Patent Application
20250186970
The present invention relates to a metal organic framework.
Metal organic frameworks are also referred to as porous coordination polymers and are a class of materials which form porous structures by coordinate bonds between metal ions and organic ligands, and are expected to adsorb and desorb gas and expected to be applied to catalysts, and the like.
For example, Patent Literature 1 discloses a metal organic framework including metal ions, first ligands, second ligands, and optional third ligands. In the metal organic framework, the metal ion is an aluminum ion; the first and second ligands are each an ion of an organic compound that includes a hetero ring with two carboxyl groups; a heteroatom and the angle formed between the carboxyl groups satisfy a predetermined condition; the third ligand is an ion of an organic compound with two carboxyl groups; and the existing proportion of each of the first to third ligands is within a predetermined range.
Patent Literature 1: Japanese Laid-Open Patent Publication No. 2020-176101
When the metal organic framework (hereinafter, may be referred to as MOF) is used to adsorb materials such as water, carbon dioxide, and hydrogen, the MOF sometimes needs to exhibit greater than or equal to a predetermined adsorption amount at a high relative pressure while the amount of a target material to be adsorbed is rapidly increased according to the variation in relative pressure. However, a MOF capable of satisfying such properties is not disclosed in the above-described Patent Literature 1.
Therefore, an object of the present invention is to provide a MOF that exhibits greater than or equal to a predetermined adsorption amount at a high relative pressure while the amount of a target material to be adsorbed is rapidly increased according to the variation in relative pressure.
The present invention that can achieve the problem is as follows.
[1]A metal organic framework, wherein
[2] The metal organic framework according to [1], wherein the point where the gradient is maximum is in a range of relative pressures (P/P0) of 0.1 to 0.4.
[3] The metal organic framework according to [1] or [2], wherein
[4] The metal organic framework according to any one of [1] to [3], wherein the adsorption amount at the relative pressure (P/P0) of 0.3 on the adsorption-side isotherm is 200 mL(STP)·g−1 or more.
[5] The metal organic framework according to any one of [1] to [4], wherein an amount of change in a water vapor adsorption amount in a section where the adsorption-side isotherm rises with an inclination of 1000 mL(STP)·g−1/relative pressure (P/P0) or more is 200 mL(STP)·g−1 or more.
[6] The metal organic framework according to any one of [1] to [5], wherein a relative pressure hysteresis ΔH obtained by formula (2) is within ±0.03.
[7] The metal organic framework according to any one of [1] to [6], wherein an adsorption amount hysteresis ΔA obtained by formula (3) is within ±30 mL(STP)·g−1.
[8] The metal organic framework according to any one of [1] to [7], wherein
[9] The metal organic framework according to any one of [1] to [8], wherein
According to the present invention, it is possible to provide the MOF that exhibits greater than or equal to a predetermined adsorption amount at a high relative pressure while the amount of the target material to be adsorbed is rapidly increased according to the variation in relative pressure.
In the present invention, the adsorption and desorption properties of a MOF are evaluated by adsorption and desorption isotherms of water vapor measured at 25° C. The adsorption and desorption isotherms is a graph in which the vertical axis represents a water vapor adsorption amount (mL(STP)·g−1) per gram of the MOF and the horizontal axis represents a relative pressure (P/P0) (P represents water vapor pressure and P0 represents saturation water vapor pressure). As for the MOF of the present invention, on the adsorption-side isotherm of water vapor measured at 25° C. in which the vertical axis represents the water vapor adsorption amount and the horizontal axis represents the relative pressure (P/P0), the inclination of a tangent line drawn at a point where the gradient of a curve is maximum is 7000 mL(STP)·g−1/relative pressure (P/P0) or more, and a water vapor adsorption amount at a relative pressure (P/P0) of 0.96 is 440 mL(STP)·g−1 or more.
On the adsorption-side isotherm of water vapor, the inclination of the tangent line drawn at the point where the gradient of the curve is maximum is preferably 8000 mL(STP)·g−1/relative pressure (P/P0) or more, more preferably 9000 mL(STP)·g−1/relative pressure (P/P0) or more, and still more preferably 14000 mL(STP)·g−1/relative pressure (P/P0) or more. The upper limit thereof is not particularly limited, and the inclination of the tangent line may be, for example, 50000 mL(STP)·g−1/relative pressure (P/P0) or less, or 40000 mL(STP)·g−1/relative pressure (P/P0) or less.
