vanadium complexes containing unsymmetrical NHC ligands of VOCl_(3)[PhCH_(2)NCH=CHNR)C:](V5',R=2,4,6-Me_(3)C_(6)H_(2);V6',R=2,4-Me_(2)-6-Ph-C_(6)H_(2);V7',R=2,6-^(i)Pr_(2)-C_(6)H_(3)) with high yield,which could not be obtained by direct coordination method.The catalytic activity and copolymerization ability would be improved by introducing unsymmetrical NHC ligands due to their less steric bulky effect.The vanadium complex V5' containing unsymmetrical NHC ligand exhibits higher catalytic activity(3.7×10^(5)g_(copolymer)·mol^(-1) of V·h^(-1)) than that of V4' containing symmetrical NHC ligand.Moreover,the higher propylene incorporation ratio(45.6 mol%) in the copolymers of ethylene with propylene could be obtained by using V5' than that(39.9%) by using V4'.The results would provide a highly efficient strategy for the synthesis of early transition metal complexes containing versitile NHC ligands,affording the catalyst with both high catalytic activity and copolymerization ability for the synthesis of high performance polyolefin elastomers.
基金supported by the National Natural Science Foundation of China under agreement number 22378026the Project of Construction of Innovative Teams and Teacher Career Development for Universities and Colleges under Beijing Municipality(IDHT20180508).
文摘The catalysis technology of propylene dimerization to form 4-methyl-1-pentene(4MP1)using a Cu-K/K_(2)CO_(3) solid base catalyst is a well-known heterogeneous catalytic reaction.In this study,the intrinsic kinetics of propylene dimerization were studied in a fixed-bed continuous reactor.Internal and external diffusion during the dimerization reaction experiments were eliminated by adjusting the flow rate of the carrier gas and the particle size of the catalyst support.Then,the concentration changes of each substance at the outlet of the catalyst bed under different residence times were investigated.Moreover,the suitable reaction kinetics equations was derived using the Langmuir Hinshelwood-Hougen-Watson kinetic model.Finally,the activation energy for each reaction involved in the dimerization reaction was calculated.The activation energies of 4MP1,branched by-products,and 1-hexene were 115.0,150.8,and 177.4 kJ/mol,respectively.The effect of process conditions on propylene dimerization with solid base catalysts was studied through kinetic model simulation.By comparing the theoretical values obtained from the simulation with the experimental results,the applicability and accuracy of the kinetic model were verified.
基金financial support from the Latvian Council of Science,Project No.lzp-2021/1-0207.
文摘The isolated hydrophilic black alder(Alnus glutinosa)bark extractives were characterized in terms of component and functional composition and converted at 150℃-170℃ into liquid green polyols using solvent-free and lowtoxic base-catalyzed modification with propylene carbonate(PC).FTIR spectroscopy,HP-LC,GC,GPC,and wet chemistry methods were used to characterize the starting constituents,intermediate and final products of the reaction and to monitor the different pathways of PC conversion.The reaction of extractives as well as the model compounds,including catechol,xylose,PEG 400,and benzoic acid,with PC indicated the ability of OH groups of different origins present in the extractives to condense with equivalent amounts of PC.The polyols obtained consist of a copolymer fraction with one oxypropyl unit grafted per OH functionality of extractive components on average and oligo oxypropyl diols with a small number of carbonate linkages in the chain,obtained as a result of remaining PC homopolymerization.The domination of the oxypropylation mechanism vs.transcarbonation for PC ring opening was observed for both copolymerization and homopolymerization processes,making the process of oxypropylation with PC similar to that of conventional oxypropylation.At optimal reaction conditions,including a PC/OH ratio of 3.0 and a 24-h duration at 150°C,uniform polyols with low viscosity of~900 mPa·s^(-1),a biomass content of~27%,and an OHV of~500 mg KOH·g^(-1) were obtained.Increasing the temperature of modification allows shortening the process but drastically increases the polyol viscosity.At fixed temperature values,increasing the PC/OH ratio not only decreases the biomass content but also strongly prolongs the processing.The significantly increased duration of the process using PC as an alternative oxyalkylation agent compared to that of oxyalkylation with propylene oxide is a reasonable trade-off for using a safer and more environmentally friendly technology.
