Metal-organic framework polymorphism for tailoring adsorption profiles

Abstract

The present invention relates inter alia to metal-organic framework (MOF) materials, more precisely to the use of porous crystalline solids composed of MOFs for gas or vapor adsorption and thermally driven water sorption-based cooling systems, such as water harvesting or production, gas (e.g., CO2, hydrocarbons, BTX and VOCs) and / or vapor capture and separation, catalysis, and sensors. The novel MOF materials of the present invention can exhibit improved sorption profiles.

Description

[Technical Field]

[0001] The present invention relates inter alia to metal-organic framework (MOF) materials, more precisely to the use of porous crystalline solids composed of metal-organic frameworks (MOFs) for gas or vapor adsorption and thermally driven water sorption based cooling systems - (e.g., water harvesting or production), capture and separation of gases and / or vapors such as CO2, hydrocarbons, BTX (benzene, toluene, xylene) and VOCs (volatile organic compounds), catalysis, sensors.

[0002] The novel MOF materials of the present invention can exhibit improved sorption profiles.

[0003] References in square brackets [X] refer to the list of references at the end of the examples. [Background technology]

[0004] The development of many sustainable technologies involving water vapor adsorption relies heavily on the discovery of high-performance porous materials. Such technologies include adsorption-driven heat conversion (AHT) and atmospheric water harvesting (AWH) [1, 2]. In water-based adsorption-driven heat exchangers, i.e., adsorption-driven chillers (ADCs) and adsorption heat pumps (AHPs), heating or cooling, e.g., for air conditioning, is achieved by reversible multi-cycle adsorption and desorption of water vapor onto / from porous adsorbents. Regeneration of the material in each cycle can be achieved by applying renewable energy (at temperatures lower than the adsorption temperature), e.g., solar or waste heat [3, 4]. ADCs and AHPs are considered clean and sustainable alternatives to conventional compressor-based chillers and heat pumps due to their potential to minimize primary electrical energy consumption and greenhouse gas emissions generated by industrial or domestic cooling [5]. On the other hand, AWHs allow water vapor to be directly captured from thin air by porous materials during relatively high humidity conditions, e.g., at night, and then released by solar heating during the day [6, 7]. Therefore, AWHs are attractive means for the provision of drinking / fresh water in remote and arid regions [8]. In both technologies, the applied porous material must, among other criteria, be able to adsorb water vapor at low relative humidity (5% ≤ RH ≤ 40%) and release it with minimal energy penalty. To meet the device's good performance / efficiency, water adsorption into the porous material must also occur within a very narrow relative pressure window, which is described by a single-step sigmoidal (S-shaped) water isotherm, and a high uptake capacity must be achieved within the pressure window of interest [9, 10].

[0005] Among the multiple types of porous adsorbents that have been investigated for both AHT and AWH, metal-organic frameworks (MOFs) are attractive materials [11, 12]. This is due to the wide range of possibilities this material class offers for tailoring water sorption profiles and the large water uptake capacity achievable through high porosity [13, 14, 15]. MOFs consist of inorganic structural units (IBUs, i.e., clusters, chains, or layers) interconnected by multidentate organic linkers to form micro- or mesoporous coordination networks [16, 17, 18]. Unlike more traditional porous materials such as zeolites and activated carbons, the water sorption profile of MOFs can be uniquely tuned through a combination of several parameters, including ligand or cluster functionalization, structure topology, pore geometry and size, and the presence of structural defects [19, 20]. Some of these strategies for designing MOFs for water-based applications have been implemented to enhance hydrophilicity (or hydrophobicity), water uptake capacity, hydrothermal stability, or to produce a steep sigmoidal water isotherm [21, 22]. Regarding the tuning of MOF pore size and / or shape, polymorphism offers a potential new approach to regulating the water sorption properties of MOFs while maintaining their structural elements. Polymorphism refers to the emergence of compounds with the same chemical composition (e.g., metal / ligand stoichiometry) but in diverse crystalline structures where the spatial arrangement of atoms differs, resulting in changes in physicochemical properties. MOF polymorphism is also referred to as framework isomerism [23, 24]. The importance of MOF polymorphism has been recognized because one topological isomer may exhibit different or enhanced properties compared to other isomers [25, 26, 27]. For example, two polymorphs of the MOF TlI(TCNQ) (TCNQ = 7,7,8,8-tetracyanoquinodimethane), which crystallize in the space groups P21 / c and P2 / c, respectively, exhibit significantly different conductivities.

[28] The nbo topology of Cu2(1,4-benzenedicarboxylate), distinct from its polymorphs with rhr and lvt topologies, respectively, has been reported to be characterized by a significantly higher affinity for linear alkanes due to its small pores.

[29] However, this approach, to the best of our knowledge, has not yet been explored for improving MOFs for vapor sorption and related applications.

[0006] MOFs, especially high-valent metal ions (M a+, a ≥ 3), have shown great potential in many applications related to gas and vapor adsorption, such as water adsorption. Among these MOFs, aluminum-based MOFs (Al-MOFs) are particularly attractive for cyclic water adsorption applications due to their hydrothermal and chemical stability, light specific gravity, non-toxicity, and low cost of aluminum. [30, 31] Many structurally similar Al-MOFs constructed from μ-OH and carboxylate-bridged {AlO6} octahedral chains share vertices via μ-OH bridges and have been thoroughly investigated for their potential in AHT and AWH applications, including MIL-53-Fum [32, 33], CAU-10H [34, 35, 36], MIL-53-TDC

[37] , CAU-23

[38] , MOF-303

[39] , MIL-160 [40, 41, 42], KMF-1

[43] , and CAU-10pydc

[44] . Interestingly, these MOFs share the same general unit formula ([Al(OH)(L)], where L = dicarboxylate linker), but the shape of the Al-(OH) chains and corresponding geometric features (e.g., pore shape and dimensions) can differ

[45] . Generally, the use of ditopic linear linkers results in Al-MOF structures with trans-μ-OH-connected (or trans-connected) corner-sharing AlO4(OH)2 octahedral chains (e.g., MIL-53 topology) [46, 47], whereas the use of "V-shaped" linkers results in Al-MOFs with cis-μ-OH-connected (or cis-connected) corner-sharing AlO4(OH)2 octahedral helical chains (e.g., CAU-10 topology) [48, 49]. Exceptions to this general observation are V-shaped 1H-pyrazole-3,5-dicarboxylate and 2,4-furandicarboxylate, which give rise to chains of alternating cis- and trans-connected corner-sharing AlO(OH) octahedra in MOF-303 and MOF-333, respectively.

[50] Similarly, V-shaped 2,5-thiophenedicarboxylate gives rise to polymorphs of either rod-like chains in MIL-53-TDC or mixed cis / trans corner-sharing AlO(OH) octahedra in CAU-23.

