Metal organic structure

Abstract

The purpose of the present invention is to provide a metal-organic structure having excellent adsorption performance with respect to a substance to be adsorbed. The present invention is a metal organic structure having a structure SM-x in which two or more metal ions are bonded to one oxygen atom of a structure Sx comprising at least one of O2-, OH2, OH-, OCH3-, and OC2H5-, and having a decomposition initiation temperature of 200 DEG C or higher.

Description

Technical Field

[0001] The present invention relates to metal-organic structures. Background Art

[0002] Metal Organic Frameworks (MOFs), also known as porous coordination polymers, are materials that form a porous structure through coordination bonds between metal ions and organic ligands. They are materials that are expected to be used in gas adsorption and desorption, catalysts, and the like.

[0003] For example, Patent Document 1 discloses a metal organic structure comprising a metal ion, a first ligand, a second ligand and an arbitrary third ligand, wherein the metal ion is an aluminum ion, the first and second ligands are organic compound ions composed of a heterocyclic ring having two carboxyl groups, the angle formed by the heteroatom and the carboxyl group satisfies specified conditions, the third ligand is an organic compound ion having two carboxyl groups, and the existence ratio of the first to third ligands is within a specified range.

[0004] Prior art literature

[0005] Patent Literature

[0006] Patent Document 1: Japanese Patent Application Publication No. 2020-176101 Summary of the invention

[0007] Problems to be solved by the invention

[0008] Metal organic structures (hereinafter sometimes referred to as MOFs) are expected to be able to adsorb a large amount of target substances, but the adsorption performance of MOFs proposed in the past still has room for improvement.

[0009] Therefore, an object of the present invention is to provide a MOF having excellent adsorption performance for an adsorption target substance (especially water).

[0010] Means for solving problems

[0011] The present invention for solving the above-mentioned problems is as follows.

[0012] [1] A metal organic structure having a structure S M-x , the decomposition starting temperature is above 200°C, the structure S M-x For O 2- OH 2 OH - 、OCH 3 - and OC 2 H 5 - Structure S formed by one or morex A structure in which two or more metal ions are bonded to one oxygen atom.

[0013] [2] The metal-organic structure according to [1], wherein the OH 2 The ratio of O to O derived from the organic ligand possessed by the metal organic structure is 0.1 or more.

[0014] [3] The metal-organic structure according to [1] or [2], wherein the metal-organic structure comprises a structure S x and metal ions, and the metal ions are connected to each other through the structure S x The cluster structure is bonded by the oxygen atoms in

[0015] There are three or four metal ions in one cluster structure.

[0016] [4] The metal-organic structure according to any one of [1] to [3], wherein the organic ligand possessed by the metal-organic structure comprises an oxalate ion (COO - ) 2 And R(COO - ) n (R is an n-valent group, and n is an integer of 2 or more) is at least one of the carboxylates represented by.

[0017] [5] The metal-organic structure according to any one of [1] to [4], wherein the metal ion is an ion of at least one metal selected from elements in Periods 3 to 6 and Groups 2 to 14 of the periodic table.

[0018] Effects of the Invention

[0019] According to the present invention, a MOF having excellent water absorption performance can be provided. DETAILED DESCRIPTION

[0020] The present invention is a MOF having a structure S M-x , the decomposition starting temperature is above 200°C, the structure S M-x For O 2- OH 2 OH - 、OCH 3 - and OC 2 H 5 - Structure S formed by one or more x A structure in which two or more metal ions are bonded to one oxygen atom. x It can coordinate and bond two or more metal ions on the oxygen atom and become a ligand. 2-OH 2 OH - 、OCH 3 - and OC 2 H 5 - Only metal ions are bonded through oxygen atoms, and no other groups are bonded. M-x It is believed that the structure based on the bonding of metal ions and organic ligands, which is not necessarily sufficient for water resistance, can protect and achieve good water absorption performance. In addition, a high decomposition starting temperature, that is, high thermal strength, can also be an important factor in achieving excellent water absorption performance.

[0021] In structure S x Two or more metal ions can be bonded to one oxygen atom through the repeating structure of the MOF minimum repeating unit, such as in the structure S x The minimum repeating unit in the repetition of bonding with the metal is used to determine.

