A method for the direct syntheses of partially and fully delaminated MWW zeolites is reported herein.Two organic amines were introduced into the hydrothermal synthetic system:hexamethyleneimine(HMI),which acted as the...A method for the direct syntheses of partially and fully delaminated MWW zeolites is reported herein.Two organic amines were introduced into the hydrothermal synthetic system:hexamethyleneimine(HMI),which acted as the structure-directing agent for the MWW layered structure;and dicyclohexylamine(DCHA),in the role of an in-situ delaminating agent.By varying the amount of DCHA,partially and fully delaminated MWW zeolites having two MWW structure layers and one single layer,respectively,were obtained.These were denoted as SCM-1(Sinopec Composite Material)and SCM-6,respectively.The delaminated materials possess ultra-large external surface areas,and the transmission electron microscopy images illustrated their layered nature.In the reaction of liquid phase benzene alkylation with ethylene,SCM-1,the double-layered MWW zeolite,exhibited far superior catalytic performance compared to zeolite MCM-22.展开更多
Precise control of catalytic selectivity is a key concept of green chemistry,and also an important driving force for the sustainable development of catalytic industry.Selectivity not only determines the atomic economy...Precise control of catalytic selectivity is a key concept of green chemistry,and also an important driving force for the sustainable development of catalytic industry.Selectivity not only determines the atomic economy of the catalytic process,but also affects the energy consumption of subsequent separation process.The objective of this review is to illustrate successful catalyst design strategies to enhance selectivity,by using several important catalytic cases of petroleum refining and petrochemicals.These industrial applications and cutting-edge research cases mainly use the strategies of coupling,decoupling or confinement of adsorption sites and active sites to tune the diffusion barrier and activation energy barrier in different routes,so as to improve the selectivity of catalyst.Based on the preliminary understanding of selectivity improvement,it is necessary to systematically investigate the selective catalytic processes using combination of multiple strategies,thereby realizing the design of highly selective catalyst over reasonable time scales and space scales.展开更多
The reaction mechanism of zeolite- or zeotype-catalyzed methanol-to-olefins（MTO） conversion is still a subject of debate. Employing periodic density functional theory calculations, the olefin-based cycle was studied...The reaction mechanism of zeolite- or zeotype-catalyzed methanol-to-olefins（MTO） conversion is still a subject of debate. Employing periodic density functional theory calculations, the olefin-based cycle was studied using tetramethylethene（TME） as a representative olefinic hydrocarbon pool in H-SAPO-18 zeotype. The overall free energy barrier at 673 K was calculated and found to be less than 150 kJ/mol in the TME-based cycle, much lower than those in the aromatic-based cycle（〉 200 kJ/mol）, indicating that olefins themselves are the dominant active hydrocarbon pool species in H-SAPO-18. The similarity of the intermediates involved between the aromatic-based cycle and the olefin-based cycle was also highlighted, revealing that both cycles were pattern-consistent. The selectivity related to the distribution of cracking precursors, such as higher olefins or carbenium ions, as a result of the olefin-based cycle for the MTO conversion. The enthalpy barrier of the crack-ing step scaled linearly with the number of carbon atoms of cracking precursors to produce ethene or propene with ethene being much less favored than propene for cracking of C7 and higher pre-cursors. This work highlighted the importance of the olefin-based cycle in H-SAPO-18 for the MTO conversion and established the similarity between the olefin-based and aromatic-based cycles.展开更多
Cr_(2)O_(3) has been recognized as a key oxide component in bifunctional catalysts to produce bridging intermediate,e.g.,methanol,from syngas.By combining density functional theory calculations and microkinetic modeli...Cr_(2)O_(3) has been recognized as a key oxide component in bifunctional catalysts to produce bridging intermediate,e.g.,methanol,from syngas.By combining density functional theory calculations and microkinetic modeling,we computationally studied the surface structures and catalytic activities of bare Cr_(2)O_(3)(001)and(012)surfaces,and two reduced(012)surfaces covered with dissociative hydrogens or oxygen vacancies.The reduction of(001)surface is much more difficult than that of(012)surface.The stepwise or the concerted reaction pathways were explored for the syngas to methanol conversion,and the hydrogenation of CO or CHO is identified as rate-determining step.Microkinetic modeling reveals that(001)surface is inactive for the reaction,and the rates of both reduced(012)surfaces(25−28 s^(-1))are about five times higher than bare(012)surface(4.3 s^(-1))at 673 K.These theoretical results highlight the importance of surface reducibility on the reaction and may provide some implications on the design of individual component in bifunctional catalysis.展开更多
文摘A method for the direct syntheses of partially and fully delaminated MWW zeolites is reported herein.Two organic amines were introduced into the hydrothermal synthetic system:hexamethyleneimine(HMI),which acted as the structure-directing agent for the MWW layered structure;and dicyclohexylamine(DCHA),in the role of an in-situ delaminating agent.By varying the amount of DCHA,partially and fully delaminated MWW zeolites having two MWW structure layers and one single layer,respectively,were obtained.These were denoted as SCM-1(Sinopec Composite Material)and SCM-6,respectively.The delaminated materials possess ultra-large external surface areas,and the transmission electron microscopy images illustrated their layered nature.In the reaction of liquid phase benzene alkylation with ethylene,SCM-1,the double-layered MWW zeolite,exhibited far superior catalytic performance compared to zeolite MCM-22.
