Method for Preparing Metal-Organic Frameworks Using Pre-ligands

Abstract

The present disclosure provides a method for preparing a metal-organic framework, comprising combining a first pre-ligand and at least one of a second pre-ligand or a first ligand with a metal source (including a metal component) to provide a plurality of reactants, wherein at least 50% by weight of the reaction mixture is the plurality of reactants, prior to adding a solvent to the plurality of reactants. The present disclosure also provides a method for preparing a metal-organic framework, the method comprising combining a pre-ligand with a metal source, the metal source being selected from metal acetates, metal hydroxyacetates, metal carbonates, metal hydroxycarbonates, and mixtures thereof.

Description

[Technical Field]

[0001] (CROSS-REFERENCE TO RELATED APPLICATIONS) This application claims the benefit of priority to U.S. Provisional Patent Application No. 63 / 480,666, filed January 19, 2023, entitled "METHODS OF MAKING METAL-ORGANIC FRAMEWORKS WITH PRE-LIGANDS," which is hereby incorporated by reference in its entirety into this disclosure.

[0002] (Field) The present disclosure relates to a method for preparing a metal-organic framework (or metal-organic framework or metal-organic framework) using a first pre-ligand (or first pre-ligand) and at least one of a second pre-ligand (or second pre-ligand) or a first ligand (or first ligand). The present disclosure also relates to a method for preparing a metal-organic framework by reacting a pre-ligand with a metal source, wherein the metal source is selected from metal acetates, metal hydroxyacetates, metal carbonates, metal hydroxycarbonates, and mixtures thereof. [Background technology]

[0003] (background) Metal-organic frameworks (or metal-organic frameworks or metal-organic frameworks or metal-organic frameworks) ("MOFs") are three-dimensional aggregates (or three-dimensional assemblies) of metal ions (or metal ions) / metal clusters (or metal clusters) and organic ligands (or organic ligands or organic ligands).

[0004] Metal-organic frameworks contain organic ligands (sometimes called "linkers") that bridge multiple metal nodes (called "secondary building units" or "SBUs") through coordination bonds, allowing them to self-assemble into a coordination network. In contrast to other porous materials, MOFs also offer unique structural diversity: uniform pore structures, structural uniformity at the atomic level, tunable porosity, wide variation, and flexibility in network topology, geometry, dimensions, and chemical functionality, which allows for the manipulation of network topology, porosity, and functionality. Tunable topology (either through isoreticular expansion of the network or functionalization of organic ligands / metal nodes) allows metal-organic frameworks to be tailored for a wide variety of applications, ranging from catalytic transformations to biomedical adsorption and separation. These applications include photocatalysis, catalysis, separation and purification (e.g., gas adsorption and separation), gas / energy storage, heating / cooling, batteries, sensing, and environmental remediation. The large surface area and high concentration of isolated metal ions enhances gas storage capacity and mass transport.

[0005] Scaling up metal-organic frameworks for commercial production is difficult due to the need for organic solvents, which are toxic and costly. In certain cases, water and / or other benign solvents with low cost may be utilized. However, in many cases, the poor solubility of organic ligands necessitates the use of polar aprotic solvents (e.g., dimethylformamide ("DMF")). In such situations, it is desirable to operate with reaction mixtures in which the reactant concentrations are as high as possible. This is difficult because certain reactions result in materials that are poorly crystallized and / or lose phase specificity at high concentrations (thus severely limiting the applications of such materials).

[0006] To date, several approaches have been undertaken to circumvent this limitation in particular ways that avoid the use of DMF, including methods that limit or avoid the use of this toxic and costly organic solvent. For example, alternative synthetic conditions include the use of water, reducing the need for dimethylformamide ("DMF") in the solvent mixture by dilution with water. Another alternative involves the use of solubilizing or solubilizing groups (e.g., amino or carboxy groups) that can be added to terephthalate ligands, thereby imparting enhanced solubility. However, such an approach increases the cost of the starting materials and may result in reduced material properties (e.g., lower crystallinity or lower intrinsic adsorption selectivity). Other methods utilize less toxic solvents, use bio-derived lactones as precursors to metal-organic frameworks, and / or use depolymerized polyethylene terephthalate (PET) as a ligand source. See the following references: Zhou, L. et al. (2019) “Direct Synthesis of Robust hcp UiO-66 (Zr) MOF Using Poly(ethylene terephthalate) Waste as Ligand Source”, Micro. Meso. Mater., v. 290, pg. 109674; Dyosiba, X. et al. (2019) “Feasibility of Varied Polyethylene Terephthalate Wastes as a Linker Source in Metal-Organic Framework UiO-66 (Zr) Synthesis”, Ind. Eng. Chem. Res., v. 58, pp. 17010-17016. PET contains two main components: benzene dicarboxylic acid (BDC) (a building block in the synthesis of BDC-based metal-organic frameworks) and ethylene glycol. PET can be extracted using a variety of techniques. The BDC derived from PET waste can then be applied in the green synthesis of functional metal-organic frameworks (ibid.). However, even with these many alternatives, commercial production lines still face the following challenges: A solvent recovery system is required.

[0007] The stability of metal-organic frameworks ("MOFs") can be attributed to the strong interactions between low polarizability ions (e.g., carboxylates) and trivalent metals. A stable metal-organic framework is initially formed by the addition of a trivalent cation (i.e., Al 3+ , Fe 3+ , Cr 3+ ) was assigned to a phthalate-based MOF derived from Later, other multivalent cations (e.g., Zr 4+ , Hf 4+ , Ti 4+) was utilized to provide an additional robust framework (or skeleton or structure) (or robust framework).

[0008] The metal-organic framework (or metal-organic framework or metal-organic framework or metal-organic framework) UiO-66 was first discovered by reacting zirconium salts with linear dicarboxylic acids. Cavka, JH et al. (2008) “A New Zirconium Inorganic Building Brick Forming Metal Organic Frameworks with Exceptional Stability”, J. Am. Chem. Soc., v. 130(42), pp. 13850-13851.

[0009] WO / 2023 / 278246 (filed June 23, 2022) (incorporated herein by reference) describes EMM-71, a metal-organic framework comprising multiple tetravalent cations and terephthalate linkers. The terephthalate linkers are crystallized in a primitive cubic lattice. EMM-71 is characterized by a high number of missing clusters / node defects (where the missing clusters / node defects correspond to highly defective UiO-66 and also fully defective UiO-66, as measured by relative intensities reflecting the degree of defects). Such EMM-71 was originally prepared by reacting a first metal precursor (particularly one capable of generating a tetravalent metal cation in solution), a second metal precursor (particularly one capable of generating a divalent metal cation in solution), and a polytopic organic carboxylic acid (e.g., one capable of generating a terephthalate linker) in a solvent such as dimethylformamide (DMF). Summary of the Invention [Problem to be solved by the invention]

[0010] Despite these advantages, new methods for producing MOFs are still needed. [Means for solving the problem]

[0011] (Abstract) In a first aspect, the present disclosure provides a method for producing a metal-organic framework (or metal-organic framework or metal-organic framework), the method comprising the following steps: a step of combining a first pre-ligand (or first pre-ligand) and at least one of a second pre-ligand (or second pre-ligand) and a first ligand (or first ligand or first ligand) with a metal source (wherein the metal source comprises a metal component, and whereby reactants are produced); adding a solvent to the reactants (to form a reaction mixture); the step of heating the reaction mixture; cooling the reaction mixture to form an insoluble portion and a soluble portion, the insoluble portion comprising the metal-organic framework(s); Each of the above metal-organic frameworks comprises at least one ligand and a metal component.

[0012] In a first aspect of the present disclosure, at least 50% by weight of the reaction mixture is the reactant(s). Upon heating the reaction mixture, the first pre-ligand is converted (or transformed or converted or converted) to the second ligand (or secondary ligand or second ligand) in the reaction mixture. Additionally, if a second pre-ligand (or second pre-ligand) is present in the reaction mixture, the second pre-ligand is converted (or transformed or converted or converted) into a third ligand (or third ligand or third ligand). The second ligand and at least one of the first ligand and the third ligand react with the metal component.

[0013] In a first embodiment of the present disclosure, the first pre-ligand is selected from the group consisting of dimethyl fumarate, dimethyl terephthalate, terephthalonitrile (1,4-dicyanobenzene), terephthalamide (1,4-benzenedicarboxamide), N 1 ,N 4-dimethyl terephthalamide, dimethyl 2-amino terephthalate, dimethyl 2-nitro terephthalate, dimethyl 2-chloro terephthalate, dimethyl 2-bromo terephthalate, trimethyl 1,2,4-benzene tricarboxylate, trimethyl 1,3,5-benzene tricarboxylate, tetramethyl 1,2,4,5-benzene tetracarboxylate, polyethylene terephthalate, and mixtures thereof.

[0014] In a first embodiment of the present disclosure, the second pre-ligand is a C2-C10 linear or branched alkyl ester selected from the group consisting of alkyl esters of fumarate, terephthalate, 2-aminoterephthalate, 2-nitroterephthalate, 2-chloroterephthalate, 2-bromoterephthalate, 1,2,4-benzenetricarboxylate, 1,3,5-benzenetricarboxylate, 1,2,4,5-benzenetetracarboxylate, and mixtures thereof.

[0015] In a first aspect of the present disclosure, the first ligand is selected from the group consisting of fumaric acid, terephthalic acid, 2-aminoterephthalic acid, 2-nitroterephthalic acid, 2-chloroterephthalic acid, 2-bromoterephthalic acid, 1,2,4-benzenetricarboxylic acid, 1,3,5-benzenetricarboxylic acid, 1,2,4,5-benzenetetracarboxylic acid, and mixtures thereof.

[0016] In a second aspect, the present disclosure provides a method or methods for producing a metal-organic framework (or metal-organic framework), the method comprising the following steps: a step of combining a pre-ligand with a metal source, the metal source including a metal component, to form a reactant or reactants; the step (or steps) of adding a solvent to the reactants (which results in (or results in) a reaction mixture); a step of heating the reaction mixture (in which the pre-ligand is converted into a ligand in the reaction mixture, and the ligand reacts with the metal component); cooling the reaction mixture to form a soluble portion, an insoluble portion, and a soluble portion, wherein the insoluble portion comprises the metal-organic framework(s); Each of the metal-organic frameworks comprises the ligand and the metal component.

[0017] In a second aspect of the present disclosure, the metal source is selected from the group consisting of metal hydroxides, metal acetates, metal hydroxyacetates, metal carbonates, metal hydroxycarbonates, and mixtures thereof. Between 15% and 50% by weight of the reaction mixture are reactants (or reactants). Additionally, the reaction mixture does not contain dimethylformamide.

[0018] These and other features and properties of the methods disclosed in this disclosure and their advantageous applications and / or uses will be apparent from the detailed description set forth below.

