A novel porous coordination polymer,iron naphthalenedicarboxylate Fe（OH）（1,4-NDC）·2H2O is hydrothermally synthesized by the reaction of FeSO4·7H2O and 1,4-naphthalenedicarboxylic acid（1,4-H2NDC） at 150...A novel porous coordination polymer,iron naphthalenedicarboxylate Fe（OH）（1,4-NDC）·2H2O is hydrothermally synthesized by the reaction of FeSO4·7H2O and 1,4-naphthalenedicarboxylic acid（1,4-H2NDC） at 150℃.The compound crystallizes in a tetragonal space group P42/nmc：a=2.1447（4） nm,c=0.68849（14） nm,V=3.1669（11） nm3,Z=8,R=0.0845,wR=0.1829.The crystal structure exhibits a three-dimensional framework which is composed of infinite chains of corner-sharing octahedral Fe（OH）2O4 with 1,4-NDC ligands forming two types of channels with square-shaped cross-sections.The large channels present a cross-section of 0.76 nm×0.76 nm,while the small channels are about 0.30 nm×0.30 nm.No structural transformation occurs after removing the vip water molecules,while a robust structure generates with permanent porosity.The adsorption measurements show that the anhydrous sample of the compound can adsorb CO2 into its pores.The adsorption isotherms for methanol,acetone,tetrahydrofuran and benzene are also measured.展开更多
In this work, a series of MIL-101-SO3H（x） polymeric materials were prepared and further used for the first time as efficient heterogeneous catalysts for the conversion of fructose-based carbohydrates into 5-ethoxyme...In this work, a series of MIL-101-SO3H（x） polymeric materials were prepared and further used for the first time as efficient heterogeneous catalysts for the conversion of fructose-based carbohydrates into 5-ethoxymethylfurfural（EMF） in a renewable mixed solvent system consisting of ethanol and tetrahydrofuran（THF）. The influence of –SO3H content on the acidity as well as on the catalytic activity of the porous coordination polymers in EMF production was also studied. High EMF yields of 67.7% and 54.2% could be successively obtained from fructose and inulin in the presence of MIL-101-SO;H（100） at 130 °C for 15 h.The catalyst could be reused for five times without significant loss of its activity and the recovery process was facile and simple. This work provides a new platform by application of porous coordination polymers（PCPs） for the production of the potential liquid fuel molecule EMF from biomass in a sustainable solvent system.展开更多
Although large amounts of engineered nanomaterials have been used for the arsenic removal, today there still remains several serious impediments to its further application, including consumption of expensive and pure ...Although large amounts of engineered nanomaterials have been used for the arsenic removal, today there still remains several serious impediments to its further application, including consumption of expensive and pure salts, and only application for the removal of inorganic arsenic. In this work, we developed an eco-economic and facile electrochemical method to synthesize iron porous coordination polymers （FePCPs） for the simultaneous removal of inorganic and organic arsenic from natural water.展开更多
Mixed matrix membrane used to selective removal of CO2 was considered as an efficient solution to energy and environmental sustainability. In this study, a MMM that consists of amide functionalized porous coordination...Mixed matrix membrane used to selective removal of CO2 was considered as an efficient solution to energy and environmental sustainability. In this study, a MMM that consists of amide functionalized porous coordination polymer filler（MIL-53-NH2） was successfully prepared, which sharply promotes the CO2/N2 selectivity from 44（neat polymeric membrane） to 75. Remarkably, the positive effect of amide group and nanochannel of MIL-53-NH2 filler was illustrated by decreased selectivity of the MMM with formic acid modified MIL-53-NH2 filler（MIL-53-NHCOH）.展开更多
We have developed porous carbons with various pore sizes from porous coordination polymers(PCPs)with Mg^(2+)and benzene carboxylate linkers.The pore sizes of the porous carbons were tuned systematically according to t...We have developed porous carbons with various pore sizes from porous coordination polymers(PCPs)with Mg^(2+)and benzene carboxylate linkers.The pore sizes of the porous carbons were tuned systematically according to the dimensionality of inorganic building blocks and the metal-oxygen-metal connectivity of the PCP frameworks.展开更多
A porous coordination polymer[(Na_(2)I_(2)CB[6])·8H_(2)O]_(n)(complex 1;CB[6]=cucurbit[6]uril),which absorbs gaseous iodine molecules and forms a polyiodide containing material I_(2)@1,has been prepared and used ...A porous coordination polymer[(Na_(2)I_(2)CB[6])·8H_(2)O]_(n)(complex 1;CB[6]=cucurbit[6]uril),which absorbs gaseous iodine molecules and forms a polyiodide containing material I_(2)@1,has been prepared and used as an absorbent for iodine uptake.The formation of halogen bonds between discrete iodide ions and iodine molecules has been demonstrated as predominant driving forces for iodine adsorption.Moreover,complex 1 demonstrates enhanced electrical conductivity upon iodine uptake,thanks to the formation of the polyiodide structure.This observation indicates that the discrete iodide matrix in the crystal lattice is an ideal and preferential molecular dock for iodine accommodation.展开更多
