WO2024095862A1 - 金属有機構造体 - Google Patents

金属有機構造体 Download PDF

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Publication number
WO2024095862A1
WO2024095862A1 PCT/JP2023/038534 JP2023038534W WO2024095862A1 WO 2024095862 A1 WO2024095862 A1 WO 2024095862A1 JP 2023038534 W JP2023038534 W JP 2023038534W WO 2024095862 A1 WO2024095862 A1 WO 2024095862A1
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Prior art keywords
hole
cross
section
pmax
maximum
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English (en)
French (fr)
Japanese (ja)
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進 北川
雅一 樋口
研一 大竹
悠太 菊地
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Sumitomo Chemical Co Ltd
Kyoto University NUC
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Sumitomo Chemical Co Ltd
Kyoto University NUC
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Priority to EP23885619.9A priority Critical patent/EP4613733A1/en
Priority to CN202380076085.9A priority patent/CN120129673A/zh
Priority to JP2024554436A priority patent/JPWO2024095862A1/ja
Publication of WO2024095862A1 publication Critical patent/WO2024095862A1/ja
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C229/00—Compounds containing amino and carboxyl groups bound to the same carbon skeleton
    • C07C229/52—Compounds containing amino and carboxyl groups bound to the same carbon skeleton having amino and carboxyl groups bound to carbon atoms of six-membered aromatic rings of the same carbon skeleton
    • C07C229/54—Compounds containing amino and carboxyl groups bound to the same carbon skeleton having amino and carboxyl groups bound to carbon atoms of six-membered aromatic rings of the same carbon skeleton with amino and carboxyl groups bound to carbon atoms of the same non-condensed six-membered aromatic ring
    • C07C229/62—Compounds containing amino and carboxyl groups bound to the same carbon skeleton having amino and carboxyl groups bound to carbon atoms of six-membered aromatic rings of the same carbon skeleton with amino and carboxyl groups bound to carbon atoms of the same non-condensed six-membered aromatic ring with amino groups and at least two carboxyl groups bound to carbon atoms of the same six-membered aromatic ring
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    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C323/00—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups
    • C07C323/50—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and carboxyl groups bound to the same carbon skeleton
    • C07C323/62—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and carboxyl groups bound to the same carbon skeleton having the sulfur atom of at least one of the thio groups bound to a carbon atom of a six-membered aromatic ring of the carbon skeleton
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    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
    • C07C51/41—Preparation of salts of carboxylic acids
    • C07C51/418—Preparation of metal complexes containing carboxylic acid moieties
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    • C07C63/14—Monocyclic dicarboxylic acids
    • C07C63/15—Monocyclic dicarboxylic acids all carboxyl groups bound to carbon atoms of the six-membered aromatic ring
    • C07C63/24—1,3 - Benzenedicarboxylic acid
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    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D207/00—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom
    • C07D207/02—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom
    • C07D207/30—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having two double bonds between ring members or between ring members and non-ring members
    • C07D207/34—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having two double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
    • C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
    • C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
    • C07D213/06—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom containing only hydrogen and carbon atoms in addition to the ring nitrogen atom
    • C07D213/22—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom containing only hydrogen and carbon atoms in addition to the ring nitrogen atom containing two or more pyridine rings directly linked together, e.g. bipyridyl
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    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
    • C07D307/02—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings
    • C07D307/34—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
    • C07D307/56—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D307/68—Carbon atoms having three bonds to hetero atoms with at the most one bond to halogen
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    • C07F15/00—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table
    • C07F15/06—Cobalt compounds
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    • C07F3/00—Compounds containing elements of Groups 2 or 12 of the Periodic Table
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    • C07F5/00—Compounds containing elements of Groups 3 or 13 of the Periodic Table
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    • C07F5/00—Compounds containing elements of Groups 3 or 13 of the Periodic Table
    • C07F5/06—Aluminium compounds
    • C—CHEMISTRY; METALLURGY
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    • C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
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    • C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
    • C07F7/28—Titanium compounds
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02C—CAPTURE, STORAGE, SEQUESTRATION OR DISPOSAL OF GREENHOUSE GASES [GHG]
    • Y02C20/00—Capture or disposal of greenhouse gases
    • Y02C20/40—Capture or disposal of greenhouse gases of CO2

Definitions

  • the present invention relates to a metal-organic framework.