[0019] To assist those skilled in the relevant art in making and using the subject matter of the present disclosure, reference is made to the following accompanying drawings, in which: [Brief explanation of the drawings]

[0020] [Figure 1A] FIG. 1A is a scanning electron microscope ("SEM") photomicrograph of the EMM-71 material of Comparative Example 1 (taken at a 5 μm scale). [Figure 1B] FIG. 1B is a scanning electron microscope (“SEM”) photomicrograph of the EMM-71 material of Comparative Example 1 (taken at a 10 μm scale). [Figure 2A] FIG. 2A is an SEM micrograph of the EMM-71 material of Comparative Example 2 (taken at a 5 μm scale). [Figure 2B] FIG. 2B is an SEM micrograph of the EMM-71 material of Comparative Example 2 (taken at a 10 μm scale). [Figure 3] FIG. 3 shows the powder X-ray diffraction patterns of the EMM-71 materials of Examples 1A-1F. [Figure 4A] FIG. 4A is an SEM micrograph (30 μm scale) of the EMM-71 material of Example 1A. [Figure 4B] FIG. 4B is an SEM micrograph (10 μm scale) of the EMM-71 material of Example 1A. [Figure 4C] FIG. 4C is an SEM micrograph (30 μm scale) of the EMM-71 material of Example 1B. [Figure 4D]FIG. 4D is an SEM micrograph (10 μm scale) of the EMM-71 material of Example 1B. [Figure 4E] FIG. 4E is an SEM micrograph (30 μm scale) of the EMM-71 material of Example 1C. [Figure 4F] FIG. 4F is an SEM micrograph (10 μm scale) of the EMM-71 material of Example 1C. [Figure 4G] FIG. 4G is an SEM micrograph (30 μm scale) of the EMM-71 material of Example 1D. [Figure 4H] FIG. 4H is an SEM micrograph (10 μm scale) of the EMM-71 material of Example 1D. [Figure 4I] FIG. 4I is an SEM micrograph (30 μm scale) of the EMM-71 material of Example 1E. [Figure 4J] FIG. 4J is an SEM micrograph (10 μm scale) of the EMM-71 material of Example 1E. [Figure 4K] FIG. 4K is an SEM micrograph (30 μm scale) of the EMM-71 material of Example 1F. [Figure 4L] FIG. 4L is an SEM micrograph (10 μm scale) of the EMM-71 material of Example 1F. [Figure 5] Figure 5 shows a plot of the mean (■) and median (◆) particle size measured by laser sizing for the EMM-71 materials of Examples 1A (0 mol% DET), 1B (10 mol% DET), 1D (40 mol% DET), and 1F (80 mol% DET). The lines in Figure 5 represent the pore volume (measured by nitrogen adsorption at 77 K and 0.8 P / P) for the EMM-71 materials of Examples 1A, 1B, 1D, and 1F. [Figure 6]FIG. 6 is a plot of the full width at half maximum (FWHM) ((111) (●) and (110) (■) peaks) of the EMM-71 materials from Example 1A (0 mol % DET), Example 1B (10 mol % DET), Example 1D (40 mol % DET), and Example 1F (80 mol % DET). [Figure 7] FIG. 7 shows the powder X-ray diffraction patterns of the EMM-71 materials of Examples 2A-2G. [Figure 8A] Figure 8A is an SEM micrograph (30 μm scale) of the EMM-71 material of Example 2B. More specifically, Figure 8A corresponds to Example 2B (10 mol% DEHT). [Figure 8B] Figure 8B is an SEM micrograph (10 μm scale) of the EMM-71 material of Example 2B. More specifically, Figure 8B corresponds to Example 2B (10 mol% DEHT). [Figure 8C] Figure 8C is an SEM micrograph (30 μm scale) of the EMM-71 material of Example 2C. More specifically, Figure 8C corresponds to Example 2C (20 mol% DEHT). [Figure 8D] Figure 8D is an SEM micrograph (10 μm scale) of the EMM-71 material of Example 2C. More specifically, Figure 8D corresponds to Example 2C (20 mol% DEHT). [Figure 8E] Figure 8E is an SEM micrograph (30 μm scale) of the EMM-71 material of Example 2D. More specifically, Figure 8E corresponds to Example 2D (40 mol% DEHT). [Figure 8F] Figure 8F is an SEM micrograph (10 μm scale) of the EMM-71 material of Example 2D. More specifically, Figure 8F corresponds to Example 2D (40 mol% DEHT). [Figure 9]Figure 9 is a plot of the FWHM ((111) (●) and (110) (■) peaks) of the EMM-71 materials of Examples 2A-2F. The lines in Figure 9 represent the pore volumes (measured by nitrogen adsorption at 77 K and 0.8 P / P0 as described in Example 2) of the EMM-71 materials of Examples 2A-2D. [Figure 10A] FIG. 10A shows the powder X-ray diffraction patterns of the EMM-71 materials of Examples 3A-3G. [Figure 10B] FIG. 10B shows the powder X-ray diffraction patterns of the EMM-71 materials of Examples 3A-3G. [Figure 11] FIG. 11 is a plot of the pore volume (or pore capacity or pore volume or pore volume) of the EMM-71 materials of Examples 3A-3G. [Figure 12] FIG. 12 shows the powder X-ray diffraction patterns of the EMM-71 materials of Examples 4A-4I (the upper curve corresponds to Example 4A; the lower curve corresponds to Example 4I). [Figure 13] FIG. 13 shows the powder X-ray diffraction pattern of the EMM-71 material of Example 5. DETAILED DESCRIPTION OF THE INVENTION

[0021] (Detailed explanation) Before the compounds, components, compositions and / or methods are disclosed and described, it is to be understood that the following applies. Unless otherwise stated, the present disclosure is not limited to specific compounds, components, compositions, reactants, reaction conditions, ligands, catalyst structures, MOF structures, etc., as these may vary unless specifically stated otherwise. You should also understand the following: The terminology used in this disclosure is for the purpose of describing particular embodiments and is not intended to be limiting.

[0022] All numerical values ​​set forth in the detailed description and claims of this disclosure are modified by the terms "about" or "approximately" to account for experimental error and variation.

[0023] For purposes of brevity, only certain ranges are explicitly disclosed in this disclosure. However, a range from any lower limit may be combined with any upper limit, thereby describing a range not expressly recited. And a range from any lower limit may be combined with any other lower limit, thereby describing a range not expressly recited. Similarly, a range from any upper limit may be combined with any other upper limit, thereby describing a range not expressly recited. Moreover, unless expressly stated otherwise, a range includes all points or individual values ​​between the endpoints of the range. Thus, every point or individual value can act as a lower or upper limit for the range itself, and every point or individual value can be combined with any other point or individual value, or any other lower or upper limit, thereby describing ranges not expressly stated.

[0024] For purposes of this disclosure, the following definitions (or definitions) apply.

[0025] As used in this disclosure, the terms "a" and "the" are understood to encompass both the plural and the singular as used in this disclosure.

[0026] As used in this disclosure, a "metal-organic framework (or metal-organic framework or metal-organic framework or 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 PCT Patent Publication WO2020 / 219907.

[0027] As used in this disclosure, a ligand (sometimes referred to as a "linker") is a compound that bridges two or more metals (metal nodes) to form a coordination network in a metal-organic framework. The protonation state (or status) of a ligand can change during a reaction, and various protonation states (or statuses) of a ligand are collectively described as one ligand (or single ligand).

[0028] As used in this disclosure, a pre-ligand or precursor (or precursor) is a compound that participates in a chemical reaction, thereby producing (or forming) a compound that produces (or forms) another compound and / or ligand.

[0029] Where the compounds described in this disclosure possess one or more chiral centers, it is understood that, unless the absolute stereochemistry is explicitly stated, each chiral center may independently be of the R or S configuration, or a mixture thereof. Thus, the compounds described in this disclosure may be enantiomerically pure or may be mixtures of stereoisomers.

[0030] It is further understood that when the compounds described in this disclosure have one or more double bond(s), the double bonds give rise to geometric isomers that can be defined as E or Z, and therefore each double bond can independently be E or Z or a mixture thereof. It is also understood that: In the compounds described in this disclosure, all tautomeric forms are intended to be included.

[0031] Furthermore, the compounds described in this disclosure may contain unnatural atomic isotope ratios at one or more of the atoms that constitute such compounds. For example, such compounds may contain radioactive isotopes (e.g., tritium ( 3 H), iodine-125( 125 I) or carbon-14 ( 14 C). It is intended that all isotopic variations of the title compounds, whether radioactive or not, may be encompassed within the scope of this disclosure.

[0032] Furthermore, the compounds described herein can include various states (or situations) of protonation (or protonation), depending on the pH of the solution. All conjugate acids and conjugate bases of such compounds are intended to be encompassed within the scope of the present disclosure.

[0033] Current methodologies offer additional alternatives for the synthesis of metal-organic frameworks containing metal ions with multivalent cations, particularly tetravalent cations (e.g., zirconium, titanium, cerium, and hafnium).

[0034] (Traditional Synthesis) Traditionally, metal-organic frameworks are prepared (or manufactured) by reacting pre-synthesized or commercially available linkers with metal ions. An alternative approach is called "in situ linker synthesis", in which a specific organic linker can be generated in situ in the reaction medium from the starting material.

[0035] When synthesizing metal-organic frameworks, organic molecules are introduced as part of the framework structure (or framework structure or framework structure), not only as structure-directing agents (or structure-directing agents) but also as reactants (or reactants). With this in mind, elevated reaction temperatures are generally used in conventional syntheses. Also, solvothermal reaction conditions, structure directing agents, mineralizers, and microwave-assisted synthesis or steam-assisted conversion are now being introduced.

[0036] As referred to in this disclosure, conventional synthesis is typically applied to reactions carried out with conventional electrical heating (without any parallel reactions). In conventional synthesis, the reaction temperature is the main parameter (or primary parameter) for the synthesis of metal-organic frameworks, and two temperature ranges (solvothermal and non-solvothermal) are usually distinguished, specifying the type of reactor (or reaction setup) that can be used. Solvothermal reactions generally proceed in a closed vessel under autogenous pressure (near the boiling point of the solvent used). Nonsolvothermal reactions proceed below or at the boiling point at ambient pressure, thereby simplifying synthetic requirements. Additionally, non-solvothermal reactions may be classified as room temperature or elevated temperature.

[0037] Conventional synthesis of metal-organic frameworks proceeds in solvents at temperatures ranging from room temperature to about 250°C. Heat is transferred from a heat source (or oven) through convection (or convection). Alternatively, energy can be introduced by electric potential, electromagnetic radiation, mechanical waves (ultrasound), or by a machine. The energy source is closely related to the duration, pressure, and energy (energy per molecule introduced into the system). Each of these parameters can have a significant impact on the resulting metal-organic framework and its morphology. Traditional synthesis is described in the following documents (which are incorporated by reference in this disclosure): McDonald, TM et al. (2015) “Cooperative Insertion of CO2in Diamine Appended Metal-Organic Frameworks”, Nature, v.519, pp. 303-308, or Shearer, GC et al. (2016) “Defect Engineering: Tuning the Porosity and Composition of the Metal-Organic Framework UiO-66 via Modulated Synthesis”, Chem. Matter., v.28, pp. 3749-3761 Further syntheses for preparing metal-organic frameworks are described further in the following references: McDonald, TM, et al. (2012) “Capture of Carbon Dioxide from Air and Flue Gas in the Alkylamine-Appended Metal-Organic Framework mmen-Mg2(dobpdc)”, J. Am. Chem. Soc., v.134, pp. 7056-7065; Shearer, GC et al. (2014) “Tuned to Perfection: Ironing Out the Defects in Metal-Organic Framework UiO-66”, Chem. Matter., v.26, pp. 4068-4071; Cavka, JH et al. (2008) “A New Zirconium Inorganic Building Brick Forming Metal Organic Frameworks with Exceptional Stability”, J. Am. Chem. Soc., v.130, pp. 113850-13851; Milner, PJ et al. (2018) “Overcoming Double-step CO2Adsorption and Minimizing Water Co-Adsorption in Bulky Diamine-Appended Variants of Mg2(dobpdc)”, Chem. Sci., v.9, pp. 160-174; U.S. Patent No. 8,653,292, and U.S. Patent Application Publication Nos. 2007 / 0202038, 2010 / 0307336, and 2016 / 0031920 The synthesis of EMM-71 is disclosed in WO2023 / 278246.