[38] Trends emerging from previously reported studies on Al-MOFs indicate that dicarboxylates with opening angles defined by the C-C bond axes of the carboxylate groups strictly greater than 150–158° result in chains of trans-connected corner-sharing AlO(OH)2 octahedra, whereas opening angles strictly less than 150° result in chains of cis-connected corner-sharing AlO(OH)2 octahedra. Opening angles of approximately 150–158° appear to be inflection points, thus resulting in Al-MOFs with either mixed cis / trans-connected corner-sharing AlO(OH)2 octahedra (CAU-23) or alternating cis- and trans-connected corner-sharing AlO(OH)2 octahedra (MOF-303, MOF-333, and MIL-53-TDC, respectively)

[51] .

[0007] To date, to the best of our knowledge, with the exception of linear dicarboxylate linkers containing triple bonds

[52] , no aliphatic dicarboxylate-based linker has yet been reported to lead to MOFs containing helical M-OH (or MO) chain clusters (where M is, for example, Al, Fe, Cr, Sc, V, Ga, In, or Ti).

[0008] However, as with the V-shaped linkers, the aliphatic linkers in Al-MOFs also allow for polymorphism with rod-like or helical chains, providing new opportunities to tune the pore shape and structure topology of established M-MOFs (where M is, for example, Al, Fe, Cr, Sc, V, Ga, In, or Ti).

[0009] In this regard, the use of aliphatic ligands (i.e., ligands with an aliphatic core that may or may not be saturated, substituted or not by small substituents, and interrupted or not by small aryl groups) may be a rational strategy.

[0010] Zigzag-spaced pseudo-linear trans, trans-muconate linker (trans, trans-1,3-butadiene-1,4-dicarboxylate: = muconate) 2-Using this linker, some of us have recently obtained a novel Al-MOF, MIL-53-muc

[53] , which exhibits the topology of MIL-53, similar to that of aluminum fumarate MOF (MIL-53-Fum)

[54] . This structure is composed of rod-like chains of trans-μ-OH-corner-sharing AlO(OH) octahedra. This was expected, since muconate can be considered as a two-fold extension element of the fumarate linker. The water sorption profile of MIL-53-muc exhibits a similar sigmoidal isotherm to MIL-53-Fum, but with a higher uptake capacity and a step position shifted to higher relative pressures (P / P = 0.5–0.6) compared to that of MIL-53-Fum, where the step is observed at a relative pressure of P / P = 0.2–0.3

[53] . This is consistent with increased hydrophobic behavior, reasonably attributable to the extension of the hydrophobic organic chains in the muconate linker and a reduced confinement effect due to the larger channels. Therefore, the resulting water sorption profile of MIL-53-muc makes this MOF unsuitable for AHT applications, among others, when combined with water as a cooling fluid, since the isotherm step position is located above P / P = 0.4. [Prior art documents] [Patent documents]

[0011] [Patent Document 1] WO2009 / 123484 [Non-patent literature]

[0012] [Non-Patent Document 1] M. Rose et al., Adv. Eng. Mater. 2011, 13, pp. 356-360 [Non-patent document 2] R. Ostermann et al., Chem. Commun. 2011, 47, pp. 442-444 [Non-patent document 3] J. Ren et al., Int. J. Hydrogen Energy 2015, 40, pp. 9382-9387 [Non-patent document 4] MR Khan et al., J. Mater. Eng. Perform. 2016, 25, pp. 1276-1283 [Non-patent document 5] Valekar et al., RSC Adv, 2017 [Non-patent document 6] Q. Ren et al., Chem. Eng. J., 2015 [Non-Patent Document 7] Gkaniatsou et al., Nano Energy, 2020 Summary of the Invention [Problem to be solved by the invention]

[0013] Thus, there remains a need to provide new MOFs that address the need to improve and fine-tune the gas or vapor sorption properties of MOFs, whether in the pure phase or doped / partially substituted with metals or ligands, particularly in the fields of gas or vapor sorption and thermally driven water sorption-based cooling systems, e.g., water harvesting or production, capture and separation of gases and / or vapors such as CO2, hydrocarbons, BTX and VOCs, catalysis, sensors. [Means for solving the problem]

[0014] To address this need, M a+ When a=3+, a helical chain of cis-μ-OH-connected corner-sharing MO4(OH)2 octahedra, or M a+ Extensive research has been carried out by the inventors to find specific synthetic conditions that can very efficiently and selectively produce the MO4(O)2 cis-μ2-O bridging style when a≥4+, resulting in a significant increase in hydrophilicity compared to that of known MOFs with trans-μ-OH connections.

[0015] The cis-μ-OH connections were shown to have an enhanced hydrophilicity increase compared to that of MOFs with trans-μ-OH connections, which is due to the increased interaction and confinement effect resulting from the preference of water molecules to bridge between two adjacent μ-OH groups of IBU, which is less likely to occur with trans-connected μ-OH groups.

[0016] Thus, the novel polymorphism induces strong changes in the hydrophilicity of the MOFs and the relative pressure positions of the steps in the water sorption isotherm. This is due to changes in the accessibility of OH (or O) sites on the inorganic chains. In the case of our newly created hydrothermally stable MOFs, particularly MIP-211, the water sorption profile and uptake capacity exceed most of the reference materials investigated for water sorption applications, while also exhibiting low regeneration temperatures. The novel MOFs are also useful for a variety of applications, including those relying on gas and / or vapor adsorption, capture and separation of gases (CO2, hydrogen, etc.), hydrocarbons (generally BTX and VOCs), catalysis, and sensors.

[0017] Before turning to a description of the invention itself, certain terms and phrases will now be defined in order to facilitate understanding of the invention.

[0018] - As used herein, except in the claims, the words "a," "an," "the," and / or "said" mean one or more. As used herein, in the claims, when used in conjunction with the words "comprise," "comprises," and / or "comprising," the words "a," "an," "the," and / or "said" may mean one or more than one. As used herein and in the claims, the words "having," "has," "is," "have," "including," "includes," and / or "include" have the same meaning as "comprising," "comprises," and "comprise." As used herein and in the claims, "another" may mean at least a second or more. As used herein and in the claims, "about" refers to the inherent measurement error or rounding of a value (e.g., a measurement, calculation of a ratio, etc.), and thus the term "about" can be used with any value and / or range.

[0019] - The phrase "combinations thereof," "mixtures thereof," following a list, the use of "and / or" as part of a list, a list within a table, the use of "such as" as part of a list, the phrase "such as," and / or a parenthetical list including "for example" or "i.e." refers to any combination (e.g., any subset) of the set of listed members, and although not directly located in such a list, combinations and / or mixtures of related species and / or embodiments described herein are also contemplated. Such related and / or similar genera, subgenera, species, and / or embodiments described herein are contemplated both in the form of individual members that may be claimed, as well as mixtures and / or combinations that may be claimed as "at least one selected from," "mixtures thereof," and / or "combinations thereof."

