Preparation and scale-up methods of the metal-organic framework Cu(Qc)2

Abstract

Methods are provided for producing metal-organic frameworks in a yield of at least about 50% by volume of the metal-organic framework in the metal-organic framework material and / or about 75% by mole of the metal-organic framework in the metal-organic framework material per liter of synthesis solution. Further provided is a method for producing the MOF Cu(Qc)2 in an aqueous solution, in which a solvent composition of less than about 30% by volume of water is combined with a buffer and a plurality of reagents to provide a synthesis solution.

Description

[Technical field]

[0001] (CROSS REFERENCE TO RELATED APPLICATIONS) This application claims priority to and the benefit of U.S. Provisional Application No. 63 / 191,579, filed May 21, 2021, which is incorporated by reference in its entirety.

[0002] The present disclosure relates generally to methods for preparing metal-organic frameworks to provide increased yields and higher mole % of the metal-organic framework in metal-organic framework materials, and more specifically, the increased yields and higher mole % relate to the MOF Cu(Qc)2 as an ethane-selective adsorbent for gas separation. [Background technology]

[0003] Metal-organic frameworks ("MOFs") are materials composed of metals and multitopic organic linkers that self-assemble to form coordination networks. MOFs can have a variety of uses for different applications, including gas storage, gas separation, catalysis, sensing, and environmental cleanup. New selective benchmarks have been realized by using inorganic linkers that tune the pore size and provide strong electrostatic properties. Molecular sieves are sometimes unattainable due to the difficulty in controlling the pore size within the 3-4 Å range that is most relevant for the separation of gas molecules. Even when pore size tuning is shown, the reaction synthesis yields can be very low. Therefore, metal-organic framework ("MOF") materials cannot be mass-produced to be suitable for commercial scale-up. Summary of the Invention

[0004] Provided herein is a method that provides a metal-organic framework yield of at least about 50% by volume in the metal-organic framework material per liter of synthesis solution. The method of producing a metal-organic framework includes mixing ethanol, at least one solvent, a metal acetate salt, and quinoline-5-carboxylic acid to provide a synthesis solution. The at least one solvent is an organic solvent. The synthesis solution is non-aqueous having a concentration of at least 0.04 to 0.4 moles of quinolone-5-carboxylic acid per liter of synthesis solution. The synthesis solution is heated to a reaction temperature. The reaction temperature is reduced to produce a metal-organic framework material having a volumetric yield of at least about 50% by volume of the metal-organic framework. In one embodiment, the concentration of the metal acetate salt in the synthesis solution is between about 0.16 moles and about 0.24 moles per liter of solvent. In one embodiment, the metal-organic framework has a solvent content of between about 9.0 to about 12.7% by volume. In one embodiment, the synthesis solution is heated for at least about 24 hours to about 72 hours. In one embodiment, the reaction temperature is decreased at a rate between about 0.1 and about 10° C. per hour. In one embodiment, the metal-organic framework material comprises MOF Cu(Qc)2. In one embodiment, MOF Cu(Qc)2 has an absorption maximum (λmax) at a wavelength of about 474 nm.

[0005] Also provided herein are methods that result in about 75 mol % metal-organic frameworks in a metal-organic framework material. These methods of producing 75 mol % metal-organic frameworks include providing a solvent composition including at least one solvent. The solvent composition is combined with a plurality of solid reagents to provide a synthesis solution. The synthesis solution is heated to a reaction temperature of at least 80° C. or higher. The reaction temperature is reduced to produce a metal-organic framework material in which 75 mol % of the metal-organic framework material is a metal-organic framework. The plurality of solid reagents include a metal acetate salt and at least 0.04-0.4 moles of quinolone-5-carboxylic acid per liter of synthesis solution. In one embodiment, the solvent composition is non-aqueous. In one embodiment, the solvent is selected from dimethylformamide and / or tetrahydrofuran. In one embodiment, the metal-organic framework has a solvent content of between about 9.0 and about 12.7 vol %. In one embodiment, the metal-organic framework has solvent inclusions of between about 9.0 and about 12.7 vol %. In one embodiment, the reaction temperature is decreased at a rate between about 0.1 and about 10° C. per hour. In one embodiment, the metal-organic framework material comprises MOF Cu(Qc)2. In one embodiment, MOF Cu(Qc)2 has an absorption maximum (λmax) at a wavelength of about 474 nm.

[0006] Further provided are methods for producing metal-organic frameworks with a 75 mol% yield per liter of synthesis solution. In these methods, ethanol, metal acetate, and quinoline-5-carboxylic acid are mixed to provide a synthesis solution. The synthesis solution is heated to a reaction temperature. The reaction temperature is reduced to produce a metal-organic framework material with a 75 mol% yield per liter of synthesis solution. In these methods, the synthesis solution is non-aqueous and has a concentration of at least 0.04 to 0.4 moles of quinolone-5-carboxylic acid per liter of synthesis solution. In one embodiment, the synthesis solution is heated for at least about 24 hours to about 72 hours. In one embodiment, the reaction temperature is reduced at a rate between about 0.1° C. and about 10° C. per hour. In one embodiment, the metal-organic framework material comprises MOF Cu(Qc)2. In one embodiment, the MOF Cu(Qc)2 has an absorption maximum (λmax) at a wavelength of about 474 nm.

[0007] Also provided is a metal-organic framework, MOF Cu(Qc)2, having an absorption maximum (λmax) at a wavelength of about 474 nm and a solvent content between about 9.0 and about 12.7% by volume. The metal-organic framework is produced by a method including mixing ethanol, dimethylformamide, copper acetate hydrate, and quinoline-5-carboxylic acid to provide a synthesis solution. The synthesis solution has a concentration of about 0.04 moles of quinolone-5-carboxylic acid per liter of synthesis solution. The synthesis solution is heated to a reaction temperature of at least 80° C. and the reaction temperature is reduced to produce a metal-organic framework material having at least 75 moles of the metal-organic framework, MOF Cu(Qc)2.

[0008] Methods for producing MOF Cu(Qc)2 in an aqueous solution are also provided. These methods include a solvent composition of less than about 30% water by volume. The solvent composition is combined with a buffer and a plurality of reagents to provide a synthesis solution. The synthesis solution is heated to a reaction temperature of at least 80° C. or greater for at least 4 hours to produce MOF Cu(Qc)2. The reagents include one or more metal salts and one or more linkers. In one embodiment, the metal salt is a metal acetate. In one embodiment, the linker is 5-carboxyquinoline. In one embodiment, the buffer includes a morpholine and a sulfonic acid bridged with an alkyl group. In one embodiment, the buffer includes a Brønsted acid and its conjugate base, or a Brønsted base and its conjugate acid. In one embodiment, the buffer is a bicarbonate or sodium carbonate. In one embodiment, the buffer is MOPS, Na MOPS, or NaHCO3. In one embodiment, the solvent composition is selected by evaluation of the Hansen solubility parameters.

