One porous framework [Zn4（μ4-O）（μ4-4-pca）3]·2（DEF）·2（H2O）（1, 4-H2Pca = 4-pyrazolecarboxylic acid, DEF = N,N-diethylformamide） with MOF-5 type topology has been synthesized solvothermally. Signifi...One porous framework [Zn4（μ4-O）（μ4-4-pca）3]·2（DEF）·2（H2O）（1, 4-H2Pca = 4-pyrazolecarboxylic acid, DEF = N,N-diethylformamide） with MOF-5 type topology has been synthesized solvothermally. Significantly, this compound exhibits high capacity of C2 hydrocarbons. C2H2 capacity could compare with the highest value of the reported MOFs, far exceeding that of MOF-5, as well as the high selectivity adsorption of C2s over C1.展开更多
A new type of covalent organic framework(COF)was achieved using combination of structrally rigid and conformationally othorganal building blocks.The N-2-aryl-substituted triazole derivative(NAT-CHO)was prepared with c...A new type of covalent organic framework(COF)was achieved using combination of structrally rigid and conformationally othorganal building blocks.The N-2-aryl-substituted triazole derivative(NAT-CHO)was prepared with co-planar conformation among the three aromatic rings as the“flat”building block.The 4,4,4,4-(ethene-1,1,2,2-tetrayl)tetraaniline)(ETTA)was applied as the“twist”building block.A 2 D sheet of network was obtained through imine formation.The resulting NAT-COF gave excellent thermal and chemical stability,survived aqueous solutions from p H 5 to 13.With large-size building blocks,the porous framework NAT-COF gave efficient gas adsorption with excellent selectivity of C3 propane over C1 me-thane,suggesting its potential application for selective gas capture and separation.展开更多
The adsorption and separation of CH4/H2 in two covalently-linked organic-inorganic hybrid frame- works polyoctaphenylsilsesquioxane （JUC-Z1） were computationally studied using the Grand Canon- ical Monte Carlo （GCM...The adsorption and separation of CH4/H2 in two covalently-linked organic-inorganic hybrid frame- works polyoctaphenylsilsesquioxane （JUC-Z1） were computationally studied using the Grand Canon- ical Monte Carlo （GCMC） simulations. The results show that JUC-Z1 with Linde type A （LTA） and polycubane （zeolite code ACO） net topologies can adsorb up to 20.32, 18.57 mmol/g of CH4 and 19.04, 17.89 mmol/g of H2 at 298 K and 10 MPa, respectively. For the adsorption of binary mixture, the selectivity of CH4 over H2 in LTA-JUC-Zl decrease gradually with the increase of the pressure or the CH4 mole fraction of the mixture. As to ACO-JUC-Z1, the selectivity first increases at low pressure or CH4 mole fraction, and then begins to decrease with the further increase of the corresponding amount. Anyhow, the two materials both exhibit excellent adsorption and separation capacities of CH4/H2.展开更多
Ethylene(C_(2)H_(4)) and propylene(C_(3)H_(6)) produced by methanol to olefin(MTO) technology are important chemical raw materials.However,the purification and separation between C_(2)H_(4) and C_(3)H_(6) mixtures is ...Ethylene(C_(2)H_(4)) and propylene(C_(3)H_(6)) produced by methanol to olefin(MTO) technology are important chemical raw materials.However,the purification and separation between C_(2)H_(4) and C_(3)H_(6) mixtures is very challenging.Herein,a novel microporous metal-organic framework(MOF) adsorbent Co_(2)(OATA)(DPA) was fabricated through mixed linkers of 5,5'-(oxalylbis(azanediyl))diisophthalic acid(H_(4)OATA) and V-shaped di(pyridin-4-yl)amine(DPA) with -NHCO- and -NH- functional groups,which was endowed with ideal small pore size,large cavity,and interesting C_(3)H_(6) trap constructed by four sets of -NH- groups.Under 298 K and a crucial low pressure(0.05 bar) for the separation in microporous materials,the MOF shows ultra-high C_(3)H_(6) preferential adsorption(97.8 cm^(3)g^(-1)) and considerable C_(3)H_(6)/C_(2)H_(4) selectivity(about 22),representing an advanced material for the reported porous materials with C_(3)H_(6)/C_(2)H_(4) separation function.The studies of single crystal X-ray diffraction and simulations showed that the customized pore limitation in the MOF provided stronger multiple attractive interactions with C_(3)H_(6),leading to significant adsorption selectivity in the process of competing adsorption for C_(3)H_(6) and C_(2)H_(4).In one separation step,the MOF generated highly pure C_(2)H_(4)(≥99.9%) and C_(3)H_(6)(≥99.6%) products respectively from C_(2)H_(4)/C_(3)H_(6) mixtures at different ratios,pressures,and temperatures.展开更多
