A lactam-functionalized copper bent diisophthalate framework displaying significantly enhanced adsorption of CO2 and C2H2 over CH4.

The design and construction of porous materials for high-efficient adsorption-based separation of CH4 from C2H2 and CO2 is a fundamental goal in the chemical industry. In this work, a lactam-functionalized bent diisophthalate linker, 5,5'-(1-methylpyridin-2(1H)-one-3,5-diyl) diisophthalic acid, was judiciously designed and utilized to construct a dicopper paddlewheel-based MOF under solvothermal conditions. Single-crystal X-ray diffraction revealed that the resulting solid is a three-dimensional mfj-type network incorporating Lewis-acidic copper sites and accessible lactam groups as two different kinds of functional sites. Furthermore, gas adsorption studies indicated that the material exhibited great promise for C2H2/CH4 and CO2/CH4 separations. In particular, compared to the unmodified parent compound, the resultant MOF exhibits 9.4% and 12.9% higher C2H2 and CO2 uptake capacities and 48.0% and 28.3% higher C2H2/CH4 and CO2/CH4 adsorption selectivities for the equimolar gas mixtures at 298 K and 1 atm, despite the lower specific surface area and pore volume. This work reported the first lactam-functionalized MOF displaying significantly enhanced adsorption of CO2 and C2H2 over CH4.

[1]  Huabin Xing,et al.  A Microporous Metal-Organic Framework Supramolecularly Assembled from a CuII Dodecaborate Cluster Complex for Selective Gas Separation. , 2019, Angewandte Chemie.

[2]  Ming-Hua He,et al.  Incorporation of bifunctional aminopyridine into an NbO-type MOF for the markedly enhanced adsorption of CO2 and C2H2 over CH4 , 2019, Inorganic Chemistry Frontiers.

[3]  Yanli Zhao,et al.  Click chemistry as a versatile reaction for construction and modification of metal-organic frameworks , 2019, Coordination Chemistry Reviews.

[4]  Yao Wang,et al.  A ligand conformation preorganization approach to construct a copper–hexacarboxylate framework with a novel topology for selective gas adsorption , 2019, Inorganic Chemistry Frontiers.

[5]  Wenjing Wang,et al.  Regulating C2H2 and CO2 Storage and Separation through Pore Environment Modification in a Microporous Ni-MOF , 2018, ACS Sustainable Chemistry & Engineering.

[6]  Guanghua Li,et al.  Two Stable Zn-Cluster-Based Metal-Organic Frameworks with Breathing Behavior: Synthesis, Structure, and Adsorption Properties. , 2018, Inorganic chemistry.

[7]  C. Su,et al.  Metal Effects on the Framework Stability and Adsorption Property of a Series of Isoreticular Metal–Organic Frameworks Based on an in-Situ Generated T-Shaped Ligand , 2018, Crystal Growth & Design.

[8]  Yaoyu Wang,et al.  Stable Indium-Pyridylcarboxylate Framework: Selective Gas Capture and Sensing of Fe3+ Ion in Water. , 2018, Inorganic chemistry.

[9]  Yaoyu Wang,et al.  A NbO-type MOF based on an aromatic-rich and N-functionalized diisophthalate ligand for high-performance acetylene storage and purification , 2018 .

[10]  Yingying Zhang,et al.  Two NbO-type MOFs based on linear and zigzag diisophthalate ligands: exploring the effect of ligand-originated MOF isomerization on gas adsorption properties , 2018 .

[11]  Zhangjing Zhang,et al.  Robustness, Selective Gas Separation, and Nitrobenzene Sensing on Two Isomers of Cadmium Metal-Organic Frameworks Containing Various Metal-O-Metal Chains. , 2018, Inorganic chemistry.

[12]  Yao Wang,et al.  Three isoreticular ssa-type MOFs derived from bent diisophthalate ligands: exploring the substituent effect on structural stabilities and selective C2H2/CH4 and CO2/CH4 adsorption properties. , 2018, Dalton transactions.

[13]  Banglin Chen,et al.  Highly selective room temperature acetylene sorption by an unusual triacetylenic phosphine MOF. , 2018, Chemical communications.

[14]  R. Krishna,et al.  Nickel-4'-(3,5-dicarboxyphenyl)-2,2',6',2″-terpyridine Framework: Efficient Separation of Ethylene from Acetylene/Ethylene Mixtures with a High Productivity. , 2018, Inorganic chemistry.

[15]  Yao Wang,et al.  Three ligand-originated MOF isomers: the positional effect of the methyl group on structures and selective C2H2/CH4 and CO2/CH4 adsorption properties. , 2018, Dalton transactions.

[16]  Yaoyu Wang,et al.  Three isoreticular MOFs derived from nitrogen-functionalized diisophthalate ligands: exploring the positional effect of nitrogen functional sites on the structural stabilities and selective C2H2/CH4 and CO2/CH4 adsorption properties , 2018 .

