This study deals with polydimethylsiloxane(PDMS)/polyvinylidene fluoride(PVDF) composite membranes for propane separation from propane/nitrogen mixtures,which is relevant to the recovery of propane in petroleum and ch...This study deals with polydimethylsiloxane(PDMS)/polyvinylidene fluoride(PVDF) composite membranes for propane separation from propane/nitrogen mixtures,which is relevant to the recovery of propane in petroleum and chemical industry.The surface and cross-section morphology of PDMS/PVDF composite membranes was observed by scanning electron microscope(SEM).The surface morphology of PDMS/PVDF composite membranes is very dense.There are three layers,the thin dense top layer,finger-like porous middle layer and s...展开更多
The separation of propylene and propane is an important but challenging process,primarily achieved through energy-intensive distillation technology in the petrochemical industry.Here,we reported two natural C4linkers ...The separation of propylene and propane is an important but challenging process,primarily achieved through energy-intensive distillation technology in the petrochemical industry.Here,we reported two natural C4linkers based metal–organic frameworks(MIP-202 and MIP-203)for C_(3)H_(6)/C_(3)H_(8)separation.Adsorption isotherms and selectivity calculations were performed to study the adsorption performance for C_(3)H_(6)/C_(3)H_(8)separation.Results show that C_(3)H_(6)/C_(3)H_(8)uptake ratios(298 K,100 kPa)for MIP-202 and MIP-203 are 2.34 and 7.4,respectively.C_(3)H_(6)/C_(3)H_(8)uptake ratio(303 K,100 k Pa)for MIP-203 is up to50.0.The mechanism for enhanced separation performance of C_(3)H_(6)/C_(3)H_(8)on MIP-203 at higher temperature(303 K)was revealed by the in situ PXRD characterization.The adsorption selectivities of C_(3)H_(6)/C_(3)H_(8)on MIP-202 and MIP-203(298 K,100 k Pa)are 8.8 and 551.4,respectively.The mechanism for the preferential adsorption of C_(3)H_(6)over C_(3)H_(8)in MIP-202 and MIP-203 was revealed by the Monte Carlo simulation.The cost of organic ligands for MIP-202 and MIP-203 was lower than that of organic ligands for those top-performance MOFs.Our work sets a new benchmark for C_(3)H_(6)sorbents with high adsorption selectivities.展开更多
SSZ-13 membranes with high separation performances were prepared using ball-milled nanosized seeds by once hydrothermal synthesis.Separation performances of SSZ-13 membranes in CO2/CH4 and N2/CH4 mixtures were enhance...SSZ-13 membranes with high separation performances were prepared using ball-milled nanosized seeds by once hydrothermal synthesis.Separation performances of SSZ-13 membranes in CO2/CH4 and N2/CH4 mixtures were enhanced after synthesis modification.Single-gas permeances of CO2,N2 and CH4 and ideal selectivities were recorded through SSZ-13 membranes.The effects of temperature,pressure,feed flow rate and humidity on separation performance of the membranes were discussed.Three membranes prepared after synthesis modifications had an average CO2 permeance of 1.16×10-6 mol·(m2·s·Pa)-1(equal to 3554 GPU)with an average CO2/CH4 selectivity of 213 in a 50 vol%/50 vol%CO2/CH4 mixture.It suggests that membrane synthesis has a good reproducible.The membrane also displayed a N2 permeance of 1.07×10-7 mol·(m2·s·Pa)-1(equal to 320 GPU)with a N2/CH4 selectivity of 13 for a 50 vol%/50 vol%N2/CH4 mixture.SSZ-13 membrane displayed stable and good separation performance in the wet CO2/CH4 mixture for a long test period over 100 h at 348 K.The current SSZ-13 membranes show great potentials for the simultaneous removals of CO2 and N2 in natural gas purification as a facile process suitable for industrial application.展开更多