[0038] (High Solid Synthesis (or High Solid Synthesis or High Solid Synthesis)) Metal-organic frameworks can be prepared by high-solid synthesis using pre-ligands as ligand precursors without formamide solvents (e.g., DMF) (as disclosed in WO 2023 / 278248). WO2023 / 278248 (filed June 23, 2022), which is incorporated by reference in this disclosure, discloses alternative methods for preparing (or manufacturing) MOFs (including UiO-66 or EMM-71). For example, high-solid synthesis (HSS) has been disclosed for producing MOFs in the presence of a solvent but without DMF. High-solid synthesis involves reacting a pre-ligand with a metal component (to produce solid reactants). In HSS, at least 50 wt. % of the reaction mixture is solid reactants. WO2023 / 278248 also discloses the use of divalent metals (e.g., Zn / Co) as crystallization aids to regulate (or adjust or regulate or manage or control) the crystalline phase.

[0039] (Mixed pre-ligand(s) or pre-ligand / ligand synthesis) In a first aspect, the present disclosure encompasses a method for preparing a metal-organic framework (or metal-organic framework) using a mixture (or mixture) of at least two different pre-ligands or a mixture (or mixture) of pre-ligands and ligands. More specifically, the present disclosure relates to a method for producing a metal-organic framework (or metal-organic framework or metal-organic framework or metal-organic framework), comprising the following steps (a) to (d): (a) combining (or blending or combining) a first pre-ligand (or first pre-ligand) and at least one of a second pre-ligand (or second pre-ligand) and a first ligand (or first ligand) with a metal source (or metal source or metal source). The metal source comprises a metal component. This process (or step) produces (or forms) reactants (or reactants). (b) adding a solvent to the above reactant(s); This process (or step) produces (or forms) a reaction mixture (or reaction mixture). (c) heating the reaction mixture (d) cooling the reaction mixture. This process (or step) produces (or forms) an insoluble portion and a soluble portion. In this process (or step), the insoluble portion comprises a metal-organic framework (or metal-organic framework or metal-organic framework or metal-organic framework)(s). The metal-organic frameworks each comprise at least one of the ligands and the metal component.

[0040] In a first aspect of the present disclosure, the pre-ligand is a derivative or precursor of a linker (or ligand), for example, a derivative or precursor of a terephthalate linker or a fumarate linker, and the pre-ligand can undergo a reaction (e.g., hydrolysis or oxidation) to form the linker (e.g., fumaric acid, terephthalic acid, or a derivative thereof). More specifically, the pre-ligands may be derivatives of any suitable linker containing groups such as cyano, amide, or ester groups that can undergo hydrolysis to give the corresponding acid, its deprotonated form, or functionalized derivatives thereof.

[0041] In a first embodiment of the present disclosure, the first pre-ligand is an amide, cyano or methyl ester, in particular dimethyl fumarate, dimethyl terephthalate, terephthalonitrile (1,4-dicyanobenzene), terephthalamide (1,4-benzenedicarboxamide), N 1 ,N 4 -dimethyl terephthalamide, dimethyl 2-amino terephthalate, dimethyl 2-nitro terephthalate, dimethyl 2-chloro terephthalate, dimethyl 2-bromo terephthalate, trimethyl 1,2,4-benzenetricarboxylate, trimethyl 1,3,5-benzenetricarboxylate, tetramethyl 1,2,4,5-benzenetetracarboxylate, polyethylene terephthalate, and mixtures thereof. More specifically, the first pre-ligand may be at least one of dimethyl fumarate, polyethylene terephthalate, or methyl ester terephthalate or a derivative thereof (e.g., dimethyl terephthalate, dimethyl 2-aminoterephthalate, dimethyl 2-nitroterephthalate, dimethyl 2-chloroterephthalate, or dimethyl 2-bromoterephthalate). Additionally / alternatively, the pre-ligand is a fumarate ester (e.g., dimethyl fumarate) or a terephthalate ester (e.g., dimethyl terephthalate).

[0042] In a first embodiment of the first aspect, step (a) comprises combining (or blending or bringing together) a first ligand with a second pre-ligand. The second pre-ligand is a C2-C10, preferably C2-C8, straight or branched chain alkyl ester selected from the group consisting of alkyl esters of fumarate, terephthalate, 2-aminoterephthalate, 2-nitroterephthalate, 2-chloroterephthalate, 2-bromoterephthalate, 1,2,4-benzenetricarboxylate, 1,3,5-benzenetricarboxylate, 1,2,4,5-benzenetetracarboxylate, and mixtures thereof. The C2-C10 straight or branched alkyl group may be functionalized with oxygen, nitrogen and / or halide functionalities, if desired. Particularly suitable alkyl groups are ethyl, octyl and 2-ethylhexyl. For example, if the ester is terephthalate, the second pre-ligand may be a compound of the following formula:

[0043] [ka]

[0044] wherein both R groups may be the same or different. In particular, both R groups are the same. Both R groups are selected from C2-C10 linear or branched alkyl groups, which may be optionally functionalized. Particularly suitable examples of such compounds are those in which R is selected from the group consisting of ethyl, octyl, and 2-ethylhexyl, such as diethylterephthalate (DET), dioctylterephthalate (DOT), and diethylhexylterephthalate (DEHT).

[0045] In particularly preferred embodiments, the second pre-ligand may be liquid at 20°C (e.g., dioctylterephthalate (DOT) and diethylhexylterephthalate (DEHT)). This allows for improved rheological properties of the reaction mixture, which allows for easier mixing (agitation benefits). Another advantage is that the by-products generated by the conversion of the pre-ligand are not water-soluble (e.g., 2-ethylhexanol, bis(2-ethylhexyl ether), 2-ethylhexyl acetate).

[0046] In this first embodiment, the first pre-ligand and the second pre-ligand may be converted (or transformed or converted) into a second ligand and a third ligand in step (c). At this time, the second ligand and the third ligand may be the same or different. The second ligand and the third ligand are preferably the same. For example, the first pre-ligand can be dimethyl fumarate, and the second pre-ligand can be a C2-C10 linear or branched alkyl ester of fumarate. Both the first pre-ligand and the second pre-ligand may be converted to fumaric acid in step (c). The second ligand and the third ligand are the same. In another example, the first pre-ligand may be dimethyl terephthalate. The second pre-ligand may be a C2-C10 linear or branched alkyl ester of terephthalate. Both the first pre-ligand and the second pre-ligand may be converted to terephthalic acid in step (c). The second and third ligands may be the same.

[0047] In this first embodiment, the molar ratio of second pre-ligand:first pre-ligand (or second pre-ligand / first pre-ligand) may be 0 (greater than 0, but not including 0) to 0.6, for example 0.05 to 0.5, or 0.1 to 0.5, for example 0.2 to 0.4.

[0048] By using a second pre-ligand (having an ester of a C2-C10 alkyl group), the pore volume can be improved (e.g., from 0.7 cc / g (or less than or not including 0.7 cc / g) to 0.7 cc / g (or greater than or not including 0.7 cc / g)). The improved pore volume indicates an increase in the % REO domain.

[0049] In a second embodiment of the first aspect, step (a) comprises combining (or blending or bringing together) a first pre-ligand with a first ligand, wherein the first ligand is selected from the group consisting of fumaric acid, terephthalic acid (or benzene dicarboxylic acid (BDC)), 2-aminoterephthalic acid, 2-nitroterephthalic acid, 2-chloroterephthalic acid, 2-bromoterephthalic acid, 1,2,4-benzenetricarboxylic acid, 1,3,5-benzenetricarboxylic acid, 1,2,4,5-benzenetetracarboxylic acid, and mixtures thereof. In particular, the first ligand may be at least one of fumaric acid and terephthalic acid or derivatives thereof. More particularly, the first ligand is terephthalic acid.

[0050] In a second embodiment, in step (c) (or step (c)), the first pre-ligand is converted (or transformed or converted or converted) into a second ligand (or second ligand). The second ligand may be the same as or different from the first ligand. Preferably, the second ligand is the same as the first ligand. For example, the first pre-ligand may be dimethyl fumarate. The first ligand may be fumaric acid. In step (c), the first pre-ligand is converted to fumaric acid. In this way, the second ligand and the first ligand become identical. In another example, the first pre-ligand may be dimethyl terephthalate. The first ligand may be terephthalic acid. The first pre-ligand is converted (or transformed or converted or converted) to terephthalic acid in step (c). In this way, the second ligand and the first ligand are the same.

[0051] In this second embodiment, the molar ratio of second pre-ligand:first pre-ligand (or second pre-ligand / first pre-ligand) may be 0 (or greater than 0, but not including 0) to 0.6 (e.g., 0.05 to 0.5, or 0.1 to 0.5, e.g., 0.2 to 0.4).

[0052] The use of pre-ligands in combination with ligands can reduce the amount of by-products (e.g., dimethyl ether, methyl acetate, and methanol (in the case of methyl esters)) derived from hydrolysis of the pre-ligand. The combination of pre-ligand and ligand is advantageous in that it can reduce costs, but the effect on product quality (including pore volume) is limited.

[0053] In a third embodiment, a first pre-ligand may be combined with both a second pre-ligand and a first ligand (as defined above). In a third embodiment, the first pre-ligand and the second pre-ligand may be converted (or transformed or converted) into a second ligand and a third ligand in step (c). The second ligand and the third ligand may be the same or different. The second ligand and the third ligand may be the same or different from the first ligand. More specifically, the first ligand, the second ligand and the third ligand are the same in step (c) (or step (c)).

[0054] In a third embodiment, the molar ratio of second pre-ligand and first ligand to first pre-ligand (or the molar ratio of second pre-ligand and first ligand / first pre-ligand) may be 0 (or greater than 0, but not including 0) to 0.6 (e.g., 0.05 to 0.5, or 0.1 to 0.5, e.g., 0.2 to 0.4).

[0055] In both the first and second embodiments of the first aspect, the metal source comprises a metal component. The metal component may be a tetravalent metal (eg, zirconium, cerium, hafnium and titanium or mixtures thereof, preferably Zr or Zr / Hf). Preferably, the metal source is capable of generating (or forming) the metal component, particularly as a tetravalent cation in solution. Suitable examples of metal sources include, but are not limited to, metal oxide, chloride, nitrate, or sulfate salts, their hydrates, or their oxyanion salts (e.g., zirconium tetrachloride, zirconyl chloride, zirconyl nitrate, zirconyl sulfate, cerium ammonium nitrate, cerium nitrate, titanium tetrachloride, titanium (or titanium) oxysulfate, hafnium tetrachloride, hafnium oxychloride, hafnium oxynitrate, or hafnium oxysulfate). In one embodiment, the molar ratio of tetravalent cation to ligand may be from about 1.75:1 to about 1:1.75.

