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WO2010130299A2 - Procédé de production de matériaux structuraux organométalliques à base d'oxyde par méthode inverse - Google Patents

Procédé de production de matériaux structuraux organométalliques à base d'oxyde par méthode inverse Download PDF

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Publication number
WO2010130299A2
WO2010130299A2 PCT/EP2009/066729 EP2009066729W WO2010130299A2 WO 2010130299 A2 WO2010130299 A2 WO 2010130299A2 EP 2009066729 W EP2009066729 W EP 2009066729W WO 2010130299 A2 WO2010130299 A2 WO 2010130299A2
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Prior art keywords
compounds
anion
mof
acid
reaction
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PCT/EP2009/066729
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German (de)
English (en)
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WO2010130299A3 (fr
Inventor
Steffen Hausdorf
Florian Mertens
Felix Baitalow
Jürgen Seidel
Roland Fischer
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Bergakademie Freiberg
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Bergakademie Freiberg
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Priority to EP09807537A priority Critical patent/EP2429981A2/fr
Publication of WO2010130299A2 publication Critical patent/WO2010130299A2/fr
Publication of WO2010130299A3 publication Critical patent/WO2010130299A3/fr
Anticipated expiration legal-status Critical
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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G9/00—Compounds of zinc
    • 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
    • C07F15/06—Cobalt compounds
    • C07F15/065—Cobalt 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
    • C07F3/00—Compounds containing elements of Groups 2 or 12 of the Periodic Table
    • C07F3/003—Compounds containing elements of Groups 2 or 12 of the Periodic Table without C-Metal linkages
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
    • C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/01—Particle morphology depicted by an image
    • C01P2004/03—Particle morphology depicted by an image obtained by SEM
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/12—Surface area

