WO2010058123A1 - Procede de preparation hydrothermale de carboxylates d'aluminium poreux cristallises de type "metal-organic framework" - Google Patents

Procede de preparation hydrothermale de carboxylates d'aluminium poreux cristallises de type "metal-organic framework" Download PDF

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WO2010058123A1
WO2010058123A1 PCT/FR2009/052208 FR2009052208W WO2010058123A1 WO 2010058123 A1 WO2010058123 A1 WO 2010058123A1 FR 2009052208 W FR2009052208 W FR 2009052208W WO 2010058123 A1 WO2010058123 A1 WO 2010058123A1
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solid
metal
mil
mixture
mof
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PCT/FR2009/052208
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English (en)
French (fr)
Inventor
Thierry Loiseau
Gérard FEREY
Christophe Volkringer
Francis Taulelle
Mohamed Haouas
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Centre National De La Recherche Scientifique -Cnrs-
Universite De Versailles-Saint Quentin En Yvelines
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Priority to JP2011543803A priority Critical patent/JP6004650B2/ja
Priority to US13/129,717 priority patent/US8658562B2/en
Priority to EP09768213.2A priority patent/EP2376503B1/fr
Publication of WO2010058123A1 publication Critical patent/WO2010058123A1/fr

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    • 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
    • C07F5/00—Compounds containing elements of Groups 3 or 13 of the Periodic Table
    • C07F5/06—Aluminium compounds
    • C07F5/069—Aluminium compounds without C-aluminium linkages
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
    • B01J20/223—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material containing metals, e.g. organo-metallic compounds, coordination complexes
    • B01J20/226—Coordination polymers, e.g. metal-organic frameworks [MOF], zeolitic imidazolate frameworks [ZIF]
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/30—Processes for preparing, regenerating, or reactivating
    • B01J20/3085—Chemical treatments not covered by groups B01J20/3007 - B01J20/3078

Definitions

  • the present invention relates to a process for the hydrothermal preparation of a solid consisting of a metal-organic network (MOF) of porous and crystallized aluminum carboxylates in an aqueous medium.
  • MOF metal-organic network
  • MOF metal-organic networks
  • references in brackets [] refer to the list of references at the end of the text.
  • the Metal-Organic Framework is a new class of microporous solids (or even mesoporous for some of them). It is based on the concept of three-dimensional assembly of rigid organic ligands (including a benzene ring, for example) with metal centers. The latter can arrange to form isolated clusters, infinite chains or inorganic layers that connect to one another via organic ligands via carboxylate or amine linkages.
  • Several groups Yaghi [1], Kitagawa [2] and Férey [3] have exhibited this type of strategy for the formation of crystallized solids offering three-dimensional frameworks with exceptional properties of porosity (BET surface area> 3000 m 2 .g " 1 ).
  • This type of material is usually characterized by their specific surface (which gives a precise idea of their accessible porosity for the incorporation of molecules). These specific surface values (expressed in m 2 per gram of material) are measured by the Brunauer-Emmett-Teller (or BET) methods which make it possible to examine the surface of the pores by chemistry-nitrogen sorption at 77 K ( multilayer model) or Langmuir using the same process with a single layer model. These new materials prove to be very good adsorbents for gases such as hydrogen [4-6], methane [7, 8] or even carbon dioxide [8]. They can therefore be used instead of active carbons or zeolites. In addition, this type of solids (some of which are biocompatible) may find applications for encapsulation and controlled release of drug molecules [9].
  • aluminum-based materials and in particular aluminum carboxylate-based materials, can have high storage capacities for molecules such as H 2 , CH 4 , CO 2 , etc.
  • the aluminum-based MOF solids obtained by most known processes may be unsuitable for the desired application because they may lead to the production of a mixture of several materials, be in amorphous form or still contain undesirable secondary impurities that are not removed during the preparation of the MOF solid.
  • said solids do not always have sufficient adsorption capacity.
  • crystallization may then be necessary to obtain a crystalline MOF solid, consisting of a single phase, high purity (free of any byproduct) and having sufficient porosity.
  • crystalstallized solid and “crystalline solid” may be used interchangeably to designate a solid in which atoms, ions or molecules form long-range ordered arrangements in the three dimensions of the space, leading to a unique signature constituted by a specific succession of diffraction peaks (X-rays for example) for each solid.