[0020] In general, the term "substituted," whether preceded by the term "optionally" or not, and substituents included in formulas herein, refers to the replacement of a hydrogen radical in a given structure with the radical of the specified substituent. When more than one position in any given structure may be substituted with more than one substituent selected from a specified group, the substituents can be the same or different at all positions. As used herein, the term "substituted" is intended to include all permissible substituents of organic compounds.

[0021] As used herein, the term "about" can refer to a variation of ±5%, ±10%, ±20%, or ±25% of the specified value. For example, "about 50" percent may have a variation of 45 to 55 percent in some embodiments. In integer ranges, the term "about" can include one or two integers greater than or less than the recited integer. Unless otherwise indicated herein, the term "about" is intended to include values, e.g., concentration values, that are close to the recited range and are equivalent in terms of functionality, composition, or embodiment of the individual components.

[0022] - As used herein, the term "and / or" means any one of the items, any combination of the items, or all of the items with which this term is associated.

[0023] As understood by those skilled in the art, all numbers, including those expressing component quantities, properties such as void / pore size and BET specific surface area, reaction conditions, etc., are approximate and are understood to be optionally modified in all cases by the term "about." These values ​​may vary depending on the desired properties sought to be obtained by the skilled artisan utilizing the teachings set forth herein. It is also understood that such values ​​inherently contain variations necessarily resulting from the standard deviation found in their respective testing measurements.

[0024] As will be understood by those skilled in the art, for all purposes, particularly in terms of providing a written description, all ranges described herein encompass all possible subranges and combinations of subranges, as well as the individual values, particularly integers, that make up the ranges. The described ranges include each specific value, integer, decimal, or unit within the range. It is readily recognizable that a recited range fully describes and enables the same range to be divided into at least equal halves, thirds, quarters, fifths, or tenths. As a non-limiting example, each range discussed herein can be readily divided into a lower third, middle third, and upper third, etc.

[0025] Those skilled in the art will also readily recognize that when members are grouped together in a common manner, such as in a Markush group, the invention encompasses not only the entire group recited as a whole, but also each member of the group individually and all possible subgroups of the main group. Moreover, for all purposes, the invention encompasses not only the main group, but also the main group absent one or more of the group members. Thus, the invention contemplates the explicit exclusion of any one or more of the members of a stated group. Accordingly, qualifications may apply to any of the disclosed categories or embodiments, whereby any one or more of the stated elements, species, or embodiments may be excluded from such category or embodiment, e.g., as used in an explicit negative limitation.

[0026] - as used herein, the expression "three-dimensional structure" is understood to mean a three-dimensional arrangement or repetition of units or moiety variants as conventionally understood in the field of MOF materials, which are also characterized as "organometallic polymers".

[0027] - as used herein, the term "solid" refers to any kind of crystalline material. Said solid may be in the form of, for example, crystals, powders, or particles of various morphologies, for example, spherical, lamellar, etc. The particles may be in the form of nanoparticles.

[0028] As used herein, "humid environment" refers to an atmospheric environment containing water vapor. This may be air containing water vapor. The amount of water vapor present in an environment, e.g., air, increases as temperature increases. The difference in the amount of water vapor within an air mass can be very large. For example, an air mass near saturation (e.g., ≈100% relative humidity) may contain 28 grams of water per cubic meter of air at 30°C, but only 8 grams of water per cubic meter of air at 8°C. Water vapor, or steam, or aqueous vapor, is the gaseous phase of water. It is one of the states of water in the hydrosphere. Under typical atmospheric conditions, water vapor is continuously generated by evaporation and removed by condensation. The vapor content of air may be measured with a device known as a hygrometer. In the present invention, the amount of water vapor in an environment, e.g., air, may range from higher than dry air to saturated, e.g., at temperatures between 10°C and 30°C, e.g., room temperature, i.e., between 18°C ​​and 28°C.

[0029] MOFs are constructed from bridging organic ligands, also called "linkers" or "spacers," which remain intact throughout the synthesis and function as linkers in the network of the resulting MOF structure. As used herein, the terms "ligand" or "linker" or "spacer" refer to ligands that coordinate to at least two metals and are responsible for providing distance between these metals and forming the empty space or pore, also called the "core," in the MOF.

[0030] As used herein, "aliphatic" refers to acyclic or cyclic, saturated or unsaturated carbon compounds, excluding aromatic compounds (IUPAC). Open-chain compounds, whether linear or branched, that do not contain any type of ring are always aliphatic. Cyclic compounds may also be aliphatic if they are not aromatic. Typically, aliphatic compounds may be saturated (alkanes) linked by single bonds, or unsaturated with double bonds (alkenes) or triple bonds (alkynes). As disclosed herein, unsaturation may preferably be understood as only double bonds (alkenes). In preferred embodiments of the present invention, the dicarboxylate linker does not contain triple bonds (alkynes). In addition to hydrogen, other elements can be attached to the carbon chain, the most common being oxygen, nitrogen, sulfur, and chlorine.

[0031] As used herein, "aromatic" refers to a cyclic conjugated molecular entity that has significantly greater stability (by delocalization) than that of a hypothetical localized structure (e.g., a Kekulé structure) that is said to have aromatic properties. The use of the term is based on the application of the Hückel (4n+2) rule and consideration of the topology of orbital overlap in the transition state (IUPAC). "Aryl" refers to a group derived from an arene by removing a hydrogen atom from a ring carbon atom, and arenes are monocyclic and polycyclic aromatic hydrocarbons (IUPAC). According to the present invention, an aryl group may have 5 to 6, preferably 6, ring members. "Heteroaryl" refers to a group derived from a heteroarene by removing a hydrogen atom from any ring atom. An alternative term is hetaryl (IUPAC). According to the present invention, a heteroaryl group may have 5 to 6, preferably 6, ring members.

[0032] The inventors have shown that the present invention can strongly improve the water sorption properties of MOFs.

[0033] In particular, the present invention provides a porous metal-organic framework material constructed from metal octahedra linked through μ-OH and / or μ-O bridges and interconnected by organic dicarboxylate linkers, the metal center is selected from Al, Fe, Cr, Sc, V, Ga, In, Ti and mixtures thereof; - the organic dicarboxylate linker is a C4-C alkyl group optionally interrupted by a 5- or 6-membered aryl or heteroaryl moiety and optionally bearing one or more substituents selected from halo groups, -OH, -NH2, C1-C3 alkyl, C1-C3 alkoxy, -CF3, -SH, -COOH, and -CHR-NH2, where R is a C1-C3 alkyl; 12 dicarboxylate aliphatic linkers formed by saturated or unsaturated linear hydrocarbon chains; - The metal center and the carboxylate groups of the organic dicarboxylate linker together form a cis-μ-OH-connected vertex-sharing MO4(OH)2 (M a+ a = 3+) octahedral spiral chain, or MO4(O)2(M a+ If a≧4+) forms a cis-μ2-O bridge pattern. This relates to porous metal-organic framework materials.

