WO2013058844A1 - Système et procédé de génération et/ou de criblage de réseaux métallo-organiques potentiels - Google Patents

Système et procédé de génération et/ou de criblage de réseaux métallo-organiques potentiels Download PDF

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WO2013058844A1
WO2013058844A1 PCT/US2012/045782 US2012045782W WO2013058844A1 WO 2013058844 A1 WO2013058844 A1 WO 2013058844A1 US 2012045782 W US2012045782 W US 2012045782W WO 2013058844 A1 WO2013058844 A1 WO 2013058844A1
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building blocks
mofs
potential
mof
organic
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PCT/US2012/045782
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Christopher E. Wilmer
Michael Leaf
Randall Q. Snurr
Omar K. Farha
Joseph T. Hupp
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Northwestern University
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Priority claimed from US13/543,283 external-priority patent/US8900352B2/en
Publication of WO2013058844A1 publication Critical patent/WO2013058844A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F1/00—Compounds containing elements of Groups 1 or 11 of the Periodic System
    • C07F1/005—Compounds containing elements of Groups 1 or 11 of the Periodic System without C-Metal linkages
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
    • B01J20/223—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material containing metals, e.g. organo-metallic compounds, coordination complexes
    • B01J20/226—Coordination polymers, e.g. metal-organic frameworks [MOF], zeolitic imidazolate frameworks [ZIF]
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F3/00—Compounds containing elements of Groups 2 or 12 of the Periodic System
    • C07F3/003—Compounds containing elements of Groups 2 or 12 of the Periodic System without C-Metal linkages
    • C—CHEMISTRY; METALLURGY
    • C40—COMBINATORIAL TECHNOLOGY
    • C40B—COMBINATORIAL CHEMISTRY; LIBRARIES, e.g. CHEMICAL LIBRARIES
    • C40B40/00—Libraries per se, e.g. arrays, mixtures
    • C40B40/04—Libraries containing only organic compounds
    • C40B40/16—Libraries containing metal-containing organic compounds
    • C—CHEMISTRY; METALLURGY
    • C40—COMBINATORIAL TECHNOLOGY
    • C40B—COMBINATORIAL CHEMISTRY; LIBRARIES, e.g. CHEMICAL LIBRARIES
    • C40B60/00—Apparatus specially adapted for use in combinatorial chemistry or with libraries
    • C40B60/08—Integrated apparatus specially adapted for both creating and screening libraries
    • G—PHYSICS
    • G16—INFORMATION AND COMMUNICATION TECHNOLOGY [ICT] SPECIALLY ADAPTED FOR SPECIFIC APPLICATION FIELDS
    • G16C—COMPUTATIONAL CHEMISTRY; CHEMOINFORMATICS; COMPUTATIONAL MATERIALS SCIENCE
    • G16C20/00—Chemoinformatics, i.e. ICT specially adapted for the handling of physicochemical or structural data of chemical particles, elements, compounds or mixtures
    • G16C20/10—Analysis or design of chemical reactions, syntheses or processes
    • G—PHYSICS
    • G16—INFORMATION AND COMMUNICATION TECHNOLOGY [ICT] SPECIALLY ADAPTED FOR SPECIFIC APPLICATION FIELDS
    • G16C—COMPUTATIONAL CHEMISTRY; CHEMOINFORMATICS; COMPUTATIONAL MATERIALS SCIENCE
    • G16C20/00—Chemoinformatics, i.e. ICT specially adapted for the handling of physicochemical or structural data of chemical particles, elements, compounds or mixtures
    • G16C20/50—Molecular design, e.g. of drugs
    • G—PHYSICS
    • G16—INFORMATION AND COMMUNICATION TECHNOLOGY [ICT] SPECIALLY ADAPTED FOR SPECIFIC APPLICATION FIELDS
    • G16C—COMPUTATIONAL CHEMISTRY; CHEMOINFORMATICS; COMPUTATIONAL MATERIALS SCIENCE
    • G16C60/00—Computational materials science, i.e. ICT specially adapted for investigating the physical or chemical properties of materials or phenomena associated with their design, synthesis, processing, characterisation or utilisation
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J19/0046—Sequential or parallel reactions, e.g. for the synthesis of polypeptides or polynucleotides; Apparatus and devices for combinatorial chemistry or for making molecular arrays
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J2219/00274—Sequential or parallel reactions; Apparatus and devices for combinatorial chemistry or for making arrays; Chemical library technology
    • B01J2219/0068—Means for controlling the apparatus of the process
    • B01J2219/007—Simulation or vitual synthesis
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J2219/00274—Sequential or parallel reactions; Apparatus and devices for combinatorial chemistry or for making arrays; Chemical library technology
    • B01J2219/00718—Type of compounds synthesised
    • B01J2219/00745—Inorganic compounds

Definitions

  • MOFs metal-organic frameworks
  • MOFs can provide exceptional characteristics or material properties.
  • MOFs include porous crystals created from modular molecular "building blocks,” which can, in principle, be combined in an almost unlimited number of combinations.
  • MOFs can provide exceptional characteristics or material properties, not only with regard to their relatively high surface area, porosity and stability, but also for the ease with which the MOFs can be synthesized based on designs conceived ⁇ priori. This latter benefit stems from the use of modular molecular "building blocks” that self-assemble into predictable crystal structures.
  • 137,953 hypothetical or potential MOFs are generated and the pore size distribution, surface area, and methane storage capacity is calculated for the hypothetical MOFs.
  • the term "hypothetical” includes predicted or potential MOFs, and is not limited to imaginary or impossible MOFs.
  • a hypothetical MOF can include an MOF that is generated using one or more embodiments described herein and that may be actually formed.
  • MOFs with better methane storage capacity than several or all known thaterials have been discovered using one or more embodiments of the systems and methods described herein.
  • One or more of these MOFs had a capacity almost 50% higher than the U.S.
  • the predictable assembly of building blocks into MOFs is used to systethatically generate a relatively large number of possible structures (within one or more constraints, as described below) given an input library of building blocks.
  • the thaterial properties or characteristics of these possible MOFs can be predicted using computational simulations.
  • a range of thaterial properties can be predicted for these MOFs, such as surface area, pore volume, pore size distribution, powder x-ray diffraction pattern, adsorption capability (e.g., methane adsorption capability, carbon dioxide adsorption capability, and the like). In doing previously unidentified structure-property relationships may be discovered.
  • one or more of the possible MOFs may be identified as MOFs of interest that can be more useful for a representative, specific application (such as but not limited to methane storage) relative to one or more other existing MOFs and/or possible MOFs.
  • the NOTT-107 MOF is identified and synthesized based on structure-property insights from the database generated by one or more embodiments described herein. This MOF is predicted to have better methane storage capacity at 35 bar than one or more other MOFs, such as PCN-14, a MOF having a known methane storage capacity that is relatively high.
  • a system for generating and/or screening one or more potential MOFs includes a generation module that is configured to receive building blocks used to form one or more of the potential MOFs.
  • the generation module is further configured to determine which of the potential MOFs that can be formed by combining the building blocks.
  • the term "module” or "unit” includes a hardware and/or software system that operates to perform one or more functions.
  • a module or unit may include a computer processor, controller, or other logic- based device that performs operations based on instructions stored on a tangible and non- transitory computer readable storage medium, such as a computer memory.
  • a module or unit may include a hard-wired device that performs operations based on hardwired logic of the device.
  • the modules and/or units shown in the attached figures may represent the hardware that operates based on software or hardwired instructions, the software that directs hardware to perform the operations, or a combination thereof.
  • the building blocks include inorganic building blocks, organic building blocks, and functional groups.
  • the generation module is configured to connect the inorganic building blocks with the organic building blocks.
  • the generation module is configured to combine the building blocks based on at least one of topological inforthation or geometrical inforthation assigned to the building blocks.
  • the system also includes an evaluation module configured to calculate one or more thaterial properties of the potential MOFs.
  • the one or more thaterial properties include one or more of surface area, pore volume, pore size distribution, powder x-ray diffraction pattern, or methane adsorption capability.
  • the evaluation module is configured to perform an atomistic grand Monte Carlo simulation to calculate at least one of the one or more thaterial properties.
  • a method for generating and/or screening one or more potential metal-organic frameworks includes receiving building blocks used to form one or more of the potential MOFs, determining which of the potential MOFs that can be formed by combining the building blocks, and forming the potential MOFs based on the building blocks that can be combined with each other.
  • the building blocks include inorganic building blocks, organic building blocks, and functional groups.
  • forming the potential MOFs includes combining the inorganic building blocks with the organic building blocks.
  • Hie method also includes calculating one or more thaterial properties of the potential MOFs.
  • the one or more thaterial properties include one or more of surface area, pore volume, pore size distribution, powder x-ray diffraction pattern, or methane adsorption capability.
  • calculating the one or more material properties includes performing an atomistic grand Monte Carlo simulation to calculate at least one of the one or more thaterial properties.
  • a computer readable storage medium for a system having a processor.
  • the computer readable storage medium includes one or more sets of instructions that direct the processor to receive building blocks used to form one or more of die potential MOFs, detennine which of the potential MOFs that can be formed by combining the building blocks, and form the potential MOFs based on the building blocks that can be combined with each other.
  • the computer readable storage medium is a tangible and non-transitory computer readable storage medium.
  • the building blocks include inorganic building blocks, organic building blocks, and functional groups.
  • the one or more sets of instructions direct the processor to combine the inorganic building blocks with the organic building blocks.
  • the one or more sets of instructions direct the processor to combine the building blocks based on at least one of topological inforthation or geometrical inforthation assigned to the building blocks.
  • the one or more sets of instructions direct the processor to calculate one or more thaterial properties of the potential MOFs.
  • the one or more thaterial properties include one or more of surface area, pore volume, pore size distribution, powder x-ray diffraction pattern, or methane adsorption capability.
  • the one or more sets of instructions direct the processor to perform an atomistic grand Monte Carlo simulation to calculate at least one of the one or more thaterial properties.
  • the method includes combining tetramethylbenzene, phenylboronic acid pinacol ester, and dioxane to form an organic body, drying the organic body, mixing the organic body with potassium hydroxide to form a solid body, mixing the solid body with copper nitrate to form a solution, and heating the solution to form a crystalline powder of the MOF.
  • the tetramethylbenzene is 1, 4-diiodo-2, 3, 5, 6- tetramethylbenzene.
  • the phenylboronic acid pinacol ester is 3, 5- bis(methoxycarbonyl) phenylboronic acid pinacol ester.
  • the method also includes adding dichloromethane with the tetramethylbenzene, the phenylboronic acid pinacol ester, and the dioxane to form the organic body.
  • the method also includes acidifying the organic body with hydrochloric acid.
