WO2015177511A1 - Procédé de préparation d'une structure métallo-organique - Google Patents

Procédé de préparation d'une structure métallo-organique Download PDF

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Publication number
WO2015177511A1
WO2015177511A1 PCT/GB2015/051383 GB2015051383W WO2015177511A1 WO 2015177511 A1 WO2015177511 A1 WO 2015177511A1 GB 2015051383 W GB2015051383 W GB 2015051383W WO 2015177511 A1 WO2015177511 A1 WO 2015177511A1
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Prior art keywords
metal ions
acid
metal
carboxylic acid
iii
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PCT/GB2015/051383
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English (en)
Inventor
Hong-cai ZHOU
Dawei Feng
Kecheng Wang
Jian Tian
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The Texas A&M University System
JASON, Ornstein
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Publication of WO2015177511A1 publication Critical patent/WO2015177511A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D487/00—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 - C07D477/00
    • C07D487/22—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 - C07D477/00 in which the condensed system contains four or more hetero rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F15/00—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table
    • C07F15/02—Iron compounds
    • C07F15/025—Iron compounds without a metal-carbon linkage
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
    • C07F7/003—Compounds containing elements of Groups 4 or 14 of the Periodic Table without C-Metal linkages
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
    • C07F7/02—Silicon compounds
    • C07F7/08—Compounds having one or more C—Si linkages
    • C07F7/0803—Compounds with Si-C or Si-Si linkages
    • C07F7/081—Compounds with Si-C or Si-Si linkages comprising at least one atom selected from the elements N, O, halogen, S, Se or Te

Definitions

  • the invention relates to methods of preparing metal organic frameworks, in particular to methods of preparing monocrystalline metal organic frameworks as well as metal organic frameworks obtained/obtainable from such methods.
  • US 8,431,744 B2 describes a solvent-free process for preparing a magnesium-based porous metal organic framework starting from magnesium metal or magnesium oxide.
  • US 8,524,932 B2 describes a process for preparing a porous metal organic framework in which the reaction is carried out in an alkaline aqueous medium. Nevertheless, there remains a need for alternative methods of preparing metal organic frameworks as well as methods that provide advantages over the prior art.
  • the invention provides a method of preparing a metal organic framework comprising metal ions and carboxylate ligands
  • the method comprises:
  • the method of the invention is more economical, and allows recycling of the solvents employed and therefore reduces solvent waste.
  • the method of the invention also provides a way of preparing metal organic frameworks in monocrystalline form.
  • the method of the invention employs carboxylic acid solvents, such as acetic acid.
  • the method of the invention employs one or more carboxylic acids in the absence of other organic solvents.
  • Previous methods for preparing metal organic frameworks have employed organic solvents such as DMF.
  • organic solvents that are not carboxylic acid solvents, such as DMF are not employed in the method of the present invention.
  • the inventors have surprisingly found that in the absence of other organic solvents, the carboxylic acid solvents employed in the method of the invention can be recycled/re-used.
  • carboxylic acid solvents such as acetic acid
  • the use of carboxylic acid solvents, such as acetic acid provides a method delivering unexpected performance with regard to other aspects of the method, e.g. yield, purity, crystallinity.
  • the method employs an organic solvent consisting of one or more carboxylic acid solvents, the organic solvent is essentially free of other organic solvents that are not carboxylic acid solvents.
  • the carboxylic acid solvent may be any carboxylic acid solvent.
  • the one or more carboxylic acid solvents may be selected from a substituted or unsubstituted Ci -4 carboxylic acid.
  • suitable carboxylic acid solvents include, but are not limited to, acetic acid, formic acid, propionic acid, and trifluroacetic acid.
  • Preferred carboxylic acids are formic acid and acetic acid. Particularly preferred is acetic acid.
  • the reaction maybe carried out in the presence of water.
  • the volume ratio of carboxylic acid solvent to water maybe greater than or equal to 1:5.