[0034] The organic dicarboxylate linker may make it possible to crosslink two inorganic structural units, preferably two inorganic chains, more preferably two inorganic helical chains.

[0035] In fact, each organic dicarboxylate linker comprises two carboxylate groups, one of which is connected to a first inorganic structural unit and the other of which is connected to a second inorganic structural unit different from the first inorganic structural unit.

[0036] For example, in MIP-211(Al), a t,t-muconate linker bridges two helical AlO chains.

[0037] "cis-μ2-OH-connected vertex-sharing MO4(OH)2(M a+ a = 3+) octahedral spiral chain, or MO4(O)2(M a+ "Cis-μ2-O bridging mode (when a≧4+)" refers to inorganic structural units in the overall structure of a porous solid MOF (or porous MOF). In the above definitions, cis and trans have their usual meanings in the art. "Cis" indicates that adjacent groups (-OH or O- lone pairs) are on the same side of a plane or point in close directions (dihedral angle <180°), and "trans" indicates that they are on opposite (transverse) sides or point in opposite directions.

[0038] Advantageously, according to the invention, the metal centre M of the porous MOF may be chosen from Al, Fe, Cr, Sc, V, Ga, In, Ti and mixtures thereof. M may alternatively be chosen from Al, Fe, Cr, Sc, V, Ga, Ti and mixtures thereof. Preferably, M is chosen from Fe, Al and mixtures thereof.

[0039] Advantageously, according to the invention, the porous MOF has a thickness of 50 m 2 / g, preferably 100m 2 The MOF material may have a specific surface area of ​​greater than 1 / g. The specific surface area can be estimated from the N2 isotherm of the MOF material at 77 K using the BET model.

[0040] Advantageously, according to the invention, the porous MOF has an average pore size of at least 0.5 nm. The average pore size can be measured using the crystallographic information file (CIF) of said MOF. It can also be calculated from the nitrogen isotherm by applying mathematical equations, such as the BJH (Barret-Joyner-Halenda), DFT (density functional theory), Horvath-Hawazoe or Dubinin-Astakhov method, which allow determining the average pore size distribution.

[0041] Advantageously, the organic dicarboxylate linker has the formula I:

[0042] [ka]

[0043] [During the ceremony, m is an integer from 1 to 5; n is an integer from 1 to 5; - p is 0 or 1, -

[0044] [ka]

[0045] represents a 5- or 6-membered aryl or heteroaryl moiety; -R 1 , R 2 , R 3 and R 4 each independently represent H, a halo group (e.g., F, Br, Cl, or I), -OH, -NH, C1-C3 alkyl (e.g., methyl or ethyl), C1-C3 alkoxy (e.g., methoxy or ethoxy), -CF3, -SH, -COOH, or -CHR-NH2 (where R is C1-C3 alkyl), or when two adjacent carbon atoms are linked by a double C=C bond (e.g., when the dicarboxylate linker is muconate, m=n=2, p=0, and R 1 , R 2 , R 3 and R 4 represents H, or represents a bond if the bond is a bond involving a C=C bond. The linker may be selected from:

[0046] As intended herein, an organic dicarboxylate linker is one whose structure is C4-C 12の It is aliphatic because it is based on a saturated or unsaturated linear hydrocarbon chain. As defined above, a linear hydrocarbon chain includes the following examples:

[0047] [ka]

[0048] It may be interrupted by a 5- or 6-membered aryl or heteroaryl moiety, such as:

[0049] C4~C 12 The saturated or unsaturated linear hydrocarbon chain may optionally bear one or more substituents selected from halo groups, -OH, -NH2, C1-C3 alkyl, C1-C3 alkoxy, -CF3, -SH, -COOH, -CHR-NH2 (wherein R is a C1-C3 alkyl group), or any of the following examples:

[0050] [ka]

[0051] It may contain a double C=C bond, such as:

[0052] Therefore, according to the above definition, the substituents such as C1-C3 alkyl are C4-C 12 The number of carbon atoms in the skeleton is not included. Also, as in the example shown above, when the substituent is COOH, the substituent is a cis-μ-OH-connected corner-sharing MO4(OH)2(M a+ a = 3+) octahedral spiral chain, or MO4(O)2(M a+ a ≥ 4+) does not participate in the cis-μ2-O cross-linking mode.

[0053] Advantageously, the organic dicarboxylate linker may be selected from succinate, maleate, tartrate, glutarate, glutamate, citrate, adipate, fumarate, glutaconate, mesaconate, hexenedioate, hydromuconate, 2-aminomuconate, muconate, traumatate, 1,4-phenylenediacetate, 1,4-phenylenediacrylate, preferably muconate, hydromuconate, 2-aminomuconate, hexenedioate, 1,4-phenylenediacetate, and 1,4-phenylenediacrylate.

[0054] Advantageously, the organic dicarboxylate linker may be free of carbon-carbon triple bonds (alkynes). Preferably, the dicarboxylate linker may be free of acetylenedicarboxylate.

[0055] Advantageously, the porous MOF according to the invention has the formula: {[Al(OH)(muc)]·xSolvent} y wherein the solvent is preferably an organic and / or inorganic solvent selected from water, alcohol (e.g., methanol, ethanol, benzyl alcohol), acid (e.g., acetic acid or formic acid), dimethylformamide, and dimethylsulfoxide, and x is 0-15 and y is ≧5.

[0056] In another aspect, the present invention relates to a method for synthesizing a porous MOF according to the present invention.

[0057] The method for synthesizing the porous MOF according to the present invention preferably comprises the steps of: a mixture of metal precursors, wherein the metal M is selected from Al, Fe, Cr, Sc, V, Ga, In, Ti and mixtures thereof; - a C4-C alkyl group optionally interrupted by a 5- or 6-membered aryl or heteroaryl moiety and optionally bearing one or more substituents selected from halo, -OH, -NH2, C1-C3 alkyl, C1-C3 alkoxy, -CF3, -SH, -COOH and -CHR-NH2, where R is C1-C3 alkyl; 12 an organic dicarboxylic acid selected from dicarboxylic aliphatic acids formed by a saturated or unsaturated linear hydrocarbon chain; The method may include reacting, in particular heating,

[0058] The reacting, especially the heating, step may last from 30 minutes to 75 hours, preferably from 1 hour to 75 hours, more preferably from 3 hours to 72 hours.

[0059] The molar ratio of metal precursor to organic dicarboxylic acid may be between 0.6 and 1.4, preferably between 0.7 and 1.3, more preferably between 0.8 and 1.2, and even more preferably between 0.9 and 1.1.