Until now, to remove the harmful organic dyes from effluents is an outstanding challenge. The design and synthesis of new porous materials capable of selectively adsorbing dyes are critical to the environment and huma...Until now, to remove the harmful organic dyes from effluents is an outstanding challenge. The design and synthesis of new porous materials capable of selectively adsorbing dyes are critical to the environment and human health. Here, a unique cluster-based cationic metal-organic framework, named{[Zn8（BTA）6（L）5Cl2]·（NO3）3}·5 DMF（NUM-4） was synthesized, which displays one-dimensional（1 D）open channels along a axis in its 3 D supramolecular stacking structure. Benefiting from the nature of cationic framework and high surface area/pore volume, NUM-4 shows rapid and selective adsorption of anionic dyes（MO, AO, CR and MB） based on the charge-exclusive effect. Besides, the adsorbed dyes can be easily released in NH4Cl saturated solution of ethanol.展开更多
Separation of C_(2) gases(C_(2)H_(2)/C_(2)H_(4),C_(2)H_(6)/C_(2)H_(4) and C_(2)H_(2)/CO_(2))mixtures is one of the most important and energy-demanding processes in chemical industry.Traditional separation methods(fine...Separation of C_(2) gases(C_(2)H_(2)/C_(2)H_(4),C_(2)H_(6)/C_(2)H_(4) and C_(2)H_(2)/CO_(2))mixtures is one of the most important and energy-demanding processes in chemical industry.Traditional separation methods(fine distillation separation and selective catalytic hydrogenation separation)have the shortages of high energy consumption and inefficient use of resources,affecting the achievement of peak carbon dioxide emissions and carbon neutrality targets.Separation based on adsorption is considered as one of the best ways to achieve low-energy separations.Therefore,it is of great importance to synthesize materials that enable the effective separation and purification of C_(2) gases under mild conditions.As an emerging class of porous materials,metal-organic frameworks(MOFs)show great promise in the field of gas separation and purification due to their ultra-high specific surface area,easily modifiable pore surfaces,structural designability and functionalization.Herein,we summarize recent research advances by use of MOFs sorbents for the separation and purification of C_(2) gases,including C_(2)H_(2)/C_(2)H_(4),C_(2)H_(6)/C_(2)H_(4) and C_(2)H_(2)/CO_(2).Relationship between structures and separation mechanism is also explored.Furthermore,challenges and possible research directions related to the further exploration are also discussed.展开更多
Trans-/cis-olefin isomers play a vital role in the petrochemical industry.The paucity of energy-efficient technologies for their splitting is mainly due to the similarities of their physicochemical properties.Herein,t...Trans-/cis-olefin isomers play a vital role in the petrochemical industry.The paucity of energy-efficient technologies for their splitting is mainly due to the similarities of their physicochemical properties.Herein,two new tailor-made anion-pillared ultramicroporous metal–organic frameworks(MOFs),ZU-36-Ni and ZU-36-Fe(GeFSIX-3-Ni and GeFSIX-3-Fe)are reported for the first time for the efficient trans-/cis-2-butene(trans-/cis-C_(4)H_(8))mixture splitting by enhanced molecular exclusion.Notably,ZU-36-Ni unexpectedly exhibited smart vip-adaptive pore channels for trapping trans-C_(4)H_(8)with a remarkable adsorption capacity(2.45 mmol∙g^(−1))while effectively rejecting cis-C_(4)H_(8)with a high purity of 99.99%.The dispersion-corrected density functional theory(DFT-D)calculation suggested that the vip-adaptive behavior of ZU-36-Ni in response to trans-C_(4)H_(8)is derived from the organic linker rotation and the optimal pore dimensions,which not only improve the favorable adsorption/diffusion of trans-C_(4)H_(8)with optimal host–vip interactions,but also enhance the size-exclusion of cis-C_(4)H_(8).This work opens a new avenue for pore engineering in advanced smart or adaptive porous materials for specific applications involving vip molecular recognition.展开更多
Developing advanced porous materials possessing both a high storage capacity and selectivity for acetylene(C_(2)H_(2))remains challenging but a sought-after endeavor.Herein we show a strategy involving synergic combin...Developing advanced porous materials possessing both a high storage capacity and selectivity for acetylene(C_(2)H_(2))remains challenging but a sought-after endeavor.Herein we show a strategy involving synergic combination of spatial confinement and commensurate stacking for enhanced C_(2)H_(2)storage and capture via maximizing the host–vip and vip–vip interactions.Two ultramicroporous metal-organic frameworks(MOFs),MIL-160 and MOF-303 are elaborately constructed to exhibit ultrahigh C_(2)H_(2)uptakes of 235 and 195 cm^(3)·g^(−1),respectively,due to the confinement effect of the suitable pore sizes and periodically dispersed molecular recognition sites.Specially,C_(2)H_(2)capacity of MIL-160 sets a new benchmark for C_(2)H_(2)storage.The exceptional separation performances of two materials for C_(2)H_(2)over both CO_(2)and ethylene(C_(2)H_(4)),which is rarely observed,outperform most of the benchmark materials for C_(2)H_(2)capture.We scrutinized the origins of ultrahigh C_(2)H_(2)loading in the confined channels via theoretical investigations.The superior separation efficiency for C_(2)H_(2)/CO_(2)and C_(2)H_(2)/C_(2)H_(4)mixtures with unprecedented C_(2)H_(2)trapping capacity(>200 L·kg^(−1))was further demonstrated by dynamic breakthrough experiments.展开更多
