Functionalization of porous materials after synthesis

Abstract

A process for producing a functionalized porous material is disclosed, comprising: mixing a base porous material containing a porous structure and an unstable ligand with a functionalizing agent to form a slurry, wherein the porous structure has open metal parts and a plurality of pores, the unstable ligand is coordinated to the open metal parts, present in the plurality of pores but not coordinated to the open metal parts, or a combination thereof, the unstable ligand has a first boiling point, and the functionalizing agent has a second boiling point higher than the first boiling point; and drying the slurry to form a functionalized porous material containing a functionalizing agent coordinated to the open metal parts.

Description

Technical Field

[0001] (Cross - reference to Related Applications) This application claims the benefit of U.S. Patent Application No. 18 / 182,089, filed Mar. 10, 2023, which is incorporated herein by reference in its entirety.

[0002] (Statement of Government Support) This invention was made, in part, in receipt of government support under Advanced Manufacturing Office (AMO) Award Number DE - EE0009419 from the U.S. Department of Energy's Energy Efficiency and Renewable Energy Office (EERE). The government has certain rights in this invention.

Background Art

[0003] This disclosure relates to the post - synthesis functionalization of porous materials, particularly the post - synthesis functionalization of metal - organic frameworks having open metal sites.

[0004] A metal - organic framework (MOF) is a three - dimensional crystalline network containing potential pores. MOFs have attracted significant attention currently mainly due to their potential use in CO2 capture, gas separation and storage, catalysis, and drug delivery. MOFs are typically formed by linking metal ions or metal clusters (often called secondary building units) together with organic linkers.

[0005] Functionalizing MOFs can improve their performance in various applications, for example, by increasing gas uptake or catalytic activity. Therefore, there is an increasing trend towards increasing the functionality of MOFs. Functionalized MOFs can be prepared by in-situ functionalization, where the functional groups are introduced during a solvothermal process for synthesizing the MOF. MOFs can also be functionalized via post-synthesis modification. As used herein, post-synthesis modification refers to the modification of the MOF material after its synthesis or after the three-dimensional extended skeleton of the MOF has been established. The post-synthesis approach can enable the incorporation of functional groups into the MOF that would otherwise not withstand MOF synthesis due to temperature, pH, or other reaction conditions. Despite advances in the art, there is still a need for processes to functionalize porous materials with improved efficiency. [Overview of the project]

[0006] A process for producing a functionalized porous material is disclosed, comprising: mixing a base porous material containing a porous structure and an unstable ligand with a functionalizing agent to form a slurry, wherein the porous structure has open metal parts and a plurality of pores, the unstable ligand is coordinated to the open metal parts, present in the plurality of pores but not coordinated to the open metal parts, or a combination thereof, the unstable ligand has a first boiling point, and the functionalizing agent has a second boiling point higher than the first boiling point; and drying the slurry to form a functionalized porous material containing a functionalizing agent coordinated to the open metal parts. [Brief explanation of the drawing]

[0007] The drawings are provided with illustrative and non-limiting descriptions. [Figure 1] This disclosure describes a process for functionalizing a base porous material having open metal moieties via post-synthesis ligand exchange, according to one embodiment of this disclosure. [Figure 2]The present invention relates to a process for producing a functionalized porous material, which includes preparing a base porous material having open metal moieties and functionalizing the base porous material via post-synthesis ligand exchange. [Modes for carrying out the invention]

[0008] A detailed description of one or more embodiments is provided herein as an example, not an limitation.

[0009] Porous materials, such as MOFs, often have open metal moieties. As used herein, the term “open metal moiety” refers to a metal ion that is not fully coordinated. Open metal moieties may also be called coordinationally unsaturated moieties.

[0010] Processes for functionalizing porous materials having open metal moieties may involve the use of organic solvents as solvents for functionalization and for subsequent washing and purification steps. However, highly polar solvents such as N,N-dimethylformamide or methanol, which are typically used in the art as solvents for the synthesis of MOFs, are often unsuitable for this process. These solvents, at high concentrations, may exert a dominant effect over the functionalizing agent in terms of coordination to the open metal moieties, potentially leading to incomplete functionalization of the porous material. Therefore, it is typically necessary to remove highly polar solvents from MOFs before functionalization by temperature / vacuum removal or by subsequent washing with less polar solvents such as acetonitrile, hexane, or toluene.