  • Metal organic frameworks also known as porous coordination polymers, are a type of material that form porous structures through coordination bonds between metal ions and organic ligands, and are expected to be used for gas adsorption/desorption, catalysis, etc.
  • Patent Document 1 discloses a metal organic structure including a metal ion, a first ligand, a second ligand, and an optional third ligand, in which the metal ion is an aluminum ion, the first and second ligands are organic compound ions consisting of a heterocycle having two carboxy groups, the angle between the heteroatom and the carboxy group satisfies a specified condition, the third ligand is an organic compound ion having two carboxy groups, and the abundance ratio of the first to third ligands is within a specified range.
  • MOFs Metal-organic frameworks
  • adsorbing substances such as water, carbon dioxide, and hydrogen
  • a specified temperature to desorb the adsorbed substances from the MOF.
  • the present invention aims to provide an MOF with excellent desorption performance.
  • the organic ligand comprises at least one organic ligand represented by the formula R(COO-) n , where R is an aromatic hydrocarbon group or pyrrole, and may have a functional group X which is -OH, -NH2 or -S-S-, and n is 2 or more and 3 or less;
  • the metal organic structure, wherein the metal ion is an ion of at least one metal selected from the group consisting of Al, Ga, In, Ti, V, Cr, Mn, Fe, Co, Cu, Zr, and Hf.
  • the cross section ab is a cut surface of the through hole Pmax in a surface parallel to the a-b surface of the unit lattice, and is a surface cut with the through hole Pmax penetrating through, and when there are a plurality of cross sections through which the through hole Pmax can be cut out in a penetrating state, the cross section with the largest overlap with the through hole Pmax is called the cross section ab.
  • the cross section ab is replaced with the cross section bc and the a-b surface is replaced with the bc surface to obtain the cross section bc
  • the cross section ab is replaced with the cross section ca and the a-b surface is replaced with the c-a surface to obtain the cross section ca.
  • the present invention can improve the desorption performance of MOFs.
  • FIG. 1 shows an example of the crystal structure of the MOF of Example 3, displayed as a space-filling model, observed from one direction.
  • FIG. 13 is an example of the crystal structure of the MOF of Example 3 displayed as a space-filling model, observed from a different direction.
  • FIG. 13 is an example of the crystal structure of the MOF of Example 3 displayed as a space-filling model, observed from yet another direction.
  • FIG. 1 is a diagram showing the maximum hole diameter L and the minimum hole diameter S of a through hole Pmax .
  • the MOF of the present invention is composed of organic ligands and metal ions, has a porosity of 20-75%, and has a ratio of maximum pore size L to minimum pore size S (maximum pore size L/minimum pore size S) determined by a specified procedure of 1.06 or more.
  • maximum pore size L/minimum pore size S determined by a specified procedure of 1.06 or more.
  • the porosity of the MOF of the present invention is 20 to 75%, preferably 25% or more, more preferably 30% or more, even more preferably 40% or more, and is preferably 70% or less, more preferably 65% or less, even more preferably 60% or less. From the viewpoint of increasing the desorption amount, the porosity may be 30% or more and 45% or less.
  • the porosity can be obtained by measuring the MOF of the present invention by XRD (X-ray diffraction), obtaining a cif (Crystallo- graphic Information File) file, reading it into software called Mercury (The Cambridge Crystallographic Data Centre), and based on the obtained information, inputting a probe radius of 1.5 ⁇ and an approximate grid spacing of 0.7 ⁇ for the void contact surface.