Membrane separation is a high-efficiency,energy-saving,and environment-friendly separation technology.Covalent organic framework(COF)-based mixed-matrix membranes(MMMs)have broad application prospects in gas separatio...Membrane separation is a high-efficiency,energy-saving,and environment-friendly separation technology.Covalent organic framework(COF)-based mixed-matrix membranes(MMMs)have broad application prospects in gas separation and are expected to provide new solutions for coal-bed methane purification.Herein,a high-throughput screening method is used to calculate and evaluate COF-based MMMs for CH_(4)/N_(2) separation.General design rules are proposed from thermodynamic and kinetic points of view using the computation-ready,experimental COFs.From our database containing 471,671 generated COFs,5 COF membrane materials were screened with excellent membrane selectivities,which were then used as the filler of MMMs for separation performance evaluation.Among them,BAR-NAP-Benzene_CF_(3) combined with polydimethylsiloxane and styrene-b-butadiene-b-styrene show high CH_(4) permeability of 4.43×10^(-13) mol·m·s^(-1)·Pa^(-1)·m^(-2) and high CH_(4)/N_(2) selectivity of 9.54,respectively.The obtained results may provide reasonable information for the design of COF-based membranes for the efficient separation of CH_(4)/N_(2).展开更多
Adsorptive separation of propylene(C_(3)H_(6))from propylene/propane(C_(3)H_(8))is desired to replace energy-intensive cryogenic distillation for its energy efficiency,economical viability,and environment friendship.I...Adsorptive separation of propylene(C_(3)H_(6))from propylene/propane(C_(3)H_(8))is desired to replace energy-intensive cryogenic distillation for its energy efficiency,economical viability,and environment friendship.In this work,we report a cupper-based robust microporous metal-organic framework,Cu-Hmpba,constructed by the hard soft acid-base principle using the bifunctional pyridylcarboxylate ligand featuring methyl group,for high-efficient separation of the propylene/propane mixture.Under the synergistic effect of the protective group and hard soft acid base principle,Cu-Hmpba possesses good solvents stability,especially water stability.Cu-Hmpba exhibits the adsorption capacity of C_(3)H_(6)with 2.10 mmol g^(-1)and good equimolar C_(3)H_(6)/C_(3)H_(8)selectivity with 2.24 at ambient conditions.The gas adsorption experiments,IAST selectivity calculations and theoretical calculations comprehensively support the selective adsorption toward C_(3)H_(6)among C_(3)H_(6)/C_(3)H_(8)mixture.Furthermore,it could maintain stable under moisture environment,suggesting its potential for the industrial separation of C_(3)H_(6)/C_(3)H_(8)mixture.The results of experiments and simulations demonstrate that the Cu-Hmpba would be a candidate adsorbent for the separation and purification of light hydrocarbons,and this work provides the insight of syn-thesizing stable MOF materials for separating high-value chemicals.展开更多
Extremely high-temperature and high-pressure requirement of Haber-Bosch process motivates the search for a sustainable ammonia synthesis approach under mild conditions.Photocatalytic technology is a potential solution...Extremely high-temperature and high-pressure requirement of Haber-Bosch process motivates the search for a sustainable ammonia synthesis approach under mild conditions.Photocatalytic technology is a potential solution to convert N2 to ammonia.However,the poor light absorption and low charge carrier separation efficiency in conventional semiconductors are bottlenecks for the application of this technology.Herein,a facile synthesis of anatase TiO_(2)nanosheets with an abundance of surface oxygen vacancies(TiO_(2)-OV)via the calcination treatment was reported.Photocatalytic experiments of the prepared anatase TiO_(2)samples showed that TiO_(2)-OV nanosheets exhibited remarkably increased ammonia yield for solar-driven N2 fixation in pure water,without adding any sacrificial agents.EPR,XPS,XRD,UV-Vis DRS,TEM,Raman,and PL techniques were employed to systematically explore the possible enhanced mechanism.Studies revealed that the introduced surface oxygen vacancies significantly extended the light absorption capability in the visible region,decreased the adsorption and activation barriers of inert N2,and improved the separation and transfer efficiency of the photogenerated electronhole pairs.Thus,a high rate of ammonia evolution in TiO_(2)-OV was realized.This work offers a promising and sustainable approach for the efficient artificial photosynthesis of ammonia.展开更多
