A pore-array intensified tube-in-tube microchannel(PA-TMC),which is characterized by high throughput and low pressure drop,was developed as a gas–liquid contactor.The sulfite oxidation method was used to determine th...A pore-array intensified tube-in-tube microchannel(PA-TMC),which is characterized by high throughput and low pressure drop,was developed as a gas–liquid contactor.The sulfite oxidation method was used to determine the oxygen efficiency(φ)and volumetric mass transfer coefficient(k_(L)a)of PA-TMC,and the mass transfer amount per unit energy(ε)was calculated by using the pressure drop.The effects of structural and operating parameters were investigated systematically,and the twophase flow behavior was monitored by using a charge-coupled device imaging system.The results indicated that the gas absorption efficiency and mass transfer performance of the PA-TMC were improved with increasing pore number,flow rate,and number of helical coil turns and decreasing pore size,row number,annular size,annular length,and surface tension.Theφ,εand k La of PA-TMC could reach 31.3%,1.73×10^(-4) mol/J,and 7.0 s-1,respectively.The Sherwood number was correlated with the investigated parameters to guide the design of PA-TMC in gas absorption and mass transfer processes.展开更多
Lithium cobalt oxide(LiCoO_(2))is proverbially employed as cathode materials of lithium-ion batteries attributed to the high theoretical capacity,and currently,it is developing towards higher cut-off voltages in the p...Lithium cobalt oxide(LiCoO_(2))is proverbially employed as cathode materials of lithium-ion batteries attributed to the high theoretical capacity,and currently,it is developing towards higher cut-off voltages in the pursuit of higher energy density.However,it suffers from serious structural degradation and surface side reactions,in particular,at the voltage above 4.60 V,leading to rapid decay of the battery life.Taking into account the desirable oxygen buffering property and the fast ion mobility characteristic of cerium oxide fluoride,in this work,we prepared Ce&F co-modified LiCoO_(2)by using the precursors of Ce(NO_(3))_(3)·6H_(2)O and NH_(4)F,and evaluated the electrochemical performance under voltages exceeding 4.60 V.The results indicated that the modified samples have multiphase heterostructure of surface CeO_(2-x)and unique Ce-O-F solid solution phase.At 3.0–4.60 V and 25℃,the preferred sample LCO-0.5Ce-0.3F has a high initial discharge specific capacity of 221.9 mA h g^(-1)at 0.1 C,with the retention of 80.3%and 89.6%after 300 cycles at 1 and 5 C,comparing with the pristine LCO(56.4%and 22.6%).And at 3.0–4.65 V,its retention is 64.0%after 300 cycles at 1 C,versus 8.5%of the pristine LCO.Through structural characterizations and DFT calculations,it suggests that Ce^(4+)&F^(-)co-doping suppresses the H3 to H1/3 irreversible phase transition,stabilizes the lattice structure,and reduces the redox activity of the lattice oxygen by modulating the Co 3d–O 2p energy band,consequently improving the electrochemical performance of LiCoO_(2)at high voltages.展开更多
The stability and activity of alkaline carbonate catalysts in supercritical water coal gasification has been investigated using density functional theory method. Our calculations present that the adsorption of Na2CO3 ...The stability and activity of alkaline carbonate catalysts in supercritical water coal gasification has been investigated using density functional theory method. Our calculations present that the adsorption of Na2CO3 on coal are more stable than that of K2CO3, but the stability of Na2CO3 is strongly reduced as the cluster gets larger. In supercritical water system, the dispersion and stability of Na2CO3 catalyst on coal support is strongly improved. During coal gasification process, Na2CO3 transforms with supercritical water into NaOH and NaHCO3, which is beneficial for hydrogen production. The transformation process has been studied via thermodynamics and kinetics ways. The selectively catalytic mechanism of NaOH and the intermediate form of sodium-based catalyst in water-gas shift reaction for higher hydrogen production has also been investigated. Furthermore, NaOH can transform back to Na2CO3 after catalyzing the water-gas shift reaction. Thus, the cooperative effects between supercritical water and Na2CO3 catalyst form a benignant circle which greatly enhances the reaction rate of coal gasification and promotes the production of hydrogen.展开更多