[0056] In both the first and second embodiments of the first aspect, the first pre-ligand and at least one of the second pre-ligand or the first ligand are combined (or blended or combined) with a metal source comprising a metal component to produce (or form or provide) reactants (or reactants). A solvent is added to the reactants to form a reaction mixture, wherein at least 50% by weight of the reaction mixture is the reactants. In further embodiments, the reaction mixture may comprise 50% to 90% by weight of the reactant(s), in particular at least 60% by weight, such as at least 65% by weight, or at least 70% by weight of the reactant(s). For example, in step (b), a solvent can be added to the reaction mixture in an amount of about 0.1 to about 1.0 weight equivalent, preferably less than 1.0 weight equivalent, relative to the reactants. For example, the solvent is added to the reaction mixture in a weight equivalent amount relative to the reactants, such as about 0.1 to about 0.9, 0.1 to 0.8, 0.1 to 0.7, 0.1 to 0.6, 0.1 to 0.5, 0.1 to 0.4, 0.1 to 0.3, or 0.1 to 0.2. If the second pre-ligand is a solid component, the reactant(s) correspond to the solid reactant(s). In step (b), the amount of solvent that can be added to the reaction mixture may be expressed relative to the solid reactant (similar to the ranges defined above).

[0057] In both the first and second embodiments of the first aspect, the solvent in step (b) (or step (b)) may typically comprise at least one of a monocarboxylic acid and / or a mineral acid, and optionally water. Suitable examples of monocarboxylic acids include acetic acid (eg, glacial acetic acid) and its analogs (or analogs), such as formic acid, propionic acid, and mixtures thereof. Suitable examples of mineral acids include hydrochloric acid (or hydrochloric acid) and its analogues (or analogues), such as hydrobromic acid.

[0058] When the solvent comprises a monocarboxylic acid, the molar ratio of monocarboxylic acid to ligand(s) in the reaction mixture is preferably from 1:1 to 20:1, in particular from 1:1 to 20:1 (or less than or not including 20:1). In this embodiment, the expression "amount of ligand(s)" refers to the amount of ligand(s) resulting from the conversion of the pre-ligand(s) during the heating step and the amount of potential ligand(s) (added to the reaction mixture as starting material). For example, it refers to the amount of fumaric acid or terephthalic acid (or their deprotonated forms or functionalized derivatives) (produced from the hydrolysis of the corresponding fumarate ester(s) or terephthalate ester(s) (or their derivatives)) and, if necessary, the amount of fumaric acid or terephthalic acid present in the reaction mixture as starting material. More specifically, the amount (expressed as a molar ratio) of monocarboxylic acid (e.g., acetic acid) to ligand(s) can be about 20:1, 19:1, 18:1, 17:1, 16:1, 15:1, 14:1, 13:1, 12:1, 11:1 or less, about 1:1, 2:1, 3:1, 4:1, 5:1, 6:1, 7:1, 8:1, 9:1, or 10:1 or more. For example, in the reaction mixture, the amount (as a molar ratio) of monocarboxylic acid to ligand(s) may be 1:1 to 10:1, 2:1 to 8:1, for example, 3:1 to 5:1.

[0059] In the first aspect of the present disclosure, when the solvent comprises a mineral acid, either as an alternative to or in addition to the monocarboxylic acid, the molar ratio of mineral acid to ligand(s) in the reaction mixture is preferably at most 5: 1. More specifically, the amount (expressed as a molar ratio) of mineral acid (e.g., HCl):ligand(s) may range from 1:10 to 5:1, or from 1:2 to 3:1, for example, from 1:1 to 2:1.

[0060] (Alternative metal sources) In a second aspect, the present disclosure encompasses a method for producing a metal-organic framework (or metal-organic framework) using an alternative metal source (or metal source or metal source). More specifically, the present disclosure relates to a method for producing a metal-organic framework (or metal-organic framework or metal-organic framework or metal-organic framework), comprising the following steps (a) to (d): (a) combining (or combining or combining) the pre-ligand with a metal source (or metal source or metal source) The metal source comprises a metal component. This process (or step) produces (or forms or provides) reactants (or reactants). In this process (or step), the metal source is selected from the group consisting of metal hydroxide (or metal hydroxide), metal acetate (or metal acetate), metal hydroxyacetate (or metal hydroxyacetate), metal carbonate (or metal carbonate), metal hydroxycarbonate (or metal hydroxycarbonate), and mixtures thereof. (b) adding a solvent to the above reactants; This process (or step) produces (or forms) a reaction mixture (or reaction mixture). (c) heating the reaction mixture In this process (or step), the pre-ligand is converted (or transformed or converted or converted) into a ligand in the reaction mixture, and the ligand reacts with the metal component. (d) cooling the reaction mixture. This process (or step) produces (or forms) an insoluble portion and a soluble portion. In this process (or step), the insoluble portion comprises metal-organic framework(s). Each of the plurality of metal-organic frameworks comprises at least one of the ligands and the metal component.

[0061] In a second aspect of the present disclosure, the pre-ligand is a derivative or precursor of a linker (or ligand), for example, a derivative or precursor of a terephthalate linker or a fumarate linker. The pre-ligand can undergo a reaction (e.g., hydrolysis or oxidation) to generate (or form) the linker (e.g., fumaric acid, terephthalic acid, or a derivative thereof). More specifically, the pre-ligands may be derivatives of any suitable linker containing groups such as cyano, amide, or ester groups, which can undergo hydrolysis to give the corresponding acid, the deprotonated form of the corresponding acid, or functionalized derivatives thereof. More specifically, the pre-ligands are amides, cyano or methyl esters, in particular dimethyl fumarate, dimethyl terephthalate, terephthalonitrile (1,4-dicyanobenzene), terephthalamide (1,4-benzenedicarboxamide), N 1 ,N 4 -dimethyl terephthalamide, dimethyl 2-aminoterephthalate, dimethyl 2-nitroterephthalate, dimethyl 2-chloroterephthalate, dimethyl 2-bromoterephthalate, trimethyl 1,2,4-benzenetricarboxylate, trimethyl 1,3,5-benzenetricarboxylate, tetramethyl 1,2,4,5-benzenetetracarboxylate, polyethylene terephthalate, and mixtures thereof. More specifically, the pre-ligand may be at least one of dimethyl fumarate, polyethylene terephthalate, or methyl ester terephthalate or a derivative thereof (e.g., dimethyl terephthalate, dimethyl 2-amino terephthalate, dimethyl 2-nitro terephthalate, dimethyl 2-chloro terephthalate, or dimethyl 2-bromo terephthalate). Additionally / alternatively, the pre-ligand is a fumarate ester (e.g., dimethyl fumarate) or a terephthalate ester (e.g., dimethyl terephthalate). In a further embodiment, the pre-ligands described above can be used in the form of a first pre-ligand in combination with at least one of a second pre-ligand or a first ligand, as described in the first aspect of the invention disclosed herein.

[0062] In a second embodiment, the metal source is selected from the group consisting of metal hydroxides, metal acetates, metal hydroxyacetates, metal carbonates, metal hydroxycarbonates, and mixtures thereof. The metal component may be a tetravalent metal (eg, zirconium, cerium, hafnium and titanium or mixtures thereof, preferably Zr or Zr / Hf). Preferably, the metal source may form (or generate) a metal component (particularly a tetravalent cation) in solution. For example, when the metal component is zirconium, the metal source may be zirconium hydroxide (Zr(OH)4), zirconium acetate (Zr(OAc)4), zirconium acetate hydroxide (Zr(OAc) x (OH) y (where x+y=about 4), zirconium carbonate (Zr(CO3)2) and / or zirconium hydroxycarbonate (Zr(OH)2CO3ZrO2). In particular, the metal source is zirconium hydroxide (Zr(OH)2CO3ZrO2). In one embodiment, the molar ratio of tetravalent cation to ligand may be from about 1.75:1 to about 1:1.75.

[0063] In a second embodiment, a metal source comprising a metal component and a pre-ligand are combined to form (or provide) reactants (or reactants). A solvent is added to the reactants (or reactants) to form (or provide) a reaction mixture. In such a reaction mixture, 15% to 50% by weight of the reaction mixture is the reactants (or reactants). In further embodiments, the reaction mixture may comprise 25% to 50% by weight (or less than or not including 50% by weight) of the reactant(s). In particular, it may comprise 30% to 50% by weight (or less than or not including 50% by weight) of the reactant(s). For example, it may comprise 30% (or 35%) to 45% by weight of the reactant(s). For example, in step (b), a solvent may be added to the reaction mixture in an amount of about 1.0 to about 4.0 weight equivalents relative to the reactants, such as 1.0 (or greater than 1.0, but not including 1.0) to 3.0 or 1.2 to 2.5 weight equivalents. If the pre-ligand is a solid component, the reactants correspond to the solid reactants. In a reaction mixture, the amount of reactants can be expressed as the amount of solid reactants in the reaction mixture (within the same ranges as defined above). Similarly, in this case, the amount of solvent that can be added to the reaction mixture in step (b) can be expressed as an amount relative to the solid reactant (within the same ranges as those defined above).

[0064] The solvent in step (b) may typically comprise at least one of a monocarboxylic acid and / or a mineral acid, and optionally water. Preferably, it may comprise at least one of a monocarboxylic acid and a mineral acid, and optionally water. Suitable examples of monocarboxylic acids include acetic acid (eg, glacial acetic acid) and its analogs (or analogs), such as formic acid, propionic acid, and mixtures thereof. Suitable examples of mineral acids include hydrochloric acid (or hydrochloric acid) and its analogues (or analogues), such as hydrobromic acid.

[0065] When the solvent comprises a monocarboxylic acid, the molar ratio of monocarboxylic acid to ligand in the reaction mixture is preferably from 1:1 to 20:1, in particular from 1:1 to 20:1 (or less than or not including 20:1). In this embodiment, the expression "amount of ligand" refers to the amount of ligand resulting from the conversion of a pre-ligand during the heating process, e.g., the amount of fumaric acid or terephthalic acid (or a deprotonated form or a functionalized derivative thereof) resulting from the hydrolysis of the corresponding fumarate or terephthalate ester (or a derivative thereof). More specifically, the amount of monocarboxylic acid (e.g., acetic acid):ligand (expressed as a molar ratio) can be about 20:1, 19:1, 18:1, 17:1, 16:1, 15:1, 14:1, 13:1, 12:1, 11:1 or less, about 1:1, 2:1, 3:1, 4:1, 5:1, 6:1, 7:1, 8:1, 9:1, or 10:1 or more. For example, in the reaction mixture, the amount of monocarboxylic acid:ligand (amount as a molar ratio) may be 1:1 to 10:1, or 2:1 to 8:1, for example, 3:1 to 5:1.

