The unique adsorption performance of metal-organic frameworks(MOFs) indicates a new direction for gas separation and purification. The low-temperature distillation, as a traditional technique for hydrogen isotope sepa...The unique adsorption performance of metal-organic frameworks(MOFs) indicates a new direction for gas separation and purification. The low-temperature distillation, as a traditional technique for hydrogen isotope separation, is limited as it is a high energy-and cost-intensive process. Instead of utilizing such a conventional separation route, we use ordered microporous frameworks based on a physical adsorption mechanism to solve the challenge of hydrogen isotope separation. Herein we analyze M-MOF-74(M=Co, Ni, Mg, Zn), featuring a hexagonal channel about 11 ? and high density of open metal sites, for their ability to separate and purify deuterium from the hydrogen isotope mixture by dynamic column breakthrough experiments. Our results show that the combination of the strength of binding sites, density of coordinatively unsaturated metal sites and hydrogen isotope adsorption capacity of materials renders Co-MOF-74 as an optimal adsorbent for the capture of deuterium from hydrogen isotope mixtures in a simulated industrial process.展开更多
Due to the similar physicochemical properties of acetylene(C_(2)H_(2))and carbon dioxide(CO_(2)),separating C_(2)H_(2)from a CO_(2)/C_(2)H_(2)mixture poses a significant challenge in the petrochemical industry.Herein,...Due to the similar physicochemical properties of acetylene(C_(2)H_(2))and carbon dioxide(CO_(2)),separating C_(2)H_(2)from a CO_(2)/C_(2)H_(2)mixture poses a significant challenge in the petrochemical industry.Herein,we successfully synthesized a novel SiF_(6)^(2) anion pillared cage metal-organic framework ZNU-15 possessing a new crs topological structure for the selective capture of C_(2)H_(2).As a linear bidentate linker,the fluorinated SiF_(6)^(2) anion partitions the pores into various sized cages.ZNU-15 displays moderate adsorption for C_(2)H_(2)with a capacity of 36.0 cm^(3)g^(-1)at 298 K and 1 bar,which is 2.7 times higher than the CO_(2)uptake.The IAST selectivity of C_(2)H_(2)/CO_(2)for ZNU-15 at 298 K and 100 kPa is 10.5,surpassing that of most reported materials.The Qst values for C_(2)H_(2)and CO_(2)at zero coverage are 54.0 and 42.8 kJ mol^(-1),respectively.Moreover,breakthrough experimental tests show that ZNU-15 is capable of effectively separating C_(2)H_(2)from a C_(2)H_(2)/CO_(2)mixture.Theoretical calculations further indicate that C_(2)H_(2)is preferentially trapped by the small cage with four cooperative hydrogen bonds.展开更多
The removal of trace propyne(C_(3)H_(4))from propyne/propylene(C_(3)H_(4)/C_(3)H_(6))mixtures is a technical and challenging task during the production of polymer-grade propylene in view of their very similar size and...The removal of trace propyne(C_(3)H_(4))from propyne/propylene(C_(3)H_(4)/C_(3)H_(6))mixtures is a technical and challenging task during the production of polymer-grade propylene in view of their very similar size and physical properties.While some progress has been made,it is still very challenging to use some highly stable and commercially available porous materials via an energy-efficient adsorptive separation process.Herein,we report the ultrafine tuning of the pore apertures in type-A zeolites for the highly efficient removal of trace amounts of C_(3)H_(4)from C_(3)H_(4)/C_(3)H_(6)mixtures.The resulting ion-exchanged zeolite 5 A exhibits a large C_(3)H_(4)adsorption capacity(2.3 mmol g^(-1)under 10^(-4)MPa)and high C_(3)H_(4)/C_(3)H_(6)selectivity at room temperature,which were mainly attributed to the ultrafine-tuned pore size that selectively blocks C_(3)H_(6)molecules,while maintaining the stro ng adsorption of C_(3)H_(4)at low pressure region.High purity of C_(3)H_(6)(>99.9999%)can be directly obtained on this material under ambient conditions,as demonstrated by the experimental breakthrough curves obtained for both 1/99 and 0.1/99.9(V V)C_(3)H_(4)/C_(3)H_(6) mixtures.展开更多