The exploration of ethane(C_(2)H_(6))-selective porous materials for the direct production of polymer-grade ethylene(C_(2)H_(4))from a C_(2)H_(6)/C_(2)H_(4) mixture in a single energy-saving adsorption step is of utmo...The exploration of ethane(C_(2)H_(6))-selective porous materials for the direct production of polymer-grade ethylene(C_(2)H_(4))from a C_(2)H_(6)/C_(2)H_(4) mixture in a single energy-saving adsorption step is of utmost importance but remains a significant challenge.Thus,developing robust C_(2)H_(6)-selective adsorbents with high C_(2)H_(6) capacity and C_(2)H_(6)/C_(2)H_(4) selectivity is urgently needed for industrial applications.In this study,we have successfully designed and synthesized two novel calix[4]resorcinarene-based porous organic cages(POCs)named CPOC-501 and CPOC-502.The POCs were formed via a Schiff-base reaction involving face-directed[6+8]condensation between a bowlshaped tetratopic tetraformylcalix[4]resorcinarene and triangular tritopic amine synthons.Analysis using single crystal X-ray crystallography revealed that both cages possess large truncated octahedral cavities with a volume of approximately 6500Å3 and 12 accessible rhombic windows with a side length of approximately 10.5Å.Furthermore,the cages exhibited excellent chemical stability under neutral,acidic,and basic conditions and high Brunauer–Emmett–Teller specific surface areas of up to 2175 m^(2) g^(−1) after desolvation.Both POCs demonstrated superior adsorption capabilities for C_(2)H_(6) over C_(2)H_(4).Notably,CPOC-502 exhibited a C_(2)H_(6) capacity and C_(2)H_(6)/C_(2)H_(4) selectivity of 83 cm^(3) g^(−1) and 2.83,respectively,surpassing most of the best-performing C_(2)H_(6)-selective porous organic materials reported to date.Moreover,breakthrough experiments confirmed that both cages efficiently produced polymer-grade C_(2)H_(4)(>99.9%)directly from the C_(2)H_(6)/C_(2)H_(4) mixture,highlighting their outstanding recyclability.展开更多
Porous organic cages(POCs)have shown great potential in many applications,and post-synthetic modification(PSM)has been confirmed to be an effective strategy to tailor their structures and related functionalities.Howev...Porous organic cages(POCs)have shown great potential in many applications,and post-synthetic modification(PSM)has been confirmed to be an effective strategy to tailor their structures and related functionalities.However,it is extremely challenging to develop a general platform for simple-to-make functional POCs for advanced applications by PSM method.Herein,we reported that octahedral calix[4]resorcinarene-based hydrazone-linked porous organic cage(HPOC-401)provides an excellent platform for post-synthetic metalation by various transition metal(TM)ions under mild conditions due to the abundance of coordination sites in its skeleton.Such metalated products(HPOC-401-TM)exhibit Brunauer-Emmett-Teller(BET)surface area up to1,456 m^(2)g^(-1),much higher than that of the pristine HPOC-401,which has a BET value of 474 m^(2)g^(-1).Moreover,the metalation and porosity increases further influence their gas capture,separation,as well as catalytic performance.For instance,HPOC-401-TM products exhibit higher CO_(2),H_(2),and C2 hydrocarbon gas uptake,as well as higher C_(2)H_(6)/C_(2)H_(4) selectivity than HPOC-401.Moreover,the HPOC-401-TM also shows better catalytic performance in the cycloaddition of CO_(2) with epoxides compared to HPOC-401.These findings uncover a simple yet effective approach for modifying the porosity characteristics of organic cages,which will undoubtedly expand their future implementations.展开更多
The high-yield synthesis of ultrastable porous organic cages(POCs)by facile methods is highly desirable but challenging.Inspired by highly stable sp^(2) carbon-conjugated(C=C)covalent organic frameworks,we used ration...The high-yield synthesis of ultrastable porous organic cages(POCs)by facile methods is highly desirable but challenging.Inspired by highly stable sp^(2) carbon-conjugated(C=C)covalent organic frameworks,we used rational design and synthesized the first family of sp^(2) carbon-linked POCs(sp^(2)c-POCs)with triangular prism shapes by a one-step Knoevenagel reaction that is a high yield[2+3]condensation reaction.The stability of sp^(2)c-POC was demonstrated under strenuous conditions involving for example concentrated HCl or saturated NaOH solution.sp^(2)c-POC was used as a robust adsorbent for efficient separation of CO_(2)/CH_(4) or CO_(2)/N_(2) mixtures.In view of their facile synthesis and unique properties,we expect widespread use of these sp^(2) C=C linkages in the development of POC materials.展开更多