[0066] When the solvent contains a mineral acid, either as an alternative to or in addition to the monocarboxylic acid, the molar ratio of mineral acid:ligand in the reaction mixture is preferably at least 1:1. More specifically, the amount of mineral acid (e.g., HCl):ligand (expressed as a molar ratio) may range from 1:1 to 20:1, or from 1:1 to 10:1, such as from 2:1 to 8:1, and most specifically from 2:1 (or greater than or not including 2:1) to 6:1.

[0067] When the solvent contains both a monocarboxylic acid and a mineral acid, the molar ratio of mineral acid:monocarboxylic acid in the reaction mixture is preferably at most 8:1. More specifically, the amount (expressed as a molar ratio) of mineral acid (e.g., HCl):monocarboxylic acid (e.g., acetic acid) may be in the range of 1:5 to 8:1, in particular 1:4 to 6:1, or 1:3 to 5:1, for example 1:2 to 4:1, or 3:4 to 3:1 (or 2:1).

[0068] The method of the second aspect of the present disclosure is advantageous in that the use of an alternative metal source allows the MOF to be prepared in the presence of at least 50 wt. % solvent, provided that formamide solvent is not present, and in particular, in the absence of DMF (i.e., each and every step of steps (a)-(d)). Furthermore, the use of alternative metal sources can result in MOFs with smaller particle sizes and narrower particle size distributions. In a second aspect of the present disclosure, it has also been discovered that MOFs with increased pore volume and increased % REO domains can be prepared by using a greater amount of mineral acid relative to the mineral acid:ligand molar ratio and / or the mineral acid:monocarboxylic acid molar ratio.

[0069] (General disclosure applicable to the first and second aspects of the present disclosure) In preferred embodiments of the first and second aspects of the present disclosure, the process (i.e., each and every step of steps (a) to (d)) is carried out in the absence of formamide solvent (particularly, without DMF). More specifically, the reaction mixture used in the method does not contain (or is formamide solvent-free) (e.g., dimethylformamide (DMF)).

[0070] In the first and second embodiments described herein, as part of heating step (c) (or heating step (c)), the reaction mixture is heated at a temperature for a sufficient time to convert (or transform or convert) the pre-ligand(s) into ligand(s) and react such ligand(s) with the metal component. The heating step can include heating the closed (or sealed or sealed) reaction mixture under static conditions for at least 4 to 6 hours. The heating step can also include heating the closed (or sealed) reaction mixture under dynamic conditions (e.g., stirring, shaking, mixing, agitation), for example, for up to about 24 hours. The heating step can include heating the sealed reaction mixture in a static oven or a rotating oven at about 70°C to about 180°C. Heating can also be performed without sealing, where the MOF is synthesized using the solvent(s) (pressure of about 1 bar, reflux). In one embodiment, the reaction mixture is generally heated to a temperature of 70°C to 220°C, e.g., 100°C to 220°C, or about 70°C to about 160°C, 100°C to 160°C, 140°C to 160°C, e.g., about 70°C, about 100°C, about 130°C, about 150°C, or about 160°C, for at least 4 hours to 7 days, or 6 hours to 5 days, or 12 hours to 3 days.

[0071] In the first and second embodiments described herein, after step (d) (e.g., cooling to room temperature), an insoluble portion and a soluble portion are formed, wherein the insoluble portion comprises a metal-organic framework (or metal-organic frameworks or metal-organic frameworks or metal-organic frameworks). The method may further include separating the insoluble portion from the soluble portion and drying the insoluble portion. Drying produces (or forms or produces) the metal-organic framework(s). This can be done by any standard means. For example, the reaction mixture can be centrifuged or filtered to obtain the metal-organic framework(s).

[0072] The methods of the first and second aspects described in this disclosure may further include washing the metal-organic framework material separated from the reaction mixture by any standard means. For example, the metal-organic framework material may be washed with a solvent (e.g., DMF, methanol, ethanol, acetone, and / or water) to remove excess organic ligands. Alternatively, the metal-organic framework material may be washed with a slightly basic solution (e.g., a borate or formate solution, such as a solution of sodium borate or sodium formate) to remove the pendant ligands.

[0073] The methods of the first and second aspects described in the present disclosure are particularly suitable for preparing (or preparing or manufacturing) zirconium-based (or zirconium-based), titanium-based (or titanium-based or titanium-based or titanium-based), cerium-based (or cerium-based) and / or hafnium-based (or hafnium-based) metal-organic frameworks, in particular Zr-based (or Zr-based) (or Zr / Hf-based) metal-organic frameworks, more specifically Zr- (or Zr / Hf-) metal-organic frameworks (composed of multitopic carboxylates), and even more specifically Zr- (or Zr / Hf-) terephthalate metal-organic frameworks and / or Zr- (or Zr / Hf-) fumarate metal-organic frameworks. For example, the method can be used to prepare (or prepare or manufacture) a metal-organic framework selected from the group consisting of UiO-66, EMM-71, Zr-Fumarate, UiO-67, MOF-808, NU-1000, or functionalized derivatives thereof.

[0074] It is extremely important that the quality of the MOF is not compromised throughout the large-scale process. Several characterization techniques (described in detail below) indicate that the new methods described in this disclosure can yield MOFs of similar or superior quality compared to traditional solvent-based and / or high-solid synthesis.

[0075] Aspects of the present disclosure will now be described in further detail by way of specific examples. The following examples are provided for illustrative purposes and are not intended to limit the present disclosure in any way (or manner). Those skilled in the relevant art will readily understand that a wide variety of parameters can be changed or modified to yield essentially the same results. [Example]

[0076] (Example) Features of the present disclosure are illustrated by the following non-limiting examples.

[0077] In the examples, the X-ray diffraction (XRD) pattern of the material was recorded either: Panalytical XPert Pro powder X-ray diffractometer fitted with an Anton Paar HTK-16N environmental stage (equipped with a Pt-strip heater) Bruker D8 Envdevor instrument (continuous mode) with Cu Kα radiation, Bragg-Bentano geometry (Lynxeye detector), and 2θ in the range 2–60°. In both cases, interplanar spacing (d-spacing) was calculated in units of angstroms (Å). The intensities are not corrected (or calibrated) for Lorentz and polarization effects. The diffraction peak (2θ) positions (or locations) and relative peak area intensities (or relative peak area intensities) of the I / I(o) lines (I(o) is the intensity of the most intense line) (above background) were determined using the MDI Jade peak fitting algorithm (using a third-order polynomial background fit). It should be understood that diffraction data described as a single line may consist of multiple overlapping lines, which may be presented as resolved or partially resolved (lines) under certain conditions (e.g., when there are differences in crystallographic (or crystalline) changes). Typically, crystallographic changes involve small changes in unit cell parameters and / or changes in crystal symmetry (changes in framework connectivity are not included). Additionally, such minor effects (including variations in relative intensity) may result from differences in cation content, framework composition, the nature and extent of pore filling, crystal size and shape, preferred orientation, thermal history, and / or hydrothermal history. All samples were analyzed as is (without further polishing or grinding).

[0078] The relative intensity is measured by the method of Shearer, GC et al. (Defect Engineering: Tuning the Porosity and Composition of the Metal-Organic Framework UiO-66 via modulated Synthesis, Chem. Mater., v. 28(11), pp. 3749-3761, 2016). Relative intensity is a characteristic that indicates the degree of defects in the framework, especially node defects. As detailed by Shearer et al., the relative intensity of the broad peak (i.e., between 3° and 7° 2θ) is a quantitative indicator of the concentration of missing cluster defects in the framework (e.g., the framework of UiO-66). The relative intensity is calculated as the integrated intensity (I) of the broad peak (approximately 5° 2θ (e.g., 2°-7° 2θ), corresponding to the aggregate integrated intensity (I) of the (100) and (110) peaks in this invention) divided by the average of the intensities (I) of the (111), (200), and (600) peaks (corresponding to peaks at approximately 7.4, 8.5, and 25.8° 2θ, respectively).

[0079]

number

[0080] The peak width ratio (or peak width ratio) is the ratio of the peak widths calculated at half maximum (or half-maximum) for peak (110) (occurring at approximately 6° 2θ) and peak (111) (occurring at approximately 7.4° 2θ) as calculated by the MDI Jade peak fitting algorithm.

[0081] Scanning electron microscopy (SEM) images of the as-synthesized materials were obtained (either on a Hitachi 4800 Scanning Electron Microscope or a Thermo Scientific Apreo Scanning Electron Microscope).

[0082] The median and mean particle size of the material, as well as the particle size distribution of the material, can be determined using methods known in the art (e.g., laser sizing). Particle size distribution data was obtained from a Horiba Scientific particle size analyzer.

[0083] The total pore volume (or total pore capacity or total pore volume or total pore volume) of this material can be determined using methods known in the relevant field. For example, the porosity of a material can be determined by measuring nitrogen adsorption (or nitrogen adsorption or nitrogen adsorption) by physical adsorption of nitrogen (77 K, 0.8 P / P).

[0084] Comparative Example 1 Solvent-based synthesis of EMM-71 EMM-71 was synthesized according to the method of WO2023 / 278246. In this solvent-based synthesis, the EMM-71 metal-organic framework was synthesized (or prepared or manufactured) using 100 milligrams (mg) of cobalt II chloride (CoCl), 350 mg of benzene dicarboxylic acid (BDC), 680 mg of zirconium(IV) oxychloride octahydrate (ZrOCl), and 10 milliliters (mL) of solvent (50% by volume DMF and 50% by volume glacial acetic acid) at approximately 100°C.

[0085] 1A and 1B are SEM micrographs (images) of EMM-71 of Comparative Example 1. These images were taken at a scale of 5 μm (FIG. 1A) and 10 μm (FIG. 1B), respectively. Large polycrystalline particles (approximately 10 μm) were formed (or made or manufactured) and had a high porosity (or porousness or porosity). However, when tested, due to the large crystallite size and intergrowth nature of the crystallites, the metal-organic frameworks exhibited limited adsorption of decalin, thereby limiting surface diffusion.

[0086] Comparative Example 2 EMM-71 High Solid Synthesis EMM-71 was synthesized according to the method of WO2023 / 278248. In this high-solids synthesis, the EMM-71 metal-organic framework was synthesized by reacting 78.8 grams (g) of dimethyl terephthalate (DMT) and 192.57 g of zirconium(IV) oxychloride octahydrate (ZrOCl2) (29.2 mL of hydrochloric acid) (approximately 37 wt%) with 81.6 mL of glacial acetic acid.

[0087] 2A and 2B are SEM micrographs (images) of EMM-71 of Comparative Example 2, taken at a scale of 5 μm (FIG. 2A) and 10 μm (FIG. 2B), respectively. As can be seen, the particles produced by high solids synthesis are smaller than those produced by the solvent-based synthesis methods described above. The particle dimensions are more uniform, and the metal-organic frameworks have increased porosity (compared to those produced by solvent-based synthetic methods). Conversely, similar results cannot be obtained from many of the conventional synthesis methods designed to adjust particle size.