[17]  R. Krishna,et al.  Exploring the Effect of Ligand-Originated MOF Isomerism and Methoxy Group Functionalization on Selective Acetylene/Methane and Carbon Dioxide/Methane Adsorption Properties in Two NbO-Type MOFs. , 2018, ACS applied materials & interfaces.

[18]  Yao Wang,et al.  A metal-organic framework based on a custom-designed diisophthalate ligand exhibiting excellent hydrostability and highly selective adsorption of C2H2 and CO2 over CH4. , 2018, Dalton transactions.

[19]  Yao Wang,et al.  Selective adsorption of C2H2 and CO2 from CH4 in an isoreticular series of MOFs constructed from unsymmetrical diisophthalate linkers and the effect of alkoxy group functionalization on gas adsorption , 2018 .

[20]  Yingying Zhang,et al.  Rational construction of an ssa-type of MOF through pre-organizing the ligand's conformation and its exceptional gas adsorption properties. , 2018, Dalton transactions.

[21]  Yao Wang,et al.  A pair of polymorphous metal-organic frameworks based on an angular diisophthalate linker: synthesis, characterization and gas adsorption properties. , 2018, Dalton transactions.

[22]  Yanxi Tan,et al.  Tetrahedral crosslinking of dia-type nets into a zeolitic GIS-type framework for optimizing stability and gas sorption , 2017 .

[23]  J. Bai,et al.  Amide-functionalized metal–organic frameworks: Syntheses, structures and improved gas storage and separation properties , 2017, Coordination Chemistry Reviews.

[24]  Arun Pal,et al.  A Water-Stable Twofold Interpenetrating Microporous MOF for Selective CO2 Adsorption and Separation. , 2017, Inorganic chemistry.

[25]  Yao Wang,et al.  A family of ssa-type copper-based MOFs constructed from unsymmetrical diisophthalates: synthesis, characterization and selective gas adsorption , 2017 .

[26]  Wei Zhou,et al.  Porous metal–organic frameworks for fuel storage , 2017, Coordination Chemistry Reviews.

[27]  Yabing He,et al.  A rare Pb9 cluster-organic framework constructed from a flexible cyclotriphosphazene-functionalized hexacarboxylate exhibiting selective gas separation , 2017 .

[28]  Yao Wang,et al.  A comparative study of C2H2 adsorption properties in five isomeric copper-based MOFs based on naphthalene-derived diisophthalates. , 2017, Dalton transactions.

[29]  Yabing He,et al.  A porous metal-organic framework based on an asymmetric angular diisophthalate for selective adsorption of C2H2 and CO2 over CH4. , 2017, Dalton transactions.

[30]  Xia Wang,et al.  A comparative study of the effect of functional groups on C2H2 adsorption in NbO-type metal–organic frameworks , 2017 .

[31]  Jinchi Zhang,et al.  A new mfj-type metal–organic framework constructed from a methoxyl derived V-shaped ligand and its H2, CO2 and CH4 adsorption properties , 2017 .

[32]  Genfeng Feng,et al.  Polar Ketone-Functionalized Metal-Organic Framework Showing a High CO2 Adsorption Performance. , 2017, Inorganic chemistry.

[33]  Yufeng Wu,et al.  Water-Stable In(III)-Based Metal-Organic Frameworks with Rod-Shaped Secondary Building Units: Single-Crystal to Single-Crystal Transformation and Selective Sorption of C2H2 over CO2 and CH4. , 2017, Inorganic chemistry.

[34]  Daofeng Sun,et al.  A multi-aromatic hydrocarbon unit induced hydrophobic metal–organic framework for efficient C2/C1 hydrocarbon and oil/water separation , 2017 .

[35]  Chao Zou,et al.  Doubly Interpenetrated Metal–Organic Framework for Highly Selective C 2 H 2 /CH 4 and C 2 H 2 /CO 2 Separation at Room Temperature , 2016 .

[36]  X. You,et al.  Finely tuning MOFs towards high performance in C2H2 storage: synthesis and properties of a new MOF-505 analogue with an inserted amide functional group. , 2016, Chemical communications.

[37]  M. O'keeffe,et al.  UTSA-74: A MOF-74 Isomer with Two Accessible Binding Sites per Metal Center for Highly Selective Gas Separation. , 2016, Journal of the American Chemical Society.

[38]  Fei Meng,et al.  The Utilization of Amide Groups To Expand and Functionalize Metal-Organic Frameworks Simultaneously. , 2016, Chemistry.

[39]  Fei Wang,et al.  A pillared-layer framework with high uptake and selective sorption of light hydrocarbons. , 2016, Dalton transactions.

[40]  R. Krishna,et al.  Extraordinary Separation of Acetylene-Containing Mixtures with Microporous Metal-Organic Frameworks with Open O Donor Sites and Tunable Robustness through Control of the Helical Chain Secondary Building Units. , 2016, Chemistry.