Solid strong base catalysts have received considerable attention in various organic reactions due to their facile separation,neglectable corrosion,and environmental friendliness.Although great progress has been made i...Solid strong base catalysts have received considerable attention in various organic reactions due to their facile separation,neglectable corrosion,and environmental friendliness.Although great progress has been made in the preparation of solid strong base catalysts,it is still challenging to avoid basic sites aggregation on support and active sites loss in reaction system.Here,we report a tandem redox strategy to prepare Na single atoms on graphene,producing a new kind of solid strong base catalyst(Na1/G).The base precursor NaNO_(3)was first reduced to Na2O by graphene(400℃)and successively to single atoms Na anchored on the graphene vacancies(800℃).Owing to the atomically dispersed of basicity,the resultant catalyst presents high activity toward the transesterification of methanol and ethylene carbonate to synthesize dimethyl carbonate(turnover frequency(TOF)value:125.7 h^(−1)),which is much better than the conventional counterpart Na2O/G and various reported solid strong bases(TOF:1.0-90.1 h^(−1)).Furthermore,thanks to the basicity anchored on graphene,the Na1/G catalyst shows excellent durability during cycling.This work may provide a new direction for the development of solid strong base catalysts.展开更多
The nitridation reaction of calcium carbide and N_(2) at high temperatures is the key step in the production of lime-nitrogen.However,the challenges faced by this process,such as high energy consumption and poor produ...The nitridation reaction of calcium carbide and N_(2) at high temperatures is the key step in the production of lime-nitrogen.However,the challenges faced by this process,such as high energy consumption and poor product quality,are mainly attributed to the lack of profound understanding of the reaction.This study aimed to improve this process by investigating the non-isothermal kinetics and reaction characteristics of calcium carbide nitridation reaction at different heating rates(10,15,20,and 30℃·min^(-1))using thermogravimetric analysis.The kinetic equation for the nitridation reaction of additive-free calcium carbide sample was obtained by combining model-free methods and model-fitting method.The effect of different calcium-based additives(CaCl_(2) and CaF_(2))on the reaction was also investigated.The results showed that the calcium-based additives significantly reduced reaction temperature and activation energy E_(a) by about 40% with CaF_(2) and by 55%-60% with CaCl_(2).The reaction model f(α)was also changed from contracting volume(R3)to 3-D diffusion models with D3 for CaCl_(2) and D4 for CaF_(2).This study provides valuable information on the mechanism and kinetics of calcium carbide nitridation reaction and new insights into the improvement of the lime-nitrogen process using calcium-based additives.展开更多
Copper has received extensive attention in the field of catalysis due to its rich natural reserves,low cost,and superior catalytic performance.Herein,we reviewed two modification mechanisms of co-catalyst on the coord...Copper has received extensive attention in the field of catalysis due to its rich natural reserves,low cost,and superior catalytic performance.Herein,we reviewed two modification mechanisms of co-catalyst on the coordination environment change of Cu-based catalysts:(1)change the electronic orbitals and geometric structure of Cu without any catalytic functions;(2)act as an additional active site with a certain catalytic function,as well as their catalytic mechanism in major reactions,including the hydrogenation to alcohols,dehydrogenation of alcohols,water gas shift reaction,reduction of nitrogenous compounds,electrocatalysis and others.The influencing mechanisms of different types of auxiliary metals on the structure-activity relationship of Cu-based catalysts in these reactions were especially summarized and discussed.The mechanistic understanding can provide significant guidance for the design and controllable synthesis of novel Cu-based catalysts used in many industrial reactions.展开更多