Definitions

  • MOF compounds are constructed in a regular grid, which has a defined pore size distribution. The high specific pore volume and the associated large equivalent surface make these compounds excellent materials for gas storage, for chemical engineering catalysis or as separation material eg in gas or liquid chromatography.
  • Metal-organic framework material hereinafter referred to as MOF (metal organic framework) represents a series of porous, crystalline organic-inorganic hybrid materials in general. In the described compounds in this invention is MOF 's, bridge the node of type M 4 O via linker molecules to each other.
  • MOF metal organic framework
  • these frameworks are referred to as 0M0F or oxide-based metal-organic frameworks.
  • the 0M0F 's may also contain nonlinear, nonaromatic, and possibly inorganic anions as linking elements (linkers) with the M 4 O node can also be done with non-oxygen donor atoms.
  • FIG. 1 shows a general scheme for establishing a 0M0F.
  • the node In the middle, the node is shown, which is the same in both structures.
  • the nodes of type M 4 O are bridged by linker molecules.
  • the left - hand structure represents a section of the lattice of an IRMOF with M 4 O (CO 2 ) 6 - SBU and a general linear linker.
  • the permanent porosity and associated high specific equivalent surface area of the OMOF materials is their most important property. Values between 2000 and 3000 mVg are generally achieved by OMOF, with the maximum currently at 4500 mVg for MOF 177 (OM Yaghi, Nature 2004, 427, 523). In the class of zeolites, which have found a variety of applications as porous, purely inorganic materials, however, a maximum of 904 m 2 / g equivalent surface area for zeolite Y are achieved. This results in excellent physisorption properties for the OMOF's for a variety of substances.
  • the density of the OMOF materials reaches unusually low values for solid, ordered materials, e.g. B. 0.57 g / cm 3 for MOF-5.
  • the gravimetric storage capacity is thereby maximized, which in particular allows the mobile application as fuel storage.
  • OMOFs can also be used both as support material for catalysts and even as catalytically active material (for example for copolymerization of CO 2 with alkoxides to polycarbonates).
  • IRMOFs can only be produced in the form of their zinc homologues, mainly according to the solvothermal method disclosed in DE600213579T2.
  • zinc nitrate in the form of one of its hydrates is dissolved together with a linear, ditopic carboxylic acid in DEF, and the resulting IRMOF is crystallized under elevated temperatures.
  • Recent studies by Mertens et al. show that an oxide source such as nitrate is imperative.
  • the application of the synthesis method to other metals or other salts is not readily possible because z. B.
  • the nitrates of the main group metals can not decompose with oxide formation.
  • this method is based on the slow hydrolytic decomposition of the solvent DEF, which leads to the deprotonation of the carboxylic acid used by liberation of diethylamine.
  • the central oxidation of the zinc oxo cluster is formed by the decomposition of the zinc nitrate hydrate, which also serves as a zinc source.
  • the nitrogen oxides liberated during this decomposition form the nitrogen oxides by reaction with the solvent carcinogenic N-nitrosodiethylamine.
  • the zinc nitrate hydrate must be used in excess since it is necessary as a pH buffer throughout the entire reaction period.
  • Variants of the "solvothermal" synthesis are the acceleration of the reaction by microwaves (L. Huang et al .: Microporous and Mesoporous Materials, 2003, 58, 105-114) and the crystallization from a solution prepared analogously at room temperature after thermal pretreatment (RA Fischer et al., J. Am. Chem. Soc., 2005, 127, 13744-13745).
  • Another method describes the slow inward diffusion of an organic base into a solution of zinc nitrate with linear, ditopic carboxylate (O.M. Yaghi et al., Nature 2004, 427, 523).
  • Ferey et al. describes under the name "controlled SBU Approach” (CSA) the anion exchange on Fe ⁇ i 3 ⁇ 7+ - centered complexes for the synthesis of MOF structures of the MIL type (Ferey et al., Angew. Chem. Int. Ed. 2004, 43, 6285-6289).
  • CSA controlled SBU Approach
  • the DEF solvent which is almost exclusively used for the thermal method, is currently not produced on an industrial scale and can therefore only be obtained at prices usual for fine chemicals. Solvent consumption thus represents the most important cost factor for a corresponding process.
  • the resulting in thermal reaction, highly carcinogenic N-Nitrosodiethylamin represents a significant, hardly solvable on an industrial scale disposal problem.
  • the invention has for its object to develop a process for the production of oxide-based metal-organic framework (OMOF), which allows the economically and ecologically acceptable production of large amounts OMOF with reproducibility of a constant maximum specific surface area.
  • OMOF oxide-based metal-organic framework
  • this object is achieved in that compounds of the type M 4 OA 6 , wherein M is a divalent metal cation and A represents an arbitrary anion, with exchange compounds from which an anion B having at least 2 functional groups and at least 4 donor atoms, to compounds of the type M 4 OB x be reacted with x ⁇ 3 in the presence of a solvent.
  • Residues of organic acids are preferably used as anions A.
  • M Co
  • M is a metal cation present in the +2 formal oxidation state selected from all subgroup elements of Sc to Zn, from Y to Cd, from La to Hg or a main metal group selected from Be, Mg, Ca, Sr, Ba, Ra, In , Tl, Sn, Pb or Bi, more preferably selected from the group of subgroup elements selected from Ti, V, Cr, Mn, Fe, Co, Cu, Zn, Zr, Nb, Mo, Tc, Ru, Rh, Pd, Cd , Hf, Ta, W, Re, Os ,, Ir, Pt, Au or Hg, especially Zn, Cd or Hg.
  • a main metal group selected from Be, Mg, Ca, Sr, Ba, Ra, In , Tl, Sn, Pb or Bi, more preferably selected from the group of subgroup elements selected from Ti, V, Cr, Mn, Fe, Co, Cu, Zn, Zr, Nb, Mo, Tc, Ru, Rh, Pd, Cd
  • Organic exchange compounds preferably aromatic di- and tricarboxylic acids or derivatives thereof, particularly preferably terephthalic acid, ⁇ -phthalic acid, benzenetricarboxylic acid, benzene tribenzoic acid or a derivative of one of these acids or mixtures of these acids and / or acid derivatives, are preferably used as the source of the anions B.
  • the reaction preferably takes place in aprotic-polar solvents, preferably in ketones or carboxylic acid amides, more preferably in acetone, DEF or. DMF.