In this work, a novel heterojunction composite Ag_(2)S/KTa_(x)Nb_(1-x)O_(3)was designed and synthesized through a combination of hydrothermal and precipitation procedures. The Ta/Nb ratio of the KTa_(x)Nb_(1-x)O_(3)an...In this work, a novel heterojunction composite Ag_(2)S/KTa_(x)Nb_(1-x)O_(3)was designed and synthesized through a combination of hydrothermal and precipitation procedures. The Ta/Nb ratio of the KTa_(x)Nb_(1-x)O_(3)and the Ag_(2)S content were optimized. The best 0.5% Ag_(2)S/KTa_(0.5)Nb_(0.5)O_(3)(KTN) sample presents an enhanced photocatalytic performance in ammonia synthesis than KTN and Ag_(2)S. Under simulated sunlight, the NH_(3)generation rate of 0.5% Ag_(2)S/KTN reaches 2.0 times that of pure KTN. Under visible light, the reaction rate ratio of the two catalysts is 6.0.XRD, XPS, and TEM analysis revealed that Ag2S was intimately decorated on the KTN nanocubes surface, which promoted the electron transfer between the two semiconductors. The band structure investigation indicated that the Ag_(2)S/KTN heterojunction established a type-Ⅱ band alignment with intimate contact, thus realizing the effective transfer and separation of photogenerated carriers. The change in charge separation was considered as the main reason for the enhanced photocatalytic performance. Interestingly, the Ag_(2)S/KTN composite exhibited higher NH3generation performance under the combined action of ultrasonic vibration and simulated sunlight. The enhanced piezo-photocatalytic performance can be ascribed that the piezoelectric effect of KTN improved the bulk separation of charge carriers in KTN. This study not only provides a potential catalyst for photocatalytic nitrogen fixation but also shows new ideas for the design of highly efficient catalysts via semiconductor modification and external field coupling.展开更多
While lithium-sulfur(Li-S)battery has attracted remarkable attention owing to the high theoretical capacity,its practical application is still hindered by the shuttle and sluggish conversion kinetics of intermediate l...While lithium-sulfur(Li-S)battery has attracted remarkable attention owing to the high theoretical capacity,its practical application is still hindered by the shuttle and sluggish conversion kinetics of intermediate lithium polysulfides(Li PSs).Defect engineering,which can regulate the electronic structure and in turn influence the surface adsorption and catalytic capability,has been regarded as a feasible strategy to deal with the above challenges.However,few studies on nitrogen vacancies and their mechanisms are reported.Herein,cobalt nitride with nitrogen vacancies grown on multi-walled carbon nanotube(CNTCo N-VN)is designed and applied as the separator modification material to investigate the enhancing mechanism of nitrogen vacancies on Li-S batteries.The experimental evidence and theoretical calculation indicate that the introduction of nitrogen vacancies into cobalt nitride can enhance the chemical affinity to Li PSs and effectively hamper the shuttle effect.Meanwhile the reduced band gap of the d-band center of Co and p-band center of N for CNT-Co N-VNand the promoted diffusion of Li^(+) can expedite the solid-liquid and liquid-liquid conversions of sulfur species.Due to these superiorities,the cell with CNT-Co NVNmodified separator delivers a favorable initial capacity of 901 m Ah g^(-1)and a capacity of 660 m Ah g^(-1)can be achieved after 250 cycles at 2 C.This work explores the application of metal nitride with nitrogen vacancies and sheds light on the development of functional separators for high-efficient Li-S batteries.展开更多
基金supported by the China Postdoctoral Science Foundation(No20060400436)the Major State Basic Research Program of China(No2009CB623404)+3 种基金National Natural Science Foundation of China(Nos20736003,20676067)National High Technology Research and Development Program of China(No2007AA06Z317)Foundation of Ministry of Education of China(No20070003130) Foundation of the State Key Laboratory of Chemical Engineering(SKL-ChE-08A01)
文摘This study deals with polydimethylsiloxane(PDMS)/polyvinylidene fluoride(PVDF) composite membranes for propane separation from propane/nitrogen mixtures,which is relevant to the recovery of propane in petroleum and chemical industry.The surface and cross-section morphology of PDMS/PVDF composite membranes was observed by scanning electron microscope(SEM).The surface morphology of PDMS/PVDF composite membranes is very dense.There are three layers,the thin dense top layer,finger-like porous middle layer and s...