  • the volume ratio of carboxylic acid solvent to water may range from about 99:1 to about 1:5, from about 50:1 to about 1:3, from about 20:1 to about 1:2, from about 10:1 to about 1:1, from about 5:1 to about 1:1, or from about 2:1 to about 1:1.
  • the volume ratio of carboxylic acid solvent to water is about 1:1.
  • the metal ions which are part of the metal organic framework are derived from the source of metal ions.
  • the metal ions may comprise metal ions selected from the transition metals of the periodic table, such as selected from Fe, Al, Cr, V, Sc, Zr, Ti, Ga and In metal ions.
  • the metal ions may be selected from Fe, Al, Zr, and Ti.
  • the metal ions comprise Fe or Zr metal ions.
  • the metal ions comprise only one metal.
  • the metal ions may be Fe, Al, Zr, or Ti.
  • the metal ions further comprise metal ions selected from Group 2 through Group 16 metal ions.
  • the metal ions may comprise a metal cation mixture of M metal ions and X metal ions; wherein M is a transition metal ion, and X is selected from the group consisting of Group 2 through Group 16 metal ions.
  • M may be selected from Fe, Al, Cr, V, Sc, Ti, Zr and In metal ions.
  • X may be a metal ion selected from Al, Fe, Co, Ni, Mn, Zn, Mg, Cr, V, Sc, Ca, Ba, and In metal ions. More specifically, X may be selected from Al(III), Fe(II), Fe(III), Co(II), Ni(II), Mn(II), Zn(II), Mg(II), Cr(III), V(III), Sc(III), Ca(II), Ba(II) and In(III) metal ions, preferably X is a metal ion selected from Fe(II), Fe(III), Co(II), Ni(II), Mn(II), Zn(II), and Mg(II) metal ions.
  • the metal ions comprise a metal cation mixture of formula M 2 X.
  • the method provides a metal organic framework comprising Fe 3+ ions and carboxylate ligands.
  • the metal organic framework may include only Fe 3+ ions or may include a metal cation mixture of Fe 3+ and X 2+ ions; wherein X is a metal ion selected from the group consisting of Group 2 through Group 16 metals.
  • X may be a metal ion selected from Al(III), Fe(II,III), Co(II), Ni(II), Mn(II), Zn(II), Mg(II), Cr(III), V(III), Sc(III), Ca(II), Ba(II) or In(III), preferably X is a metal ion selected from Fe(II,III), Co(II), Ni(II), Mn(II), Zn(II), and Mg(II).
  • the metal ions may comprise M 2+ metal ions, M 3+ metal ions, or M 4+ metal ions.
  • the source of metal ions may be in the form of a metal salt, a metal ion coordination complex, or a hydrate thereof.
  • Suitable metal salts include but are not limited to a salt selected from a halide salt (e.g. a chloride salt), a nitrate salt (e.g. N0 3 ), acetate salts, sulphate salts or hydrates of the same.
  • the metal salt may be an iron salt such as an iron nitrate, an iron halide, or a hydrate thereof.
  • metal salts include but are not limited to FeCl 3 , Fe(N0 3 ) 3 .9H 2 0, A1C1 3 , A1(N0 3 ) 3 , ZrCl 4 and VC1 3 .
  • a preferred metal salt is Fe(N0 3 ) 3 .9H 2 0.
  • Suitable metal ion coordination complexes include but are not limited to acetate complexes, and hydrates of the same.
  • suitable metal ion coordination complexes include but are not limited to Fe 3 0(CH 3 COO)6 and Fe 2 CoO(CH 3 COO)6.
  • metal ion coordination complexes include but are not limited to iron (III) acetate, i.e. [Fe 3 0(OAc)6(H 2 0) 3 ]OAc, and FeM 2 0(CH 3 COO) 6 , wherein each M is independently selected from Fe, Al, Cr, V, Sc, and In.
  • the carboxylate ligands of the metal organic framework are derived from the carboxylic acid precursor (or salt thereof) employed in the method of the invention.
  • the term "derived" means that the carboxylic acid compounds are present in partly deprotonated or fully deprotonated form.