[0009] These and other features and attributes of the present disclosure, as well as their advantageous applications and / or uses, will become apparent from the following detailed description. [Brief description of the drawings]

[0010] To assist those of ordinary skill in the relevant art in making and using the subject matter herein, reference is made to the accompanying drawings, in which: [Figure 1] FIG. 13 provides the results of thermogravimetric analysis of the synthesized MOF Cu(Qc)2, showing a solvent content of 9-12.7%. [Figure 2A] 1 shows the powder X-ray diffraction pattern of a synthesized material of the present invention. [Figure 2B] 1 shows the powder X-ray diffraction pattern of a synthesized material of the present invention. [Figure 2C] 1 shows the powder X-ray diffraction pattern of a synthesized material of the present invention. [Figure 2D] 1 shows the powder X-ray diffraction pattern of a synthesized material of the present invention. [Diagram 3]FIG. 3 is an SEM image of the MOF Cu(Qc)2 material (crystal) synthesized by the method of the present invention in Experiment 1, taken at 3.0 kV, 8.8 mm×2.00 k SE (L). [Figure 4] FIG. 4 is a SEM image taken at 3.0 kV, 8.8 mm×400 SE(L) of the MOF Cu(Qc)2 material synthesized by the method of the present invention in experiment 1. [Diagram 5] FIG. 5 is a SEM image taken at 3.0 kV, 8.7 mm×10.0 k SE(L) of the MOF Cu(Qc)2 material synthesized by the method of the present invention in experiment 1. [Figure 6] FIG. 6 is a SEM image taken at 3.0 kV, 8.7 mm×2.00 k SE(L) of the MOF Cu(Qc)2 material synthesized by the method of the present invention in experiment 1. [Figure 7] FIG. 7 is a SEM image taken at 3.0 kV, 8.7 mm×400 SE(L) of the MOF Cu(Qc)2 material synthesized by the method of the present invention in experiment 1. [Figure 8] FIG. 8 shows the dashed vertical line and the absorption maxima in the UV-Visible for MOF Cu(Qc)2 material made by the prior art synthesis and for material made by the method of the present invention. [Figure 9] FIG. 9 shows the CO2 adsorption isotherms at 195° K for the MOF Cu(Qc)2 synthesized with Cu(OAc)2 at 600 mL and 2 L scales. [Figure 10] FIG. 10 shows the CO2 adsorption data at 195° K for the MOF Cu(Qc)2 material of Example 1. [Figure 11] Figure 11 shows the powder X-ray diffraction pattern of MOF Cu(Qc)2 synthesized in alternative solvents (other than dimethylformamide). [Figure 12] FIG. 12 is an SEM image taken at 3.0 kV, 8.4 mm×10.0 k SE(L) of the comparative MOF Cu(Qc)2 material synthesized by the prior art method. [Figure 13]FIG. 13 is an SEM image taken at 3.0 kV, 8.4 mm×2.00 k SE(L) of the comparative MOF Cu(Qc)2 material synthesized by the prior art method. [Figure 14] FIG. 14 is an SEM image taken at 3.0 kV, 8.4 mm×2.00 k SE(L) of the comparative MOF Cu(Qc)2 material synthesized by the prior art method. [Figure 15] FIG. 15 is an SEM image taken at 3.0 kV, 8.5 mm×2.00 k SE(L) of the comparative MOF Cu(Qc)2 material synthesized by the prior art method. [Figure 16] FIG. 16 is an SEM image taken at 3.0 kV, 8.5 mm×400 k SE(L) of the comparative MOF Cu(Qc)2 material synthesized by the prior art method. [Figure 17] FIG. 17 shows the powder X-ray diffraction patterns of the MOF Cu(Qc)2 materials synthesized in Example 3 with different solvent compositions. [Figure 18] FIG. 18 is a powder X-ray diffraction pattern of the MOF Cu(Qc)2 material synthesized in an aqueous solvent composition containing a buffer at a concentration of 1.25 equivalents relative to the combined organic linker and metal. [Figure 19] FIG. 19 is a graph showing the thermogravimetric analysis of the MOF Cu(Qc)2 materials synthesized in the aqueous solvent compositions of Run 11, Run 12, Run 13, and Run 14 of Example 3. [Figure 20A] FIG. 13 is an SEM image of MOF Cu(Qc)2 material (crystalline) from experiment 11 of Example 3 taken at 2.0 kV, 13.4 mm×4.50 k SE(L). [Figure 20B] FIG. 13 is an SEM image of MOF Cu(Qc)2 material (crystalline) from experiment 11 of Example 3 taken at 2.0 kV, 13.4 mm×3.50 k SE(L). [Figure 21A] 13 is an SEM image taken at 2.0 kV, 13.2 mm×22.0 k SE(L) of MOF Cu(Qc)2 material from run 12 of Example 3. [Figure 21B] 13 is an SEM image taken at 2.0 kV, 13.2 mm×4.50 k SE(L) of the MOF Cu(Qc)2 material of run 12 of Example 3. [Figure 22A] 13 is an SEM image taken at 2.0 kV, 13.1 mm×20.0 k SE(L) of the MOF Cu(Qc)2 material of run 13 of Example 3. [Figure 22B] 13 is an SEM image taken at 2.0 kV, 13.1 mm×4.50 k SE(L) of the MOF Cu(Qc)2 material of run 13 of Example 3. [Figure 23A] 13 is an SEM image taken at 2.0 kV, 13.1 mm×10.0 k SE(L) of MOF Cu(Qc)2 material from run 14 in Example 3. [Figure 23B] 13 is an SEM image taken at 2.0 kV, 13.1 mm×5.00 k SE(L) of MOF Cu(Qc)2 material from run 14 in Example 3. [Figure 24] 1 shows the powder X-ray diffraction patterns of MOF Cu(Qc)2 materials of Run 1 and Run 2 of Example 3 prepared by acetone / water synthesis. [Diagram 25] 1 is a graph showing thermogravimetric analysis of mass Cu(BF4)2·6H2O versus various temperatures in the acetone / water synthesis of run 1 and run 2 of Example 3. [Figure 26A] 13 is an SEM image taken at 2.0 kV, 13.6 mm×19.2 k SE(L) of the MOF Cu(Qc)2 material of run 1 of Example 3. [Figure 26B] 13 is an SEM image taken at 2.0 kV, 13.6 mm×5.00 k SE(L) of the MOF Cu(Qc)2 material of run 1 of Example 3. [Figure 27A] FIG. 13 is an SEM image taken at 2.0 kV, 13.3 mm×25.0 k SE(L) of the MOF Cu(Qc)2 material of run 2 of Example 3. [Figure 27B] FIG. 13 is an SEM image taken at 2.0 kV, 13.3 mm×4.50 k SE(L) of the MOF Cu(Qc)2 material of run 2 of Example 3. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0011] Before the present methods and devices are disclosed and described, it is to be understood that unless otherwise specified, the disclosure is not limited to particular compounds, components, compositions, reactants, reaction conditions, ligands, catalyst structures, metallocene structures, etc. It is also to be understood that the terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting.

[0012] For purposes of this disclosure, the following definitions apply. As used herein, the terms "a" and "the" are understood to encompass the plural as well as the singular.

[0013] As used herein, the term "Periodic Table" refers to the International Union of Pure and Applied Chemistry (IUPAC) Periodic Table of the Elements, dated December 2015.

[0014] As used herein, "isotherm" refers to the adsorption of an adsorbate as a function of concentration while the temperature of the system is held constant.

[0015] The term "salt" includes salts of compounds prepared by neutralization of an acid or base, depending on the particular ligand or substituent found on the compounds described herein. When compounds of the present disclosure contain relatively acidic functional groups, base addition salts can be obtained by contacting the neutral form of such compounds, neat or in a suitable inert solvent, with a sufficient amount of the desired base. Examples of base addition salts include sodium, potassium, calcium, ammonium, organic amino, or magnesium salts, or similar salts. Examples of acid addition salts include salts derived from inorganic acids such as hydrochloride, hydrobromide, nitrate, carbonate, monohydrogen carbonate, phosphate, monohydrogen phosphate, dihydrogen phosphate, sulfate, monohydrogen sulfate, hydroiodide, phosphate, and the like, as well as salts derived from relatively non-toxic organic acids such as acetic acid, propionic acid, isobutyric acid, butyric acid, maleic acid, malic acid, malonic acid, benzoic acid, succinic acid, suberic acid, fumaric acid, lactic acid, mandelic acid, phthalic acid, benzenesulfonic acid, p-tolylsulfonic acid, citric acid, tartaric acid, methanesulfonic acid, and the like. Certain compounds of the present disclosure contain both basic and acidic functionalities, allowing the compounds to be converted into either base or acid addition salts. Hydrates of salts are also included.

[0016] The term "solvent" refers to a system used to dissolve molecules and form a solution that is a major component of the solution, including where the dissolved molecules constitute a minor component or solute.