文摘Precise control of catalytic selectivity is a key concept of green chemistry,and also an important driving force for the sustainable development of catalytic industry.Selectivity not only determines the atomic economy of the catalytic process,but also affects the energy consumption of subsequent separation process.The objective of this review is to illustrate successful catalyst design strategies to enhance selectivity,by using several important catalytic cases of petroleum refining and petrochemicals.These industrial applications and cutting-edge research cases mainly use the strategies of coupling,decoupling or confinement of adsorption sites and active sites to tune the diffusion barrier and activation energy barrier in different routes,so as to improve the selectivity of catalyst.Based on the preliminary understanding of selectivity improvement,it is necessary to systematically investigate the selective catalytic processes using combination of multiple strategies,thereby realizing the design of highly selective catalyst over reasonable time scales and space scales.
基金supported by the National Key Research and Development Program of China (2016YFB0701100, 2017YFB0702800)the National Natural Science Foundation of China (21673295)~~
文摘The reaction mechanism of zeolite- or zeotype-catalyzed methanol-to-olefins（MTO） conversion is still a subject of debate. Employing periodic density functional theory calculations, the olefin-based cycle was studied using tetramethylethene（TME） as a representative olefinic hydrocarbon pool in H-SAPO-18 zeotype. The overall free energy barrier at 673 K was calculated and found to be less than 150 kJ/mol in the TME-based cycle, much lower than those in the aromatic-based cycle（〉 200 kJ/mol）, indicating that olefins themselves are the dominant active hydrocarbon pool species in H-SAPO-18. The similarity of the intermediates involved between the aromatic-based cycle and the olefin-based cycle was also highlighted, revealing that both cycles were pattern-consistent. The selectivity related to the distribution of cracking precursors, such as higher olefins or carbenium ions, as a result of the olefin-based cycle for the MTO conversion. The enthalpy barrier of the crack-ing step scaled linearly with the number of carbon atoms of cracking precursors to produce ethene or propene with ethene being much less favored than propene for cracking of C7 and higher pre-cursors. This work highlighted the importance of the olefin-based cycle in H-SAPO-18 for the MTO conversion and established the similarity between the olefin-based and aromatic-based cycles.
基金This work was supported by the National Natural Science Foundation of China(No.92045303)the China Postdoctoral Science Foundation(No.2020M681444).The computational resources from Sinopec Geophysical Research Institute are acknowledged.
文摘Cr_(2)O_(3) has been recognized as a key oxide component in bifunctional catalysts to produce bridging intermediate,e.g.,methanol,from syngas.By combining density functional theory calculations and microkinetic modeling,we computationally studied the surface structures and catalytic activities of bare Cr_(2)O_(3)(001)and(012)surfaces,and two reduced(012)surfaces covered with dissociative hydrogens or oxygen vacancies.The reduction of(001)surface is much more difficult than that of(012)surface.The stepwise or the concerted reaction pathways were explored for the syngas to methanol conversion,and the hydrogenation of CO or CHO is identified as rate-determining step.Microkinetic modeling reveals that(001)surface is inactive for the reaction,and the rates of both reduced(012)surfaces(25−28 s^(-1))are about five times higher than bare(012)surface(4.3 s^(-1))at 673 K.These theoretical results highlight the importance of surface reducibility on the reaction and may provide some implications on the design of individual component in bifunctional catalysis.