Hydrogen isotope separation is a challenging task due to their similar properties.Herein,based on the chemical affinity quantum sieve(CAQS)effect,the D_(2)/H_(2)separation performance of M_(2)(m-dobdc)(M=Co,Ni,Mg,Mn;m...Hydrogen isotope separation is a challenging task due to their similar properties.Herein,based on the chemical affinity quantum sieve(CAQS)effect,the D_(2)/H_(2)separation performance of M_(2)(m-dobdc)(M=Co,Ni,Mg,Mn;m-dobdc^(4-)=4,6-dioxido-1,3-benzenedicarboxylate),a series of honeycomb-shaped MOFs with high stability and abundant open metal sites,are studied by gases sorption and breakthrough experiments,in which two critical factors,gas uptake and adsorption enthalpy,are taken into consideration.Among these MOFs,Co_(2)(m-dobdc)exhibits the longest D_(2)retention time of 180 min/g(H_(2)/D_(2)/Ne:1/1/98)at 77 K because of its second-highest adsorption enthalpy(10.7 kJ/mol for H_(2)and 11.8 kJ/mol for D_(2))and the best sorption capacity(5.22 mmol/g for H_(2)and 5.49 mmol/g for D_(2))under low pressure of 1 kPa and 77 K,which make it a promising material for industrial hydrogen isotope separation.Moreover,the results indicate that H_(2)and D_(2)capacities under low pressure(about 1 kPa)dominate the final D_(2)/H_(2)separation property of MOFs.展开更多
A three-dimensional copper metal-organic framework with the rare chabazite(CHA)topology namely FJI-Y11 has been constructed with flexibly carboxylic ligand 5,5'-[(1,4-phenylenebis(methylene))bis(oxy)]diisophthalic...A three-dimensional copper metal-organic framework with the rare chabazite(CHA)topology namely FJI-Y11 has been constructed with flexibly carboxylic ligand 5,5'-[(1,4-phenylenebis(methylene))bis(oxy)]diisophthalic acid(H_(4)L).FJI-Y11 exhibits high water stability with the pH range from 2 to 12 at temperature as high as 373 K.Importantly,FJI-Y11 also shows high efficiency of hydrogen isotope separation using dynamic column breakthrough experiments under atmospheric pressure at 77 K.Attributed to its excellent structural stability,FJI-Y11 possesses good regenerated performance and maintains high separation efficiency after three cycles of breakthrough experiments.展开更多
Hierarchically porous materials play an important role in facilitating mass transport and improving efficiency of adsorption and separation processes. In this paper, a new strategy is proposed to realize a hierarchica...Hierarchically porous materials play an important role in facilitating mass transport and improving efficiency of adsorption and separation processes. In this paper, a new strategy is proposed to realize a hierarchically porous metal-organic framework （[Cu2（OH）（L）]＇（DMF）0.8 （FJU-11, H3L=3,5-（4-carboxybenzyloxy）benzoic acid, DMF= N,N-dimethylformamide） via using semi-rigid multi-carboxylic acids. Interestingly, FJU-11 possesses the large adsorption capacities and small isosteric heats toward CO2. The column breakthrough experiment for FJU-11 highlights its potential application in the separation of the flue gas.展开更多
It is extremely challenging to construct three-dimensional(3D)crystalline covalent organic frameworks(COFs)with flexible building blocks and to further explore their tunable or adaptive characteristics due to crystall...It is extremely challenging to construct three-dimensional(3D)crystalline covalent organic frameworks(COFs)with flexible building blocks and to further explore their tunable or adaptive characteristics due to crystallization and structure determination difficulties.Herein,we constructed three crystalline isostructural 3D-OC-COFs based on a newly synthesized flexible organic cage(6NH_(2)-OC.4HCl)through a novel in situ acid–base neutralization strategy.展开更多
基金supported by the National Natural Science Foundation of China (21771177)the Strategic Priority Research Program of Chinese Academy of Sciences (XDB20000000)the Key Research Program of Frontier Sciences, Chinese Academy of Sciences (QYZDB-SSW-SLH019)。
文摘The unique adsorption performance of metal-organic frameworks(MOFs) indicates a new direction for gas separation and purification. The low-temperature distillation, as a traditional technique for hydrogen isotope separation, is limited as it is a high energy-and cost-intensive process. Instead of utilizing such a conventional separation route, we use ordered microporous frameworks based on a physical adsorption mechanism to solve the challenge of hydrogen isotope separation. Herein we analyze M-MOF-74(M=Co, Ni, Mg, Zn), featuring a hexagonal channel about 11 ? and high density of open metal sites, for their ability to separate and purify deuterium from the hydrogen isotope mixture by dynamic column breakthrough experiments. Our results show that the combination of the strength of binding sites, density of coordinatively unsaturated metal sites and hydrogen isotope adsorption capacity of materials renders Co-MOF-74 as an optimal adsorbent for the capture of deuterium from hydrogen isotope mixtures in a simulated industrial process.
