Mordenite with different Si/Al ratios were synthesized by solvent-free method and used for dimethyl ether(DME)carbonylation reaction.The influence of Si/Al ratio in the feedstock on the structure,porosity and acid sit...Mordenite with different Si/Al ratios were synthesized by solvent-free method and used for dimethyl ether(DME)carbonylation reaction.The influence of Si/Al ratio in the feedstock on the structure,porosity and acid sites were systematically investigated.The characterization results showed that with the increase of Si/Al ratio in the feedstock,part of silicon species fail to enter the skeleton and the specific surface area and pore volume of the samples decreased.The amount of weak acid and medium strong acid decreased alongside with the increasing Si/Al ratio,and the amount of strong acid slightly increased.The Al atoms preferentially enter the strong acid sites in the 8 member ring(MR)channel during the crystallization process.The high Si/Al ratio sample had more acid sites located in the 8 MR channel,leading to more active sites for carbonylation reaction and higher catalytic performance.Appropriately increasing the Si/Al ratio was beneficial for the improvement of carbonylation reaction activity over the mordenite(MOR)catalyst.展开更多
The Ru-catalyzed carbonylation of alkenes with CO_(2)as a C1 surrogate and imidazole chlorides as the promotor is investigated by a combination of computational and experimental study.The conversion rate of CO_(2)to C...The Ru-catalyzed carbonylation of alkenes with CO_(2)as a C1 surrogate and imidazole chlorides as the promotor is investigated by a combination of computational and experimental study.The conversion rate of CO_(2)to CO is positively correlated with the efficiency of both hydroesterification and hydroformylation,which is found facilitated in the presence of chloride additives with a decreasing order of BmimCl~B3MimCl>BmmimCl~LiCl.Taking the hydroesterification with MeOH as a representative example,BmimCl bearing C-H functionality at the C^(2)site of the cation assists the reduction of CO_(2)to CO as a hydrogen donor medium,with the anion and cation acting in a synergistic fashion.Subsequent insertion of CO_(2)into the formed Ru-H bond with the assistance of chloride anion produces the Ru-COOH species,which ultimately accelerates the activation of CO_(2).展开更多
Membrane contactor is regarded as a promising method for reaction and process intensification. The feasibility of formaldehyde carbonylation to synthesize glycolic acid using polytetrafluoroethylene(PTFE)membrane cont...Membrane contactor is regarded as a promising method for reaction and process intensification. The feasibility of formaldehyde carbonylation to synthesize glycolic acid using polytetrafluoroethylene(PTFE)membrane contactor has been proved in our previous study. In this paper, the effect of membrane microstructure on process performance was further investigated. Three porous PTFE hollow fibers with different pore sizes and one polydimethylsiloxane(PDMS)/PTFE composite membrane with dense layer were fabricated for comparison. The physical and chemical properties of four membranes, including chemical composition, morphology, contact angle, liquid entry pressure, thermodynamic analysis and gas permeability, were systemically characterized. Experiments of formaldehyde carbonylation under different reaction conditions were conducted. The results indicated that the yield of glycolic acid increased with decreasing pore size for porous membranes, which was due to the improvement of wetting behavior. The dense layer of PDMS in composite hollow fiber could effectively prevent the solvent from entering membrane pores, thus the membrane exhibited the best performance. At reaction temperature of 120℃ and operation pressure of 3.0 MPa, the yield of glycolic acid was always higher than 90% as the mass ratio of trioxane and phosphotungstic acid increased from 0.2:1 to 0.8:1. The highest turnover frequency was up to 26.37 mol·g^(-1)·h^(-1). This study provided a reference for the understanding and optimization of membrane contactors for the synthesis of glycolic acid using solvent with low surface tension.展开更多
The gas-phase synthesis of dimethyl carbonate (DMC) from methanol, carbon monoxide and oXygen has here Studied in a flow system at atomspheric Pressure. A series of Catalyst used in this reaCtion have been prepared an...The gas-phase synthesis of dimethyl carbonate (DMC) from methanol, carbon monoxide and oXygen has here Studied in a flow system at atomspheric Pressure. A series of Catalyst used in this reaCtion have been prepared and evaluated. The influence of trivared carbon supporters, alkaline metal Promoters and operation conditions on DMC opthesis reaction has been discussed. Under the conditions of 130℃, CO/O2=1 .96, SV=3340h-1, the space-time yield (STY) of DMC over PdCl2-CuCl2-CH3COOK/ac. catalyst is 217g/l-cat h,which is higher than what is published in the literatUre so far.展开更多