  • each such linker/ligand component can comprise a plurality of terminal groups for metal center coordination, such groups as can be selected from carboxy (protonated in the acid form, or at least partially unprotonated as a corresponding conjugate base) and corresponding nitrogenous groups (e.g., without limitation, nitrile, pyridyl, pyrazyl, etc., as described below), and combinations thereof, such terminal groups coupled by R, wherein R can be a covalent bond, or moieties of the sort illustrated in Figure 3 and combinations thereof coupled to one another, such linker/ligand block components as can be optionally substituted with one or more groups of the sort also described in Figure 3.
  • groups for metal center coordination such groups as can be selected from carboxy (protonated in the acid form, or at least partially unprotonated as a corresponding conjugate base) and corresponding nitrogenous groups (e.g., without limitation, nitrile, pyridyl, pyrazyl, etc., as described below), and combinations
  • such a nitrogenous group can be considered as replacement of a carboxy group with a ring nitrogen center to provide the corresponding heterocyclic moiety.
  • such a nitrogenous group can be considered as replacement of a carboxy group with a terminal nitrogen to provide the corresponding nitrile.
  • inventive subject matter can comprise compositions of one or more of the present MOFs together with a binder, organic viscosity-enhancing compound, liquid, or combinations thereof.
  • a system for generating and/or screening one or more potential metal-organic frameworks includes a generation module that is configured to receive identifications of building blocks for determining if the building blocks can be used to form one or more of the potential MOFs.
  • the generation module is further configured to determine which of the potential MOFs that can be formed by simulating a combining of the building blocks in different arrangements.
  • a method for generating and/or screening one or more potential metal-organic frameworks includes receiving building blocks used to form one or more of the potential MOFs, determining which of the potential MOFs that can be formed by simulating a combining of different arrangements of the building blocks, and outputting an identification of the potential MOFs that can be formed from the building blocks based on the simulating of the combining of the building blocks.
  • a computer readable storage medium for a system having a processor.
  • the computer readable storage medium includes one or more sets of instructions that are configured to direct the processor to receive an identification of building blocks for one or more of the potential MOFs, determine which of the potential MOFs that can be formed by performing a simulation of combining of the building blocks, and output an identification of the potential MOFs that can be formed from the building blocks based on the building blocks that can be combined with each other in the simulation.
  • a metal organic framework includes a polymeric structure of an inorganic metal center block component; an organic linker block component; and, optionally a solvent, said linker block component comprising a plurality of terminal groups selected from carboxy groups and nitrogenous groups coupled by R, wherein R is selected from a covalent bond and moieties selected from C, arylene moieties, arylene tetracarboxydiimide moieties, fused arylene moieties, fused arylenetetrayl moieties, heteroarylene moieties, di-valent multicyclo moieties, ethynylene moieties and ethenylene moieties and combinations of said moieties coupled one to another.
  • R is selected from a covalent bond and moieties selected from C, arylene moieties, arylene tetracarboxydiimide moieties, fused arylene moieties, fused arylenetetrayl moieties, heteroarylene moieties, di
  • a metal organic framework includes a polymeric crystalline structure comprising the coordination product of a metal component selected from Zn 4 O, Zn 2 , Cu 2 , V 3 O 3 and Zr 6 O 6 , an organic ligand component selected from the ligands of Figures 3B-C and combinations thereof, and optionally a solvent.
  • a metal organic framework includes a polymeric crystalline structure of a Cu 2 metal component, a ligand component of a formula
  • a metal organic framework includes a polymeric crystalline structure of a Zn 4 O metal component, a first ligand component of a formula
  • a metal organic framework (MOF) building block comprising a compound of a formula
  • a method of gas sorption includes providing a metal organic framework (MOF) comprising a polymeric crystalline structure comprising the coordination product of a metal component selected from Zn 4 O, Zn 2 , Cu 2 , V 3 O 3 and Zr 6 O 6 , an organic ligand component selected from the ligands of Figures 3B-C and combinations thereof, and optionally a solvent
  • MOF metal organic framework
  • the method also includes contacting said MOF and a gas under at least one of a pressure and a temperature sufficient for gas sorption with said MOF.
  • a method of using a metal organic framework includes building block comprising a ligand component of a compound of a formula
  • the method includes providing a MOF comprising a building block of a compound of a formula
  • a metal organic framework comprises a polymeric crystalline structure including the coordination product of a metal component comprising a metal center selected from Zn 4 O, Zn 2 , Cu 2 , V 3 O 3 and Zr 6 O 6 , an organic ligand component selected from the Iigands of Figures 3B-C and combinations thereof, and optionally a solvent.
  • a metal organic framework includes a polymeric crystalline structure of a Cu 2 metal component, a ligand component of a formula
  • a metal organic framework includes a polymeric crystalline structure of a Zn 4 O metal component, a first ligand component of a formula
  • a metal organic framework (MOF) building block that includes a compound of a formula
  • a method of gas sorption includes providing a metal organic framework (MOF) that includes a polymeric crystalline structure comprising the coordination product of a metal component comprising a metal center selected from Zn 4 O, Zn 2 , Cu 2 , V 3 O 3 and Zr 6 O 6 , an organic ligand component selected from the ligands of Figures 3B-C and combinations thereof, and optionally a solvent.
  • MOF metal organic framework
  • the method also includes contacting said MOF and a gas under at least one of a pressure and a temperature sufficient for gas sorption with said MOF.
  • a method of using a metal organic framework (MOF) building block comprising a ligand component of a formula
  • a container for at least one of up-taking, storing and releasing at least one gas is provided.
  • the container includes at least one of an inlet component and an outlet component; a pressure control component to maintain a gas under pressure in said container; and a metal organic framework thaterial comprising a metal organic framework (MOF) that includes a polymeric crystalline structure comprising the coordination product of a metal component comprising a metal center selected from Zn 4 O, Zn 2 , Cu 2 , V 3 O 3 and Zr 6 O 6 , an organic ligand component selected from the ligands of Figures 3B-C and combinations thereof, and optionally a solvent, and optionally a gas.
  • MOF metal organic framework thaterial comprising a metal organic framework (MOF) that includes a polymeric crystalline structure comprising the coordination product of a metal component comprising a metal center selected from Zn 4 O, Zn 2 , Cu 2 , V 3 O 3 and Zr 6 O 6 , an organic ligand component selected from the ligands of Figures 3B-C and combinations thereof, and optionally a solvent, and optionally a gas
  • Figure 1 is a schethatic diagram that provides a visual summary of one embodiment of a hypothetical MOF generation strategy
  • Figure 2 is a schethatic diagram of components of a hypothetical MOF in accordance with one embodiment
  • Figures 3 A and 4 provide diagrams of a library of several building blocks that may be used to generate a database for hypothetical MOFs in accordance with one embodiment
  • Figures 3B and 3C provide, respectively, non-limiting carboxy-terminated and analogous nitrogen-teminated linker/ligand components corresponding to the carboxylate building block components of Figure 3 A, as can be used in the generation and synthesis of one or more metal organic frameworks of the inventive subject thatter;
  • Figure 5 illustrates examples of such topological information and geometrical inforthation
  • Figure 6 illustrates a flowchart of a method for generating a hypothetical MOF in accordance with one embodiment
  • Figure 7 illustrates two structure-property relationships found in a database of the MOFs generated using the techniques described above that are geometric in nature
  • Figure 8 illustrates a comparison of absolute methane adsorption isotherms at 298 K for six diverse MOFs, using two different sets of force field parameters
  • Figure 9 illustrates comparisons of simulated methane adsorption isotherms at 298 K for experimental, pseudo and pseudo-optimized structures of (a) HKUST-1, (b) IRMOF-1, (c) PCN-14, and (d) MIL-47;
  • Figure 10 provides a partial list of the building blocks used for screening the promising MOFs for high pressure methane storage
  • Figure 11 illustrates the methane adsorption versus hypothetical MOF rank for various MOFs in accordance with one or more embodiments
  • Figure 12 illustrates structure-property relationships obtained from a database of hypothetical MOFs in accordance with one embodiment
  • Figure 13 illustrates a comparison of excess methane adsorption isotherms of NOTT-107 (ligand 13b) and PCN-14 (ligand 13c) in accordance with one embodiment
  • Figure 14 illustrates simulated and experimental methane adsorption isotherms for PCN-14 at 290 K and N2 isotherm at 77K;
  • Figure 15 illustrates synthesis of tetracarboxylate ligand 4 in accordance with one embodiment
  • Figure 16 provides powder x-ray diffraction patterns of NOTT-107, including both experimental (below) and simulated (above) in accordance with one embodiment
  • Figure 17 is a schethatic diagram of one embodiment of a system for generating potential metal-organic frameworks (MOFs);
  • Figures 18A-B provide, in accordance herewith, (A) a schethatic synthesis of the triazolyl ligand 5,5',5"-(4,4',4"-(benzene-1,3,5-triyl)tris(1H-1,2,3-triazole-4,l- diyl))triisophthalic acid (and salts thereof), as can be used (B) in the generation and synthesis of one or more metal organic frameworks of the inventive subject thatter, with a representative metal center;
  • Figures 19A-C provide experimental crystal structures of a non-limiting representative metal organic framework of the inventive subject thatter, NU-125;
  • Figure 20 compares simulated and actual PXRD patterns of NU-125
  • Figure 21 shows methane sorption measurements, per the National Institute of Standards and Technology (NIST) and, by comparison, methane sorption simulated by the inventive subject thatter;
  • Figure 22 provides a schethatic synthesis of a representative non-limiting metal organic framework of the inventive subject thatter, wMOF-1;
  • Figure 23 provides experimental crystal structures of wMOF-1 ;
  • Figure 25 shows BET surface area measurements for wMOF-1 .
  • Figure 26 is a schethatic diagram of one embodiment of a MOF generation system.
  • Figure 1 is a schethatic diagram that provides a visual summary of one embodiment of a hypothetical MOF generation strategy or process 134.
  • black circles or spheres 124 represent atoms belonging to one of two interpenetrated frameworks.
  • Grey spheres 126, red spheres 128, blue spheres 130, and turquoise spheres 132 represent carbon, oxygen, nitrogen, and zinc atoms, respectively. However, other atoms may be included or used. Hydrogen atoms have been omitted from Figure 1 for clarity.
  • Crystal structures of existing MOFs 100, 102 can be obtained from x-ray diffraction data and be divided into building blocks 104, 106, 108, 110, 112.
  • the building blocks represent subsets or portions of the MOFs 100, 102.
  • a building block can represent an entire MOF (e.g., where an entire MOF is combined with one or more additional building blocks or other MOFs to form a new potential MOF).
  • the building blocks 104, 106, 108, 110, 112 can be computationally combined (e.g., by the system 1700 shown in Figure 17) to form new, hypothetical MOFs 114, 116.
