Metal-Organic Frameworks(MOFs)have been developed as solid sorbents for CO_(2) capture applications and their properties can be controlled by tuning the chemical blocks of their crystalline units.A number of MOFs(e.g....Metal-Organic Frameworks(MOFs)have been developed as solid sorbents for CO_(2) capture applications and their properties can be controlled by tuning the chemical blocks of their crystalline units.A number of MOFs(e.g.,HKUST-1)have been developed but the question remains how to deploy them for gas-solid contact.Unfortunately,the direct use of MOFs as nanocrystals would lead to serious problems and risks.Here,for the first time,we report a novel MOF-based hybrid sorbent that is produced via an innovative in-situ microencapsulated synthesis.Using a custom-made double capillary microfluidic assembly,double emulsions of the MOF precursor solutions and UV-curable silicone shell fluid are produced.Subsequently,HKUST-1 MOF is successfully synthesized within the droplets enclosed in the gas permeable microcapsules.The developed MOF-bearing microcapsules uniquely allow the deployment of functional nanocrystals without the challenge of handling ultrafine particles,and further,can selectively reject undesired compounds to protect encapsulated MOFs.展开更多
Global warming caused by excess carbon dioxide(CO_(2))emission has been a focus of the world.The development of neutral carbon technologies becomes a strategic choice for the sustainable human society.Integrating CO_(...Global warming caused by excess carbon dioxide(CO_(2))emission has been a focus of the world.The development of neutral carbon technologies becomes a strategic choice for the sustainable human society.Integrating CO_(2) capture and conversion(iCCC)technology can simultaneously convert the captured CO_(2) from flue gas into value-added chemicals,which saves great energies and expenses incurred in CO_(2) compression and transportation processes of conventional carbon capture,utilization,and storage(CCUS)technology.The present review criti-cally discusses the dual-function materials(DFMs)and the iCCC technology at intermediate temperature for methane production and high temperature for syngas production.The design of reactor and optimization of operation conditions are emphasized from the perspective of industrial applications.The dual-fixed-bed reactors mode by switching the flue gas and reactant gases,and the dual-fluidized-bed reactors mode by the circulation of DFMs particles are comparatively reviewed.We hope this review can stimulate further studies including designing and fabricating feasible DFMs,exploring realistic catalytic process for CO_(2) conversion to high value-added chemicals,developing workable reactor modes and optimizing operation conditions,and establishing industrial demonstration for real applications of iCCC technology in the future.展开更多
An unexpected in-situ hydrolysis reaction occurred during the solvothermal reaction of N,N’-bis(4-carboxy-2-methylphenyl)pyromellitic di-imide)and Ba(NO3)2,and a novel porous Ba-MOF,[H_(2)N(CH_(3))_(2)]_(0.5)[Ba_(1.5...An unexpected in-situ hydrolysis reaction occurred during the solvothermal reaction of N,N’-bis(4-carboxy-2-methylphenyl)pyromellitic di-imide)and Ba(NO3)2,and a novel porous Ba-MOF,[H_(2)N(CH_(3))_(2)]_(0.5)[Ba_(1.5)(L)(DMA)]·1.5 DMA·1.5 H_(2)O(UPC-70,H_(3)L=2-(4-ca rboxy-2-methylphenyl)-1,3-dioxoisoindoline-5,6-dicarboxylic acid,DMA=N,N-dimethylacetamide),was obtained on the basis of the partial hydrolysate.The as-synthesized 3 D network with 1 D open channels of different sizes(24 A and 10 A)contains abundant open metal sites after removal of solvents,which is conducive to the preferential adsorption of CO_(2).The subsequent gas sorption measurement reveals the high separation selectivity of UPC-70 for CO_(2)/CH_(4)(15)and CO_(2)/N_(2)(32)at ambient conditions,and GCMC theoretical simulation provides good verification of the experimental results,indicating that UPC-70 is a potential candidate for CO_(2)capture from flue gas and natural gas.展开更多
基金National Science Foundation (CBET 1927336)Saudi Aramco,and the Lenfest Center for Sustainable Energy at the Earth Institute at Columbia University for financially supporting this work+3 种基金performed at GeoSoilEnviroCARS (The University of Chicago,Sector 13)Advanced Photon Source (APS),Argonne National Laboratory.GeoSoilEnviroCARS is supported by the National Science Foundation-Earth Sciences (EAR-1634415)the Department of Energy-GeoSciences (DE-FG02-94ER14466)the Advanced Photon Source,a U.S.Department of Energy (DOE)Office of Science User Facility operated for the DOE Office of Science by Argonne National Laboratory under Contract No.DE-AC02-06CH11357.