  • the reaction is carried out in solution or suspension.
  • the solution or suspension of the metal oxo complex is preferably initially introduced, and the solution or suspension of the exchange compound which delivers the anions B is added.
  • the reaction takes place at temperatures between 0 0 C and the boiling point of the solvent, particularly preferably between 0 0 C and 200 0 C.
  • the rate of addition of solution or suspension of B is a function of the concentration of the to be reproduced solution or suspension between 0, 1 and 1 ml / min.
  • MOF-5 materials of varying quality could be prepared by varying the reaction conditions as shown in Table 1.
  • Method 1 rapid pouring of the H 2 BDC solution 7 ⁇ T ⁇ TM) Tn " 3 solution of the precursor (O.Ol M).
  • Method 2 Stirring a suspension of the precursor and H 2 BDC in the stoichiometric ratio at the boiling point of the solvent,
  • Method 3 Add the H 2 BDC solution (0.03 M) at 1.5 ml / min to the precursor solution (0.01 M).
  • Bz benzoate.
  • Ac acetate.
  • the exchange reaction according to the invention can be carried out.
  • the following views can be considered as established in the art: a) in the transacidification of Zinkoxosalzen with carboxylic acids it comes to the protonation of the central oxide to form water and the binary zinc salts of the corresponding acids b) in the attempt of transacidification of Berylliumoxoacetat with Terephthalic acid remains the replacement incomplete.
  • IRMOFs having M 4 O nodes which contain metals other than zinc can be produced for the first time by the process according to the invention.
  • Examples 2 and 3 the preparation of the isomers and co-isomorphs to MOF-5 is described by way of example. This is shown in FIG. 2 as a section of its crystal lattice.
  • an increase in the specific storage capacity, eg. B. for gaseous fuels are achieved at the same time increased chemical and thermal stability.
  • valuable catalytic, electrical and magnetic properties can be obtained.
  • FIG. 2 shows a 4 ⁇ 3 -node of the crystal lattice of MOF-5
  • FIG. 3 X-ray powder diffractograms and adsorption curves of some after the inverse
  • FIG. 2 shows a 4 * 3 -neck of the crystal lattice of MOF-5. It is formed by tetrahedral [Zn 4 O] 6+ knots linked by terephthalate ions (BDC 2 " ), resulting in a cubic framework.
  • Zinc oxobenzoate is undecomposed soluble in DEF and acetone.
  • the identification of the powder obtained was carried out by powder diffractometry.
  • Figure 3 shows X-ray powder diffraction patterns and adsorption curves of some samples prepared by the inverse method.
  • the vertical lines describe the theoretical
  • Deso lvatiens b prepared in DEF by slow dropwise addition
  • c prepared in acetone by the method described above
  • d prepared in DMF by slow dropwise addition
  • Embodiment 2 Preparation Be-MOF-5
  • FIG. 2 shows a 4 * 3-node section of the MOF-5 crystal lattice analogous to Be-MOF-5 but formed by tetrahedral [Be 4 O] 6+ nodes formed by terephthalation (BDC 2 " ). which results in a cubic framework.
  • Be 4 OACo it is possible by the exchange reaction according to the invention to obtain a MOF-5-isomorphic compound: a 0.0 IM solution of Be 4 OAc 6 in boiling DMF (153 ° C) was introduced and into this a 0 , 03 M solution of H 2 BDC in DMF was added at a rate of 1 ml / min with stirring. Equal volumes of the starting solutions were used.
  • FIG. 4 shows a Rietveld plot after evaluation by means of the program FullProf.
  • the powder diffractometric measurement is represented by points and the diffractogram calculated from the structure simulation by a solid line. In the middle, the reflex positions are shown.
  • the quality of the correlation characterized by a Bragg R factor of 1.59, is illustrated by the difference curve in the lower part of the figure.
  • Example 2 Proof of porosity was provided as in Example 1 by incorporation of the N 2 adsorption isotherms at 77K.
  • the pore volumes can be determined for the amorphous material to be about 0.28 cm 3 / g, for the crystalline, prepared in DEF to about 0.87 cm 3 / g.
  • an even higher synthesis temperature 178 0 C, boiling DEF
  • a material with a specific pore volume of 1.23 cmVg be prepared.
  • MOF-5 crystalline MOF-5
  • Zn already decomposes at 350 ° C.
  • MOF-5 (Be) appears to be practically indefinitely stable.
  • Beryllium oxyacetate can be prepared very easily by dissolving beryllium hydroxide in glacial acetic acid, which contains a small amount of water.
  • Figure 2 shows a 4 * 3 knot of the crystal lattice of MOF-5 which is analogous to Co-MOF-5, but formed by tetrahedral [Co 4 O] 6+ knots formed by terephthalation (BDC 2 " ). which results in a cubic framework.
  • (Co 4 OPiVo) 2 Coso 2 PiVi 2 manages to pass through the inventive exchange reaction to a MOF-5 isomorphous compound: a 0.005 M solution of C ⁇ sO 2 Pivi 2 in DEF at 90 0 C was charged and to this was added a 0.03 M solution of H 2 BDC in DEF at a rate of 1 ml / min with stirring. The volumes of the starting solutions were set equal according to the stoichiometry of 1: 6. After completion of the addition, the resulting blue solid was filtered off and re-solubilized as in Example 1 and dried. The yield was almost quantitative.
  • the diffractogram of the obtained powder ( Figure 5) can be completely indexed by assuming a MOF-5 analogue structure, space group F m -3 m with replacement of Zn 2+ by Co 2+ .
  • the lattice constant of the MOF-5 (Co) thus prepared is 25.83 ⁇ compared to 25.76 ⁇ in the original structure.
  • FIG. 5 shows a Rietveld plot after evaluation by means of the program FullProf.
  • the powder diffractometric measurement is represented by points and the diffractogram calculated from the structure simulation by a solid line. In the middle, the reflex positions are shown.
  • the quality of the correlation characterized by a Bragg R factor of 1.59, is illustrated by the difference curve in the lower part of the figure.
  • the porosity was detected as in Example 1 and 2 by adsorption with nitrogen.
  • the pore volume which can be determined from the isotherm by means of t-plot was 0.87 cm 3 / g.
  • cobalt oxo pivalate required as a precursor is based on (H.-L. Tsai, Inorg. Chem., 2008, 47, 1925-1939) and (Zhou H, et al, Inorganica Chimica Acta 1997, 266, 91-102) Cobalt (II) carbonate and pivalic acid available via the following path:
  • MOF metal-organic framework
  • Metal-organic framework Metal-organic framework
  • OMOF oxide-based metal-organic framwork
  • IRMOF isoreticular metal-organic framework (division of Yaghi)