[0011] The inventors have discovered a novel process for functionalizing porous materials, in which functionalization is achieved through post-synthesis ligand exchange within the porous material having open metal moieties. In this process, unstable ligands are first placed in the open metal moieties within the porous material either after or during synthesis, and then these unstable ligands are replaced with functionalizing agents that form adducts with the open metal moieties.

[0012] The process described herein allows for the use of ligands having a higher boiling point than polar solvents (unstable ligands) for functionalization. The ability to use water as the unstable ligand for this process is particularly advantageous. Since this process eliminates the need for organic solvents, it reduces manufacturing costs and waste, which is especially beneficial when the process is implemented on a large scale in a commercial setting. Furthermore, this process eliminates multiple steps by allowing the formation of a functionalized porous material from a slurry of a functionalizing agent and a porous material having an unstable ligand, and simultaneous drying, without the need for further filtration and washing.

[0013] Functionalized porous materials prepared by the processes disclosed herein may have performance equivalent to that of functionalized porous materials prepared by known processes. While not theoretically bound, the processes disclosed herein are considered to enable the functionalization of porous materials without damaging their structure. Exemplarily, the crystallinity and porosity of porous materials can be preserved after functionalization.

[0014] Referring to Figure 1, the process for producing the functionalized porous material (140) includes mixing a base porous material (110) with a functionalizing agent (120) to form a slurry (130), and drying the slurry to form the functionalized porous material (140). Optionally, a slurry solvent (150) is added and mixed with the base porous material (110) and the functionalizing agent (120) to form a slurry (130).

[0015] The base porous material (110) comprises a porous structure and an unstable ligand. The porous structure has open metal portions and multiple pores and forms the skeleton of the base porous material. Preferably, the porous structure may be an MOF. The MOF includes inorganic nodes connected by organic linkers.

[0016] The inorganic node includes an open metal moiety. The open metal moiety may be at least one ion from Mg, Ca, Ba, Al, Sc, Zr, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Ti, Cd, or Eu, preferably at least one ion from Mg, Mn, Zn, or Ni. The organic linker may include at least one from carboxylate, triazolate, or imidazolate, preferably carboxylate. Examples of organic linkers include 4,4'-dihydroxy-(1,1'-biphenyl)-3,3'-dicarboxylate, 2,5-dihydroxybenzene-1,4-dicarboxylate, 4,6-dihydroxybenzene-1,3-dicarboxylate, benzene-1,4-dicarboxylate, benzene-1,3,5-tricarboxylate, 3,3',4,4'-benzophenone-tetracarboxylate, benzene-1,2,4,5-tetracarboxylate, trans-1,4-cyclohexanedicarboxylate, 1H,7H-[1,4]dioxyno[2,3-F:5,6-F']bisbenzotriazolate, 1 Examples include, but are not limited to, 5-dihydrobenzo[1,2-d:4,5-d']bis([1,2,3]triazolate, 3,5-dimethyl-1H-pyrazole-4-carboxylate, 5-(pyridine-3-yl)benzene-1,3-dicarboxylate, 1,3,5-tri(1H-tetrazole-5-yl)benzene, 2-methylimidazolate, 2-ethylimidazolate, and 1-benzyl-1H-imidazolate. Other suitable known organic linkers may also be used. Preferably, the organic linker includes 4,4'-dihydroxy-(1,1'-biphenyl)-3,3'-dicarboxylate.

[0017] Examples of MOFs having open metal moieties include, but are not limited to, MOF-74, MOF-274, HKUST-1, MIL-100, MIL-101, MOF-525, MOF-2, MOF-505, and UiO-66. Further MOFs include, but are not limited to, those described in Chem.Soc.Rev.2020, 49, 2751-2798. A preferred MOF is Mg2(dobpdc), where the inorganic node contains a Mg ion and the organic linker contains 4,4'-dihydroxy-(1,1'-biphenyl)-3,3'-dicarboxylate(dobpdc).