As an emerging class of crystalline materials,porous coordination polymers(PCPs)with regular and flexible nanopores have become particularly promising for adsorption applications.Here,we report a new method to synthes...As an emerging class of crystalline materials,porous coordination polymers(PCPs)with regular and flexible nanopores have become particularly promising for adsorption applications.Here,we report a new method to synthesize PCPs with varied flexibility by shifting the position of the methyl group,the shortest alkyl chain,around the coordination sites of T-shaped ligands of H_(2)NL^(1)(5-(2′-methyl-imidazol-1-yl)-isophthalic acid)and H_(2)NL^(2)(5-(4′-methyl-imidazol-1-yl)-isophthalic acid).The two generated PCPs(NTU-40 and NTU-41)showed a significant change in gate opening pressure(P/P0:0.25 to 0.0001)under the stimulus of N_(2)at 77 K.In addition,the square window(5×5Å^(2))of the one-dimensional(1D)zigzag channel was divided into two small triangular and straight channels in NTU-41.More importantly,the synergistic effect of structural flexibility,channel type and the micro-pores enabled highly efficient CO_(2)/CH_(4)and C_(2)H_(4)/CH_(4)separation under both equilibrium state and dynamic conditions,as well as having good potential for challenging C_(2)H_(4)/C_(2)H_(6)separation.展开更多
In this work,cerium-based porous coordination polymers(Ce-CPs)with hierarchical superstructures have been successfully synthesized on a large scale employing cerium nitrate as the metal salt and 2,5-pyridinedicarboxyl...In this work,cerium-based porous coordination polymers(Ce-CPs)with hierarchical superstructures have been successfully synthesized on a large scale employing cerium nitrate as the metal salt and 2,5-pyridinedicarboxylic acid(2,5-H2pdc)as the ligand by a mixed-solvothermal route.The as-obtained products were characterized by scanning electron microscopy(SEM),Fourier transform infrared spectroscopy(FTIR),X-ray powder diffraction(XRD),X-ray photoelectron spectroscopy(XPS),thermogravimetry and differential thermal analysis(TG-DTA).It was found that the hierarchical superstructures are composed of asymmetric branches with lengths ranging from 10 to 50μm.The reaction parameters such as reaction temperature,total concentrations of the reactants,solvent composition,and the reaction time were investigated systematically.A possible formation mechanism for the hierarchical superstructures has been proposed to interpret the growth process.CeO_(2)with similar hierarchical structures could be obtained after thermolysis of the Ce-CP precursors at 450℃for 4 h.The UV-vis adsorption spectrum of the obtained CeO_(2)shows that the band gap energy(Eg)is 2.64 eV,which is lower than that of bulk ceria.Moreover,the as-obtained CeO_(2)also exhibited remarkable ability to remove rhodamine B(RhB).展开更多
Water adsorption at room temperature in NOTT-400 was investigated along with its ability to perform CO_(2) capture under relative humidity(RH)conditions.Thus,the CO_(2) capture was increased from 4.2 wt%(anhydrous con...Water adsorption at room temperature in NOTT-400 was investigated along with its ability to perform CO_(2) capture under relative humidity(RH)conditions.Thus,the CO_(2) capture was increased from 4.2 wt%(anhydrous conditions)to 10.2 wt%at 20%RH and 30℃.展开更多
Porous coordination polymers(PCPs)or metal-organic frameworks(MOFs)hold promise as photocatalyst candidates for the remediation of toxic metal ions and organic pollutants.However,they often exhibit inferior removal an...Porous coordination polymers(PCPs)or metal-organic frameworks(MOFs)hold promise as photocatalyst candidates for the remediation of toxic metal ions and organic pollutants.However,they often exhibit inferior removal and catalytic efficiency due to the rapid recombination of photoexcited electrons and holes.This review presents synthetic strategies for MOFs and MOFbased composites and elucidates the underlying mechanisms for the photocatalytic reduction of metal ions and degradation of organic pollutants.Furthermore,this review highlights the opportunities,challenges,and future perspectives of MOFs and MOF composite photocatalysts,aiming to design more innovative MOF-based photocatalytic systems using green and sustainable strategies.It is anticipated that this review will serve as a guide for the systematic development and optimization of highly efficient MOF-based photocatalysts.展开更多
During the last two decades,porous coordination polymers(PCPs),usually called as metal-organic frameworks(MOFs),have been developed rapidly due to their versatile structural diversities and potential physical and chem...During the last two decades,porous coordination polymers(PCPs),usually called as metal-organic frameworks(MOFs),have been developed rapidly due to their versatile structural diversities and potential physical and chemical functions.This article provides a short review of recent advances in the design and constructions of porous coordination polymers based on three planar rigid ligands,including imidazole-4,5-dicarboxlate(H3IDC),1H-tetrazole(HTz),as well as 1H-tetrazole-5-carboxylate(H2Tzc).Their preparations,crystal structures,and desirable properties have been reviewed.展开更多
Recently,research of crystalline-state transformation involving the removal/inclusion of vip molecules in porous coordination polymers(PCPs) was underway.Crystalline-state transformation,especially,single-crystal to...Recently,research of crystalline-state transformation involving the removal/inclusion of vip molecules in porous coordination polymers(PCPs) was underway.Crystalline-state transformation,especially,single-crystal to single-crystal(SC-SC) transformation as new method for the direct observation of host-vip chemistry,can reveal the intrinsic relevance and interaction between the framework and vip molecules.This review describes our work concerning PCPs and recent investigations of others,within the last four years,from the viewpoint of crystalline-state transformations of PCPs on vip removal or inclusion processes.Ligand substitution reaction and postsynthetic modification