基金the financial support from National Natural Science Foundation of China(22108034,21878101)Guangdong Basic and Applied Basic Research Foundation(2020A1515110945,2020A1515110234,2021A1515011336 and 2020A1515110325)+4 种基金National Key Research and Development Program(2019YFC1805804)Guangdong Natural Science Foundation(2017A030313052)Key Program of Marine Economy Development(Six Marine Industries)Special Foundation of Department of Natural Resources of Guangdong Province(GDNRC[2020]036)Characteristic Innovation Research Project of University Teachers(2020XCC08)Foshan Engineering and Technology Research Center for Novel Porous Materials。
文摘The separation of propylene and propane is an important but challenging process,primarily achieved through energy-intensive distillation technology in the petrochemical industry.Here,we reported two natural C4linkers based metal–organic frameworks(MIP-202 and MIP-203)for C_(3)H_(6)/C_(3)H_(8)separation.Adsorption isotherms and selectivity calculations were performed to study the adsorption performance for C_(3)H_(6)/C_(3)H_(8)separation.Results show that C_(3)H_(6)/C_(3)H_(8)uptake ratios(298 K,100 kPa)for MIP-202 and MIP-203 are 2.34 and 7.4,respectively.C_(3)H_(6)/C_(3)H_(8)uptake ratio(303 K,100 k Pa)for MIP-203 is up to50.0.The mechanism for enhanced separation performance of C_(3)H_(6)/C_(3)H_(8)on MIP-203 at higher temperature(303 K)was revealed by the in situ PXRD characterization.The adsorption selectivities of C_(3)H_(6)/C_(3)H_(8)on MIP-202 and MIP-203(298 K,100 k Pa)are 8.8 and 551.4,respectively.The mechanism for the preferential adsorption of C_(3)H_(6)over C_(3)H_(8)in MIP-202 and MIP-203 was revealed by the Monte Carlo simulation.The cost of organic ligands for MIP-202 and MIP-203 was lower than that of organic ligands for those top-performance MOFs.Our work sets a new benchmark for C_(3)H_(6)sorbents with high adsorption selectivities.
基金the financial support of this study from National Key Research and Development Program of China(No.2017YFB0603402)the National Natural Science Foundation of China(No.21576131,21938007 and 21366013)support of Jiangsu College Student Innovation Training Project(201910291049Z)。
文摘SSZ-13 membranes with high separation performances were prepared using ball-milled nanosized seeds by once hydrothermal synthesis.Separation performances of SSZ-13 membranes in CO2/CH4 and N2/CH4 mixtures were enhanced after synthesis modification.Single-gas permeances of CO2,N2 and CH4 and ideal selectivities were recorded through SSZ-13 membranes.The effects of temperature,pressure,feed flow rate and humidity on separation performance of the membranes were discussed.Three membranes prepared after synthesis modifications had an average CO2 permeance of 1.16×10-6 mol·(m2·s·Pa)-1(equal to 3554 GPU)with an average CO2/CH4 selectivity of 213 in a 50 vol%/50 vol%CO2/CH4 mixture.It suggests that membrane synthesis has a good reproducible.The membrane also displayed a N2 permeance of 1.07×10-7 mol·(m2·s·Pa)-1(equal to 320 GPU)with a N2/CH4 selectivity of 13 for a 50 vol%/50 vol%N2/CH4 mixture.SSZ-13 membrane displayed stable and good separation performance in the wet CO2/CH4 mixture for a long test period over 100 h at 348 K.The current SSZ-13 membranes show great potentials for the simultaneous removals of CO2 and N2 in natural gas purification as a facile process suitable for industrial application.