  • XRD X-ray diffraction
  • Mercury The Cambridge Crystallographic Data Centre
  • Ratio of maximum pore diameter L to minimum pore diameter S (maximum pore diameter L/minimum pore diameter S)
  • the ratio of maximum pore size L/minimum pore size S is 1.06 or more, preferably 1.09 or more, more preferably 1.11 or more, even more preferably 1.17 or more, and most preferably 2. It is preferably 0 or more and 4.0 or less, more preferably 3.5 or less, and further preferably 3.0 or less.
  • the maximum pore size L/minimum pore size S is determined by the following steps (a1) to (a3).
  • a crystal structure determined by X-ray crystal structure analysis is displayed as a space-filling model, the outer periphery of the through hole is displayed without being missing, the presence or absence of a through hole is observed from all directions, and the through hole Pmax with the maximum diameter of the inscribed circle is identified.
  • X-ray crystal structure analysis is performed by XRD measurement to obtain a cif file, and when the cif file is read into the Mercury, a single space-filling model (crystal structure) is obtained.
  • Figures 1 to 3 show the state when the obtained crystal structure is rotated and the through hole is observed from a predetermined direction.
  • Figure 3 shows an inscribed circle 11 when the through hole is observed from the direction shown in Figure 3, and such an inscribed circle is identified for all the through holes observed from each direction, and the through hole Pmax with the largest diameter of the inscribed circle among all the observed through holes is identified.
  • the cross section ab is a cut surface of the through hole Pmax in a plane parallel to the a-b plane of the unit lattice, and is a plane cut with the through hole Pmax penetrating through.
  • the cross section bc is a cross section obtained by replacing the cross section ab with the cross section bc and replacing the ab plane with the bc plane in the above-mentioned cross section ab.
  • the cross section ca is a cross section obtained by replacing the cross section ab with the cross section ca and the ab plane with the ca plane. The observation regions in these cross sections ab, bc, and ca follow the observation regions in step (a1).
  • the maximum length of the inner diameter of the through hole Pmax cut along a line perpendicular to the central axis of the through hole Pmax is found, and the maximum of the maximum lengths of the cross sections ab, bc, and ca is defined as the maximum hole diameter L of the through hole Pmax .
  • the minimum length of the inner diameter of the through hole Pmax cut along a line perpendicular to the central axis of the through hole Pmax is defined as the minimum hole diameter S.
  • FIG. 4 shows a cross section 21 (any of cross sections ab, bc, or ca) on which the maximum hole diameter L25 of the through hole P max 22 was determined.
  • 23a and 23b are the outer periphery of the through hole P max 22, and 24 is the central axis of the through hole P max 22.
  • 26 which is the minimum length of the inner diameter of the through hole P max 22 cut by a line perpendicular to the central axis 24 of the through hole P max 22, is the minimum hole diameter S.
  • maximum pore size L/minimum pore size S determined in this way being 1.06 or more means that the shape of the through-hole is tortuous, and the surface area inside the through-hole is large, which is thought to make it easier for substances such as water, carbon dioxide, and hydrogen to be adsorbed.
  • the values of the maximum pore diameter L and the minimum pore diameter S are not limited as long as the maximum pore diameter L/minimum pore diameter S is 1.06 or more, but the maximum pore diameter L is, for example, 2.5 to 20 ⁇ , and the minimum pore diameter S is, for example, 1.5 to 15 ⁇ .
  • the metal ions constituting the MOF are ions of at least one metal selected from the group consisting of Al, Ga, In, Ti, V, Cr, Mn, Fe, Co, Cu, Zr and Hf, preferably at least one metal ion selected from the group consisting of Al, Ga, In, Ti, V, Co, Zr and Hf, more preferably at least one metal ion selected from the group consisting of Al, Ga, In, Ti, V, Zr and Hf, even more preferably at least one metal ion selected from the group consisting of Al, In and Ti, and particularly preferably Al ions, or In and/or Ti ions.
