Flexibility in metal-organic framework materials: Impact on sorption properties

Recent years have seen the development of a new class of porous coordination polymers known collectively as metal organic framework materials (MOFs). This review outlines recent progress in understanding how adsorption characteristics of these systems differ from rigid classical sorbents such as activated carbon and zeolites. Gas/vapor adsorption studies for characterization of the porous structures of MOF materials are reviewed and differences in adsorption characteristics based on detailed measurement of equilibrium and dynamical sorption behavior, compared with previous generations of sorbents, are highlighted. The role of framework flexibility and specific structural features, such as windows and pore cavities, within the MOF porous structures are discussed in relation to adsorption mechanisms.     

Selective gas sorption within a dynamic metal-organic framework

A microporous metal-organic framework 1 Co(NDC)(4,4'-Bipy)(0.5).G(x) (NDC = 2,6-naphthalenedicarboxylate; 4,4'-Bipy = 4,4'-bipyridine; G = guest molecules) was synthesized and structurally characterized of a doubly interpenetrated primitive cubic net. To make use of the framework flexibility, 1 was activated at temperatures of 150 and 200 degrees C to form 1a and 1b, respectively, exhibiting highly selective sorption behaviors of hydrogen over nitrogen-gas molecules.     

Flexible sorption and transformation behavior in a microporous metal-organic framework

Crystals of the metal-organic framework material Ni(2)(4,4'-bipyridine)(3)(NO(3))(4) (A) have been grown by reaction of Ni(NO(3))(2).6H(2)O and 4,4'-bipyridine in methanol solution. Single-crystal X-ray diffraction experiments show that the ladder structure of the framework is maintained after desolvation of the material, resulting in the production of a porous solid stable to 215(4) degrees C. Powder X-ray diffraction has been employed to confirm the bulk purity and temperature stability of this material. The crystal structure indicates that the pore window has an area of 12.3 A(2). However, sorption experiments show these windows will admit toluene, which has a minimum cross-sectional area of 26.6 A(2), with no significant change in the structure. Monte Carlo docking calculations show that toluene can be accommodated within the large pores of the structure. Exposure of the related microporous material Ni(2)(4,4'-bipyridine)(3)(NO(3))(4).2C(2)H(5)OH (B) to methanol vapor causes a guest-driven solid-state transformation to A which is observed using powder X-ray diffraction. This structural rearrangement proceeds directly from crystalline B to crystalline A and is complete in less than 1 day. Mechanisms for the transformation are proposed which require breaking of at least one in six of the covalent bonds that confer rigidity on the framework.     

Enantioselective sorption of alcohols in a homochiral metal-organic framework

Single-crystal X-ray diffraction study reveals the host-guest interactions between a homochiral metal-organic framework and two enantiomers of a chiral alcohol providing the key driving force for the enantioselective sorption of alcohols in the framework.     

Porous metal-organic framework based on mu4-oxo tetrazinc clusters: sorption and guest-dependent luminescent properties

A three-dimensional, highly porous metal-organic framework [Zn 4O(bdc)(bpz) 2].4DMF.6H 2O ( 1) (bdc = 1,4-benzenedicarboxylate, bpz = 3,3',5,5'-tetramethyl-4,4'-bipyrazolate) constructed by Zn 4O clusters with bdc and bpz linkers, has been prepared and structurally characterized. The N 2 sorption measurements reveal that 1 exhibits high porosity with a Langmuir surface area of 1908 m (2)/g and a pore volume of 0.58 cm (3)/g. Compound 1 features hydrophobic channels with a free passage of approximately 8.2 A defined by the methyl groups from bpz, and it exhibits nice sorption capability for benzene and toluene and interesting two-step sorption behavior for methanol. Meanwhile, 1 also exhibits interesting guest-dependent luminescent properties.     

A three-dimensional microporous metal-organic framework with large hydrogen sorption hysteresis

A three-dimensional microporous metal-organic framework [Cd(2)(Tzc)(2)](n), which is dehydrated from [Cd(2)(Tzc)(2)(H(2)O)(2)](n), exhibits selective gas adsorption and large hydrogen sorption hysteresis.     