[0017] The term "reagent" means a molecule, compound, or mixture added to a system to bring about a chemical reaction or to test whether a reaction has occurred, including those that may or may not be consumed or transformed in the course of the reaction.

[0018] The term "Hansen Solubility Parameters" refers to the separation of the cohesive energy density of any molecule into three components that approximate the dispersion forces, the permanent dipole-permanent dipole forces, and the molecular hydrogen bonding forces. Similarity in the respective Hansen Solubility Parameters between two different molecules suggests that solubility is likely to be high. Conversely, molecules with significantly different Hansen Solubility Parameters are unlikely to dissolve. A complete and exhaustive definition and explanation of the Hansen Solubility Parameters can be found in "Hansen Solubility Parameters: A User's Handbook, 2nd Ed." by Charles M. Hansen.

[0019] The term "Powder X-ray Diffraction" or PXRD refers to a scientific technique that uses the diffraction of X-rays to characterize the structural properties of materials. Because the atoms in a material are arranged with a symmetric and regular periodicity, constructive interference of scattered X-rays occurs, resulting in path length differences that are integer multiples of the wavelength, resulting in diffraction maxima according to Bragg's law.

[0020] In compounds described herein having one or more chiral centers, when the absolute stereochemistry is not specified, it is understood that each center may be independently R-configuration or S-configuration, or a mixture thereof. Thus, the compounds provided herein may be enantiomerically pure or may be a mixture of stereoisomers. In addition, in compounds described herein having one or more double bonds that generate geometric isomers that can be defined as E or Z, it is understood that each double bond may be independently E or Z, or a mixture thereof. Similarly, it is understood that in any compound described, all tautomeric forms are also intended to be included.

[0021] Furthermore, the compounds provided herein may contain unnatural proportions of atomic isotopes at one or more of the atoms that constitute such compounds. For example, the compounds may contain isotopes of, for example, tritium ( 3H), Iodine-125( 125 I) or carbon-14 ( 14 C). All isotopic variations of the subject compounds, whether radioactive or not, are intended to be encompassed within the scope of the present disclosure.

[0022] Additionally, all numerical values ​​within the detailed description and claims herein are intended to be modified by "about" or "approximately" the indicated value to take into account experimental error and variations that would be expected by one of ordinary skill in the art.

[0023] Furthermore, a metal-organic framework ("MOF" or "MOFs" in the plural) is a material that contains both metals and multitopic organic linkers that self-assemble to form a coordination network. As used herein, a "metal-organic framework" may be a mixed metal-organic framework or a metal-organic framework system, or a mixed metal mixed organic framework system as described in U.S. Patent Application No. 62 / 839,261.

[0024] MOFs have a wide range of potential applications in many different applications including gas storage, gas separation, catalysis, sensing, and environmental cleanup. The metal-organic framework, MOF Cu(Qc)2 (Qc is quinolone-5-carboxylate), has potential applications in the separation of olefins from paraffins, specifically ethane from ethylene.

[0025] Ethane and ethylene are light hydrocarbons used as chemical feedstocks in the petrochemical industry. Traditionally, energy-intensive cryogenic distillation has been used to separate and recover these molecules from natural gas. Recently, adsorption has proven to be an effective alternative separation method. Adsorption can be operated at room temperature, resulting in significant energy savings. However, the adsorbent must be effective and stable. Metal-organic frameworks have been shown to be effective. Moreover, metal-organic frameworks can provide high adsorption rates at a relatively low cost. However, metal-organic frameworks have a slightly lower selectivity and stability issues compared to cryogenic distillation.

[0026] In terms of gas adsorption for the petroleum industry, metal-organic frameworks are divided into two categories: ethylene-selective adsorbents and ethane-selective adsorbents. In commercial applications, using ethane-selective adsorbents to separate ethylene from classical crack gas (C2H6 / C2H4=1:12-15 vol:vol) is often more effective than ethylene-selective adsorbents, especially for producing polymer-grade ethylene with a purity of 99.8%. Ethane-selective adsorbents usually only require one cycle of adsorption step to obtain polymer-grade ethylene. Liang et al., 2018. These ethane-selective MOF adsorbents include metal-organic framework Cu(Qc)2 ("MOF Cu(Qc)2"). See Chen et al., Tuning Pore Size in Square-Lattice Coordination Networks for Size Selective Sieving of CO2, Chem. Int. Ed., 55, 10268-10272, 2016; Lin et al., Ethane / Ethylene Separation in a Metal Organic Framework With Iron-Peroxo Sites, Science 362, 2018. MOF Cu(Qc)2 preferentially adsorbs ethane over ethylene through van der Waals interactions. Among other ethane-selective MOFs, MOF Cu(Qc)2 has high selectivity for ethane from natural gas ("NG") due to its molecular-dimension ultrafine pore structure.

[0027] As described by Chen et al., 2016, reticulation chemistry can be used to generate metal-organic framework materials, allowing control over pore dimensions and molecular chemistry in ways that are difficult to achieve with other classes of porous materials. In hybrid ultramicroporous materials, pore sizes can be achieved by short organic linkers. Furthermore, molecular sieving (or molecular sieving) can exclude molecules with kinetic diameters larger than the pores, allowing the passage of smaller molecules while achieving ultrahigh selectivity. Unfortunately, molecular sieving in the separation of gas molecules is difficult to achieve because it is difficult to control pore sizes in the range of 3-4 angstroms ("Å"). Furthermore, the large uptake differences observed at low temperatures may be an artifact of pore shrinkage, slower gas diffusion rates, and slower thermal motion. Indeed, these dynamics are undesirable in sieving materials, as they can induce gate opening effects and loss of sieving ability.

[0028] Also, only a handful of molecular sieves are known for CO2 over CH4 and / or N2 under ambient or near-ambient conditions, as reported by Chen et al., 2016. In some of these examples, uncharacterized activated structures are involved in the observed molecular sieves. The coordination networks invariably show a preference for CO2 over N2 and / or CH4 due to weaker adsorbate-adsorbent interactions.

[0029] Nevertheless, Chen et al. (2016) reported that fine tuning of the pore size allows for supramolecular isomerization, i.e., the generation of networks with the same chemical composition but different topologies. An illustrative example is the solvothermal synthesis of quinoline-5-carboxylic acid and the respective metal salts of the formula [M(quinoline-5-carboxylate)2]. n, Qc‐5‐M‐dia (M = Co, Ni, Zn and Cu, dia = 2-fold, 3D diamond network) and Qc‐5‐Cu‐sql‐α (sql = 2D square lattice network).

[0030] Furthermore, Qc-5-M-die and Qc-5-Cu-sol-α were found to be supramolecular isomers. The materials were then studied by single-component gas sorption, kinetic breakthrough of mixed gases, temperature-programmed desorption ("TPD"), and molecular modeling. Upon desolvation, Qc-5-Cu-sql-α undergoes an irreversible phase change to Qc-5-Cu-sql-β, a more stable polymorph of Qc-5-Cu-sql-α. The b phase does not revert to the a phase even upon attempts at desolvation. The b phase does not revert to the a phase even upon attempts at resolvation, heating, or immersion in water for 21 days. Interestingly, Qc-5-Cu-sql-β adsorbs moderate amounts of CO2 at 293 K and 1 atm, but hardly adsorbs CH4 or N2 under the same conditions, suggesting a sieving effect. Qc-5-M-dia crystallizes as a twice-interpenetrated dia network in the tetragonal space group, whereas Qc-5-Cu-sql-α crystallizes in the monoclinic space group P21 / c. Each metal is coordinated to four oxygen atoms (from two carboxylate groups) and two nitrogen atoms (from two quinoline rings). Due to the difference in the orientation of the linker ligands, supramolecular isomerism occurs in Qc-5-Cu. Qc-5-Cu-dia and Qc-5-Cu-sql-α exhibit one-dimensional channels with diameters of 4.8 Å and 3.8 Å, respectively, with network void space of 34.7% and 23.5%, respectively.