基金financially supported by the National Key Research & Development Program of China (2021YFB3802200)the National Natural Science Foundation of China (Nos. 22078004 and 21978005)
文摘Membrane separation is a high-efficiency,energy-saving,and environment-friendly separation technology.Covalent organic framework(COF)-based mixed-matrix membranes(MMMs)have broad application prospects in gas separation and are expected to provide new solutions for coal-bed methane purification.Herein,a high-throughput screening method is used to calculate and evaluate COF-based MMMs for CH_(4)/N_(2) separation.General design rules are proposed from thermodynamic and kinetic points of view using the computation-ready,experimental COFs.From our database containing 471,671 generated COFs,5 COF membrane materials were screened with excellent membrane selectivities,which were then used as the filler of MMMs for separation performance evaluation.Among them,BAR-NAP-Benzene_CF_(3) combined with polydimethylsiloxane and styrene-b-butadiene-b-styrene show high CH_(4) permeability of 4.43×10^(-13) mol·m·s^(-1)·Pa^(-1)·m^(-2) and high CH_(4)/N_(2) selectivity of 9.54,respectively.The obtained results may provide reasonable information for the design of COF-based membranes for the efficient separation of CH_(4)/N_(2).
基金financially supported by the National Natural Science Foundation of China(22275102)the Natural Science Foundation of Tianjin(20JCYBJC01330).
文摘Adsorptive separation of propylene(C_(3)H_(6))from propylene/propane(C_(3)H_(8))is desired to replace energy-intensive cryogenic distillation for its energy efficiency,economical viability,and environment friendship.In this work,we report a cupper-based robust microporous metal-organic framework,Cu-Hmpba,constructed by the hard soft acid-base principle using the bifunctional pyridylcarboxylate ligand featuring methyl group,for high-efficient separation of the propylene/propane mixture.Under the synergistic effect of the protective group and hard soft acid base principle,Cu-Hmpba possesses good solvents stability,especially water stability.Cu-Hmpba exhibits the adsorption capacity of C_(3)H_(6)with 2.10 mmol g^(-1)and good equimolar C_(3)H_(6)/C_(3)H_(8)selectivity with 2.24 at ambient conditions.The gas adsorption experiments,IAST selectivity calculations and theoretical calculations comprehensively support the selective adsorption toward C_(3)H_(6)among C_(3)H_(6)/C_(3)H_(8)mixture.Furthermore,it could maintain stable under moisture environment,suggesting its potential for the industrial separation of C_(3)H_(6)/C_(3)H_(8)mixture.The results of experiments and simulations demonstrate that the Cu-Hmpba would be a candidate adsorbent for the separation and purification of light hydrocarbons,and this work provides the insight of syn-thesizing stable MOF materials for separating high-value chemicals.
基金supported by the National Natural Science Foundation of China(No.22108108,22205108,and No.22108106)China Postdoctoral Science Foundation No.2022M721381.
文摘Extremely high-temperature and high-pressure requirement of Haber-Bosch process motivates the search for a sustainable ammonia synthesis approach under mild conditions.Photocatalytic technology is a potential solution to convert N2 to ammonia.However,the poor light absorption and low charge carrier separation efficiency in conventional semiconductors are bottlenecks for the application of this technology.Herein,a facile synthesis of anatase TiO_(2)nanosheets with an abundance of surface oxygen vacancies(TiO_(2)-OV)via the calcination treatment was reported.Photocatalytic experiments of the prepared anatase TiO_(2)samples showed that TiO_(2)-OV nanosheets exhibited remarkably increased ammonia yield for solar-driven N2 fixation in pure water,without adding any sacrificial agents.EPR,XPS,XRD,UV-Vis DRS,TEM,Raman,and PL techniques were employed to systematically explore the possible enhanced mechanism.Studies revealed that the introduced surface oxygen vacancies significantly extended the light absorption capability in the visible region,decreased the adsorption and activation barriers of inert N2,and improved the separation and transfer efficiency of the photogenerated electronhole pairs.Thus,a high rate of ammonia evolution in TiO_(2)-OV was realized.This work offers a promising and sustainable approach for the efficient artificial photosynthesis of ammonia.