of PCPs in SC-SC fashion which were distinguished from conventional crystalline-state transformation triggered by vip removal or exchange were highlighted in this review.The research status of crystalline-state transformation in China was briefly introduced as well.Series of structure analysis techniques including single-crystal X-ray diffraction,powder X-ray diffraction,neutron diffraction,inelastic neutron scattering as well as the application of synchrotron radiation light source will inevitably promote the advance of study of crystalline-state transformation.And as a hotspot,deep investigations of crystalline-state transformation also help us to overcome the challenge of achieving multifunction and the correlation among them,such as sorption,magnetism,optical or electrical properties simultaneously in PCPs and contribute to design stimulate-oriented porous intelligent materials in the future.展开更多
Designing efficient proton-conductive materials is crucial in fuel cells.Yet,it remains a substantial challenge because of the issues in proton mobility,proton-carrier amount,and orientation of proton host materials.H...Designing efficient proton-conductive materials is crucial in fuel cells.Yet,it remains a substantial challenge because of the issues in proton mobility,proton-carrier amount,and orientation of proton host materials.Herein,we report an in-situ protonation strategy to produce a locally flexible porous coordination polymer(PCP)to enhance the proton-carrier loading and proton conductivity.The local dipole flipping of the ligand allows effective proton exchange with low activation energy,promoting interpore proton transport through the pore apertures and pore walls.The protonation induces substantial charges to the frameworks and enhances the interaction with proton carriers,thereby increasing the loading of the proton carriers.By this design strategy,the resulting PCP exhibits enhanced phosphoric acid loading and extraordinary proton conductivities under both aqueous and anhydrous conditions compared to its isoreticular analog that features rigidity without proton-exchange capability.Our work provides a new avenue for designing proton-conductive materials that combine structural dynamics with performance merits.展开更多
A novel three-dimensional porous dysprosium coordination polymer{[Dy_(2)L_(2)(bpdo)_(2)(H_(2)O)(CH_(3)OH)]·2ClO4·2CH_(3)CN}_(n)(1)has been successfully assembled by combining a superparamagnetic building blo...A novel three-dimensional porous dysprosium coordination polymer{[Dy_(2)L_(2)(bpdo)_(2)(H_(2)O)(CH_(3)OH)]·2ClO4·2CH_(3)CN}_(n)(1)has been successfully assembled by combining a superparamagnetic building block of[DyLCl(CH_(3)OH)]_(2)with the organic ligand 4,4’-bipyridine-N,N’-dioxide(bpdo)(H_(2)L=N’-(_(2)-hydroxybenzylidene)picolinohydrazide).展开更多
Aqueous zinc ion batteries (AZIBs) have received increasing attention because of their low cost, environmental benefits and material abundance. However, the intercalation of zinc ions in the cathode materials is chall...Aqueous zinc ion batteries (AZIBs) have received increasing attention because of their low cost, environmental benefits and material abundance. However, the intercalation of zinc ions in the cathode materials is challenging and complex. To tackle the above-mentioned issue, we demonstrate an AZIBs system which consists of a porous metal-organic coordination polymers (MOCP) nanosheets cathode, a Zn foil anode, and a ZnSO_(4)/MnSO_(4) solution electrolyte. The zinc cell delivers a high reversible capacity of 240.3 mA h g^(-1) at 150 mA g^(-1) and an excellent capacity retention of approximately 100% over 1500 cycles at 600 mA g^(-1). The superior electrochemical performance is ascribed to the addition of MnSO_(4), which results in the formation of MnO_(2), and the MnO_(2) can enhance the electrochemical performance of the AZIBs. The synergy effects between MOCP and MnO_(2) may open new opportunities for the development of low-cost, high performance rechargeable aqueous batteries.展开更多
A new three-dimensional porous lanthanide coordination polymer{[Dy(L)(μ2-bpdo)0.5(μ_(4)-bpdo)0.5(CH_(3)OH)]·ClO_(4)·3CH_(3)OH}_(n)(2)featuring slow magnetic relaxation has been successfully assembled by re...A new three-dimensional porous lanthanide coordination polymer{[Dy(L)(μ2-bpdo)0.5(μ_(4)-bpdo)0.5(CH_(3)OH)]·ClO_(4)·3CH_(3)OH}_(n)(2)featuring slow magnetic relaxation has been successfully assembled by reacting a superparamagnetic chain complex{[Dy(HL)(H_(2)O)_(2)(CH_(3)OH)_(2)]·2Cl·CH_(3)OH}_(n)(1)with an organic bridging ligand,namely,_(4),_(4)’-bipyridine-N,N’-dioxide(bpdo)(H2L=N’-(2-hydroxybenzylidene)-picolinohydrazide).展开更多
Host-vip engineering of donor-acceptor(D-A)coordination polymer(CP)materials has been proved to be a promising emission modulation strategy for the fabrication of highly tunable luminophores.Herein,it is shown that ...Host-vip engineering of donor-acceptor(D-A)coordination polymer(CP)materials has been proved to be a promising emission modulation strategy for the fabrication of highly tunable luminophores.Herein,it is shown that the fluorescence modulation of host-vip D-A CPs could be achieved through subtle structural engineering.Two isoreticular CPs,{M_(3)(μ_(3)-F)(BDC)_(3)(TPT)(solvents)}_(n)(M=Cd^(2+)for 1 and Zn^(2+)for 2,TPT=2,4,6-tri(4-pyridyl)-1,3,5-triazine,H_(2)BDC=1,4-benzenedicarboxylic acid),were selected as porous host CPs for investigation.By introducing different polyaromatic hydrocarbon(PAH)vips(anthracene;phenanthrene;pyrene;triphenylene;perylene;and coronene)into the host framework,two series of host-vip D-A CPs(PAHs@1 and PAHs@2)were obtained.Detailed investigation indicates that the subtle structural differences originated from the metal center affected D-A interactions between the PAH and TPT ligand,which result in distinct emission properties of PAHs@1 and PAHs@2.These results suggest the potential of structural modulation in the property tuning of the D-A CPs.展开更多