Magnesium-related solid bases have long been considered catalysts with weak or medium basicity.Here we report the fabrication of Mg single-atom catalysts with superbasicity for the first time.A sublimation-migration-a...Magnesium-related solid bases have long been considered catalysts with weak or medium basicity.Here we report the fabrication of Mg single-atom catalysts with superbasicity for the first time.A sublimation-migration-anchoring strategy is employed,in which the Mg net is sublimated,transported by Ar,and trapped by defective graphene(producing Mg_(1)/G).Simulated and experimental results demonstrate that Mg single atoms are anchored on graphene in tetra-coordination,and Mg single atoms cooperating with C atoms give superbasicity,which differs from conventional alkali/alkaline earth metal oxides with basicity originating from O atoms.This new solid base is highly active in the synthesis of dimethyl carbonate through transesterification of ethylene carbonate with methanol,which is usually catalyzed by strong bases.The turnover frequency value reaches 99.6 h^(-1) on Mg_(1)/G,which is much higher than that of traditional Mg-related counterparts(1.0–5.6 h^(-1))and even superior to that of typical Na and K-related solid superbases(29.8–36.2 h^(-1))under similar conditions.展开更多
As an advanced and new technology in molecular simulation fields, ReaxFF reactive force field has been developed and widely applied during the last two decades. ReaxFF bridges the gap between quantum chemistry （QC） ...As an advanced and new technology in molecular simulation fields, ReaxFF reactive force field has been developed and widely applied during the last two decades. ReaxFF bridges the gap between quantum chemistry （QC） and non-reactive empirical force field based molecular simulation methods, and aims to provide a transferable potential which can describe many chemical reactions with bond formation and breaking. This review presents an overview of the development and applications of ReaxFF reactive force field in the fields of reaction processes, biology and materials, including （1） the mechanism studies of organic reactions under extreme conditions （like high temperatures and pressures） related with high-energy materials, hydrocarbons and coals, （2） the structural properties ofnanomaterials such as graphene oxides, carbon nanotubes, silicon nanowires and metal nanoparticles, （3） interfacial interactions of solid-solid, solid-liquid and biological/inorganic surfaces, （4） the catalytic mechanisms of many types of metals and metal oxides, and （5） electrochemical mechanisms of fuel cells and lithium batteries. The limitations and challenges of ReaxFF reactive force field are also mentioned in this review, which will shed light on its future applications to a wider range of chemical environments.展开更多
Supercritical water gasification is a promising technology in dealing with the degradation of hazardous waste,such as oily sludge,accompanied by the production of fuel gases.To evaluate the mechanism of Fe_(2)O_(3) ca...Supercritical water gasification is a promising technology in dealing with the degradation of hazardous waste,such as oily sludge,accompanied by the production of fuel gases.To evaluate the mechanism of Fe_(2)O_(3) catalyst and the migration pathways of heteroatoms and to investigate the systems during the process,reactive force field molecular dynamics simulations are adopted.In terms of the catalytic mechanisms of Fe_(2)O_(3),the surface lattice oxygen is consumed by small carbon fragments to produce CO and CO_(2),improving the catalytic performance of the cluster due to more unsaturated coordination Fe sites exposed.Lattice oxygen combines with*H radicals to form water molecules,improving the catalytic performance.Furthermore,the pathway of asphaltene degradation was revealed at an atomic level,as well as products.Moreover,the adsorption of hydroxyl radical on the S atom caused breakage of the two C-S bonds in turn,forming·HSO intermediate,so that the organic S element was fixed into the inorganic liquid phase.The heteroatom O was removed under the effects of supercritical water.Heavy metal particles presented in the oily sludge,such as iron in association with Fe_(2)O_(3) catalyst,helped accelerate the degradation of asphaltenes.展开更多
In order to better unite and lead young chemical engineering scholars,the Chemical Industry and Engineering Society of China will establish Youth Working Committee.At the time of the establishment of Youth Working Com...In order to better unite and lead young chemical engineering scholars,the Chemical Industry and Engineering Society of China will establish Youth Working Committee.At the time of the establishment of Youth Working Committee,we were invited as guest editors to organize the special issue of Frontiers of Chemical Science and Engineering on green chemical process and intensification,aiming to inspire the innovative ideas and build an energetic and academic communication platform for young scholars.展开更多