Hydrogen adsorption in a highly stable porous rare-earth metal-organic framework: sorption properties and neutron diffraction studies

A highly stable porous lanthanide metal-organic framework, Y(BTC)(H2O).4.3H2O (BTC = 1,3,5-benzenetricarboxylate), with pore size of 5.8 A has been constructed and investigated for hydrogen storage. Gas sorption measurements show that this porous MOF exhibits highly selective sorption behaviors of hydrogen over nitrogen gas molecules and can take up hydrogen of about 2.1 wt % at 77 K and 10 bar. Difference Fourier analysis of neutron powder diffraction data revealed four distinct D2 sites that are progressively filled within the nanoporous framework. Interestingly, the strongest adsorption sites identified are associated with the aromatic organic linkers rather than the open metal sites, as occurred in previously reported MOFs. Our results provide for the first time direct structural evidence demonstrating that optimal pore size (around 6 A, twice the kinetic diameter of hydrogen) strengthens the interactions between H2 molecules and pore walls and increases the heat of adsorption, which thus allows for enhancing hydrogen adsorption from the interaction between hydrogen molecules with the pore walls rather than with the normally stronger adsorption sites (the open metal sites) within the framework. At high concentration H2 loadings (5.5 H2 molecules (3.7 wt %) per Y(BTC) formula), H2 molecules form highly symmetric novel nanoclusters with relatively short H2-H2 distances compared to solid H2. These observations are important and hold the key to optimizing this new class of rare metal-organic framework (RMOF) materials for practical hydrogen storage applications.     

Understanding hydrogen sorption in a polar metal-organic framework with constricted channels

A high fidelity molecular model is developed for a metal-organic framework (MOF) with narrow (approximately 7.3 A?) nearly square channels. MOF potential models, both with and neglecting explicit polarization, are constructed. Atomic partial point charges for simulation are derived from both fragment-based and fully periodic electronic structure calculations. The molecular models are designed to accurately predict and retrodict material gas sorption properties while assessing the role of induction for molecular packing in highly restricted spaces. Thus, the MOF is assayed via grand canonical Monte Carlo (GCMC) for its potential in hydrogen storage. The confining channels are found to typically accommodate between two to three hydrogen molecules in close proximity to the MOF framework at or near saturation pressures. Further, the net attractive potential energy interactions are dominated by van der Waals interactions in the highly polar MOF - induction changes the structure of the sorbed hydrogen but not the MOF storage capacity. Thus, narrow channels, while providing reasonably promising isosteric heat values, are not the best choice of topology for gas sorption applications from both a molecular and gravimetric perspective.     

Porous metal-organic framework with coordinatively unsaturated Mn(II) sites:sorption properties for various gases

A 3D porous metal-organic framework generating 1D channels, [Mn(NDC)(DEF)]n (1), has been prepared from the solvothermal reaction of Mn(II) and 2,6-naphthalenedicarboxylic acid (H2NDC) in diethylformamide (DEF). When DEF molecules coordinating Mn(II), which occupy the channels, are removed from 1 by heating the crystal of 1 at 250 degrees C under vacuum for 18 h, structural change occurs as evidenced by X-ray powder diffraction patterns. Desolvated solid [Mn(NDC)]n (2), which contains coordinatively unsaturated Mn(II) sites, reveals remarkable sorption capabilities for N2, H2, CO2, and CH4 gases and exhibits type I sorption behavior indicative of permanent microporosity.     

A triply interpenetrated microporous metal-organic framework for selective sorption of gas molecules

A microporous metal-organic framework Zn(ADC)(4,4'-Bpe)(0.5).xG [1; ADC = 4,4'-azobenzenedicarboxylate, 4,4'-Bpe = trans-bis(4-pyridyl)ethylene, G = guest molecules] with a triply interpenetrative primitive cubic net was synthesized and characterized. With pores of about 3.4 x 3.4 A, the activated 1a exhibits highly selective sorption behavior toward H(2)/N(2), H(2)/CO, and CO(2)/CH(4).     

Microporous manganese formate: a simple metal-organic porous material with high framework stability and highly selective gas sorption properties

Novel microporous metal-organic framework material composed of Mn(II) and formate ions displays permanent porosity, high thermal stability, and size-selective gas sorption behavior. The framework is stable enough to maintain single crystallinity after the complete guest removal at 150 degrees C under a reduced pressure. Most importantly, it selectively adsorbs H2 and CO2 but not N2 and other gases with larger kinetic diameters, which appears to be due to the small aperture of the channels. Despite a moderate H2 storage capacity, which is however still higher than that of any zeolite, its H2 surface coverage is one of the highest among the known microporous materials. Thus this new zeolite-like material made of a simple organic building block may find useful applications in gas separation and sensor.     

Microporous sensor: gas sorption, guest exchange and guest-dependant luminescence of metal-organic framework

Zn(II)-containing metal-organic framework (MOF) [Zn(4)(dmf)(ur)(2)(ndc)(4)] (ndc(2-) = 2,6-naphtalenedicarboxylate, ur = urotropin, dmf = N,N'-dimethylformamide) was synthesized and characterized by X-ray crystallography and gas sorption analysis. Host MOF retains its crystallinity after guest removal and exchange. Single-crystal to single-crystal formation of different host-guest systems with benzene and ferrocene was investigated. Interesting guest-depended luminescence properties of the porous host framework were observed.     