The safe storage and separation of acetylene(C_(2)H_(2))is difficult and essential,due to its explosive properties and wide usage for various industrial products.With a generally low energy cost,highly efficient adsor...The safe storage and separation of acetylene(C_(2)H_(2))is difficult and essential,due to its explosive properties and wide usage for various industrial products.With a generally low energy cost,highly efficient adsorption separation has been considered as a promising solution.Taking advantage of the inbuilt nature of a tunable pore space,a porous coordination polymer(NTU-56)was prepared from a selenium-containing carboxylate ligand and Cu2+ions.Triggered by water at different temperatures,NTU-56 transformed into two other porous frameworks(NTU-57 and NTU-58)with different topologies and pore environments.Single-component gas adsorption experiments showed that this new group of porous isomers featured systematically varied adsorption selectivity for C_(2)H_(2)/CO_(2),two gases that have extremely similar molecular sizes and boiling points.More interestingly,among the isomers,NTU-58,a rare 2D,flexible,and water-stable framework,has the highest C_(2)H_(2) uptake(60 cm^(3) g^(-1))and C_(2)H_(2)/CO_(2) selectivity(13.9,1/1,v/v,1 bar)at 273 K,derived from the synergetic effect of the unique pore sizes(4.5 and 5.5Å)and pore surface polarity,where the Cu^(2+)and selenium sites are exposed for preferred C_(2)H_(2) interactions.Efficient and recyclable C_(2)H_(2)/CO_(2) separation was also confirmed via breakthrough experiments,even with wet feed-gas.展开更多
Metal–organic frameworks(MOFs)represent a unique class of porous materialswith tremendous potential for diverse applications.A key factor contributing totheir versatility is their ability to precisely introduce funct...Metal–organic frameworks(MOFs)represent a unique class of porous materialswith tremendous potential for diverse applications.A key factor contributing totheir versatility is their ability to precisely introduce functional groups at specificpositions within pores and crystals.This review explores two prominent strategiesfor achieving the positional functionalization of MOFs:post-synthetic ligand exchange(PSE)and MOF-on-MOF.In PSE,the existing ligands within solid-stateMOFs can be selectively replaced by the desired functional groups in solutionthrough ligand dynamics.This invasive functionalization provides a flexibleapproach to fine-tuning the surface of the MOFs with the target functionality.Conversely,MOF-on-MOF strategies are additive methodologies involving thecontrolled growth of one MOF layer onto another.The functionality of the core andshell(or surface)can be independently controlled.This review critically examinesthe examples,strengths,limitations,and applications of these strategies,emphasizingtheir significance in advancing the field of MOF functionalization andpaving the way for tailored multifunctional materials with precise and specificproperties.展开更多
Main observation and conclusion Magnifying the controllable directional motions of molecular machines to the macroscopic levels is a significant topic for chemists.Flexible metal–organic frameworks with long-range or...Main observation and conclusion Magnifying the controllable directional motions of molecular machines to the macroscopic levels is a significant topic for chemists.Flexible metal–organic frameworks with long-range order and responsive structural transformation under external stimuli may be an appropriate platform for achieving the target.By taking advantage of the single-crystal to single-crystal manner of soft porous crystals,we utilize single-crystal X-ray diffraction to directly observe the dynamic structural inversion of a new three-fold interpenetrated pillared-layer metal-organic framework[Co(edba)(bpy)](MCF-83,H2edba=4,4’-(ethyne-1,2-diyl)dibenzoic acid,bpy=4,4’-bipyridine).More interestingly,the dynamic inversions of the pillars and layers are selectively vip-controllable and independent,allowing precise control of the directional shape changes,which is the key of constructing intelligent materials to accomplish a complex task.The mechanism is further studied by combining the X-ray diffraction analyses,sorption measurements and molecular simulations.展开更多
基金The Natural Science Foundation of Jiangsu Province(No.BK2009262)the Scientific Research Foundation for the Returned Overseas Chinese Scholars,State Education Ministry
文摘A novel porous coordination polymer,iron naphthalenedicarboxylate Fe（OH）（1,4-NDC）·2H2O is hydrothermally synthesized by the reaction of FeSO4·7H2O and 1,4-naphthalenedicarboxylic acid（1,4-H2NDC） at 150℃.The compound crystallizes in a tetragonal space group P42/nmc：a=2.1447（4） nm,c=0.68849（14） nm,V=3.1669（11） nm3,Z=8,R=0.0845,wR=0.1829.The crystal structure exhibits a three-dimensional framework which is composed of infinite chains of corner-sharing octahedral Fe（OH）2O4 with 1,4-NDC ligands forming two types of channels with square-shaped cross-sections.The large channels present a cross-section of 0.76 nm×0.76 nm,while the small channels are about 0.30 nm×0.30 nm.No structural transformation occurs after removing the vip water molecules,while a robust structure generates with permanent porosity.The adsorption measurements show that the anhydrous sample of the compound can adsorb CO2 into its pores.The adsorption isotherms for methanol,acetone,tetrahydrofuran and benzene are also measured.