  • the recombination process may occur by stepwise addition of the building blocks 104, 106, 108, 110, 112, which may be attached at their connection sites 118 (e.g., the X's in Figure 1).
  • the building blocks 104, 106, 108, 110, 112 may also be connected across periodic boundaries 120 (e.g., shown as hashed circles that indicate mirror images in Figure 1).
  • the process shown in Figure 1 may repeat until all connection sites 118 or at least a predetermined traction of the connection sites 118 is utilized.
  • An interpenetrated MOF 122 may be generated if enough space exists.
  • a MOF generation procedure creates hypothetical MOFs by recombining building blocks derived from crystallographic data of previously synthesized MOFs. Atoms can be grouped into building blocks based on reagents used in the actual synthesis. A building block can combine with one or more other (e.g., different) building blocks provided that the geometry and chemical composition local to the point of connection between the building blocks is the same as or similar to in crystallographically determined structures. Building blocks may be combined stepwise, and when a collision occurs at particular step, a different building block may be chosen or a different connection site may be used, until all or at least a predetermined fraction of the possibilities are exhausted.
  • Figure 2 is a schethatic diagram of components of a hypothetical MOF in accordance with one embodiment. Estithates on the number of possible hypothetical MOFs for a given library or corpus of modular building blocks can be obtained for hypothetical MOFs of no more than a finite or designated size (from here on assumed to be 100 building blocks or less, although a different number may be used) and by applying several simplifying assumptions.
  • the system 1700 shown in Figure 17 may be used to determine the hypothetical MOFs.
  • L be the number of organic building blocks (L as in "linkers")
  • C the number of inorganic building blocks from which to choose (C as in "corners").
  • Linkers 200, 202 may connect with corners 204, and vice-versa.
  • linkers 200, 202 may not directly connect with each other and/or comers 204 may not directly connect with each other in one embodiment.
  • a unit-cell of a MOF contains M linkers (not to be confused with L: the number of linker types), which can be either of two types: A or B.
  • L the number of linker types
  • the diversity of possible structures spans two dimensions: the ratio of A-linkers to B- linkers, and the number of possible arrangements of A and B linkers at a fixed ratio.
  • MOFs that include two distinct linkers may vary in the ratio of A to B linkers (e.g, MOF 206 versus MOF 208) or in the arrangement of those linkers at a fixed ratio (e.g., MOF 206 versus MOF 210).
  • a larger fragment of a schethatic MOF framework 212 is shown in Figure 2 for clarity.
  • a lower bound on the number of unique crystals can be estithated by the number of ratios of component types (e.g., a unit-cell with two A-linkers 200 and one B- linker 202 may not be the same crystal as one with one A-Iinker 200 and two B-linkers 202). Calculating this lower bound can be similar to finding the number of unordered sets of M linkers of L linker types (the answer is: M + L - 1 choose L - 1).
  • two crystals, both with two A-linkers 200 and one B-linker 202 but in different positions can either be physically identical (e.g., related by a symmetry operation) or unique (for example, if the corner is asymmetrical as in Figure 2).
  • linkers 200, 202 may be made from modular organic components, the number of hypothetical MOFs can increase considerably.
  • a linker 200, 202 can be defined as a combination of a backbone (e.g., benzene- 1,4- dicarboxylic acid) and a functional group (e.g., methyl).
  • B and F represent the number of backbones and functional groups in the library, respectively.
  • a single choice of backbone and functional group may result in many possible linkers 200, 202, due to the number of ways the functional group may be arranged on the backbone (e.g., meta-, para-, and ortho-xylene) or simply due to the total number of functional groups (e.g., toluene vs. xylene). If it is convervatively estithated that every backbone has a limited number of possible arrangements for any given choice of functional group (e.g., two), then the number of linkers, L, can be given by:
  • Equation 5 Substituting Equation 5 into Equation 3, and assuming a library of 10 corners,
  • the number of potential MOFs corresponds to a lower bound of 25,600,000 and an upper bound of 89,560,000.
  • all building blocks in this library are assumed to be chemically compatible so that every piece is interchangeable (which may be a reasonable assumption for an appropriately chosen chemical library).
  • one or more constraints may be implemented to reduce the number of potential MOFs, such as by restricting one or more building blocks from being used with one or more other building blocks.
  • a library of 5 corners, 42 backbones, and 13 functional groups can be used, although not all of the comers, backbones, and/or functional groups may be chemically and/or geometrically compatible.
  • Figures 3 A-C provide diagrams of a library 302 of several building blocks 300 that may be used to generate a database for hypothetical MOFs in accordance with one embodiment.
  • the library 302 shown in Figure 3 includes sixty building blocks 300, but alternatively may include a smaller or larger number of building blocks 300.
  • the building blocks shown in Figure 3 (including the nitrogen-terminated organic analogs; see Figure 4) may be used to generate the database of approxithately 137,000 hypothetical MOFs that are described above.
  • the building blocks 300 numbered 1 through 5 are inorganic building blocks 304, the building blocks 300 numbered 6 through 47 are organic building blocks 306, and the building blocks 300 numbered 48 through 60 are functional groups 308.
  • the inorganic building blocks 304 numbered 2 and 3 are able to coordinate to nitrogen containing compounds (e.g., pyrazine). Not shown then, in Figure 3, are one or more of the analogous building blocks terminated by nitrogen atoms instead of carboxylic acid groups.
  • the building blocks 300 shown in Figure 3 are shown with terminal carboxylate groups. In one embodiment, however, one or more of the building blocks 300 may also exist with a nitrogen terminated group, as well, for coordinating to paddlewheels 400, as shown in Figure 4.
  • topological and geometrical inforthation may be assigned to one or more of the building blocks 300 by a system 1700 shown and described below in connection with Figure 17.
  • Figure 5 illustrates examples of such topological inforthation and geometrical inforthation. While Figure 5 provides some examples, other types of inforthation, and/or other types of topological and/or geometrical inforthation that may be assigned to the building blocks by the system 1700.
  • encoded in the building blocks 300 in a database or other memory structure of the system 1700 may be the (a) atom composition and geometry, (b) topological inforthation via numbered connection sites, and (c) geometrical inforthation via pseudo- atoms (schethatically shown as red dots 500, green dots 502, and blue dots 504 representative of R, G, and B pseudo atoms, respectively) and lists of angles 506 for alternative orientations.
  • the topological inforthation may take the form of numbered connection sites so that a MOF generation algorithm used by the system 1700 (shown in Figure 17) to generate the potential MOFs can interpret instructions such as "connect building block 2, site 3, to building block 10, site 1." Additionally, this information can be used as part of a termination criteria used by the system 1700 to determine when construction of a MOF is complete; such as by determining that a single MOF generation is complete when every connection site or at least a predetermined number or fraction of the connection sites has been connected.
  • the geometrical inforthation takes the form of three "pseudoatoms" 500, 502, 504 and a list of angles 506 for every connection site (or at least a designated number of connection sites) in the building block 300.
  • the pseudo-atoms 500, 502, 504 each possess a coordinate in 3d space, as well as a label (here referred to arbitrarily as red, green, or blue dots 500, 502, 504, or red, green, or blue dots R, G, or B.
  • One purpose of the pseudoatoms 500, 502, 504 is to specify the relative orientation of two connected building blocks 300.
  • the building blocks 300 may be oriented correctly when the coordinates of RX equal RY, the coordinates of GX equal GY, and the vector RXBX is anti-parallel to the vector RYBY.
  • the list of angles can specify alternate orientations, which may be equivalent to rotating the pseudo- atoms about the RB axis by the specified angle.
  • the system 1700 shown in Figure 17 can determine a variety of possible combinations of building blocks 300 in a variety of possible arrangements to identify potential MOFs. This can be possible because the building blocks may be numbered or otherwise separately identified in a database or other memory structure of the system 1700, and also because a variety of possible arrangements of building blocks 300 can be written or stored as enumerable strings in the database or other memory structure of the system 1700.
  • the string "1, 2-3-1-2-3" as stored in the system 1700 can mean:
  • Figure 6 illustrates a flowchart of a method 600 for generating a hypothetical MOF in accordance with one embodiment
  • the method 600 can be implemented by the system 1700 shown in Figure 17 to create a database of potential MOFs.
  • the method 600 depicts how hypothetical MOFs can be enumeratively generated from a library of building blocks.
  • various types of building blocks are selected for use in constructing potential MOFs.
  • the upper and lower limits of i, j, k, and m can refer to the numbered building blocks in Figure 3.
  • the i th and j th building block types may be inorganic building blocks, and the m th building block type may be a functional group building block.
  • a total number and arrangement of building blocks is encoded in an enumerable string.
  • functional groups could be connected in a variety of locations where a hydrogen atom is otherwise bonded to a carbon atom, provided no atomic collisions occur.
  • a collision and/or incompatible chemistry between building blocks may be identified if any two atoms of the building blocks were closer than one angstrom apart in one embodiment. This distance was used so as not to discard potentially interesting MOFs due slight structural errors introduced in the generation process. Alternatively, another distance threshold other than one angstrom is used.
  • the potential MOF that is attempted to be formed by the colliding or incompatible building blocks may be discarded.
  • Flow of the method 600 may return to 610, where the next building block is attempted to be combined and/or another potential MOF is constructed.
  • flow of the method 600 may proceed to 614, where the potential MOF formed by the building blocks is exported, such as by storing the potential MOF in a memory of the system 1700, outoutting (e.g., displaying, printing, or otherwise communicating) the potential MOF to a user of the system 1700, or the like.
  • a screening procedure used to generate the hypothetical MOFs if no logical MOF structure could be generated (e.g., a potential MOF that satisfies the criteria at 612 such that the method 600 proceeds from 612 to 614) in the first 64,000 arrangements (or other number of arrangements) of the chosen building blocks, then the arrangement string was incremented by a large random value (e.g., "1,2-3-1-2-4" might jump to "4,1-3-2-4-4"). If no MOF structure could be found after 5 such increments (or another number of increments), then the next set of building blocks was chosen (see Figure 6) in an attempt to build another, different potential MOF.
  • a large random value e.g., "1,2-3-1-2-4" might jump to "4,1-3-2-4-4"
  • flow of the method 600 can return to 608, where another m type building block is selected in an attempt to build another potential MOF.
  • flow of the method 600 may return to 610, where another compositional arrangement of building blocks is formed in an attempt to identify an additional potential MOF.
  • the method 600 may sequentially or randomly proceed through the different i th , j th , k th , and/or m th building block types until all or a designated number of potential combinations of building blocks are examined as potential MOFs, as shown in Figure 6. Once all or at least the designated number of combinations are examined, the method 600 may proceed to 618.