[0088] Examples 1A to 1F Synthesis of EMM-71 using a mixture of dimethylterephthalate (DMT) and diethylterephthalate (DET) For a given reaction, 2.64 g of zirconium oxychloride octahydrate and 0.84 g of hafnium oxychloride hydrate (yielding an 80 / 20 (expressed in moles) mixture of ZrOCl2 and HfOCl2) were mixed with 6.8 mmol of terephthalate (total) (having the following composition: DET / DMT): 0 mol% DET (Example 1A) 10 mol % DET (Example 1B) 20 mol % DET (Example 1C) 40 mol% DET (Example 1D) 60 mol % DET (Example 1E) 80 mol % DET (Example 1F) For example, for 0% DET (Example 1A), 1.35 g of DMT was used. For the terephthalate mixture DET / DMT (40 mole % DET) (Example 1D), 0.81 g of DMT and 0.606 g of DET were used. This physical mixture was then wetted with 1.5 mL of glacial acetic acid and 0.5 mL of hydrochloric acid (or hydrochloric acid) (approximately 37% by weight). The mixture was then stirred until homogeneous and loaded into a Teflon-coated 23 mL acid digestion vessel. The container was placed in a room temperature rotary oven, heated to 80°C, and left for 5 hours, then the temperature was increased to 150°C and left for an additional 10-18 hours.

[0089] The reaction mixture was then cooled and the solid was suspended in 25 mL of water (pH adjusted to 3.5 with sodium formate) and heated at 85° C. for 2 hours. The solution was then filtered and washed with 75-150 mL of 0.05 M formic acid and 75-150 mL of ethanol. The wet cake was then dried to give dry EMM-71.

[0090] FIG. 3 shows the powder X-ray diffraction patterns of the EMM-71 materials of Examples 1A to 1F. From the XRD patterns, it can be seen that good quality EMM-71 materials were obtained for all of Examples 1A to 1F.

[0091] 4A to 4L are SEM micrographs of the EMM-71 materials of Examples 1A to 1F, with scales of 30 μm and 10 μm, respectively. More specifically, the following is true. 4A-4B correspond to Example 1A (0 mol % DET). 4C-4D correspond to Example 1B (10 mol % DET). 4E-4F correspond to Example 1C (20 mol % DET). 4G-4H correspond to Example 1D (40 mol % DET). 4I-4J correspond to Example 1E (60 mol % DET). 4K-4L correspond to Example 1F (80 mol % DET).

[0092] Figure 5 is a plot of the mean (■) and median (♦) particle sizes measured by laser sizing for EMM-71 materials from Example 1A (0 mol% DET), Example 1B (10 mol% DET), Example 1D (40 mol% DET), and Example 1F (80 mol% DET).

[0093] The lines in Figure 5 represent the pore volumes (cc / g) of EMM-71 materials (Example 1A (0 mol% DET), Example 1B (10 mol% DET), Example 1D (40 mol% DET), and Example 1F (80 mol% DET)) as measured by nitrogen adsorption (or nitrogen adsorption or nitrogen adsorption) at 77 K and 0.8 P / P.

[0094] FIG. 6 plots the full width at half maximum (FWHM) of peak (111) (●) and peak (110) (■) for EMM-71 materials (Example 1A (0 mol% DET), Example 1B (10 mol% DET), Example 1D (40 mol% DET), and Example 1F (80 mol% DET)).

[0095] From Examples 1A to 1F, it can be seen that the particle size of the metal-organic framework (or metal-organic framework) formed (or produced) can be affected by using a combination of DMT (first pre-ligand) and DET (second pre-ligand) in the reaction mixture. In particular, for amounts of DET between about 10 mol% and about 50 mol%, the median and mean particle sizes decrease. Examples 1A-1F also demonstrate that the pore volume of the metal-organic framework increases with increasing amounts of DET present in the reaction mixture. While such an increase in pore volume (or pore capacity or pore volume or pore volume) may be modest, in fact, a significant increase in REO domain % has been shown. When some DET is present (e.g., 10–80 mol % DET), the FWHM of the (110) and (111) peaks for the EMM-71 materials (Examples 1A, 1B, 1D, and 1F) shows a significantly lower peak width ratio (i.e., the ratio of the peak widths calculated at half maximum for the (110) and (111) peaks).

[0096] Examples 2A to 2G Synthesis of EMM-71 using a mixture of dimethylterephthalate (DMT) and diethylhexylterephthalate (DEHT) For a given reaction, 3.3 g of zirconium oxychloride octahydrate was mixed with 6.8 mmol of terephthalate (total amount), which had the following DEHT / DMT composition: 0 mol% DEHT (Example 2A) 10 mol% DEHT (Example 2B) 20 mol% DEHT (Example 2C) 40 mol% DEHT (Example 2D) 60 mol% DEHT (Example 2E) 80 mol% DEHT (Example 2F) 100 mol% DEHT (Example 2G) For example, with 0 mol% DEHT (Example 2A), 1.35 g of DMT was used. For 40 mol% DEHT (Example 2D), 0.81 g of DMT and 1.064 g of DEHT were used. The pre-ligand was then combined with 1.5 mL of glacial acetic acid and 0.5 mL of hydrochloric acid (or hydrochloric acid). The mixture was then stirred until homogenous and loaded into a Teflon-coated 23 mL acid digestion vessel. The vessel was placed in a room temperature rotary oven and heated to 80° C. for 5 hours. The temperature was then increased to 150° C. for an additional 10 to 18 hours.

[0097] The reaction mixture was cooled and the solid was suspended in 25 mL of water. The pH was adjusted to 3.5 with sodium formate and heated at 85 °C for 2 h. The solution was filtered and washed with 75–150 mL of 0.05 M formic acid and 75–150 mL of ethanol. The wet cake was dried to obtain dry EMM-71 (or dry EMM-71).

[0098] 7 shows the powder X-ray diffraction patterns of the EMM-71 materials of Examples 2A to 2G. From these XRD patterns, it can be seen that good quality EMM-71 materials were obtained for at least Examples 2A to 2E. Examples 2F-2G (performed using 80 mol % DEHT and 100 mol % DEHT, respectively) showed lower diffraction intensities and the presence of small amounts of impurities.

[0099] 8A to 8F are SEM micrographs of the EMM-71 materials of Examples 2B, 2C, and 2D (30 μm and 10 μm scales, respectively). More specifically, the following is true. 8A-8B correspond to Example 2B (10 mol % DEHT). 8C-8D correspond to Example 2C (20 mol % DEHT). 8E-8F correspond to Example 2D (40 mol % DEHT).

[0100] FIG. 9 plots the FWHM of peak (111) (●) and peak (110) (■) for the EMM-71 materials of Examples 2A to 2F.

[0101] The lines in Figure 9 represent the pore volumes (cc / g) of the EMM-71 materials of Examples 2A-2D as measured by nitrogen adsorption (or nitrogen adsorption) at 77 K and 0.8 P / P.

[0102] From Examples 2A-2G, it can be seen that the combined use of DMT (first pre-ligand) and DEHT (second pre-ligand) in the reaction mixture results in the formation (preparation or production or production) of larger, more uniform crystals. However, it can also be seen that a greater degree of REO phase is formed (as evidenced by the XRD patterns and increased pore volume).

[0103] Examples 3A to 3G Synthesis of EMM-71 using a mixture of dimethylterephthalate (DMT) and benzene dicarboxylic acid (BDC) For a given reaction, 2.64 g of zirconium oxychloride octahydrate and 0.84 g of hafnium oxychloride hydrate (resulting in an 80 / 20 mixture (expressed in moles) of ZrOCl2 / HfOCl2) were charged into a reactor along with 6.9 mmol (total) of a BDC / DMT blend resulting in the following composition: 5 mol% BDC (Example 3A) 10 mol % BDC (Example 3B) 15 mol% BDC (Example 3C) 20 mol% BDC (Example 3D) 25 mol% BDC (Example 3E) 30 mol% 10 mol% BDC (Example 3F) 35 mol% BDC (Example 3G) For example, for the mixture BDC / DMT (containing 5 mol % BDC) (Example 3A), 1.3 g of DMT and 0.06 g of BDC were used. For the mixture BDC / DMT (containing 20 mol % BDC) (Example 3D), 1.1 g of DMT and 0.23 g of BDC were used. 0.5 mL of hydrochloric acid (or hydrochloric acid) (approximately 37% by weight) was added, followed by 1.5 mL of glacial acetic acid. The mixture was mixed and sealed. The reactor was heated to 150° C. over a period of 6 hours and then allowed to soak for at least 10 hours. The reaction mixture was then cooled, diluted, neutralized, filtered, and washed with aqueous formic acid and ethanol.

[0104] 10A and 10B show the powder X-ray diffraction patterns of the EMM-71 materials of Examples 3A-3G. From the above XRD patterns, it can be seen that good quality EMM-71 materials were obtained for all Examples 3A to 3G.

[0105] FIG. 11 is a plot of the pore volume (cc / g) of the EMM-71 materials of Examples 3A through 3G. As shown in FIG. 11, when the reaction mixture contains more than 15 mol% BDC, the pore volume of the metal-organic framework becomes smaller. This is consistent with the excess BDC shown in the X-ray diffraction pattern (Figure 10B).

[0106] Examples 4A to 4I Synthesis of EMM-71 using Zr(OH)4 For a given reaction, DMT and Zr(OH)4 (an alternative metal source) were charged to a reactor ("reactants"). Hydrochloric acid (or hydrochloric acid) (approximately 37% by weight) was added, followed by glacial acetic acid (the "solvent"). Table 1 below lists the amounts of reactants and solvents in the reaction mixture (reactants are included in weight percent (amount of reactant by weight relative to the total amount of the mixture including reactants and solvent)). The reaction mixture was mixed and sealed. The reactor was heated to 80° C. for 5 hours, then heated to 150° C. and then allowed to soak for at least 10 hours. The reaction mixture was then cooled, diluted, neutralized, filtered, and washed with aqueous formic acid and ethanol.

[0107] [Table 1]

[0108] The powder X-ray diffraction patterns of the EMM-71 materials of Examples 4A to 4I are shown in FIG. 12 (the upper curve corresponds to Example 4A, and the lower curve corresponds to Example 4I). As can be seen from Figure 12, good quality EMM-71 material was obtained for Examples 4A to 4F, while the materials of Examples 4G, 4H, and 4I yielded lower quality EMM-71 material (lower diffraction intensity).

[0109] These examples demonstrate that good quality EMM-71 material can be prepared using Zr(OH)4 (an alternative starting material), provided that a sufficient amount of solvent is provided in the reaction mixture.

[0110] These examples also demonstrate that increasing the amount of mineral acid (e.g., HCl) relative to the ligand and / or monocarboxylic acid (e.g., acetic acid) increases the pore volume of the EMM-71 material, which is particularly advantageous. They also demonstrate an increase in the % REO domain.

[0111] Finally, and most importantly, it has been surprisingly discovered that the use of Zr(OH)4 (an alternative starting material) resulted in EMM-71 with a smaller particle size and a narrower particle size distribution, as shown below.