[0018] As used herein, an unstable ligand refers to a ligand that can initially coordinate to an open metal portion of a porous structure but can later be replaced by a functionalizing agent. Unstable ligands have oxygen and / or nitrogen atoms and can be used as solvents for the synthesis or purification / washing of porous structures. Examples of unstable ligands include, but are not limited to, water, methanol, ethanol, acetonitrile, and N,N-dimethylformamide. A base porous material may contain multiple unstable ligands. In one embodiment, based on the total weight of unstable ligands in the base porous material, more than 50% by weight, more than 70% by weight, more than 80% by weight, more than 90% by weight, more than 95% by weight, or 100% by weight of the unstable ligands in the base porous material is water. In another embodiment, based on the total weight of unstable ligands in the base porous material, more than 50% by weight, more than 70% by weight, more than 80% by weight, more than 90% by weight, more than 95% by weight, or 100% by weight of the unstable ligands in the base porous material is methanol, ethanol, or a combination thereof.

[0019] Unstable ligands are either coordinated to open metal sites, present in multiple pores but not to open metal sites, or a combination of these. The weight ratio of unstable ligands to porous structures in the base porous material can be approximately 25:1 to 1:0.5, 25:1 to 1:1, 20:1 to 3:1, 15:1 to 5:1, or 10:1 to 7:1.

[0020] A base porous material can be mixed with an unstable ligand and a functionalizing agent to form a slurry. The functionalizing agent can substitute for the unstable ligand and coordinate to the open metal moieties. A suitable functionalizing agent has a boiling point higher than that of the unstable ligand. In particular, the unstable ligand has a first boiling point, and the functionalizing agent has a second boiling point higher than the first boiling point. In one embodiment, the functionalizing agent has a boiling point of about 70°C to about 340°C, preferably about 120°C to about 200°C. The difference between the second boiling point and the first boiling point may be about 50°C to about 150°C, or about 60°C to about 120°C.

[0021] Examples of functionalizing agents include, but are not limited to, monoamines, primary / primary diamines, primary / secondary diamines, primary / tertiary diamines, secondary / secondary diamines, and other diamines, as well as bifunctional ligands, and polyamines such as triamines, tetramines, and aminopolymers.

[0022] Monoamines may be monoalkylamines, dialkylamines, trialkylamines, monoarylamines, diarylamines, triarylamines, and mixed alkyl-arylamines. Examples of monoamines include, but are not limited to, aniline, n-butylamine, n-pentylamine, n-hexylamine, diphenylamine, and triethylamine.

[0023] Examples of diamines include, but are not limited to, ethylenediamine, 2,2-dimethyl-1,3-propanediamine, 1,3-diaminopentane, 2-methylpropane-1,2-diamine, N-ethylethylenediamine, N-isopropylethylenediamine, N-butylethylenediamine, N-pentylethylenediamine, N-hexylethylenediamine, N,N-dimethylethane-1,2-diamine, N,N-diethylethylenediamine, N,N-diisopropylethylenediamine, N,N-dimethylpropylenediamine, N,N'-dimethylethane-1,2-diamine, 2-(aminomethyl)piperidine, and N,N-diethyl-N-methylethylenediamine.

[0024] [[ID=~4]]As used herein, a bifunctional ligand refers to a single organic molecule having two different functional groups. Examples of bifunctional ligands include, but are not limited to, amino alcohols (also known as alkanolamines).

[0025] Suitable polyamines include, but are not limited to, bis(3-aminopropyl)amine, N,N'-bis(3-aminopropyl)-1,4-butanediamine, tetraethylenepentamine, polyethyleneimine, and polypropyleneimine. Preferably, the functionalizing agent includes the primary / secondary diamines disclosed herein.

[0026] The molar ratio of the functionalizing agent to the open metal sites in the porous structure is at least 1 to achieve 100% coverage of the open metal sites. Depending on the conditions, during the drying process, some of the functionalizing agent may evaporate with the labile ligands. In this case, a slightly excess amount of the functionalizing ligand can be used. Generally, the molar ratio of the functionalizing agent to the open metal sites can be about 3:1 to about 1:1, about 2:1 to about 1:1, about 1.8:1 to about 1.2:1, or about 1.5.