  • Hypothetical MOF structures generated in accordance with one embodiment can be investigated by comparing coordinates of the atoms in the MOF structures against the coordinates of the atoms in the experimental and energetically optimized structures. If the unit cell dimensions of two structures differed even only slightly, however, then the distance between corresponding atoms in either structure may eventually diverge. For at least this reason, fragments of crystals that shared one atom (chosen arbitrarily) identically at the origin may be compared. These fragments were superimposed using the feature by the same name in a software application or program such as Materials Studio provided by Accelrys.
  • Fragments were defined by selecting a metal atom center and a variety of atoms that could be reached from the metal atom by traversing 7 bonds (an alternative approach would have been to include atoms within a specified radius of a chosen atom center, but this does not guarantee that each fragment has the same total number of atoms).
  • the program orients and translates one fragment relative to the other such that the interatomic distances between the atoms of both fragments are reduced below a threshold or minimized.
  • the degree to which one fragment thatches the other is measured by the average root-mean-squared distance over all pairs of nearest atoms in one embodiment. Hydrogen atoms can be ignored as the hydrogen atoms are often missing from crystallographic data. Average differences in atomic positions were less than approxithately 0.1 angstrom except in the case of the optimized PCN-14, although even in this case the methane adsorption isotherm may not be greatly affected (see Figure 9 and accompanying discussion).
  • Table 1 below provides comparisons of generated versus empirical structures by thatching interatomic distances.
  • the table below shows average root-mean-squared distance between thatched atoms.
  • these geometry optimizations were performed with the Forcite module of Materials Studio using an algorithm which is a cascade of the steepest descent, adjusted basis set Newton-Raphson, and quasi-Newton methods.
  • the bonded and the short range (van der Waals) non-bonded interactions between the atoms were modeled using the Universal Force Field (UFF).
  • UPF Universal Force Field
  • bond stretching can be described by a harmonic term, angle bending by a three-term Fourier cosine expansion, torsions and inversions by cosine-Fourier expansion terms, and the van der Waals interactions by the Lennard-Jones potential.
  • crystal structures that resembled the MOFs HKUST-1 e.g., from Chui et al., A chemically furictionalizable nanoporous thaterial [Cu 3 (TMA) 2 (H 2 O) 3 ]n, Science 283, 1148-1150 (1999)
  • IRMOF-1 e.g., from Li et al., Design and synthesis of an exceptionally stable and highly porous metal-organic framework, Nature 402, 276-279 (1999)
  • PCN-14 e.g., from Ma et al., Metal-organic framework from an anthracene derivative containing nanoscopic cages exhibiting high methane uptake, J. Am. Chem. Soc.
  • MIL-47 e.g., from Barthelet et al., A breathing hybrid organic-inorganic solid with very large pores and high magnetic characteristics, Angew. Chem. Int. Ed. 41, 281-284 (2002).
  • These MOFs may significantly differ in their pore topology and chemical composition.
  • the generated structures are referred to as pseudo-HKUST-1, pseudo-IRMOF-1, pseudo-PCN-14, and pseudo-MIL-47 to indicate that, albeit not hypothetical, they are nonetheless not identical to empirical structures.
  • pseudo-MOFs are then allowed to relax their structures energetically via the UFF implemented in the Forcite module in the Materials Studio software application, as described above.
  • Systethatic screening of hypothetical MOFs may depend directly on the accuracy of the predicted properties rather than indirectly on the accuracy of the crystal structures.
  • methane adsorption isotherms are computationally predicted for the hypothetical MOFs (experimental, pseudo, and pseudo after relaxation/optimization) at 298 K using grand canonical Monte Carlo (GCMC) simulations and in one or more of Snurr et al., Design of new thaterials for methane storage, Langmuir 20, 2683-2689 (2004) and/or Snurr et al., Assessment of isoreticular metal-organic frameworks for adsorption separations: A molecular simulation study of methane/n-butane mixtures, J.
  • Figure 9 illustrates comparisons of simulated methane adsorption isotherms at 298 K for experimental, pseudo and pseudo-optimized structures of (a) HKUST-1 (top left graph 900 of Figure 9), (b) IRMOF-1 (top right graph 902 of Figure 9), (c) PCN-14 (bottom left graph 904 of Figure 9), and (d) MIL-47 (bottom right graph 906 of Figure 9).
  • the graph 900 illustrates a first curve 908 that represents simulated methane adsorption for pseudo-optimized-HKUST-1, a second curve 910 that represents simulated methane adsorption for pseudo-HKUST-1, and a third curve 912 that represents simulated methane adsorption for HKUST-1.
  • the graph 902 illustrates a first curve 914 that represents simulated methane adsorption for pseudo-optimized-IRMOF-1, a second curve 916 that represents simulated methane adsorption for pseudo-IRMOF-1, and a third curve 918 that represents simulated methane adsorption for IRMOF-1.
  • the graph 904 illustrates a first curve 920 that represents simulated methane adsorption for pseudo -optimized-PCN- 14, a second curve 922 that represents simulated methane adsorption for pseudo-PCN-14, and a third curve 924 that represents simulated methane adsorption for PCN-14.
  • the graph 906 illustrates a first curve 926 that represents simulated methane adsorption for pseudo- optimized-MIL-47, a second curve 928 that represents simulated methane adsorption for pseudo-MIL-47, and a third curve 930 that represents simulated methane adsorption for MIL- 47.
  • Figure 17 is a schethatic diagram of one embodiment of a system 1700 for generating and/or screening potential MOFs.
  • the system 1700 may be used to determine one or more potential MOFs for various uses.
  • the system 1700 may be used to predict a library or database of potential MOFs, as described above.
  • the system 1700 is used to carry out one or more operations described above in connection with the method 600 shown in Figure 6.
  • the system 1700 includes an input/output assembly 1706, such as a system or assembly having an input device (e.g., electronic mouse, stylus, touchscreen, microphone, and the like) and an output device (e.g., the touchscreen or other display monitor or printer).
  • the input/output assembly 1706 is coupled with a processor 1702, such as a computer processor, controller, or other logic-based device that operates based on one or more sets of instructions (e.g., software applications) stored on a memory 1704 and/or hard-wired into the circuitry of the processor 1702.
  • the memory 1704 can include a tangible and non-transitory computer readable storage medium, such as a computer hard drive, flash drive, CD, DVD, and the like.
  • a database (e.g., a list, table, or other logical structure of inforthation) may be stored on (or represented by) the memory 1704 that includes the library of building blocks, the topological and/or geographical inforthation associated with the building blocks, the pseudo atoms and/or angles associated with connection sites of the building blocks, identified potential MOFs, and the like.
  • the processor 1702 includes or represents several functional modules, which may be embodied in a single processor 1702 and/or multiple processors 1702 operating based on sets of instructions to perform various functions.
  • the processor 1702 includes an input/output module 1708 that receives input from the input/output assembly 1706 and directs the input/output assembly 1706 to present data to a user of the system 1700.
  • the input/output module 1708 may receive a user input selection of a plurality of building blocks from which the hypothetical or potential MOFs may be formed by the system 1700.
  • the module 1708 can receive topological and/or geometric inforthation associated with building blocks, pseudo atoms and/or angles associated with connection sites of the building blocks, identified potential MOFs, and the like.
  • a generation module 1710 creates one or more potential MOFs based on the input received from the input/output module 1708 and/or from a library or database of building blocks stored on the memory 1704. As described above in connection with the method 600 shown in Figure 6, the generation module 1710 may create the potential MOFs based on a variety of inorganic building blocks, organic building blocks, and/or functional groups. The generation module 1710 may receive topological and/or geometrical inforthation assigned to the various building blocks from the input/output module 1708 and/or from the memory 1704 and use such inforthation to form the potential MOFs, as described above.
  • the generation module 1710 may direct the input/output module 1708 to present the user with one or more of the potential MOFs (e.g., images of the MOFs) on the input/output assembly 1706.
  • the assembly 1706 may visually display the potential MOFs to the user, may print out a bard copy image of the potential MOFs, or the like.
  • At least one technical effect of the system 1700 is to take, as input, various building blocks and to output potential MOFs that can be created after attempting various combinations of the building blocks to identify those MOFs that are feasible.
  • This output may be an electronically presented output, such as graphics, text, and the like, presented on a graphical user interface of a computing device, a hard copy printed version of the graphics, text, and the like, an audibly presented recitation of the potential MOF structures, or some other output.
  • An evaluation module 1712 examines one or more of the potential MOFs to estithate one or more properties of the potential MOFs. These properties can include chemical and/or mechanical characteristics of the potential MOFs. Alternatively or additionally, these properties can include an estithate cost for actually creating the potential MOFs.
  • the building blocks that are used by the system 1700 to identify the potential MOFs may be associated with estithated costs for acquiring, storing, dispensing, combining, and the like, the building blocks. These costs may be associated with the building blocks in the memory of the system 1700.
  • the costs can be used to generate an estithated production cost for producing each (or one or more of) the potential MOFs should a user of the system 1700 desire to manufacture the potential MOF.
  • the estithated production costs can be presented to the user with the potential MOFs to allow the user to compare the potential MOFs in order to decide which MOFs to produce.
  • the evaluation module 1712 may estithate the chemical characteristics, mechanical characteristics, and/or costs in order to allow for the user to determine which of the potential MOFs may be useful for, or better than one or more other MOFs for, providing a function, such as gas storage.
  • the evaluation module 1712 may estithate one or more of surface area, pore volume, pore size distribution, powder x-ray diffraction pattern, methane adsorption capability, or the like, associated with each of the potential MOFs.
  • the evaluation module 1712 can use a variety of calculations to determine the thaterial properties of the MOFs.
  • the evaluation module 1712 may use an atomistic grand canonical Monte Carlo simulation to estithate adsorption isotherms of methane in the potential MOFs.
  • the evaluation module 1712 can output the characteristics to the input/output assembly 1706 via the input/output module 1708 so that the user can view and/or determine which potential MOF to synthesize for a particular purpose, such as methane or other gas storage.
  • a systethatic screening process may be used to identify promising MOFs for one or more uses, such as methane storage in one example.
  • a library of 60 building blocks that varied significantly in their geometries, number of connection sites, and chemical composition were used.
  • the system 1700 may systethatically screen the potential MOFs that are identified for a variety of other applications, such as hydrogen storage, hazardous gas storage, or the like.
  • the evaluation module 1712 can examine one or more of the potential MOFs that may be useful for the storage of hazardous gases, which may include (but is not limited to) acetylene, arsine, hydrogen selenide, or the like.
  • FIG. 26 is a schethatic diagram of one embodiment of a MOF generation system 2500.
  • the generation system 2500 includes a front end component 2502 that includes the system 1700 for generating potential MOFs based on one or more libraries of building blocks, as described above.
  • the generation system 2500 includes a back end component 2504 that represents a fabrication system for creating actual MOFs from the potential MOFs generated by the system 1700.
