A novel cloisite modified solid catalyst was prepared in a single step from commercially available starting materials for the first time. The ring opening polymerization of L-lactide and D-lactide using this cloisite ...A novel cloisite modified solid catalyst was prepared in a single step from commercially available starting materials for the first time. The ring opening polymerization of L-lactide and D-lactide using this cloisite modified solid catalyst resulted in homopolymers of 75,000 and PDI = 1.6 and the maximum molecular weight (Mw) i.e. 180,000 with PDI = 1.9 were obtained. The catalytic activity ofcloisite modified solid catalyst was compared with the conventional stannous octoate catalyst and found superior to stannous octoate in all respect such as conversion, molecular weight and molecular weight distribution etc.. Moreover, the maximum molecular weight i.e. 180,000 was obtained at 220 ℃, whereas, transesterification reaction predominate in presence of stannous octoate The linear structure was confirmed by quantitative ^13C NMR Spectroscopy. Blend films were obtained by casting mixed solutions of poly (D-lactide) and poly (L-lactide) at various compositions, and stereocomplex was formed at 50/50 composition with molecular weight of 75,000.展开更多
Iron-based perovskite-type compounds modified by Ru were prepared through sol-gel process to study its catalytic activity of NOx direct decomposition at low temperature and evaluate the conversion of NO under the expe...Iron-based perovskite-type compounds modified by Ru were prepared through sol-gel process to study its catalytic activity of NOx direct decomposition at low temperature and evaluate the conversion of NO under the experimental conditions. The catalytic activity of La 0.9Ce 0.1Fe 0.8-nCo 0.2RunO3 (n=0.01,0.03,0.05,0.07,0.09)series for the NO, NO-CO two components, CO-HC-NO three components were also analyzed. The catalytic investigation evidenced that the presence of Ru is necessary for making highly activity in decomposition of nitric oxide even at low temperature(400 ℃)and La 0.9Ce 0.9Fe 0.75Co 0.2Ru 0.05O3 (n=0.05) has better activity in all the samples, the conversion of it is 58.5%. With the reducing gas(CO,C3H6)added into the gas, the catalyst displayed very high activity in decomposition of NO and the conversion of it is 80% and 92.5% separately.展开更多
A well-dispersed metallic palladium catalyst modified by polymer-anchored thioether ligands was used for the hydrogenation of cyclopentadiene to cyclopentene with high activity and selectivity in ambient condition. Th...A well-dispersed metallic palladium catalyst modified by polymer-anchored thioether ligands was used for the hydrogenation of cyclopentadiene to cyclopentene with high activity and selectivity in ambient condition. The evidences to show the modification of catalytic properties by polymer anchored ligands were given.展开更多
Tuning the surface acidity of ZSM-5 catalyst is essential to achieve desired propene selectivity and yield.Here several ratios of Zr were utilized to modify ZSM-5 via flame spray pyrolysis technique coupled with a pul...Tuning the surface acidity of ZSM-5 catalyst is essential to achieve desired propene selectivity and yield.Here several ratios of Zr were utilized to modify ZSM-5 via flame spray pyrolysis technique coupled with a pulse spray evaporation system.The interaction between Zr and ZSM-5 in the flame influenced the physicochemical and acidity properties of the Zr/ZSM-5.The increasing Zr ratio in ZSM-5 shows coated layers of irregular nano-sized Zr with an increase in crystallite sizes due to the synergetic effect between Zr and ZSM-5.The surface chemical analysis revealed increased lattice oxygen on the Zr modified ZSM-5(1:4) sample compared to other catalysts.The acidity analysis revealed the Lewis and Br?nsted acid distribution in the weak and medium acid sites on the catalyst surface.However,the increase in Zr loading decreased the concentration of Br?nsted acid sites and tuned the catalyst surface to more Lewis acidity,promoting propene selectivity and hindering the over-oxidation of propene.The modified ZSM-5 catalysts were examined in a fixed bed reactor within 300℃-700℃ at a gas hourly space velocity(GHSV) of 6000 mL·g(catalysts)^(-1)·h^(-1) for the oxidative dehydrogenation of propane(ODHP) to propene.Among the catalysts,Zr/ZSM-5(1:4) exhibited the best propene yield, with 57.19% propane conversion and 75.54% selectivity to propene and the highest stability.This work provides a promising strategy for tuning the surface acidity of ZSM-5 with Zr for ODHP applications.展开更多