In addition, the water vapor adsorption amount at the relative pressure (P/P0) of 0.96 is 440 mL(STP)·g−1 or more, preferably 470 mL(STP)·g−1 or more, and more preferably 500 mL(STP)·g−1 or more. The upper limit thereof is not particularly limited, and the water vapor adsorption amount may be 800 mL(STP)·g−1 or less, or 700 mL(STP)·g−1 or less.
Furthermore, the MOF of the present invention also preferably satisfies any one or a combination of two or more of requirements (a) to (f) described below.
(a) Relative Pressure (P/P0) at a Point where the Gradient of an Adsorption-Side Isotherm Curve is Maximum
The relative pressure (P/P0) at the point where the gradient of the adsorption-side isotherm curve is maximum is preferably 0.1 to 0.4. In this case, a large amount of a target material such as water vapor can be adsorbed at low relative pressure. The relative pressure (P/P0) at the point where the gradient of the adsorption-side isotherm curve is maximum is preferably 0.15 or more, and is preferably 0.3 or less.
The adsorption amount ratio L on a side of low relative pressure obtained by the following formula (1) is also preferably 1.3 or more.
Thus, the adsorption amount on the side of low relative pressure can be made larger than that on the side of high relative pressure. The value of the above-described L is preferably 2.0 or more, more preferably 3.0 or more, and further preferably 5.0 or more. The upper limit of the value of L is not particularly limited, and the value of L may be, for example, 9.0 or less, or 8.0 or less.
The adsorption amount at the relative pressure (P/P0) of 0.3 on the adsorption-side isotherm is preferably 200 mL(STP)·g−1 or more, more preferably 300 mL(STP)·g−1 or more, and further preferably 350 mL(STP)·g−1 or more. The upper limit thereof is not particularly limited, and the adsorption amount may be, for example, 800 mL(STP)·g−1 or less, or 700 mL(STP)·g−1 or less.
(d) Amount of Change in the Water Vapor Adsorption Amount in the Section where the Adsorption-Side Isotherm Rises with an Inclination of 1000 mL(STP)·g−1/Relative Pressure (P/P0) or More
The amount of change in the water vapor adsorption amount in the section where the adsorption-side isotherm rises with the inclination of 1000 mL(STP)·g−1/relative pressure (P/P0) or more is a value of the difference between the maximum value and the minimum value of the adsorption amount, in the section where the inclination of the adsorption-side isotherm satisfies the condition of being 1000 mL(STP)·g−1/relative pressure (P/P0) or more. The amount of change is preferably 200 mL(STP)·g−1 or more, more preferably 250 mL(STP)·g−1 or more, and further preferably 350 mL(STP)·g−1 or more. The upper limit thereof is not particularly limited, and the amount of change may be 600 mL(STP)·g−1 or less or 500 mL(STP)·g−1 or less.
The relative pressure hysteresis ΔH obtained by the following formula (2) is preferably within ±0.03.
When the humidity hysteresis ΔH is in the above range, water that has been adsorbed can be efficiently desorbed, and the ratio of a desorption amount to an adsorption amount, as evaluated in Examples described below, can be increased, for example. AH is preferably within ±0.025, more preferably within ±0.02, and even more preferably within ±0.01. AH may be 0.002 or more or −0.002 or less.
The adsorption amount hysteresis ΔA obtained by formula (3) is preferably within ±30 mL(STP)·g−1.
When the adsorption amount hysteresis ΔA is within the above range, same as described above for the humidity hysteresis ΔH, water that has been adsorbed can be efficiently desorbed, and the ratio of the desorption amount to the adsorption amount, as evaluated in Examples described below, can be increased, for example. ΔA is preferably within ±27 mL(STP)·g−1, and more preferably within ±20 mL(STP)·g−1. AA may be 3 mL(STP)·g−1 or more, 5 mL(STP)·g−1 or more, or −3 mL(STP) g−1 or less.