One-step harvest of high-purity methane(CH_(4))from ternary propane/ethane/methane(C_(3)H_(8)/C_(2)H_(6)/CH_(4))mixtures remains a desirable yet challenging goal for natural gas purification.However,adsorbents either ...One-step harvest of high-purity methane(CH_(4))from ternary propane/ethane/methane(C_(3)H_(8)/C_(2)H_(6)/CH_(4))mixtures remains a desirable yet challenging goal for natural gas purification.However,adsorbents either suffer from high capacity and selectivity,or are caught in a dilemma of scalable synthesis.Herein,we demonstrate a scalable pillar layered metal-organic framework Ni-MOF for highly efficient one-step CH_(4)purification.Ni-MOF exhibits high C_(2)H_(6)and C_(3)H_(8)uptakes of 83.3 and 86.1 cm^(3)/g at 298 K and 100 kPa and remarkable C_(2)H_(6)/CH_(4)(50/50,volume ratio,21.5)and C_(3)H_(8)/CH_(4)(50/50,volume ratio,212.0)selectivities.Notably,high C_(2)H_(6)(42.2 cm^(3)/g at 10 kPa)and C_(3)H_(8)(64.7 cm^(3)/g at 5 kPa)capacities in the low-pressure region at 298 K were realized on Ni-MOF,suggesting the strong affinities of Ni-MOF towards C_(2)H_(6)and C_(3)H_(8).Furthermore,the dynamic breakthrough experiments revealed that purifying CH_(4)from natural gas in one-step can be achieved in Ni-MOF with high-purity(>99.8%)and productivity(346.0 cm^(3)/g).Most significantly,the production of Ni-MOF can be scalably synthesized at room temperature,rendering it promising potential for industrial application.The combined advantages of exceptional separation performance,scalability,and cycle stability of Ni-MOF pave the way for one-step CH_(4)purification from natural 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
As promising engineering materials for green and sustainable processes, porous metalorganic framework(MOF)-polymer composites show great potential in applications, including adsorption, separation, catalysis, and bioe...As promising engineering materials for green and sustainable processes, porous metalorganic framework(MOF)-polymer composites show great potential in applications, including adsorption, separation, catalysis, and bioengineering. Owing to the mild and scalable operation, porous polymeric materials derived from high internal phase emulsion templates(polyHIPE) have received great interests in recent decades. In this contribution, research progress of the preparation of porous MOF@polyHIPE composites and their applications are reviewed, highlighting how can MOF particles be shaped by HIPE templates, in particular the polymerizable ones. Four different emulsion templates stabilized by MOFs and the applications of corresponding MOF@polyHIPE are included. Hopefully,both the state-of-art and future directions present herein can give rise to the development of highperformance porous MOF@polyHIPEs.展开更多
Controlling interpenetration and flexibility behaviors is intriguing and fundamental for porous coordination polymers.We report exceptional interpenetration behaviors involving controllable partial order–disorder str...Controlling interpenetration and flexibility behaviors is intriguing and fundamental for porous coordination polymers.We report exceptional interpenetration behaviors involving controllable partial order–disorder structural transformations.A new bis-benzotriazolate ligand(NaH2sbbta)with a twisted and anionic backbone was designed and synthesized.The solvothermal reaction of ZnCl_(2) and NaH_(2)sbbta yielded(Et_(2)NH_(2))_(3)[Zn_(5)Cl_(4)(sbbta)_(3)]·6DEF(2)possessing two-fold interpenetrated anionic pcu networks with symmetry,shape,and charge different from the known analogues.More interestingly,powder and single-crystal X-ray diffractions showed that 2 can undergo solvent-induced structural transformation to form a noninterpenetrated anionic pcu network with larger pores(1).Consequently,1/2 can selectively adsorb/exchange cationic dyes fromneutral and anionic dyes with tunable size selectivity.However,since the transformations are reversible without obvious change of crystal sizes,the network that disappeared in X-ray crystallography should be mainly disordered rather than decomposed.Further,the structural transformations can be suppressed by thermal decomposition/removal of Et_(2)NH_(2)^(+)/Et_(2)NH.Computational simulations indicate that the ordered and disordered structures are stabilized by relatively large and small solvent molecules,respectively.展开更多
基金supported financially by the National Natural Science Foundation of China(No.21601080)the Key Scientific Research Projects of Higher Education of He'nan Province(16A150016)
文摘One porous framework [Zn4（μ4-O）（μ4-4-pca）3]·2（DEF）·2（H2O）（1, 4-H2Pca = 4-pyrazolecarboxylic acid, DEF = N,N-diethylformamide） with MOF-5 type topology has been synthesized solvothermally. Significantly, this compound exhibits high capacity of C2 hydrocarbons. C2H2 capacity could compare with the highest value of the reported MOFs, far exceeding that of MOF-5, as well as the high selectivity adsorption of C2s over C1.
