Tonalid,an important fragrance ingredient with widespread applicatio n,was synthesized via two FriedelCrafts reactions,which were catalyzed by AlCl_(3).The traditional tonalid production was conducted in batch stirrin...Tonalid,an important fragrance ingredient with widespread applicatio n,was synthesized via two FriedelCrafts reactions,which were catalyzed by AlCl_(3).The traditional tonalid production was conducted in batch stirring tank reactors,suffering from low production capacity and the safety hazard of temperature runaway.To solve these problems,the continuous-flow technologies were developed for the highefficiency and intrinsically safe synthesis of tonalid in microreactors.Catalyst AlCl_(3)was neatly homogenized in proper solvents by forming complex with reactant,which was a necessary step for the continuous synthesis in microreactors.Several reaction conditions,including reactant molar ratio,catalyst concentration,temperature,and microchannel hydrodynamic diameter,were investigated for the two Friedel-Crafts reactions in micro reactors.At optimized conditions,the yields of the two Friedel-Crafts reactions were 44.15%and 97.55%,respectively.In comparison with the batch reactors,the reaction times of these two reactions could both be reduced by nearly two thirds in microreactors at the similar yield.展开更多
The development of efficient systems for the catalytic oxidation of 2-nitro-4-methylsulfonyltoluene(NMST)to 2-nitro-4-methylsulfonyl benzoic acid(NMSBA)with atmospheric air or molecular oxygen in alkaline medium prese...The development of efficient systems for the catalytic oxidation of 2-nitro-4-methylsulfonyltoluene(NMST)to 2-nitro-4-methylsulfonyl benzoic acid(NMSBA)with atmospheric air or molecular oxygen in alkaline medium presents a significant challenge for the chemical industry.Here,we report the synthesis of FeOOH/Fe_(3)O_(4)/metal-organic framework(MOF)polygonal mesopores microflower templated from a MIL-88B(Fe)at room temperature,which exposes polygonal mesopores with atomistic edge steps and lattice defects.The obtained FeOOH/Fe_(3)O_(4)/MOF catalyst was adsorbed onto glass beads and then introduced into the microchannel reactor.In the alkaline environment,oxygen was used as oxidant to catalyze the oxidation of NMST to NMSBA,showing impressive performance.This sustainable system utilizes oxygen as a clean oxidant in an inexpensive and environmentally friendly NaOH/methanol mixture.The position and type of substituent critically affect the products.Additionally,this sustainable protocol enabled gram-scale preparation of carboxylic acid and benzyl alcohol derivatives with high chemoselectivities.Finally,the reactions can be conducted in a pressure reactor,which can conserve oxygen and prevent solvent loss.Moreover,compared with the traditional batch reactor,the self-built microchannel reactor can accelerate the reaction rate,shorten the reaction time,and enhance the selectivity of catalytic oxidation reactions.This approach contributes to environmental protection and holds potential for industrial applications.展开更多
To address the energy challenges,scientists have designed various artificial light-harvesting systems inspired by photosynthesis.Notably,for light-harvesting systems,an energytransfer efficiency close to 100%with an a...To address the energy challenges,scientists have designed various artificial light-harvesting systems inspired by photosynthesis.Notably,for light-harvesting systems,an energytransfer efficiency close to 100%with an antenna effect greater than 10 is generally considered a good application criterion.[1]Today,building an efficient light-harvesting system at a low cost is still demanding.展开更多
The concept of liquid-solid hybrid catalyst that featuring a truly homogeneous liquid microenvironment together with insoluble solid characteristics has been established recently by our group,which enables us to conve...The concept of liquid-solid hybrid catalyst that featuring a truly homogeneous liquid microenvironment together with insoluble solid characteristics has been established recently by our group,which enables us to conveniently bridge the gap between homo-and heterogeneous catalysis.In this study,we extend this general concept to the confinement of molecular rhodium phosphine complexes,including Rh-TPPTS,Rh-TPPMS and Rh-SXP,for olefin hydroformylation reactions.A series of hybrid catalyst materials consisting a modulated liquid interior([BMIM]NTf_(2),[BMIM]PF_(6),[BMIM]BF_(4) or H_(2)O)and a permeable silica crust were fabricated through our developed Pickering emulsion-based method,showing 9.4–24.2-fold activity enhancement and significantly improved aldehyde selectivity(from 72.2%,61.8%to 86.6%)compared to their biphasic counterparts or traditional supported liquid phase system in the hydroformylation of 1-dodecene.Interestingly,the catalytic efficiency was demonstrated to be tunable by rationally engineering the thickness of porous crust and dimensions of the liquid pool.The thus-attained hybrid catalyst could also successfully catalyze the hydroformylation of a variety of olefin substrates and be recycled without a significant loss of activity for at least seven times.展开更多