  • the organic ligands constituting the MOF include at least one organic ligand which is a group (carboxylate) represented by R(COO ⁇ ) n , where R is an aromatic hydrocarbon group or pyrrole, and which may have a functional group X which is —OH, —NH2 or —S—S—, and n is 2 or more and 3 or less.
  • R is an aromatic hydrocarbon group or pyrrole
  • Preferred ranges of the number of carbon atoms in the aromatic hydrocarbon group are, in order, 6 or more and 30 or less, 6 or more and 24 or less, 6 or more and 18 or less, 6 or more and 12 or less, and 6 or more and 10 or less.
  • Specific examples include groups in which n hydrogen atoms (preferably 2 or 3) have been removed from benzene or biphenyl and which may contain a functional group X (particularly -OH, -NH2 or -S-S-).
  • R(COO ⁇ ) n is a compound in which n protons have been eliminated from R(COOH) n .
  • the dicarboxylic acid is preferably at least one selected from the group consisting of isophthalic acid, 1H-pyrrole-2,5-dicarboxylic acid, terephthalic acid, 2-aminoterephthalic acid, 2,2'-dithiodibenzoic acid, and 4,4'-dihydroxybiphenyl-3,3'-dicarboxylic acid.
  • R(COOH) n those where n is 3, i.e., tricarboxylic acids, include trimellitic acid, trimesic acid (benzene tricarboxylate), biphenyl-3,4',5-tricarboxylic acid, 1,3,5-tris(4-carboxyphenyl)benzene, etc., of which trimellitic acid, benzene tricarboxylate, or 1,3,5-tris(4-carboxyphenyl)benzene is preferred, and benzene tricarboxylate is particularly preferred.
  • R is any one of the following (A-1) to (A-10).
  • At least one of the hydrogen atoms bonded to the carbon atom may be substituted with -OH or -NH2 , and -X- represents -S-S- or a single bond.
  • the organic ligand constituting the MOF of the present invention may further contain an organic ligand of a type different from the carboxylate represented by R(COO ⁇ ) n described above.
  • 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, pteridine, 2,2′-bipyridine, and 4,4′-bipyridine, with 4,4′-bipyridine being particularly preferred.
  • the molar ratio of metal ions to organic ligands (total amount when multiple types are used) (metal ions/organic ligands) is preferably 0.1 or more, more preferably 0.3 or more, even more preferably 0.5 or more, particularly preferably 0.9 or more, and preferably 5 or less, more preferably 4 or less, even more preferably 3 or less, particularly preferably 2.5 or less.
  • the molar ratio is particularly preferably 0.9 or more and 4 or less, and most preferably 0.9 or more and 2.5 or less.
  • the MOF of the present invention can be obtained by reacting a metal compound containing the metal ions constituting the MOF with one or more organic compounds that serve as organic ligands constituting the MOF in a solvent.
  • a metal compound containing the metal ions constituting the MOF with one or more organic compounds that serve as organic ligands constituting the MOF in a solvent.
  • solution A in which either a metal compound containing metal ions or an organic compound serving as an organic ligand is completely dissolved in a solvent, and then drip the other (it is also preferable to drip solution B in which the other is also dissolved in a solvent).
  • solution X in which both a metal compound containing metal ions and an organic compound serving as an organic ligand are completely dissolved in a solvent, and drip a metal compound or organic compound of a different kind from the metal compound and organic compound in solution X, or drip solution Y in which a metal compound or organic compound of a different kind from the metal compound and organic compound in solution X is completely dissolved in a solvent.
  • the temperature of the dripping is preferably room temperature (specifically, about 20 to 30°C). It is also preferable to drip the amount of the metal compound or organic compound to be dripped so that it is 1.0 mmol/min or less.
  • the dripping speed is preferably 0.8 mmol/min or less, and may be 0.01 mmol/min or more, preferably 0.1 mmol/min or more, and more preferably 0.3 mmol/min or more. In particular, it is preferable to drop a metal compound or a liquid in which a metal compound is dissolved in a solvent into a liquid in which an organic compound is dissolved in a solvent, and it is even more preferable to drop the metal compound at the above-mentioned dropping speed.