[0022] Structure S x Preferably by O 2- OH 2 OH - and OCH 3 - More preferably, O 2- OH 2 and OH - The MOF of the present invention preferably has multiple structures S M-x , various structures S M-x The structure S x They can be the same or different from each other.

[0023] In structure S x The number of metal ions bonded to one oxygen atom is two or more, usually four or less. x The types of metal ions bonded to one oxygen atom of the ion may be the same or different.

[0024] The MOF of the present invention preferably has a cluster structure, which means that the metal ions and the structure S x The metal ions are connected to each other through the structure S x MOF is a structure with metal ions and organic ligands (excluding OCH that are not bonded to groups other than metal ions). 3 - and OC 2 H 5 -) structure, when the MOF of the present invention has a cluster structure, the cluster structures are bonded to each other via organic ligands.

[0025] When MOF has a cluster structure, as the structural S x O 2- OH 2 and OH - The total number of is preferably 2 or more and 15 or less, more preferably 2 or more and 8 or less, and further preferably 4 or more and 8 or less in one cluster structure. x O 2- OH 2 and OH - When the total number of is within the above range, a cluster structure is easily generated, and the basic skeleton of MOF is stabilized. As a result, the water absorption performance of MOF is easily improved.

[0026] When MOF has a cluster structure, the number of metal ions in one cluster structure is preferably 2 or more, more preferably 3 or more, and further preferably 10 or less, more preferably 8 or less. The number of metal ions in one cluster structure is particularly preferably 3 or 4, in which case the water absorption performance is particularly improved.

[0027] Derived from the aforementioned structure S x OH 2 The ratio of O derived from OH to O derived from the organic ligands of MOF is preferably 0.1 or more. This can improve the water absorption performance. 2 The ratio of O to O derived from the organic ligand is preferably 0.12 or more, more preferably 0.14 or more, and may be 0.20 or less.

[0028] Derived from the aforementioned structure S x O 2- The ratio of O to O derived from the organic ligands of MOF is 0.2 or more and can be 0.4 or less. x OH - The ratio of O to O derived from the organic ligand possessed by MOF is preferably 0.1 or more, more preferably 0.15 or more, and still more preferably 0.25 or less.

[0029] The MOF of the present invention has a cluster structure, wherein the number of metal ions in one cluster structure is three or four and is derived from OH 2 In particular, the ratio of O to O derived from the organic ligand is preferably 0.14 or more.

[0030] The decomposition starting temperature of the MOF of the present invention is 200°C or higher, more preferably more than 200°C, further preferably 250°C or higher, further preferably 270°C or higher, further preferably 500°C or lower, more preferably 400°C or lower, further preferably 350°C or lower.

[0031] The metal ions constituting the MOF of the present invention are preferably ions of at least one metal selected from the elements of the 3rd to 6th periods and the 2nd to 14th groups of the periodic table. It should be noted that in this specification, the metal connotation includes semimetals such as Si and Ge. The metal ions constituting the MOF are more preferably ions of at least one metal selected from Mg, Al, Ga, In, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zr and Hf, and are further preferably ions of at least one metal selected from Al, Ti, Cu, In and Mg, and are particularly preferably ions of at least one metal selected from Cu, In and Mg.

[0032] The organic ligands constituting MOF preferably include oxalate ions (COO - ) 2 And R(COO - ) n (R is an n-valent group, n is an integer greater than 2) is at least one of the carboxylates represented by. R is preferably an aliphatic chain hydrocarbon group, an aliphatic cyclic hydrocarbon group, an aliphatic heterocyclic hydrocarbon group (a group in which one or more carbon atoms of the aliphatic cyclic hydrocarbon group are replaced by heteroatoms), an aromatic hydrocarbon group, an aromatic heterocyclic hydrocarbon group (a group in which one or more carbon atoms of the aromatic hydrocarbon group are replaced by heteroatoms). The aliphatic chain hydrocarbon group may be straight-chain or branched, and may be a saturated hydrocarbon group or an unsaturated hydrocarbon group. The heteroatom in the aliphatic heterocyclic hydrocarbon group or the aromatic heterocyclic hydrocarbon group is preferably nitrogen.