The addition of Au as a promoter/modifier for alumina supported Co catalyst has been studied by combined in-situ high temperature, high pressure Fourier transform infrared (FTIR) and on-line gas chromatography. The ...The addition of Au as a promoter/modifier for alumina supported Co catalyst has been studied by combined in-situ high temperature, high pressure Fourier transform infrared (FTIR) and on-line gas chromatography. The combination of these tools permitted the state of the active catalyst surface to be monitored while following the elution of reaction products during the first 5-7 h on stream of the catalyst. The catalysts under study were a 10%Co/ A1203 and a 2.5%Au/10%Co/A1203. Samples were characterised before use using Raman and temperature programmed reduction (TPR). During the initial stages of reaction, hydrocarbons were built up on the surface of the catalyst as monitored by FTIR and the nature and amount of these species were assessed in terms of CH2/CH3 ratio and the density of these alkyl fragments by employing absorption coefficients for the individual components. The nature and reducibility of the Co particles were modified by the presence of Au while the later also shifted the CO/ H2 balance by acting as an effective water-gas shift catalyst during the early stages of reaction. This characteristic was lost during reaction as a consequence of redistribution of the two metallic phases.展开更多
The direct catalytic conversion of syngas to aromatics offers a promising route to manufacture fine chemicals by employing non-petroleum carbon resources,because aromatic constituents are the key platform for producin...The direct catalytic conversion of syngas to aromatics offers a promising route to manufacture fine chemicals by employing non-petroleum carbon resources,because aromatic constituents are the key platform for producing polymers.However,this remains a great challenge due to the low yield of aromatics and poor catalyst stability,which restrict further development.In recent years,extensive research has been reported on the design of effective catalysts and the optimization of operating conditions to obtain better catalytic performance.In this review,we focus on these related achievements and present a comprehensive overview of different kinds of catalysts,mainly including modified Fischer-Tropsch(FT)catalysts and composite catalysts,as well as their performance and reaction mechanisms.The thermodynamic analysis of the reactions involved in this innovative conversion process and the comparison of different methods are also described in detail in this updated review.Finally,the challenges and prospects for direct syngas conversion are discussed to provide general guidelines for the construction of a well-designed reaction route.展开更多
A Pt-Rh three-way catalyst(M-DS) supported on CeO_2-ZrO_2-La_2O_3-Nd_2O_3 and its analogous supported catalyst(DS) were developed via a modified double-solvent method and conventional double-solvent method, respec...A Pt-Rh three-way catalyst(M-DS) supported on CeO_2-ZrO_2-La_2O_3-Nd_2O_3 and its analogous supported catalyst(DS) were developed via a modified double-solvent method and conventional double-solvent method, respectively. The as-prepared catalysts were characterized by N_2 adsorption-desorption, X-ray diffraction(XRD), CO-chemisorption, X-ray photoelectron spectroscopy(XPS) and hydrogen temperature-programmed reduction(H_2-TPR). The preformed Pt nanoparticles generated using ethanol as a reducing agent on M-DS presented enhanced Pt dispersion regardless of aging treatment as confirmed by XRD and CO-chemisorption measurements. The textural properties and reduction ability of M-DS were maintained to a large extent after aging treatment. This result was consistent with those of the N_2 adsorption-desorption and H_2-TPR, respectively. Meanwhile, the XPS analysis demonstrated that higher Pt^0 species and larger Ce^(3+) concentration could be obtained for M-DS. In the conversion of a simulated compressed natural gas(CNG) vehicle exhaust, both fresh and aged M-DS showed a significant enhancement in the activity and N_2-selectivity. Particularly, the complete conversion temperature(T_(90)) of CH_4 over the aged M-DS catalyst was 65 oC lower than that over the aged catalyst by conventional double-solvent method.展开更多
文摘A novel cloisite modified solid catalyst was prepared in a single step from commercially available starting materials for the first time. The ring opening polymerization of L-lactide and D-lactide using this cloisite modified solid catalyst resulted in homopolymers of 75,000 and PDI = 1.6 and the maximum molecular weight (Mw) i.e. 180,000 with PDI = 1.9 were obtained. The catalytic activity ofcloisite modified solid catalyst was compared with the conventional stannous octoate catalyst and found superior to stannous octoate in all respect such as conversion, molecular weight and molecular weight distribution etc.. Moreover, the maximum molecular weight i.e. 180,000 was obtained at 220 ℃, whereas, transesterification reaction predominate in presence of stannous octoate The linear structure was confirmed by quantitative ^13C NMR Spectroscopy. Blend films were obtained by casting mixed solutions of poly (D-lactide) and poly (L-lactide) at various compositions, and stereocomplex was formed at 50/50 composition with molecular weight of 75,000.