基金supported by National Key Research and Development Program(No.2016YFD0501402-04)National Natural Science Foundation of China(Nos.21776179,21621004)the Program for Changjiang Scholars and Innovative Research Team in University(No.IRT_15R46)。
文摘A pore-array intensified tube-in-tube microchannel(PA-TMC),which is characterized by high throughput and low pressure drop,was developed as a gas–liquid contactor.The sulfite oxidation method was used to determine the oxygen efficiency(φ)and volumetric mass transfer coefficient(k_(L)a)of PA-TMC,and the mass transfer amount per unit energy(ε)was calculated by using the pressure drop.The effects of structural and operating parameters were investigated systematically,and the twophase flow behavior was monitored by using a charge-coupled device imaging system.The results indicated that the gas absorption efficiency and mass transfer performance of the PA-TMC were improved with increasing pore number,flow rate,and number of helical coil turns and decreasing pore size,row number,annular size,annular length,and surface tension.Theφ,εand k La of PA-TMC could reach 31.3%,1.73×10^(-4) mol/J,and 7.0 s-1,respectively.The Sherwood number was correlated with the investigated parameters to guide the design of PA-TMC in gas absorption and mass transfer processes.
基金partially supported by the Major Program of the National Natural Science Foundation of China(No.22090034)the Haihe Laboratory of Sustainable Chemical Transformations for financial support。
文摘Lithium cobalt oxide(LiCoO_(2))is proverbially employed as cathode materials of lithium-ion batteries attributed to the high theoretical capacity,and currently,it is developing towards higher cut-off voltages in the pursuit of higher energy density.However,it suffers from serious structural degradation and surface side reactions,in particular,at the voltage above 4.60 V,leading to rapid decay of the battery life.Taking into account the desirable oxygen buffering property and the fast ion mobility characteristic of cerium oxide fluoride,in this work,we prepared Ce&F co-modified LiCoO_(2)by using the precursors of Ce(NO_(3))_(3)·6H_(2)O and NH_(4)F,and evaluated the electrochemical performance under voltages exceeding 4.60 V.The results indicated that the modified samples have multiphase heterostructure of surface CeO_(2-x)and unique Ce-O-F solid solution phase.At 3.0–4.60 V and 25℃,the preferred sample LCO-0.5Ce-0.3F has a high initial discharge specific capacity of 221.9 mA h g^(-1)at 0.1 C,with the retention of 80.3%and 89.6%after 300 cycles at 1 and 5 C,comparing with the pristine LCO(56.4%and 22.6%).And at 3.0–4.65 V,its retention is 64.0%after 300 cycles at 1 C,versus 8.5%of the pristine LCO.Through structural characterizations and DFT calculations,it suggests that Ce^(4+)&F^(-)co-doping suppresses the H3 to H1/3 irreversible phase transition,stabilizes the lattice structure,and reduces the redox activity of the lattice oxygen by modulating the Co 3d–O 2p energy band,consequently improving the electrochemical performance of LiCoO_(2)at high voltages.
基金supported by the National High-Tech Research and Development Program of China(2011AA05A201)the National Natural Science Foundation of China(21106094)Tianjin Science Foundation for Youths,China(12JCQNJC03100)
文摘The stability and activity of alkaline carbonate catalysts in supercritical water coal gasification has been investigated using density functional theory method. Our calculations present that the adsorption of Na2CO3 on coal are more stable than that of K2CO3, but the stability of Na2CO3 is strongly reduced as the cluster gets larger. In supercritical water system, the dispersion and stability of Na2CO3 catalyst on coal support is strongly improved. During coal gasification process, Na2CO3 transforms with supercritical water into NaOH and NaHCO3, which is beneficial for hydrogen production. The transformation process has been studied via thermodynamics and kinetics ways. The selectively catalytic mechanism of NaOH and the intermediate form of sodium-based catalyst in water-gas shift reaction for higher hydrogen production has also been investigated. Furthermore, NaOH can transform back to Na2CO3 after catalyzing the water-gas shift reaction. Thus, the cooperative effects between supercritical water and Na2CO3 catalyst form a benignant circle which greatly enhances the reaction rate of coal gasification and promotes the production of hydrogen.