Continuous-flow upgrading of pentaerythritol synthesis technology via base-catalyzed aldol and Cannizzaro reactions of formaldehyde and acetaldehyde faces the challenge of effectively controlling the critical side rea...Continuous-flow upgrading of pentaerythritol synthesis technology via base-catalyzed aldol and Cannizzaro reactions of formaldehyde and acetaldehyde faces the challenge of effectively controlling the critical side reaction of hydroxymethyl acetaldehyde(HA)to the acrolein intermediate.Here,we first identified the forms of industrial formaldehyde as methane diol that easily converts to the alkaline formaldehyde under alkaline(NaOH)environment.The carbonyl group of alkaline formaldehyde induces deprotonation of acetaldehyde instead of the recognized base-hydroxyl group-induced deprotonation,and it needs to overcome only 18.31 kcal·mol^(-1)(1 kcal=4.186 kJ)energy barrier to form key intermediates of HA.The sodium solvation cage formed by NaOH hexa-coordinated formaldehyde effectively inhibits the alkalinity,thus contributing to a high energy barrier(46.21 kcal·mol^(-1))to unwanted acrolein formation.In addition,the solvation cage gradually opens to increase the alkalinity with the consumption of formaldehyde,thus facilitating the subsequent Cannizzaro reaction(to overcome 11.77 kcal·mol^(-1)).In comparison,strong alkalinity promotes the formation of acrolein(36.65 kcal·mol^(-1))to initiate the acetal side reaction,while weak alkalinity reduces the possibility of the Cannizzaro reaction(to overcome 20.44 kcal·mol^(-1)).This theoretically reveals the importance of the segmented feeding of weak and strong bases to successively control the aldol reaction and Cannizzaro reaction,and the combination of Na_(2)CO_(3) or HCOONa with NaOH improves the pentaerythritol yield by 7%to 13%compared to that of NaOH alone(70%yield)within 1 min at a throughput of 155.7 ml·min^(-1).展开更多
Low-dimensional hybrid nanocrystals are newly emerging active photo catalysts for separating electron-hole pairs,but the instability and low quantum efficiency caused by particle aggregation and hybrid structure relax...Low-dimensional hybrid nanocrystals are newly emerging active photo catalysts for separating electron-hole pairs,but the instability and low quantum efficiency caused by particle aggregation and hybrid structure relaxation remain great challenges.To this end,herein we constructed amorphous FeO_(x)(A-FeO_(x))and crystalline LaFeO_(3)hybrids by a sol-gel method.The amorphous-crystalline hybrids,A-FeO_(x)/LaFeO_(3),not only improve the surface area and alter the band position,but also form numerous channels that are conducive to the transport of electrons and separation of electron-hole pairs,acting as microreactors.Photocatalytic tests show that the A-FeO_(x)/LaFeO_(3)is highly active for the degradation of various organic pollutants,with reaction rate constant of 1.19×10^(-2)min-1for cipro floxacin degradation,for example,which is 1.82 and 1.87 times higher than that of LaFeO_(3)and Fe_(2)O_(3)/LaFeO_(3),respectively,owing to the formation of microreactors between A-FeO_(x)and LaFeO_(3).Cycling tests show that the mate rial has good stability in the reaction,and trapping experiments demonstrate that the photo-induced holes are the main reactive species of the reaction.This work provides a novel and feasible insight into the design of high performance low-dimensional hybrid nanocatalysts for photocatalysis.展开更多
Fluorosurfactants play a crucial role in ensuring the stability and uniformity of droplet microreactors,which significantly broaden their applications in chemical and biological research.This review covers structure d...Fluorosurfactants play a crucial role in ensuring the stability and uniformity of droplet microreactors,which significantly broaden their applications in chemical and biological research.This review covers structure diversity and functional versatility of fluorosurfactants.Fluorosurfactants can be divided into two basic types according to their structure,linear and dendritic types,which both provides individual advantages.Linear fluorosurfactants are easily synthesized and commercially available,whereas dendritic fluorosurfactants have a branched structure that greatly reduces molecular cross-talk between droplets.Based on the application point of view,fluorosurfactants can be further classified into two categories:reactive and responsive fluorosurfactants.The hydrophilic head of reactive fluorosurfactants contains a reactive functional group,making them very useful in other applications,such as microcapsule preparation or protein crystallization.In contrast,responsive fluorosurfactants would change their properties with respect to external stimuli,such as temperature or light,making them perfect candidates for the on-demand control of droplet behavior.Development of these new classes of fluorosurfactants has expanded the capabilities and applications of droplet microreactors that enables interdisciplinary challenges to be solved.展开更多