  • the back end component 2504 includes a control unit 2506 that is communicatively coupled with the system 1700 by one or more wired and/or wireless communication connections.
  • the control unit 2506 is communicatively coupled with one or more sources 2508, 2510, 2512 of building blocks from which the MOFs identified by the system 1700 can be fabricated.
  • the sources 2508 may include containers, tanks, or other receptacles that store and dispense inorganic building blocks
  • the sources 2510 may include containers, tanks, or other receptacles that store and dispense building blocks
  • the sources 2 12 may include containers, tanks, or other receptacles that store and dispense functional group building blocks.
  • one or more other sources or the sources shown in Figure 26 may include catalysts or other species used to create the MOFs identified by the system 1700.
  • the system 1700 outputs one or more potential MOFs that are identified as described above to the control unit 2506.
  • the system 1700 may notify the control unit 2506 as to which building blocks are used to create the potential MOFs. Using this information, the control unit 2506 directs or controls the sources 2508, 2510, 2512 to dispense the appropriate building blocks (or compounds having the appropriate building blocks) into a receptacle 2514 or other volume.
  • the building blocks may be combined (e.g., either autothatically under control of the control unit 2506 or manually under control of a human user) in the receptacle 2 14 to create the potential MOF identified by the system 1700.
  • the system 1700 may output to the user (e.g., by visually displaying, playing audible instructions, printing onto paper, and the like) instructions on how to create the potential MOFs that are identified by the system 1700.
  • Figure 10 provides a partial list of the building blocks used for screening the promising MOFs for high pressure methane storage.
  • the building blocks shown in Figure 3 may provide additional building blocks.
  • a purple group 1000, a red group 1002, a green group 1004, and a blue group 1006 show examples of 1-, 2-, 3- and 4-connected building blocks, respectively.
  • the 1 -connected building blocks are functional groups while the others (that do not contain metals) are organic building blocks.
  • An orange group 1008 shows three inorganic buildings blocks that are 4-, 6-and 12-connected.
  • the building blocks may fall conceptually into three groups: inorganic, organic and functional groups.
  • generation algorithm used by the system 1700 is normally blind to these distinctions, it was constrained in one embodiment to produce crystals with at most one kind of inorganic building block, two kinds of organic building blocks, and one kind of functional group. This constraint resulted in MOFs that were reasonable synthetic targets. This constraint may be removed to investigate, for example, the "multivariate" MOFs reported in Deng et al., Multiple functional groups of varying ratios in metal-organic frameworks, Science 327, 846-850 (2010), that include up to nine unique building blocks within one crystal.
  • Atomistic grand canonical Monte Carlo (GCMC) simulations can be performed by the system 1700 to estithate the adsorption isotherms of methane (CH 4 ) in the hypothetical MOFs.
  • Interaction energies between non-bonded atoms can be computed through the Lennard- Jones (U) potential represented by:
  • LJ parameters between atoms of different types can be calculated using the Lorentz-Berthelot mixing rules (e.g., geometric average of well depths and arithmetic average of diameters).
  • LJ parameters for framework atoms can be obtained from the Universal Force Field (UFF) described in Rappe et al., UFF, a full periodic table force field for molecular mechanics and molecular dynamics simulations, J. Am. Chem. Soc. 114, 10024-10035 (1992).
  • the methane molecules may be modeled using the TraPPE2 force field, which was originally fit to reproduce the vapor-liquid coexistence curve of methane.
  • methane is modeled as a single sphere (parameters shown in Table 2 below).
  • Table 2 provides LJ parameters for methane and framework atoms in hypothetical MOFs.
  • Framework parameters may be taken from the Dreiding force field, Mayo et al., A generic force field for molecular simulations, J. Phys. Chem. 94, 8897-8909 (1990), and from UFF when a parameter did not exist in Dreiding. Alternatively, only parameters from UFF may be used. The effect of using parameters from Dreiding and/or UFF or using parameters only from UFF can be examined by comparing methane simulations using both parameter sets (Dreiding + UFF versus UFF only) on six MOFs that are diverse in chemical composition and geometry (see Figure 8).
  • Figure 8 illustrates a comparison of absolute methane adsorption isotherms at 298 K for six diverse MOFs, using two different sets of force field parameters.
  • the red symbols and curves 800 represent data obtained using framework parameters taken from Dreiding when available and otherwise with using framework parameters from UFF.
  • the blue symbols and curves 802 represent data obtained using framework parameters taken from UFF only.
  • the MOF structures used include CoVDOBDC (e.g., from Dietzel et al. An in situ high-temperature single-crystal investigation of a dehydrated metal-organic framework compound and field-induced magnetization of one-dimensional metal-oxygen chains, Angew. Chem. Int. Ed.
  • IRMOF-3 e.g., from Eddaoudi, Systethatic design of pore size and functionality in isoreticular MOFs and their application in methane storage, Science 295, 469-472 (2002)
  • MOF-177 e.g., from Chae et al., A route to high surface area, porosity and inclusion of large molecules in crystals, Nature 427, 523-527 (2004)
  • Pd(2- pymo)2 e.g., from Navarro et al., H 2 , N 2 , CO, and CO2 sorption properties of a series of robust sodalite-type microporous coordination polymers, Inorganic Chemistry 45, 2397-2399 (2006)
  • UMCM-1 Koh et al., A crystalline mesoporous coordination copolymer with high microporosity, Angew.
  • the GCMC simulations of methane adsorption included an M-cycle equilibration period followed by an M-cycle production run, where M was 500, 2500, or 12,500 as described below (as shown in Figure 11).
  • a cycle consists of n Monte Carlo steps; where n is equal to the number of molecules (which fluctuates during a GCMC simulation).
  • the simulations included random insertion, deletion, and translation moves of molecules with equal probabilities.
  • Atoms in the MOF were held fixed at their crystallographic positions. An LJ cutoff distance of 12.8 angstroms was used for the simulations. A 2x2x2 unit cell of every crystal was used for the simulations.
  • Methane adsorption was simulated at a single pressure, 35 bar, at 298 K for all crystals. In addition, a complete isotherm was calculated (over a wide range of pressures) for the four MOFs (HKUST-1, IRMOF-1, PCN-14, and MIL ⁇ 7) described in Figure 9. Fugacities needed to run the GCMC simulations were calculated using the Peng-Robinson equation of state. GCMC simulations report the absolute adsorption data, which are then used to compute the excess adsorption data for comparison with experimental data using the relation:
  • V p is the pore volume calculated by the helium insertion method as described in Snurr et al., Effects of surface area, free volume, and heat of adsorption on hydrogen uptake in metal-organic frameworks, J. Phys. Chem. B 110, 9565- 9570 (2006).
  • the structure labeled "MOF-#l” in (f) of Figure 11 is composed of building blocks 3, 31 (nitrogen teiminated), 35, and 52, as shown in Figure 3.
  • the structure labeled "MOF-#20" in (e) of Figure 11 is composed of building blocks 2, 19, 25 (nitrogen terminated) and 52 as depicted in Figure 3.
  • CDF structures also are available along with others.
  • Figure 14 illustrates simulated and experimental methane adsorption isotherms for PCN-14 at 290 K and the simulated N 2 isotherm at 77 K.
  • the simulated and experimental methane adsorption is shown in the left side of Figure 14 (experimental data from Ma et al.), and the simulated N 2 isotherm is shown on the right side of Figure 14.
  • Figure 11 illustrates the methane adsorption versus hypothetical MOF rank for various MOFs in accordance with one or more embodiments.
  • initial stage approxithately 137k MOFs were screened for methane storage at 35 bar via short simulations (e.g., the left graph (a) in Figure 11).
  • the top 5% of the first stage e.g., shown in the middle graph (b) in Figure 11
  • second stage e.g., shown in the right graph (c) in Figure 11
  • graphs (a) through (c) the MOFs are rank-ordered (best to worst runs from left to right in Figure 11) with statistical error indicated via bars 1100.
  • orange spheres 1102 and green spheres 1104 represent the carbon atoms of methyl and ethyl functional groups, respectively, and grey spheres 1106, red spheres 1108, blue spheres 1110, turquoise spheres 1112, and brown spheres 1114 represent carbon, oxygen, nitrogen, zinc and copper atoms, respectively. Largest pore diameters are indicated by purple spheres 1116 and hydrogen atoms have been omitted for clarity.
  • the third stage (e.g., highest quality) GCMC predictions indicate that approxithately 300 MOFs have higher methane storage capacity at 35 bar than one or more currently known storage capacities, such a known capacity of 230 v(STP)/v.
  • one hypothetical MOF shown in (fj of Figure 11) is predicted to store approxithately 267 v(STP)/v methane at 298 K.
  • a clear linear relationship may exist between volumetric methane adsorption and volumetric surface area, but not between volumetric methane adsorption and gravimetric surface area.
  • Increasing or maximizing gravimetric surface area can be a common strategy in MOF design, but going past an "optimal" point, such as a gravimetric surface area of approxithately 2500 to 3000 m 2 /g, may worsen the methane storage capability of the MOF.
  • MOFs with methyl, ethyl and propyl functional groups dominate the best performers; over 75% of MOFs with adsorption over 205 v(STP)/v may include methyl, ethyl, or propyl functional groups, as shown in (d) and (e) of Figure 12.
  • Figure 7 illustrates two structure-property relationships found in a database of the MOFs generated using the techniques described above that are geometric in nature.
  • the data shown in Figure 7 suggests that volumetric surface area may be fundamentally capped to a value determined by the probe size used, whereas gravimetric surface area may not show a clear limit.
  • Figure 12 illustrates structure-property relationships obtained from a database of hypothetical MOFs in accordance with one embodiment.
  • the volumetric methane adsorption may show a clear linear relationship with volumetric surface area (e.g., as shown in (a) of Figure 12), but may not show such a relationship between volumetric methane adsorption and gravimetric surface area (e.g., as shown in (b) of Figure 12).
  • red dots 1200 correspond to MOFs that have enough space to interpenetrate, but are not interpenetrated.
  • methane adsorption initially increases with gravimetric surface area, but then begins to decrease with the optimal gravimetric surface area approxithately 2500-3000 m 2 /g.
  • a void fraction of approxithately 0.8 may be optimal or better than one or more other void fractions for volumetric methane uptake at 35 bar.
  • methyl, ethyl and propyl groups occur more frequently in MOFs that have volumetric and gravimetric methane adsorption greater than 205 v(STP)/v and 325 cm3(STP)/g, respectively.
  • Halogen functional groups may be sub-optimal for methane storage and may be weakly represented amongst the best MOFs for volumetric storage and completely absent from the top MOFs by gravimetric adsorption.
  • MOFs in the database have a range of dominant pore sizes.