As for the MOF of the present invention, as long as the inclination of the tangent line drawn at the point where the gradient of the curve is maximum is 7000 mL(STP)·g−1/relative pressure (P/P0) or more, and the water vapor adsorption amount at a relative pressure (P/P0) of 0.96 is 440 mL(STP)·g−1 or more on the adsorption-side isotherm of water vapor measured at 25° C., a metal and an organic ligand constituting the MOF are not particularly limited, and examples thereof are as follows.
A metal ion constituting the MOF is preferably an ion of at least one metal selected from elements in groups 2 to 14 in the third to sixth periods in the periodic table. In the present specification, the term “metal” is used to include metalloids such as Si and Ge. The metal ion constituting the MOF is preferably an ion of at least one metal selected from the group consisting of Al, Ga, In, Ti, Zr, Hf, V, Cr, Mn, Fe, Co, Ni, and Cu, and is more preferably an ion of at least one metal selected from the group consisting of Al, Ti, and Cu.
An organic ligand constituting the MOF preferably includes at least one selected from the group consisting of carboxylates (carboxylato) represented by R(COO−)n (R represents an n-valent group, and n represents an integer of 2 or more) and an oxalate ion (COO−)2. R preferably represents an aliphatic chain hydrocarbon group, an aliphatic cyclic hydrocarbon group, an aliphatic heterocyclic hydrocarbon group (group in which one or more carbon atoms of an aliphatic cyclic hydrocarbon group are substituted with heteroatoms), an aromatic hydrocarbon group, or an aromatic heterocyclic hydrocarbon group (group in which one or more carbon atoms of an aromatic hydrocarbon group are substituted with heteroatoms). The aliphatic chain hydrocarbon group may be a linear chain structure or a branched chain structure, and may be a saturated hydrocarbon group or an unsaturated hydrocarbon group. A heteroatom in the aliphatic heterocyclic hydrocarbon group or the aromatic heterocyclic hydrocarbon group is preferably nitrogen.
n is 2 or more, preferably 4 or less, more preferably 2 or more and 3 or less, and most preferably 2.
The above-described aliphatic chain hydrocarbon group, aliphatic cyclic hydrocarbon group, aliphatic heterocyclic hydrocarbon group, aromatic hydrocarbon group, and aromatic heterocyclic hydrocarbon group further include one or more functional groups X selected from the group consisting of a carboxylic acid anhydride group, —OH, —OR1, —NH2, —NHR1, —N(R1)2, —CN, a halogeno group, —C(═S)SH, —C(═O)SH and a tautomer thereof, and —SO3H. Each R1 represents an alkyl group having 1 or 2 carbon atoms. As the above functional group X, —OH or —NH2 is particularly preferable.
Examples of the aromatic heterocyclic hydrocarbon group include pyrazole, imidazole, thiazole, oxazole, pyridine, pyrimidine, pyridazine, pyrazine, and triazine, and pyrazole is particularly preferable.
R preferably represents at least one of an unsaturated linear hydrocarbon group, an aromatic hydrocarbon group, and a hydrocarbon group containing an aromatic ring that includes a nitrogen atom, which may have the above-described functional group X.
The number of carbon atoms of R is preferably 1 or more, and more preferably 2 or more, and is preferably 18 or less, more preferably 12 or less, and further preferably 10 or less.