Hydrogel microcapsules are powerful microreactor vessels that have attracted widespread attention and research.Among the various methods for their generation,the aqueous two-phase system(ATPS)is by far the most straig...Hydrogel microcapsules are powerful microreactor vessels that have attracted widespread attention and research.Among the various methods for their generation,the aqueous two-phase system(ATPS)is by far the most straightforward approach.However,the high viscosity of ATPS solutions significantly limits the generation throughput of hydrogel microcapsule.In this study,we developed a novel high-throughput approach for generating hydrogel microcapsules using a microfluidic bubble-triggering strategy.By integrating constant-pressure air flow with droplet microfluidics devices,we efficiently manipulated the formation of ATPS droplet through bubble-induced Rayleigh-Plateau instability,enabling the production of uniform,monodisperse microcapsules.Additionally,the droplet generation frequency in the bubble-triggering method exceeded 36 kHz.We further demonstrated the encapsulation of genetically engineered Escherichia coli strains,which acted as biosensors for arsenic ions and caprolactam,highlighting the potential of these microcapsules for biosensing applications.This advancement in hydrogel microcapsule generation offers promising implications for scalable applications in biosensing,organoid culture,and high-throughput screening.展开更多
This paper describes the application of ultrasound waves on hydrodynamics and mass transfer characteristics in the gas–liquid flow in a T-shape microreactor with a diameter of 800 μm. A 1.7 MHz piezoelectric transdu...This paper describes the application of ultrasound waves on hydrodynamics and mass transfer characteristics in the gas–liquid flow in a T-shape microreactor with a diameter of 800 μm. A 1.7 MHz piezoelectric transducer(PZT) was employed to induce the vibration in this microreactor. Liquid side volumetric mass transfer coefficients were measured by physical and chemical methods of CO_2 absorption into water and Na OH solution. The approach of absorption of CO_2 into a 1 mol·L^(-1) Na OH solution was used for analysis of interfacial areas. With the help of a photography system, the fluid flow patterns inside the microreactor were analyzed. The effects of superficial liquid velocity, initial concentration of Na OH, superficial CO_2 gas velocity and length of microreactor on the mass transfer rate were investigated. The comparison between sonicated and plain microreactors(microreactor with and without ultrasound) shows that the ultrasound wave irradiation has a significant effect on kLa and interfacial area at various operational conditions. For the microreactor length of 12 cm, ultrasound waves improved kLa and interfacial area about 21% and 22%, respectively. From this study, it can be concluded that ultrasound wave irradiation in microreactor has a great effect on the mass transfer rate. This study suggests a new enhancement technique to establish high interfacial area and kLa in microreactors.展开更多
Fixed-bed reactors for the partial oxidation of methane to produce synthetic gas still pose hotspot problems. An alternative reactor, which is known as the shell-and-tube-typed microreactor, has been developed to reso...Fixed-bed reactors for the partial oxidation of methane to produce synthetic gas still pose hotspot problems. An alternative reactor, which is known as the shell-and-tube-typed microreactor, has been developed to resolve these problems. The microreactor consists of a 1 cm outside-diameter, 0.8 cm insidediameter and 11 cm length tube, and a 1.8 cm inside-diameter shell. The tube is made of dense alumina and the shell is made of quartz. Two different methods dip and spray coating were performed to line the tube side with the LaNixOy catalyst. Combustion and reforming reactions take place simultaneously in this reactor. Methane is oxidized in the tube side to produce flue gases （CO2 and H2O） which flow counter-currently and react with the remaining methane in the shell side to yield synthesis gas. The methane conversion using the higher-loading catalyst spray-coated tube reaches 97% at 700 ℃, whereas that using the lower-loading catalyst dip-coated tube reaches only 7.78% because of poor adhesion between the catalyst film and the alumina support. The turnover frequencies （TOFs） using the catalyst spray-and dip-coated tubes are 5.75×10^-5 and 2.24×10^-5 mol/gcat· s, respectively. The catalyst spray-coated at 900 ℃ provides better performance than that at 1250 ℃ because sintering reduces the surface-area. The hydrogen to carbon monoxide ratio produced by the spray-coated catalyst is greater than the stoichiometric ratio, which is caused by carbon deposition through methane cracking or the Boudouard reaction.展开更多