基金financially supported by the Natural Science Foundation of China(no.21576059)the Key Technologies R&D Program(no.2011BAE06B02)+1 种基金the International Science&Technology Cooperation Program of China(2010DFB60840)the Science and Technology Project of Guizhou Province(nos.[2012]6012 and[2011]3016)
文摘In this work, a series of MIL-101-SO3H（x） polymeric materials were prepared and further used for the first time as efficient heterogeneous catalysts for the conversion of fructose-based carbohydrates into 5-ethoxymethylfurfural（EMF） in a renewable mixed solvent system consisting of ethanol and tetrahydrofuran（THF）. The influence of –SO3H content on the acidity as well as on the catalytic activity of the porous coordination polymers in EMF production was also studied. High EMF yields of 67.7% and 54.2% could be successively obtained from fructose and inulin in the presence of MIL-101-SO;H（100） at 130 °C for 15 h.The catalyst could be reused for five times without significant loss of its activity and the recovery process was facile and simple. This work provides a new platform by application of porous coordination polymers（PCPs） for the production of the potential liquid fuel molecule EMF from biomass in a sustainable solvent system.
基金the National Natural Science Foundation of China (Nos. 21575092 and 21622508) for financial support
文摘Although large amounts of engineered nanomaterials have been used for the arsenic removal, today there still remains several serious impediments to its further application, including consumption of expensive and pure salts, and only application for the removal of inorganic arsenic. In this work, we developed an eco-economic and facile electrochemical method to synthesize iron porous coordination polymers （FePCPs） for the simultaneous removal of inorganic and organic arsenic from natural water.
基金financial support of the National Natural Science Foundation of China (No. 21671102)Natural Science Foundation of Jiangsu Province (No. BK20161538)+2 种基金Innovative Research Team Program by the Ministry of Education of China (No. IRT17R54)Six Talent Peaks Project in Jiangsu Province (No. JY-030)State Key Laboratory of Materials-Oriented Chemical Engineering (No. ZK201406)
文摘Mixed matrix membrane used to selective removal of CO2 was considered as an efficient solution to energy and environmental sustainability. In this study, a MMM that consists of amide functionalized porous coordination polymer filler（MIL-53-NH2） was successfully prepared, which sharply promotes the CO2/N2 selectivity from 44（neat polymeric membrane） to 75. Remarkably, the positive effect of amide group and nanochannel of MIL-53-NH2 filler was illustrated by decreased selectivity of the MMM with formic acid modified MIL-53-NH2 filler（MIL-53-NHCOH）.
基金supported by the PRESTO of the Japan Science and Technology Agency(JST),a Grant-in-Aid for Scientific Research on the Innovative Areas:“Fusion Materials”Grant-in-Aid for Young Scientists(A)from the Ministry of Education,Culture,Sports,Science and Technology,Japanthe World Premier International Research Center Initiative on Institute for Integrated Cell-Material Sciences(WPI-iCeMS)from MEXT,Japan.
文摘We have developed porous carbons with various pore sizes from porous coordination polymers(PCPs)with Mg^(2+)and benzene carboxylate linkers.The pore sizes of the porous carbons were tuned systematically according to the dimensionality of inorganic building blocks and the metal-oxygen-metal connectivity of the PCP frameworks.
基金financial support from the 973 Program(Grants 2012CB821705 and 2014CB845605)the NSFC(Grants 21401109,21450110413,and 21571177)+1 种基金the Strategic Priority Research Program of the Chinese Academy of Sciences(Grant XDA09030)the State Key Laboratory of Structural Chemistry(Grant 20150023).
文摘A porous coordination polymer[(Na_(2)I_(2)CB[6])·8H_(2)O]_(n)(complex 1;CB[6]=cucurbit[6]uril),which absorbs gaseous iodine molecules and forms a polyiodide containing material I_(2)@1,has been prepared and used as an absorbent for iodine uptake.The formation of halogen bonds between discrete iodide ions and iodine molecules has been demonstrated as predominant driving forces for iodine adsorption.Moreover,complex 1 demonstrates enhanced electrical conductivity upon iodine uptake,thanks to the formation of the polyiodide structure.This observation indicates that the discrete iodide matrix in the crystal lattice is an ideal and preferential molecular dock for iodine accommodation.
