Method for producing metal-organic framework compound

Abstract

A method for producing a metal-organic framework (MOF) compound comprising a MOF metal and a MOF linker is disclosed. The method includes forming a mixture comprising a MOF metal precursor, a MOF linker precursor, a solvent, and optionally a base. The method also includes reacting the mixture under reaction conditions selected from the group consisting of ambient reaction pressure, a mixture temperature below about the boiling point of the solvent, an aqueous reaction mixture, and combinations thereof. The MOF compound produced by the method is also disclosed.

Description

[Technical Field]

[0001] The present disclosure relates generally to methods for producing metal-organic framework (MOF) compounds and the MOF compounds produced by the same, and more specifically to a facile method for synthesizing MOF compounds. [Background technology]

[0002] MOF compounds are useful in a wide variety of applications, for example, they are useful in carbon capture sorbent systems such as those used in post-combustion and direct air capture of CO2.

[0003] MOF compounds are often produced by solvothermal methods. For example, one known solvothermal method involves reacting a MOF metal precursor and a MOF linker precursor in dimethylformamide (DMF) and methanol (MeOH) or ethanol (EtOH) under pressure in a sealed vessel at a temperature above the boiling point of one of the solvents (e.g., at 120°C), followed by washing the product with methanol. However, such solvothermal methods have safety, toxicity, scalability, and cost challenges associated with the specific solvents used, and require a reaction vessel capable of being exposed to high pressures and temperatures. Furthermore, some MOF compounds produced by these solvothermal methods, such as Mg2(dobpdc), are known to be unstable in the presence of moisture and / or water under various conditions. For example, as described in Wang, et al., ACS Appl. Mater. Interfaces, 2021, 13, 17517, Mg2(dobpdc) prepared by a known solvothermal method in DMF / methanol at 120 °C in a high-pressure sealed vessel exhibits new reflections and a 28% increase in full width at half maximum (FWHM) in powder X-ray diffraction (PXRD) upon exposure to deionized water. This increase in FWHM indicates partial dissolution or amorphization of the MOF framework structure. As another example, as described in Vitillo, et al., Mater. Chem. Front., 2017, 1, 444, Mg2(dobpdc) was found to lose more than 80% of its surface area upon storage in humid air at humidity levels >86% for 24 hours. Similarly, as described in Schoenecker, et. al., Ind. Eng. Chem. Red., 2012, 51, 6513, a related Mg2(dobdc) material prepared by a known solvothermal method lost 83% of its BET surface area upon reactivation by exposure to 80% relative humidity (RH). Furthermore, PXRD analysis of this material showed a slight loss of crystallinity, which, combined with the loss of BET surface area, suggests structural degradation. Therefore, opportunities for pursuing alternative, facile reaction schemes are limited. Therefore, a facile method for the preparation of MOF compounds is needed. [Prior art documents] [Non-patent literature]

[0004] [Non-Patent Document 1] Wang, et. al., ACS Appl. Mater. Interfaces, 2021, 13, 17517 [Non-patent document 2] Vitillo, et al, Mater. Chem. Front., 2017, 1, 444 [Non-patent document 3] Schoenecker, et. al., Ind. Eng. Chem. Red., 2012, 51, 6513 Summary of the Invention

[0005] In one aspect, the present application provides a method for producing a metal-organic framework (MOF) compound comprising a MOF metal and a MOF linker, the method comprising: I) forming a mixture comprising a MOF metal precursor, a MOF linker precursor, a solvent, and optionally a base; and II) reacting the mixture under reaction conditions selected from the group consisting of ambient reaction pressure, a mixture temperature below about the boiling point of the solvent, an aqueous reaction mixture, and combinations thereof.

[0006] In another aspect, the present application provides a metal-organic framework (MOF) compound comprising a MOF metal and a MOF linker, wherein the MOF compound is produced by a process comprising: I) forming a mixture comprising a MOF metal precursor, a MOF linker precursor, a solvent, and optionally a base; and II) reacting the mixture under reaction conditions selected from the group consisting of ambient reaction pressure, a mixture temperature below about the boiling point of the solvent, an aqueous reaction mixture, and combinations thereof. [Brief explanation of the drawings]

[0007] These and other features, aspects, and advantages of the present disclosure will become better understood by reference to the following detailed description taken in conjunction with the accompanying drawings, in which like reference numerals represent like elements throughout. [Figure 1] 1 is a flowchart of an exemplary method according to the present disclosure. [Figure 2] FIG. 1 shows a first representative reaction according to the present disclosure. [Figure 3] FIG. 1 shows a second exemplary reaction according to the present disclosure. [Figure 4] FIG. 10 shows a third exemplary reaction according to the present disclosure.