  • amorphous solid is a solid where atoms, ions or molecules, although locally ordered, pile up in a disordered manner at long distances. This results in a signature of one or more diffraction peaks (X-rays for example) very wide which does not allow the precise identification of the material (since several solids can co-exist and lead to the same signature by diffraction).
  • atoms, ions or molecules can adopt several arrangements depending on the conditions of their formation. These different arrangements are the different "phases" existing in a given chemical system. The physical properties such as the melting point and the density of the different phases are different, which allows the differentiation of solids.
  • MOF type aluminum with the required purity, porosity and crystallinity properties.
  • the present invention is specifically intended to meet this need by providing a hydrothermal preparation process of a solid consisting of metal-organic network (MOF) of porous and crystallized aluminum carboxylates, comprising at least the following steps: ) at least one inorganic metal precursor in the form of Al metal, an Al 3+ metal salt or a coordination complex comprising the Al 3+ metal ion is mixed in an aqueous solvent; and at least one organic precursor of ligand L, L being a di-, tri- or tetracarboxylate ligand of formula R ° (COO " ) q where R 0 represents
  • a hydrothermal preparation process is a process that allows the crystallization of materials (chemical compounds), directly from an aqueous solution that may be water. This type of process is a cheaper and more environmentally friendly method of preparation related to the absence of solvents organic substances (which are possibly only used for washing operations with a view to their activation).
  • hydrophilmal refers to a heterogeneous reaction protocol in the presence of water under conditions of high pressures and temperatures that permit dissolution and crystallization of materials; which are relatively insoluble at ambient temperature and pressure [25].
  • Rabenau [26] states that reactions under hydrothermal conditions are carried out from heterogeneous chemical systems that take place in water at a pressure greater than 10 5 Pa and a temperature above 100 ° C.
  • "Alkyl” at Within the meaning of the present invention, an optionally substituted saturated linear or branched carbon radical comprising 1 to 12 carbon atoms, for example 1 to 10 carbon atoms, for example 1 to 8 carbon atoms, for example 1 to 6 carbon atoms. .
  • an alkyl radical may be a methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, n-pentyl, sec-pentyl, isopentyl or tert-pentyl radical.
  • alkene means a linear or branched, cyclic or acyclic unsaturated hydrocarbon radical comprising at least one carbon-carbon double bond.
  • the alkenyl radical may comprise from 2 to 20 carbon atoms, for example from 2 to 10 carbon atoms, more particularly from 2 to 8 carbon atoms, even more particularly from 2 to 6 carbon atoms.
  • an alkenyl radical may be an allyl, ethenyl, propenyl, butenyl, 1-methyl-2-buten-1-yl radical or similar radicals.
  • alkyne refers to a linear or branched, cyclic or acyclic unsaturated hydrocarbon radical comprising at least one carbon-carbon triple bond.
  • the alkynyl radical may comprise from 2 to 20 carbon atoms, preferably from 2 to 10 carbon atoms, more particularly from 1 to 8 carbon atoms, even more particularly from 2 to 6 carbon atoms.
  • an alkynyl radical may be an ethynyl, 2-propynyl (propargyl), 1-propynyl radical or similar radicals.
  • aryl means an aromatic system comprising at least one ring which satisfies Hekel's aromaticity rule. Said aryl is optionally substituted and may comprise from 6 to 50 carbon atoms, for example 6 to 27 carbon atoms, especially 6 to 14 carbon atoms, more particularly 6 to 12 carbon atoms.
  • an aryl radical may be a phenyl, naphthyl, tetrahydronaphthyl, indanyl, indenyl or similar group.
  • heteroaryl means a system comprising at least one aromatic ring of 4 to 50 carbon atoms, for example of 4 to 20 carbon atoms, and at least one heteroatom chosen from the group comprising especially sulfur, oxygen, nitrogen. Said heteroaryl may be substituted.
  • a heteroaryl radical may be pyridyl, pyrazinyl, pyrimidinyl, pyrrolyl, pyrazolyl, imidazolyl, thiazolyl, oxazolyl, isooxazolyl, thiadiazolyl, oxadiazolyl, thiophenyl, furanyl, quinolinyl, isoquinolinyl, and similar radicals.
  • cycloalkyl in the sense of the present invention, a cyclic carbon radical, saturated or unsaturated, optionally substituted, which may comprise 3 to 10 carbon atoms.
  • cyclopropyl cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, 2-methylcyclobutyl, 2,3-dimethylcyclobutyl, 4-methylcyclobutyl and 3-cyclopentylpropyl.