基金financial support of the National Natural Science Foundation of China(21671102)the Natural Science Foundation of Jiangsu Province(BK20161538)+2 种基金the Innovative Research Team Program by the Ministry of Education of China(IRT13070)the Six Talent Peaks Project in Jiangsu Province(JY-030)the State Key Laboratory of Materials-Oriented Chemical Engineering(ZK201406).
文摘As an emerging class of crystalline materials,porous coordination polymers(PCPs)with regular and flexible nanopores have become particularly promising for adsorption applications.Here,we report a new method to synthesize PCPs with varied flexibility by shifting the position of the methyl group,the shortest alkyl chain,around the coordination sites of T-shaped ligands of H_(2)NL^(1)(5-(2′-methyl-imidazol-1-yl)-isophthalic acid)and H_(2)NL^(2)(5-(4′-methyl-imidazol-1-yl)-isophthalic acid).The two generated PCPs(NTU-40 and NTU-41)showed a significant change in gate opening pressure(P/P0:0.25 to 0.0001)under the stimulus of N_(2)at 77 K.In addition,the square window(5×5Å^(2))of the one-dimensional(1D)zigzag channel was divided into two small triangular and straight channels in NTU-41.More importantly,the synergistic effect of structural flexibility,channel type and the micro-pores enabled highly efficient CO_(2)/CH_(4)and C_(2)H_(4)/CH_(4)separation under both equilibrium state and dynamic conditions,as well as having good potential for challenging C_(2)H_(4)/C_(2)H_(6)separation.
基金supporting projects from the National Natural Science Foundation of China(No.21201089,21261010,61201104)Jiangxi Provincial Education Department(no.KJLD13021)Jiangxi Provincial Department of Science and Technology(no.20144BCB23039).
文摘In this work,cerium-based porous coordination polymers(Ce-CPs)with hierarchical superstructures have been successfully synthesized on a large scale employing cerium nitrate as the metal salt and 2,5-pyridinedicarboxylic acid(2,5-H2pdc)as the ligand by a mixed-solvothermal route.The as-obtained products were characterized by scanning electron microscopy(SEM),Fourier transform infrared spectroscopy(FTIR),X-ray powder diffraction(XRD),X-ray photoelectron spectroscopy(XPS),thermogravimetry and differential thermal analysis(TG-DTA).It was found that the hierarchical superstructures are composed of asymmetric branches with lengths ranging from 10 to 50μm.The reaction parameters such as reaction temperature,total concentrations of the reactants,solvent composition,and the reaction time were investigated systematically.A possible formation mechanism for the hierarchical superstructures has been proposed to interpret the growth process.CeO_(2)with similar hierarchical structures could be obtained after thermolysis of the Ce-CP precursors at 450℃for 4 h.The UV-vis adsorption spectrum of the obtained CeO_(2)shows that the band gap energy(Eg)is 2.64 eV,which is lower than that of bulk ceria.Moreover,the as-obtained CeO_(2)also exhibited remarkable ability to remove rhodamine B(RhB).
基金Dr A.Tejeda-Cruz(X-ray,IIM-UNAM),CONACyT Mexico(212318)PAPIIT UNAM Mexico(IN100415)for financial support+2 种基金SEP-CONACyT(154626)UNAM-DGAPA-PAPIIT(IG-100315)CONACyT(156801 and 236879),Mexico for financial support.
文摘Water adsorption at room temperature in NOTT-400 was investigated along with its ability to perform CO_(2) capture under relative humidity(RH)conditions.Thus,the CO_(2) capture was increased from 4.2 wt%(anhydrous conditions)to 10.2 wt%at 20%RH and 30℃.
基金supported by the National Natural Science Foundation of China(NSFC-22305212,52371240,U1904215)the Changjiang Scholars Program of the Ministry of Education(Q2018270).
文摘Porous coordination polymers(PCPs)or metal-organic frameworks(MOFs)hold promise as photocatalyst candidates for the remediation of toxic metal ions and organic pollutants.However,they often exhibit inferior removal and catalytic efficiency due to the rapid recombination of photoexcited electrons and holes.This review presents synthetic strategies for MOFs and MOFbased composites and elucidates the underlying mechanisms for the photocatalytic reduction of metal ions and degradation of organic pollutants.Furthermore,this review highlights the opportunities,challenges,and future perspectives of MOFs and MOF composite photocatalysts,aiming to design more innovative MOF-based photocatalytic systems using green and sustainable strategies.It is anticipated that this review will serve as a guide for the systematic development and optimization of highly efficient MOF-based photocatalysts.
文摘During the last two decades,porous coordination polymers(PCPs),usually called as metal-organic frameworks(MOFs),have been developed rapidly due to their versatile structural diversities and potential physical and chemical functions.This article provides a short review of recent advances in the design and constructions of porous coordination polymers based on three planar rigid ligands,including imidazole-4,5-dicarboxlate(H3IDC),1H-tetrazole(HTz),as well as 1H-tetrazole-5-carboxylate(H2Tzc).Their preparations,crystal structures,and desirable properties have been reviewed.