In particular, the organic ligand constituting the MOF preferably includes at least one selected from the group consisting of carboxylates represented by R(COO−)2 and an oxalate ion (COO−)2, and, specifically, examples thereof include a ligand in which two protons are removed from two carboxyl groups (—COOH) of the following dicarboxylic acid. Examples of the dicarboxylic acid include oxalic acid, succinic acid, fumaric acid, tartaric acid, 1,4-butanedicarboxylic acid, 1,4-butenedicarboxylic acid, 4-oxopyran-2,6-dicarboxylic acid, 1,6-hexanedicarboxylic acid, decanedicarboxylic acid, 1,8-heptadecanedicarboxylic acid, 1,9-heptadecanedicarboxylic acid, heptadecanedicarboxylic acid, acetylenedicarboxylic acid, 1,2-benzene dicarboxylic acid (phthalic acid), 1,3-benzene dicarboxylic acid (isophthalic acid), 2,3-pyridine dicarboxylic acid, 1,3-butadiene-1,4-dicarboxylic acid, 1,4-benzene dicarboxylic acid (terephthalic acid), 2-aminoterephthalic acid, 2,5-dihydroxyterephthalic acid, imidazole-2,4-dicarboxylic acid, 3,5-pyrazole dicarboxylic 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, tetrahydropyran-4,4-dicarboxylic acid, perylene-3,9-dicarboxylic acid, perylene dicarboxylic acid, Pluriol E 200-dicarboxylic acid, 3,6-dioxaoctane dicarboxylic acid, 3,5-cyclohexadiene-1,2-dicarboxylic acid, octane dicarboxylic acid, 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-anilino anthraquinone-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, phenylindan dicarboxylic 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 E 300-dicarboxylic acid, Pluriol E 400-dicarboxylic acid, Pluriol E 600-dicarboxylic acid, pyrazole-3,4-dicarboxylic acid, 2,3-pyrazine dicarboxylic acid, 5,6-dimethyl-2,3-pyrazine dicarboxylic 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-sulfo-2,3-naphthalene dicarboxylic acid, anthracene-2,3-dicarboxylic acid, 2′,3′-diphenyl-p-terphenyl-4,4″-dicarboxylic acid, (diphenyl ether)-4,4′-dicarboxylic acid, imidazole-4,5-dicarboxylic acid, 4(1H)-oxothiochromene-2,8-dicarboxylic acid, 5-tert-butyl-1,3-benzene dicarboxylic acid, 7,8-quinoline dicarboxylic acid, 4,5-imidazole dicarboxylic acid, 4-cyclohexene-1,2-dicarboxylic acid, hexatriacontane dicarboxylic acid, tetradecanedicarboxylic acid, 1,7-heptanedicarboxylic acid, 5-hydroxy-1,3-benzene dicarboxylic acid, 2,5-dihydroxy-1,4-benzene dicarboxylic acid, pyrazine-2,3-dicarboxylic acid, furan-2,5-dicarboxylic acid, 1-nonene-6,9-dicarboxylic acid, eicosene dicarboxylic 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-pyridine dicarboxylic acid, cyclohexene-2,3-dicarboxylic acid, 2,9-dichlorofluorubine-4,11-dicarboxylic acid, 7-chloro-3-methylquinoline-6,8-dicarboxylic acid, 2,4-dichlorobenzophenone-2′,5′-dicarboxylic acid, 1,3-benzene dicarboxylic acid, 2,6-pyridine dicarboxylic acid, 1-methylpyrrole-3,4-dicarboxylic acid, 1-benzyl-1H-pyrrole-3,4-dicarboxylic acid, anthraquinone-1,5-dicarboxylic acid, 3,5-pyrazole dicarboxylic acid, 2-nitrobenzene-1,4-dicarboxylic acid, heptane-1,7-dicarboxylic acid, cyclobutane-1,1-dicarboxylic acid, 1,14-tetradecanedicarboxylic acid, 5,6-dehydronorbornane-2,3-dicarboxylic acid, 5-ethyl-2,3-pyridine dicarboxylic acid, and camphordicarboxylic acid. The dicarboxylic acid is preferably at least one selected from the group consisting of fumaric acid, isophthalic acid, 2-aminoterephthalic acid, 2,5-dihydroxyterephthalic acid, and 3,5-pyrazole dicarboxylic acid.
As the organic ligand constituting the MOF of the present invention, a different type of an organic ligand other than carboxylates represented by R(COO−)n and an oxalate ion (COO−)2 may be further included, and examples of the organic ligand include 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.
In addition, the MOF of the present invention may include an inorganic ligand, and examples of the inorganic ligand include OH− (hydroxide), O2− (oxo), and OH2 (aqua).
The molar ratio of the metal ion to the organic ligand (total amount thereof, in a case of a plurality of kinds of organic ligands) (metal ion/organic ligand) is preferably 0.05 or more, more preferably 0.1 or more, further preferably 0.2 or more, and even more preferably 0.5 or more, and the molar ratio is preferably 10 or less, more preferably 8 or less, and further preferably 5 or less.
In particular, the molar ratio of the metal ion to the total of the carboxylates represented by R(COO−)n and an oxalate ion (COO−)2, among organic ligands, (metal ion/organic ligands) is preferably 0.2 or more, more preferably 0.5 or more, and further preferably 1 or more, and the molar ratio is preferably 15 or less, more preferably 10 or less, and further preferably 8 or less.