  • haloalkyl in the sense of the present invention, an alkyl radical as defined above, said alkyl system comprising at least one halogen selected from the group consisting of fluorine, chlorine, bromine, iodine.
  • heteroalkyl in the sense of the present invention, an alkyl radical as defined above, said alkyl system comprising at least one heteroatom, especially selected from the group consisting of sulfur, oxygen, nitrogen, phosphorus.
  • heterocycle in the sense of the present invention, a cyclic carbon radical comprising at least one heteroatom, saturated or unsaturated, optionally substituted, and which may comprise 3 to 20 carbon atoms, preferably 5 to 20 carbon atoms, preferably 5 to 10 carbon atoms.
  • the heteroatom may for example be selected from the group consisting of sulfur, oxygen, nitrogen and phosphorus.
  • a heterocyclic radical may be pyrrolidinyl, pyrazolinyl, pyrazolidinyl, imidazolinyl, imidazolidinyl, piperidinyl, piperazinyl, oxazolidinyl, isoxazolidinyl, morpholinyl, thiazolidinyl, isothiazolidinyl, or tetrahydrofuryl.
  • alkoxy in the sense of the present invention, respectively, an alkyl, aryl, heteroalkyl and heteroaryl radical bonded to an oxygen atom.
  • an alkoxy radical may be methoxy, ethoxy, propoxy, isopropoxy, n-butoxy, tert-butoxy, neopentoxy, n-hexoxy, or a similar radical.
  • substituted denotes, for example, the replacement of a hydrogen atom in a given structure with a group as defined above. When more than one position may be substituted, the substituents may be the same or different at each position.
  • the aqueous solvent may consist exclusively of water. It may also consist of a solvent mixture containing at least 75% by weight, preferably 85% by weight, more preferably at least 95% by weight of water relative to the total weight of all the solvents.
  • the solvents that can be used in a mixture with water may be chosen from the group comprising primary, secondary or tertiary alcohols, in particular methanol, ethanol, n-propanol, isopropanol, n-butanol isobutanol or tert-butanol.
  • the inorganic metal precursor in step (i) may be in the form of Al metal, an Al 3+ metal salt or a coordination complex comprising the Al 3+ metal ion.
  • the inorganic metal precursor present in the form of Al metal or an Al 3+ metal salt.
  • the counterion may be an inorganic ion selected from the group consisting of sulphate, nitrate, nitrite, sulphite, bisulphite, phosphate, phosphite, chloride, perchlorate, bromide, iodide, carbonate, bicarbonate.
  • the counterion may also be an organic ion selected from the group consisting of acetates, formates, oxalates, isopropoxides, ethoxides.
  • the crystalline spatial organization of the solids of the present invention is the basis of the particular characteristics and properties of these materials. In particular, it governs the size of the pores, which has an influence on the specific surface of the materials and adsorption characteristics. It also governs the density of materials, which is relatively low, the proportion of metal in these materials, the stability of materials, the rigidity and flexibility of structures, and so on.
  • the pore size can be adjusted by choosing appropriate ligands L.
  • the appropriate ligands L may be a di-, tri- or tetracarboxylate ligand selected from the group consisting of: C 2 H 2 (CO 2 " ) 2 (fumarate), C 2 H 4 ( CO 2) 2 (succinate), C 3 H 6 (CO 2 " ) 2 (glutarate), C 4 H 4 (CO 2 " ) 2 (muconate), C 4 H 8 (CO 2 " ) 2 (adipate), C 5 H 3 S (CO 2 " ) 2 (2,5-thiophene dicarboxylate), C 6 H 4 (CO 2 " ) 2 (terephthalate), C 6 H 2 N 2 (CO 2 " ) 2 (2.5- pyrazine dicarboxylate), C 10 H 6 (CO 2 " ) 2 (naphthalene-2,6-dicarboxylate), C 2 H 8 (CO 2 " ) 2 (biphenyl
  • the organic precursor of the ligand L may be, for example, in the acid or ester form.
  • the ester may be, for example, an alkyl ester in which the alkyl radical may be a methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl or octyl radical.
  • step (i) the inorganic metal precursor and the organic precursor of the ligand L can be mixed in a molar ratio of between 1 and 5.
  • the MOF solids according to the invention have a crystallized structure which gives these materials specific properties.
  • An important parameter that can influence crystallization is pH.
  • the pH of the mixture is adjusted to a pH of less than 3.
  • the pH of the mixture can be further adjusted to a pH between 0.2 and 2.9.