基金supported by the National Natural Science Foundation of China(Nos.22205207 and 22378369)major project of NSF of Zhejiang Province(LD24B060001).
文摘Due to the similar physicochemical properties of acetylene(C_(2)H_(2))and carbon dioxide(CO_(2)),separating C_(2)H_(2)from a CO_(2)/C_(2)H_(2)mixture poses a significant challenge in the petrochemical industry.Herein,we successfully synthesized a novel SiF_(6)^(2) anion pillared cage metal-organic framework ZNU-15 possessing a new crs topological structure for the selective capture of C_(2)H_(2).As a linear bidentate linker,the fluorinated SiF_(6)^(2) anion partitions the pores into various sized cages.ZNU-15 displays moderate adsorption for C_(2)H_(2)with a capacity of 36.0 cm^(3)g^(-1)at 298 K and 1 bar,which is 2.7 times higher than the CO_(2)uptake.The IAST selectivity of C_(2)H_(2)/CO_(2)for ZNU-15 at 298 K and 100 kPa is 10.5,surpassing that of most reported materials.The Qst values for C_(2)H_(2)and CO_(2)at zero coverage are 54.0 and 42.8 kJ mol^(-1),respectively.Moreover,breakthrough experimental tests show that ZNU-15 is capable of effectively separating C_(2)H_(2)from a C_(2)H_(2)/CO_(2)mixture.Theoretical calculations further indicate that C_(2)H_(2)is preferentially trapped by the small cage with four cooperative hydrogen bonds.
基金financial support from the National Natural Science Foundation of China(21922810,21908153,21908155)program of Innovative Talents of Higher Education Institutions of Shanxithe supported by Cultivate Scientific Research Excellence Programs of Higher Education Institutions in Shanxi(CSREP)。
文摘The removal of trace propyne(C_(3)H_(4))from propyne/propylene(C_(3)H_(4)/C_(3)H_(6))mixtures is a technical and challenging task during the production of polymer-grade propylene in view of their very similar size and physical properties.While some progress has been made,it is still very challenging to use some highly stable and commercially available porous materials via an energy-efficient adsorptive separation process.Herein,we report the ultrafine tuning of the pore apertures in type-A zeolites for the highly efficient removal of trace amounts of C_(3)H_(4)from C_(3)H_(4)/C_(3)H_(6)mixtures.The resulting ion-exchanged zeolite 5 A exhibits a large C_(3)H_(4)adsorption capacity(2.3 mmol g^(-1)under 10^(-4)MPa)and high C_(3)H_(4)/C_(3)H_(6)selectivity at room temperature,which were mainly attributed to the ultrafine-tuned pore size that selectively blocks C_(3)H_(6)molecules,while maintaining the stro ng adsorption of C_(3)H_(4)at low pressure region.High purity of C_(3)H_(6)(>99.9999%)can be directly obtained on this material under ambient conditions,as demonstrated by the experimental breakthrough curves obtained for both 1/99 and 0.1/99.9(V V)C_(3)H_(4)/C_(3)H_(6) mixtures.
基金financially supported by the Strategic Priority Research Program of Chinese Academy of Sciences(No.XDB20000000)the Key Research Program of Frontier Sciences,Chinese Academy of Sciences(No.QYZDB-SSW-SLH019)the National Natural Science Foundation of China(Nos.21771177,51603206 and 21203117).