The BET specific surface area of the MOF is preferably 495 cm2/g or more, more preferably 600 cm2/g or more, and further preferably 700 cm2/g or more. The upper limit of the BET specific surface area is not particularly limited, and the BET specific surface area is, for example, 2000 cm2/g or less.
Next, a method for producing the MOF of the present invention will be described. The MOF of the present invention can be obtained by reacting, in a solvent, a metal compound containing the metal ion constituting the MOF and one or more kinds of organic compounds for the organic ligands constituting the MOF. In addition, an inorganic compound for the inorganic ligands is also preferably mixed with the solvent together with the metal compound and the organic compounds, as necessary.
The metal compound that contains the metal ion constituting the MOF is preferably metal sulfate, metal acetate, metal chloride, or metal alkoxide.
The organic compound for the organic ligands constituting the MOF is preferably one or more selected from the group consisting of polyvalent carboxylic acids represented by R(COOH)n and oxalic acid. R and n are equivalent to R and n described above for the carboxylates represented by R(COO−)n, and all the above descriptions about R and n, also including preferable aspects thereof, can be referred to.
The organic compound preferably includes dicarboxylic acid. For specific examples of the dicarboxylic acid, the dicarboxylic acids described for the carboxylates represented by R(COO−)n and preferable ranges thereof can be referred to.
As the organic compound for the organic ligands, in addition to one or more selected from the group consisting of the polyvalent carboxylic acids represented by R(COOH)n and oxalic acid, 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 preferably used. In addition, as the above-described inorganic compound for the inorganic ligands, alkali metal hydroxide is preferably used. Furthermore, in some cases, an inorganic ligand such as OH−, O2−, or OH2 derived from the solvent for dissolving the metal compound and the organic compound, water in the air, and the like is included in the MOF.
The solvent is not particularly limited as long as the solvent is capable of dissolving the metal compound, the organic compound for the organic ligands, and the inorganic compound for the inorganic ligands to be used as necessary, and an appropriate solvent can be selected from water and an organic solvent. The solvent is preferably water, an alcohol-based solvent such as methanol, or an amide-based solvent such as dimethylformamide.
The ratio of the metal compound to the solvent (metal compound/solvent) is preferably 0.005 mol/L or more, more preferably 0.01 mol/L or more, and further preferably 0.05 mol/L or more, and the ratio is preferably 5 mol/L or less, more preferably 3 mol/L or less, and further preferably 2 mol/L or less.
The ratio of the organic compound for the organic ligands to the solvent (organic compound/solvent) is preferably 0.001 mol/L or more, more preferably 0.1 mol/L or more, and further preferably 0.2 mol/L or more, and the ratio is preferably 3 mol/L or less, more preferably 2 mol/L or less, and further preferably 1 mol/L or less. The ratio of (the total amount of) the polyvalent carboxylic acids, represented by R(COOH)n and oxalic acid, as a preferable aspect of the organic compound for the organic ligand, to the solvent is preferably 0.001 mol/L or more, more preferably 0.1 mol/L or more, and further preferably 0.2 mol/L or more, and the ratio is preferably 2 mol/L or less, more preferably 1 mol/L or less, and further preferably 0.5 mol/L or less.
The ratio of the inorganic compound for the inorganic ligands to the solvent (inorganic compound/solvent) is preferably 0.01 mol/L or more, and more preferably 0.05 mol/L or more, and the ratio is preferably 3 mol/L or less, more preferably 2 mol/L or less, and further preferably 1 mol/L or less.
The molar ratio between the metal compound and the organic compound may be adjusted such that the ratio of the molar quantity of metal atoms in the metal compound to the molar quantity of the organic compound is equal to the above-described molar ratio of the metal ion to the organic ligand.
In order to obtain the MOF of the present invention, it is important to appropriately adjust, particularly, at least any of: (i) the order of mixing of the metal compound and the organic compound for the organic ligand; (ii) the temperature of stirring or being left as they are, after the metal compound and the organic compound for the organic ligand are mixed; (iii) a post-treatment condition (washing condition) for the reaction product of the metal compound and the organic compound for the organic ligand; and (iv) a drying condition after the washing.