[0027] Mixing is performed before drying and is generally carried out for a slightly longer time than necessary to achieve a uniform consistency in the resulting slurry. Better results may be observed in the case of a uniform slurry than in a heterogeneous mixture. This could be achieved in at least 5 minutes, but good results can be obtained by extending the slurry mixing to 90 minutes. Mixing can be carried out at room temperature (23°C) and atmospheric pressure. However, mixing can also be carried out at high temperatures, for example, above 23°C but below 50°C. In one embodiment, a slurry solvent is optionally added during mixing to prepare the slurry. Advantageously, it is not necessary to add a solvent. When used, the slurry solvent may contain unstable ligands such as those described herein. In one embodiment, when used, the slurry solvent contains more than 50% by weight, more than 70% by weight, more than 80% by weight, more than 90% by weight, more than 95% by weight, or 100% by weight of water based on the total weight of the slurry solvent. In another embodiment, the slurry solvent comprises more than 50% by weight, more than 70% by weight, more than 80% by weight, more than 90% by weight, more than 95% by weight, or 100% by weight of methanol, ethanol, or a combination thereof, based on the total weight of the slurry solvent.

[0028] During the drying process, temperatures of 20°C to 150°C, 23°C to 110°C, 40°C to 110°C, or 60°C to 100°C can be applied to the slurry to form a functionalized porous material. The temperature affects the time required to remove unstable ligands and form a dried functionalized product, with higher temperatures resulting in faster drying. In one embodiment, temperatures of about 70°C to 90°C or about 80°C can be applied because these temperatures can be conveniently and safely reached using a water bath in a rotary evaporator, resulting in a rapid drying rate.

[0029] Pressures ranging from atmospheric pressure (101,325 Pascals) to 100 Pascals, for example, from about 15,000 Pascals to about 100 Pascals, can be applied, and all properly functionalized materials can be obtained. The lower the pressure, the faster the removal of unstable ligands. Preferably, the strongest vacuum that can be applied in a given apparatus is used without causing bumping (foaming of the material into the body of the drying apparatus).

[0030] Any apparatus capable of applying temperature and vacuum is suitable for the drying process. In extreme cases, the slurry can be dried at room temperature and room pressure (provided that the criteria for unstable ligands to evaporate under atmospheric conditions are met) to obtain a properly functionalized material.

[0031] If the porous structure is an MOF, the base porous material can be prepared by the reaction of a metal salt with an organic crosslinking ligand in the presence of a reaction solvent. The metal salt may be at least one of Mg, Ca, Ba, Al, Sc, Zr, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Ti, Cd, or Eu. The salt may be an acetate, hydroxide, carbonate, nitrate, chloride, sulfate, or a combination thereof.

[0032] The organic crosslinking ligand may be at least one of a carboxylic acid, a triazole, or an imidazole, preferably a carboxylic acid. Examples of organic crosslinking ligands include 4,4'-dihydroxy-(1,1'-biphenyl)-3,3'-dicarboxylic acid, 2,5-dihydroxybenzene-1,4-dicarboxylic acid, 4,6-dihydroxybenzene-1,3-dicarboxylic acid, benzene-1,4-dicarboxylic acid, benzene-1,3,5-tricarboxylic acid, 3,3',4,4'-benzophenone-tetracarboxylic acid, benzene-1,2,4,5-tetracarboxylic acid, trans-1,4-cyclohexanedicarboxylic acid, and 1H,7H-[1,4]dioxyno[2,3-F:5,6-F']bisben Examples include, but are not limited to, zotriazole, 1,5-dihydrobenzo[1,2-d:4,5-d']bis([1,2,3]triazole, 3,5-dimethyl-1H-pyrazole-4-carboxylic acid, 5-(pyridine-3-yl)benzene-1,3-dicarboxylic acid, 1,3,5-tri(1H-tetrazole-5-yl)benzene, 2-methylimidazole, 2-ethylimidazole, and 1-benzyl-1H-imidazole. Other suitable known organic crosslinking ligands may also be used. Multiple organic crosslinking ligands may be used.

[0033] The reaction solvent may include unstable ligands such as water, methanol, ethanol, acetonitrile, N,N-dimethylformamide, or combinations thereof. Preferably, the reaction solvent contains more than 50% by weight, more than 70% by weight, more than 80% by weight, more than 90% by weight, more than 95% by weight, or 100% by weight of water, based on the total weight of the reaction solvent.

[0034] The reaction can be carried out at a temperature of approximately 50°C to 120°C or approximately 60°C to 100°C, or under reflux, for a period of approximately 10 minutes to 24 hours, depending on the specific reactants used. A base may be present during the reaction. The reaction can be carried out at atmospheric pressure to obtain the crude reaction product.

[0035] After the reaction is complete, the reaction can be quenched by cooling the reaction mixture. The reaction can be quenched by adding water, preferably cold water, to the reaction mixture.