[0033] n is 2 or more, preferably 4 or less, more preferably 2 or more and 3 or less, and most preferably 2.

[0034] The above-mentioned aliphatic chain hydrocarbon group, aliphatic cyclic hydrocarbon group, aliphatic heterocyclic hydrocarbon group, aromatic hydrocarbon group, aromatic heterocyclic hydrocarbon group may further contain a carboxylic acid anhydride group, -OH, -OR 1 、-NH 2 、-NHR 1 、-N(R 1 ) 2 , -CN, halogen groups, -C(=S)SH, -C(=O)SH and tautomers thereof, -SO 3 One or more functional groups X in H. 1 The functional group X is preferably -OH or -NH2 , more preferably -NH 2 .

[0035] Examples of the aromatic heterocyclic hydrocarbon group include pyrazole, imidazole, thiazole, oxazole, pyridine, pyrimidine, pyridazine, pyrazine, and triazine, and pyrazole is particularly preferred.

[0036] The aforementioned R is at least one of an unsaturated straight-chain hydrocarbon group, an aromatic hydrocarbon group, and a hydrocarbon group having an aromatic ring containing a nitrogen atom, and is preferably a group that may have the aforementioned functional group X, and more preferably a group having the aforementioned functional group X (especially -NH 2 ) of an aromatic hydrocarbon group.

[0037] The number of carbon atoms of the aforementioned R is preferably 1 or more, more preferably 2 or more, and further preferably 30 or less. The number of carbon atoms of the aforementioned R is further preferably 6 or more, 10 or more, 15 or more, and 20 or more, and the upper limit may be 28 or less, 24 or less, 18 or less, 12 or less, and 10 or less.

[0038] In particular, the organic ligands constituting the MOF preferably include oxalate ions (COO - ) 2 And R(COO - ) 2 At least one of the carboxylates represented by , specifically, a substance obtained by releasing two protons from two carboxyl groups (—COOH) of a dicarboxylic acid or a substance obtained by releasing three protons from three carboxyl groups of a tricarboxylic acid.