[0060] For example, the molar ratio of metal precursor to organic dicarboxylic acid is 1.

[0061] The reacting step may be carried out by mechanochemistry or by heating.

[0062] In one exemplary embodiment, the reacting step may be performed by mechanochemistry.

[0063] In one exemplary embodiment, the reacting step may be performed by heating. In other words, the reacting step may be a heating step.

[0064] The heating step may be carried out in a solvent.

[0065] The heating step may be carried out at a temperature of 60° C. or higher, preferably 70° C. or higher, more preferably 80° C. or higher, and even more preferably under reflux conditions.

[0066] The heating step may be performed by microwave heating.

[0067] In one exemplary embodiment, the reacting step may be carried out at atmospheric pressure.

[0068] In one exemplary embodiment, the reacting step may be carried out under pressure.

[0069] For example, the reacting step is carried out under a pressure of more than 5 bar and less than 50 bar.

[0070] Advantageously, the step of heating under reflux conditions in a solvent may last from 3 to 9 hours.

[0071] Advantageously, the metal precursor in the method is a precursor of the metal center of the MOF according to the invention. The metal precursor may be selected from precursors in which the metal M is selected from Al, Fe, Cr, Sc, V, Ga, In, Ti and mixtures thereof. Alternatively, the metal precursor may be selected from precursors in which the metal M is selected from Al, Fe, Cr, Sc, V, Ga, Ti and mixtures thereof. Preferably, the metal precursor is selected from precursors in which the metal M is selected from Fe, Al and mixtures thereof. The metal precursor may be selected from sulfates, acetates, halides (e.g. chlorides), nitrates, metal hydroxides, metal oxides and mixed metal oxides (e.g. sodium aluminate).

[0072] When the metal precursor is selected from precursors in which the metal M is Al, the metal precursor is preferably selected from sulfates and hydroxides.

[0073] In one exemplary embodiment, the metal precursor is selected from precursors where the metal M is Al, preferably aluminum sulfate, such as, for example, Al2(SO4)3·18H2O, and aluminum hydroxide, such as, for example, Al(OH)3·3H2O.

[0074] Advantageously, the organic dicarboxylic acid in the process is a precursor of the organic dicarboxylate linker of the MOF according to the invention.

[0075] Advantageously, the organic dicarboxylic acid is of formula II:

[0076] [ka]

[0077] [During the ceremony, m is an integer from 1 to 5; n is an integer from 1 to 5; - p is 0 or 1, -

[0078] [ka]

[0079] represents a 5- or 6-membered aryl or heteroaryl moiety; -R 1 , R 2 , R 3 and R 4 each independently represent H, a halo group (e.g., F, Br, Cl, or I), -OH, -NH, C1-C3 alkyl (e.g., methyl or ethyl), C1-C3 alkoxy (e.g., methoxy or ethoxy), -CF3, -SH, -COOH, or -CHR-NH2 (where R is C1-C3 alkyl), or a bond when two adjacent carbon atoms are connected by a double C=C bond (e.g., when the dicarboxylic acid is muconic acid). The acid may be selected from the following:

[0080] Advantageously, the dicarboxylic acid may be chosen from succinic acid, malic acid, tartaric acid, glutaric acid, glutamic acid, citric acid, adipic acid, fumaric acid, glutaconic acid, mesaconic acid, hexenedioic acid, hydromuconic acid, 2-aminomuconic acid, muconic acid, traumatic acid, 1,4-phenylenediacetic acid, 1,4-phenylenediacrylic acid.

[0081] Advantageously, the dicarboxylic acid does not contain any carbon-carbon triple bonds (alkynes). Preferably, the dicarboxylic acid may not be acetylenedicarboxylic acid.

[0082] In one exemplary embodiment, the organic dicarboxylic acid is t,t-muconic acid (H2-muc).

[0083] Advantageously, the solvent may be chosen from water or a mixture of water and an organic solvent, the organic solvent being preferably chosen from ethanol, benzyl alcohol, acetic or formic acid, dimethyl sulfoxide, methanol, dimethylformamide, and mixtures thereof.

[0084] The solvent may have a water content of between 30% and 100% by volume, preferably between 40% and 100% by volume, more preferably between 50% and 100% by volume, and even more preferably between 60% and 100% by volume.

[0085] In one exemplary embodiment, the solvent may have a water content between 70% and 100% by volume and an organic solvent content between 0% and 30% by volume.

[0086] Therefore, the method according to the invention is particularly advantageous as it may be possible to minimize the organic solvent content in the solvent.

[0087] The process according to the invention may also comprise a step of cooling the reaction medium obtained at the end of the reacting step to room temperature.

[0088] Room temperature may be between 10°C and 40°C, preferably between 15°C and 30°C, more preferably between 15°C and 25°C.

[0089] The process according to the invention may also comprise a step of centrifuging and / or filtering the reaction medium obtained at the end of the reacting step.

[0090] The method according to the invention may also include the step of collecting the solid product at the end of the centrifugation and / or filtering steps.

[0091] The process according to the invention may also comprise a step of washing the solid product, preferably with an organic solvent and / or water.

[0092] For example, the step of washing the solid product may include a substep of washing the solid product with an organic solvent followed by a substep of washing the solid product with water.

[0093] The organic solvent may be selected from ethanol, dimethylformamide, dimethylsulfoxide and mixtures thereof.

[0094] The organic solvent may be heated to a temperature above 40°C, preferably above 50°C, more preferably above 60°C, even more preferably above 70°C.

[0095] The process according to the invention may also include a step of drying the solid product, preferably in air.

[0096] The method according to the invention may comprise the step of activating the solid product by heating.

[0097] The step of activating the solid product may be carried out under dynamic vacuum.

[0098] The step of activating the solid product may be carried out at a temperature above 110°C, preferably above 120°C, more preferably above 130°C, even more preferably above 140°C.

[0099] The step of activating the solid product may be carried out for a period of at least 6 hours, preferably at least 7 hours, more preferably at least 8 hours.

[0100] For example, the step of activating the solid product is carried out under dynamic vacuum at 150° C. for at least 8 hours, or under dynamic vacuum at 120° C. for at least 16 hours.

[0101] The cooling step is preferably carried out before the centrifugation and / or filtration steps.

[0102] A centrifugation and / or filtration step is preferably performed before the collecting step.

[0103] The collecting step is preferably carried out before the washing step.

[0104] The washing step is preferably carried out before the drying step.

[0105] A drying step is preferably carried out before the activation step.

[0106] Advantageously, the method according to the invention comprises: - cooling at room temperature (e.g., 15 to 25°C); - collecting the solid product by centrifugation and / or filtration; and - washing with an organic solvent, preferably chosen from ethanol and dimethyl sulfoxide, and / or with water Further includes:

[0107] The method for synthesizing a porous MOF according to the present invention may have a reaction yield of 70% or more, preferably 75% or more, more preferably 80% or more, and even more preferably 85% or more, based on the organic dicarboxylic acid.