Regarding (i), in mixing of the metal compound and the organic compound for the organic ligand, it is important that the metal compound and the organic compound are completely dissolved. Specifically, it is preferable that one of the metal compound and the organic compound is completely dissolved in the solvent and then the other is added (at this time, it is preferable that the other is also completely dissolved in the solvent), and it is preferable that the metal compound is added and also completely dissolved in a liquid of the organic compound which has been completely dissolved in the solvent, or that a liquid of the metal compound which has been completely dissolved in the solvent is added to a liquid of the organic compound which has been completely dissolved in the solvent.
In the case where the MOF of the present invention further includes, in addition to the metal ion and at least one kind of the organic ligand selected from the group consisting of R(COO−)n and an oxalate ion (COO−)2, a different type of an inorganic ligand and/or an organic ligand other than R(COO−)n and an oxalate ion (COO−)2, it is preferable that the metal compound is added to a liquid including such ligands or that such ligands are added at the same time when the metal compound is added.
Regarding (ii), after the metal compound and the organic compound for the organic ligand are mixed, specifically, the obtained mixture may be stirred and/or left as they are at a temperature from room temperature (for example, 25° C.) to 170° C. for 5 minutes to 40 hours (preferably, 10 to 40 hours).
Regarding (iii), in the post-treatment condition for the reaction product of the metal compound and the organic compound for the organic ligand, specifically, it is preferable that the reaction product is washed (for example, three times or more) with a solvent same as the solvent used during the reaction of the metal compound and the organic compound, and it is also preferable that the washed reaction product is, thereafter, further washed with an alcohol-based solvent.
Regarding (iv), the drying may be performed under reduced pressure at a temperature of 80 to 170° C. for 10 to 100 hours, or in an air atmosphere at a temperature of 25 to 150° C. for 20 to 100 hours. The temperature for drying under reduced pressure is preferably 100 to 170° C., and the time for drying under reduced pressure is preferably 10 to 50 hours, and more preferably 24 to 48 hours.
The temperature and the time may be optionally combined within the above ranges. The MOF of the present invention can be suitably used to adsorb and remove gas or organic molecules, for example. Examples of the gas include carbon dioxide, hydrogen, carbon monoxide, oxygen, nitrogen, hydrocarbon having 1 to 4 carbon atoms, noble gas, hydrogen sulfide, ammonia, sulfur oxide, nitrogen oxide, and siloxane. Examples of the organic molecule include hydrocarbon having 5 to 8 carbon atoms, alcohol having 1 to 8 carbon atoms, aldehyde having 1 to 8 carbon atoms, carboxylic acid having 1 to 8 carbon atoms, ketone having 1 to 8 carbon atoms, amine having 1 to 8 carbon atoms, ester having 1 to 8 carbon atoms, and amide having 1 to 8 carbon atoms. The organic molecule may contain an aromatic ring.
This application claims the benefit of priority based on the Japanese Patent Application No. 2022-042376 filed on Mar. 17, 2022. The entire contents of the Japanese Patent Application No. 2022-042376 filed on Mar. 17, 2022, are incorporated herein by reference.
The present invention will be described in more detail below by means of examples. The present invention. The present invention is not limited by the following examples, and can also be carried out with appropriate modifications being made within the scope of the gist described above and below, and any of these modifications are included in the technical scope of the present invention.
In a 50 mL pressure-resistant container (including a Teflon (registered trademark) inner cylinder) made of SUS-304, 3.000 mmol of 2-aminoterephthalic acid was dissolved in 25 mL of a mixture obtained by mixing DMF and MeOH at a ratio of 1/1 (volume ratio), and 1.518 mmol of Ti[OCH(CH3)2]4 was mixed with the resulting product at 25° C., and the obtained mixture was stirred for 5 minutes by putting in a stirrer chip to completely dissolve. Then, the resulting product was left as it was at 150° C. for 16 hours. The obtained precipitated solid product was subjected to three times of washing with 10 mL of DMF and filtering, and the obtained filter cake was dried in a vacuum drying oven at 120° C. for 24 hours and at 150° C. for 24 hours, to obtain 0.62 g of a product (yield: 89.4%).