文摘Hydrogen isotope separation is a challenging task due to their similar properties.Herein,based on the chemical affinity quantum sieve(CAQS)effect,the D_(2)/H_(2)separation performance of M_(2)(m-dobdc)(M=Co,Ni,Mg,Mn;m-dobdc^(4-)=4,6-dioxido-1,3-benzenedicarboxylate),a series of honeycomb-shaped MOFs with high stability and abundant open metal sites,are studied by gases sorption and breakthrough experiments,in which two critical factors,gas uptake and adsorption enthalpy,are taken into consideration.Among these MOFs,Co_(2)(m-dobdc)exhibits the longest D_(2)retention time of 180 min/g(H_(2)/D_(2)/Ne:1/1/98)at 77 K because of its second-highest adsorption enthalpy(10.7 kJ/mol for H_(2)and 11.8 kJ/mol for D_(2))and the best sorption capacity(5.22 mmol/g for H_(2)and 5.49 mmol/g for D_(2))under low pressure of 1 kPa and 77 K,which make it a promising material for industrial hydrogen isotope separation.Moreover,the results indicate that H_(2)and D_(2)capacities under low pressure(about 1 kPa)dominate the final D_(2)/H_(2)separation property of MOFs.
基金the Strategic Priority Research Program of CAS(No.XDB20000000),the Key Research Program of Frontier Sciences,CAS(No.QYZDB-SSW-SLH019)the Natural Nature Science Foundation of China(Nos.21771177,51603206,21203117).
文摘A three-dimensional copper metal-organic framework with the rare chabazite(CHA)topology namely FJI-Y11 has been constructed with flexibly carboxylic ligand 5,5'-[(1,4-phenylenebis(methylene))bis(oxy)]diisophthalic acid(H_(4)L).FJI-Y11 exhibits high water stability with the pH range from 2 to 12 at temperature as high as 373 K.Importantly,FJI-Y11 also shows high efficiency of hydrogen isotope separation using dynamic column breakthrough experiments under atmospheric pressure at 77 K.Attributed to its excellent structural stability,FJI-Y11 possesses good regenerated performance and maintains high separation efficiency after three cycles of breakthrough experiments.
基金This work was financially supported by the National Natural Science Foundation of China （21207018, 21273033, 21573042 and 21203024） and the Fujian Science and Technology Department （2014J06003 and 2014H6007）. S. X. gratefully acknowledges the support of the Recruitment Program of Global Young Experts, Program for New Century Excellent Talents in University （NCET- 10-0108）, and the Award ＇MinJiang Scholar Program＇ in Fujian Province.sity （NCET- 10-0108）, and the Award ＇MinJiang Scholar Program＇ in Fujian Province.
文摘Hierarchically porous materials play an important role in facilitating mass transport and improving efficiency of adsorption and separation processes. In this paper, a new strategy is proposed to realize a hierarchically porous metal-organic framework （[Cu2（OH）（L）]＇（DMF）0.8 （FJU-11, H3L=3,5-（4-carboxybenzyloxy）benzoic acid, DMF= N,N-dimethylformamide） via using semi-rigid multi-carboxylic acids. Interestingly, FJU-11 possesses the large adsorption capacities and small isosteric heats toward CO2. The column breakthrough experiment for FJU-11 highlights its potential application in the separation of the flue gas.
基金supported by the National Key R&D Program of China(no.2017YFA0700102)the National Natural Science Foundation of China(nos.22071244 and 21771177)+2 种基金the Key Research Program of Frontier Sciences of the Chinese Academy of Sciences(no.QYZDB-SSWSLH019)the Fujian Science&Technology Innovation Laboratory for Optoelectronic Information of China(no.2021ZZ106)the Advanced Energy Science and Technology Guangdong Laboratory.
文摘It is extremely challenging to construct three-dimensional(3D)crystalline covalent organic frameworks(COFs)with flexible building blocks and to further explore their tunable or adaptive characteristics due to crystallization and structure determination difficulties.Herein,we constructed three crystalline isostructural 3D-OC-COFs based on a newly synthesized flexible organic cage(6NH_(2)-OC.4HCl)through a novel in situ acid–base neutralization strategy.