[0036] The quenched product contains a base porous material, which can be separated from the quenched product by filtration. The filtered solid can be washed or rinsed with a rinsing solvent to remove any unreacted starting materials or by-products. The rinsing solvent may contain unstable ligands such as water, methanol, ethanol, acetonitrile, N,N-dimethylformamide, or combinations thereof. For example, the rinsing solvent may contain more than 50% by weight, more than 70% by weight, more than 80% by weight, more than 90% by weight, more than 95% by weight, or 100% by weight of water, based on the total weight of the rinsing solvent. Alternatively, the rinsing solvent may contain more than 50% by weight, more than 70% by weight, more than 80% by weight, more than 90% by weight, more than 95% by weight, or 100% by weight of methanol, ethanol, or combinations thereof, based on the total weight of the rinsing solvent. The product is usually obtained in the form of a wet filtration cake as a result of using a filter plate press.

[0037] Referring to Figure 2, the process for producing the functionalized porous material (140) includes (a) reacting a metal salt with an organic crosslinking ligand in the presence of a reaction solvent containing an unstable ligand to form a crude product (20) (10); (b) adding water and / or other unstable ligands (30) to the crude product (20) to obtain a quenched product (40); (c) filtering the quenched product (40) to obtain a filter cake (50); (d) rinsing the filter cake (50) to obtain a rinsed filter cake (60) containing the base porous material; (e) mixing the rinsed filter cake (60) with a functionalizing agent (120) and optionally a slurry solvent (150) to form a slurry (130); and (f) drying the slurry (130) to form the functionalized porous material (140). The "other unstable ligands" (30) may be the same as or different from the unstable ligands in the reaction solvent.

[0038] As a specific example, the process for producing a functionalized porous material involves (a) reacting a magnesium salt with 4,4'-dihydroxy-(1,1'-biphenyl)-3,3'-dicarboxylic acid in the presence of a reaction solvent containing more than 50% by weight, more than 70% by weight, more than 80% by weight, more than 90% by weight, more than 95% by weight, or 100% by weight of water, based on the total weight of the reaction solvent, in order to form a crude product; (b) adding an unstable ligand such as water to the crude product to obtain a quenched product; (c) filtering the quenched product to obtain a filter cake; and (d) adding more than 50% by weight, more than 70% by weight, based on the total weight of the rinsing solvent, to obtain a rinsed filter cake containing the base porous material. (a) rinsing the filtration cake with a rinsing solvent containing more than 80% by weight, more than 90% by weight, more than 95% by weight, or 100% by weight of water, to form a slurry, (e) mixing the rinsed filtration cake with a functionalizing agent and optionally, a slurry solvent containing more than 50% by weight, more than 70% by weight, more than 80% by weight, more than 90% by weight, more than 95% by weight, or 100% by weight of water, based on the total weight of the slurry solvent, and (f) drying the slurry at a temperature of about 20°C to about 150°C, preferably about 40°C to about 110°C, and at a pressure of about 101,325 Pascals to about 1,200 Pascals, preferably about 15,000 Pascals to about 1,200 Pascals, to form a functionalized porous material containing the functionalizing agent.

[0039] Advantageously, no further purification is required after the drying process. Functionalized porous materials prepared from the processes described herein may have less than 40% by weight, less than 30% by weight, less than 20% by weight, less than 10% by weight, less than 5% by weight, less than 2% by weight, or less than 1% by weight of unstable ligands based on the total weight of the functionalized porous material. In one embodiment, the functionalized porous material does not contain unstable ligands. In other words, unstable ligands can be completely replaced by the functionalizing agent. Furthermore, the functionalized porous material may not contain open metal moieties because the open metal moieties are coordinated with the functionalizing agent. In one embodiment, all open metal moieties in the functionalized porous structure are coordinately bonded with the functionalizing agent.

[0040] This process enables the production of functionalized porous materials with far greater efficiency in terms of time, cost, and waste compared to known processes. Furthermore, this process is applicable to a wide variety of porous materials and ligand types, allowing for the design or improvement of the manufacturing process for many different products.

[0041] Functionalized porous materials produced by the processes described herein may have similar or improved performance compared to functionalized porous materials produced by other known processes and can be used in applications such as CO2 sequestering, gas separation and storage, and catalytic activity.