[0108] According to the present invention, the porous MOF is preferably in a form that allows a large exchange surface between the MOF and the environment in which gases or vapors need to be captured by adsorption. The MOF may be in the form of, for example, powders; granules; pellets; extrudates; monoliths; films; composites embedded in foams, polymers, or fibers; or composites coated on or grown on the surface of polymeric materials, paper sheets, fibers, or metals. For example, document WO2009 / 123484

[55] , published in October 2009, discloses a useful method for producing polyurethane foam filter materials with adsorption capacity that can be used to support MOFs for implementing the present invention. Another example is the electrospinning of polymer-containing MOF particles, as disclosed in the documents M. Rose et al., Adv. Eng. Mater. 2011, 13, pp. 356-360

[56] , R. Ostermann et al., Chem. Commun. 2011, 47, pp. 442-444

[57] , J. Ren et al., Int. J. Hydrogen Energy 2015, 40, pp. 9382-9387

[58] , and MR Khan et al., J. Mater. Eng. Perform. 2016, 25, pp. 1276-1283

[59] , which provides a final composite fiber material supported on MOFs, simplifying the application of MOFs for the adsorption of volatile organic compounds. Other examples may include using MOFs in various shapes, such as in the form of granules or pellets as previously disclosed in the literature Valekar et al., RSC Adv, 2017

[60] , Q. Ren et al., Chem. Eng. J., 2015

[61] , or by coating specific supports as disclosed by Gkaniatsou et al., Nano Energy, 2020

[62] .

[0109] According to the invention, the MOF material or the MOF in the form described in the previous paragraph may be comprised in a device. The invention therefore further relates to a device selected from an air dehumidifier or purifier, a sensor, a catalyst, an adsorption column, a filter, a respirator, an adsorption tower, a hygiene protection product, a wipe or a diaper, comprising a MOF according to the invention or a MOF as described in the previous paragraph.

[0110] The invention makes it possible to strongly increase water sorption, and therefore the novel MOFs according to the invention can be advantageously used in the following applications: air water harvesting, freezers and cooling systems, or water purification.

[0111] The following experiments and results demonstrate the benefits of the present invention over prior art solutions.

[0112] The following representative examples and figures are intended to serve to illustrate the present invention and are not intended to, and should not be construed as, limiting the scope of the present invention. Indeed, various modifications of the invention and many further embodiments thereof, in addition to those shown and described herein, will become apparent to those skilled in the art from the entire contents of this document, including the examples which follow and the references to the scientific and patent literature cited herein. It should be further understood that the contents of the cited references are incorporated herein by reference to help describe the state of the art.

[0113] The following examples contain important additional information, exemplification, and guidance applicable to the practice of this invention in its various embodiments and equivalents thereof. MOFs were prepared by different synthetic methods and their water sorption properties were compared. In particular, comparing MIP-211 (invention) with MIL-53 (comparison example) resulted in a shift in the steepness of the water sorption step to lower relative pressures (approximately 0.29 vs. approximately 0.55 at 25°C, respectively). [Brief explanation of the drawings]

[0114] [Figure 1](Top) Helical Al-O chains of MIP-211(Al) made from cis-connected corner-sharing AlO6 octahedra bridged by μ2-OH (hydrogen atoms not shown). (Bottom) Rod-like Al-O chains of MIL-53(Al)-muc made from trans-connected corner-sharing AlO6 octahedra bridged by μ2-OH (hydrogen atoms not shown). [Figure 2] FIG. 1 is a projection along the

[0001] direction revealing one-dimensional channels with square cross-sections in MIP-211(Al). [Figure 3] Comparison of experimental and simulated powder X-ray diffraction patterns of MIP-211(Al) ((a) simulated and (b) experimental) and MIL-53(Al)-muc ((c) simulated and (d) experimental). Experimental patterns were measured with Cu-Kα radiation (λ = 1.5418 Å). [Figure 4] Nitrogen sorption isotherms for (a) MIP-211(Al) and (b) MIL-53(Al)-muc at 77 K. Adsorption and desorption branches are represented by solid and empty symbols, respectively. [Figure 5] FIG. 1 shows water sorption isotherms of (a) MIP-211(Al) and (b) MIL-53(Al)-muc measured at 25° C. [Figure 6] FIG. 1 shows experimental and calculated PXRD patterns for "Water-based synthesis of MIP-211(Al) (according to the present invention)." [Figure 7] FIG. 1 shows experimental and calculated PXRD patterns of "Water-based synthesis of MIL-53-muc (comparative example)." DETAILED DESCRIPTION OF THE INVENTION

[0115] In accordance with the present invention, usable MOF materials and their preparation can be further understood through examples illustrating some of the ways in which these materials are prepared or used. However, it is understood that these examples should not be construed as limiting the invention. Variations of the invention, now known or further developed, are considered to be within the scope of the invention described herein and hereinafter claimed. [Example]

[0116] Example 1 Material synthesis MIP-211(Al): 2.176 g (3.26 mmol) of Al2(SO4)3·18H2O and 0.464 g (3.26 mmol) of t,t-muconic acid (H2-muc) were introduced into a solvent mixture prepared from 15 mL of water and 5 mL of N,N-dimethylformamide (DMF). The suspension was heated under reflux with stirring for 6 h in a 100 mL round-bottom flask. After cooling to room temperature, the solid product was collected by centrifugation and washed three times with 10 mL of DMF and three times with 10 mL of water. The product was activated by heating at 120 °C under dynamic vacuum for 16 h and then dried in air. 520 mg of material was obtained (92% yield based on H2-muc).

[0117] Alternative green synthesis of MIP-211(Al): 5.4 g (41 mmol) of Al(OH)3·3H2O and 5.8 g (41 mmol) of t,t-muconic acid were added to 500 mL of water and heated under reflux with stirring in a 1 L round-bottom flask for 6 h. After cooling to room temperature, the solid product was collected by centrifugation and washed three times with DMSO (200 mL) and three times with water (200 mL). 6.8 g of material was obtained (90% yield based on H2-muc).

[0118] MIL-53(Al)-muc (Comparative Example): 1.2 g (3.2 mmol) of Al(NO3)3·9H2O and 0.5 g (3.52 mmol) of t,t-muconic acid were dissolved in a solvent mixture made from 11.2 mL of water and 3.8 mL of DMF. The mixture was sealed in a Teflon-lined autoclave and heated in an oven at 120 °C for 6 h. After the reactor was cooled to room temperature, the product was isolated and washed as described above. 450 mg of material was obtained (69% yield based on H2-muc).