基金supported by the Shandong Taishan Scholarship, the Yantai double-hundreds talents planthe Shandong Natural Science Founda-tion (ZR2015BM006)~~
文摘The catalytic cracking of light diesel oil （235–337 ＆#176;C） over gold‐modified ZSM‐5 was investigated in a small confined fluidized bed at 460 ＆#176;C and ambient pressure. Different Au/ZSM‐5 catalysts were prepared by a modified deposition‐precipitation method by changing the preparation procedure and the amount of gold loading and were characterized by X‐ray diffraction, N2 adsorp‐tion‐desorption, temperature‐programmed desorption of NH3, transmission electron microscopy and inductively coupled plasma spectrometer. It was found that a small amount of gold had a posi‐tive effect on the catalytic cracking of light diesel oil and increased propylene production at a rela‐tively low temperature. The maintenance of the ZSM‐5 MFI structure, pore size distribution and the density of weak and strong acid sites of the Au/ZSM‐5 catalysts depended on the preparation pa‐rameters and the Au loading. Simultaneous enhancement of the micro‐activity and propylene pro‐duction relies on a synergy between the pore size distribution and the relative intensity of the weak and strong acid sites. A significant improvement in the micro‐activity index with an increase of 4.5 units and in the propylene selectivity with an increase of 23.2 units was obtained over the Au/ZSM‐5 catalyst with an actual Au loading of 0.17 wt%.
基金The National Natural Science Foundation of China(No.20406016)the Project of Fujian Petrochemical Company of SIN-OPEC (No.MS/FJ-08-JS-15-2005-01).
文摘The elementary reactions of propylene polymerization catalyzed by conventional Ziegler-Natta catalysts was proposed according to the comprehensive view and without considering the effect of any impurity in the material on propylene polymerization. The Monte Carlo simulation technique was employed to investigate the kinetics of propylene polymerization in order to determine the validity of the stationary state assumption and the effects of the polymerization temperature on the polymerization. The simulated total amount of active species, which only increases quickly at the beginning of the polymerization, indicates that the stationary state assumption in the studied system is valid. Moreover, significant effects of polymerization temperature on the polymerization conversion, and the molecular weight and its distribution were also analyzed. The simulated results show that the consumption rate of propylene increases with the increase of polymerization temperature; the maximum values of the number-average degree of polymerization are constant at different polymerization temperatures, however, the peak appears earlier with the higher temperature; as the polymerization temperature increases, the average molecular weight decreases and the molecular weight distribution changes greatly.
基金Supported by Technology Research,Demonstration and Promotion Project of Beijing Vocational College of Agriculture(XY-YF-14-17,XY-YF-14-11)~~
文摘In order to further study the postpartum care technology of dairy cows,the effects of oral administration of propylene glycol or Ca-P-Mg mixture and compound oral rehydration salts on milk quality and SCC of dairy cows after birth were investigated. The results showed that the milk fat and dry matter contents in the dairy cows administered with Ca-P-Mg mixture and compound oral rehydration salts were higher than those in the dairy cows administered with propylene glycol（P 〈0.05）. However, there were no significant differences in milk sugar and protein contents and SCC between the two administration groups.
基金financially supported by the National Basic Research Program of China (No. 2010CB732300)
文摘The unsupported Cu and Ag catalysts with different oxidation states were prepared, and their catalytic performances for propylene epoxidation were investigated.The metallic Cu catalyst exhibits much higher catalytic activity and propylene oxide(PO) selectivity than Cu2 O and Cu O catalysts.The Cu0 species are the main active sites for propylene epoxidation, but Cu2 O and Cu O species are in favor of CO2 and acrolein production.The PO selectivity of 54.2 % and propylene conversion of 2.6 % can be achieved over the metallic Cu catalyst at 160 °C in initial stage, but metallic Cu catalyst would be oxidized to Cu2 O during propylene epoxidation, resulting in a sharp decrease in the PO selectivity and propylene conversion.Nanosize Ag Cuxbimetallic catalysts were prepared.It is found that adding Ag to the metallic Cu catalysts can prevent the oxidation of Cu and make Ag Cuxbimetallic catalysts more stable under the condition of propylene epoxidation.The Ag/Cu molar ratio can remarkably affect the catalytic performance of Ag Cuxcatalyst and the selectivity to PO and acrolein.After Ag Cuxwas supported on MOx-modified a-Al2O3, its catalytic performance can be improved and has a close relationship with the acid–base property of support.
基金supported by National Basic Research Program of China (2013CB933200)Commission of Science and Technology of Shanghai Municipality (15DZ1205305)~~
文摘Ag‐Cu‐Cl/BaCO3 catalysts with different Cl and Cu loadings, prepared by the reduction deposition impregnation method, were investigated for gas‐phase epoxidation of propylene by molecular oxygen and characterized by X‐ray diffraction, X‐ray photoelectron spectroscopy and O2 temperatureprogrammed desorption. Ag‐Cu‐Cl/BaCO3 catalyst with 0.036 wt% Cu and 0.060 wt% Cl exhibitedthe highest catalytic performance for gas‐phase epoxidation of propylene by molecular oxygen. Apropylene oxide selectivity of 83.7% and propylene conversion of 1.2% were achieved under thereaction conditions of 20% C3H6‐10% O2‐70% N2, 200 °C, 0.1 MPa and 3000 h?1. Increasing the Clloading allowed Ag to ensemble easier, whereas changing the Cu loading showed little effect on Agcrystallite size. The appropriate Cl loading of Ag‐Cu‐Cl/BaCO3 catalyst can reduce the dissociationadsorption of oxygen to atomic oxygen species leading to the combustion of propylene to CO2, whichbenefits epoxidation of propylene by molecular oxygen. Excessive Cl loading of Ag‐Cu‐Cl/BaCO3catalyst decreases propylene conversion and propylene oxide selectivity remarkably because of Clpoisoning. The appropriate Cu loading of Ag‐Cu‐Cl/BaCO3 catalyst is efficient for the epoxidation ofpropylene by molecular oxygen, and an excess Cu loading decreases propylene oxide selectivitybecause the aggregation of Cu species increases the exposed surfaces of Ag nanoparticles, whichwas shown by slight increases in atomic oxygen species adsorbed. The appropriate loadings of Cu and Cl of Ag‐Cu‐Cl/BaCO3 catalyst are important to strike the balance between molecular oxygen and atomic oxygen species to create a favorable epoxidation of propylene by molecular oxygen.