Due to their tunable acidity,shape selectivity,and excellent stability,zeolites are of great importance as solid acid materials in industrial catalysis.Tuning the properties of the acid sites in zeolites allows for th...Due to their tunable acidity,shape selectivity,and excellent stability,zeolites are of great importance as solid acid materials in industrial catalysis.Tuning the properties of the acid sites in zeolites allows for the rational design and fabrication of catalysts for target reactions.Dimethyl ether(DME)carbonylation,a critical chain-growth reaction for C1 resource utilization,is selectively catalyzed by the Brønsted acid sites within the eight-membered rings(8-MRs)of mordenite(MOR).It is anticipated that strengthening the Brønsted acidity—particularly in 8-MRs—will improve the catalytic performance of MOR.In this work,density functional theory(DFT)calculations are first employed and the results used to design a modified MOR with stannum(Sn)and to predict the corresponding changes in acidity.Guided by the theoretical studies,a series of Sn-modified MOR are synthesized via a defect-engineering and subsequent heteroatom-substitution strategy.After partial desilication,isolated tetrahedral Sn species in an open configuration are successfully synthesized for the first time,within which tetrahedrally coordinated Al sites are preserved.An acidic characterization is used to confirm that the acidity of the Brønsted acid sites is enhanced by the introduction of the Sn species;as a result,the sample exhibits excellent activity in DME carbonylation reaction.Kinetic and DFT studies reveal that this strengthened acidity facilitates the adsorption of DME and reduces the activation barriers of DME dissociation and acetyl formation,accounting for the improved activity.The work demonstrates mechanistic insights into the promoting effects of strong acidity on DME carbonylation and offers a promising strategy to precisely control the acidic strength of zeolites.展开更多
Rydberg state excitation(RSE) is a highly non-linear physical phenomenon that is induced by the ionization of atoms or molecules in strong femtosecond laser fields. Here we observe that both parent and fragments(S, C,...Rydberg state excitation(RSE) is a highly non-linear physical phenomenon that is induced by the ionization of atoms or molecules in strong femtosecond laser fields. Here we observe that both parent and fragments(S, C, OC) of the triatomic molecule carbonyl sulfide(OCS) can survive strong 800 nm or 400 nm laser fields in high Rydberg states. The dependence of parent and fragment RSE yields on laser intensity and ellipticity is investigated in both laser fields, and the results are compared with those for strong-field ionization. Distinctly different tendencies for laser intensity and ellipticity are observed for fragment RSE compared with the corresponding ions. The mechanisms of RSE and strong-field ionization of OCS molecules in different laser fields are discussed based on the experimental results. Our study sheds some light on the strong-field excitation and ionization of molecules irradiated by femtosecond NIR and UV laser fields.展开更多
Scholars aim for the improved impedance matching (Z) of materials while maintaining their excellent wave absorption properties. Based on the hydrolysis characteristics of isopropyl titanate, a simple preparation proce...Scholars aim for the improved impedance matching (Z) of materials while maintaining their excellent wave absorption properties. Based on the hydrolysis characteristics of isopropyl titanate, a simple preparation process for the coating of carbonyl iron powder(CIP) with TiO_(2) was designed. Given the TiO2coating, the Z of the CIP@TiO_(2) composite was adjusted well by decreasing the dielectric constant. Moreover, the interfacial polarization of CIP@TiO_(2) was enhanced. Ultimately, the electromagnetic-wave (EMW) absorption property of the CIP@TiO_(2)composite was improved substantially, the minimum reflection loss reached-46.07 dB, and the effective absorption bandwidth can reach 8 GHz at the composite thickness of 1.5 mm. Moreover, compared with CIP, the oxidation resistance of CIP@TiO_(2)showed remarkable improvement. The results revealed that the oxidation starting temperature of CIP@TiO_(2) as about 400℃,whereas the uncoated CIP had an oxidation starting temperature of approximately 250℃. Moreover, the largest oxidation rate temperature of CIP@TiO_(2) increased to around 550℃. This work opens up a novel strategy for the production of high-performance EMW absorbers via structural design.展开更多
基金supported by China National Natural Science Foundation(22008260,21908123)。
文摘Mordenite with different Si/Al ratios were synthesized by solvent-free method and used for dimethyl ether(DME)carbonylation reaction.The influence of Si/Al ratio in the feedstock on the structure,porosity and acid sites were systematically investigated.The characterization results showed that with the increase of Si/Al ratio in the feedstock,part of silicon species fail to enter the skeleton and the specific surface area and pore volume of the samples decreased.The amount of weak acid and medium strong acid decreased alongside with the increasing Si/Al ratio,and the amount of strong acid slightly increased.The Al atoms preferentially enter the strong acid sites in the 8 member ring(MR)channel during the crystallization process.The high Si/Al ratio sample had more acid sites located in the 8 MR channel,leading to more active sites for carbonylation reaction and higher catalytic performance.Appropriately increasing the Si/Al ratio was beneficial for the improvement of carbonylation reaction activity over the mordenite(MOR)catalyst.