[0008] Unless otherwise indicated, the drawings accompanying this application illustrate features of embodiments of the disclosed technology. These features are contemplated as being applicable to a wide variety of systems incorporating one or more embodiments of the disclosed technology. As such, the drawings may not include all of the conventional features known to those skilled in the art to be required to practice the embodiments disclosed herein. DETAILED DESCRIPTION OF THE INVENTION

[0009] Embodiments described herein address at least some of the shortcomings of known methods for producing MOF compounds and known MOF compounds. Exemplary embodiments described herein include methods for producing metal-organic framework (MOF) compounds comprising a MOF metal and a MOF linker, comprising: I) forming a mixture comprising a MOF metal precursor, a MOF linker precursor, a solvent, and optionally a base; and II) reacting the mixture under reaction conditions selected from the group consisting of ambient reaction pressure, a mixture temperature below about the boiling point of the solvent, an aqueous reaction mixture, and combinations thereof. Embodiments of the methods described herein use less toxic solvents, lower pressures, and / or require lower reaction temperatures compared to known methods. Accordingly, exemplary embodiments offer advantages in scalability, safety, cost, and waste handling compared to at least some known methods for producing MOF compounds.

[0010] Embodiments described herein include metal-organic framework (MOF) compounds comprising a MOF metal and a MOF linker, the MOF compounds being prepared by a process comprising: I) forming a mixture comprising a MOF metal precursor, a MOF linker precursor, a solvent, and optionally a base; and II) reacting the mixture under reaction conditions selected from the group consisting of ambient reaction pressure, a mixture temperature below about the boiling point of the solvent, an aqueous reaction mixture, and combinations thereof. The MOF compound embodiments described herein have improved properties compared to the same MOF compounds prepared by known processes. Such improved properties include higher guest adsorption and / or higher surface area and / or higher pore volume compared to at least some known MOF compounds prepared by known processes.

[0011] The MOF compounds described herein are generally easier to purify, for example, by solvent washing, than the same MOF compounds prepared by known methods. This improved purification results from the relative ease of removing solvent molecules (e.g., water) from the MOF compounds described herein compared to the tightly bound solvent molecules (e.g., DMF) utilized in preparing the same MOF compounds by known methods. Furthermore, the purified MOF compounds do not contain tightly bound solvent molecules that would reduce gas absorption, surface area, and / or overall pore volume. Furthermore, purification is improved by the reduced toxicity of the required purification methods.

[0012] The above-mentioned advantages and improved properties are surprising in view of the instability of known MOF compounds in water when prepared by known methods.

[0013] 1 is an exemplary method flowchart 110. In this exemplary embodiment, method flowchart 110 illustrates basic steps of a method embodiment described herein, but is not intended to be limiting of the method embodiment. Method step 112 includes forming a mixture including a MOF metal precursor, a MOF linker precursor, a solvent, and optionally a base. Method step 114 includes reacting the mixture under reaction conditions selected from the group consisting of ambient reaction pressure, a mixture temperature below about the boiling point of the solvent, an aqueous reaction mixture, and combinations thereof.

[0014] 2 is a first exemplary reaction according to the present disclosure. In this exemplary embodiment, water is used as the solvent.

[0015] 3 is a second exemplary reaction according to the present disclosure. In this exemplary embodiment, a mixture of DMF and ethylene glycol is used as the solvent.

[0016] 4 is a third exemplary reaction according to the present disclosure. In this exemplary embodiment, a mixture of DMF and ethylene glycol is used as the solvent.

[0017] In some embodiments, the MOF metal precursor can be any suitable MOF metal precursor known in the art that is conducive to the methods described herein. In other embodiments, the MOF metal precursor is a metal selected from the group consisting of alkali metals, alkaline earth metals, transition metals, Ca, Mn, Cr, Fe, Co, Ni, Cu, Zn, ions thereof, hydrates thereof, salts thereof, halides thereof, fluorides thereof, chlorides thereof, bromides thereof, iodides thereof, nitrates thereof, acetates thereof, sulfates thereof, phosphates thereof, carbonates thereof, oxides thereof, formates thereof, carboxylates thereof, and combinations thereof. In some embodiments, the MOF metal precursor comprises Mg. In some embodiments, the MOF metal precursor is Mg(NO3)2. In some embodiments, the MOF metal precursor is MgBr2.

[0018] In some embodiments, the MOF linker precursor can be any suitable MOF linker precursor known in the art that is conducive to the methods described herein. In at least some embodiments, the MOF linker precursor can be a polytopic linker, 4,4'-dihydroxy-[1,1'-biphenyl]-3,3'-dicarboxylic acid (H4dobpdc), 4,4'-dioxidobiphenyl-3,3'-dicarboxylate (dobpdc), or 4- ), 4,4”-dioxide-[1,1':4',1”-terphenyl]-3,3”-dicarboxylate (dotpdc 4- ), 2,5-dioxidobenzene-1,4-dicarboxylate (dobdc 4- ), 4,6-dihydroxyisophthalic acid (m-DOBDC 4- ), 3,3'-dioxide-biphenyl-4,4'-dicarboxylate (para-carboxylate-dobpdc 4- ), 4,4'-[oxalylbis(imino)]bis(2-hydroxybenzoic acid) (H4ODA), 4,4'-[1,4-phenylenebis-(carbonylimino)]bis(2-hydroxybenzoic acid) (H4TDA), 4,4'-dihydroxyazobenzene-3,3'-dicarboxylic acid (H4OSA), their protonated forms, partially or fully deprotonated forms, and combinations thereof.