文摘A new type of covalent organic framework(COF)was achieved using combination of structrally rigid and conformationally othorganal building blocks.The N-2-aryl-substituted triazole derivative(NAT-CHO)was prepared with co-planar conformation among the three aromatic rings as the“flat”building block.The 4,4,4,4-(ethene-1,1,2,2-tetrayl)tetraaniline)(ETTA)was applied as the“twist”building block.A 2 D sheet of network was obtained through imine formation.The resulting NAT-COF gave excellent thermal and chemical stability,survived aqueous solutions from p H 5 to 13.With large-size building blocks,the porous framework NAT-COF gave efficient gas adsorption with excellent selectivity of C3 propane over C1 me-thane,suggesting its potential application for selective gas capture and separation.
文摘The adsorption and separation of CH4/H2 in two covalently-linked organic-inorganic hybrid frame- works polyoctaphenylsilsesquioxane （JUC-Z1） were computationally studied using the Grand Canon- ical Monte Carlo （GCMC） simulations. The results show that JUC-Z1 with Linde type A （LTA） and polycubane （zeolite code ACO） net topologies can adsorb up to 20.32, 18.57 mmol/g of CH4 and 19.04, 17.89 mmol/g of H2 at 298 K and 10 MPa, respectively. For the adsorption of binary mixture, the selectivity of CH4 over H2 in LTA-JUC-Zl decrease gradually with the increase of the pressure or the CH4 mole fraction of the mixture. As to ACO-JUC-Z1, the selectivity first increases at low pressure or CH4 mole fraction, and then begins to decrease with the further increase of the corresponding amount. Anyhow, the two materials both exhibit excellent adsorption and separation capacities of CH4/H2.
基金supported by the National Natural Science Foundation of China (22371226)the Natural Science Basic Research Program of Shaanxi (2024JC-JCQN-18)the Shaanxi Fundamental Science Research Project for Chemistry&Biology (23JHZ004)。
文摘Ethylene(C_(2)H_(4)) and propylene(C_(3)H_(6)) produced by methanol to olefin(MTO) technology are important chemical raw materials.However,the purification and separation between C_(2)H_(4) and C_(3)H_(6) mixtures is very challenging.Herein,a novel microporous metal-organic framework(MOF) adsorbent Co_(2)(OATA)(DPA) was fabricated through mixed linkers of 5,5'-(oxalylbis(azanediyl))diisophthalic acid(H_(4)OATA) and V-shaped di(pyridin-4-yl)amine(DPA) with -NHCO- and -NH- functional groups,which was endowed with ideal small pore size,large cavity,and interesting C_(3)H_(6) trap constructed by four sets of -NH- groups.Under 298 K and a crucial low pressure(0.05 bar) for the separation in microporous materials,the MOF shows ultra-high C_(3)H_(6) preferential adsorption(97.8 cm^(3)g^(-1)) and considerable C_(3)H_(6)/C_(2)H_(4) selectivity(about 22),representing an advanced material for the reported porous materials with C_(3)H_(6)/C_(2)H_(4) separation function.The studies of single crystal X-ray diffraction and simulations showed that the customized pore limitation in the MOF provided stronger multiple attractive interactions with C_(3)H_(6),leading to significant adsorption selectivity in the process of competing adsorption for C_(3)H_(6) and C_(2)H_(4).In one separation step,the MOF generated highly pure C_(2)H_(4)(≥99.9%) and C_(3)H_(6)(≥99.6%) products respectively from C_(2)H_(4)/C_(3)H_(6) mixtures at different ratios,pressures,and temperatures.
基金financially supported by the National Natural Science Foundation of China (Nos. 21371102, 21531005 and 21673120)the Natural Science Foundation of Tianjin (Nos. 16JCZDJC36900 and 15JCZDJC38800)
文摘Until now, to remove the harmful organic dyes from effluents is an outstanding challenge. The design and synthesis of new porous materials capable of selectively adsorbing dyes are critical to the environment and human health. Here, a unique cluster-based cationic metal-organic framework, named{[Zn8（BTA）6（L）5Cl2]·（NO3）3}·5 DMF（NUM-4） was synthesized, which displays one-dimensional（1 D）open channels along a axis in its 3 D supramolecular stacking structure. Benefiting from the nature of cationic framework and high surface area/pore volume, NUM-4 shows rapid and selective adsorption of anionic dyes（MO, AO, CR and MB） based on the charge-exclusive effect. Besides, the adsorbed dyes can be easily released in NH4Cl saturated solution of ethanol.
基金The Postgraduate Innovative Research Projects of Tianjin。
文摘Separation of C_(2) gases(C_(2)H_(2)/C_(2)H_(4),C_(2)H_(6)/C_(2)H_(4) and C_(2)H_(2)/CO_(2))mixtures is one of the most important and energy-demanding processes in chemical industry.Traditional separation methods(fine distillation separation and selective catalytic hydrogenation separation)have the shortages of high energy consumption and inefficient use of resources,affecting the achievement of peak carbon dioxide emissions and carbon neutrality targets.Separation based on adsorption is considered as one of the best ways to achieve low-energy separations.Therefore,it is of great importance to synthesize materials that enable the effective separation and purification of C_(2) gases under mild conditions.As an emerging class of porous materials,metal-organic frameworks(MOFs)show great promise in the field of gas separation and purification due to their ultra-high specific surface area,easily modifiable pore surfaces,structural designability and functionalization.Herein,we summarize recent research advances by use of MOFs sorbents for the separation and purification of C_(2) gases,including C_(2)H_(2)/C_(2)H_(4),C_(2)H_(6)/C_(2)H_(4) and C_(2)H_(2)/CO_(2).Relationship between structures and separation mechanism is also explored.Furthermore,challenges and possible research directions related to the further exploration are also discussed.