[0031] Although these reports seem promising, MOF Cu(Qc)2 currently faces challenges such as high production costs or water vapor instability. There is a need to synthesize MOFs simply and quickly without compromising performance. To further reduce the cost of MOF Cu(Qc)2, various synthesis methods have been investigated. In addition, post-synthesis or pre-synthesis modifications have been proposed to increase the water vapor stability of MOFs without compromising performance. For example, a simple room temperature synthesis of copper-based Cu(Qc)2 has been explored for its performance for ethane / ethylene separation and ethane capture from natural gas. Tang, Y. et al., Room Temperature Synthesis of Cu(Qc)2and its Application for Ethane Capture from Light Hydrocarbons, Chem. Eng. Sci., 213, 2020. Prior to the discovery of the method of the present invention, only small amounts of this material were produced.

[0032] The methods of the present invention provide several advances in metal-organic framework materials and the production of metal-organic frameworks, including: (1) producing metal-organic framework materials with alternative crystallite morphologies and CO2 volumes by varying synthesis conditions (including different metal salts); (2) increasing the volumetric yield of the metal-organic frameworks produced by varying synthesis concentrations; and (3) scale-up of the synthesis of metal-organic frameworks (as a result of other variations in synthesis conditions).

[0033] Conventional synthesis Traditionally, metal-organic frameworks are prepared by the reaction of presynthesized or commercially available linkers with metal ions. In another approach, called "in situ linker synthesis", specific organic linkers (linkers) can be generated in situ in the reaction medium from starting materials. In the synthesis of metal-organic frameworks, organic molecules are not only structure-directing agents but also reactants that are incorporated as part of the framework structure. With this in mind, traditional syntheses generally employ elevated reaction temperatures. Solvothermal reaction conditions, structure-directing agents, mineralizing agents, and microwave-assisted synthesis or steam-assisted transformations have also been recently introduced.

[0034] As referred to herein, conventional synthesis is an applied reaction typically carried out by conventional electrical heating without parallel reactions. In conventional synthesis, the reaction temperature is the main parameter for the synthesis of metal-organic frameworks, and two temperature ranges are usually distinguished, solvothermal and nonsolvothermal, which determine the type of reaction setup used. Solvothermal reactions are generally carried out in a closed vessel under autogenous pressure, around the boiling point of the solvent used. Nonsolvothermal reactions are carried out below or at the boiling point under ambient pressure, simplifying the synthesis requirements. Nonsolvothermal reactions can be further classified as room temperature or elevated temperature.

[0035] Traditional synthesis of metal-organic frameworks is carried out in a solvent at temperatures between room temperature and about 250 °C. Heat is transferred from a high temperature source, an oven, by convection. Alternatively, energy can be introduced mechanically, by electrical potential, electromagnetic radiation, mechanical waves (ultrasound), or mechanically. The energy source is closely related to the time, pressure, and energy per molecule introduced into the system, and each of these parameters can have a strong influence on the metal-organic framework formed and its morphology.

[0036] As described herein, the original synthesis of the MOF Cu(Qc)2 involved a solvothermal method that required high temperatures (105 °C) and long reaction times (48 h). The formula [M(quinoline-5-carboxylate)2] by Chen et al. n Five coordination networks, Qc‐5‐M‐dia (M = Co, Ni, Zn and Cu, dia = 2-fold, 3D diamond network) and Qc‐5‐Cu‐sql‐α (sql = 2D square lattice network), were synthesized from HQc (quinoline‐5‐carboxylic acid) and the respective metal salts by a solvothermal method.

[0037] However, since this time, the room temperature synthesis of MOF Cu(Qc)2 has been recently developed. See, for example, Tang, Y. et al., 2020. Here, ZnO (23.49 mg, 0.29 mmol) and aqueous Cu(BF4)2·6H2O (0.44 g, 0.58 mmol) were dispersed in 12 mL of ethanol and sonicated at room temperature for 10 min to obtain an intermediate solution called (Zn,Cu) hydroxy double salt [(Zn,Cu)(OH)BF4]. Then, a DMF solution (12 mL) of HQc (0.10 g, 0.58 mmol) was added. At the same time, the mixture was stirred and the synthesis reaction was carried out for 1 to 12 h. After that, RT-Cu(Qc)2 was collected as a purple powder by filtration, washed with DMF, and then immersed in ethanol for 1 day. The sample was dried in vacuum at 393 K for 8 h. The addition of ZnO to Cu(BF4)2 6H2O solution was found to be important for promoting the room-temperature synthesis of Cu(Qc)2. ZnO and Cu(BF4)2 in solution form a (Zn,Cu) hydroxyl double salt as an intermediate, which has been reported to have excellent anion exchange properties (Zhao et al., 2015; Li et al., 2017; Wu et al., 2019). - From OH - and BF4 - This facilitated rapid exchange of

[0038] Current methods for producing metal-organic frameworks The method of the present invention is directed to the synthesis of the metal-organic framework MOF Cu(Qc)2 in large quantities and its subsequent use in adsorptive separation applications, in particular the separation of ethane and ethylene. Due to the small pore size of this MOF Cu(Qc)2 material, it has the potential to be used in other separation applications as well.

[0039] The MOF Cu(Qc)2 produced by the method of the present invention has been shown to be useful for the adsorptive separation of ethane / ethylene mixtures. The method of the present invention provides an improved synthesis of metal-organic framework materials at scale with properties different from the synthesis methods originally reported in the literature. The use of metal acetate salts allows the production of metal-organic framework materials of comparable or improved quality compared to previously synthesized materials. The change in metal salt allows the concentration to be significantly increased, improving the volumetric yield of the product without compromising quality. Different crystal sizes and morphologies have been shown compared to lower concentration / different metal salt syntheses. The changes in the metal-organic framework materials are shown, for example, in the UV-Vis spectrum.

[0040] As further described in the Examples below, the method of the present invention for producing a metal-organic framework can yield at least about 50% by volume of the metal-organic framework in the metal-organic framework material per liter of synthesis solution. The method includes mixing ethanol, at least one solvent, a metal acetate salt, and quinoline-5-carboxylic acid to provide a synthesis solution. In this particular methodology, the solvent is an organic solvent. The synthesis solution is non-aqueous having a concentration of at least 0.04-0.4 moles of quinolone-5-carboxylic acid per liter of synthesis solution. The synthesis solution is heated to a reaction temperature. The reaction temperature is reduced to produce a metal-organic framework material having a volumetric yield of at least about 50% by volume of the metal-organic framework.

[0041] According to various embodiments of this methodology, the concentration of the metal acetate in the synthesis solution is between about 0.16 moles and about 0.24 moles per liter of solvent. Additionally, the metal-organic framework can have a solvent content between about 9.0 and about 12.7% by volume. In embodiments, the synthesis solution is heated for at least about 24 hours to about 72 hours. In one embodiment, the reaction temperature is decreased at a rate between about 0.1 and about 10° C. per hour. In one embodiment, the metal-organic framework material is MOF Cu(Qc)2, and in one embodiment, the MOF Cu(Qc)2 has an absorption maximum (λmax) at a wavelength of about 474 nm.

[0042] Also provided herein are methods for producing metal-organic frameworks in about 75 mol % yield in metal-organic framework materials. These methods for producing metal-organic frameworks use a solvent composition having at least one solvent. The solvent composition is combined with a plurality of solid reagents to produce a synthesis solution. The synthesis solution is heated to a reaction temperature of at least 80° C. or greater. Reducing the reaction temperature produces a metal-organic framework material in which about 75 mol % of the metal-organic framework material is the metal-organic framework. The methodology uses a plurality of solid reagents including metal acetate salts and at least 0.04-0.4 moles of quinolone-5-carboxylic acid per liter of synthesis solution. In one embodiment, the solvent composition is non-aqueous. In one embodiment, the solvent is selected from dimethylformamide and / or tetrahydrofuran. In one embodiment, the metal-organic framework has a solvent content of between about 9.0 and about 12.7 vol. %. In one embodiment, the metal-organic framework has a solvent inclusion of between about 9.0 and about 12.7 vol. %. In one embodiment, the synthesis solution is heated for at least about 24 hours to about 72 hours. In one embodiment, the reaction temperature is decreased at a rate between about 0.1 and about 10° C. per hour. In one embodiment, the metal-organic framework material comprises MOF Cu(Qc)2. In one embodiment, MOF Cu(Qc)2 has an absorption maximum (λmax) at a wavelength of about 474 nm.