  • the metal compound containing the metal ion that constitutes the MOF is preferably a metal sulfate, nitrate, acetate, chloride, bromide or alkoxide.
  • the organic compound serving as the organic ligand constituting the MOF preferably contains one or more selected from the group consisting of polyvalent carboxylic acids represented by R(COOH) n .
  • R and n are the same as R and n in the carboxylate represented by R(COO ⁇ ) n described above, and all of the above descriptions of R and n, including preferred embodiments, can be referred to.
  • the organic compound serving as the organic ligand preferably contains a dicarboxylic acid or a tricarboxylic acid, and specific examples thereof, including preferred ranges thereof, can be referenced to the dicarboxylic acids or tricarboxylic acids described in the carboxylate represented by R(COO ⁇ ) n .
  • the organic compound to be the organic ligand in addition to one or more selected from the group consisting of polyvalent carboxylic acids represented by R(COOH) n , it is preferable to use at least one selected from the group consisting of urea, pyrazine, oxazole, isoxazole, thiazole, imidazole, pyrazole, 1,2,3-thiadiazole, pyridazine, pyrimidine, purine, pteridine, 2,2'-bipyridine, and 4,4'-bipyridine.
  • an alkali metal hydroxide or an alkali metal azide as the inorganic compound to be the inorganic ligand.
  • the MOF may contain an inorganic ligand that is OH - , O 2- , or OH 2 due to the solvent that dissolves the metal compound or organic compound, moisture in the air, or the like.
  • the solvent for dissolving the metal compound containing the metal ion or the organic compound that serves as the organic ligand is preferably water; an alcohol solvent such as methanol or ethanol; or an amide solvent such as dimethylformamide, and one of these may be used alone or two or more of them may be mixed together.
  • the ratio of the metal compound to the solvent in these solutions is preferably 0.01 mol/L or more, more preferably 0.1 mol/L or more, even more preferably 0.18 mol/L or more, and preferably 1 mol/L or less, more preferably 0.7 mol/L or less, even more preferably 0.5 mol/L or less, and particularly preferably 0.370 mol/L or less.
  • the ratio is particularly preferably 0.18 mol/L or more and 0.5 mol/L or less, and most preferably 0.18 mol/L or more and 0.370 mol/L or less.
  • the ratio of the organic compound to the solvent in each of these solutions is preferably 0.01 mol/L or more, more preferably 0.1 mol/L or more, even more preferably 0.2 mol/L or more, and is preferably 1.5 mol/L or less, more preferably 1 mol/L or less, even more preferably 0.7 mol/L or less.
  • the ratio of the inorganic compound to the solvent in each of these solutions is preferably 0.05 mol/L or more and 1 mol/L or less.
  • the molar ratio of the metal compound containing the metal ion to the organic compound that serves as the organic ligand can be adjusted so that the ratio of the molar amount of the metal atom in the metal compound to the molar amount of the organic compound is equal to the molar ratio of the metal ion to the organic ligand described above.
  • DMF dimethylformamide
  • solution A the ratio of isophthalic acid to the solvent was 1.29 mol/L
  • solution B the ratio of Al 2 (SO 4 ) 3.nH 2 O to the solvent was 0.369 mol/L, and the drop rate of Al 2 (SO 4 ) 3.nH 2 O was 0.739 mmol/min.
  • the mixture was then refluxed at 125° C. for 24 hours to obtain a suspension. This was decanted, and the precipitated solid was washed three times with 10 ml of water by centrifugation, and the obtained filter cake was dried in a vacuum drying oven at 80°C for 24 hours, 100°C for 24 hours and 120°C for 48 hours to obtain 0.66 g of a product (yield 99%).