  • the carboxylic acid may be any carboxylic acid.
  • the carboxylic acid may be any di-, tri-, tetra-, hexa-, or octa-carboxylic acid.
  • the carboxylic acids may be substituted or unsubstituted.
  • the carboxylic acids may be substituted by one or more substituents independently selected from -OH, -NH 2 , -OCH 3 , -NH(CH 3 ), -N(CH 3 ) 2 , - CN and halides (e.g. -CI, -F, -I).
  • substituents independently selected from -OH, -NH 2 , -OCH 3 , -NH(CH 3 ), -N(CH 3 ) 2 , - CN and halides (e.g. -CI, -F, -I).
  • halides e.g. -CI, -F, -I
  • the carboxylic acid precursor is 3,5-dicarboxyl-(3,5- dicarboxylazophenyl)benzene (ABTC), ([5,io,i5,20-Tetrakis(4- methoxycarbonylphenyl)porphyrinato]-Co(II)), i.e. Co-TCPP, SiTD, or BTC.
  • ABTC 3,5-dicarboxyl-(3,5- dicarboxylazophenyl)benzene
  • ABTC 3,5-dicarboxyl-(3,5- dicarboxylazophenyl)benzene
  • ABTC 3,5-dicarboxyl-(3,5- dicarboxylazophenyl)benzene
  • ABTC 3,5-dicarboxyl-(3,5- dicarboxylazophenyl)benzene
  • II 3,5-dicarboxyl-(3,5- dicarboxylazophenyl)benzene
  • Co-TCPP 3,5-dica
  • the reaction is carried out at an elevated temperature.
  • the reaction is carried out under reflux conditions.
  • the reaction may be carried out at a temperature of about 120°C or greater, preferably at a temperature of about 150°C or greater.
  • the reaction may be carried out at about atmospheric pressure (101.325 kPa;
  • the reaction is preferably carried out at a pressure of less than or equal to about 400 kPa (about 4 bar), more preferably less than or equal to about 200 kPa (about 2 bar).
  • the reaction may be carried out at atmospheric pressure. In this case, however, slightly over pressures or under pressures may be employed due to the apparatus. Therefore, in the context of the present invention, the term "atmospheric pressure" is to be taken to mean a pressure range which results from the actual atmospheric pressure ⁇ 15 kPa (150 mbar).
  • frameworks comprising metal ions and carboxylate ligands in monocrystalline or polycrystalline forms. Particularly useful is the fact that the method of the present invention provides a new way of preparing such metal organic frameworks in monocrystalline form.
  • the method of the invention may be employed to prepare monocrystalline metal organic frameworks comprising metal ions and carboxylate ligands.
  • a monocrystalline metal organic framework prepared by a method of the invention may have a crystal size of greater than about 0.05mm, 0.1mm, 0.2mm, 0.3mm, 0.4mm, 0.5mm, 0.6mm, 0.7mm, 0.8mm, or 0.9mm.
  • the crystal size may range from about 0.1mm to about 5mm, preferably from about 0.3mm to about 4mm, more preferably from about 0.5mm to about 2mm, more preferably from about imm to about 3mm.
  • the present invention provides a monocrystalline metal organic framework obtained/obtainable by the method of the present invention.
  • the metal-organic frameworks according to the invention have a wide range of applications.
  • the invention provides a method comprising uptaking at least one substance by a metal-organic framework of the present invention.
  • the substance may be hydrogen, methane, carbon dioxide, oxygen or nitrogen.
  • the invention provides a method of storing a gas in a metal- organic framework according to the present invention.
  • the invention provides the use of a metal-organic framework according to any embodiment of the present invention for storing a gas. This may be achieved by binding the gas in a plurality of linker channel sites present in the metal-organic framework, for example using van der Waals forces.
  • the use/method of storing gases in this way may optimise gas storage density and volumetric gas storage.
  • the gas may be hydrogen, methane, carbon dioxide, oxygen or nitrogen.
  • the metal-organic framework may be configured to store methane or hydrogen, for example for fuelling vehicles.