[0043] The method of the present invention can also provide a metal-organic framework yield of 75 mol% per liter of synthesis solution, wherein ethanol, metal acetate, and quinoline-5-carboxylic acid are mixed to provide a synthesis solution. The synthesis solution is non-aqueous and the concentration of quinoline-5-carboxylic acid is at least 0.04-0.4 moles per liter of synthesis solution. The synthesis solution is heated to a reaction temperature. The reaction temperature is reduced to produce a metal-organic framework material comprising a metal-organic framework yield of 75 mol% per liter of synthesis solution. In one embodiment, the synthesis solution is heated for at least about 24 hours to about 72 hours. In one embodiment, the reaction temperature is reduced at a rate between about 0.1 and about 10° C. per hour. In one embodiment, the metal-organic framework material comprises MOF Cu(Qc)2. In one embodiment, the MOF Cu(Qc)2 has an absorption maximum (λmax) at a wavelength of about 474 nm.

[0044] Further provided herein is a metal-organic framework, MOF Cu(Qc)2, having an absorption maximum (λmax) at a wavelength of about 474 nm and a solvent content between about 9.0 and about 12.7% by volume. The metal-organic framework is produced by a method that includes mixing ethanol, dimethylformamide, copper acetate hydrate, and quinoline-5-carboxylic acid to obtain a synthesis solution. To produce MOF Cu(Qc)2, the synthesis solution has a concentration of about 0.04 moles of quinolone-5-carboxylic acid per liter of synthesis solution and is heated to a reaction temperature of at least 80°C. The reaction temperature is then reduced to produce a metal-organic framework material that includes at least 75 moles of the metal-organic framework MOF Cu(Qc)2.

[0045] As further described in the Examples, alternative novel methods for producing MOF Cu(Qc)2 using aqueous solutions are provided herein. In these methodologies, a solvent composition is combined with a buffer and a plurality of reagents to provide a synthesis solution. The reagents include one or more metal salts and one or more linkers. The solvent composition is about 30% water by volume or less. In one embodiment of this methodology, the solvent composition can be selected by evaluation of Hansen solubility parameters. In one embodiment, the solvent composition includes water and acetone. The synthesis solution is heated to a reaction temperature of at least 85°C or more for at least 4 hours to produce MOF Cu(Qc)2. In one embodiment, the synthesis solution may be heated under static, tumbling or stirring conditions.

[0046] Further, according to one embodiment of this methodology, the metal salt is a metal acetate and the linker is 5-carboxyquinoline. Materials made with the acetate have the same structure and have been shown to have the same, if not greater, surface area and separation performance. The buffer may be morpholine and sulfonic acid bridged with an alkyl group. The buffer may be a Bronsted acid and its conjugate base, or a Bronsted base and its conjugate acid. Furthermore, the buffer may be a bicarbonate or sodium carbonate, such as MOPS, Na MOPS, or NaHCO3.

[0047] According to any one of the embodiments of the methods provided herein, the MOF Cu(Qc)2 can have a particle size between about 0.5 μm and about 755 μm. Further, in one aspect, the MOF Cu(Qc)2 can have a particle size between about 200 and about 300 μm. 2 / g BET surface area. In one embodiment, MOF Cu(Qc)2 has a CO2 capacity of about 40 to about 90 cubic centimeters per gram at 0.5 bar and 195°K. As also provided by the methods described herein, MOF Cu(Qc)2 can have a CO2 capacity of between about 60 cubic centimeters per gram at 0.5 bar and 195°K. In one embodiment, MOF Cu(Qc)2 can have an ethane adsorption capacity of between about 1.8 millimoles per gram and about 2.6 millimoles per gram at 303°K. In one embodiment, MOF Cu(Qc)2 has an ethane adsorption capacity of between about 2.0 to about 2.4.

[0048] Any one of the methods described herein can further include filtering the metal-organic framework material. In addition, the method can optionally include washing the metal-organic framework material and / or triturating the metal-organic framework material. The filtering, washing, and trituration can be repeated at least one time.

[0049] Additionally, any one of the methods described herein can provide metal-organic frameworks that produce X-ray powder diffraction peaks at 2θ values ​​between about 10° and about 15°, and between about 25° and about 30° for the dried metal-organic framework Cu(Qc)2. Additionally, the methods of the present invention can produce MOF Cu(Qc)2 with X-ray powder diffraction peaks at 2θ values ​​equivalent to metal-organic framework Cu(Qc)2 produced by conventional synthesis.

[0050] The synthesis of metal-organic framework materials on a large scale can provide metal-organic frameworks with different properties than the original synthesis reported in the literature. The MOF Cu(Qc)2 has been shown to be useful for adsorptive separation of ethane / ethylene mixtures. In the method of the present invention, metal acetates or similar metal salts are used to produce metal-organic framework materials of comparable or improved quality compared to those previously synthesized. In the experiments described below, it was discovered that the use of metal acetates allows for a significant increase in concentration, improving the volumetric yield of the metal-organic framework product without compromising quality. Furthermore, different crystal sizes and morphologies as well as changes in the material itself, e.g., UV-Vis spectra, were evident compared to the low concentration / different metal salt synthesis.

[0051] The method improves the synthesis of metal-organic framework materials and their production. First, the modification of the synthesis conditions (including different metal salts) results in metal-organic frameworks with different crystallite morphologies, resulting in materials that can accommodate CO2 volumes not available in the prior art. Second, the concentration of the reaction synthesis was adjusted to increase the volumetric yield. Third, as a result of other modifications of the synthesis conditions, the scale-up of the reaction synthesis allows the production of metal-organic framework materials to a larger scale.

[0052] This method increases the yield of MOF Cu(Qc)2, where Qc is quinolone-5-carboxylate, and tests the same and subsequently uses the MOF in an ethane / ethylene adsorptive separation application. This material has the potential to be used in other separation applications due to its small pore size. EXAMPLES

[0053] Features of the present invention are illustrated in the following non-limiting examples.

[0054] Example 1: Increase in process yield and adsorption capacity Two reactions were carried out using the methodology of the present invention. In one reaction, the MOF Cu(Qc)2 was synthesized by mixing 240 milliliters ("mL") of ethanol, 240 mL of dimethylformamide, 8.40 grams ("g") of copper acetate hydrate [Cu(OAc)2·xH2O], and 16.0 g of quinoline-5-carboxylic acid in a 600 mL stainless steel autoclave. The reactor was sealed, stirred at 250 rpm, and heated to a reaction temperature of 105°C for 72 hours ("h"). The synthesis solution was cooled at a rate of 6°C per hour under stirring, and was opened when the synthesis solution reached room temperature. The metal-organic framework material was filtered and a purple solid was collected. The metal-organic framework material was washed with 300 mL of dimethylformamide, 300 mL of ethanol, then triturated with 600 mL of dimethylformamide with stirring at 60 °C, filtered, triturated with 600 mL of ethanol at 60 °C for 3 h, filtered, triturated with 600 mL of methanol at 60 °C for 12 h, and filtered to give 13.13 g of purple powder. As shown in Figure 1, thermogravimetric analysis ("TGA") indicated that this powder contained 12.7% solvent, with a final yield of 11.46 g (61%) of Cu(Qc)2. Other samples contained as little as 9-10% solvent.