[0039] Examples of the dicarboxylic acid include oxalic acid, succinic acid, fumaric acid, tartaric acid, 1,4-butanedicarboxylic acid, 1,4-butenedioic acid, 4-oxopyran-2,6-dicarboxylic acid, 1,6-hexanedicarboxylic acid, sebacic acid, 1,8-heptadecanedioic acid, 1,9-heptadecanedioic acid, heptadecanedioic acid, butynedioic acid, 1,2-phthalic acid (o-phthalic acid), 1,3-phthalic acid (isophthalic acid), 2,3-pyridinedicarboxylic acid, 1,3-butadiene-1,4-dicarboxylic acid, 1,4-phthalic acid (terephthalic acid), 2-aminoterephthalic acid, 2,5-dihydroxyterephthalic acid, imidazole-2,4-dicarboxylic acid, 3,5-pyrazoledicarboxylic acid, 2-methylquinoline-3,4-dicarboxylic acid, quinoline-2,4-dicarboxylic acid, quinoxaline-2,3-dicarboxylic acid, 6-chloroquinoxaline-2,3-dicarboxylic acid, 4,4'-diaminodiphenylmethane-3,3'-dicarboxylic acid, quinoline-3,4-dicarboxylic acid, 7-chloro-4-hydroxyquinoline-2,8-dicarboxylic acid, diimide dicarboxylic acid, pyridine-2,6-dicarboxylic acid, 2-methylimidazole-4,5-dicarboxylic acid, thiophene-3,4-dicarboxylic acid, 2-isopropylimidazole-4,5-dicarboxylic acid, tetrahydrofuran-4,4-dicarboxylic acid, perylene-3,9-dicarboxylic acid, perylene dicarboxylic acid, Pluriol E200-dicarboxylic acid, 3,6-dioxanoic acid, 3,5-cyclohexadiene-1,2-dicarboxylic acid, suberic acid, n-pentane-3,3-carboxylic acid, 4,4'-diamino-1,1'-biphenyl-3,3'-dicarboxylic acid, 4,4'-diaminobiphenyl-3,3'-dicarboxylic acid, benzidine-3,3'-dicarboxylic acid, 1,4-bis(phenylamino)benzene-2,5-dicarboxylic acid, 1,1'-binaphthyl dicarboxylic acid, 7-chloro-8-methylquinoline-2,3-dicarboxylic acid, 1-anilinoanthraquinone-2,4'-dicarboxylic acid, polytetrahydrofuran 250-dicarboxylic acid, 1,4-bis(carboxymethyl)piperazine-2,3-dicarboxylic acid, 7-chloroquinoline-3,8 -dicarboxylic acid, 1-(4-carboxy)phenyl-3-(4-chloro)phenylpyrazoline-4,5-dicarboxylic acid, 1,4,5,6,7,7-hexachloro-5-norbornene-2,3-dicarboxylic acid, phenylindanedicarboxylic acid, 1,3-dibenzyl-2-oxoimidazolidine-4,5-dicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, naphthalene-1,8-dicarboxylic acid, 2-benzoylbenzene-1,3-dicarboxylic acid, 1,3-dibenzyl-2-oxoimidazolidine-4,5-cis-dicarboxylic acid, 2,2'-biquinoline-4,4'-dicarboxylic acid, pyridine-3,4-dicarboxylic acid, 3,6,9-trioxaundecanedicarboxylic acid, hydroxybenzophenone dicarboxylic acid, Pluriol E300-dicarboxylic acid, Pluriol E400-dicarboxylic acid, Pluriol E600-dicarboxylic acid, pyrazole-3,4-dicarboxylic acid, 2,3-pyrazinedicarboxylic acid, 5,6-dimethyl-2,3-pyrazinedicarboxylic acid, bis(4-aminophenyl)ether diimide-dicarboxylic acid, 4,4'-diaminodiphenylmethane diimide-dicarboxylic acid, bis(4-aminophenyl)sulfone diimide-dicarboxylic acid, 1,4-naphthalene dicarboxylic acid, 2,6-naphthalene dicarboxylic acid, 1,3-adamantane dicarboxylic acid, 1,8-naphthalene dicarboxylic acid, 2,3-naphthalene dicarboxylic acid, 8-methoxy-2,3-naphthalene dicarboxylic acid, 8-nitro-2,3-naphthalene dicarboxylic acid, 8-sulfonic acid-2,3-naphthalene dicarboxylic acid, anthracene-2,3-dicarboxylic acid, 2',3'-biphenyl-p-terphenyl-4,4"-dicarboxylic acid, (biphenyl ether)-4, 4'-dicarboxylic acid, imidazole-4,5-dicarboxylic acid, 4(1H)-oxothiochromene-2,8-dicarboxylic acid, 5-tert-butyl-1,3-phthalic acid, 7,8-quinolinedicarboxylic acid, 4,5-imidazoledicarboxylic acid, 4-cyclohexene-1,2-dicarboxylic acid, trihexadioic acid, tetradecanedioic acid, 1,7-heptanedioic acid, 5-hydroxy-1,3-phthalic acid, 2,5-dihydroxy-1,4-phthalic acid, pyrazine-2,3-dicarboxylic acid, furan-2,5-dicarboxylic acid, 1-nonene-6,9-dicarboxylic acid Acid, eicosenedioic acid, 4,4'-dihydroxy-diphenylmethane-3,3'-dicarboxylic acid, 1-amino-4-methyl-9,10-dioxo-9,10-dihydroanthracene-2,3-dicarboxylic acid, 2,5-pyridinedicarboxylic acid, cyclohexene-2,3-dicarboxylic acid, 2,9-dichlorofluorescein ring-4,11-dicarboxylic acid, 7-chloro-3-methylquinoline-6,8-dicarboxylic acid, 2,4-dichlorobenzophenone-2',5'-dicarboxylic acid, 1,3-phthalic acid, 2,6-pyridinedicarboxylic acid, 1-methyl The dicarboxylic acid is preferably at least one selected from terephthalic acid and 2-aminoterephthalic acid.

[0040] Examples of the tricarboxylic acid include trimellitic acid, aconitic acid, trimesic acid, trimesic acid, biphenyl-3,4',5-tricarboxylic acid, and 1,3,5-tris(4-carboxyphenyl)benzene, and 1,3,5-tris(4-carboxyphenyl)benzene is preferred.