Polysulfide chalcogels with ion-exchange properties and highly efficient mercury vapor sorption

We report the synthesis of metal-chalcogenide aerogels from Pt(2+) and polysulfide clusters ([S(x)](2-), x = 3-6). The cross-linking reaction of these ionic building blocks in formamide solution results in spontaneous gelation and eventually forms a monolithic dark brown gel. The wet gel is transformed into a highly porous aerogel by solvent exchanging and subsequent supercritical drying with CO(2). The resulting platinum polysulfide aerogels possess a highly porous and amorphous structure with an intact polysulfide backbone. These chalcogels feature an anionic network that is charged balanced with potassium cations, and hosts highly accessible S-S bonding sites, which allows for reversible cation exchange and mercury vapor capture that is superior to any known material.     

Benzene-templated hydrothermal synthesis of metal-organic frameworks with selective sorption properties

In this paper, we report two metal-organic frameworks [Co3(ndc)3(bipyen)(1.5)]H2O (1) and [Co2(ndc)2bipyen)]C6H6.H2O (2) (bipyen=trans-1,2-bis(4-pyridyl)ethylene, H2ndc=2,6-naphthalenedicarboxylic acid). These compounds were both synthesized from identical hydrothermal reaction conditions except that benzene was added to the reaction for 2. Crystal structures show that the two compounds have triply interpenetrated three-dimensional frameworks and these frameworks have the same primary structure of a two-dimensional network of interconnected [Co2(O2CR)(4/2)] (R=naphthalene group) paddle-wheels and bridging bipyen ligands. Both compounds have guest water molecules and, in addition, 2 has guest benzene molecules. Structural transformations of the host accompanied guest removal, which can be monitored by powder X-ray diffraction. N2 adsorption data of 2 show that there are two different types of pores corresponding to the benzene and water pores. Upon exposure to vapors of several organic molecules, the heat-treated sample of 2 adsorbs benzene and cyclohexene, but does not adsorb toluene, (o-, m-, and p-)xylenes, cycloheptatriene, or cyclohexane.     

Rationally designed micropores within a metal-organic framework for selective sorption of gas molecules

A microporous metal-organic framework, MOF, Cu(FMA)(4,4'-Bpe)0.5 (3a, FMA = fumarate; 4,4'-Bpe = 4,4'-Bpe = trans-bis(4-pyridyl)ethylene) was rationally designed from a primitive cubic net whose pores are tuned by double framework interpenetration. With pore cavities of about 3.6 A, which are interconnected by pore windows of 2.0 x 3.2 A, 3a shows highly selective sorption behaviors of gas molecules.     

Pore partition effect on gas sorption properties of an anionic metal-organic framework with exposed Cu2+ coordination sites

Presented here is an anionic nanoporous framework material with mobile guest cations which can perform ion exchanges with different tetraalkylammonium cations, and the resulting tunable pore structures exhibit interesting pore partition effects on gas storage and separation.     

金属有机骨架HKUST-1及其衍生材料在催化中的应用进展

金属有机骨架材料(MOFs)作为异相催化剂受到了日益广泛的关注。在众多经典MOFs结构中,HKUST-1及其衍生材料是研究最多的类型之一。HKUST-1具有原料简单、易于合成、结构稳定、孔隙率高等多种优点,在异相催化领域中具有广阔的应用前景。已有多种HKUST-1相关材料被用作催化剂,包括HKUST-1本身、缺陷型结构、负载活性客体分子的复合型材料以及HKUST-1衍生的多孔碳纳米材料等。本文围绕HKUST-1作为催化剂的结构设计以及在不同催化反应中的应用展开总结与介绍,以期为相关MOFs材料的设计和催化研究提供一定参考。     

The first metal-organic framework (MOF) of Imazethapyr and its SHG, piezoelectric and ferroelectric properties

Hydrothermal reaction of H-Imazethapyr (2-(4,5-dihydro-4-methyl-4-(1-methylethyl)-5-oxo-1H-imidazol-2-yl)-5-ethyl-3-pyridinecarboxylic acid) with Cd(ClO4)2.6H2O offers a diamond-like MOF Cd(Imazethapyr)2 in which it crystallizes in a non-centrosymmetric space group (Fdd2) belonging to polar point group (C2v). MOF displays a strong SHG response, and good ferroelectric and piezoelectric properties.