  • the pH may be adjusted to a pH of between 0.4 and 2.9.
  • the pH of the mixture is at a pH of between 0.4 and 0.7.
  • the initial pH of the mixture is adjusted to 0.6 and the final pH to a pH ranging from 1.5 to 1.8.
  • the pH will be adjusted according to the exact composition of the mixture and the dynamics of the reaction based on the estimated values given in the examples.
  • step (ii) the pH of the mixture can be adjusted by addition of an acid or a base.
  • the acids which may be suitable in stage (ii) are advantageously those which have neither influence on the structure of the MOFs nor on their preparation process.
  • mineral acids chosen from the group comprising HCl, HNO 3 , H 2 SO 4 .
  • the acid is HNO 3 .
  • the base when the pH is adjusted by addition of a mineral base, the base may advantageously be an alkali metal hydroxide selected from the group consisting of LiOH, NaOH, KOH.
  • the process for preparing a solid according to the invention is carried out at a temperature greater than 130 ° C.
  • the mixture obtained in (ii) is heated to a temperature of 140 0 C to 220 ° C.
  • the mixture may be heated for 1 to 48 hours, for example for 1 to 24 hours, for example for 1 to 5 hours.
  • Step (iii) is advantageously carried out at an autogenous pressure greater than 10 5 Pa.
  • "Autogenous" pressure is the pressure generated by the reactants at a given temperature in a closed reaction cell.
  • the solid obtained at the end of step (iii) may, in addition, be subjected to an activation step (iv) in which said solid is heated at a temperature of from 50 ° C. to 450 ° C., advantageously from 80 ° C to 350 ° C. In this step, the solid can be heated for 1 to 36 hours.
  • the activation step (iv) may optionally be carried out in a solvent selected from the group comprising dimethylformamide or DMF, diethylformamide or DEF, methanol, ethanol, dimethylsulfoxide or DMSO.
  • This activation step (iv) makes it possible to empty the pores of the MOF solid of the invention and to make them accessible for the intended use of said solid.
  • the emptying can be done, for example, by the departure of the molecules of water, acid, base, solvent and / or optionally ligand L molecules present in the reaction medium.
  • the resulting MOF solids will then have a higher adsorption and storage capacity.
  • the subject of the present invention is also a solid consisting of porous and crystallized aluminum carboxylate (MOF) metal network capable of being obtained by the method of the invention, comprising a three-dimensional succession of units of formula (I) :
  • D Al represents the metal ion Al 3+ ;
  • D m is from 1 to 15, for example from 1 to 8;
  • D k is 0 to 15, for example 1 to 8;
  • DI is 0 to 10, for example 1 to 8;
  • D p is 1 to 10, for example 1 to 5;
  • m, k, I and p are chosen so as to respect the neutrality of the charges of said pattern;
  • DX is an anion selected from the group consisting of OH “ , CI “ , F “ , I “ , Br “ , SO 4 2" , NO 3 " ,
  • MOF solids of aluminum carboxylates prepared by the process of the invention have certain advantages, in particular:
  • X is selected from the group consisting of OH “ , CI “ , F “ , CIO 4 “ .
  • the MOF solids according to the invention preferably comprise a mass percentage of Al in the dry (or dehydrated) phase of 5 to 50%.
  • the MOF solids obtainable by the process of the invention have pores, and more particularly micro- and / or mesopores.
  • micropores can be defined as pores having a diameter less than or equal to 2 nm (diameter ⁇ 2 nm) and mesopores as pores with a diameter greater than 2 nm and up to 50 nm (2 nm ⁇ diameter ⁇
  • the pore diameter of the MOF solid of the invention is 0.2 to 6 nm.
  • the presence of micro- and mesopores can be followed by sorption measurements to determine the capacity of the MOF solid to absorb nitrogen at 77K according to DIN 66131.
  • the specific surface of the solids constituted by metal-organic networks (MOF) of porous and crystallized aluminum carboxylates that can be obtained by the process of the invention can be measured by the BET method and / or determined and calculated by the model.
  • Said solids may have a BET specific surface area ranging from 50 to 4200 m 2 / g, in particular ranging from 100 to 2500 m 2 / g. They can also have a Langmuir specific surface ranging from 50 to 6000 m 2 / g, in particular ranging from 150 to 3500 m 2 / g.
  • the MOF solids according to the invention advantageously have a pore volume of 0.1 to 4 cm 3 / g. In the context of the invention, the pore volume means the accessible volume for the molecules of gas or liquid per gram of product.