[0019] In an exemplary embodiment, the MOF linker precursor is 4,4'-dihydroxy-[1,1'-biphenyl]-3,3'-dicarboxylic acid (H4dobpdc) and / or 4,4'-dioxidobiphenyl-3,3'-dicarboxylate (dobpdc 4- In some embodiments, dobpdc includes 4,4'-dihydroxy-[1,1'-biphenyl]-3,3'-dicarboxylic acid, its monocarboxylate form, its dicarboxylate form, its monophenoxide form, its diphenoxide form, and combinations thereof.

[0020] In some embodiments, the MOF linker precursor is one or more of the linkers shown below.

[0021] [ka]

[0022] [ka]

[0023] [ka]

[0024] In many embodiments, the solvent can be any suitable solvent known in the art conducive to the methods described herein. In some embodiments, the solvent is a solvent selected from the group consisting of aqueous solvents, organic solvents, and combinations thereof. In some embodiments, the solvent is a solvent selected from the group consisting of water, dimethylformamide, ethylene glycol, ethanol, methanol, propanol, isopropanol, and combinations thereof.

[0025] In some embodiments, the solvent is an aqueous solvent. In some embodiments, the solvent is water. In some embodiments, the solvent is a water mixture.

[0026] In many embodiments, the base can be any suitable base known in the art that is conducive to the methods described herein. In some embodiments, the base is a base selected from the group consisting of a strong base, a weak base, an inorganic base, a hydroxide, sodium hydroxide, potassium hydroxide, lithium hydroxide, cesium hydroxide, magnesium hydroxide, calcium hydroxide, an organic base, an amine, and combinations thereof. In some embodiments, the base is sodium hydroxide.

[0027] In many embodiments, the reaction conditions can include any suitable reaction conditions known in the art conducive to the methods described herein. In many embodiments, the reaction conditions do not include solvothermal reaction conditions. In many embodiments, the reaction conditions include reaction conditions selected from the group consisting of ambient reaction pressure, a mixture temperature below about the boiling point of the solvent, an aqueous reaction mixture, and combinations thereof.

[0028] In some embodiments, the reaction conditions include ambient reaction pressure. In some embodiments, reacting the mixture includes reacting the mixture in an open reaction vessel. In some embodiments, reacting the mixture includes reacting the mixture without pressure. In some embodiments, when reacting the mixture, the reaction does not occur in a closed vessel.

[0029] In some embodiments, the reaction conditions include ensuring that the mixture temperature is below about the boiling point of the solvent. In some embodiments, the reaction conditions include ensuring that the mixture temperature is below about 200°C. In some embodiments, the reaction conditions include ensuring that the mixture temperature is below about 190°C. In some embodiments, the reaction conditions include ensuring that the mixture temperature is below about 180°C. In some embodiments, the reaction conditions include ensuring that the mixture temperature is below about 170°C. In some embodiments, the reaction conditions include ensuring that the mixture temperature is below about 160°C. In some embodiments, the reaction conditions include ensuring that the mixture temperature is below about 150°C. In some embodiments, the reaction conditions include ensuring that the mixture temperature is below about 140°C. In some embodiments, the reaction conditions include ensuring that the mixture temperature is below about 130°C. In some embodiments, the reaction conditions include ensuring that the mixture temperature is below about 120°C. In some embodiments, the reaction conditions include ensuring that the mixture temperature is below about 115°C. In some embodiments, the reaction conditions include ensuring the mixture temperature is less than about 110°C. In some embodiments, the reaction conditions include ensuring the mixture temperature is less than about 105°C. In some embodiments, the reaction conditions include ensuring the mixture temperature is less than about 100°C. In some embodiments, the reaction conditions use a mixture temperature of less than about 100°C. In some embodiments, the reaction conditions use a mixture temperature of less than about 97°C. In some embodiments, the reaction conditions use a mixture temperature in the range of about 80°C to about 100°C. In some embodiments, the method includes heating the mixture under reflux. In some embodiments, the method includes heating the mixture under gentle reflux.

[0030] In many embodiments, reacting the mixture can be carried out for any suitable time known in the art conducive to the methods described herein. In some embodiments, the mixture is reacted for about 1 hour to about 72 hours. In some embodiments, the mixture is reacted for about 1 hour to about 24 hours. In some embodiments, the mixture is reacted for about 1 hour to about 12 hours. In some embodiments, the mixture is reacted for about 1 hour to about 8 hours. In some embodiments, the mixture is reacted for about 1 hour to about 4 hours. In some embodiments, the mixture is reacted for about 1 hour to about 2 hours.

[0031] In many embodiments, the method may further include suitable process steps known in the art that contribute to the success of the methods described herein. Such process steps include washing, drying, filtering, purifying, centrifugation, and combinations thereof. In some embodiments, the method also includes washing the MOF compound with a wash solvent selected from the group consisting of alcohol, isopropanol, propanol, ethanol, methanol, water, and combinations thereof. In some embodiments, the method further includes washing the MOF compound with isopropanol.