  • the inset in Figure 12 shows that pore sizes of 4 angstroms and 8 angstroms are more common in the "best” MOFs, while the “worst" MOFs specifically exclude pore sizes in the range of 4 to 8 angstroms.
  • the term “best” refers to MOFs having methane adsorption greater than 220 v(STP)/v, but may or may not include the highest methane adsorptions.
  • the term “worst” refers to MOFs having methane adsorption less man 120 v(STP)/v, but may or may not include the lowest methane adsorptions.
  • NOTT-107 can be investigated as a candidate methane storage thaterial.
  • NOTT-107 is in the top 2% of MOFs in the database described above, and it also may be attractive to study because NOTT- 107 can be easily compared to PCN-14, a MOF that is currently reported to have the highest methane storage at 35 bar or a methane storage at 35 bar that is higher than one or more other MOFs.
  • Figure 13 illustrates a comparison of excess methane adsorption isotherms of NOTT-107 and PCN-14 in accordance with one embodiment.
  • the isotherm data is at 298 K except experimental data for PCN-14, which is taken from Ma et al., Metal-organic framework from an anthracene derivative containing nanoscopic cages exhibiting high methane uptake, J. Am. Chem. Soc. 130, 1012-1016 (2008) and is at 290 K.
  • NOTT-107 is structurally identical to PCN-14 except for the organic building block, which has four methyl groups (e.g., as shown in (b) of Figure 13) in the place of two fused arothatic rings (e.g., as shown in (c) of Figure 13). J. Am Chem. Soc., 131, 2159 (2009).
  • MOFs NOTT-107 and PCN-14
  • MOFs with many arothatic rings have relatively high methane uptake, methyl functional groups can have a greater effect.
  • GCMC simulations show NOTT-107 to be a slightly better methane storage thaterial than PCN-14 at 298 K as shown in Figure 13.
  • Absolute storage quantities for NOTT-107 and PCN-14 at 35 bar were calculated to be 213 v(STP)/v and 197 v(STP)/v, respectively. Note that Figure 13 displays the excess adsorption, which is more directly measured in adsorption experiments.
  • simulations may over-predict methane storage by approxithately 9% at 35 bar for NOTT-107. This may partly be attributed to incomplete pore activation, which is corroborated by a difference between the simulated BET surface area (2207 m2/g) (e.g., from Snurr et al., Applicability of the BET method for determining surface areas of microporous metal-organic frameworks, J. Am. Chem. Soc 129, 8552-8556 (2007)) versus the measured BET surface area (1770 m2/g).
  • the sample was held at 298 K in a circulating water bath.
  • a 2 cc stainless steel sample holder was loaded with the activated sample (258 mg) in an argon atmosphere glove box and sealed prior to analysis. All gases (He, N2, and CH4) used for analysis were of ultra-high purity grade (>99.99% pure) from Airgas and were used without further purification.
  • Microwave heating was carried out using an automatic single-mode synthesizer (InitiatorTM 2.0) from Biotage, which produces a radiation frequency of 2.45 GHz.
  • Figure 15 illustrates synthesis of tetracarboxylate ligand 4 in accordance with one embodiment.
  • the synthesis of (3) shown in Figure 15 includes, in one embodiment, combining 1,4-diiodo-2,3,5,6-tetramethylbenzene (shown as (1) in Figure 15 and can be purchased from VWR) (0.60 g, 1.55 mmol) and 3,5-Bis(methoxycarbonyl) phenylboronic acid pinacol ester (shown as (2) in Figure 15 and prepared following Chen et al., A new multidentate hexacarboxylic acid for the construction of porous metal-organic frameworks of diverse structures and porosities, Cryst. Growth Des.
  • the chamber was sealed and the temperature was raised to 38°C (i.e., above tile critical temperature for carbon dioxide), at which time the chamber was slowly vented over the course of 15 hours.
  • the color of the MOF changed from teal to dark blue.
  • the collected MOF sample was then stored inside an inert-atmosphere glovebox until further analysis. Prior to sorption measurements, the sample was evacuated at room temperature for three hours, then brought to 110°C over four hours.
  • Figure 16 provides powder x-ray diffraction patterns of NOTT- 107, including both experimental (below) and simulated (above) in accordance with one embodiment.
  • the MOFs disclosed herein can be considered in the context of coordination of an inorganic metal center block component with one or more organic linker/ligand block components comprising terminal carboxy (e.g., via coordination with a carboxylate group, such group in the presence of a suitable counter ion such as but not limited to an alkaline or alkaline-earth metal ion) and/or analogous nitrogenous groups, such linker/ligand block components of the sort represented in Figures 3A-C.
  • a suitable counter ion such as but not limited to an alkaline or alkaline-earth metal ion
  • metals contemplated include, but are not limited to, any oxidation state of magnesium, calcium, strontium, barium, radium, aluminum, gallium, indium, thallium, silicon, germanium, tin, lead, arsenic, antimony, scandium, titanium, vanadium, chromium, manganese, iron, cobalt, nickel, copper, zinc, yttrium, zirconium, niobium, molybdenum, technetium, rubidium, rhodium, palladium, silver, cadmium, hafnium, tantalum, tungsten, rhenium, osmium, iridium, platinum, gold, mercury, lanthanum, cerium, praseodymium, neodymium, promethium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, and ytterb
  • Metal components that can coordinate to such ligands comprise metal ions such as but not limited to Mg2+, Ca2+, Sr2+, Ba2+, Sc3+, Y3+, Ti4+, Zr4+, Hf4+, V4+, V3+, V2+, b3+, Ta3+, Cr3+, Mo3+, W3+, Mn3+, Mn2+, Re3+, Re2+, Fe3+, Fe2+, Ru3+, Ru2+, Os3+, Os2+, Co3+, C2+, Rh2+, Rh+, Ir2+, Ir+, Ir+, Ir+, Ir+, Ir+, Ir+, Ni2+, Ni+, Pd2+, Pd+, P 2+, P , Cu2+, Cu+, Ag+, Au+, Zn2+, Cd2+, Hg2+, A13+, Ga3+, In3+, T13+, Si4+,
  • metal ions are available through corresponding metal salts, in conjunction with any acceptable counter ion(s), such as but not limited to nitrate.
  • such metals can be transition metals, such as any oxidation state of vanadium, copper, zinc and zirconium.
  • Specific metals and oxidation states contemplated for use in the MOFs disclosed herein include, but are not limited to, Zr4+, V4+, V3+, Cu2+, Cu+, and Zn2+.
  • metal centers associated with inorganic block components can include Cu2, Zn40, Zn2, V303, and Zr606.
  • polymeric crystalline structures can refer to polymers of inorganic metal center block components coordinated to one or more organic linker/ligand block components.
  • the thaterials produced herein can be "crystalline,” which refers to the ordered definite crystalline structure such a thaterial which is unique and thus identifiable by a characteristic X-ray diffraction pattern.
  • the MOFs disclosed herein are substantially free of solvents.
  • substantially free means that solvents are present in the MOF at levels less than I wt % by weight of the MOF, and preferably from 0 wt % to about 0.5 wt % by weight of the MOF.
  • the solvent can be removed from the MOF by exposing the MOF to elevated temperatures under reduced pressure, or by soaking the MOF in a low boiling solvent to exchange the coordinated solvent for the low boiling solvent, then exposing the MOF to reduced pressure.
  • the amount of solvent in the MOF can be determined by elemental analysis or other known analytical techniques.
  • the pore size of the MOFs disclosed herein can be altered depending upon the number of solvent molecules coordinated or partially coordinated to the metal center. Typically, the pore size of the MOF will be about 3 A to about 11 A, but can be about 4 A to about 8 A.
  • the Brunauer, Emmett, and Teller (BET) surface area of the MOFs disclosed herein can be about 100 to about 3500 m 2 /g. In some cases, the BET surface area is about 100 to about 2500 m 2 /g, about 150 to about 2000 m 2 /g, about 150 to about 1500 m 2 /g, about 150 to about 1000 m 2 /g, and about 100 to about 250 m 2 /g.
  • compositions comprising MOFs of the sort disclosed herein.
  • Such compositions can include one or more MOF and a binder, an organic viscosity-enhancing compound, and/or a liquid for converting the MOF into a paste.
  • Such compositions can, optionally, be molded, extruded, co-extruded, foamed, spray dried and/or granulated or otherwise processed to form a shaped body. Possible configurations of such a shaped body include but are not limited to pellets, pills, spheres, granules and extrudates, and the like.
  • compositions can be deposited or coated on or otherwise coupled to a substrate such as but not limited to a porous support. Such a composition can then be used as a means of storing gas, by exposing the composition to a gas and allowing the MOF of the composition to uptake gas.
  • a number of inorganic compounds known in the art can be used as binders.
  • Non-limiting examples include titanium dioxide, hydrated titanium dioxide, hydrated alumina or other aluminum-containing binders, mixtures of silicon and aluminum compounds, silicon compounds, clay minerals, alkoxysilanes, and amphophilic substances.
  • Other binders are in principle all compounds used to date for the purpose of achieving adhesion in powdery thaterials.
  • Compounds, in particular oxides, of silicon, of aluminum, of boron, of phosphorus, of zirconium and/or of titanium are preferably used.
  • silica Of particular interest as a binder is silica, where the Si(3 ⁇ 4 may be introduced into the shaping step as a silica sol or in the form of tetraalkoxysilanes.
  • Oxides of magnesium and of beryllium and clays, for example montmorillonites, kaolins, bentonites, halloysites, dickites, nacrites and anauxites, may furthermore be used as binders.
  • the binder may have a concentration of from 0.1 to 20% by weight. Alternatively, no binder is used.
  • organic viscosity-enhancing substances and/or hydrophilic polymers e.g. cellulose or polyacrylates
  • the organic viscosity-enhancing substance used may likewise be any substance suitable for this purpose.
  • organic, in particular hydrophilic polymers e.g., cellulose, starch, polyacrylates, polymethacrylates, polyvinyl alcohol, polyvinylpyrrolidone, polyisobutene and polytetrahydrofuran.
  • the optional liquid which may be used to create a paste-like composition of the MOFs disclosed herein.
  • alcohols may be used. Accordingly, both monoalcohols of 1 to 4 carbon atoms and water- miscible polyhydric alcohols may be used. In particular, methanol, ethanol, propanol, n- butanol, isobutanol, tert-butanol and mixtures of two or more thereof are used.
  • Amines or amine-like compounds for example tetraalkylammonium compounds or aminoalcohols, and carboriate-containing substances, such as calcium carbonate, may be used as further additives in the disclosed compositions.
  • Such further additives are described in EP-A 0 389 041, EP-A 0 200 260 and WO 95/19222, which are incorporated fully by reference in the context of the present application.
  • the additive substances mentioned above may be removed from such a composition by drying or heating, optionally in a protective atmosphere or under vacuum.