基金financial support for this work from the National Natural Science Foundation of China(No.21706034)the Natural Science Foundation of Fujian Province(No.2021J01645)the Key Program of Qingyuan Innovation Laboratory(No.00221004)。
文摘Tonalid,an important fragrance ingredient with widespread applicatio n,was synthesized via two FriedelCrafts reactions,which were catalyzed by AlCl_(3).The traditional tonalid production was conducted in batch stirring tank reactors,suffering from low production capacity and the safety hazard of temperature runaway.To solve these problems,the continuous-flow technologies were developed for the highefficiency and intrinsically safe synthesis of tonalid in microreactors.Catalyst AlCl_(3)was neatly homogenized in proper solvents by forming complex with reactant,which was a necessary step for the continuous synthesis in microreactors.Several reaction conditions,including reactant molar ratio,catalyst concentration,temperature,and microchannel hydrodynamic diameter,were investigated for the two Friedel-Crafts reactions in micro reactors.At optimized conditions,the yields of the two Friedel-Crafts reactions were 44.15%and 97.55%,respectively.In comparison with the batch reactors,the reaction times of these two reactions could both be reduced by nearly two thirds in microreactors at the similar yield.
基金supported by the National Natural Science Foundation of China(22078251)Hubei Province Key Research and Development Program(2023DJC167)the research project of Hubei Provincial Department of Education(D20191504).
文摘The development of efficient systems for the catalytic oxidation of 2-nitro-4-methylsulfonyltoluene(NMST)to 2-nitro-4-methylsulfonyl benzoic acid(NMSBA)with atmospheric air or molecular oxygen in alkaline medium presents a significant challenge for the chemical industry.Here,we report the synthesis of FeOOH/Fe_(3)O_(4)/metal-organic framework(MOF)polygonal mesopores microflower templated from a MIL-88B(Fe)at room temperature,which exposes polygonal mesopores with atomistic edge steps and lattice defects.The obtained FeOOH/Fe_(3)O_(4)/MOF catalyst was adsorbed onto glass beads and then introduced into the microchannel reactor.In the alkaline environment,oxygen was used as oxidant to catalyze the oxidation of NMST to NMSBA,showing impressive performance.This sustainable system utilizes oxygen as a clean oxidant in an inexpensive and environmentally friendly NaOH/methanol mixture.The position and type of substituent critically affect the products.Additionally,this sustainable protocol enabled gram-scale preparation of carboxylic acid and benzyl alcohol derivatives with high chemoselectivities.Finally,the reactions can be conducted in a pressure reactor,which can conserve oxygen and prevent solvent loss.Moreover,compared with the traditional batch reactor,the self-built microchannel reactor can accelerate the reaction rate,shorten the reaction time,and enhance the selectivity of catalytic oxidation reactions.This approach contributes to environmental protection and holds potential for industrial applications.
文摘To address the energy challenges,scientists have designed various artificial light-harvesting systems inspired by photosynthesis.Notably,for light-harvesting systems,an energytransfer efficiency close to 100%with an antenna effect greater than 10 is generally considered a good application criterion.[1]Today,building an efficient light-harvesting system at a low cost is still demanding.
文摘The concept of liquid-solid hybrid catalyst that featuring a truly homogeneous liquid microenvironment together with insoluble solid characteristics has been established recently by our group,which enables us to conveniently bridge the gap between homo-and heterogeneous catalysis.In this study,we extend this general concept to the confinement of molecular rhodium phosphine complexes,including Rh-TPPTS,Rh-TPPMS and Rh-SXP,for olefin hydroformylation reactions.A series of hybrid catalyst materials consisting a modulated liquid interior([BMIM]NTf_(2),[BMIM]PF_(6),[BMIM]BF_(4) or H_(2)O)and a permeable silica crust were fabricated through our developed Pickering emulsion-based method,showing 9.4–24.2-fold activity enhancement and significantly improved aldehyde selectivity(from 72.2%,61.8%to 86.6%)compared to their biphasic counterparts or traditional supported liquid phase system in the hydroformylation of 1-dodecene.Interestingly,the catalytic efficiency was demonstrated to be tunable by rationally engineering the thickness of porous crust and dimensions of the liquid pool.The thus-attained hybrid catalyst could also successfully catalyze the hydroformylation of a variety of olefin substrates and be recycled without a significant loss of activity for at least seven times.