[0032] In some embodiments, the MOF compound is a MOF-74 family MOF compound. In some embodiments, the MOF compound is Mg2(dobpdc).

[0033] In many embodiments, the MOF compounds have improved properties compared to the same MOF compounds prepared by known methods. In some embodiments, the MOF compounds have similar or higher guest adsorption and / or higher surface area and / or higher absorption compared to the same MOF compounds prepared by known methods. For example, Mg2(dobpdc) prepared by known methods such as those described in Milner, et al., Chem. Sci., 2017, 160-174; Choe, et al., Commun. Mater., 2021, 2, 3; and Kim et al., Science, 2020, 369, 392-396, have a surface area of ​​800-900 cm, respectively.3 / g and 3100-3300m 2 / g N2 absorption and BET surface area, whereas Mg2(dobpdc) produced by the method described in this application has an N2 absorption and BET surface area of ​​800-1000 cm2 depending on the solvent combination used. 3 / g N2 absorption and 3100-3400m 2 / g BET surface area.

[0034] In many embodiments, the MOF compounds may be used for any suitable purpose known in the art. In some embodiments, the MOF compounds are used in sorbent systems. In some embodiments, the MOF compounds are used in carbon sorbent systems. In some embodiments, the MOF compounds are used in moisture sorbent systems. In some embodiments, the MOF compounds are used in gas capture. In some embodiments, the MOF compounds are used in post-combustion capture of CO2 and / or direct air capture of CO2.

[0035] Additional aspects of the present invention are presented in the following embodiments section.

[0036] [Embodiment Item 1] 1. A method for producing a metal-organic framework (MOF) compound comprising a MOF metal and a MOF linker, the method comprising: I) forming a mixture comprising a MOF metal precursor, a MOF linker precursor, a solvent, and optionally a base; and II) reacting the mixture under reaction conditions selected from the group consisting of ambient reaction pressure, a mixture temperature below about the boiling point of the solvent, an aqueous reaction mixture, and combinations thereof.

[0037] [Embodiment 2] 2. The method of embodiment 1, wherein the MOF metal precursor comprises a metal selected from the group consisting of alkali metals, alkaline earth metals, transition metals, Mg, Ca, Mn, Cr, Fe, Co, Ni, Cu, Zn, ions thereof, hydrates thereof, salts thereof, halides thereof, fluorides thereof, chlorides thereof, bromides thereof, iodides thereof, nitrates thereof, acetates thereof, sulfates thereof, phosphates thereof, carbonates thereof, oxides thereof, formates thereof, carboxylates thereof, and combinations thereof.

[0038] [Embodiment 3] The MOF linker precursors consisted of a polytopic linker, 4,4'-dihydroxy-[1,1'-biphenyl]-3,3'-dicarboxylic acid (H4dobpdc), 4,4'-dioxidobiphenyl-3,3'-dicarboxylate (dobpdc 4- ), 4,4”-dioxide-[1,1':4',1”-terphenyl]-3,3”-dicarboxylate (dotpdc 4- ), 2,5-dioxidobenzene-1,4-dicarboxylate (dobdc 4- ), 4,6-dihydroxyisophthalic acid (m-DOBDC 4- ), 3,3'-dioxide-biphenyl-4,4'-dicarboxylate (para-carboxylate-dobpdc 4- 4,4'-[oxalylbis(imino)]bis(2-hydroxybenzoic acid) (H4ODA), 4,4'-[1,4-phenylenebis-(carbonylimino)]bis(2-hydroxybenzoic acid) (H4TDA), 4,4'-dihydroxyazobenzene-3,3'-dicarboxylic acid (H4OSA), protonated, partially or fully deprotonated forms thereof, and combinations thereof.

[0039] [Embodiment 4] The method of any one of embodiments 1 to 3, wherein the solvent comprises a solvent selected from the group consisting of aqueous solvents, organic solvents, and combinations thereof.

[0040] [Embodiment 5] The method of any one of embodiments 1 to 4, wherein the solvent is an aqueous solvent.

[0041] [Embodiment 6] The method of any one of embodiments 1 to 5, wherein the solvent comprises a solvent selected from the group consisting of water, dimethylformamide, ethylene glycol, ethanol, methanol, propanol, isopropanol, and combinations thereof.

[0042] [Embodiment 7] The process of any one of embodiments 1 to 6, wherein the base comprises a base selected from the group consisting of a strong base, a weak base, an inorganic base, a hydroxide, sodium hydroxide, potassium hydroxide, lithium hydroxide, cesium hydroxide, magnesium hydroxide, calcium hydroxide, an organic base, an amine, and combinations thereof.

[0043] [Embodiment 8] The method of any one of embodiments 1 through 7, wherein reacting the mixture comprises reacting the mixture in an open reaction vessel.