基金Sponsored by the National Natural Science Foundation of China(Grant No.20271019 and 20576027), Natural Science Foundation of Heilongjiang Prov-ince(Grant No.B200504), Postdoctoral Foundationof Heilongjiang Province(Grant No.LBH-Z05066) and Education Department Foundation of Hei-longjiang Province(Grant No.11511270).
文摘Iron-based perovskite-type compounds modified by Ru were prepared through sol-gel process to study its catalytic activity of NOx direct decomposition at low temperature and evaluate the conversion of NO under the experimental conditions. The catalytic activity of La 0.9Ce 0.1Fe 0.8-nCo 0.2RunO3 (n=0.01,0.03,0.05,0.07,0.09)series for the NO, NO-CO two components, CO-HC-NO three components were also analyzed. The catalytic investigation evidenced that the presence of Ru is necessary for making highly activity in decomposition of nitric oxide even at low temperature(400 ℃)and La 0.9Ce 0.9Fe 0.75Co 0.2Ru 0.05O3 (n=0.05) has better activity in all the samples, the conversion of it is 58.5%. With the reducing gas(CO,C3H6)added into the gas, the catalyst displayed very high activity in decomposition of NO and the conversion of it is 80% and 92.5% separately.
文摘A well-dispersed metallic palladium catalyst modified by polymer-anchored thioether ligands was used for the hydrogenation of cyclopentadiene to cyclopentene with high activity and selectivity in ambient condition. The evidences to show the modification of catalytic properties by polymer anchored ligands were given.
基金financial support from the National Natural Science Foundation of China (No. 52161145105/51888103/51976216)Ministry of Science and Technology of China (2017YFA0402800)+5 种基金Beijing Municipal Natural Science Foundation (JQ20017)K.C. Wong Education Foundation (GJTD-2020-07)Recruitment of Global Youth Expertsthe financial support of the Belt and Road scholarshipthe financial support of the ANSO scholarshipthe support of the Chinese Academy of Sciences for the CAS project (Grant No.2018/43)。
文摘Tuning the surface acidity of ZSM-5 catalyst is essential to achieve desired propene selectivity and yield.Here several ratios of Zr were utilized to modify ZSM-5 via flame spray pyrolysis technique coupled with a pulse spray evaporation system.The interaction between Zr and ZSM-5 in the flame influenced the physicochemical and acidity properties of the Zr/ZSM-5.The increasing Zr ratio in ZSM-5 shows coated layers of irregular nano-sized Zr with an increase in crystallite sizes due to the synergetic effect between Zr and ZSM-5.The surface chemical analysis revealed increased lattice oxygen on the Zr modified ZSM-5(1:4) sample compared to other catalysts.The acidity analysis revealed the Lewis and Br?nsted acid distribution in the weak and medium acid sites on the catalyst surface.However,the increase in Zr loading decreased the concentration of Br?nsted acid sites and tuned the catalyst surface to more Lewis acidity,promoting propene selectivity and hindering the over-oxidation of propene.The modified ZSM-5 catalysts were examined in a fixed bed reactor within 300℃-700℃ at a gas hourly space velocity(GHSV) of 6000 mL·g(catalysts)^(-1)·h^(-1) for the oxidative dehydrogenation of propane(ODHP) to propene.Among the catalysts,Zr/ZSM-5(1:4) exhibited the best propene yield, with 57.19% propane conversion and 75.54% selectivity to propene and the highest stability.This work provides a promising strategy for tuning the surface acidity of ZSM-5 with Zr for ODHP applications.