[0055] On a larger scale, Cu(Qc)2 was synthesized by mixing 800 mL of ethanol, 800 mL of dimethylformamide, 28.0 g of copper acetate hydrate [Cu(OAc)2·xH2O], and 53.33 g of quinoline-5-carboxylic acid (in that order) in a 2 liter ("L") stainless steel autoclave equipped with a paddle overhead stirrer. The reactor was sealed, stirred at 250 rpm, and heated to a reaction temperature of 105 °C for 72 h. The synthesis solution was cooled at a rate of 6 °C / h under stirring and opened when room temperature was reached. The metal-organic framework material was filtered and a purple solid was collected. The solid was washed with 300 mL of dimethylformamide, 300 mL of ethanol, then triturated with 600 mL of dimethylformamide with stirring at 60 °C, filtered, triturated with 60 mL of ethanol for 3 h, filtered, triturated with 60 mL of methanol for 12 h, and filtered to give 48.6 g (after removing the calculated solvent in the pores as measured by thermogravimetric analysis) of a purple powder. The powder X-ray diffraction patterns of the synthesized material are shown in Figure 2A, Figure 2B, Figure 2C, and Figure 2D.

[0056] The present methodology differs from prior art methods in several notable respects, as summarized in Table 1. The Cu salt was changed to Cu(OAc)2·xH2O from Cu(BF4)2 or Cu(BF4)2·6H2O used in the prior art methods. Furthermore, the concentration of the metal was increased from 0.024 mol / L Cu to 0.096 mol / L Cu. TIFF2024521103000001.tif94164

[0057] As shown in Figures 3 to 7, the morphology of the crystallites produced in this synthesis is crucial in determining the formulation of the material. For this purpose, SEM images of the crystallites were obtained. As shown in Figures 3, 4, 5, and 6, square prism-like rods of 10 μm to 150 μm were observed, with the square dimensions being small compared to the length dimensions.

[0058] The CO2 adsorption properties were measured at 195 K, which can be used as a proxy to determine the surface area of ​​the material and its capacity for ethane / ethylene separation. The produced MOF Cu(Qc)2 was determined to have a CO2 capacity of 2.30 mmol / g at 1 bar. The BET surface area determined from this CO2 adsorption was 229 m 2 / g and the pore volume is 0.10 cm 3 / g.

[0059] As points of comparison, Chen, K. et al., Tuning Pore Size in Square-Lattice Coordination Networks for Size-Selective Sieving of CO2, Angew. Chem. Int. Ed., 55, 10268-10272, 2018. (Comparative Example 1), and Lin, W. et al., Boosting Ethane / Ethylene Separation within Isoreticular Ultramicroporous Metal-Organic Frameworks, J. Am. Chem. Soc., 140, 12940-12946, 2018. (Comparative Example 2) were reproduced for comparison with the data from the synthesis of this method. Figures 12-16 are SEM images of comparative MOF Cu(Qc)2 materials synthesized by prior art methods. As shown in Table 2 below, significantly different particle sizes were observed, with the present compositions having, on average, an order of magnitude higher particle size as well as a significantly larger (more polydisperse) range of particle sizes compared to the prior art samples. TIFF2024521103000002.tif59141

[0060] Additionally, the different materials exhibit differences in color as seen through UV-Vis spectroscopy, as shown in Figure 8. The other materials exhibit a maximum absorption at 458 nm. As shown in Figure 8, the metal-organic framework material produced by the method of the present invention exhibits a maximum absorption at 474 nm.

[0061] As shown in Figures 9 and 10, CO2 uptake at 195K was measured for some of these samples to determine the overall porosity of the material (as it is not porous to N2 at 77K, which is typically used to measure the surface area of ​​the material). The CO2 capacity of the metal-organic framework materials is higher than values ​​found in the literature indicating that they are superior materials with high surface area. For example, Tengjiao, H. et al., Ultramicroporous Metal-Organic Framework Qc-5-Cu for Highly Selective Adsorption of CO2from C2H4Stream, Ind. Eng. Chem. Res. 59, 7, 3153-3161, 2020.

[0062] Example 2: MOF Cu(Qc) 2 Alternative solvent composition for producing The MOF Cu(Qc)2 was synthesized in an alternative solvent composition intended to replace the toxic dimethylformamide in conventional syntheses. The reaction parameters are shown in Table 3 below. TIFF2024521103000003.tif39144

[0063] The alternative solvent compositions produced MOF Cu(Qc)2 according to the powder X-ray diffraction pattern in Figure 11. The method of the present invention for producing MOF Cu(Qc)2 is highly practical in that toxic and hazardous dimethylformamide is replaced with a milder and potentially cheaper solvent.

[0064] Example 3: MOF Cu(Qc) in an aqueous solvent composition 2 Manufacturing A method for producing MOF Cu(Qc)2 without the use of polar aprotic solvents is described in this example. As described herein, conventional syntheses for producing metal-organic frameworks typically involve the use of hazardous and expensive polar aprotic solvents, particularly dimethylformamide ("DMF"). By utilizing Hansen solubility parameters and incorporating inexpensive general-purpose buffers to match the pH, the alternative solvent formulation ("solvent composition") does not require hazardous and expensive polar aprotic solvents. The resulting method is a water / acetone system with sodium carbonate / sodium bicarbonate buffers, which reduces costs from making metal-organic frameworks in DMF and / or using other polar aprotic solvents.

[0065] The conventional synthesis of MOF Cu(Qc)2 was used as follows: 500 mg of 5-carboxyquinoline (CAS 7250.53-5) and 500 mg of Cu(BF4)2 (MIDAS 18-084608-0; CAS 15684-35-2) were mixed in 30 mL of a 1:1 DMF / methanol solution. The synthesis solution was then heated to 105 °C overnight. The reagents were mixed in a round-bottom flask and refluxed with a jacketed condenser.

[0066] Considering the Hansen solubility parameters of 1:1 DMF / methanol solutions, there are various options. The above preparations were repeated substituting DMF / methanol for the solvent compositions mentioned above. The solvent compositions are listed in Table 4 below. One synthesis was attempted at 85°C. A conventional synthesis to make MOF Cu(Qc)2 was performed in DMF / MeOH at 105°C as a control. TIFF2024521103000004.tif55159

[0067] Figure 17 shows the powder X-ray diffraction ("PXRD") data obtained from these syntheses. The control of Cu(Qc)2 is different from that expected. Similar peaks to the control were observed for materials synthesized in alternative solvents.

[0068] Although known to play a role in MOF synthesis, pH was not controlled in the syntheses described in Table 4. This may explain why the solvent compositions performed poorly; however, this did not provide any insight into the results of the control experiments.

[0069] Therefore, in subsequent experiments, weak acid / base pairs (i.e., buffers) were included to control that aspect of the synthesis and achieve the intended phase. The behavior of buffers is determined by the identity of the solvent in which they are dissolved. Most buffers are only known for aqueous solutions. Thus, in the additional syntheses shown in Table 5 below, the minimum volume fraction of water was set to 25%.

[0070] One solvent composition identified as 25% water, 5% n-propanol, 33% tetrahydrofuran, and 37% acetonitrile (Table 5), and another identified as 73% acetone and 27% water (Table 6) were investigated for the synthesis of MOF Cu(Qc)2. The synthesis included a buffer concentration of 1.25 equivalents ("eq") relative to the total of the organic linker and metal. Figures 18 and 19 show the PXRD data for the compositions listed in Table 5. TIFF2024521103000005.tif44157

[0071] Powder X-ray diffraction analysis indicates that a common phase similar to that expected for Cu(Qc)2 is obtained, as shown in Figure 18. Thermogravimetric analysis data reveal a common decomposition temperature and consistent inorganic content in the samples, as shown in Figure 19. SEM images in Figures 20A, 20B, 21A, 21B, 22A, 22B, 23A, and 23B show that complex morphologies are obtained, progressing from moderately well-defined intergrown capped geometric prisms to predominantly wire-like aggregates as a function of synthesis pH.