[0044] [Embodiment Item 9] The method of any one of paragraphs 1 through 8, wherein reacting the mixture comprises reacting the mixture under reflux.

[0045] [Embodiment Item 10] The method of any one of embodiments 1 to 9, wherein the method further comprises washing the MOF compound with a wash solvent selected from the group consisting of alcohol, isopropanol, propanol, ethanol, methanol, water, and combinations thereof.

[0046] [Embodiment Item 11] A metal-organic framework (MOF) compound comprising a MOF metal and a MOF linker, the MOF compound comprising: I) forming a mixture comprising a MOF metal precursor, a MOF linker precursor, a solvent, and optionally a base; and II) reacting the mixture under reaction conditions selected from the group consisting of ambient reaction pressure, a mixture temperature below about the boiling point of the solvent, an aqueous reaction mixture, and combinations thereof. The MOF compound is produced by a method comprising:

[0047] [Embodiment Item 12] 12. The MOF compound of embodiment 11, wherein the MOF metal precursor comprises a metal selected from the group consisting of alkali metals, alkaline earth metals, transition metals, Mg, Ca, Mn, Cr, Fe, Co, Ni, Cu, Zn, ions thereof, hydrates thereof, salts thereof, halides thereof, fluorides thereof, chlorides thereof, bromides thereof, iodides thereof, nitrates thereof, acetates thereof, sulfates thereof, phosphates thereof, carbonates thereof, oxides thereof, formates thereof, carboxylates thereof, and combinations thereof.

[0048] [Embodiment Item 13] The MOF linker precursors consisted of a polytopic linker, 4,4'-dihydroxy-[1,1'-biphenyl]-3,3'-dicarboxylic acid (H4dobpdc), 4,4'-dioxidobiphenyl-3,3'-dicarboxylate (dobpdc 4- ), 4,4”-dioxide-[1,1':4',1”-terphenyl]-3,3”-dicarboxylate (dotpdc 4- ), 2,5-dioxidobenzene-1,4-dicarboxylate (dobdc 4- ), 4,6-dihydroxyisophthalic acid (m-DOBDC 4- ), 3,3'-dioxide-biphenyl-4,4'-dicarboxylate (para-carboxylate-dobpdc 4-13. The MOF compound according to embodiment 11 or embodiment 12, comprising a linker selected from the group consisting of 4,4'-[oxalylbis(imino)]bis(2-hydroxybenzoic acid) (H4ODA), 4,4'-[1,4-phenylenebis-(carbonylimino)]bis(2-hydroxybenzoic acid) (H4TDA), 4,4'-dihydroxyazobenzene-3,3'-dicarboxylic acid (H4OSA), their protonated forms, partially or fully deprotonated forms, and combinations thereof.

[0049] [Embodiment Item 14] 14. The MOF compound according to any one of embodiments 11 to 13, wherein the MOF compound is Mg2(dobpdc).

[0050] [Embodiment Item 15] The MOF compound of any one of embodiments 11 to 14, wherein the solvent comprises a solvent selected from the group consisting of aqueous solvents, organic solvents, and combinations thereof.

[0051] [Embodiment 16] The MOF compound according to any one of embodiments 11 to 15, wherein the solvent is an aqueous solvent.

[0052] [Embodiment Item 17] 17. The MOF compound of any one of embodiments 11 to 16, wherein the solvent comprises a solvent selected from the group consisting of water, dimethylformamide, ethylene glycol, ethanol, methanol, propanol, isopropanol, and combinations thereof.

[0053] [Embodiment Item 18] 18. The MOF compound of any one of embodiments 11 to 17, wherein the base comprises a base selected from the group consisting of a strong base, a weak base, an inorganic base, a hydroxide, sodium hydroxide, potassium hydroxide, lithium hydroxide, cesium hydroxide, magnesium hydroxide, calcium hydroxide, an organic base, an amine, and combinations thereof.

[0054] [Embodiment Item 19] The method of any one of embodiments 1 through 18, wherein reacting the mixture comprises reacting the mixture in an open reaction vessel.

[0055] [Embodiment Item 20] The MOF compound of any one of paragraphs 11 through 19, wherein reacting the mixture comprises reacting the mixture under reflux.

[0056] [Embodiment Item 21] The MOF compound of any one of embodiments 11 to 20, wherein the process further comprises washing the MOF compound with a wash solvent selected from the group consisting of alcohol, isopropanol, propanol, ethanol, methanol, water, and combinations thereof.

[0057] [Embodiment Item 22] A sorbent system comprising the MOF compound of any one of paragraphs 11 through 21.

[0058] [Embodiment Item 23] A method of using the MOF compound according to any one of embodiments 11 to 21, comprising using the MOF compound for capturing gas.

[0059] [Embodiment Item 24] A method of using the MOF compound according to any one of embodiments 11 to 21, comprising using the MOF compound for post-combustion capture of CO2 and / or direct air capture of CO2.

[0060] References herein to "some embodiments" should not be interpreted as excluding the existence of additional embodiments that also comprise the recited features.