[0112] Table 2 compares the particle sizes (mean, median, mode, D10, D90 (measured by laser sizing)) and width (span) of the particle size distributions of the EMM-71 materials of Examples 3A and 3B (prepared using Zr(OH)4 as the metal source) compared to the EMM-71 material of Comparative Example 2 (prepared using ZrOCl2 as the metal source). The average (or mean) particle size is a calculated value, similar to the concept of an average reported on a volumetric (or volumetric) basis. The median particle size (or D50) is defined as the particle size (by volume) above and below which the distribution is split in half. The mode particle size represents the most commonly found particle size (by volume) in the distribution, i.e., the statistically most common particle size (or the peak of the frequency distribution, corresponding to the highest peak found in the particle size distribution). Similar to the D50 (median), the D10 and D90 correspond to the values ​​below which 10% and 90% (by volume) of the population lie, respectively. The span (or width) of the particle size distribution is given by the formula (D90-D10) / D50, where D50 is the median particle size.

[0113] [Table 2]

[0114] A reduction in particle size is particularly advantageous because it results in a reduction in molecular diffusion and an enhancement of the adsorption process.

[0115] Example 5 Synthesis of EMM-71 using Zr(OH)4 in a mixture of hydrochloric acid (or hydrochloric acid) and propionic acid Also, the following examples yielded good quality EMM-71 material. 12.8 g of dimethyl terephthalate (DMT) and 15.7 g of zirconium hydroxide (Zr(OH)4) were weighed into a reactor. 31.3 g of hydrochloric acid (or hydrochloric acid) (approximately 37% by weight) and 20.8 g of propionic acid (100% by weight) were added to the reactor. The reactor was sealed and heated to 120°C using a slow ramp (maintained at 30-80°C for 2-6 hours during the initial heating step). The reactor was then maintained at 120°C for 6 to 20 hours. The reactor was then cooled to room temperature and the reaction contents were diluted with water to 200 mL and neutralized with sodium formate to a pH of 3-4. The neutralized slurry was heated to 85° C. for 2 hours, then filtered and washed with water, 0.1 wt % aqueous formic acid, and ethanol.

[0116] FIG. 13 shows the powder X-ray diffraction pattern of the EMM-71 material of Example 5.

[0117] Additional Embodiments Additionally / alternatively, the present invention relates to the following embodiments:

[0118] Embodiment 1 A method for producing a metal-organic framework (or metal-organic framework), the method comprising the following steps (a) to (d): (a) combining (or blending or combining) a first pre-ligand (or first pre-ligand) and at least one of a second pre-ligand (or second pre-ligand) and a first ligand (or first ligand) with a metal source (or metal source or metal source). In this process, the metal source comprises a metal component, and such process provides a reactant(s). (b) adding a solvent to the above reactants; This step produces (or forms) a reaction mixture. In this process, at least 50% by weight of the reaction mixture is the reactants. (c) heating the reaction mixture In this step, the first pre-ligand is converted (or transformed or converted or converted) into the second ligand (or second ligand) in the reaction mixture described above. If a second pre-ligand is present, the second pre-ligand is converted (or transformed or converted or converted) into a third ligand (or third ligand) in the reaction mixture. The second ligand and at least one of the first ligand and the third ligand react with the metal component. (d) cooling the reaction mixture. This process produces (or forms) an insoluble portion and a soluble portion. In this process, the insoluble portion comprises a plurality of metal-organic frameworks (or metal-organic frameworks or metal-organic frameworks), each of which comprises at least one of the ligands and the metal component. In this method, the first pre-ligand is selected from the group consisting of dimethyl fumarate, dimethyl terephthalate, terephthalonitrile (1,4-dicyanobenzene), terephthalamide (1,4-benzenedicarboxamide), N 1 ,N 4 -dimethyl terephthalamide, dimethyl 2-amino terephthalate, dimethyl 2-nitro terephthalate, dimethyl 2-chloro terephthalate, dimethyl 2-bromo terephthalate, trimethyl 1,2,4-benzenetricarboxylate, trimethyl 1,3,5-benzene tricarboxylate, tetramethyl 1,2,4,5-benzenetetracarboxylate, polyethylene terephthalate, and mixtures thereof. In the method, the second pre-ligand is a C2-C10 linear or branched alkyl ester selected from the group consisting of alkyl esters of fumarate, terephthalate, 2-aminoterephthalate, 2-nitroterephthalate, 2-chloroterephthalate, 2-bromoterephthalate, 1,2,4-benzenetricarboxylate, 1,3,5-benzenetricarboxylate, 1,2,4,5-benzenetetracarboxylate, and mixtures thereof. In the method, the first ligand is selected from the group consisting of fumaric acid, terephthalic acid, 2-aminoterephthalic acid, 2-nitroterephthalic acid, 2-chloroterephthalic acid, 2-bromoterephthalic acid, 1,2,4-benzenetricarboxylic acid, 1,3,5-benzenetricarboxylic acid, 1,2,4,5-benzenetetracarboxylic acid, and mixtures thereof.

[0119] Embodiment 2 2. The method of embodiment 1, wherein the molar ratio of second pre-ligand and / or first ligand to first pre-ligand (or the molar ratio of second pre-ligand and / or first ligand to first pre-ligand) is 0 (greater than or equal to 0) to 0.6, preferably 0.05 to 0.5, more preferably 0.1 to 0.5, and most preferably 0.2 to 0.4.

[0120] Embodiment 3 The method of embodiment 1 or 2, wherein the first pre-ligand is combined with the second pre-ligand, and the second and third ligands are the same. Specifically, the second and third ligands are both fumaric acid or terephthalic acid, and more specifically, the second and third ligands are both terephthalic acid.

[0121] Embodiment 4 The method of embodiment 1 or 2, wherein the first pre-ligand is combined (or blended or combined) with the first ligand, and the first and second ligands are the same, particularly, the first and second ligands are both fumaric acid or terephthalic acid, more particularly, the first and second ligands are both terephthalic acid.

[0122] Embodiment 5 The method of any one of embodiments 1 to 4, wherein the first pre-ligand is at least one of dimethyl fumarate, polyethylene terephthalate, or methyl ester terephthalate or a derivative thereof (e.g., dimethyl terephthalate, dimethyl 2-amino terephthalate, dimethyl 2-nitro terephthalate, dimethyl 2-chloro terephthalate, or dimethyl 2-bromo terephthalate), more preferably at least one of dimethyl fumarate and dimethyl terephthalate, and particularly dimethyl terephthalate.

[0123] Embodiment 6 6. The method of any one of embodiments 1-5, wherein the second pre-ligand is selected from the group consisting of C2-C8 straight or branched chain alkyl esters, in particular, the alkyl group is selected from ethyl, octyl, and 2-ethylhexyl.

[0124] Embodiment 5 5. The method of any one of embodiments 1-4, wherein the second pre-ligand is a compound of the formula:

[0125] [ka]

[0126] wherein R is independently selected from the group of C2 to C10 straight or branched chain alkyl groups. Preferably, R is independently selected from ethyl, octyl and 2-ethylhexyl. More preferably, both R are the same. Most preferably, the second pre-ligand is selected from diethyl terephthalate, dioctyl terephthalate and diethylhexyl terephthalate.

[0127] Embodiment 7 7. The method of any one of embodiments 1 to 6, wherein at least one of the second pre-ligands is liquid at 20°C.

[0128] Embodiment 8 The method of any one of embodiments 1-7, wherein the first ligand is at least one of fumaric acid and terephthalic acid or derivatives thereof, more specifically terephthalic acid.

[0129] Embodiment 9 The method of any one of embodiments 1 to 8, wherein the solvent comprises at least one of a monocarboxylic acid and / or a mineral acid, and further comprises water as needed, and preferably comprises a monocarboxylic acid and a mineral acid.

[0130] Embodiment 10 The method of any one of embodiments 1-9, wherein the solvent is added to the reaction mixture in an amount of 0.1 weight equivalent to 1.0 weight equivalent relative to the reactants, preferably 0.1 weight equivalent to 1.0 weight equivalent (or less than or equal to 10 weight equivalents), and more preferably up to 0.9, 0.8, 0.7, 0.6, 0.5, 0.4, 0.3, or 0.2 weight equivalents.

[0131] Embodiment 11 11. The method of any one of embodiments 1-10, wherein the solvent comprises a mineral acid, and the amount (molar ratio) of mineral acid:ligand(s) in the reaction mixture is at most 5:1, preferably 1:10 to 5:1, more preferably 1:2 to 3:1, and most preferably 1:1 to 2:1.

[0132] Embodiment 12 The method of any one of embodiments 1 to 11, wherein the reaction mixture does not comprise (or does not contain) dimethylformamide.

[0133] Embodiment 13 A method for producing a metal-organic framework (or metal-organic framework or metal-organic framework or metal-organic framework), the method comprising the following steps: Combining (or combining or bringing together) the pre-ligand with the metal source In this process, the metal source (or metal source or metal source) comprises a metal component (or metal component), and by this process, the reactants (plurality of reactants) are generated (or formed), and the metal source (or metal hydroxide) is selected from the group consisting of metal hydroxide, metal acetate, metal hydroxyacetate, metal carbonate, metal hydroxycarbonate, and mixtures thereof. adding a solvent to the above reactants; This step produces (or forms) a reaction mixture. In this step, 15% to 50% by weight of the reaction mixture is the reactant(s). the step of heating the reaction mixture; In this step, the pre-ligand is converted into a ligand in the reaction mixture, and the ligand reacts with the metal component. cooling the reaction mixture; This process produces (or forms) an insoluble portion and a soluble portion. In this process, the insoluble portion comprises a plurality of metal-organic frameworks (or metal-organic frameworks or metal-organic frameworks or metal-organic frameworks), each of which comprises the ligand and the metal component. In this step, the reaction mixture does not contain (or does not contain) dimethylformamide.

[0134] Embodiment 14 14. The method of embodiment 13, wherein the pre-ligand is selected from the group consisting of dimethyl fumarate, dimethyl terephthalate, terephthalonitrile (1,4-dicyanobenzene), terephthalamide (1,4-benzenedicarboxamide), N 1 ,N 4 -dimethyl terephthalamide, dimethyl 2-amino terephthalate, dimethyl 2-nitro terephthalate, dimethyl 2-chloro terephthalate, dimethyl 2-bromo terephthalate, trimethyl 1,2,4-benzene tricarboxylate, trimethyl 1,3,5-benzene tricarboxylate, tetramethyl 1,2,4,5-benzene tetracarboxylate, polyethylene terephthalate, and mixtures thereof. Preferably, the pre-ligand is at least one of dimethyl fumarate, polyethylene terephthalate, or methyl ester terephthalate or a derivative thereof (e.g., dimethyl terephthalate, dimethyl 2-amino terephthalate, dimethyl 2-nitro terephthalate, dimethyl 2-chloro terephthalate, or dimethyl 2-bromo terephthalate). More preferably, the pre-ligand is at least one of dimethyl fumarate and dimethyl terephthalate. The pre-ligand is particularly dimethyl terephthalate.

[0135] Embodiment 15 15. The method of any one of embodiments 13-14, wherein the metal component is zirconium. The metal source is selected from the group consisting of zirconium hydroxide (Zr(OH)), zirconium acetate (Zr(OAc)), zirconium acetate hydroxide (Zr(OAc) x (OH) y , where x+y=about 4), zirconium carbonate (Zr(CO3)2), zirconium hydroxycarbonate (Zr(OH)2CO3ZrO2), and mixtures thereof. In particular, the metal source is zirconium hydroxide.