基金funded by the National Natural Science Foundation of China(22478632)Key Scientific and Technological Project of Henan Province(242102321032).
文摘Continuous-flow upgrading of pentaerythritol synthesis technology via base-catalyzed aldol and Cannizzaro reactions of formaldehyde and acetaldehyde faces the challenge of effectively controlling the critical side reaction of hydroxymethyl acetaldehyde(HA)to the acrolein intermediate.Here,we first identified the forms of industrial formaldehyde as methane diol that easily converts to the alkaline formaldehyde under alkaline(NaOH)environment.The carbonyl group of alkaline formaldehyde induces deprotonation of acetaldehyde instead of the recognized base-hydroxyl group-induced deprotonation,and it needs to overcome only 18.31 kcal·mol^(-1)(1 kcal=4.186 kJ)energy barrier to form key intermediates of HA.The sodium solvation cage formed by NaOH hexa-coordinated formaldehyde effectively inhibits the alkalinity,thus contributing to a high energy barrier(46.21 kcal·mol^(-1))to unwanted acrolein formation.In addition,the solvation cage gradually opens to increase the alkalinity with the consumption of formaldehyde,thus facilitating the subsequent Cannizzaro reaction(to overcome 11.77 kcal·mol^(-1)).In comparison,strong alkalinity promotes the formation of acrolein(36.65 kcal·mol^(-1))to initiate the acetal side reaction,while weak alkalinity reduces the possibility of the Cannizzaro reaction(to overcome 20.44 kcal·mol^(-1)).This theoretically reveals the importance of the segmented feeding of weak and strong bases to successively control the aldol reaction and Cannizzaro reaction,and the combination of Na_(2)CO_(3) or HCOONa with NaOH improves the pentaerythritol yield by 7%to 13%compared to that of NaOH alone(70%yield)within 1 min at a throughput of 155.7 ml·min^(-1).
基金Project supported by the National Natural Science Foundation of China(42277485,21976141)the Department of Science and Technology of Hubei Province(2021CFA034)the Knowledge Innovation Program of Wuhan-Shuguang Project(2023020201020369)。
文摘Low-dimensional hybrid nanocrystals are newly emerging active photo catalysts for separating electron-hole pairs,but the instability and low quantum efficiency caused by particle aggregation and hybrid structure relaxation remain great challenges.To this end,herein we constructed amorphous FeO_(x)(A-FeO_(x))and crystalline LaFeO_(3)hybrids by a sol-gel method.The amorphous-crystalline hybrids,A-FeO_(x)/LaFeO_(3),not only improve the surface area and alter the band position,but also form numerous channels that are conducive to the transport of electrons and separation of electron-hole pairs,acting as microreactors.Photocatalytic tests show that the A-FeO_(x)/LaFeO_(3)is highly active for the degradation of various organic pollutants,with reaction rate constant of 1.19×10^(-2)min-1for cipro floxacin degradation,for example,which is 1.82 and 1.87 times higher than that of LaFeO_(3)and Fe_(2)O_(3)/LaFeO_(3),respectively,owing to the formation of microreactors between A-FeO_(x)and LaFeO_(3).Cycling tests show that the mate rial has good stability in the reaction,and trapping experiments demonstrate that the photo-induced holes are the main reactive species of the reaction.This work provides a novel and feasible insight into the design of high performance low-dimensional hybrid nanocatalysts for photocatalysis.
基金support of the National Key Research and Development Program of China(2021YFC2104300)the National Natural Science Foundation of China(T2322011,22308146,22278214)the support of the State Key Laboratory of Materials-Oriented Chemical Engineering(SKL-MCE-22A06,KL20-02).