[0042] The process of functionalizing porous materials is further illustrated by the following non-limiting examples. [Examples]

[0043] General procedure for preparing base MOFs The organic crosslinking ligand is stirred with the base for 15 minutes. Then, the magnesium salt dissolved in water is added to the slurry, and the resulting mixture is heated under reflux for 1 hour with vigorous stirring. Next, water is added to quench the reaction mixture, and the resulting slurry is filtered and washed with water to remove impurities. The resulting solid is dried briefly with a nitrogen stream to obtain a material called a "wet-based MOF," which is collected from a filtration device.

[0044] Example 1 In a glass round-bottom flask, the wet base MOF and diamine were mixed until a slurry of uniform consistency was reached. The flask was mounted on a rotary evaporator and heated to 80°C while gently rotating. Most of the water was removed at a set pressure of 150 mbar to avoid bumping (bubbling into the apparatus). The pressure was slowly reduced to 12 mbar, and water was removed until the resulting substance was dry.

[0045] Example 2 In a large bucket, the wet base MOF and diamine were mixed until a slurry of uniform consistency was reached. The material was evaporated at room temperature (23°C) and atmospheric pressure until dry.

[0046] Example 3 In a large glass crystallization dish, the wet base MOF and diamine were mixed until a slurry of uniform consistency was reached. The material was heated to 110°C and held at a pressure of 12 mbar until dry.

[0047] Example 4 In a large bucket, the wet base MOF and diamine were mixed until a slurry of uniform consistency was achieved. The resulting slurry was poured into a stainless steel tray and placed in a vacuum oven. The material was heated to 65°C, while being held at a pressure of 150 mbar under a slow purge of nitrogen gas until dry.

[0048] Example 5 In a glass round-bottom flask, the wet base MOF and diamine were mixed until a slurry of uniform consistency was reached. The flask was mounted on a rotary evaporator and heated to 80°C while gently rotating. Most of the water was removed at a set pressure of 150 mbar to avoid bumping (bubbling into the apparatus). The pressure was slowly reduced to 12 mbar, and water was removed until the resulting substance was dry.

[0049] Example 6 In a glass round-bottom flask, the wet base MOF and diamine were mixed until a slurry of uniform consistency was reached. The flask was mounted on a rotary evaporator and heated to 80°C while gently rotating. Most of the water was removed at a set pressure of 150 mbar to avoid bumping (bubbling into the apparatus). The pressure was slowly reduced to 12 mbar, and water was removed until the resulting substance was dry.

[0050] Example 7 In a large glass crystallization dish, the wet base MOF and diamine were mixed until a uniform consistency was achieved. The material was heated to 40°C and held at a pressure of 150 mbar under a slow purge of nitrogen gas until dry.

[0051] The conditions for Examples 1 to 7 are summarized in the table.

[0052] [Table 1] The base MOF used in the examples is Mg2(dobpdc). Rotar evaporator: Rotary evaporator * Atmospheric pressure ** 150 mbar with inert nitrogen purging

[0053] Characterization of the functionalized MOFs prepared in Examples 1-7 Thermogravimetric analysis was used to determine 100% CO2 adsorption isobar data for functionalized MOFs synthesized by the processes described in Examples 1-7 and functionalized MOFs synthesized by a “state-of-the-art” solution-based method. The results show that the functionalized MOF materials produced from the processes described herein have comparable CO2 adsorption / desorption performance to the baseline material.

[0054] Various aspects of this disclosure are described.

[0055] Embodiment 1. A process for producing a functionalized porous material, comprising: mixing a base porous material containing a porous structure and an unstable ligand with a functionalizing agent to form a slurry, wherein the porous structure has open metal parts and a plurality of pores, the unstable ligand is coordinated to the open metal parts, present in the plurality of pores but not coordinated to the open metal parts, or a combination thereof, the unstable ligand has a first boiling point, and the functionalizing agent has a second boiling point higher than the first boiling point; and drying the slurry to form a functionalized porous material containing a functionalizing agent coordinated to the open metal parts.

[0056] Embodiment 2. The process according to any prior embodiment, wherein the porous material is an organometallic skeleton material.

[0057] Embodiment 3. The process according to any preceding embodiment, wherein the second boiling point is about 50°C to about 150°C higher than the first boiling point.