In a 20 mL eggplant flask, 3.233 mmol of isophthalic acid was mixed with 2.5 mL of DMF at 25° C. and completely dissolved, to obtain a solution A. Separately, 3.693 mmol of Al2(SO4)3·nH2O (n=14 to 18) and 10 mL of ion-exchanged water were mixed and Al2(SO4)3·nH2O was completely dissolved to prepare a solution B, and the solution B was added dropwise to the solution A at 25° C. over 5 minutes. Then, the resulting solution was refluxed at 125° C. for 24 hours, to obtain a suspension. Decantation was performed on the suspension. The precipitated solid product was separated by centrifugation and washed three times with 10 ml of water. The obtained filter cake was dried in a vacuum drying oven at 80° C. for 24 hours, at 100° C. for 24 hours, and at 120° C. for 48 hours, to obtain 0.66 g of a product (yield: 99%).
In a 100 mL pressure-resistant container (including a Teflon (registered trademark) inner cylinder) made of SUS-304, 6.226 mmol of fumaric acid, 6.402 mmol of urea, and 30.549 mmol of Al2(SO4)3·nH2O (n=14 to 18) were added to 20 ml of ion-exchanged water in this order, and were mixed at 25° C. for 10 minutes, to be completely dissolved. Then, the resulting product was left as it was at 110° C. for 32 hours. The obtained precipitated solid product was subjected to three times of washing with 30 ml of ethanol and filtering, and the obtained filter cake was dried at 25° C. for 72 hours, to obtain 0.91 g of a product (yield: 23%).
In a 100 mL pressure-resistant container (including a Teflon (registered trademark) inner cylinder) made of SUS-304, 4.43 mmol of 3,5-pyrazole dicarboxylic acid monohydrate was mixed with 72 ml of ion-exchanged water and completely dissolved, to obtain a solution A. Separately, 6.580 mmol of LiOH. H2O was mixed with 2.4 ml of ion-exchanged water, and was completely dissolved by applying ultrasonic waves at 50° C., to obtain a solution B. The solution B was added to the solution A, and 4.333 mmol of AlCl3·6H2O and 53.017 mmol of pyrazine were further added in this order, and were mixed at 25° C. for 5 minutes. Then, the resulting product was left as it was at 100° C. for 15 hours. The obtained precipitated solid product was subjected to three times of washing with ion-exchanged water and filtering (60 ml of ion-exchanged water was used for washing in total), and was further subjected to three times of washing with methanol and filtering (60 ml of methanol was used for washing in total). The obtained filter cake was dried in a vacuum drying oven at 100° C. for 24 hours, to obtain 0.52 g of a product (yield: 41.8%).
In a 20 mL eggplant flask, 2.123 mmol of fumaric acid and 6.39 mmol of NaOH were mixed with 3 ml of ion-exchanged water, to obtain a solution A in which the fumaric acid and NaOH were completely dissolved. Separately, 1.064 mmol of Al2(SO4)3·18H2O was mixed with 3.61 ml of ion-exchanged water and completely dissolved, to obtain a solution B. The solution B was added to the solution A at 60° C. over 25 minutes, and the resulting solution was stirred at 60° C. for 5 minutes. The obtained precipitated solid product was subjected to three times of washing with ion-exchanged water and filtering (50 ml of ion-exchanged water was used for washing in total), and the obtained filter cake was dried in an oven in air at 100° C. for 24 hours and at 130° C. for 24 hours, to obtain 0.14 g of a product (yield: 99%).
In a 200 mL eggplant flask, 2.071 mmol of Cu(OAc)2·H2O was mixed with 168 ml of methanol and completely dissolved, to obtain a solution A. Separately, 1.014 mmol of 2,5-dihydroxyterephthalic acid was mixed with 16.8 ml of methanol and completely dissolved, to obtain a solution B. The solution B was added to the solution A at 25° C. over 60 minutes, and the resulting solution was stirred at 25° C. to 30° C. for 12 hours. The obtained precipitated solid product was separated by centrifugation, and then was washed five times with 15 ml of methanol, and the obtained cake was dried in a vacuum drying oven at 120° C. for 24 hours, to obtain 0.30 g of a product (yield: 92.1%).