[0119] Water-based synthesis of MIP-211(Al) (according to the present invention): 0.142 g (1 mmol) of t,t-muconic acid (H2-muc) and 0.132 mg (1 mmol) of Al(OH)3.xH2O (x = 3) were introduced into 20 mL of deionized water. The mixture was heated at 80 °C for 16 h under ambient pressure in a 100 mL round-bottom flask (reflux apparatus: flask and condenser). The solid product was collected by centrifugation and washed twice with hot ethanol. The product was activated by heating at 150 °C for at least 8 h under dynamic vacuum and then dried in air.

[0120] The synthesis yields MIP-211(Al) even when the synthesis time is extended from 16 hours to 42 hours, 48 ​​hours, or 72 hours.

[0121] MIP-211(Al) was also synthesized using 2.5 mmol of t,t-muconic acid and 2.5 mmol of Al(OH)3.xH2O (x=3), or 2.75 mmol of t,t-muconic acid and 2.75 mmol of Al(OH)3.xH2O (x=3), or 3 mmol of t,t-muconic acid and 3 mmol of Al(OH)3.xH2O (x=3), or 6 mmol of t,t-muconic acid and 6 mmol of Al(OH)3.xH2O (x=3).

[0122] Water-based synthesis of MIL-53-muc (comparative example): 1.7 g (12 mmol) of t,t-muconic acid (H2-muc) and 1.9 g (12 mmol) of basic aluminum acetate were introduced into 20 mL of deionized water. The mixture was heated under reflux with stirring in a 100 mL round-bottom flask (nominal heating plate temperature 120 °C) for 24 h. The solid product was collected by centrifugation and washed twice with hot ethanol. The product was activated by heating at 150 °C under dynamic vacuum for at least 8 h and then dried in air (yield approximately 68% based on H2-muc).

[0123] The synthesis affords MIL-53-muc even when ethanol and water are used as reaction solvents in a 1:1 ratio by volume.

[0124] MIL-53-muc can also be synthesized using 3.5 mmol of t,t-muconic acid (H2-muc) and 3.5 mmol of basic aluminum acetate, or 6 mmol of t,t-muconic acid (H2-muc) and 6 mmol of basic aluminum acetate, or 8 mmol of t,t-muconic acid (H2-muc) and 8 mmol of basic aluminum acetate, or 10 mmol of t,t-muconic acid (H2-muc) and 10 mmol of basic aluminum acetate, or 15 mmol of t,t-muconic acid (H2-muc) and 15 mmol of basic aluminum acetate, or 16 mmol of t,t-muconic acid (H2-muc) and 16 mmol of basic aluminum acetate, or 20 mmol of t,t-muconic acid (H2-muc) and 20 mmol of basic aluminum acetate.

[0125] The synthesis yields MIL-53-muc even if the synthesis time is increased from 24 hours to 2 days.

[0126] The crystal structure of MIP-211, shown in Figures 1 and 2, was determined from high-resolution powder X-ray diffraction (HR-PXRD) data using the direct-space method in FOX and subsequently refined by the Rietveld method. HR-PXRD data for the crystal structure determination were collected using a PANalytical Empyrean diffractometer equipped with a PIXcel 1D detector (CuKα radiation, λ = 1.540598 Å, with a Ge

[0111] monochromator) with the sample sealed in a 0.7 mm glass capillary.

[0127] The experimental and calculated PXRD patterns for "Water-based synthesis of MIP-211(Al) (according to the present invention)" are shown in Figure 6.

[0128] The experimental and calculated PXRD patterns for the "Water-based synthesis of MIL-53-muc (comparative example)" are shown in FIG.

[0129] The experimental PXRD patterns shown in Figures 3, 6, and 7 were collected using a high-throughput Bruker D8 Advance diffractometer equipped with a focusing Goebel mirror operating in transmission mode. The X-ray source was Cu-Kα radiation (λ = 1.5418 Å).

[0130] Example 2 Results and Discussion Nitrogen sorption data at 77 K shown in Figure 4 were collected on a Micromeritics Tristar instrument using an LN bath to control the temperature. HO isotherms at 298 K shown in Figure 5 were recorded on a Micromeritics Triflex instrument. In all cases, measurements were recorded using ultra-high purity gases (≥4.8 grade). Prior to adsorption measurements, samples were degassed at 200 °C for 8 h. Degassing was performed in one step using a Micromeritics SmartVacPrep degasser: the degassing port (P = 10 -6 The gas was evacuated at 200° C. under a pressure of 1000 psi (mbar) at which point the outgassing rate was ≦2 μbar / min.

[0131] The above examples demonstrate that the cis-μ-OH connectivity of MOFs according to the present invention actually leads to a dramatic increase in hydrophilicity compared to MOFs with trans-μ-OH connectivity. Thus, the novel polymorphism induces strong changes in the adsorption properties, and thus in the hydrophilicity of M-MOFs and the relative pressure positions of the steps in the water sorption isotherm. In the case of the newly discovered hydrothermally stable MOF according to the present invention, represented by Example MIP-211, the water sorption profile and uptake capacity exceed those of most of the reference materials investigated for water sorption applications, while exhibiting very low regeneration temperatures. (References) TIFF2026506553000007.tif230150TIFF2026506553000008.tif230150TIFF20265065530 00009.tif230150TIFF2026506553000010.tif223150TIFF2026506553000011.tif101150

Claims

1. μ 2 -OH bridges and / or μ 2 A porous metal-organic framework (MOF) material constructed from metal (III or IV) octahedra linked through -O bridges and interconnected by organic dicarboxylate linkers, the metal center is selected from Al, Fe, Cr, Sc, V, Ga, In, Ti and mixtures thereof; - the organic dicarboxylate linker may be optionally interrupted by a 5- or 6-membered aryl or heteroaryl moiety, and may optionally contain a halo group, -OH, -NH 2 , C 1 ~C 3 Alkyl, C 1 ~C 3 Alkoxy, -CF 3 , -SH, -COOH and -CHR-NH 2 (Wherein R is C 1 ~C 3 C may have one or more substituents selected from 4 ~C 12 dicarboxylate aliphatic linkers formed by saturated or unsaturated linear hydrocarbon chains; - the metal center and the carboxylate group of the organic dicarboxylate linker together form M a+ When a=3, cis-μ 2 -OH connected vertex-sharing MO 4 (OH) 2 Forming a spiral chain of octahedra or M a+ If a ≥ 4, MO 4 (O) 2 Sys-μ 2 -O bridged, Porous metal-organic framework materials.