[0061] [Example] Without further explanation, it is believed that those skilled in the art can utilize the present invention to its fullest extent from the above description. The following examples are merely illustrative and do not limit the present disclosure. The starting materials for the following examples are not necessarily prepared by the specific preparation procedures described in the procedures of other embodiments. Furthermore, numerical ranges described herein encompass all values ​​between the lower and upper limits. For example, when a range is stated as 10 to 50, values ​​such as 12 to 30, 20 to 40, and 30 to 50 are expressly recited herein. The starting materials for the following examples are not necessarily prepared by the specific preparation procedures described in the procedures of other embodiments. Furthermore, numerical ranges described herein encompass all values ​​between the lower and upper limits. For example, when a range is stated as 10 to 50, values ​​such as 12 to 30, 20 to 40, and 30 to 50 are intended to be expressly recited herein. These are merely examples of what is specifically intended, and it is understood that all possible combinations of numerical values ​​between the stated lower and upper limits are expressly recited herein. [Example]

[0062] Example 1. Synthesis of Mg in aqueous media under simple reaction conditions 2 Preparation of (dobpdc) Mg2(dobpdc) was prepared on a 2.5 L scale according to the reaction scheme in Figure 2. First, sodium hydroxide (1 mol, 40.0 g) was dissolved in water (2.0 L) in an open flask. Next, H4(dobpdc) (0.250 mol, 68.5 g) was added via an addition funnel to form a slurry, which was then sparged with N2 for 1 h. Simultaneously, MgCl2 hexahydrate (0.562 mol, 114.25 g) was dissolved in 500 mL of water in a separate container and sparged with N2 for 1 h. This metal salt solution was added to the slurry via an addition funnel to precipitate the MOF. The mixture was reacted under gentle reflux at approximately 97 °C in an open flask under ambient pressure for 14 to 72 h. The reaction produced the MOF compound Mg2(dobpdc), which was washed twice with water and three times with isopropanol before being stored in alcohol. For surface area measurements, the material was washed with methanol. The yield was approximately 80 g of Mg2(dobpdc) in each of three separate batches.

[0063] The resulting Mg2(dobpdc) was found to have improved properties (e.g., high N2 gas adsorption capacity at 77 K, high surface area, and high pore volume) compared to Mg2(dobpdc) prepared in DMF / EtOH solvent. For example, Mg2(dobpdc) prepared in DMF / EtOH solvent exhibited a high N2 gas adsorption capacity of 800-900 cm3. 3 / g absorption, 3100-3300 (3700-4000) m 2 / g BET (Langmuir) surface area and 1.25 cm 3 / g, whereas Mg2(dobpdc) prepared in aqueous solvents has a pore volume of 1120 cm 3 / g absorption, 3341 (5430) m 2 / g BET (Langmuir) surface area and 1.73 cm 3Pore ​​volumes in mol / g are shown. A Micromeritics ASAP 2020 gas sorption analyzer was used to measure the isotherms. Samples were placed in weighed analytical tubes, capped with TranSeal, and transferred to the degassing station. Activation was performed under vacuum at various temperatures until the static outgassing rate was less than 10 μmHg / min. After degassing, the tubes were removed from the degassing station and weighed under N2 to determine the mass of the sample inside the tube. For cryogenic N2 measurements, the tubes were fitted with an isothermal jacket. BET measurements with N2 at 77 K were performed on the samples, and the surface area was calculated using Micromeritics software. [Example]

[0064] Example 2. Synthesis of Mg in non-aqueous solvents under simple reaction conditions 2 Preparation of (dobpdc) Mg2(dobpdc) was prepared on a 5 g scale according to the reaction scheme in Figure 3. MgCl2 hexahydrate (6.0 g), H4(dobpdc) (4.0 g), and DMF / ethylene glycol (40 mL / 40 mL) were combined in an open flask to form a mixture. The mixture was reacted in the open flask under ambient pressure at a temperature of approximately 130 °C with gentle stirring for approximately 72 hours. The reaction produced the MOF compound Mg2(dobpdc), which was washed with DMF and ethanol and dried. The yield was approximately 4.5 g of Mg2(dobpdc).

[0065] The resulting Mg2(dobpdc) was found to have similar properties (e.g., similar N2 gas adsorption capacity at 77 K, similar surface area, and similar pore volume) to Mg2(dobpdc) prepared in DMF / EtOH solvent. For example, Mg2(dobpdc) prepared in DMF / EtOH solvent had a pore volume of 800–900 cm 3 / g absorption, 3100-3300 (3700-4000) m 2 / g BET (Langmuir) surface area and 1.25 cm 3 / g, whereas Mg2(dobpdc) prepared in DMF / ethylene glycol solvent has a pore volume of 780 cm 3 / g absorption, 2070(3428)m 2 / g BET (Langmuir) surface area and 1.21 cm 3 Pore ​​volumes in mol / g are shown. A Micromeritics ASAP 2020 gas sorption analyzer was used to measure the isotherms. Samples were placed in weighed analytical tubes, capped with TranSeal, and transferred to the degassing station. Activation was performed under vacuum at various temperatures until the static outgassing rate was less than 10 μmHg / min. After degassing, the tubes were removed from the degassing station and weighed under N2 to determine the mass of the sample inside the tube. For cryogenic N2 measurements, the tubes were fitted with an isothermal jacket. BET measurements with N2 at 77 K were performed on the samples, and the surface area was calculated using Micromeritics software. [Example]