[0058] Embodiment 4. The process according to any preceding embodiment, wherein the unstable ligand comprises at least one of water, methanol, ethanol, acetonitrile, or N,N-dimethylformamide.

[0059] Embodiment 5. The process according to any preceding embodiment, wherein the unstable ligand in the base porous material comprises more than 50% by weight of methanol, ethanol, or a combination thereof, based on the total weight of the unstable ligand.

[0060] Embodiment 6. The process according to any preceding embodiment, wherein the unstable ligand in the base porous material contains more than about 50% by weight of water based on the total weight of the unstable ligand.

[0061] Embodiment 7. The process according to any preceding embodiment, wherein the functionalizing agent comprises at least one of a monoamine, a diamine, a polyamine, or a bifunctional ligand.

[0062] Embodiment 8. The process according to any preceding embodiment, wherein the open metal portion comprises at least one ion from among Mg, Ca, Ba, Al, Sc, Zr, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Ti, Cd, or Eu.

[0063] Embodiment 9. The process according to any preceding embodiment, wherein the mixing is carried out in the presence of a slurry solvent.

[0064] Embodiment 10. The process according to any preceding embodiment, wherein the mixing is carried out in the absence of a solvent.

[0065] Embodiment 11. The process according to any preceding embodiment, wherein the slurry is dried at a temperature of about 20°C to about 150°C and a pressure of about 101,325 Pascals to about 100 Pascals to form a functionalized porous material.

[0066] Embodiment 12. The process according to any preceding embodiment, wherein the slurry is dried at a temperature of about 40°C to about 110°C and a pressure of about 15,000 Pascals to about 1,200 Pascals to form a functionalized porous material.

[0067] Embodiment 13. The process according to any preceding embodiment, wherein the weight ratio of the unstable ligand to the porous structure is approximately 25:1 to approximately 0.5:1.

[0068] Embodiment 14. The process according to any preceding embodiment, wherein the molar ratio of the functionalizing agent to the open metal portions in the base porous material is about 3:1 to about 1:1.

[0069] Embodiment 15. The process according to any preceding embodiment, wherein the content of unstable ligands in the functionalized porous material is less than 40% by weight or less than 10% by weight based on the total weight of the functionalized porous material.

[0070] Embodiment 16. The process according to any preceding embodiment, further comprising preparing a base porous material by reaction of a metal salt with an organic crosslinking ligand in the presence of a reaction solvent containing an unstable ligand.

[0071] Embodiment 17. A process according to any preceding embodiment, comprising: (a) reacting a metal salt with an organic crosslinking ligand in the presence of a reaction solvent containing an unstable ligand to form a crude product; (b) adding water and / or other unstable ligands to the crude product to obtain a quenched product; (c) filtering the quenched product to obtain a filter cake; (d) rinsing the filter cake to obtain a rinsed filter cake containing a base porous material; (e) mixing the rinsed filter cake with a functionalizing agent to form a slurry; and (f) drying the slurry to form a functionalized porous material containing a functionalizing agent coordinated to open metal moieties.

[0072] Embodiment 18. The process according to any prior embodiment, wherein a slurry solvent is combined with a rinsed filter cake and a functionalizing agent, and as a result, the rinsed filter cake and the functionalizing agent are mixed in the presence of the slurry solvent to form a slurry.

[0073] Embodiment 19. The process according to any preceding embodiment, wherein no solvent is added to the rinsed filter cake or the functionalizing agent, and the rinsed filter cake and the functionalizing agent are mixed in the absence of any added solvent to form a slurry.

[0074] Embodiment 20. The process according to any preceding embodiment, wherein the open metal portion contains magnesium ions and the organic crosslinking ligand contains 4,4'-dioxide biphenyl-3,3'-dicarboxylate.

[0075] Embodiment 21. The process according to any preceding embodiment, wherein the slurry is dried at a temperature of about 20°C to about 150°C and a pressure of about 101,325 Pascals to about 100 Pascals.

[0076] Embodiment 22. The process according to any of the preceding embodiments, wherein the unstable ligands in the base porous material contain more than 50% by weight of water based on the total weight of the unstable ligands.