  • the present invention provides the use of any metal-organic framework according to the invention for adsorbing a guest molecule, for example a gas molecule such as hydrogen, methane, carbon dioxide, oxygen or nitrogen.
  • a method of adsorbing a guest molecule for example a gas molecule such as hydrogen, methane, carbon dioxide, oxygen or nitrogen, comprising contacting a metal-organic framework of the invention with a guest molecule source.
  • the invention also provides a metal-organic framework according to any embodiment of the present invention, further comprising one or more than one type of guest molecule.
  • the guest molecule may be a gas molecule such as hydrogen, methane, carbon dioxide, oxygen or nitrogen.
  • the substance, gas molecule, or gas maybe selected from: (a) H 2 , N 2 , Ar, 0 2 , C0 2 , NO, N0 2 or CO; or
  • alkane may be selected from CH 4 , C 2 H 6 , C 3 Hs, C 4 H 10 , C 5 H 12 or ⁇ 14 ; or a cycloalkane (C3-6) selected from the group consisting of C 3 H6, C 4 H8, C 5 H 10 and ⁇ 14 ;
  • alkene may be C 2 H 4 , C 3 H6, C 4 Hs, C 5 H 10 or 0 ⁇ 12 ; wherein the alkyne may be C 2 H 2 ;
  • the alcohol may be methanol, ethanol, n-propanol, isopropanol, n-butanol or isobutanol; or
  • arene may be a substituted arene (C6-8) such as is nitrobenzene, 1,2-dinitrobenzene, 1,3-dinitrobenzene, 1,4-dinitrobenzene,
  • Figure 1 illustrates the differences between amorphous, polycrystalline, and
  • Figure 2 shows an optical microscope image of PCN-250-Fe.
  • Figure 3 shows the N 2 adsorption isotherms of PCN-250-Fe.
  • Figure 4 shows the powder x-ray diffraction pattern (PXRD) of PCN-250-Fe.
  • FIG. 5 shows the thermogravimetric (TG) analysis for PCN-250-Fe.
  • Figure 6 shows an optical microscope image of PCN-224-Zr.
  • Figure 7 shows the N 2 adsorption isotherms of PCN-224-Zr.
  • Figure 8 shows the powder x-ray diffraction pattern (PXRD) of PCN-224-Zr.
  • Figure 9 shows the thermogravimetric (TG) analysis for PCN-224-Zr.
  • Figure 10 shows the powder x-ray diffraction pattern (PXRD) of PCN-651-Fe.
  • Figure 11 shows the powder x-ray diffraction pattern (PXRD) of PCN-652-Fe.
  • a monocrystalline MOF (or a single crystal MOF) consists of a MOF in which the crystal lattice of the entire solid is continuous, unbroken (with no grain boundaries) to its edges.
  • Monocrystalline is opposed to amorphous material, in which the atomic order is limited to short range order only.
  • Polycrystalline materials lie between these two extremes; they are made up of small crystals.
  • a polycrystalline solid or polycrystal is comprised of many individual grains or crystallites. There is no relationship between the grains. Therefore, on a large enough length scale, there is no periodicity across a polycrystalline sample. They are different from monocrystalline materials. Large single crystals are very rare in nature and can be difficult to produce in the laboratory. It is desired that metal organic framework materials should be free from objectionable or incompatible impurities which detrimentally affect the crystal structure or the physical properties of the crystal. The material should be finely divided and uniform in size. Due to the absence of the defects associated with grain boundaries,
  • monocrystalline metal organic frameworks have high surface areas and provide control over the crystallization process.
  • the differences between amorphous, polycrystalline and (mono)crystalline are illustrated in Figure l.
  • the monocrystalline metal organic frameworks comprise a low occurrence of twinning.
  • the monocrystalline metal organic frameworks may comprise less than about 5% twinning crystals.
  • the monocrystalline metal organic frameworks comprise no twinning crystals.
  • a carboxylic acid precursor is employed in the method of the present invention.
  • This carboxylic acid forms the carboxylate ligands.