[0066] Example 3. Synthesis of Mg in non-aqueous solvents under simple reaction conditions 2 Preparation of (ODA) Mg2(ODA) was prepared on a 5 g scale according to the reaction scheme in Figure 4. MgCl2 hexahydrate (4.066 g), H4(ODA) (3.60 g), and DMF / ethylene glycol (40 mL / 40 mL) were combined in an open flask to form a mixture. The mixture was reacted in an open flask under ambient pressure at a temperature of approximately 130 °C with gentle stirring for approximately 72 hours. The reaction produced the MOF compound Mg2(ODA), which was washed with DMF and ethanol and dried. The yield was approximately 4 g of Mg2(ODA). [Example]

[0067] Example 4. Comparison of physical properties The physical properties of Mg2(dobpdc) produced according to the present disclosure and Mg2(dobpdc) produced by conventional synthetic methods were determined and compared, and the comparison is shown in the table below.

[0068] [Table 1]

[0069] The pore volume was calculated from the N2 absorption measurement at 77 K, based on the density of liquid N2 at 77 K (0.8064 gN2 / cm3 ), the molecular weight of N2 (28.02 g / mol) and the molar gas constant of 22.4 L / mol can be easily calculated. For example, the N2 absorption measured at 77 K is 1120 cm 3 / g, the following is 1.737cm 3 The pore volume in g can be derived.

[0070]

number

[0071] The data in Table 1 demonstrate that the physical properties of Mg2(dobpdc) produced according to the present disclosure are comparable to or superior to those of Mg2(dobpdc) produced by conventional synthetic methods.

[0072] Unless otherwise stated, approximation terms such as "approximately," "substantially," and "about" used herein indicate that the modified term is not absolute or precise, but merely an approximation that would be obvious to one of ordinary skill in the art. Thus, values ​​modified by terms such as "approximately," "substantially," and "substantially" are not limited to their exact numerical values. In at least some cases, approximation terms correspond to the accuracy of the instrument used to measure the value. Furthermore, unless otherwise stated, terms such as "first," "second," and "second" are merely descriptive terms used herein and do not impose numerical, positional, or hierarchical requirements on the entity to which they are attached. Furthermore, for example, a reference to "second" does not require or exclude the presence of, for example, a "first" or less, or a "third" or more.

[0073] Although specific features of various embodiments of the invention may be shown in some drawings and not in others, this is for convenience only. Moreover, references to "some embodiments" in the above description should not be interpreted as excluding the existence of additional embodiments that incorporate the recited features. Consistent with the principles of the invention, features shown in one drawing may be referenced and / or claimed in combination with features shown in other drawings.

[0074] This specification has used examples to disclose the invention, including the best mode, and to enable any person skilled in the art to practice the invention, including making and using the devices or systems and practicing the methods. The patentable scope of the disclosure is defined by the claims, and may include other examples that would be obvious to those skilled in the art. Such other examples are within the scope of the claims if they have elements that do not literally differ from the claims, or equivalent elements that differ only insubstantially from the literal language of the claims.

Claims

1. 1. A method for producing a metal-organic framework (MOF) compound comprising a MOF metal and a MOF linker, the method comprising: I) forming a mixture comprising a MOF metal precursor, a MOF linker precursor, a solvent, and optionally a base; and II) reacting the mixture under reaction conditions selected from the group consisting of ambient reaction pressure, a mixture temperature below about the boiling point of the solvent, an aqueous reaction mixture, and combinations thereof. A method comprising:

2. 10. The method of claim 1, wherein the MOF metal precursor comprises a metal selected from the group consisting of alkali metals, alkaline earth metals, transition metals, Mg, Ca, Mn, Cr, Fe, Co, Ni, Cu, Zn, ions thereof, hydrates thereof, salts thereof, halides thereof, fluorides thereof, chlorides thereof, bromides thereof, iodides thereof, nitrates thereof, acetates thereof, sulfates thereof, phosphates thereof, carbonates thereof, oxides thereof, formates thereof, carboxylates thereof, and combinations thereof.