基金the US Department of Energy,Office of Science,Office of Basic Energy Sciences(DE-SC0019902)for the partial support of this workShikai Xian,Junjie Peng,and Hao Wang acknowledge the financial support from National Natural Science Foundation of China(21908069 and 21901166)+1 种基金Guangdong Natural Science Foundation(2019A1515010692)Shenzhen Science and Technology Program(JCYJ20190809145615620 and RCYX20200714114539243).
文摘开发高吸附量和选择性的高效吸附剂,用于天然气中C_(2)H_(6)和C_(3)H_(8)的分离和回收,是一项重要且具有挑战性的任务。在本研究中,我们证明高表面极性和合适的孔径直径是协同增强分离性能的两个关键因素,以金属-有机框架(MOF)-303和Matériaux de l'Institut Lavoisier(MIL)-160为例,它们都具有高杂原子密度和所需孔径大小(5~7Å)的一维开放通道。值得注意的是,MOF-303对C_(3)H_(8)的吸附量在298 K和5 kPa时达到了3.38 mmol·g^(−1),与所有已报道的MOFs相比,C_(3)H_(8)/CH4(5:85,v/v)的理想吸附溶液理论(IAST)选择性达到了创纪录的5114。此外,MOF-303还显示出高C_(2)H_(6)吸附量(在10 kPa时)和C_(2)H_(6)/CH4(10:85,v/v)选择性,分别达到1.59 mmol·g^(−1)和26。由于其一维通道内较大的孔径直径和较低的杂原子密度,与MOF-303相比,MIL-160的吸附量和选择性显然更低,尽管这些值超过了大多数报道的MOFs。密度泛函理论(DFT)计算验证了高表面极性和合适的孔径直径协同增强了框架对C_(3)H_(8)和C_(2)H_(6)的亲和力,导致了对C_(3)H_(8)和C_(2)H_(6)的高负载能力和选择性。两种MOFs都具有显著的湿度稳定性,在暴露于95%相对湿度(RH)一个月后没有结构变化。此外,通过一锅反应可以轻松地扩大合成这两种化合物,以获得高结晶度的约5 g样品。最后,通过三元突破实验、再生测试和循环评估,展示了MOF-303和MIL-160作为高级吸附剂,用于高效分离C_(3)H_(8)/C_(2)H_(6)/CH4的巨大潜力。优异的分离性能、高稳定性、低成本和良好的可扩展性,使得这两种MOFs成为天然气净化及C_(2)H_(6)和C_(3)H_(8)回收的有前途的吸附剂。
基金supported by the Zhejiang Provincial Natural Science Foundation of China (LZ18B060001)the National Natural Science Foundation of China (21725603, 21476192, and U1862110)
文摘Trans-/cis-olefin isomers play a vital role in the petrochemical industry.The paucity of energy-efficient technologies for their splitting is mainly due to the similarities of their physicochemical properties.Herein,two new tailor-made anion-pillared ultramicroporous metal–organic frameworks(MOFs),ZU-36-Ni and ZU-36-Fe(GeFSIX-3-Ni and GeFSIX-3-Fe)are reported for the first time for the efficient trans-/cis-2-butene(trans-/cis-C_(4)H_(8))mixture splitting by enhanced molecular exclusion.Notably,ZU-36-Ni unexpectedly exhibited smart vip-adaptive pore channels for trapping trans-C_(4)H_(8)with a remarkable adsorption capacity(2.45 mmol∙g^(−1))while effectively rejecting cis-C_(4)H_(8)with a high purity of 99.99%.The dispersion-corrected density functional theory(DFT-D)calculation suggested that the vip-adaptive behavior of ZU-36-Ni in response to trans-C_(4)H_(8)is derived from the organic linker rotation and the optimal pore dimensions,which not only improve the favorable adsorption/diffusion of trans-C_(4)H_(8)with optimal host–vip interactions,but also enhance the size-exclusion of cis-C_(4)H_(8).This work opens a new avenue for pore engineering in advanced smart or adaptive porous materials for specific applications involving vip molecular recognition.
基金the National Natural Science Foundation of China(No.21868002)Dean Project of Guangxi Key Laboratory of Petrochemical Resource Processing and Process Intensification Technology(No.2021Z010).