文摘Fluorosurfactants play a crucial role in ensuring the stability and uniformity of droplet microreactors,which significantly broaden their applications in chemical and biological research.This review covers structure diversity and functional versatility of fluorosurfactants.Fluorosurfactants can be divided into two basic types according to their structure,linear and dendritic types,which both provides individual advantages.Linear fluorosurfactants are easily synthesized and commercially available,whereas dendritic fluorosurfactants have a branched structure that greatly reduces molecular cross-talk between droplets.Based on the application point of view,fluorosurfactants can be further classified into two categories:reactive and responsive fluorosurfactants.The hydrophilic head of reactive fluorosurfactants contains a reactive functional group,making them very useful in other applications,such as microcapsule preparation or protein crystallization.In contrast,responsive fluorosurfactants would change their properties with respect to external stimuli,such as temperature or light,making them perfect candidates for the on-demand control of droplet behavior.Development of these new classes of fluorosurfactants has expanded the capabilities and applications of droplet microreactors that enables interdisciplinary challenges to be solved.
基金sponsored by the National Key R&D Program of China(no.2023YFB3208203)the National Natural Science Foundation of China(no.62374170)the Science and Technology Commission of Shanghai Municipality(no.23J21900200).
文摘Hydrogel microcapsules are powerful microreactor vessels that have attracted widespread attention and research.Among the various methods for their generation,the aqueous two-phase system(ATPS)is by far the most straightforward approach.However,the high viscosity of ATPS solutions significantly limits the generation throughput of hydrogel microcapsule.In this study,we developed a novel high-throughput approach for generating hydrogel microcapsules using a microfluidic bubble-triggering strategy.By integrating constant-pressure air flow with droplet microfluidics devices,we efficiently manipulated the formation of ATPS droplet through bubble-induced Rayleigh-Plateau instability,enabling the production of uniform,monodisperse microcapsules.Additionally,the droplet generation frequency in the bubble-triggering method exceeded 36 kHz.We further demonstrated the encapsulation of genetically engineered Escherichia coli strains,which acted as biosensors for arsenic ions and caprolactam,highlighting the potential of these microcapsules for biosensing applications.This advancement in hydrogel microcapsule generation offers promising implications for scalable applications in biosensing,organoid culture,and high-throughput screening.
文摘This paper describes the application of ultrasound waves on hydrodynamics and mass transfer characteristics in the gas–liquid flow in a T-shape microreactor with a diameter of 800 μm. A 1.7 MHz piezoelectric transducer(PZT) was employed to induce the vibration in this microreactor. Liquid side volumetric mass transfer coefficients were measured by physical and chemical methods of CO_2 absorption into water and Na OH solution. The approach of absorption of CO_2 into a 1 mol·L^(-1) Na OH solution was used for analysis of interfacial areas. With the help of a photography system, the fluid flow patterns inside the microreactor were analyzed. The effects of superficial liquid velocity, initial concentration of Na OH, superficial CO_2 gas velocity and length of microreactor on the mass transfer rate were investigated. The comparison between sonicated and plain microreactors(microreactor with and without ultrasound) shows that the ultrasound wave irradiation has a significant effect on kLa and interfacial area at various operational conditions. For the microreactor length of 12 cm, ultrasound waves improved kLa and interfacial area about 21% and 22%, respectively. From this study, it can be concluded that ultrasound wave irradiation in microreactor has a great effect on the mass transfer rate. This study suggests a new enhancement technique to establish high interfacial area and kLa in microreactors.
文摘Fixed-bed reactors for the partial oxidation of methane to produce synthetic gas still pose hotspot problems. An alternative reactor, which is known as the shell-and-tube-typed microreactor, has been developed to resolve these problems. The microreactor consists of a 1 cm outside-diameter, 0.8 cm insidediameter and 11 cm length tube, and a 1.8 cm inside-diameter shell. The tube is made of dense alumina and the shell is made of quartz. Two different methods dip and spray coating were performed to line the tube side with the LaNixOy catalyst. Combustion and reforming reactions take place simultaneously in this reactor. Methane is oxidized in the tube side to produce flue gases （CO2 and H2O） which flow counter-currently and react with the remaining methane in the shell side to yield synthesis gas. The methane conversion using the higher-loading catalyst spray-coated tube reaches 97% at 700 ℃, whereas that using the lower-loading catalyst dip-coated tube reaches only 7.78% because of poor adhesion between the catalyst film and the alumina support. The turnover frequencies （TOFs） using the catalyst spray-and dip-coated tubes are 5.75×10^-5 and 2.24×10^-5 mol/gcat· s, respectively. The catalyst spray-coated at 900 ℃ provides better performance than that at 1250 ℃ because sintering reduces the surface-area. The hydrogen to carbon monoxide ratio produced by the spray-coated catalyst is greater than the stoichiometric ratio, which is caused by carbon deposition through methane cracking or the Boudouard reaction.