[41]  Zu-Jin Lin,et al.  Water-Stable Anionic Metal-Organic Framework for Highly Selective Separation of Methane from Natural Gas and Pyrolysis Gas. , 2016, ACS applied materials & interfaces.

[42]  Nicolaas A. Vermeulen,et al.  Non-Interpenetrated Metal-Organic Frameworks Based on Copper(II) Paddlewheel and Oligoparaxylene-Isophthalate Linkers: Synthesis, Structure, and Gas Adsorption. , 2016, Journal of the American Chemical Society.

[43]  T. Yildirim,et al.  A NbO-type metal-organic framework exhibiting high deliverable capacity for methane storage. , 2015, Chemical communications.

[44]  W. Jin,et al.  Natural gas purification using a porous coordination polymer with water and chemical stability. , 2015, Inorganic chemistry.

[45]  Xuebo Zhao,et al.  Enhanced uptake and selectivity of CO(2) adsorption in a hydrostable metal-organic frameworks via incorporating methylol and methyl groups. , 2014, ACS applied materials & interfaces.

[46]  Zhijuan Zhang,et al.  High storage capacity and separation selectivity for C2 hydrocarbons over methane in the metal–organic framework Cu–TDPAT , 2014 .

[47]  Fei Wang,et al.  Porous anionic indium-organic framework with enhanced gas and vapor adsorption and separation ability. , 2014, ChemSusChem.

[48]  Yi Li,et al.  An N-rich metal-organic framework with an rht topology: high CO2 and C2 hydrocarbons uptake and selective capture from CH4. , 2014, Chemical communications.

[49]  A. Nalaparaju,et al.  "Click"-extended nitrogen-rich metal-organic frameworks and their high performance in CO2-selective capture. , 2014, Chemical communications.

[50]  Hong‐Cai Zhou,et al.  Isostructural metal-organic frameworks assembled from functionalized diisophthalate ligands through a ligand-truncation strategy. , 2013, Chemistry.

[51]  Yongxin Li,et al.  A Rationally Designed Nitrogen-Rich Metal-Organic Framework and Its Exceptionally High CO2 and H2 Uptake Capability , 2013, Scientific Reports.

[52]  Jing Li,et al.  MOFs for CO2 capture and separation from flue gas mixtures: the effect of multifunctional sites on their adsorption capacity and selectivity. , 2013, Chemical communications.

[53]  W. Zhou,et al.  Microporous metal-organic frameworks for storage and separation of small hydrocarbons. , 2012, Chemical communications.

[54]  Yanli Zhao,et al.  Significant gas uptake enhancement by post-exchange of zinc(II) with copper(II) within a metal-organic framework. , 2012, Chemical communications.

[55]  Hong-Cai Zhou,et al.  Metal-organic frameworks for separations. , 2012, Chemical reviews.

[56]  Kenji Sumida,et al.  Carbon dioxide capture in metal-organic frameworks. , 2012, Chemical reviews.

[57]  Jing Li,et al.  Enhanced binding affinity, remarkable selectivity, and high capacity of CO2 by dual functionalization of a rht-type metal-organic framework. , 2012, Angewandte Chemie.

[58]  R. Krishna,et al.  A microporous metal-organic framework for highly selective separation of acetylene, ethylene, and ethane from methane at room temperature. , 2012, Chemistry.

[59]  M. Fröba,et al.  An interpenetrated metal-organic framework and its gas storage behavior: simulation and experiment. , 2011, Inorganic chemistry.

[60]  J. Navarro,et al.  Cation-exchange porosity tuning in anionic metal-organic frameworks for the selective separation of gases and vapors and for catalysis. , 2010, Angewandte Chemie.

[61]  Jie‐Peng Zhang,et al.  Optimized acetylene/carbon dioxide sorption in a dynamic porous crystal. , 2009, Journal of the American Chemical Society.

[62]  Anthony L. Spek,et al.  Structure validation in chemical crystallography , 2009, Acta crystallographica. Section D, Biological crystallography.

[63]  S. Kitagawa,et al.  Storage and sorption properties of acetylene in jungle-gym-like open frameworks. , 2008, Chemistry, an Asian journal.

[64]  Yinyong Sun,et al.  Microporous magnesium and manganese formates for acetylene storage and separation. , 2007, Chemistry, an Asian journal.

[65]  Y. Kawazoe,et al.  Highly controlled acetylene accommodation in a metal–organic microporous material , 2005, Nature.

[66]  A. Spek.  PLATON SQUEEZE: a tool for the calculation of the disordered solvent contribution to the calculated structure factors. , 2015, Acta crystallographica. Section C, Structural chemistry.

[67]  Alan L. Myers,et al.  Thermodynamics of mixed‐gas adsorption , 1965 .