文摘Developing advanced porous materials possessing both a high storage capacity and selectivity for acetylene(C_(2)H_(2))remains challenging but a sought-after endeavor.Herein we show a strategy involving synergic combination of spatial confinement and commensurate stacking for enhanced C_(2)H_(2)storage and capture via maximizing the host–vip and vip–vip interactions.Two ultramicroporous metal-organic frameworks(MOFs),MIL-160 and MOF-303 are elaborately constructed to exhibit ultrahigh C_(2)H_(2)uptakes of 235 and 195 cm^(3)·g^(−1),respectively,due to the confinement effect of the suitable pore sizes and periodically dispersed molecular recognition sites.Specially,C_(2)H_(2)capacity of MIL-160 sets a new benchmark for C_(2)H_(2)storage.The exceptional separation performances of two materials for C_(2)H_(2)over both CO_(2)and ethylene(C_(2)H_(4)),which is rarely observed,outperform most of the benchmark materials for C_(2)H_(2)capture.We scrutinized the origins of ultrahigh C_(2)H_(2)loading in the confined channels via theoretical investigations.The superior separation efficiency for C_(2)H_(2)/CO_(2)and C_(2)H_(2)/C_(2)H_(4)mixtures with unprecedented C_(2)H_(2)trapping capacity(>200 L·kg^(−1))was further demonstrated by dynamic breakthrough experiments.
基金financially supported by the National Nature Science Foundation of China(grant nos.22071244 and 22275191)the Youth Innovation Promotion Association CAS(grant no.2022305)the Natural Science Foundation of Fujian Province of China(grant nos.2022J01503,2020J05087,and 2022I0037).
文摘The exploration of ethane(C_(2)H_(6))-selective porous materials for the direct production of polymer-grade ethylene(C_(2)H_(4))from a C_(2)H_(6)/C_(2)H_(4) mixture in a single energy-saving adsorption step is of utmost importance but remains a significant challenge.Thus,developing robust C_(2)H_(6)-selective adsorbents with high C_(2)H_(6) capacity and C_(2)H_(6)/C_(2)H_(4) selectivity is urgently needed for industrial applications.In this study,we have successfully designed and synthesized two novel calix[4]resorcinarene-based porous organic cages(POCs)named CPOC-501 and CPOC-502.The POCs were formed via a Schiff-base reaction involving face-directed[6+8]condensation between a bowlshaped tetratopic tetraformylcalix[4]resorcinarene and triangular tritopic amine synthons.Analysis using single crystal X-ray crystallography revealed that both cages possess large truncated octahedral cavities with a volume of approximately 6500Å3 and 12 accessible rhombic windows with a side length of approximately 10.5Å.Furthermore,the cages exhibited excellent chemical stability under neutral,acidic,and basic conditions and high Brunauer–Emmett–Teller specific surface areas of up to 2175 m^(2) g^(−1) after desolvation.Both POCs demonstrated superior adsorption capabilities for C_(2)H_(6) over C_(2)H_(4).Notably,CPOC-502 exhibited a C_(2)H_(6) capacity and C_(2)H_(6)/C_(2)H_(4) selectivity of 83 cm^(3) g^(−1) and 2.83,respectively,surpassing most of the best-performing C_(2)H_(6)-selective porous organic materials reported to date.Moreover,breakthrough experiments confirmed that both cages efficiently produced polymer-grade C_(2)H_(4)(>99.9%)directly from the C_(2)H_(6)/C_(2)H_(4) mixture,highlighting their outstanding recyclability.
基金supported by the National Natural Science Foundation of China(22071244)the Youth Innovation Promotion Association CAS(2022305)+1 种基金the Natural Science Foundation of Fujian Province of China(2022J01503,2020J05087)the China Postdoctoral Science Foundation(2020M671954)。
文摘Porous organic cages(POCs)have shown great potential in many applications,and post-synthetic modification(PSM)has been confirmed to be an effective strategy to tailor their structures and related functionalities.However,it is extremely challenging to develop a general platform for simple-to-make functional POCs for advanced applications by PSM method.Herein,we reported that octahedral calix[4]resorcinarene-based hydrazone-linked porous organic cage(HPOC-401)provides an excellent platform for post-synthetic metalation by various transition metal(TM)ions under mild conditions due to the abundance of coordination sites in its skeleton.Such metalated products(HPOC-401-TM)exhibit Brunauer-Emmett-Teller(BET)surface area up to1,456 m^(2)g^(-1),much higher than that of the pristine HPOC-401,which has a BET value of 474 m^(2)g^(-1).Moreover,the metalation and porosity increases further influence their gas capture,separation,as well as catalytic performance.For instance,HPOC-401-TM products exhibit higher CO_(2),H_(2),and C2 hydrocarbon gas uptake,as well as higher C_(2)H_(6)/C_(2)H_(4) selectivity than HPOC-401.Moreover,the HPOC-401-TM also shows better catalytic performance in the cycloaddition of CO_(2) with epoxides compared to HPOC-401.These findings uncover a simple yet effective approach for modifying the porosity characteristics of organic cages,which will undoubtedly expand their future implementations.
基金financially supported by the National Nature Science Foundation of China(grant nos.22071244 and 22275191)Youth Innovation Promotion Association CAS(grant no.2022305)+2 种基金Natural Science Foundation of Fujian Province of China(grant nos.2022J01503 and 2020J05087)The Fujian Science&Technology Innovation Laboratory for Optoelectronic Information of China(grant no.2021ZZ106)Advanced Energy Science and Technology Guangdong Laboratory(grant no.HND20TDZLZL00).