基金Financial support from National Natural Science Foundation of China (22078336, U1662133, 21773158, 22008238)Innovation Academy for Green Manufacture, CAS (IAGM2020C13) is gratefully acknowledged
文摘The Ru-catalyzed carbonylation of alkenes with CO_(2)as a C1 surrogate and imidazole chlorides as the promotor is investigated by a combination of computational and experimental study.The conversion rate of CO_(2)to CO is positively correlated with the efficiency of both hydroesterification and hydroformylation,which is found facilitated in the presence of chloride additives with a decreasing order of BmimCl~B3MimCl>BmmimCl~LiCl.Taking the hydroesterification with MeOH as a representative example,BmimCl bearing C-H functionality at the C^(2)site of the cation assists the reduction of CO_(2)to CO as a hydrogen donor medium,with the anion and cation acting in a synergistic fashion.Subsequent insertion of CO_(2)into the formed Ru-H bond with the assistance of chloride anion produces the Ru-COOH species,which ultimately accelerates the activation of CO_(2).
基金the financial support from Dalian Institute of Chemical Physics (DMTO201604)Focus Area Innovation Team Support Plan of Dalian (2021RT03)+1 种基金National Natural Science Foundation of China (21878284)Regional Development Young Scholars of the Chinese Academy of Sciences。
文摘Membrane contactor is regarded as a promising method for reaction and process intensification. The feasibility of formaldehyde carbonylation to synthesize glycolic acid using polytetrafluoroethylene(PTFE)membrane contactor has been proved in our previous study. In this paper, the effect of membrane microstructure on process performance was further investigated. Three porous PTFE hollow fibers with different pore sizes and one polydimethylsiloxane(PDMS)/PTFE composite membrane with dense layer were fabricated for comparison. The physical and chemical properties of four membranes, including chemical composition, morphology, contact angle, liquid entry pressure, thermodynamic analysis and gas permeability, were systemically characterized. Experiments of formaldehyde carbonylation under different reaction conditions were conducted. The results indicated that the yield of glycolic acid increased with decreasing pore size for porous membranes, which was due to the improvement of wetting behavior. The dense layer of PDMS in composite hollow fiber could effectively prevent the solvent from entering membrane pores, thus the membrane exhibited the best performance. At reaction temperature of 120℃ and operation pressure of 3.0 MPa, the yield of glycolic acid was always higher than 90% as the mass ratio of trioxane and phosphotungstic acid increased from 0.2:1 to 0.8:1. The highest turnover frequency was up to 26.37 mol·g^(-1)·h^(-1). This study provided a reference for the understanding and optimization of membrane contactors for the synthesis of glycolic acid using solvent with low surface tension.
文摘The gas-phase synthesis of dimethyl carbonate (DMC) from methanol, carbon monoxide and oXygen has here Studied in a flow system at atomspheric Pressure. A series of Catalyst used in this reaCtion have been prepared and evaluated. The influence of trivared carbon supporters, alkaline metal Promoters and operation conditions on DMC opthesis reaction has been discussed. Under the conditions of 130℃, CO/O2=1 .96, SV=3340h-1, the space-time yield (STY) of DMC over PdCl2-CuCl2-CH3COOK/ac. catalyst is 217g/l-cat h,which is higher than what is published in the literatUre so far.
