A novel central hole-expansion phenomenon is identified, in which the cation-exchange resin is pyrolyzed in a mixed atmosphere of nitrogen and oxygen at 400–500 ℃. In this reaction, the reaction path is predictable ...A novel central hole-expansion phenomenon is identified, in which the cation-exchange resin is pyrolyzed in a mixed atmosphere of nitrogen and oxygen at 400–500 ℃. In this reaction, the reaction path is predictable and always starts from the center of the resin particle to form a central hole, then continues and expands around the hole, finally forming a uniformly distributed hole group;the particle surface remains intact. Analysis shows that this formation mode is due to the different reaction paths of sulfonic groups between the surface and interior of the particle, caused by the temperature difference. On the surface, transformation reactions happen at high temperatures(410–500 ℃) to form stable organic sulfur structures, while decomposition occurs inside the particle at a relatively low temperature(<410 ℃) and promotes complete pyrolysis of the copolymer matrix to form holes.展开更多
The problematic calcareous microfossil Halysis is abundant in the Middle Ordovician Darriwilian Stage of the western edge of the Ordos Basin,North China.The rich and well-preserved specimens of Halysis in this area fa...The problematic calcareous microfossil Halysis is abundant in the Middle Ordovician Darriwilian Stage of the western edge of the Ordos Basin,North China.The rich and well-preserved specimens of Halysis in this area facilitate detailed studies for its skeletal construction and tube microstructure.Halysis differs from calcified cyanobacteria and calcareous red and green algae in morphology,skeletal construction and microstructure,as well as reproduction mode.Halysis typically consists of multiple juxtaposed parallel tubes arranged in sheets(‘multiple-tube'type)or is just composed of one tube(‘single-tube'type).In‘multiple-tube'Halysis,tube fission by bifurcation results from the insertion of a microcrystalline wall at the center of a mother tube.This study demonstrates for the first time that the tube walls of Halysis have a laminofibrous(fibronormal)microstructure,composed of fibrous calcite perpendicular to wall surface,and recognizes the‘single-tube'type Halysis composed of one tube;in addition,for the first time,this study finds out that‘multiple-tube'Halysis develops buddings from the conjunction of two tubes and‘single-tube'Halysis shows wide-angle Y-shaped branchings.Based on these findings,this study further compares Halysis with tabulate corals.Halysis appears stratigraphically earlier than Catenipora and Aulopora,and has a smaller tube size.‘Multiple-tube'Halysis resembles Catenipora and‘single-tube'Halysis resembles Aulopora in skeletal construction and microstructure,and in their tube walls of laminofibrous microstructure composed of fibrous calcite perpendicular to the tube wall surface.Catenipora and Halysis are both characterized by the absence of septal spines.The similarities suggest that Halysis may be the ancestor of Catenipora-like and Aulopora-like tabulate corals.展开更多
A co-reaction of methane with methanol over zeolite catalysts has emerged as a new approach to the long-standing challenge of methane transformation.However,the effect of catalyst acid properties on the co-reaction ha...A co-reaction of methane with methanol over zeolite catalysts has emerged as a new approach to the long-standing challenge of methane transformation.However,the effect of catalyst acid properties on the co-reaction has been rarely studied.In this study,a series of HZSM-5 zeolites with comparable diffusion abilities and various acidities were synthesized directly through steaming with 100%water vapor at 693 K.The co-reaction of methane and methanol was subsequently evaluated.Br?nsted acidity at 0.262 mmol/g was detected to reach the maximum methane conversion of 5.42%at 673 K,which was also the odd point in the relationship between acid concentration and C4 hydrogen transfer index.Moreover,the influence of methanol feed was investigated over parent and steamed ZSM-5 catalyst,with results showing that excessive acid sites or methanol molecules reduce methane conversion.It is proposed that acid sites adsorbed with methanol molecules construct the methane activation sites.Hence,a proper design of zeolite acidity should be achieved to obtain higher methane conversion in the co-reaction process.展开更多
In this study, a series of aryloxy-aluminoxanes originated directly from the hydrolysis of reaction products of A1Me3 and phenols were synthesized, which could serve as effective polymer-retarding activators for the i...In this study, a series of aryloxy-aluminoxanes originated directly from the hydrolysis of reaction products of A1Me3 and phenols were synthesized, which could serve as effective polymer-retarding activators for the iron-catalyzed ethylene oligomerization. The molar ratios of [PhOH]/[AlMe3] and [H2O]/[Al] during the preparation were explored and their impacts on the oligomerization activity and product distribution were discussed. To obtain the effective activators with good polymer-retarding effect and relatively high activity, the optimized conditions were proposed to be [PhOH]/[AlMe3] = 0.5 and [H2O]/[Al] = 0.7. Various aluminoxanes with different [-OH] sources confirmed the importance of using phenols in preparing the effective polymer-retarding activators. By utilizing these aryloxy-aluminoxanes, the mass fraction of polymers in the total products could be reduced to lower than 1.0 wt%, which is much lower than that of the MAO-activated systems (〉 30 wt%). This is a potential benefit for the industrial application of the iron-catalyzed oligomerization process.展开更多
基金Project supported by the National Natural Science Foundation of China(No.20490200)the National Key Technology R&D Program of China(Nos.85-516-06-03,2001BA305B03,and 2007BAF22B08)+1 种基金the National High-Tech R&D Program(863 Program)of China(No.2007AA04Z182)the SINOPEC Technology Project(No.406005),China
基金supported by the National Natural Science Foundation of China(No.91434205)the National Science Fund for Distinguished Young Scholars(No.21525627)+1 种基金the Zhejiang Provincial Natural Science Foundation of China(No.LR14B060001)the Specialized Research Fund for the Doctoral Program of Higher Education of China(No.20130101110063)
基金supported by the Joint Funds of the National Natural Science Foundation of China (No. U21B2095)the Major Research Project of National Natural Science Foundation of China (No. 91834303)the Science Fund for Creative Research Groups of National Natural Science Foundation of China (No. 61621002)。
文摘A novel central hole-expansion phenomenon is identified, in which the cation-exchange resin is pyrolyzed in a mixed atmosphere of nitrogen and oxygen at 400–500 ℃. In this reaction, the reaction path is predictable and always starts from the center of the resin particle to form a central hole, then continues and expands around the hole, finally forming a uniformly distributed hole group;the particle surface remains intact. Analysis shows that this formation mode is due to the different reaction paths of sulfonic groups between the surface and interior of the particle, caused by the temperature difference. On the surface, transformation reactions happen at high temperatures(410–500 ℃) to form stable organic sulfur structures, while decomposition occurs inside the particle at a relatively low temperature(<410 ℃) and promotes complete pyrolysis of the copolymer matrix to form holes.