[0072] The conditions pursued for the acetone / water synthesis are shown in Table 6 below. Characterization data is shown in Figures 24 and 25, and SEM images of the same are shown in Figures 26A, 26B, 27A, and 27B. Sample 2 was run with higher metal loading to test whether the initial preparation was done with anhydrous or hydrated metal due to the different molar volumes of Cu. This result suggests that metal loading is not a significant factor in the synthesis. TIFF2024521103000006.tif38161

[0073] In this specification, when a numerical lower limit and a numerical upper limit are described, a range from any lower limit to any upper limit is envisioned. Although the exemplary embodiments of the present disclosure have been described with particularity, it is understood that various other modifications will be apparent to and can be easily made by those skilled in the art without departing from the spirit and scope of the present disclosure. Therefore, the scope of the claims appended hereto is not intended to be limited to the examples and descriptions described herein, but rather, the claims are to be interpreted as including all features of patentable novelty present in the present disclosure and all features that are treated as equivalents by those skilled in the art to which the present disclosure pertains.

[0074] Additionally or alternatively, the present invention relates to:

[0075] EMBODIMENT 1 (a) mixing ethanol, at least one solvent, a metal acetate salt, and quinoline-5-carboxylic acid to provide a synthesis solution; (b) heating the synthesis solution to a reaction temperature; and (c) reducing the reaction temperature to produce a metal-organic framework material having a volumetric yield of at least about 50% by volume of the metal-organic framework per liter of synthesis solution. Including, 11. A method for preparing a metal-organic framework, wherein the solvent is an organic solvent and the synthesis solution is non-aqueous having a concentration of at least 0.04-0.4 moles of quinolone-5-carboxylic acid per liter of synthesis solution.

[0076] EMBODIMENT 2 (a) providing a solvent composition comprising at least one solvent; (b) combining the solvent composition with a plurality of solid reagents to provide a synthesis solution; (c) heating the synthesis solution to a reaction temperature of at least 80° C.; and (d) reducing the reaction temperature to produce the metal-organic framework material. Including, the plurality of solid reagents comprising a metal acetate and at least 0.04 to 0.4 moles of quinolone-5-carboxylic acid per liter of synthesis solution; A method for producing a metal-organic framework, wherein the metal-organic framework material comprises about 75 mol % of the metal-organic framework.

[0077] EMBODIMENT 3 3. The method of claim 2, wherein the solvent composition is non-aqueous.

[0078] EMBODIMENT 4 The method for preparing a metal-organic framework according to embodiment 2 or 3, wherein the solvent is selected from dimethylformamide and / or tetrahydrofuran.

[0079] EMBODIMENT 5 3. The method for producing a metal-organic framework according to embodiment 1 or 2, wherein the concentration of metal acetate in the synthesis solution is about 0.16-0.24 moles per liter of solvent.

[0080] EMBODIMENT 6 6. The method of any one of the preceding claims, wherein the metal-organic framework has a solvent content between about 9.0 and about 12.7 vol.%.

[0081] EMBODIMENT 7 (a) mixing ethanol, a metal acetate and quinoline-5-carboxylic acid to provide a synthesis solution; (b) heating the synthesis solution to a reaction temperature; and (c) reducing the reaction temperature to produce the metal-organic framework material. Including, the synthesis solution is non-aqueous having a concentration of at least 0.04 to 0.4 moles of quinolone-5-carboxylic acid per liter of synthesis solution; A method for producing a metal-organic framework, wherein the metal-organic framework material comprises a metal-organic framework yield of 75 mol % per liter of synthesis solution.

[0082] EMBODIMENT 8 8. The method of any one of the preceding claims, wherein the synthesis solution is heated for at least about 24 hours to about 72 hours.

[0083] EMBODIMENT 9 9. The method of any one of the preceding claims, wherein the reaction temperature is decreased at a rate of about 0.1 to about 10 °C per hour.

[0084] EMBODIMENT 10 10. The method of any one of claims 1 to 9, wherein the metal-organic framework material comprises MOF Cu(Qc)2.

[0085] EMBODIMENT 11 11. The method of producing the metal-organic framework of embodiment 10, wherein the MOF Cu(Qc)2 has an absorption maximum (λmax) at a wavelength of about 474 nm.

[0086] EMBODIMENT 12 A metal-organic framework MOF Cu(Qc)2 having an absorption maximum (λmax) at a wavelength of about 474 nm and a solvent content between about 9.0 and about 12.7% by volume, wherein the metal-organic framework MOF Cu(Qc)2 is (a) mixing ethanol, dimethylformamide, copper acetate hydrate, and quinoline-5-carboxylic acid to provide a synthesis solution; (b) heating the synthesis solution to a reaction temperature of at least 80° C.; and (c) reducing the reaction temperature to produce a metal-organic framework material comprising at least 75 mol % of the metal-organic framework MOF Cu(Qc)2. and producing the product by a process comprising: The metal-organic framework MOF Cu(Qc)2, wherein the synthesis solution has a concentration of about 0.04 moles of quinolone-5-carboxylic acid per liter of synthesis solution.

[0087] EMBODIMENT 13 (a) providing a solvent composition; (b) combining the solvent composition with a buffer and a plurality of reagents to provide a synthesis solution; and (c) heating the synthesis solution to a reaction temperature of at least 85° C. for at least 4 hours to produce the MOF Cu(Qc)2. Including, the solvent composition comprising less than about 30% by volume water; A method for producing MOF Cu(Qc)2, wherein the reagent comprises one or more metal salts and one or more linkers.

[0088] EMBODIMENT 14 The method for producing MOF Cu(Qc)2 according to embodiment 13, wherein the metal salt is a metal acetate.

[0089] EMBODIMENT 15 The method for producing MOF Cu(Qc)2 according to embodiment 13, wherein the linker is quinolone-5-carboxylate.

[0090] EMBODIMENT 16 14. The method for producing MOF Cu(Qc)2 according to embodiment 13, wherein the buffer comprises morpholine and sulfonic acid bridged with alkyl groups.

[0091] EMBODIMENT 17 14. The method for producing MOF Cu(Qc)2 according to embodiment 13, wherein the buffer comprises a Brønsted acid and its conjugate base, or a Brønsted base and its conjugate acid.

[0092] EMBODIMENT 18 The method for producing MOF Cu(Qc)2 according to embodiment 13, wherein the buffer is bicarbonate or sodium carbonate.

[0093] EMBODIMENT 19 The method for producing MOF Cu(Qc)2 according to embodiment 13, wherein the buffer is MOPS, Na MOPS or NaHCO3.

[0094] EMBODIMENT 20 20. The method for producing MOF Cu(Qc)2 according to embodiment 13, 14, 15, 16, 17, 18 or 19, wherein the synthesis solution is heated between about 100°C and about 160°C.

[0095] EMBODIMENT 21 The method for producing MOF Cu(Qc)2 according to embodiment 13, 14, 15, 16, 17, 18, 19 or 20, wherein the solvent composition comprises water, an alcohol and / or tetrahydrofuran.

[0096] EMBODIMENT 22 22. The method for producing MOF Cu(Qc)2 according to embodiment 21, wherein the alcohol is selected from n-propanol, isopropanol, methanol, ethanol, n-butanol.

[0097] EMBODIMENT 23 22. The method for producing MOF Cu(Qc)2 according to embodiment 13, 14, 15, 16, 17, 18, 19, 20 or 21, wherein the solvent composition is selected by evaluation of the Hansen solubility parameters.

[0098] EMBODIMENT 24 The method for producing MOF Cu(Qc)2 according to embodiment 13, 14, 15, 16, 17, 18, 19, 20, 21, 22 or 23, wherein the synthesis solution is heated under static, tumbling or stirring conditions.

[0099] EMBODIMENT 25 The method for producing MOF Cu(Qc)2 according to embodiment 13, wherein the solvent composition comprises water and acetone.

[0100] EMBODIMENT 26 26. The method of any one of the preceding claims, wherein the MOF Cu(Qc)2 has a particle size of about 0.5 μm to about 755 μm.