文摘Metal-Organic Frameworks(MOFs)have been developed as solid sorbents for CO_(2) capture applications and their properties can be controlled by tuning the chemical blocks of their crystalline units.A number of MOFs(e.g.,HKUST-1)have been developed but the question remains how to deploy them for gas-solid contact.Unfortunately,the direct use of MOFs as nanocrystals would lead to serious problems and risks.Here,for the first time,we report a novel MOF-based hybrid sorbent that is produced via an innovative in-situ microencapsulated synthesis.Using a custom-made double capillary microfluidic assembly,double emulsions of the MOF precursor solutions and UV-curable silicone shell fluid are produced.Subsequently,HKUST-1 MOF is successfully synthesized within the droplets enclosed in the gas permeable microcapsules.The developed MOF-bearing microcapsules uniquely allow the deployment of functional nanocrystals without the challenge of handling ultrafine particles,and further,can selectively reject undesired compounds to protect encapsulated MOFs.
基金The authors are grateful to the financial support from Shanghai Science and Technology Committee(No.19160712100)National Natural Science Foundation of China(No.21878076).
文摘Global warming caused by excess carbon dioxide(CO_(2))emission has been a focus of the world.The development of neutral carbon technologies becomes a strategic choice for the sustainable human society.Integrating CO_(2) capture and conversion(iCCC)technology can simultaneously convert the captured CO_(2) from flue gas into value-added chemicals,which saves great energies and expenses incurred in CO_(2) compression and transportation processes of conventional carbon capture,utilization,and storage(CCUS)technology.The present review criti-cally discusses the dual-function materials(DFMs)and the iCCC technology at intermediate temperature for methane production and high temperature for syngas production.The design of reactor and optimization of operation conditions are emphasized from the perspective of industrial applications.The dual-fixed-bed reactors mode by switching the flue gas and reactant gases,and the dual-fluidized-bed reactors mode by the circulation of DFMs particles are comparatively reviewed.We hope this review can stimulate further studies including designing and fabricating feasible DFMs,exploring realistic catalytic process for CO_(2) conversion to high value-added chemicals,developing workable reactor modes and optimizing operation conditions,and establishing industrial demonstration for real applications of iCCC technology in the future.
基金supported by the National Natural Science Foundation of China(NSFC,No.21771191)the Fundamental Research Funds for the Central Universities(No.19CX05001A)。
文摘An unexpected in-situ hydrolysis reaction occurred during the solvothermal reaction of N,N’-bis(4-carboxy-2-methylphenyl)pyromellitic di-imide)and Ba(NO3)2,and a novel porous Ba-MOF,[H_(2)N(CH_(3))_(2)]_(0.5)[Ba_(1.5)(L)(DMA)]·1.5 DMA·1.5 H_(2)O(UPC-70,H_(3)L=2-(4-ca rboxy-2-methylphenyl)-1,3-dioxoisoindoline-5,6-dicarboxylic acid,DMA=N,N-dimethylacetamide),was obtained on the basis of the partial hydrolysate.The as-synthesized 3 D network with 1 D open channels of different sizes(24 A and 10 A)contains abundant open metal sites after removal of solvents,which is conducive to the preferential adsorption of CO_(2).The subsequent gas sorption measurement reveals the high separation selectivity of UPC-70 for CO_(2)/CH_(4)(15)and CO_(2)/N_(2)(32)at ambient conditions,and GCMC theoretical simulation provides good verification of the experimental results,indicating that UPC-70 is a potential candidate for CO_(2)capture from flue gas and natural gas.