基金supported by the National Natural Science Foundation of China(91022015 & 20871034)Guangxi Science Foundation of China (0832001Z)the Program for New Century Excellent Talents in University of the Ministry of Education of China and Guangxi Province (NCET-07-217,2006201)
文摘Recently,research of crystalline-state transformation involving the removal/inclusion of vip molecules in porous coordination polymers(PCPs) was underway.Crystalline-state transformation,especially,single-crystal to single-crystal(SC-SC) transformation as new method for the direct observation of host-vip chemistry,can reveal the intrinsic relevance and interaction between the framework and vip molecules.This review describes our work concerning PCPs and recent investigations of others,within the last four years,from the viewpoint of crystalline-state transformations of PCPs on vip removal or inclusion processes.Ligand substitution reaction and postsynthetic modification of PCPs in SC-SC fashion which were distinguished from conventional crystalline-state transformation triggered by vip removal or exchange were highlighted in this review.The research status of crystalline-state transformation in China was briefly introduced as well.Series of structure analysis techniques including single-crystal X-ray diffraction,powder X-ray diffraction,neutron diffraction,inelastic neutron scattering as well as the application of synchrotron radiation light source will inevitably promote the advance of study of crystalline-state transformation.And as a hotspot,deep investigations of crystalline-state transformation also help us to overcome the challenge of achieving multifunction and the correlation among them,such as sorption,magnetism,optical or electrical properties simultaneously in PCPs and contribute to design stimulate-oriented porous intelligent materials in the future.
基金supported by the National Natural Science Foundation of China(21975078)the Fundamental Research Funds for the Central Universitiesthe start-up foundation of Sichuan University。
文摘Designing efficient proton-conductive materials is crucial in fuel cells.Yet,it remains a substantial challenge because of the issues in proton mobility,proton-carrier amount,and orientation of proton host materials.Herein,we report an in-situ protonation strategy to produce a locally flexible porous coordination polymer(PCP)to enhance the proton-carrier loading and proton conductivity.The local dipole flipping of the ligand allows effective proton exchange with low activation energy,promoting interpore proton transport through the pore apertures and pore walls.The protonation induces substantial charges to the frameworks and enhances the interaction with proton carriers,thereby increasing the loading of the proton carriers.By this design strategy,the resulting PCP exhibits enhanced phosphoric acid loading and extraordinary proton conductivities under both aqueous and anhydrous conditions compared to its isoreticular analog that features rigidity without proton-exchange capability.Our work provides a new avenue for designing proton-conductive materials that combine structural dynamics with performance merits.
基金supported by the National Natural Science Foundation of China(No 21671024)National Key Basic Research Program of China(2013CB933402).
文摘A novel three-dimensional porous dysprosium coordination polymer{[Dy_(2)L_(2)(bpdo)_(2)(H_(2)O)(CH_(3)OH)]·2ClO4·2CH_(3)CN}_(n)(1)has been successfully assembled by combining a superparamagnetic building block of[DyLCl(CH_(3)OH)]_(2)with the organic ligand 4,4’-bipyridine-N,N’-dioxide(bpdo)(H_(2)L=N’-(_(2)-hydroxybenzylidene)picolinohydrazide).
基金Shandong Province Natural Science Foundation(ZR2012EMM009,ZR2013EMQ005 and ZR2018MEM012)Foundation of Key Laboratory of Pulp and Paper Science and Technology of Ministry of Education/Shandong Province of China(No.KF201602)+2 种基金Scientific Research Foundation for the Returned Overseas Scholars in Jinan(20100406)National Training Program of Innovation and Entrepreneurship for Undergraduates(201610431033 and 201810431008)National Natural Science Foundations of China(31570566,31500489,51372140,51303086,51403111,51503107 and 51172130)。
文摘Aqueous zinc ion batteries (AZIBs) have received increasing attention because of their low cost, environmental benefits and material abundance. However, the intercalation of zinc ions in the cathode materials is challenging and complex. To tackle the above-mentioned issue, we demonstrate an AZIBs system which consists of a porous metal-organic coordination polymers (MOCP) nanosheets cathode, a Zn foil anode, and a ZnSO_(4)/MnSO_(4) solution electrolyte. The zinc cell delivers a high reversible capacity of 240.3 mA h g^(-1) at 150 mA g^(-1) and an excellent capacity retention of approximately 100% over 1500 cycles at 600 mA g^(-1). The superior electrochemical performance is ascribed to the addition of MnSO_(4), which results in the formation of MnO_(2), and the MnO_(2) can enhance the electrochemical performance of the AZIBs. The synergy effects between MOCP and MnO_(2) may open new opportunities for the development of low-cost, high performance rechargeable aqueous batteries.
基金supported by the National Natural Science Foundation of China(No.21671024)the National Key Basic Research Program of China(2013CB933402).We thank Prof.Zhenqiang Wang of the University of South Dakota for helpful comments.
文摘A new three-dimensional porous lanthanide coordination polymer{[Dy(L)(μ2-bpdo)0.5(μ_(4)-bpdo)0.5(CH_(3)OH)]·ClO_(4)·3CH_(3)OH}_(n)(2)featuring slow magnetic relaxation has been successfully assembled by reacting a superparamagnetic chain complex{[Dy(HL)(H_(2)O)_(2)(CH_(3)OH)_(2)]·2Cl·CH_(3)OH}_(n)(1)with an organic bridging ligand,namely,_(4),_(4)’-bipyridine-N,N’-dioxide(bpdo)(H2L=N’-(2-hydroxybenzylidene)-picolinohydrazide).