  • the MOF solids may have a gas loading capacity of 0.5 to 50 mmol of gas per gram of dry solid.
  • the carrying capacity means the gas storage capacity or the amount of gas adsorbed by the solid. These values and this definition also apply to the liquid load capacity.
  • the MOF solids of the present invention may in particular have the advantage of having a thermal stability up to a temperature of 500 ° C. More particularly, these solids may have a thermal stability between 250 ° C. and 430 ° C.
  • the MOF solids of the invention are crystallized and may preferably be in the form of crystallites with a length that ranges from 0.1 ⁇ m to 150 ⁇ m. They are in particular, in the form of small crystals having a particular morphology (needles, platelets, octahedra etc.) which also allows their precise identification by examination using a scanning electron microscope (SEM).
  • SEM scanning electron microscope
  • the MOF solids according to the invention have a crystallized structure and a high purity which provide these materials with specific properties.
  • the MOF solids of aluminum carboxylates obtained according to the invention consist of a single single phase free of impurities, crystallized and well identified. This means that the other phases ( ⁇ 2% by weight) that may exist in the chemical system in question are not present in a mixture with the MOF solid according to the invention.
  • the MOF solids of aluminum carboxylates which can be obtained by a hydrothermal preparation process as described above also have a degree of purity of at least 95%, in particular of at least 98% by weight.
  • the purity of the MOF solids of the invention can be determined in particular by elemental chemical analysis, X-ray diffraction, scanning electron microscopy and NMR of the aluminum 27 ( 27 Al) and 13 carbon ( 13 C) solid.
  • the MOF solids obtained contain no or little secondary product, for example aluminum hydroxide of formula AI (OH) 3 or AlO (OH), or the other phases of the chemical system considered appearing in other synthesis conditions (for example by operating at pH ranges different from those indicated in the process of the invention).
  • This may be a consequence of the hydrothermal preparation method which makes it possible to obtain MOF solids of aluminum carboxylates directly from an aqueous solution which may be water, and this with appropriate control of thermodynamic variables (temperature, pressure etc.)
  • the particular structural characteristics of the solids of the present invention make them adsorbents with high loading capacity, high selectivity and high purity. They thus make possible the selective adsorption and thus the selective separation of gas molecules, for example molecules of NO, N 2 , H 2 S, H 2 , CH 4 , O 2 , CO, CO 2 .
  • the subject of the present invention is also the use of a solid consisting of porous and crystallized aluminum carboxylate (MOF) metal network for the storage of liquid or gaseous molecules, for the selective separation of gases [27] or for catalysis [28].
  • MOF metal carboxylate
  • Figure 1 shows the X-ray diffraction pattern of the MIL-100 (Al) (CUKQ) phase.
  • the abscissa represents the angular variation in 2D (°).
  • the ordinate represents the relative intensity of the diffraction peaks.
  • Figure 2 shows the N 2 adsorption isotherm at 77K of the MIL-100 phase.
  • the ratio p / p ° which corresponds to the relative pressure is given on the abscissa.
  • the volume of adsorbed gas per gram of product (cm 3 .g -1 ) is represented in ordinate.
  • Fig. 3 shows the thermogravimetric analysis curve of MIL-100 (Al) (under O 2 flow, 3 ° C.min -1 ) The percentage of the mass loss is shown as ordinate. Heating is represented on the abscissa.
  • FIG. 4 shows the photograph (scanning electron microscopy) of a sample of MIL-100 (Al) showing crystallites in the form of one micron octahedra.
  • FIG. 5 shows the X-ray diffraction pattern of the MIL-120 (Al) (CUKQ) phase.
  • the abscissa represents the angular variation in 2D (°).
  • the ordinate represents the relative intensity of the diffraction peaks.
  • Figure 6 shows the N 2 adsorption isotherm at 77K of the MIL-120 (Al) phase.
  • the ratio p / p ° which corresponds to the relative pressure is given on the abscissa.
  • the volume of adsorbed gas per gram of product (cm 3 .g -1 ) is represented in ordinate.
  • MIL-120 Al (under O 2 flow, 3 ° C.min "1 ) The percentage of the mass loss is represented on the ordinate The heating temperature is represented on the abscissa.
  • FIG. 8 shows the photograph (scanning electron microscopy) of a sample of MIL-120 (A1) showing crystallites in the form of 5 to 30 micron needles.