2. The organic dicarboxylate linker is represented by Formula I: 【Chemistry 1】 [During the ceremony, m is an integer from 1 to 5; n is an integer from 1 to 5; - p is 0 or 1, - 【Chemistry 2】 represents a 5- or 6-membered aryl or heteroaryl moiety; -R 1 , R 2 , R 3 and R 4 are each independently H, a halo group, -OH, or -NH 2 , C 1 ~C 3 Alkyl, C 1 ~C 3 Alkoxy, -CF 3 , -SH, -COOH, -CHR-NH 2 (Wherein R is C 1 ~C 3 alkyl), or a bond when two adjacent carbon atoms are connected by a double C=C bond.

2. The porous MOF material of claim 1, wherein the linker is selected from the group consisting of:

3. 3. The porous MOF material of claim 1, wherein the organic dicarboxylate linker is selected from succinate, maleate, tartrate, glutarate, glutamate, citrate, adipate, fumarate, glutaconate, mesaconate, hexenedioate, hydromuconate, 2-aminomuconate, muconate, traumatate, 1,4-phenylenediacetate, 1,4-phenylenediacrylate.

4. Formula: {[Al(OH)(muc)]・xSolvent} y (wherein Solvent is an organic and / or inorganic solvent, preferably a solvent selected from water, alcohol, acid, dimethylformamide and dimethylsulfoxide, x is 0 to 15, and y is 5 or more).

4. The porous MOF material according to claim 1, wherein

5. A method for synthesizing a porous MOF material according to any one of claims 1 to 4, comprising the steps of: a mixture of metal precursors, wherein the metal M is selected from Al, Fe, Cr, Sc, V, Ga, In, Ti and mixtures thereof; It may be optionally interrupted by a 5- or 6-membered aryl or heteroaryl moiety, and may optionally be a halo group, -OH, -NH 2 , C 1 ~C 3 Alkyl, C 1 ~C 3 Alkoxy, -CF 3 , -SH, -COOH and -CHR-NH 2 (Wherein R is C 1 ~C 3 C may have one or more substituents selected from 4 ~C 12 an organic dicarboxylic acid selected from dicarboxylic aliphatic acids formed by a saturated or unsaturated linear hydrocarbon chain; The method comprises reacting

6. The organic dicarboxylic acid is represented by formula II: 【Transformation 3】 [During the ceremony, m is an integer from 1 to 5; n is an integer from 1 to 5; - p is 0 or 1, - 【Chemistry 4】 represents a 5- or 6-membered aryl or heteroaryl moiety; -R 1 , R 2 , R 3 and R 4 are each independently H, a halo group, -OH, or -NH 2 , C 1 ~C 3 Alkyl, C 1 ~C 3 Alkoxy, -CF 3 , -SH, -COOH or -CHR-NH 2 (Wherein R is C 1 ~C 3 alkyl), or a bond when two adjacent carbon atoms are connected by a double C=C bond.

6. The method of claim 5, wherein the acid is selected from the group consisting of:

7. 7. The method according to claim 5 or 6, wherein the organic dicarboxylic acid is selected from succinic acid, malic acid, tartaric acid, glutaric acid, glutamic acid, citric acid, adipic acid, fumaric acid, glutaconic acid, mesaconic acid, hexenedioic acid, hydromuconic acid, 2-aminomuconic acid, muconic acid, traumatic acid, 1,4-phenylenediacetic acid, and 1,4-phenylenediacrylic acid.

8. 8. The method of claim 5, wherein the organic dicarboxylic acid is t,t-muconic acid.

9. the solvent is selected from water or a mixture of water and an organic solvent; 9. The process according to any one of claims 5 to 8, wherein the organic solvent is preferably selected from ethanol, benzyl alcohol, acetic or formic acid, dimethylformamide, dimethylsulfoxide, methanol, and mixtures thereof.

10. 10. The method according to claim 9, wherein the solvent has a water content between 30% and 100% by volume, preferably between 40% and 100% by volume, more preferably between 50% and 100% by volume, and even more preferably between 60% and 100% by volume.

11. 11. The method according to any one of claims 5 to 10, wherein the reacting step lasts from 30 minutes to 75 hours, preferably from 1 hour to 75 hours, more preferably from 3 hours to 72 hours.

12. 12. The method according to any one of claims 5 to 11, wherein the molar ratio of metal precursor to organic dicarboxylic acid is between 0.6 and 1.4, preferably between 0.7 and 1.3, more preferably between 0.8 and 1.2, even more preferably between 0.9 and 1.

1.

13. 13. The method of any one of claims 5 to 12, wherein the reacting step is carried out by mechanochemistry.

14. 13. The method of any one of claims 5 to 12, wherein the reacting step is a heating step.

15. 15. The method of claim 14, wherein the heating step is carried out in a solvent.

16. 16. The method according to claim 14 or 15, wherein the heating is carried out at a temperature of 60°C or higher, preferably 70°C or higher, more preferably 80°C or higher, even more preferably under reflux conditions.

17. 17. The method of any one of claims 14 to 16, wherein the heating step is carried out by microwave heating.

18. 18. A method according to any one of claims 5 to 17, wherein the metal precursor is selected from precursors in which the metal M is aluminium, preferably aluminium sulphate and aluminium hydroxide.

19. 19. The process according to any one of claims 5 to 18, comprising a step of cooling the reaction medium obtained at the end of the reacting step to room temperature.

20. 20. The method according to any one of claims 5 to 19, comprising a step of centrifuging and / or filtering the reaction medium obtained at the end of the reacting step.

21. 21. The method of claim 20, further comprising collecting the solid product at the end of the centrifugation and / or filtering steps.

22. 22. The method of claim 21, comprising the step of washing the solid product, preferably with an organic solvent and / or water.

23. 23. The method of claim 21 or 22, comprising the step of drying the solid product, preferably in air.

24. 24. The method of any one of claims 21 to 23, comprising activating the solid product by heating.

25. 25. The process according to any one of claims 5 to 24, having a reaction yield of 70% or more, preferably 75% or more, more preferably 80% or more, even more preferably 85% or more, based on the organic dicarboxylic acid.

26. Use of at least one porous metal-organic framework (MOF) material according to any one of claims 1 to 4, Adsorption-driven air conditioning and water harvesting from air, adsorption of water, gases, or vapors, and heat-driven water sorption-based cooling systems (e.g., water harvesting or production), gases (e.g., CO 2 Uses in capture and separation of organic solvents (e.g., hydrocarbons, BTX and VOCs) and / or vapors, catalysis, sensors.

27. 5. The porous MOF material according to any one of claims 1 to 4 in the form of a powder; granules; pellets; extrudates; monoliths; films; composites embedded in the form of foams, polymers or fibres; or composites coated or grown on the surface of polymeric materials, paper sheets, fibres or metals.

28. A device comprising a porous MOF material according to any one of claims 1 to 4 or a porous MOF material according to claim 27, The device is selected from an air dehumidifier, a cooler, a heater or purifier, a sensor, a catalyst, an adsorption column, a filter, a respirator, an adsorption tower, a hygiene protection product, a wipe or a diaper.

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