  • Example 3 In a 50 mL SUS-304 pressure vessel (including a Teflon (registered trademark) inner cylinder), 3.000 mmol of 2-aminoterephthalic acid was completely dissolved in 25 mL of a 1/1 (volume ratio) mixture of dimethylformamide (DMF) and MeOH to obtain solution A. 1.518 mmol of Ti[OCH(CH 3 ) 2 ] 4 was added dropwise to the solution at 25° C. over 20 minutes, and the solution was stirred for 5 minutes with a stirrer chip inserted. In solution A, the ratio of 2-aminoterephthalic acid to the solvent was 0.12 mol/L, and the drop rate of Ti[OCH(CH 3 ) 2 ] 4 was 0.0759 mmol/min.
  • SUS-304 pressure vessel including a Teflon (registered trademark) inner cylinder
  • Example 4 In a 50 mL vial, 5 ml of DMF was added to 2.496 mmol of terephthalic acid, and the mixture was stirred with a stirrer chip to completely dissolve the acid, obtaining solution A. Separately, 5 ml of dimethylformamide (DMF) was added to 2.654 mmol of indium nitrate (III) hydrate, and then 2 ml of ethanol was added and the mixture was completely dissolved with a stirrer chip to obtain solution B. Solution B was added dropwise to solution A over 20 minutes and stirred for 20 minutes.
  • DMF dimethylformamide
  • III indium nitrate
  • Example 5 In a 1L eggplant flask, 3.05 mmol of cobalt(II) chloride hexahydrate, 10.42 mmol of 2,2'-dithiodibenzoic acid, 10.40 mmol of sodium azide, and 150 mL of DMF were mixed at 25°C and completely dissolved to obtain solution A. Separately, 3.08 mmol of benzene tricarboxylate, 3.10 mmol of 4,4'-bipyridine, and 150 mL of ethanol were mixed and completely dissolved to prepare solution B, which was then added dropwise to solution A at 25°C over 3 hours.
  • Example 6 In a 100 mL SUS-304 pressure vessel (including a Teflon (registered trademark) inner cylinder), 7.483 mmol of terephthalic acid was completely dissolved in 25 mL of a mixture of dimethylformamide (DMF) and MeOH at a ratio of 9/1 (volume ratio) to obtain solution A. This solution A was added dropwise to 4.523 mmol of Ti[OCH(CH 3 ) 2 ] 4 at 25 ° C. over 30 minutes, mixed, and stirred for 5 minutes with a stirrer tip. In solution A, the ratio of terephthalic acid to the solvent was 0.299 mol / L, and the dropping rate of terephthalic acid was 0.249 mmol / min.
  • DMF dimethylformamide
  • the obtained precipitated solid was washed and filtered three times with 30 mL of DMF and three times with 30 mL of methanol, and the obtained filter cake was dried under reduced pressure at 80° C. for 24 hours in a vacuum drying oven to obtain 0.65 g of the product (yield 48.2%).
  • solution A the ratio of 2,5-furandicarboxylic acid to the solvent was 0.336 mol/L
  • solution B the ratio of AlCl 3 ⁇ 6H 2 O to the solvent was 0.504 mol/L, and the drop rate of AlCl 3 ⁇ 6H 2 O was 0.168 mmol/min.
  • the mixture was then refluxed at 25° C. for 18 hours to obtain a suspension.
  • the obtained precipitated solid was centrifuged and washed three times with 50 mL of water, and the obtained cake was dried in a vacuum drying oven at 80° C. for 24 hours to obtain a product.
  • the MOF of the present invention is suitable for use in, for example, adsorption and removal of gases and organic molecules.
  • gases include water (water vapor), carbon dioxide, hydrogen, carbon monoxide, oxygen, nitrogen, hydrocarbons with 1 to 4 carbon atoms, rare gases, hydrogen sulfide, ammonia, sulfur oxides, nitrogen oxides, and siloxanes.
  • organic molecules examples 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.
  • the organic molecules may contain aromatic rings.

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