基金supported by the National Natural Science Foundation of China(22005153)Haihe Laboratory of Sustainable Chemical Transformations(No.YYJC202101).
文摘Host-vip engineering of donor-acceptor(D-A)coordination polymer(CP)materials has been proved to be a promising emission modulation strategy for the fabrication of highly tunable luminophores.Herein,it is shown that the fluorescence modulation of host-vip D-A CPs could be achieved through subtle structural engineering.Two isoreticular CPs,{M_(3)(μ_(3)-F)(BDC)_(3)(TPT)(solvents)}_(n)(M=Cd^(2+)for 1 and Zn^(2+)for 2,TPT=2,4,6-tri(4-pyridyl)-1,3,5-triazine,H_(2)BDC=1,4-benzenedicarboxylic acid),were selected as porous host CPs for investigation.By introducing different polyaromatic hydrocarbon(PAH)vips(anthracene;phenanthrene;pyrene;triphenylene;perylene;and coronene)into the host framework,two series of host-vip D-A CPs(PAHs@1 and PAHs@2)were obtained.Detailed investigation indicates that the subtle structural differences originated from the metal center affected D-A interactions between the PAH and TPT ligand,which result in distinct emission properties of PAHs@1 and PAHs@2.These results suggest the potential of structural modulation in the property tuning of the D-A CPs.
基金the National Natural Science Foundation of China(21671102,21973029)the Young and Middle-aged Academic Leader of Jiangsu Blue Project,the State Key Laboratory of Materials-Oriented Chemical Engineering(ZK201803)the Hunan Provincial Natural Science Foundation of China(2020JJ4290).
文摘The safe storage and separation of acetylene(C_(2)H_(2))is difficult and essential,due to its explosive properties and wide usage for various industrial products.With a generally low energy cost,highly efficient adsorption separation has been considered as a promising solution.Taking advantage of the inbuilt nature of a tunable pore space,a porous coordination polymer(NTU-56)was prepared from a selenium-containing carboxylate ligand and Cu2+ions.Triggered by water at different temperatures,NTU-56 transformed into two other porous frameworks(NTU-57 and NTU-58)with different topologies and pore environments.Single-component gas adsorption experiments showed that this new group of porous isomers featured systematically varied adsorption selectivity for C_(2)H_(2)/CO_(2),two gases that have extremely similar molecular sizes and boiling points.More interestingly,among the isomers,NTU-58,a rare 2D,flexible,and water-stable framework,has the highest C_(2)H_(2) uptake(60 cm^(3) g^(-1))and C_(2)H_(2)/CO_(2) selectivity(13.9,1/1,v/v,1 bar)at 273 K,derived from the synergetic effect of the unique pore sizes(4.5 and 5.5Å)and pore surface polarity,where the Cu^(2+)and selenium sites are exposed for preferred C_(2)H_(2) interactions.Efficient and recyclable C_(2)H_(2)/CO_(2) separation was also confirmed via breakthrough experiments,even with wet feed-gas.
基金supported by the National Research Foundation of Korea(NRF)funded by the Ministry of Science and ICT(2022R1A2C1009706).
文摘Metal–organic frameworks(MOFs)represent a unique class of porous materialswith tremendous potential for diverse applications.A key factor contributing totheir versatility is their ability to precisely introduce functional groups at specificpositions within pores and crystals.This review explores two prominent strategiesfor achieving the positional functionalization of MOFs:post-synthetic ligand exchange(PSE)and MOF-on-MOF.In PSE,the existing ligands within solid-stateMOFs can be selectively replaced by the desired functional groups in solutionthrough ligand dynamics.This invasive functionalization provides a flexibleapproach to fine-tuning the surface of the MOFs with the target functionality.Conversely,MOF-on-MOF strategies are additive methodologies involving thecontrolled growth of one MOF layer onto another.The functionality of the core andshell(or surface)can be independently controlled.This review critically examinesthe examples,strengths,limitations,and applications of these strategies,emphasizingtheir significance in advancing the field of MOF functionalization andpaving the way for tailored multifunctional materials with precise and specificproperties.
基金supported by NSFC(Nos.22090061,21731007,21821003&22001160)Local Innovative and Research Teams Project of Guangdong Pearl River Talents Program(No.2017BT01C161).
文摘Main observation and conclusion Magnifying the controllable directional motions of molecular machines to the macroscopic levels is a significant topic for chemists.Flexible metal–organic frameworks with long-range order and responsive structural transformation under external stimuli may be an appropriate platform for achieving the target.By taking advantage of the single-crystal to single-crystal manner of soft porous crystals,we utilize single-crystal X-ray diffraction to directly observe the dynamic structural inversion of a new three-fold interpenetrated pillared-layer metal-organic framework[Co(edba)(bpy)](MCF-83,H2edba=4,4’-(ethyne-1,2-diyl)dibenzoic acid,bpy=4,4’-bipyridine).More interestingly,the dynamic inversions of the pillars and layers are selectively vip-controllable and independent,allowing precise control of the directional shape changes,which is the key of constructing intelligent materials to accomplish a complex task.The mechanism is further studied by combining the X-ray diffraction analyses,sorption measurements and molecular simulations.