  • the carboxylic acid may be any suitable carboxylic acid including but not limited to carboxylic acids having two or more carboxylic acid groups.
  • the carboxylic acid maybe a dicarboxylic acid, a tricarboxylic acid, a tetracarboxylic acid, a hexacarboxylic acid, or an octacarboxylic acid.
  • the carboxylic acids may be substituted or unsubstituted.
  • the carboxylic acids maybe substituted by one or more substituents independently selected from - OH, -NH 2 , -OCH 3 , -NH(CH 3 ), -N(CH 3 ) 2 , -CN and halides (e.g. -CI, -F, -I).
  • the carboxylate ligands may be derived from any such carboxylic acids.
  • the carboxylic acid may be a dicarboxylic acid, such as, for instance, oxalic acid, succinic acid, tartaric acid, 1,4-butanedicarboxylic acid, 1,4-butenedicarboxylic acid, 4-oxopyran-2,6-dicarboxylic acid, 1,6-hexanedicarboxylic acid,
  • dicarboxylic acid such as, for instance, oxalic acid, succinic 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, 1,3-benzenedicarboxylic acid, 2,3- pyridinedicarboxylic acid, pyridine-2,3-dicarboxylic acid, i,3-butadiene-i,4- dicarboxylic acid, 1,4-benzene-dicarboxylic acid, p-benzenedicarboxylic acid, imidazole-2,4-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'-diaminoph
  • octanedicarboxylic acid pentane-3,3-dicarboxylic acid, 4,4'-diamino-i,i'-diphenyl-3,3'- dicarboxylic acid, 4,4'-diaminodiphenyl-3,3'-dicarboxylic acid, benzidine-3,3'- dicarboxylic acid, i,4-bis(phenylamino)benzene-2,5-dicarboxylic acid, 1,1'- binaphthyidicarboxylic acid, 7-chloro-8-methylquinoline-2,3-dicarboxylic acid, 1 - anilinoanthraquinone-2,4'-dicarboxylic acid, poly-tetrahydrofuran-250-dicarboxylic acid, i,4-bis(carboxymethyl)piperazine-2,3-dicarboxylic acid, 7-chloroquinoline-3,8- dicarboxylic acid,
  • the carboxylic acid may be a tricarboxylic acid, such as for instance 2- hydroxy-i,2,3-propanetricarboxylic acid, 7-chloro-2,3,8-quinolinetricarboxylic acid, 1,2,3-, 1,2,4-benzenetricarboxylic acid, 1,2,4-butanetricarboxylic acid, 2-phosphono- 1,2,4-butanetricarboxylic acid, 1,3,5-benzenetricarboxylic acid, l-hydroxy- 1,2,3- propanetricarboxylic acid, 4,5-dihydro-4,5-dioxo-iH-pyrrolo[2,3-F]quinoline-2,7,9- tricarboxylic acid, 5-acetyl-3-amino-6-methyl-benzene-i,2,4-tri carboxylic acid, 3- amino-5-benzoyl-6-methylbenzene-i ,2,4-tricarboxylic acid, 1,2,3-propanetricar
  • the carboxylic acid may be a tetracarboxylic acid, such as, for instance, i,i-dioxidoperylo[i,i2-BCD]thiophene-3,4,9,io-tetracarboxylic acid, perylene- tetracarboxylic acids such as perylene-3,4,9,io-tetracarboxylic acid or perylene-1,12- sulfone-3,4,9,io-tetracarboxylic acid, butanetetracarboxylic acids such as 1,2,3,4- butanetetracarboxylic acid or meso-i,2,3,4-butanetetracarboxylic acid, decane-2,4,6,8- tetracarboxylic acid, i,4,7,io,i3,i6-hexaoxacyclooctadecane-2,3,n,i2-tetracarboxylic acid, 1,2,4,5-benzenetetrac acid,
  • benzophenonetetracarboxylic acid 3,3',4,4'-benzophenonetetracarboxylic acid, tetrahydrofurantetracarboxylic acid or cyclopentanetetracarboxylic acids such as cyclopentane-i,2,3,4-tetracarboxylic acid.