[0077] The terms “a,” “an,” and “the,” and the use of similar references, should be interpreted as encompassing both singular and plural forms unless otherwise stated herein or unless explicitly contradicted by the context. Furthermore, it should be noted that terms such as “first,” “second,” etc., in this specification do not indicate any order, quantity, or importance, but rather are used to distinguish one element from another. The terms “about,” “substantially,” and “generally” are intended to include the degree of error associated with the measurement of a particular quantity based on the apparatus available at the time of filing this application. For example, “about” and / or “substantially” and / or “generally” may include a range of ±8%, 5%, or 2% of a given value.

[0078] Unless otherwise defined, the technical and scientific terms used herein have the same meanings as those generally understood by those skilled in the art to which this invention pertains.

[0079] All references cited herein are incorporated by reference in their entirety. Typical embodiments are described for illustrative purposes, but the foregoing description should not be considered a limitation to the scope of this specification. A person skilled in the art will be able to come up with various modifications, adaptations, and alternatives without departing from the spirit and scope of this specification.

Claims

1. A process for manufacturing a functionalized porous material (140), The process involves mixing a base porous material (110) containing a porous structure and an unstable ligand with a functionalizing agent (120) in order to form a slurry (130). The porous structure has open metal parts and a plurality of pores, The unstable ligand is either coordinated to the open metal portion, present in the plurality of pores but not coordinated to the open metal portion, or a combination thereof. The unstable ligand has a first boiling point, and the functionalizing agent has a second boiling point higher than the first boiling point, and the mixture is formed by mixing the two. A process characterized by drying the slurry (130) in order to form a functionalized porous material (140) containing the functionalizing agent coordinated to the open metal portion.

2. The process according to claim 1, wherein the porous material is an organometallic skeleton material.

3. The process according to claim 1, wherein the second boiling point is about 50°C to about 150°C higher than the first boiling point.

4. The process according to claim 1, wherein the unstable ligand comprises at least one of water, methanol, ethanol, acetonitrile, or N,N-dimethylformamide.

5. The process according to claim 1, wherein the unstable ligand in the base porous material comprises more than 50% by weight of methanol, ethanol, or a combination thereof, based on the total weight of the unstable ligand.

6. The process according to claim 1, wherein the unstable ligand in the base porous material contains more than 50% by weight of water based on the total weight of the unstable ligand.

7. The functionalizing agent comprises at least one of a monoamine, a diamine, a polyamine, or a bifunctional ligand. The process according to claim 1, wherein the open metal portion contains at least one ion from among Mg, Ca, Ba, Al, Sc, Zr, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Ti, Cd, or Eu.

8. The process according to claim 1, wherein the slurry is dried at a temperature of about 20°C to about 150°C and a pressure of about 101,325 Pascals to about 100 Pascals in order to form the functionalized porous material.

9. The process according to claim 1, wherein the weight ratio of the unstable ligand to the porous structure is about 25:1 to about 0.5:

1.

10. The process according to claim 1, wherein the molar ratio of the functionalizing agent to the open metal portion in the base porous material is about 3:1 to about 1:

1.

11. The process according to claim 1, further characterized by preparing the base porous material by a reaction between a metal salt and an organic crosslinking ligand in the presence of a reaction solvent containing the unstable ligand.

12. (a) In order to form the crude product (20), the metal salt and the organic crosslinking ligand are reacted in the presence of a reaction solvent containing the unstable ligand, (b) Adding water or another unstable ligand (30) to the crude product (20) in order to obtain a quenched product (40), (c) In order to obtain a filtered cake (50), the quenched product (40) is filtered, (d) Rinsing the filter cake (50) in order to obtain a rinsed filter cake (60) containing the base porous material, (e) Mixing the rinsed filtered cake (60) with the functionalizing agent (120) in order to form a slurry (130), and (f) The process according to any one of claims 1 to 11, comprising drying the slurry (130) to form the functionalized porous material (140) containing the functionalizing agent coordinated to the open metal portion.

13. The process according to claim 12, wherein the slurry solvent is combined with the rinsed filter cake and the functionalizing agent, and as a result, the rinsed filter cake and the functionalizing agent are mixed in the presence of the slurry solvent to form the slurry.

14. The process according to claim 12, wherein no solvent is added to the rinsed filter cake or the functionalizing agent, and the rinsed filter cake and the functionalizing agent are mixed in the absence of any added solvent to form the slurry.

15. The process according to claim 12, wherein the open metal portion contains magnesium ions and the organic crosslinking ligand contains 4,4'-dioxide biphenyl-3,3'-dicarboxylate.

Images