文摘The high-yield synthesis of ultrastable porous organic cages(POCs)by facile methods is highly desirable but challenging.Inspired by highly stable sp^(2) carbon-conjugated(C=C)covalent organic frameworks,we used rational design and synthesized the first family of sp^(2) carbon-linked POCs(sp^(2)c-POCs)with triangular prism shapes by a one-step Knoevenagel reaction that is a high yield[2+3]condensation reaction.The stability of sp^(2)c-POC was demonstrated under strenuous conditions involving for example concentrated HCl or saturated NaOH solution.sp^(2)c-POC was used as a robust adsorbent for efficient separation of CO_(2)/CH_(4) or CO_(2)/N_(2) mixtures.In view of their facile synthesis and unique properties,we expect widespread use of these sp^(2) C=C linkages in the development of POC materials.
基金supported by the National Natural Science Foundation of China(Nos.22035003,22371139,22305130)the Programme of Introducing Talents of Discipline to Universities,China(No.B18030).
文摘One-step harvest of high-purity methane(CH_(4))from ternary propane/ethane/methane(C_(3)H_(8)/C_(2)H_(6)/CH_(4))mixtures remains a desirable yet challenging goal for natural gas purification.However,adsorbents either suffer from high capacity and selectivity,or are caught in a dilemma of scalable synthesis.Herein,we demonstrate a scalable pillar layered metal-organic framework Ni-MOF for highly efficient one-step CH_(4)purification.Ni-MOF exhibits high C_(2)H_(6)and C_(3)H_(8)uptakes of 83.3 and 86.1 cm^(3)/g at 298 K and 100 kPa and remarkable C_(2)H_(6)/CH_(4)(50/50,volume ratio,21.5)and C_(3)H_(8)/CH_(4)(50/50,volume ratio,212.0)selectivities.Notably,high C_(2)H_(6)(42.2 cm^(3)/g at 10 kPa)and C_(3)H_(8)(64.7 cm^(3)/g at 5 kPa)capacities in the low-pressure region at 298 K were realized on Ni-MOF,suggesting the strong affinities of Ni-MOF towards C_(2)H_(6)and C_(3)H_(8).Furthermore,the dynamic breakthrough experiments revealed that purifying CH_(4)from natural gas in one-step can be achieved in Ni-MOF with high-purity(>99.8%)and productivity(346.0 cm^(3)/g).Most significantly,the production of Ni-MOF can be scalably synthesized at room temperature,rendering it promising potential for industrial application.The combined advantages of exceptional separation performance,scalability,and cycle stability of Ni-MOF pave the way for one-step CH_(4)purification from natural 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.
基金supported by the National Natural Science Foundation of China (21808140, 21978089)Shanghai Rising-Star Program (22QA1402800)the Fundamental Research Funds for the Central Universities
文摘As promising engineering materials for green and sustainable processes, porous metalorganic framework(MOF)-polymer composites show great potential in applications, including adsorption, separation, catalysis, and bioengineering. Owing to the mild and scalable operation, porous polymeric materials derived from high internal phase emulsion templates(polyHIPE) have received great interests in recent decades. In this contribution, research progress of the preparation of porous MOF@polyHIPE composites and their applications are reviewed, highlighting how can MOF particles be shaped by HIPE templates, in particular the polymerizable ones. Four different emulsion templates stabilized by MOFs and the applications of corresponding MOF@polyHIPE are included. Hopefully,both the state-of-art and future directions present herein can give rise to the development of highperformance porous MOF@polyHIPEs.
基金supported by NSFC(nos.21731007,22090061,21821003,and 22071272)the Guangdong Pearl River Talents Program(no.2017BT01C161).The。
文摘Controlling interpenetration and flexibility behaviors is intriguing and fundamental for porous coordination polymers.We report exceptional interpenetration behaviors involving controllable partial order–disorder structural transformations.A new bis-benzotriazolate ligand(NaH2sbbta)with a twisted and anionic backbone was designed and synthesized.The solvothermal reaction of ZnCl_(2) and NaH_(2)sbbta yielded(Et_(2)NH_(2))_(3)[Zn_(5)Cl_(4)(sbbta)_(3)]·6DEF(2)possessing two-fold interpenetrated anionic pcu networks with symmetry,shape,and charge different from the known analogues.More interestingly,powder and single-crystal X-ray diffractions showed that 2 can undergo solvent-induced structural transformation to form a noninterpenetrated anionic pcu network with larger pores(1).Consequently,1/2 can selectively adsorb/exchange cationic dyes fromneutral and anionic dyes with tunable size selectivity.However,since the transformations are reversible without obvious change of crystal sizes,the network that disappeared in X-ray crystallography should be mainly disordered rather than decomposed.Further,the structural transformations can be suppressed by thermal decomposition/removal of Et_(2)NH_(2)^(+)/Et_(2)NH.Computational simulations indicate that the ordered and disordered structures are stabilized by relatively large and small solvent molecules,respectively.