3. The MOF linker precursor comprises a polytopic linker, 4,4'-dihydroxy-[1,1'-biphenyl]-3,3'-dicarboxylic acid (H ４ dobpdc), 4,4'-dioxidobiphenyl-3,3'-dicarboxylate (dobpdc ４－ ), 4,4"-dioxide-[1,1':4',1"-terphenyl]-3,3"-dicarboxylate (dotpdc ４－ ), 2,5-dioxidobenzene-1,4-dicarboxylate (dobdc ４－ ), 4,6-dihydroxyisophthalic acid (m-dobdc ４－ ), 3,3'-dioxide-biphenyl-4,4'-dicarboxylate (para-carboxylate-dobpdc ４－ ), 4,4'-[oxalylbis(imino)]bis(2-hydroxybenzoic acid) (H ４ ODA), 4,4'-[1,4-phenylenebis-(carbonylimino)]bis(2-hydroxybenzoic acid) (H ４ TDA), 4,4'-dihydroxyazobenzene-3,3'-dicarboxylic acid (H ４ 10. The method of claim 1, comprising a linker selected from the group consisting of: a hydroxybenzoate (OSA), a protonated form thereof, a partially or fully deprotonated form thereof, and combinations thereof.

4. 10. The method of claim 1, wherein the solvent comprises a solvent selected from the group consisting of aqueous solvents, organic solvents, and combinations thereof.

5. The method of claim 1 , wherein the solvent is an aqueous solvent.

6. 10. The method of claim 1, wherein the solvent comprises a solvent selected from the group consisting of water, dimethylformamide, ethylene glycol, ethanol, methanol, propanol, isopropanol, and combinations thereof.

7. 10. The method of claim 1, wherein the base comprises a base selected from the group consisting of a strong base, a weak base, an inorganic base, a hydroxide, sodium hydroxide, potassium hydroxide, lithium hydroxide, cesium hydroxide, magnesium hydroxide, calcium hydroxide, an organic base, an amine, and combinations thereof.

8. 10. The method of claim 1, wherein reacting the mixture comprises reacting the mixture in an open reaction vessel.

9. 10. The method of claim 1, wherein reacting the mixture comprises reacting the mixture under reflux.

10. 10. The method of claim 1, wherein the method further comprises washing the MOF compound with a wash solvent selected from the group consisting of alcohol, isopropanol, propanol, ethanol, methanol, water, and combinations thereof.

11. A metal-organic framework (MOF) compound comprising a MOF metal and a MOF linker, the MOF compound comprising: I) forming a mixture comprising a MOF metal precursor, a MOF linker precursor, a solvent, and optionally a base; and II) reacting the mixture under reaction conditions selected from the group consisting of ambient reaction pressure, a mixture temperature below about the boiling point of the solvent, an aqueous reaction mixture, and combinations thereof. The MOF compound is produced by a method comprising:

12. 12. The MOF compound of claim 11, wherein the MOF metal precursor comprises a metal selected from the group consisting of alkali metals, alkaline earth metals, transition metals, Mg, Ca, Mn, Cr, Fe, Co, Ni, Cu, Zn, ions thereof, hydrates thereof, salts thereof, halides thereof, fluorides thereof, chlorides thereof, bromides thereof, iodides thereof, nitrates thereof, acetates thereof, sulfates thereof, phosphates thereof, carbonates thereof, oxides thereof, formates thereof, carboxylates thereof and combinations thereof.

13. The MOF linker is a polytopic linker, 4,4'-dihydroxy-[1,1'-biphenyl]-3,3'-dicarboxylic acid (H ４ dobpdc), 4,4'-dioxidobiphenyl-3,3'-dicarboxylate (dobpdc ４－ ), 4,4"-dioxide-[1,1':4',1"-terphenyl]-3,3"-dicarboxylate (dotpdc ４－ ), 2,5-dioxidobenzene-1,4-dicarboxylate (dobdc ４－ ), 4,6-dihydroxyisophthalic acid (m-dobdc ４－ ), 3,3'-dioxide-biphenyl-4,4'-dicarboxylate (para-carboxylate-dobpdc ４－ ), 4,4'-[oxalylbis(imino)]bis(2-hydroxybenzoic acid) (H ４ ODA), 4,4'-[1,4-phenylenebis-(carbonylimino)]bis(2-hydroxybenzoic acid) (H ４ TDA), 4,4'-dihydroxyazobenzene-3,3'-dicarboxylic acid (H ４ 12. The MOF compound according to claim 11, comprising a linker selected from the group consisting of: aryloxysilanes, ...

14. The MOF compound is Mg ２ 12. The MOF compound according to claim 11, wherein the compound is (dobpdc).

15. 12. The MOF compound of claim 11, wherein the solvent comprises a solvent selected from the group consisting of aqueous solvents, organic solvents, and combinations thereof.

16. 12. The MOF compound of claim 11, wherein the base comprises a base selected from the group consisting of a strong base, a weak base, an inorganic base, a hydroxide, sodium hydroxide, potassium hydroxide, lithium hydroxide, cesium hydroxide, magnesium hydroxide, calcium hydroxide, an organic base, an amine, and combinations thereof.

17. 12. The MOF compound of claim 11, wherein reacting the mixture comprises reacting the mixture in an open reaction vessel.

18. A sorbent system comprising the MOF compound of claim 11.

19. 12. Use of MOF compounds according to claim 11, wherein the MOF compounds are used for gas capture.

20. The MOF compound was ２ Post-combustion capture of and / or CO ２ 12. Use of the MOF compound according to claim 11 for the direct air capture of

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