[0136] Embodiment 16 The method of any one of embodiments 13 to 15, wherein the solvent comprises at least one of a monocarboxylic acid and / or a mineral acid, and optionally water, and preferably comprises a monocarboxylic acid and a mineral acid.

[0137] Embodiment 17 17. The method of any one of embodiments 13 to 16, wherein 15% to 50% by weight of the reaction mixture is reaction mixture(s), preferably 25% to 50% by weight (or less than or not including 50% by weight), in particular 30% to 50% by weight (or less than or not including 50% by weight), more particularly 30% (or 35% by weight) to 45% by weight.

[0138] Embodiment 18 The method of any one of embodiments 13-17, wherein the solvent is added to the reaction mixture in an amount of 1.0 to 4.0 weight equivalents relative to the reactants, preferably 1.0 (greater than or equal to 1.0) to 3.0, and more preferably 1.2 to 2.5 weight equivalents.

[0139] Embodiment 19 19. The method of any one of embodiments 13-18, wherein the solvent comprises a mineral acid, and the amount (molar ratio) of mineral acid:ligand in the reaction mixture is from 1:1 to 20:1, preferably from 1:1 to 10:1, more preferably from 2:1 to 8:1, and most preferably from 2:1 (or greater than or not including 2:1) to 6:1.

[0140] Embodiment 20 The method of any one of embodiments 13 to 19, wherein the solvent comprises both a monocarboxylic acid and a mineral acid, and the amount (molar ratio) of mineral acid:monocarboxylic acid in the reaction mixture is at most 8:1, preferably 1:5 to 8:1, more preferably 1:4 to 6:1, more preferably 1:3 to 5:1, particularly 1:2 to 4:1, and more particularly 3:4 to 3:1 (or 2:1).

[0141] Embodiment 21 21. The method of any one of embodiments 1 to 20, wherein the metal component is a tetravalent metal selected from the group consisting of zirconium, titanium, cerium, hafnium, and combinations thereof. The metal component is preferably Zr or Zr / Hf.

[0142] Embodiment 22 The method of any one of embodiments 1 to 21, wherein the reaction mixture is heated to a temperature of about 100°C to 220°C, preferably 100°C to 160°C, more preferably 140°C to 160°C.

[0143] Embodiment 23 23. The method of any one of embodiments 1-22, wherein the solvent comprises a monocarboxylic acid, preferably the monocarboxylic acid is selected from the group consisting of acetic acid, formic acid, propionic acid, and mixtures thereof.

[0144] Embodiment 24 24. The method of any one of embodiments 1-23, wherein the solvent comprises a mineral acid. Preferably, the mineral acid is selected from the group consisting of hydrochloric acid (or hydrochloric acid), hydrobromic acid, and mixtures thereof.

[0145] Embodiment 25 25. The method of any one of embodiments 1 to 24, wherein the solvent comprises a monocarboxylic acid, and the amount (molar ratio) of monocarboxylic acid:ligand(s) in the reaction mixture is 1:1 to 20:1, in particular 1:1 to 20:1 (or less than or not including 20:1), preferably 1:1 to 10:1, more preferably 2:1 to 8:1, and most preferably 3:1 to 5:1.

[0146] Embodiment 26 The method of any one of embodiments 1-25, further comprising separating the insoluble portion from the soluble portion and / or drying the insoluble portion, wherein the drying step produces (or forms or produces) the metal-organic framework(s).

[0147] Embodiment 27 27. The method of any one of embodiments 1 to 26, wherein the metal-organic framework is selected from the group consisting of UiO-66, EMM-71, zirconium fumarate, MOF-808, NU-1000, or functionalized derivatives thereof, and in particular, EMM-71.

[0148] Embodiment 28 The method of any one of embodiments 1 to 27, wherein the metal-organic framework is a Zr-terephthalate metal-organic framework or a Zr—Hf-terephthalate metal-organic framework.

[0149] In light of the above description, it will be apparent to those skilled in the art that many alternatives, modifications, and variations are possible where lower and upper numerical limits are recited in this disclosure, and do not deviate from the spirit or scope of the present disclosure.

Claims

1. 1. A method for preparing a metal-organic framework, the method comprising: combining the first pre-ligand and at least one of the second pre-ligand or the first ligand together with a metal source to provide a plurality of reactants, the metal source comprising a metal component; adding a solvent to the plurality of reactants to form a reaction mixture, wherein at least 50% by weight of the reaction mixture is the plurality of reactants; heating the reaction mixture, In the reaction mixture, a first pre-ligand is converted to a second ligand; If a second pre-ligand is present, the second pre-ligand is converted to a third ligand in the reaction mixture; reacting both the second ligand and at least one of the first ligand or the third ligand with the metal component; cooling the reaction mixture to form an insoluble portion and a soluble portion, the insoluble portion comprising the plurality of metal-organic frameworks, each of the plurality of metal-organic frameworks comprising at least one ligand and a metal component; Including, The first pre-ligand is dimethyl fumarate, dimethyl terephthalate, terephthalonitrile (1,4-dicyanobenzene), terephthalamide (1,4-benzenedicarboxamide), N １ , N ４ dimethyl terephthalamide, dimethyl 2-aminoterephthalate, dimethyl 2-nitroterephthalate, dimethyl 2-chloroterephthalate, dimethyl 2-bromoterephthalate, trimethyl 1,2,4-benzenetricarboxylate, trimethyl 1,3,5-benzenetricarboxylate, tetramethyl 1,2,4,5-benzenetetracarboxylate, polyethylene terephthalate, and mixtures thereof; the second pre-ligand is a C2-C10 straight or branched chain alkyl ester selected from the group consisting of alkyl esters of fumarate, terephthalate, 2-aminoterephthalate, 2-nitroterephthalate, 2-chloroterephthalate, 2-bromoterephthalate, 1,2,4-benzenetricarboxylate, 1,3,5-benzenetricarboxylate, 1,2,4,5-benzenetetracarboxylate, and mixtures thereof; the first ligand is selected from the group consisting of fumaric acid, terephthalic acid, 2-aminoterephthalic acid, 2-nitroterephthalic acid, 2-chloroterephthalic acid, 2-bromoterephthalic acid, 1,2,4-benzenetricarboxylic acid, 1,3,5-benzenetricarboxylic acid, 1,2,4,5-benzenetetracarboxylic acid, and mixtures thereof; method.

2. 2. The method of claim 1, wherein the molar ratio of the second pre-ligand and / or the first ligand to the first pre-ligand is between 0 and 0.6 (but not including 0).

3. The first pre-ligand is combined with the second pre-ligand; the second ligand and the third ligand are the same; In particular, the second ligand and the third ligand are both fumaric acid or terephthalic acid; More specifically, the method of claim 1 or 2, wherein the second ligand and the third ligand are both terephthalic acid.

4. The first pre-ligand is combined with the first ligand; the first ligand and the second ligand are the same; In particular, the first ligand and the second ligand are both fumaric acid or terephthalic acid; More specifically, the method of claim 1 or 2, wherein the first ligand and the second ligand are both terephthalic acid.

5. The second pre-ligand has the formula: 【Chemistry 1】 wherein R is independently selected from the group of C2-C10 straight or branched chain alkyls, in particular ethyl, octyl and 2-ethylhexyl. The method according to any one of claims 1 to 4, wherein the compound is

6. The method of any one of claims 1 to 5, wherein at least one of the second pre-ligands is liquid at 20°C.

7. 7. The method of claim 1, wherein the solvent is added to the reaction mixture in an amount of 0.1 to 1.0 weight equivalents relative to the plurality of reactants.

8. The method of any one of claims 1 to 7, wherein the reaction mixture is free of dimethylformamide.

9. 1. A method for preparing a metal-organic framework, the method comprising: combining the pre-ligand with a metal source to provide a plurality of reactants, said metal source comprising a metal component, said metal source being selected from the group consisting of metal hydroxides, metal acetates, metal hydroxyacetates, metal carbonates, metal hydroxycarbonates, and mixtures thereof; adding a solvent to the plurality of reactants to form a reaction mixture, wherein the reaction mixture is 15% to 50% by weight of the plurality of reactants; heating the reaction mixture, In the reaction mixture, the pre-ligand is converted to a ligand; reacting the ligand with the metal component; cooling the reaction mixture to form an insoluble portion and a soluble portion, the insoluble portion comprising the plurality of metal-organic frameworks, each of the plurality of metal-organic frameworks comprising the ligand and the metal component, the reaction mixture being free of dimethylformamide; A method comprising:

10. The pre-ligands are dimethyl fumarate, dimethyl terephthalate, terephthalonitrile (1,4-dicyanobenzene), terephthalamide (1,4-benzenedicarboxamide), N １ , N ４ 10. The method of claim 9, wherein the carboxylic acid is selected from the group consisting of dimethyl terephthalamide, dimethyl 2-aminoterephthalate, dimethyl 2-nitroterephthalate, dimethyl 2-chloroterephthalate, dimethyl 2-bromoterephthalate, trimethyl 1,2,4-benzenetricarboxylate, trimethyl 1,3,5-benzenetricarboxylate, tetramethyl 1,2,4,5-benzenetetracarboxylate, polyethylene terephthalate, and mixtures thereof.

11. 11. The method of claim 9 or 10, wherein the solvent is added to the reaction mixture in an amount of 1.0 to 4.0 weight equivalents relative to the plurality of reactants.

12. 12. The method of any one of claims 1 to 11, wherein the metal component is a tetravalent metal, the metal being selected from the group consisting of zirconium, titanium, cerium, hafnium, and combinations thereof, and preferably the metal-organic framework is a zirconium metal-organic framework or a zirconium-based metal-organic framework further comprising hafnium.

13. The process of any one of claims 1 to 12, wherein the reaction mixture is heated to a temperature of about 100°C to 220°C.

14. The method according to any one of claims 1 to 13, wherein the solvent comprises at least one of a monocarboxylic acid and / or a mineral acid, and optionally water.

15. 15. The method of claim 14, wherein the monocarboxylic acid is selected from the group consisting of acetic acid, formic acid, propionic acid, and mixtures thereof.

16. 15. The method of claim 14, wherein the mineral acid is selected from the group consisting of hydrochloric acid, hydrobromic acid, and mixtures thereof.

17. 17. The method of any one of claims 1 to 16, wherein the solvent comprises a monocarboxylic acid, and the amount of monocarboxylic acid:ligand in the reaction mixture is in a molar ratio of 1:1 to 20:

1.

18. The method according to any one of claims 9 to 11, wherein the solvent comprises a monocarboxylic acid and a mineral acid, and the amount of mineral acid:monocarboxylic acid in the reaction mixture is in a molar ratio of 1:5 to 8:

1.

19. Separating the insoluble portion from the soluble portion; and / or drying the insoluble portion to form the plurality of metal-organic frameworks. The method of any one of claims 1 to 18, further comprising:

20. 20. The method of any one of claims 1 to 19, wherein the metal-organic framework is selected from the group consisting of UiO-66, EMM-71, zirconium fumarate, MOF-808, NU-1000 or functionalized derivatives thereof.

21. The method of any one of claims 1 to 20, wherein the metal-organic framework is a Zr-terephthalate metal-organic framework or a Zr-Hf-terephthalate metal-organic framework.

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