文摘The addition of Au as a promoter/modifier for alumina supported Co catalyst has been studied by combined in-situ high temperature, high pressure Fourier transform infrared (FTIR) and on-line gas chromatography. The combination of these tools permitted the state of the active catalyst surface to be monitored while following the elution of reaction products during the first 5-7 h on stream of the catalyst. The catalysts under study were a 10%Co/ A1203 and a 2.5%Au/10%Co/A1203. Samples were characterised before use using Raman and temperature programmed reduction (TPR). During the initial stages of reaction, hydrocarbons were built up on the surface of the catalyst as monitored by FTIR and the nature and amount of these species were assessed in terms of CH2/CH3 ratio and the density of these alkyl fragments by employing absorption coefficients for the individual components. The nature and reducibility of the Co particles were modified by the presence of Au while the later also shifted the CO/ H2 balance by acting as an effective water-gas shift catalyst during the early stages of reaction. This characteristic was lost during reaction as a consequence of redistribution of the two metallic phases.
基金the National Key R&D Program of China(2016YFA0202804)the Strategic Priority Research Program of the Chinese Academy of Sciences(XDB17020400)+2 种基金the Youth Innovation Promotion Association CAS for financial supportthe National Natural Science Foundation of China(21506204,21476226)Dalian Science Foundation for Distinguished Young Scholars(2016RJ04)~~
文摘The direct catalytic conversion of syngas to aromatics offers a promising route to manufacture fine chemicals by employing non-petroleum carbon resources,because aromatic constituents are the key platform for producing polymers.However,this remains a great challenge due to the low yield of aromatics and poor catalyst stability,which restrict further development.In recent years,extensive research has been reported on the design of effective catalysts and the optimization of operating conditions to obtain better catalytic performance.In this review,we focus on these related achievements and present a comprehensive overview of different kinds of catalysts,mainly including modified Fischer-Tropsch(FT)catalysts and composite catalysts,as well as their performance and reaction mechanisms.The thermodynamic analysis of the reactions involved in this innovative conversion process and the comparison of different methods are also described in detail in this updated review.Finally,the challenges and prospects for direct syngas conversion are discussed to provide general guidelines for the construction of a well-designed reaction route.
基金supported by the National Key Research and Development Program of China(2016YFC0204902)
文摘A Pt-Rh three-way catalyst(M-DS) supported on CeO_2-ZrO_2-La_2O_3-Nd_2O_3 and its analogous supported catalyst(DS) were developed via a modified double-solvent method and conventional double-solvent method, respectively. The as-prepared catalysts were characterized by N_2 adsorption-desorption, X-ray diffraction(XRD), CO-chemisorption, X-ray photoelectron spectroscopy(XPS) and hydrogen temperature-programmed reduction(H_2-TPR). The preformed Pt nanoparticles generated using ethanol as a reducing agent on M-DS presented enhanced Pt dispersion regardless of aging treatment as confirmed by XRD and CO-chemisorption measurements. The textural properties and reduction ability of M-DS were maintained to a large extent after aging treatment. This result was consistent with those of the N_2 adsorption-desorption and H_2-TPR, respectively. Meanwhile, the XPS analysis demonstrated that higher Pt^0 species and larger Ce^(3+) concentration could be obtained for M-DS. In the conversion of a simulated compressed natural gas(CNG) vehicle exhaust, both fresh and aged M-DS showed a significant enhancement in the activity and N_2-selectivity. Particularly, the complete conversion temperature(T_(90)) of CH_4 over the aged M-DS catalyst was 65 oC lower than that over the aged catalyst by conventional double-solvent method.