[0041] As the organic ligand constituting the MOF of the present invention, the organic ligand may further contain an oxalate ion (COO - ) 2 and the aforementioned R(COO - ) n The organic ligands may be different types of carboxylates, and examples of such organic ligands include at least one selected from urea, pyrazine, oxazole, isoxazole, thiazole, imidazole, pyrazole, 1,2,3-thiadiazole, pyridazine, pyrimidine, purine, and pteridine.

[0042] The molar ratio of metal ions to organic ligands (total amount in the case of multiple types) (metal ions / organic ligands) is preferably greater than 0.1, more preferably greater than 0.5, further preferably greater than 1.0, and further preferably less than 5, more preferably less than 4, and further preferably less than 3.

[0043] The BET specific surface area of ​​MOF is preferably 200 cm 2 / g or more, more preferably 600cm 2 / g or more, more preferably 1000cm 2 There is no particular upper limit on the BET specific surface area, for example, 2000 cm 2 / g or less.

[0044] Next, the method for producing the MOF of the present invention will be described. The MOF of the present invention can be obtained by reacting a metal compound containing a metal ion constituting the MOF with one or more organic compounds serving as organic ligands constituting the MOF in a solvent.

[0045] The metal compound containing the metal ion constituting MOF is preferably a metal sulfate, acetate, nitrate, halide (especially chloride) or alkoxide, more preferably a nitrate, chloride or alkoxide, and still more preferably a nitrate.

[0046] The organic compound that becomes the organic ligand constituting MOF is preferably selected from oxalic acid and R(COOH) n One or more polycarboxylic acids represented by R(COO - ) n R and n in the carboxylate represented by are synonymous, and the above description of R and n including preferred aspects can be referred to in their entirety.

[0047] The organic compound preferably contains at least one selected from tricarboxylic acids and dicarboxylic acids. For specific examples thereof, including preferred ranges, reference can be made to the examples in the formula R(COO - ) n The tricarboxylic acids and dicarboxylic acids described in the carboxylates are represented.

[0048] As the organic compound to be the organic ligand, it is preferably selected from oxalic acid and R(COOH) n In addition to one or more of the polycarboxylic acids represented by the above, at least one selected from the group consisting of urea, pyrazine, oxazole, isoxazole, thiazole, imidazole, pyrazole, 1,2,3-thiadiazole, pyridazine, pyrimidine, purine and pteridine is used.

[0049] The solvent is not particularly limited as long as it can dissolve the metal compound and the organic compound that becomes the organic ligand, and can be appropriately selected from water and organic solvents. The solvent is preferably water; an alcohol solvent such as methanol; an amide solvent such as dimethylformamide and dimethylacetamide, and more preferably at least an amide solvent. The structure S of the MOF of the present invention x It is produced from these solvents or from moisture in the air during the manufacturing process.

[0050] The ratio of the metal compound to the solvent (metal compound / solvent) is preferably 0.01 mol / L or more, more preferably 0.03 mol / L or more, further preferably 0.05 mol / L or more, and is also preferably 1 mol / L or less, more preferably 0.5 mol / L or less, further preferably 0.2 mol / L or less.

[0051] In addition, the ratio of the organic compound serving as the organic ligand to the solvent (organic compound / solvent) is preferably 0.005 mol / L or more, more preferably 0.01 mol / L or more, further preferably 0.02 mol / L or more, and also preferably 3 mol / L or less, more preferably 1 mol / L or less, further preferably 0.1 mol / L or less.

[0052] The molar ratio of the metal compound to the organic compound may be adjusted so that the ratio of the molar amount of metal atoms in the metal compound to the molar amount of the organic compound is equal to the molar ratio of metal ions to organic ligands in the MOF.

[0053] In order to obtain the MOF of the present invention, it is particularly necessary to make (i) the mixing of the metal compound and the organic compound that serves as the organic ligand under appropriate conditions. In addition to requirement (i), it is further preferred to appropriately adjust at least one of (ii) the stirring or standing temperature after mixing the metal compound and the organic compound that serves as the organic ligand and (iii) the post-treatment conditions of the reaction product of the metal compound and the organic compound that serves as the organic ligand.