  • the ligands may also be derived from a carboxylic acid selected from compounds of formula Li to L30 and combinations thereof:
  • ligands include ligands derived from L31 and L32:
  • the ligand may be derived from a carboxylic acid selected from the following compounds or combinations thereof:
  • the carboxylate ligands maybe selected from but not limited t ⁇ tri-, and tetra-carboxylate ligands.
  • the carboxylate ligands may b ⁇ derived from 2 ',3",5",6'-tetramethyl-[i,i':4',i":4",i'"-quaterphenyl] 3,3'",5,5"' - - ⁇ 5 - tetracarboxylic acid, 1,3,5-benzenetribenzoic acid, or 4,4',4"-s-triazine-2,4,6- triyltribenzoic acid.
  • 1,3,5-benzenetribenzoic acid has the chemical structure:
  • the carboxylic acid is L22 (also referred to as ABTC): 3,5- dicarboxyl-(3,5-dicarboxylazophenyl)benzene:
  • a 100 ml round-bottomed flask was fitted with a Claisen adapter on which a condenser was attached.
  • the flask was charged with 0.88 g (127 mmol) of Li, 20 ml of anhydrous diethyl ether and a magnetic stirring bar.
  • the system was flushed with N2 and 10.34 m l (60.3 mmol) of 4-bromotoluene in 30 ml of anhydrous diethyl ether was added slowly with rapid stirring. An immediate exothermic reaction caused the ether to start boiling.
  • the mixture was stirred for 30 min and 1.14 ml (10 mmol) of silicon tetrachloride was added dropwise.
  • BTC 1,3,5-benzenetricarboxylic acid
  • Figure 2 shows an optical microscope image of PCN-250-Fe.
  • Figure 3 shows the N 2 adsorption isotherms of PCN-250-Fe.
  • Figure 4 shows the powder x-ray diffraction pattern (PXRD) of PCN-250-Fe.
  • FIG. 5 shows the thermogravimetric (TG) analysis for PCN-250-Fe.
  • Figure 6 shows an optical microscope image of PCN-224-Zr.
  • Figure 7 shows the N 2 adsorption isotherms of PCN-224-Zr.
  • Figure 8 shows the powder x-ray diffraction pattern (PXRD) of PCN-224-Zr.
  • Figure 9 shows the thermogravimetric (TG) analysis for PCN-224-Zr.
  • Figure 10 shows the powder x-ray diffraction pattern (PXRD) of PCN-651-Fe.
  • PXRD powder x-ray diffraction pattern
  • Figure 11 shows the powder x-ray diffraction pattern (PXRD) of PCN-652-Fe.
  • the use of a carboxylic acid solvent surprisingly provides a metal organic framework in comparable yield to the method described in the reference example.
  • the solvents employed in the methods of the invention can also be recycled and reused in a subsequent method of preparing a metal organic framework.
  • the solvents employed in the method of the reference example cannot be recycled and reused. This represents a significant advantage of the present invention compared to the methods that have been described earlier. Without wishing to be bound by theory, the applicants believe that organic solvents such as DMF undergo decomposition and hence cannot be recycled but carboxylic acid solvents are not being decomposed and therefore can be recycled and reused.
  • the method of the invention provides metal organic frameworks exhibiting a high degree of crystallinity.
  • the methods of the invention provide monocrystalline metal organic frameworks comprising metal ions and carboxylate ligands.
  • the carboxylic acid acts as a modulator and competing controlling reagent, which helps grow single crystal products.
  • the presence of the carboxylic acid e.g. acetic acid
  • the carboxylic acid slows down the reaction of the carboxylic acid ligand precursor with the source of metal ions (e.g a metal salt or a metal ion coordination complex). This reduction in the reaction rate allows crystals to grow slower and larger.