  • the composition is preferably not exposed to temperatures exceeding 300° C. Heating/drying the composition under the mild conditions, in particular drying in vacuo, preferably well below 300° C, is sufficient to at least remove organic compounds out of the pores of the MOF.
  • the conditions are adapted and chosen depending upon the additive substances used.
  • the order of addition of the components is not critical. It is possible either to add first the binder, then, for example, the MOF thaterial and, if required, the additive and finally the mixture containing at least one alcohol and/or water or to interchange the order with respect to any of the aforementioned components.
  • MOFs based upon the present inorganic metal center and organic linker/ligand block components can be prepared by known solvothermal methods, as follows.
  • a ligand component is mixed with a metal salt (e.g., a metal nitrate) corresponding to a desired metal center (e.g., a transition metal) in a molar proportion of about l:n, where n is greater than or equal to 1, in an organic solvent or mixture of organic solvents, such as dimethylformamide, diethylformamide, ethanol, isopropanol, methanol, butanol, or pyridine.
  • a metal salt e.g., a metal nitrate
  • a desired metal center e.g., a transition metal
  • organic solvent or mixture of organic solvents such as dimethylformamide, diethylformamide, ethanol, isopropanol, methanol, butanol, or pyridine.
  • the solvent is decanted, and the resulting MOF is collected and washed one or several times with organic solvent to afford the desired MOF thaterial.
  • an MOF can then be further modified by removing coordinated solvent molecules under elevated temperature and reduced pressure. Confirmation of removal of all solvent molecules from the MOF can be confirmed via elemental analysis.
  • MOF-#20 a molar excess of a metal salt precursor of metal center Zn 2 and a combination of ethyl-substituted naphthalene dicarboxylate and ethyl-substituted dinitrile linker/ligand components (see, components 19 and 25 of Fig. 3) are mixed in a suitable solvent, such as DMF, with subsequent introduction of ethanol and/or HCl. After reaction at elevated temperatures for up to 24 hours or more, MOF-#20 thaterial is isolated. (Reference is, again, made to the synthesis of NOTT-107, above.)
  • 1,3,5-acetylenebenzene (C, 1.75 g, 11.7 mmol), compound B (10 g, 45.2 mmol), CuS0 4 .4H 2 0 (10 g, 45.2 mmol), and sodium ascorbate (10 g, 45.2 mmol) were added in 1 L Schlenk flask equipped with a magnetic stir bar and a rubber stopper. The mixture was taken into a drybox and dry DMF (600 ml) was added into this solution. The solution was capped and taken out of drybox then stirred for 24 h at 90 °C, giving a pinkish solution with large amount of precipitate.
  • Metal organic frameworks of this invention can be incorporated into a container, as discussed elsewhere herein.
  • NU-125 powder or a related thaterial is placed in a container before closure.
  • One or more gases are then introduced from an external supply source, through an inlet component using techniques understood by those skilled in the art
  • a gas includes but is not limited to those disclosed elsewhere herein.
  • gas e.g., methane
  • any such MOF and/or composition comprising an MOF can be prepared according to procedures of the sort described herein or would otherwise be understood by those skilled in the art, such MOFs/compositions limited only by available metal center block, linker/ligand and substituent group components, such components as are commercially- available or can be prepared with suitable precursors through synthetic procedures known in the art.
  • MOF compounds and related compositions can be prepared using procedures of the sort described in U.S. Patent Nos. 7,824,473, 7,862,647, and 7,744,842-each of which, together with the references cited therein, is incorporated herein by reference in its entirety.
  • MOF compounds can suitably comprise, consist of, or consist essentially of any of the aforementioned metal center components, linker/ligand components and moieties and/or functional/substituent groups thereof.
  • Each such compound, component or moiety/group thereof is compositionally distinguishable, characteristically contrasted and can be utilized in conjunction with one or more embodiments of the inventive subject thatter separate and apart from another.
  • inventive compounds, compositions and/or methods can be practiced or utilized in the absence of any one compound, component or moiety/group thereof and/or step, such compound, component, moiety/group and/or step which may or may not be specifically disclosed, referenced or inferred herein, the absence of which may or may not be specifically disclosed, referenced or inferred herein.
  • a container for up-taking, storing and/or releasing at least one gas such a container as can comprise at least one of an inlet component and an outlet component, a pressure control component to maintain such a gas under pressure within such a container, and a metal organic framework thaterial comprising a metal organic framework (MOF) of the inventive subject thatter, and optionally a gas.
  • a gas or gases can be under a pressure up to about 10 bar, up to about SO bar, up to about 100 bar or up to about 200 bar or more inside such a container.
  • such a container can comprise a porous metal organic framework thaterial comprising a metal center component and one or more linker/ligand components of the sort described herein coupled with or coordinated to such a metal center component
  • one or more such containers can be incorporated with a gas storage system and/or a gas delivery system.
  • one or more such containers can be incorporated with a fuel cell.
  • such a container and/or system can be used in conjunction with a fuel cell and/or fuel tank for supplying power to stationary and/or mobile and/or mobile portable applications such as but not limited to power plants, automotive vehicles (e.g., without limitation, cars, trucks and buses) and cordless power tools.
  • the container may include a MOF that stores a gas used to power one or more devices.
  • a container may be a fuel cell (e.g., a device that uses an electrochemical reaction involving the stored gas to produce energy for powering one or more devices), a fuel tank (e.g., a chamber that stores the gas for supply to a device that consumes the gas for generating energy and/or power), and the like.
  • the volume of such a container can be a thatter of choice and adapted to the specific needs of the respective application for which such a container is used.
  • the volume of such a container as can be used with a fuel cell on a passenger car, can be about 3001 or less.
  • the volume of such a container can be about ISO 1 or about 100 1 or less.
  • such a container used with a fuel cell of a truck can be about 5001 or less.
  • the volume of such container can be about 400 1 or about 300 1 or less.
  • any such container can be, for instance, used in conjunction with a gas storage or gas delivery system - for example, as in a gas station where the volume of such a container may be within the aforementioned parameters, but may well exceed such volumes.
  • a container of the inventive subject thatter can be manufactured from a thaterial stable when exposed to pressures of the sort discussed above.
  • Materials can vary depending upon a gas(es) to be uptaken and/or stored and/or released.
  • Thaterials include but are not limited to stainless steel and aluminum, together with various synthetic thaterials composite thaterials, fiber reinforced synthetic thaterials, fiber reinforced composite thaterials, carbon fiber composite thaterials and combinations thereof, the manufacture thereof as would be known to those skilled in the art made aware of the inventive subject thatter.
  • such containers can be designed and constructed to meet one or more recognized standards, in particular, such containers can meet ISO 11439 and/or NGV2 standards for natural gas storage and use in conjunction with automotive vehicles, each such standard as is incorporated herein by reference in its entirety.
  • a system for generating and/or screening one or more potential metal-organic frameworks includes a generation module that is configured to receive identifications of building blocks for determining if the building blocks can be used to form one or more of the potential MOFs.
  • the generation module is further configured to determine which of the potential MOFs that can be formed by simulating a combining of the building blocks in different arrangements.
  • the system also includes a fabrication system coupled with the generation module.
  • the fabrication system includes one or more sources of actual building blocks that are identified for the generation module.
  • the fabrication system is configured to autothatically combine the actual building blocks that are used to form the potential MOFs as simulated by the generation module.
  • the building blocks include inorganic building blocks, organic building blocks, and functional groups.
  • the generation module is configured to connect the inorganic building blocks with the organic building blocks.
  • the generation module is configured to simulate the combining of the building blocks that are identified based on at least one of topological inforthation or geometrical inforthation assigned to the building blocks.
  • the generation module is configured to determine whether two or more of the building blocks that are identified cannot be combined with each other without resulting in collisions between atoms of the building blocks in the simulating of the combining of the building blocks.
  • the system also includes an evaluation module configured to calculate one or more thaterial properties of the potential MOFs.
  • the one or more thaterial properties include one or more of surface area, pore volume, pore size distribution, powder x-ray diffraction pattern, or adsorption capability.
  • the evaluation module is configured to perform an atomistic grand Monte Carlo simulation to calculate at least one of the one or more thaterial properties.
  • a method for generating and/or screening one or more potential metal-organic frameworks includes receiving building blocks used to form one or more of the potential MOFs, detennining which of the potential MOFs that can be formed by simulating a combining of different arrangements of the building blocks, and outputting an identification of the potential MOFs that can be formed from the building blocks based on the simulating of the combining of the building blocks.
  • the method also includes outputting instructions to a fabrication system for autothatically creating one or more of the potential MOFs from one or more sources of the building blocks.
  • the building blocks include inorganic building blocks, organic building blocks, and functional groups.
  • detennining which of the potential MOFs can be formed includes combining the building blocks based on at least one of topological inforthation or geometrical inforthation assigned to the building blocks.
  • the method also includes calculating one or more thaterial properties of the potential MOFs.
  • the one or more thaterial properties include surface area, pore volume, pore size distribution, powder x-ray diffraction pattern, or adsorption capability.
  • calculating the one or more thaterial properties includes performing an atomistic grand Monte Carlo simulation to calculate at least one of the one or more thaterial properties.
  • a computer readable storage medium for a system having a processor.
  • the computer readable storage medium includes one or more sets of instructions that are configured to direct the processor to receive an identification of building blocks for one or more of the potential MOFs, determine which of the potential MOFs that can be formed by performing a simulation of combining of the building blocks, and output an identification of the potential MOFs that can be formed from the building blocks based on the building blocks that can be combined with each other in the simulation.
  • the computer readable storage medium is a tangible and non-transitory computer readable storage medium.
  • the one or more sets of instructions are configured to direct the processor to autothatically direct a fabrication system having one or more sources of the building blocks to create one or more of the potential MOFs.
  • the building blocks include inorganic building blocks, organic building blocks, and functional groups.
  • the one or more sets of instructions are configured to direct the processor to combine the inorganic building blocks with the organic building blocks.
  • the one or more sets of instructions are configured to direct the processor to combine the building blocks based on at least one of topological inforthation or geometrical inforthation assigned to the building blocks.
  • the one or more sets of instructions are configured to direct the processor to calculate one or more thaterial properties of the potential MOFs.
  • the one or more thaterial properties include one or more of surface area, pore volume, pore size distribution, powder x-ray diffraction pattern, or adsorption capability.
  • the one or more sets of instructions are configured to direct the processor to perform an atomistic grand Monte Carlo simulation to calculate at least one of the one or more thaterial properties.
  • a metal organic framework includes a polymeric structure of an inorganic metal center block component; an organic linker block component; and, optionally a solvent, said linker block component comprising a plurality of terminal groups selected from carboxy groups and nitrogenous groups coupled by R, wherein R is selected from a covalent bond and moieties selected from C, arylene moieties, arylene tetracarboxydiimide moieties, fused arylene moieties, fused arylenetetrayl moieties, heteroarylene moieties, di-valent multicycle moieties, ethynylene moieties and ethenylene moieties and combinations of said moieties coupled one to another.