基金the National Natural Science Foundation of China(20374043)SINOPEC(X501025)
文摘Ansa-Cyclohexyl-bis（4,5,6,7-tertrahydro-l-indenyl） zirconium dichloride （5） was used as catalyst for propylene and ethylene polymerization together with methyl aluminoxane （MAO） as the cocatalyst. Isotactic polypropylene （PP） was obtained with the highest activity of 6.37× 107g PP （molZr）^-1h^-1. The mesomeso （mmmmm） pentads sequence content of PP was determined by 13C NMR spectroscopy. The dependence of the microstructure on the reaction temperature and the AI/Zr molar ratio was examined and the catalytic activity of complex 5 was compared with that of the similar ansa-zirconocene 3. The high activity of the new zirconocene 5 for propylene isospectic polymerization at high temperature （60℃） is the result of its unique bridged-group structure. Complex 5/MAO displays also high catalytic activity of 0.46× 10^6 to 9.87× 10^6g PE（molZr）^-h^-in the homo-polymerization of ethylene, The visometric molecular weight of PE ranges from 0.97×10^4 to 11.16×10^4 g.mol^- under the given conditions.^13C NMR spectroscopy analysis proves the PE to be linear polyethylene （LPE）.
基金supported by the One Hundred Talent Program of CASthe National Natural Science Foundation of China Petroleum & Chemical Corporation Joint Fund(U1662129)+1 种基金the National Natural Science Foundation of China(91434203)the Key Research Program of Frontier Sciences,Chinese Academy of Sciences(QYZDY-SSW-JSC011)~~
文摘A series of acetate ionic liquids were synthesized using a typical two‐step method.The ionic liquids were used as environmentally benign catalysts in the production of propylene glycol ethers from propylene oxide and alcohols under mild conditions.The basic strengths of the ionic liquids were evaluated by determination of their Hammett functions,obtained using ultraviolet‐visible spectroscopy,and the relationship between their catalytic activities and basicities was established.The catalytic efficiencies of the ionic liquids were higher than that of the traditional basic catalyst NaOH.This can be attributed to the involvement of a novel reaction mechanism when these ionic liquids are used.A possible electrophilic‐nucleophilic dual activation mechanism was proposed and confirmed using electrospray ionization quadrupole time‐of‐flight mass spectrometry.In addition,the effects of significant reaction parameters such as concentration of catalyst,molar ratio of alcohol to propylene oxide,reaction temperature,and steric hindrance of the alcohol were investigated in detail.
基金Supported by the China Postdoctoral Science Foundation(2017 M612374)the Natural Science Foundation of Shandong Province(ZR2017BB007)+5 种基金the Postdoctoral Research Funding of Shandong Province(201703016)the Qingdao Postdoctoral Research Funding(BY20170210)the Fundamental Research Funding of Qingdao(17-1-1-67-jch,17-1-1-80-jch)the Fundamental Research Funds for the Central Universities(18CX02145A,17CX02017A)the New Faculty Start-up Funding from China University of Petroleum(YJ201601058)the Natural Science Foundation of China(21606254)
文摘Selective propylene epoxidation to propylene oxide(PO) with hydrogen peroxide(H_2O_2) was carried out in a catalytic semi-batch reactor.High propylene epoxidation activity(44 h^(-1)) was observed over Nb based mesoporous silicate materials Nb-TUD-1 under mild operating conditions.The physical and chemical properties of the Nb based silicates characterized using BET,FTIR,TPD,TEM and UV–Vis revealed that the site isolation and surface acidity are crucial for PO production.Catalyst synthesis methods were investigated for their effects on PO productivity,PO selectivity and H_2O_2 utilization efficiency.It is found that Nb-TUD-1 material synthesized by the sol–gel method is more active and selective than impregnated materials for liquid phase propylene epoxidation.Surface characterization confirms that thus synthesized Nb-TUD-1 catalysts have more Lewis acidity and less Bronsted acidity compared to the catalysts by impregnation.