基金the National Science Fund for Distinguished Young Scholars(No.22125804)the National Natural Science Foundation of China(Nos.22078155 and 22178163)the Jiangsu Funding Program for Excellent Postdoctoral Talent.
文摘Solid strong base catalysts have received considerable attention in various organic reactions due to their facile separation,neglectable corrosion,and environmental friendliness.Although great progress has been made in the preparation of solid strong base catalysts,it is still challenging to avoid basic sites aggregation on support and active sites loss in reaction system.Here,we report a tandem redox strategy to prepare Na single atoms on graphene,producing a new kind of solid strong base catalyst(Na1/G).The base precursor NaNO_(3)was first reduced to Na2O by graphene(400℃)and successively to single atoms Na anchored on the graphene vacancies(800℃).Owing to the atomically dispersed of basicity,the resultant catalyst presents high activity toward the transesterification of methanol and ethylene carbonate to synthesize dimethyl carbonate(turnover frequency(TOF)value:125.7 h^(−1)),which is much better than the conventional counterpart Na2O/G and various reported solid strong bases(TOF:1.0-90.1 h^(−1)).Furthermore,thanks to the basicity anchored on graphene,the Na1/G catalyst shows excellent durability during cycling.This work may provide a new direction for the development of solid strong base catalysts.
基金supported by the National Natural Science Foundation of China(Grant Nos.U20A20151 and 21978210)the Haihe Laboratory of Sustainable Chemical Transformations.
文摘The nitridation reaction of calcium carbide and N_(2) at high temperatures is the key step in the production of lime-nitrogen.However,the challenges faced by this process,such as high energy consumption and poor product quality,are mainly attributed to the lack of profound understanding of the reaction.This study aimed to improve this process by investigating the non-isothermal kinetics and reaction characteristics of calcium carbide nitridation reaction at different heating rates(10,15,20,and 30℃·min^(-1))using thermogravimetric analysis.The kinetic equation for the nitridation reaction of additive-free calcium carbide sample was obtained by combining model-free methods and model-fitting method.The effect of different calcium-based additives(CaCl_(2) and CaF_(2))on the reaction was also investigated.The results showed that the calcium-based additives significantly reduced reaction temperature and activation energy E_(a) by about 40% with CaF_(2) and by 55%-60% with CaCl_(2).The reaction model f(α)was also changed from contracting volume(R3)to 3-D diffusion models with D3 for CaCl_(2) and D4 for CaF_(2).This study provides valuable information on the mechanism and kinetics of calcium carbide nitridation reaction and new insights into the improvement of the lime-nitrogen process using calcium-based additives.
基金This work was supported by the National Natural Science Foundation of China(Grant No.21576205)。
文摘Copper has received extensive attention in the field of catalysis due to its rich natural reserves,low cost,and superior catalytic performance.Herein,we reviewed two modification mechanisms of co-catalyst on the coordination environment change of Cu-based catalysts:(1)change the electronic orbitals and geometric structure of Cu without any catalytic functions;(2)act as an additional active site with a certain catalytic function,as well as their catalytic mechanism in major reactions,including the hydrogenation to alcohols,dehydrogenation of alcohols,water gas shift reaction,reduction of nitrogenous compounds,electrocatalysis and others.The influencing mechanisms of different types of auxiliary metals on the structure-activity relationship of Cu-based catalysts in these reactions were especially summarized and discussed.The mechanistic understanding can provide significant guidance for the design and controllable synthesis of novel Cu-based catalysts used in many industrial reactions.