基金the National Natural Science Foundation of China(21978209 and 22008177)the Royal Society International Collaboration Award(ICA\R1\180317).
文摘Due to their tunable acidity,shape selectivity,and excellent stability,zeolites are of great importance as solid acid materials in industrial catalysis.Tuning the properties of the acid sites in zeolites allows for the rational design and fabrication of catalysts for target reactions.Dimethyl ether(DME)carbonylation,a critical chain-growth reaction for C1 resource utilization,is selectively catalyzed by the Brønsted acid sites within the eight-membered rings(8-MRs)of mordenite(MOR).It is anticipated that strengthening the Brønsted acidity—particularly in 8-MRs—will improve the catalytic performance of MOR.In this work,density functional theory(DFT)calculations are first employed and the results used to design a modified MOR with stannum(Sn)and to predict the corresponding changes in acidity.Guided by the theoretical studies,a series of Sn-modified MOR are synthesized via a defect-engineering and subsequent heteroatom-substitution strategy.After partial desilication,isolated tetrahedral Sn species in an open configuration are successfully synthesized for the first time,within which tetrahedrally coordinated Al sites are preserved.An acidic characterization is used to confirm that the acidity of the Brønsted acid sites is enhanced by the introduction of the Sn species;as a result,the sample exhibits excellent activity in DME carbonylation reaction.Kinetic and DFT studies reveal that this strengthened acidity facilitates the adsorption of DME and reduces the activation barriers of DME dissociation and acetyl formation,accounting for the improved activity.The work demonstrates mechanistic insights into the promoting effects of strong acidity on DME carbonylation and offers a promising strategy to precisely control the acidic strength of zeolites.
基金Project supported by the National Key Program for S&T Research and Development(Grant No.2019YFA0307700)the National Natural Science Foundation of China(Grant Nos.12174148,11874179,12074144,and 12074146)。
文摘Rydberg state excitation(RSE) is a highly non-linear physical phenomenon that is induced by the ionization of atoms or molecules in strong femtosecond laser fields. Here we observe that both parent and fragments(S, C, OC) of the triatomic molecule carbonyl sulfide(OCS) can survive strong 800 nm or 400 nm laser fields in high Rydberg states. The dependence of parent and fragment RSE yields on laser intensity and ellipticity is investigated in both laser fields, and the results are compared with those for strong-field ionization. Distinctly different tendencies for laser intensity and ellipticity are observed for fragment RSE compared with the corresponding ions. The mechanisms of RSE and strong-field ionization of OCS molecules in different laser fields are discussed based on the experimental results. Our study sheds some light on the strong-field excitation and ionization of molecules irradiated by femtosecond NIR and UV laser fields.
基金financially supported by the National Natural Science Foundation of China (No.51872058)the Supporting Program for Innovation Team of Outstanding Youth in Colleges and Universities of Shandong Province(No.2020KJA005)。
文摘Scholars aim for the improved impedance matching (Z) of materials while maintaining their excellent wave absorption properties. Based on the hydrolysis characteristics of isopropyl titanate, a simple preparation process for the coating of carbonyl iron powder(CIP) with TiO_(2) was designed. Given the TiO2coating, the Z of the CIP@TiO_(2) composite was adjusted well by decreasing the dielectric constant. Moreover, the interfacial polarization of CIP@TiO_(2) was enhanced. Ultimately, the electromagnetic-wave (EMW) absorption property of the CIP@TiO_(2)composite was improved substantially, the minimum reflection loss reached-46.07 dB, and the effective absorption bandwidth can reach 8 GHz at the composite thickness of 1.5 mm. Moreover, compared with CIP, the oxidation resistance of CIP@TiO_(2)showed remarkable improvement. The results revealed that the oxidation starting temperature of CIP@TiO_(2) as about 400℃,whereas the uncoated CIP had an oxidation starting temperature of approximately 250℃. Moreover, the largest oxidation rate temperature of CIP@TiO_(2) increased to around 550℃. This work opens up a novel strategy for the production of high-performance EMW absorbers via structural design.