[0054] In the mixing of the metal compound of the aforementioned (i) and the organic compound that becomes the organic ligand, it is important to dissolve the metal compound and the organic compound completely. Specifically, when the metal compound and the organic compound are mixed at once, it is necessary to carry out ultrasonic treatment for more than 2 minutes after mixing. In addition, when either the metal compound and the organic compound are first completely dissolved in the solvent and then the other party is added, it is necessary to carry out stirring operation for more than 5 minutes, for example, stirring treatment using a stirrer can be carried out, or ultrasonic treatment can be carried out.

[0055] The stirring temperature after mixing the metal compound and the organic compound serving as the organic ligand in the above step (ii) may be room temperature or above, and the subsequent standing conditions are preferably set at 100° C. to 200° C. for about 10 hours to 6 days.

[0056] Regarding the post-treatment conditions of the reaction product of the metal compound and the organic compound serving as the organic ligand in (iii), it is preferred to wash the reaction product three or more times with the solvent used in the reaction between the metal compound and the organic compound. In this case, it is particularly preferred that the solvent contains an amide solvent such as dimethylformamide or dimethylacetamide.

[0057] The MOF of the present invention is suitable for, for example, adsorption and removal of gases and organic molecules. Examples of gases include carbon dioxide, hydrogen, carbon monoxide, oxygen, nitrogen, hydrocarbons with 1 to 4 carbon atoms, rare gases, hydrogen sulfide, ammonia, sulfur oxides, nitrogen oxides, siloxanes, etc. Examples of organic molecules include hydrocarbons with 5 to 8 carbon atoms, alcohols with 1 to 8 carbon atoms, aldehydes with 1 to 8 carbon atoms, carboxylic acids with 1 to 8 carbon atoms, ketones with 1 to 8 carbon atoms, amines with 1 to 8 carbon atoms, esters with 1 to 8 carbon atoms, and amides with 1 to 8 carbon atoms. It should be noted that the aforementioned organic molecules may contain aromatic rings.

[0058] This application claims the benefit of priority based on Japanese Patent Application No. 2022-042377 filed on March 17, 2022. The entire contents of the specification of Japanese Patent Application No. 2022-042377 filed on March 17, 2022 are incorporated herein by reference in their entirety.

[0059] Example

[0060] The present invention is not limited to the following examples, and can be implemented with modifications within the scope consistent with the above and below-mentioned purposes, and all of them are included in the technical scope of the present invention.

[0061] Example 1

[0062] In a 50 mL SUS-304 pressure-resistant container (with a Teflon (registered trademark) inner tube), 3.000 mmol of 2-aminoterephthalic acid was dissolved in 25 mL of a solution prepared by mixing dimethylformamide (DMF) and MeOH at a volume ratio of 1 / 1. 1.518 mmol of Ti[OCH(CH 3 ) 2 ] 4, stirred with a stirring bar for 5 minutes. Thereafter, the mixture was allowed to stand at 150°C for 16 hours. The precipitated solid was washed and filtered three times with 10 mL of DMF, and the filter cake was dried under reduced pressure in a vacuum drying oven at 120°C for 24 hours and 150°C for 24 hours to obtain 0.62 g of the product (yield 89.4%).

[0063] Example 2

[0064] In a 50 mL SUS-304 pressure-resistant container (with a Teflon (registered trademark) inner tube), 0.348 mmol of In(NO 3 ) 3 ·5H 2 O, 0.955 mmol Mg(NO 3 ) 2 6H 2 O, 0.518 mmol of 1,3,5-tris(4-carboxyphenyl)benzene, 2.5 mL of H 2 O and 13.5 mL of DMF, and ultrasonic waves were applied for 3 minutes to dissolve it. Thereafter, it was allowed to stand at 100°C for 5 days. The precipitated solid was washed and filtered three times with 10 mL of dimethylacetamide (DMA), and the filter cake was dried at room temperature for 3 days to obtain 0.24 g of the product (yield 90%).