基金supported by the National Science Fund for Distinguished Young Scholars(22125804)the National Natural Science Foundation of China(22078155,21878149,U20A20151)the Project of Priority Academic Program Development of Jiangsu Higher Education Institutions。
文摘Magnesium-related solid bases have long been considered catalysts with weak or medium basicity.Here we report the fabrication of Mg single-atom catalysts with superbasicity for the first time.A sublimation-migration-anchoring strategy is employed,in which the Mg net is sublimated,transported by Ar,and trapped by defective graphene(producing Mg_(1)/G).Simulated and experimental results demonstrate that Mg single atoms are anchored on graphene in tetra-coordination,and Mg single atoms cooperating with C atoms give superbasicity,which differs from conventional alkali/alkaline earth metal oxides with basicity originating from O atoms.This new solid base is highly active in the synthesis of dimethyl carbonate through transesterification of ethylene carbonate with methanol,which is usually catalyzed by strong bases.The turnover frequency value reaches 99.6 h^(-1) on Mg_(1)/G,which is much higher than that of traditional Mg-related counterparts(1.0–5.6 h^(-1))and even superior to that of typical Na and K-related solid superbases(29.8–36.2 h^(-1))under similar conditions.
文摘As an advanced and new technology in molecular simulation fields, ReaxFF reactive force field has been developed and widely applied during the last two decades. ReaxFF bridges the gap between quantum chemistry （QC） and non-reactive empirical force field based molecular simulation methods, and aims to provide a transferable potential which can describe many chemical reactions with bond formation and breaking. This review presents an overview of the development and applications of ReaxFF reactive force field in the fields of reaction processes, biology and materials, including （1） the mechanism studies of organic reactions under extreme conditions （like high temperatures and pressures） related with high-energy materials, hydrocarbons and coals, （2） the structural properties ofnanomaterials such as graphene oxides, carbon nanotubes, silicon nanowires and metal nanoparticles, （3） interfacial interactions of solid-solid, solid-liquid and biological/inorganic surfaces, （4） the catalytic mechanisms of many types of metals and metal oxides, and （5） electrochemical mechanisms of fuel cells and lithium batteries. The limitations and challenges of ReaxFF reactive force field are also mentioned in this review, which will shed light on its future applications to a wider range of chemical environments.
基金the National Natural Science Foundation of China(Grant Nos.21978210 and U20A20151)Tianjin Natural Science Foundation,China(Grant No.19JCYBJC20000)the National Key R&D Program of China(Grant No.2018YFA0702403)。
文摘Supercritical water gasification is a promising technology in dealing with the degradation of hazardous waste,such as oily sludge,accompanied by the production of fuel gases.To evaluate the mechanism of Fe_(2)O_(3) catalyst and the migration pathways of heteroatoms and to investigate the systems during the process,reactive force field molecular dynamics simulations are adopted.In terms of the catalytic mechanisms of Fe_(2)O_(3),the surface lattice oxygen is consumed by small carbon fragments to produce CO and CO_(2),improving the catalytic performance of the cluster due to more unsaturated coordination Fe sites exposed.Lattice oxygen combines with*H radicals to form water molecules,improving the catalytic performance.Furthermore,the pathway of asphaltene degradation was revealed at an atomic level,as well as products.Moreover,the adsorption of hydroxyl radical on the S atom caused breakage of the two C-S bonds in turn,forming·HSO intermediate,so that the organic S element was fixed into the inorganic liquid phase.The heteroatom O was removed under the effects of supercritical water.Heavy metal particles presented in the oily sludge,such as iron in association with Fe_(2)O_(3) catalyst,helped accelerate the degradation of asphaltenes.
文摘In order to better unite and lead young chemical engineering scholars,the Chemical Industry and Engineering Society of China will establish Youth Working Committee.At the time of the establishment of Youth Working Committee,we were invited as guest editors to organize the special issue of Frontiers of Chemical Science and Engineering on green chemical process and intensification,aiming to inspire the innovative ideas and build an energetic and academic communication platform for young scholars.