[0101] EMBODIMENT 27 MOF Cu(Qc)2 is about 200 to about 300m 2 27. The method of any one of the preceding claims, having a BET surface area of ​​1 / g.

[0102] EMBODIMENT 28 The MOF Cu(Qc)2 has a thermal conductivity of about 40 to about 90 cm at 0.5 bar and 195°K. 3 28. The method according to any one of the preceding claims, having a CO2 capacity of 100 / g.

[0103] EMBODIMENT 29 The MOF Cu(Qc)2 has a thermal conductivity of about 60 cm at 0.5 bar and 195°K. 3 29. The method according to any one of the preceding claims, having a CO2 capacity of 100 / g.

[0104] EMBODIMENT 30 30. The method of any one of the preceding claims, wherein the MOF Cu(Qc)2 has an ethane adsorption capacity of about 1.8 to about 2.6 mmol / g at 303°K.

[0105] EMBODIMENT 31 31. The method of any one of the preceding embodiments, wherein the MOF Cu(Qc)2 has an ethane adsorption capacity of about 2.0 to about 2.4.

[0106] EMBODIMENT 32 32. The method of any one of the preceding embodiments, further comprising filtering the metal-organic framework material.

[0107] EMBODIMENT 33 33. The method of any one of the preceding embodiments, further comprising washing the metal-organic framework material.

[0108] EMBODIMENT 34 34. The method of any one of the preceding embodiments, further comprising triturating the metal-organic framework material in a solvent.

[0109] EMBODIMENT 35 The method according to any one of embodiments 1 to 34, wherein the steps of embodiments 28, 29 and 30 are repeated at least once.

[0110] EMBODIMENT 36 36. The method of any one of the preceding claims, wherein the metal-organic framework produces powder X-ray diffraction peaks at 2θ values ​​between about 10° and about 15°, and between about 25° and about 30° for the dried metal-organic framework Cu(Qc)2.

[0111] EMBODIMENT 37 37. The method according to any one of the preceding claims, wherein the MOF Cu(Qc)2 gives rise to powder X-ray diffraction peaks at 2θ values ​​equal to those of the metal-organic framework Cu(Qc)2 produced by conventional synthetic methods.

Claims

1. mixing ethanol, at least one solvent, a metal acetate salt, and quinoline-5-carboxylic acid to provide a synthesis solution; heating the synthesis solution to a reaction temperature; and Reducing the reaction temperature to produce a metal-organic framework material having a volumetric yield of at least about 50 volume percent of the metal-organic framework per liter of synthesis solution. Including, A method for preparing a metal-organic framework, wherein the solvent is an organic solvent and the synthesis solution is non-aqueous having a concentration of at least 0.04 to 0.4 moles of quinolone-5-carboxylic acid per liter of synthesis solution.

2. providing a solvent composition comprising at least one solvent; combining the solvent composition with a plurality of solid reagents to provide a synthesis solution; Heating the synthesis solution to a reaction temperature of at least 80° C. or higher; and Reducing the reaction temperature to produce the metal-organic framework material. Including, the plurality of solid reagents comprising a metal acetate salt and at least 0.04 to 0.4 moles of quinolone-5-carboxylic acid per liter of synthesis solution; A method for producing a metal-organic framework, wherein the metal-organic framework material comprises about 75 mol % of the metal-organic framework.

3. The method of claim 2 , wherein the solvent composition is non-aqueous.

4. The method for preparing a metal-organic framework according to claim 2, wherein the solvent is selected from dimethylformamide and / or tetrahydrofuran.

5. The method for preparing a metal-organic framework according to claim 1 or 2, wherein the concentration of metal acetate in the synthesis solution is about 0.16 to 0.24 moles per liter of solvent.

6. The method of claim 1 or 2, wherein the metal-organic framework has a solvent content between about 9.0 and about 12.7 vol.%.

7. mixing ethanol, a metal acetate salt and quinoline-5-carboxylic acid to provide a synthesis solution; heating the synthesis solution to a reaction temperature; and Reducing the reaction temperature to produce the metal-organic framework material. Including, the synthesis solution is non-aqueous having a concentration of at least 0.04 to 0.4 moles of quinolone-5-carboxylic acid per liter of synthesis solution; A method for producing a metal-organic framework, wherein the metal-organic framework material comprises a metal-organic framework yield of 75 mol % per liter of synthesis solution.

8. The method of claim 1, 2 or 7, wherein the synthesis solution is heated for at least about 24 hours to about 72 hours.

9. The method of claim 1, 2 or 7, wherein the reaction temperature is decreased at a rate of about 0.1 to about 10° C. per hour.

10. The metal-organic framework material is MOF Cu(Qc), where Qc is quinolone-5-carboxylate. ２ A method for preparing the metal-organic framework of claim 1 , 2 or 7, comprising:

11. MOF Cu(Qc) ２ 11. The method of claim 10, wherein the metal-organic framework has an absorption maximum (λmax) at a wavelength of about 474 nm.

12. Metal-organic framework MOF Cu(Qc) having an absorption maximum (λmax) at a wavelength of about 474 nm and a solvent content between about 9.0 and about 12.7% by volume, where Qc is quinolone-5-carboxylate. ２ And, The metal-organic framework MOF Cu(Qc) ２ but, mixing ethanol, dimethylformamide, copper acetate hydrate, and quinoline-5-carboxylic acid to provide a synthesis solution; heating the synthesis solution to a reaction temperature of at least 80° C.; and By lowering the reaction temperature, at least 75 mol % of the metal-organic framework MOF Cu(Qc) ２ A process for producing a metal-organic framework material comprising: The method includes the steps of: The synthesis solution has a concentration of about 0.04 moles of quinolone-5-carboxylic acid per liter of synthesis solution. ２ .

13. providing a solvent composition; combining the solvent composition with a buffer and a plurality of reagents to provide a synthesis solution; and The synthesis solution is heated to a reaction temperature of at least 85° C. for at least 4 hours to obtain MOF Cu(Qc). ２ The process of manufacturing Including, the solvent composition comprising less than about 30% by volume water; The reagent comprises one or more metal salts and one or more linkers, and Qc is a quinolone-5-carboxylate. ２ Manufacturing method.

14. 14. The MOF Cu(Qc) of claim 13, wherein the metal salt is a metal acetate. ２ Manufacturing method.

15. 14. The MOF Cu(Qc) of claim 13, wherein the buffer comprises morpholine and sulfonic acid bridged with alkyl groups. ２ Manufacturing method.

16. 14. The MOF Cu(Qc) of claim 13, wherein the buffer comprises a Brønsted acid and its conjugate base, or a Brønsted base and its conjugate acid. ２ Manufacturing method.

17. 14. The MOF Cu(Qc) of claim 13, wherein the buffer is bicarbonate or sodium carbonate. ２ Manufacturing method.

18. The MOF Cu(Qc) of claim 13, wherein the synthesis solution is heated between about 100° C. and about 160° C. ２ Manufacturing method.

19. 14. The MOF Cu(Qc) of claim 13, wherein the solvent composition comprises water, an alcohol and / or tetrahydrofuran. ２ Manufacturing method.

20. 20. The MOF Cu(Qc) of claim 19, wherein the alcohol is selected from n-propanol, isopropanol, methanol, ethanol, n-butanol. ２ Manufacturing method.

21. 14. The MOF Cu(Qc) of claim 13, wherein the solvent composition is selected by evaluation of the Hansen solubility parameters. ２ Manufacturing method.

22. 14. The MOF Cu(Qc) of claim 13, wherein the solvent composition comprises water and acetone. ２ Manufacturing method.

23. filtering the metal-organic framework material; washing the metal-organic framework material; and 14. The method of claim 1, 2, 7 or 13, further comprising at least one step of triturating the metal-organic framework material in a solvent.

24. 24. The method of claim 23, wherein the steps of claim 23 are repeated at least once.

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