In a 50 mL pressure-resistant container (including a Teflon (registered trademark) inner cylinder) made of SUS-304, 1.058 mmol of InCl3 and 8 ml of DMF were mixed, 2.081 mmol of terephthalic acid was added thereinto, and the resulting mixture was stirred at 25° C. for 8 hours to form a gel. Then, the resulting mixture was left as it was at 160° C. for 3 days. The obtained solid product was separated by centrifugation, and then was washed five times with 15 ml of methanol, and the obtained cake was dried in a vacuum drying oven at 120° C. for 24 hours, to obtain 0.46 g of a product (yield: 99%).
In a 100 mL pressure-resistant container (including a Teflon (registered trademark) inner cylinder) made of SUS-304, 0.5 mmol of terephthalic acid, 3.691 mmol of Al(NO3)3·9H2O, and 40.2 ml of methanol were mixed, 1.8 ml of a 2 M solution of NaOH in methanol was added thereinto at room temperature, and the resulting mixture was mixed at 25° C. for 5 minutes. Then, the resulting mixture was left as it was at 125° C. for 20 hours. The obtained precipitated solid product was subjected to three times of washing with 30 ml of methanol and filtering, and the obtained filter cake was dried at room temperature for 72 hours, to obtain 0.17 g of a product (yield: 99%).
The substances obtained in Examples and Comparative Examples were evaluated by the following methods.
Device: TG-DTA manufactured by Rigaku Corporation
Pre-treatment condition: each substance was held at 25° C. for 12 hours under an air atmosphere in which the humidity was adjusted so that the relative pressure was 0.5.
Desorbed amount: after the above pre-treatment, the temperature was increased at a heating rate of 5° C./min. while nitrogen was caused to flow, and the substance was held at 50° C. for 30 minutes. A weight reduction amount W25-50 in this range (25 to 50° C.) was measured and W25-50 was defined as a desorption amount.
After the desorption amount was measured, the temperature was further increased at a heating rate of 5° C./min. while nitrogen was caused to flow at 25° C. at a relative pressure of 0.5, and the substance was held at 200° C. for 1 hour. A weight reduction amount W50-200 in this range (50 to 200° C.) was measured, and the total of the amount W25-50 and the amount W50-200 was defined as an adsorption amount.
The ratio (%) of the desorption amount to the adsorption amount as measured according to the above procedure was obtained.
Measurement device: BELSORP-max manufactured by MicrotracBEL
Since the adsorption occupation area of nitrogen molecules is known in advance, the amount of gas molecules adsorbed on only the surface of the sample was measured, and the surface area of the sample was measured according to a BET adsorption isotherm.
Pre-treatment condition: according to the measurement results from TG-DTA described above, the temperature at which water contained in the sample was able to be removed was checked, and heating under reduced pressure was performed overnight.
Device: BELSORP-mini manufactured by MicrotracBEL
Pre-treatment condition: (i) A glass bar (for a standard sample tube) for reducing the volume was set in a standard sample tube, and the standard sample tube was sealed with a quick seal. The above sample-tube sets, the number of which corresponded to the number of samples to be measured (a maximum of 3 samples per measurement), were prepared and connected to a pre-treatment device (BELPREP VACII). The air inside the sample tube was discharged, and then N2 gas (having a purity of 99.999% or more) was introduced therein until the pressure reached atmospheric pressure;
The sample tube was removed from the device;
With respect to Examples and Comparative Examples, the inclination of a tangent line drawn at a point where the gradient of a curve is maximum, a relative pressure at the point where the gradient is maximum, water vapor adsorption amounts at relative pressures of 0.3 and 0.96, an adsorption amount ratio L on a side of low relative pressure, and the amount of change in the water vapor adsorption amount in the section where an adsorption-side isotherm rises with an inclination of 1000 mL(STP)·g−1/relative pressure (P/P0) or more, each of which is determined by adsorption and desorption isotherms of water vapor, as well as the results of the above-described (1) and (3), are shown in Table 1. Each organic ligand in Table 1 is indicated by the name of carboxylic acid in a state before protons are removed from carboxyl groups. In addition, the adsorption-side isotherms of Example 1 and Comparative Example 2 are respectively shown in
| Number | Date | Country | Kind |
|---|---|---|---|
| 2022-042376 | Mar 2022 | JP | national |
| Filing Document | Filing Date | Country | Kind |
|---|---|---|---|
| PCT/JP2023/010263 | 3/16/2023 | WO |