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Abstract

La présente invention concerne un procédé de préparation d'une structure métallo-organique comprenant des ions métalliques et des ligands carboxylates. Le procédé consiste à : faire réagir (i) une source d'ions métalliques, avec (ii) un précurseur acide carboxylique des ligands carboxylates, dans un solvant organique constitué d'un ou de plusieurs solvants de type acide carboxylique, à une température d'environ 75 °C ou plus, éventuellement en présence d'eau. La présente invention concerne également le même procédé pour la préparation de structures monocristallines métallo-organiques ainsi que les structures métallo-organiques obtenues à partir de tels procédés.
PCT/GB2015/051383 2014-05-23 2015-05-11 Procédé de préparation d'une structure métallo-organique WO2015177511A1 (fr)

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CN109400890A (zh) * 2017-08-18 2019-03-01 中国石化扬子石油化工有限公司 一种多级孔金属有机骨架材料的制备方法
WO2019157013A1 (fr) * 2018-02-07 2019-08-15 Rutgers, The State University Of New Jersey Compositions et procédés pour la séparation sélective d'isomères d'hydrocarbures
GB2573886A (en) * 2018-04-25 2019-11-20 Vapor Point Llc Process of preparing metal-organic framework material
CN110575818A (zh) * 2019-08-06 2019-12-17 杭州电子科技大学 快速高效选择性吸附痕量污染物的羧基修饰的离子型金属有机框架材料及其制备方法和应用
CN110743503A (zh) * 2019-10-25 2020-02-04 哈尔滨工程大学 Pcn金属有机骨架与氧化石墨烯复合吸附材料及制备方法
WO2020060873A3 (fr) * 2018-09-14 2020-04-23 Rutgers, The State University Of New Jersey Compositions de mof pour la séparation sélective d'hydrocarbures
CN112839733A (zh) * 2018-07-26 2021-05-25 研究三角协会 涉及在微孔催化剂内的毛细凝结的反应工艺
CN113045761A (zh) * 2021-02-07 2021-06-29 南通沃兰化工有限公司 一种吡唑羧酸锰配位聚合物光催化剂及其制备方法和应用

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CN105999280A (zh) * 2016-05-16 2016-10-12 浙江大学 装载有阴离子型药物的纳米级锆基阳离子金属有机框架材料的制备方法
CN109400890A (zh) * 2017-08-18 2019-03-01 中国石化扬子石油化工有限公司 一种多级孔金属有机骨架材料的制备方法
WO2019157013A1 (fr) * 2018-02-07 2019-08-15 Rutgers, The State University Of New Jersey Compositions et procédés pour la séparation sélective d'isomères d'hydrocarbures
GB2573886A (en) * 2018-04-25 2019-11-20 Vapor Point Llc Process of preparing metal-organic framework material
CN112839733A (zh) * 2018-07-26 2021-05-25 研究三角协会 涉及在微孔催化剂内的毛细凝结的反应工艺
WO2020060873A3 (fr) * 2018-09-14 2020-04-23 Rutgers, The State University Of New Jersey Compositions de mof pour la séparation sélective d'hydrocarbures
US11918951B2 (en) 2018-09-14 2024-03-05 Rutgers, The State University Of New Jersey MOF compositions for selective separation of hydrocarbons
CN110575818A (zh) * 2019-08-06 2019-12-17 杭州电子科技大学 快速高效选择性吸附痕量污染物的羧基修饰的离子型金属有机框架材料及其制备方法和应用
CN110575818B (zh) * 2019-08-06 2022-08-23 杭州电子科技大学 快速高效选择性吸附痕量污染物的羧基修饰的离子型金属有机框架材料及其制备方法和应用
CN110743503A (zh) * 2019-10-25 2020-02-04 哈尔滨工程大学 Pcn金属有机骨架与氧化石墨烯复合吸附材料及制备方法
CN110743503B (zh) * 2019-10-25 2023-04-18 哈尔滨工程大学 Pcn金属有机骨架与氧化石墨烯复合吸附材料及制备方法
CN113045761A (zh) * 2021-02-07 2021-06-29 南通沃兰化工有限公司 一种吡唑羧酸锰配位聚合物光催化剂及其制备方法和应用

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