[0065] Example 3

[0066] In a 100 mL SUS-304 pressure-resistant container (with a Teflon (registered trademark) inner tube), 0.864 mmol of Cu(NO) was mixed with stirring at room temperature. 3 ) 3 ·3H 2 O, 0.351mmol In(NO 3 ) 3 ·5H 2 O, 0.513 mmol of 1,3,5-tris(4-carboxyphenyl)benzene, 2.5 mL of H 2 O and 13.5 mL of DMF, and ultrasonic waves were applied for 2 minutes to dissolve it. Thereafter, it was allowed to stand at 100°C for 5 days. The precipitated solid was washed and filtered three times with 30 mL of DMA, and the filter cake was dried under reduced pressure at 120°C for 24 hours in a vacuum drying oven to obtain 0.39 g of the product (yield 84.9%).

[0067] Example 4

[0068] In a 100 mL SUS-304 pressure-resistant container (with a Teflon (registered trademark) inner tube), 5.1 mmol of AlCl 3, 2.089mmol of terephthalic acid and 60mL of DMF were all mixed, and ultrasonic waves were applied at room temperature for 5 minutes to dissolve it. Thereafter, it was allowed to stand at 110°C for 20 hours. The precipitated solid was washed and filtered three times with 30mL of DMF, and the filter cake was dried under reduced pressure in a vacuum drying oven at 60°C for 30 minutes and 150°C for 12 hours to obtain 0.38g of the generated substance (yield 90%).

[0069] Comparative Example 1

[0070] In a 100 mL SUS-304 pressure-resistant container (containing a Teflon (registered trademark) inner tube), 20 mL of tetrahydrofuran (THF) and 1.556 mmol of 2,5-dihydroxyterephthalic acid were mixed to obtain a mixture A. Separately, 3.028 mmol of [Zn(NO 3 ) 2 ]·6H 2 O, 6 mL of NaOH aqueous solution (1 M) and 10 mL of ion exchange water to obtain a mixture B. Mixture B was added to mixture A and allowed to stand at 110°C for 3 days. The precipitated solid was washed and filtered three times with 30 mL of THF, and the filter cake was dried in a vacuum drying oven at 80°C for 24 hours to obtain 0.16 g of the product (yield: 32.9%).

[0071] Comparative Example 2

[0072] In a 100 mL SUS-304 pressure-resistant container (containing a Teflon (registered trademark) inner tube), 40 mL of N-methylpyrrolidone (NMP) and 3.839 mmol of 2,5-dihydroxyterephthalic acid were mixed to obtain a mixture A. Separately, 7.605 mmol of Mn(CH 3 COO 2 ·4H 2 O and 5 mL of ion exchange water to obtain mixture B. Mixture B was added to mixture A and allowed to stand at 110°C for 24 hours. The precipitated solid was washed and filtered three times with 30 mL of ion exchange water, and the filter cake was dried in a vacuum drying oven at 100°C for 24 hours to obtain 0.66 g of the product (yield: 55.1%).

[0073] The materials obtained in Examples and Comparative Examples were evaluated by the following methods.

[0074] (1) Determination of decomposition starting temperature

[0075] After pretreatment at 25°C in an air atmosphere with the relative humidity adjusted to 50%, the obtained MOF was kept for 12 hours, and then heated at a rate of 5°C / min under nitrogen purge. When the temperature was raised to 500°C, the point at which decomposition behavior was confirmed in the DTA measurement specified in the general rules for thermal analysis of JIS K0129 in this range (25-500°C) was taken as the decomposition start temperature.

[0076] (2) Evaluation of MOF structure

[0077] XRD (X-ray diffraction) was measured under the following conditions to obtain a cif (Crystallographic Information File) file, which was imported into Mercury software (The Cambridge Crystallographic Data Center) to calculate the O content in one cluster structure from the obtained image. 2- OH 2 and OH - The number of metal ions in a cluster structure, the number of metal ions bonded to each structure S x The number of metal ions of oxygen atoms and the number of metal ions derived from each structure S x and the ratio of O to organic ligands.

[0078] Device: SmartLab by Rigaku

[0079] Radiation source: Cu

[0080] Measuring range: 2θ = 3 to 40°

[0081] Step size: 0.01°

[0082] Scanning speed: 3° / min

[0083] Measurement temperature: room temperature (25°C)

[0084] (3) Evaluation of water absorption

[0085] The resulting materials (MOF) obtained in the examples and comparative examples were placed in an air atmosphere adjusted to a relative humidity of 50% at a temperature of 25° C. for 12 hours, and the mass W was measured. 1 . Then, the mass W will be obtained 1 The MOF was heated at a rate of 5°C / min under nitrogen purge, and the mass W was measured after being left at 200°C for 1 hour. 2 The value calculated according to the following formula (1) is regarded as the water absorption rate A.