基金financially supported by National Natural Science Foundation of China (Grant No. 22172144)Nature Science Foundation of Zhejiang Province (Grant No. LY20B030004)。
文摘In this work, a novel heterojunction composite Ag_(2)S/KTa_(x)Nb_(1-x)O_(3)was designed and synthesized through a combination of hydrothermal and precipitation procedures. The Ta/Nb ratio of the KTa_(x)Nb_(1-x)O_(3)and the Ag_(2)S content were optimized. The best 0.5% Ag_(2)S/KTa_(0.5)Nb_(0.5)O_(3)(KTN) sample presents an enhanced photocatalytic performance in ammonia synthesis than KTN and Ag_(2)S. Under simulated sunlight, the NH_(3)generation rate of 0.5% Ag_(2)S/KTN reaches 2.0 times that of pure KTN. Under visible light, the reaction rate ratio of the two catalysts is 6.0.XRD, XPS, and TEM analysis revealed that Ag2S was intimately decorated on the KTN nanocubes surface, which promoted the electron transfer between the two semiconductors. The band structure investigation indicated that the Ag_(2)S/KTN heterojunction established a type-Ⅱ band alignment with intimate contact, thus realizing the effective transfer and separation of photogenerated carriers. The change in charge separation was considered as the main reason for the enhanced photocatalytic performance. Interestingly, the Ag_(2)S/KTN composite exhibited higher NH3generation performance under the combined action of ultrasonic vibration and simulated sunlight. The enhanced piezo-photocatalytic performance can be ascribed that the piezoelectric effect of KTN improved the bulk separation of charge carriers in KTN. This study not only provides a potential catalyst for photocatalytic nitrogen fixation but also shows new ideas for the design of highly efficient catalysts via semiconductor modification and external field coupling.
基金supported by the Beijing Institute of Technology Research Fund Program for Young Scholars and the Analysis&Testing Center(Beijing Institute of Technology)the National Natural Science Foundation of China(22179007)。
文摘While lithium-sulfur(Li-S)battery has attracted remarkable attention owing to the high theoretical capacity,its practical application is still hindered by the shuttle and sluggish conversion kinetics of intermediate lithium polysulfides(Li PSs).Defect engineering,which can regulate the electronic structure and in turn influence the surface adsorption and catalytic capability,has been regarded as a feasible strategy to deal with the above challenges.However,few studies on nitrogen vacancies and their mechanisms are reported.Herein,cobalt nitride with nitrogen vacancies grown on multi-walled carbon nanotube(CNTCo N-VN)is designed and applied as the separator modification material to investigate the enhancing mechanism of nitrogen vacancies on Li-S batteries.The experimental evidence and theoretical calculation indicate that the introduction of nitrogen vacancies into cobalt nitride can enhance the chemical affinity to Li PSs and effectively hamper the shuttle effect.Meanwhile the reduced band gap of the d-band center of Co and p-band center of N for CNT-Co N-VNand the promoted diffusion of Li^(+) can expedite the solid-liquid and liquid-liquid conversions of sulfur species.Due to these superiorities,the cell with CNT-Co NVNmodified separator delivers a favorable initial capacity of 901 m Ah g^(-1)and a capacity of 660 m Ah g^(-1)can be achieved after 250 cycles at 2 C.This work explores the application of metal nitride with nitrogen vacancies and sheds light on the development of functional separators for high-efficient Li-S batteries.