基金This work was financially supported by the National Science and Technology Major Projea(Grant Nos.2016ZX05004-006 and 2016ZX05004-004)the Strategic Priority Research Program(B)of the Chinese Academy of Sciences(Grant No.XDB26000000)and the National Natural Science Foundation of China(Grant Nos.41502004 and 41902110).
文摘The problematic calcareous microfossil Halysis is abundant in the Middle Ordovician Darriwilian Stage of the western edge of the Ordos Basin,North China.The rich and well-preserved specimens of Halysis in this area facilitate detailed studies for its skeletal construction and tube microstructure.Halysis differs from calcified cyanobacteria and calcareous red and green algae in morphology,skeletal construction and microstructure,as well as reproduction mode.Halysis typically consists of multiple juxtaposed parallel tubes arranged in sheets(‘multiple-tube'type)or is just composed of one tube(‘single-tube'type).In‘multiple-tube'Halysis,tube fission by bifurcation results from the insertion of a microcrystalline wall at the center of a mother tube.This study demonstrates for the first time that the tube walls of Halysis have a laminofibrous(fibronormal)microstructure,composed of fibrous calcite perpendicular to wall surface,and recognizes the‘single-tube'type Halysis composed of one tube;in addition,for the first time,this study finds out that‘multiple-tube'Halysis develops buddings from the conjunction of two tubes and‘single-tube'Halysis shows wide-angle Y-shaped branchings.Based on these findings,this study further compares Halysis with tabulate corals.Halysis appears stratigraphically earlier than Catenipora and Aulopora,and has a smaller tube size.‘Multiple-tube'Halysis resembles Catenipora and‘single-tube'Halysis resembles Aulopora in skeletal construction and microstructure,and in their tube walls of laminofibrous microstructure composed of fibrous calcite perpendicular to the tube wall surface.Catenipora and Halysis are both characterized by the absence of septal spines.The similarities suggest that Halysis may be the ancestor of Catenipora-like and Aulopora-like tabulate corals.
基金Project supported by the National Natural Science Foundation of China(No.U1663222)。
文摘A co-reaction of methane with methanol over zeolite catalysts has emerged as a new approach to the long-standing challenge of methane transformation.However,the effect of catalyst acid properties on the co-reaction has been rarely studied.In this study,a series of HZSM-5 zeolites with comparable diffusion abilities and various acidities were synthesized directly through steaming with 100%water vapor at 693 K.The co-reaction of methane and methanol was subsequently evaluated.Br?nsted acidity at 0.262 mmol/g was detected to reach the maximum methane conversion of 5.42%at 673 K,which was also the odd point in the relationship between acid concentration and C4 hydrogen transfer index.Moreover,the influence of methanol feed was investigated over parent and steamed ZSM-5 catalyst,with results showing that excessive acid sites or methanol molecules reduce methane conversion.It is proposed that acid sites adsorbed with methanol molecules construct the methane activation sites.Hence,a proper design of zeolite acidity should be achieved to obtain higher methane conversion in the co-reaction process.
基金support and encouragement of the National Natural Science Foundation of China(Nos.U1663222 and 21176208)
文摘In this study, a series of aryloxy-aluminoxanes originated directly from the hydrolysis of reaction products of A1Me3 and phenols were synthesized, which could serve as effective polymer-retarding activators for the iron-catalyzed ethylene oligomerization. The molar ratios of [PhOH]/[AlMe3] and [H2O]/[Al] during the preparation were explored and their impacts on the oligomerization activity and product distribution were discussed. To obtain the effective activators with good polymer-retarding effect and relatively high activity, the optimized conditions were proposed to be [PhOH]/[AlMe3] = 0.5 and [H2O]/[Al] = 0.7. Various aluminoxanes with different [-OH] sources confirmed the importance of using phenols in preparing the effective polymer-retarding activators. By utilizing these aryloxy-aluminoxanes, the mass fraction of polymers in the total products could be reduced to lower than 1.0 wt%, which is much lower than that of the MAO-activated systems (〉 30 wt%). This is a potential benefit for the industrial application of the iron-catalyzed oligomerization process.