[0086] Water absorption rate A=(W 1 -W 2 ) / W2 (1)

[0087] (4) Determination of BET specific surface area

[0088] Since the adsorption area of ​​nitrogen molecules is known in advance, the amount of gas molecules adsorbed only on the sample surface is measured, and the surface area of ​​the sample is determined using the BET adsorption isotherm equation.

[0089] Pretreatment conditions: The temperature at which the water contained in the sample is removed was determined based on the results of the above TG-DTA measurement, and heating was performed under reduced pressure overnight.

[0090] Device: BELSORP-mini manufactured by MicrotracBEL Corp.

[0091] Pre-treatment conditions:

[0092] (1) Place a glass rod (for standard sample tube) in the standard sample tube to reduce the volume and seal it with a quick seal. Prepare a sample tube set with the number of samples to be tested (maximum 3 samples per measurement), connect it to the pretreatment device (BELPREP VACII), exhaust the air in the sample tube and introduce it into the N 2 Gas (purity 99.999% or more) up to atmospheric pressure.

[0093] (2) Afterwards, the sample tube is removed from the pretreatment device and its weight is measured three times using a precision balance (accurate to 4 decimal places or more) to obtain the average (W1). When using a precision balance, an ionizer is used to eliminate the influence of static electricity.

[0094] (3) Measure about 50 mg of the sample to be tested on the medicine paper and use a long funnel to add the sample directly into the spherical part at the bottom of the standard sample tube.

[0095] (4) Place the glass rod back into the sample tube, seal it with a quick seal, and measure the overall weight to provisionally estimate the amount of sample to be added.

[0096] (5) Connect the sample tube containing the sample to the pretreatment device and exhaust the gas in the sample tube.

[0097] (6) When the pressure inside the sample tube reaches a sufficiently low level, heating is started (continuous vacuum extraction).

[0098] Determination conditions:

[0099] (1) After the pretreatment (vacuum heating) is completed, the sample tube is kept under reduced pressure to release heat, and N is introduced after reaching room temperature. 2 Gas to atmospheric pressure and remove from the device.

[0100] (2) Measure the weight of the sample tube containing the sample after three pretreatments using a precision balance and obtain the average (W2). Calculate W2-W1 to obtain the weight of the sample.

[0101] (3) Input the sample weight, liquid nitrogen temperature, and N 2 The gas information (second Virial coefficient, etc.), the relative pressure to be measured, and the measurement start button are pressed. Then, according to the instructions of the software, the Dewar flask filled with liquid nitrogen and the sample tube are set up to start the measurement.

[0102] The results are shown in Table 1. In addition, the organic ligand in Table 1 represents the name of the carboxylic acid before the proton is released from the carboxyl group. In addition, the number of cores of the cluster structure in Table 1 represents the number of metal ions in one cluster structure.

[0103]

Claims

1. A metal organic structure having a structure S M-x , the decomposition starting temperature is above 200°C, the structure S M-x For O 2- OH2, OH - 、OCH3 - and OC2H5 - Structure S formed by one or more x A structure in which two or more metal ions are bonded to one oxygen atom.

2. The metal-organic structure according to claim 1, wherein The ratio of O derived from the OH 2 to O derived from the organic ligand possessed by the metal organic structure is 0.1 or more.

3. The metal-organic structure according to claim 1 or 2, wherein: Metal organic structures are composed of structure S x and metal ions, and the metal ions are connected to each other through the structure S x The cluster structure is bonded by the oxygen atoms in There are three or four metal ions in one cluster structure.

4. The metal-organic structure according to claim 1 or 2, wherein: The organic ligands of the metal organic structure include oxalate ions (COO - )2 and R(COO - ) n At least one of the carboxylates represented by , wherein R is an n-valent group, and n is an integer of 2 or more.

5. The metal-organic structure according to claim 1 or 2, wherein: The metal ion is an ion of at least one metal selected from elements of Periods 3 to 6 and Groups 2 to 14 of the periodic table.

Images