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  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Catalysts (AREA)

Abstract

L'invention concerne un procédé de production de composés structuraux organométalliques à base d'oxyde, appelés OMOF, de la formule générale M4OBx (M = métal bivalent, x ≤ 3). Les composés OMOF sont construits dans un réseau uniforme qui présente une distribution définie de la grosseur des pores. Le volume spécifique de pores élevé et la grande surface équivalente qui en résulte font de ces composés des matériaux exceptionnels notamment pour les gazomètres, la catalyse chimique, ou comme matériau de séparation par exemple en chromatographie en phase gazeuse ou en phase liquide. Les composés selon l'invention sont produits de telle manière que les composés du type M4OA6, où M représente un cation métallique bivalent et A un anion quelconque, sont mis en réaction en présence d'un solvant avec des composés de substitution à partir desquels est produit un anion B ayant au moins 2 groupes fonctionnels et au moins 4 atomes donneurs, pour obtenir des composés du type M4OBx, où x ≤ 3.
PCT/EP2009/066729 2009-05-15 2009-12-09 Procédé de production de matériaux structuraux organométalliques à base d'oxyde par méthode inverse Ceased WO2010130299A2 (fr)

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DE102009021479.8 2009-05-15
DE102009021479A DE102009021479A1 (de) 2008-06-04 2009-05-15 Verfahren zur Herstellung von oxidbasierten metall-organischen Gerüstmaterialien mittels inverser Synthese

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115819792A (zh) * 2022-12-16 2023-03-21 陕西煤业化工技术研究院有限责任公司 混金属基三羧酸配位聚合物及其制备方法和吸附方法
US12459877B1 (en) 2025-06-23 2025-11-04 King Fahd University Of Petroleum And Minerals Recyclable catalyst for carbon dioxide capture

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114632496B (zh) * 2020-12-15 2023-02-28 中国科学院大连化学物理研究所 一种沸石咪唑酯骨架材料的可逆晶格转变的方法

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Publication number Priority date Publication date Assignee Title
DE602004027036D1 (de) * 2003-05-09 2010-06-17 Univ Michigan MOFs mit einer hohen Oberfläche und Methode zu deren Herstellung
CA2640300A1 (fr) * 2006-02-10 2007-08-16 Basf Se Procede de preparation de chassis organiques poreux
DE102006048043A1 (de) * 2006-10-11 2008-04-17 Bayer Materialscience Ag Verfahren zur Herstellung metallorganischer Gerüstverbindungen

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115819792A (zh) * 2022-12-16 2023-03-21 陕西煤业化工技术研究院有限责任公司 混金属基三羧酸配位聚合物及其制备方法和吸附方法
CN115819792B (zh) * 2022-12-16 2023-08-18 陕西煤业化工技术研究院有限责任公司 混金属基三羧酸配位聚合物及其制备方法和吸附方法
US12459877B1 (en) 2025-06-23 2025-11-04 King Fahd University Of Petroleum And Minerals Recyclable catalyst for carbon dioxide capture

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WO2010130299A3 (fr) 2011-03-31
EP2429981A2 (fr) 2012-03-21

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