  • the MOF is substantially absent a solvent
  • a said linker component is substituted with at least one group selected from halo, C1-C3 alkyl, amino, phenyl, hydroxy, cyano, and C1-C3 alkoxy groups and combinations thereof.
  • the metal of a said metal center block component is selected from a component comprising Mg2+, Ca2+, Sr2+, Ba2+, Sc3+, Y3+, Ti4+, Zr4+, Hf4+, V4+, V3+, V2+, Nb3+, Ta3+, Cr3+, Mo3+, W3+, Mn3+, Mh2+, Re3+, Re2+, Fe3+, Fe2+, Ru3+, Ru2+, Os3+, Os2+, Co3+, C2+, Rh2+, Rh+, Ir2+, ⁇ +, Ni2+, Ni+, Pd2+, Pd+, Pt2+, Pt+ ⁇ Ca2+, Cu+, Ag+, Au+, Zn2+, Cd2+, Hg2+, A13+, Ga3+, In3+, ⁇ 3+, Si4+ 5 Si2+, Ge4+, Ge2+,
  • said metal center block component is selected from Zn ⁇ O, Zn 3 ⁇ 4 Cu 2 , V 3 0 3 and Zr 6 0 6 .
  • said metal center is Cu 2 .
  • the MOF includes nitrogenous linker component and linker component
  • At least one said linker component is substituted with at least one ethyl group.
  • each said linker component is substituted with a plurality of ethyl groups, and the pore size is about 4- about 8 A.
  • said metal center is Zn 2 .
  • the MOF includes linker component and nitrogenous linker component NC - CN.
  • at least one said linker component is substituted with at least one ethyl group.
  • each said linker component is substituted with a plurality of ethyl groups, and the pore size is about 4- about 8 A.
  • the MOF is in a composition comprising one or more of a binder, an organic viscosity-enhancing agent and a liquid.
  • a metal organic framework includes a polymeric crystalline structure comprising the coordination product of a metal component selected from Zn 4 O, Zn 2 , Cu 2 , V 3 O 3 and Zr 6 O 6 , an organic ligand component selected from the ligands of Figures 3B-C and combinations thereof, and optionally a solvent.
  • said metal component is selected from Cu 2 and Zn 4 O.
  • the MOF is in a composition comprising one or more of a binder, an organic viscosity-enhancing agent and a liquid.
  • the MOF is substantially absent a solvent.
  • a metal organic framework includes a polymeric crystalline structure of a Q12 metal component, a ligand component of a formula
  • the MOF is substantially absent a solvent.
  • the MOF is a composition comprising one or more of a binder, an organic viscosity-enhancing agent and a liquid.
  • a metal organic framework includes a polymeric crystalline structure of a ZojO metal component, a first ligand component of a formula
  • the MOF is substantially absent a solvent.
  • the MOF is in a composition comprising one or more of a binder, an organic viscosity-enhancing agent and a liquid.
  • a metal organic framework (MOF) building block comprising a compound of a formula
  • H ⁇ C and a metal component is provided.
  • the metal component is Cu 2 .
  • a method of gas sorption includes providing a metal organic framework (MOF) comprising a polymeric crystalline structure comprising the coordination product of a metal component selected from Zn 4 O, Zr3 ⁇ 4, Cu 2 , V 3 O 3 and Zr 6 O 6 , an organic ligand component selected from the ligands of Figures 3B-C and combinations thereof, and optionally a solvent.
  • MOF metal organic framework
  • the method also includes contacting said MOF and a gas under at least one of a pressure and a temperature sufficient for gas sorption with said MOF.
  • said gas comprises methane.
  • a method of using a metal organic framework includes building block comprising a ligand component of a compound of a formula
  • the method includes providing a MOF comprising a building block of a compound of a formula
  • said metal component of said building block is Cu 2 .
  • said methane storage is about 240v[STP]/v at about 65 bar.
  • a metal organic framework comprises a polymeric crystalline structure including the coordination product of a metal component comprising a metal center selected from Zn 4 O, Zn 2 , Cu 2 , V 3 O 3 and ZrgOe, an organic ligand component selected from the ligands of Figures 3B-C and combinations thereof, and optionally a solvent.
  • said metal center is selected from Cu 2 and Zn 4 O.
  • the MOF is in a composition comprising one or more of a binder, an organic viscosity-enhancing agent, and a liquid.
  • the MOF is substantially absent a solvent.
  • the embodiment includes a sorbed gas selected from hydrogen, oxygen, nitrogen, the noble gases, acetylene, methane, ethane, propane, natural gases, synthesis gases, carbon monoxide, carbon dioxide, arsine, hydrogen selenide, and combinations thereof.
  • a sorbed gas selected from hydrogen, oxygen, nitrogen, the noble gases, acetylene, methane, ethane, propane, natural gases, synthesis gases, carbon monoxide, carbon dioxide, arsine, hydrogen selenide, and combinations thereof.
  • the embodiment includes sorbed natural gas.
  • a metal organic framework includes a polymeric crystalline structure of a Cu 2 metal component, a ligand component of a formula
  • die MOF is substantially absent a solvent
  • the MOF is in a composition comprising one or more of a binder, an organic viscosity-enhancing agent, and a liquid.
  • the embodiment includes a sorbed gas selected from hydrogen, oxygen, nitrogen, the noble gases, acetylene, methane, ethane, propane, natural gases, synthesis gases, carbon monoxide, carbon dioxide, arsine, hydrogen selenide, and combinations thereof.
  • a sorbed gas selected from hydrogen, oxygen, nitrogen, the noble gases, acetylene, methane, ethane, propane, natural gases, synthesis gases, carbon monoxide, carbon dioxide, arsine, hydrogen selenide, and combinations thereof.
  • the embodiment includes sorbed natural gas.
  • a metal organic framework includes a polymeric crystalline structure of a Zn 4 O metal component, a first ligand component of a formula a second ligand component of a formula and optionally a solvent.
  • the MOF is substantially absent a solvent.
  • the MOF is in a composition comprising one or more of a binder, an organic viscosity-enhancing agent, and a liquid.
  • a metal organic framework (MOF) building block includes a compound of a formula OjH
  • said metal component is Cu 2 .
  • a method of gas sorption includes providing a metal organic framework (MOF) that includes a polymeric crystalline structure comprising the coordination product of a metal component comprising a metal center selected from ZnjO, Zn 2 , Cu 2 , V 3 O 3 and Zr 6 0 6 , an organic ligand component selected from the ligands of Figures 3B-C and combinations thereof, and optionally a solvent.
  • MOF metal organic framework
  • the method also includes contacting said MOF and a gas under at least one of a pressure and a temperature sufficient for gas sorption with said MOF.
  • the MOF includes comprising a sorbed gas selected from hydrogen, oxygen, nitrogen, the noble gases, acetylene, methane, ethane, propane, natural gases, synthesis gases, carbon monoxide, carbon dioxide, arsine, hydrogen selemde, and combinations thereof.
  • a sorbed gas selected from hydrogen, oxygen, nitrogen, the noble gases, acetylene, methane, ethane, propane, natural gases, synthesis gases, carbon monoxide, carbon dioxide, arsine, hydrogen selemde, and combinations thereof.
  • the MOF includes sorbed natural gas.
  • said gas comprises methane.
  • a method of using a metal organic framework (MOF) building block comprising a ligand component of a formula
  • the method includes providing a MOF comprising a building block that includes a compound of a formula
  • said metal component of said building block is Cu 2 .
  • said methane storage is at least about 240v[STP]/v at least about 65 bar.
  • a container for at least one of up-taking, storing and releasing at least one gas includes at least one of an inlet component and an outlet component; a pressure control component to maintain a gas under pressure in said container; and a metal organic framework thaterial comprising a metal organic framework (MOF) that includes a polymeric crystalline structure comprising the coordination product of a metal component comprising a metal center selected from Zn 4 O, Zn 2 , Cu 2 , V 3 O 3 and 3 ⁇ 40 6 , an organic ligand component selected from the ligands of Figures 3B-C and combinations thereof, and optionally a solvent, and optionally a gas.
  • MOF metal organic framework
  • the container includes a gas therein that is selected from hydrogen, oxygen, nitrogen, the noble gases, acetylene, methane, ethane, propane, natural gases, synthesis gases, carbon monoxide, carbon dioxide, arsine, hydrogen selenide, and combinations thereof
  • said gas comprises natural gas.
  • said metal organic framework thaterial comprises a MOF that includes a polymeric crystalline structure of a Cu 2 metal component, a ligand component of a formula
  • the container includes a gas therein that is selected from hydrogen, oxygen, nitrogen, the noble gases, acetylene, methane, ethane, propane, natural gases, synthesis gases, carbon monoxide, carbon dioxide, arsine, hydrogen selenide, and combinations thereof.
  • said gas comprises natural gas.
  • the container is incorporated into a gas storage system.
  • the container is incorporated into a fuel cell.
  • the container is incorporated into a fuel cell of an automotive vehicle.
  • the container is selected from cylindrical and non- cylindrical configurations.
  • the above description is intended to be illustrative, and not restrictive.
  • the above-described embodiments (and/or aspects thereof) may be used in combination with each other.
  • many modifications may be made to adapt a particular situation or thaterial to the teachings of the inventive subject thatter described herein without departing from its scope. While the dimensions and types of thaterials described herein are intended to define the parameters of one or more embodiments of the inventive subject thatter, they are by no means limiting and are example embodiments. Many other embodiments will be apparent to one of ordinary skill in the art upon reviewing the above description.

Abstract

L'invention concerne un système et un procédé de génération systématique de structures de réseaux métallo-organiques potentiels (MOF) à partir d'une bibliothèque d'entrée donnée d'éléments constitutifs. Une ou plusieurs propriétés de matériau des MOF potentiels sont évaluées par simulations computationnelles. Une gamme de propriétés de matériau (surface, volume poreux, distribution de la taille des pores, diagramme de diffraction des rayons X, capacité d'adsorption du méthane et similaire) peuvent être estimées, et ainsi, mettre en évidence des relations propriétés-structure non identifiées qui auraient été reconnues seulement par une vue globale des structures MOF. Outre l'identification des relations propriétés-structure, cette approche systématique d'identification des MOF considérés est utilisée pour identifier un ou plusieurs MOF pouvant être utiles pour le stockage de méthane sous haute pression.
PCT/US2012/045782 2011-07-06 2012-07-06 Système et procédé de génération et/ou de criblage de réseaux métallo-organiques potentiels WO2013058844A1 (fr)

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