  • Fig. 9 shows the X-ray diffraction pattern of the MIL-121 (Al) (CUKQ) phase.
  • the abscissa represents the angular variation in 2D (°).
  • the ordinate represents the relative intensity of the diffraction peaks.
  • Fig. 10 shows the N 2 adsorption isotherm at 77K of the MIL-121 (Al) phase.
  • the ratio p / p ° which corresponds to the relative pressure is given on the abscissa.
  • the volume of adsorbed gas per gram of product (cm 3 .g -1 ) is represented in ordinate.
  • Fig. 11 shows the thermogravimetric analysis curve of MIL-121 (Al) (under O 2 flow, 1 ° C. min -1 ) The percentage of the mass loss is represented on the ordinate. Heating is represented on the abscissa.
  • FIG. 12 shows the photograph (scanning electron microscopy) of a sample of MIL-121 (A1) showing crystallites in the form of parallelepipeds of 2 to 5 microns.
  • Figure 13 shows the MAS 27 AI NMR spectrum (30 kHz) of MIL-100 (Al), measured with a Bruker AVANCE-500 spectrometer (2.5 mm rotor).
  • Fig. 14 shows the 13 C ⁇ 1 H ⁇ CPMAS NMR spectrum (12.5 kHz) of MIL-100 (Al), measured with a Bruker AVANCE-500 spectrometer (2.5 mm rotor).
  • Figure 15 shows the MAS NMR spectrum 27 AI (30kHz) of MIL-120 (Al), measured with a Bruker AVANCE-500 spectrometer (2.5 mm rotor).
  • Fig. 16 shows the 13 C ⁇ 1 H ⁇ CPMAS NMR spectrum (10 kHz) of MIL-120 (Al), measured with a TecMag Apollo-200 spectrometer (4 mm rotor).
  • FIG. 17 shows the MAS 27 AI (30 kHz) NMR spectrum of MIL-121 (Al), measured with a Bruker AVANCE-500 spectrometer (2.5 mm rotor).
  • Fig. 18 shows the CPMAS 13 C ⁇ 1 H ⁇ NMR spectrum (12.5 kHz) of
  • MIL-121 Al
  • Bruker AVANCE-500 spectrometer 2.5 mm rotor
  • D Figure 19 shows NMR spectra 1 H (a) MAS and (b) 1 H ⁇ 27 ⁇ AI TRAPDOR MIL-I OO (AI) showing the water signals D 5 ppm, of the additional structure to btc D 8 ppm, and structure btc at D 9 ppm. All the pectres are recorded at 500 MHz and with a spin speed of 30 kHz.
  • Figure 20 shows 27 NMR MAS NM of MIL-100 (a), and subsequent heat treatment at 130 ° C (b), and then re-hydration overnight (c) above NaCl solution in a closed separator (d) showing the reversible formation of unsaturated coordination sites (CUS) on a dehydration / rehydration cycle.
  • the duration of the heat treatment is 4 to 6 hours.
  • the spectra in (a) and (b) are obtained by experiments with single pulses, while in (b) and (c) by experiments with whole echo.
  • FIG. 21 represents the 27 Multi-Quanta NMR spectrum with Magic Angle Rotation (MQMAS) of MIL-100 dehydrated at 150 ° C. From 0 to -10 ppm, the hexacoordinated sites are present and can be solved in FIG. the indirect dimension (vertical on the drawing) by their chemical shifts, and from 30 to 40 ppm of the pentacoordinated sites are present, and the indirect dimension shows that they are solved in two types of sites.
  • MQMAS Magic Angle Rotation
  • Fig. 22 shows the X-ray diffractograms (copper radiation) of samples of MIL-100 (AI) _as (as synthesized), MIL-100 (AI) _ac
  • the diffraction diagrams were recorded using a diffractometer (Siemens D5000) in Bragg-Brentano geometry in reflection on a 2theta angular range of 2 to 40 ° with a step and a counting time of 0.02 ° and 1 second, respectively (radiation CuK D i, 2 ).
  • Thermogravimetric analysis (TA Instrument 2050) was carried out from a sample of 5 or 20 mg heated on a scale of 20 to 600 0 C under an oxygen flow with a heating rate of 3 ° C.min " 1 .
  • the compound MIL-100 (Al) is an analogue of the chromium (III) and iron (III) materials already described in the literature by our laboratory.
  • This phase is obtained from a mixture of 1.31 g of aluminum nitrate (Al (NO 3 ) 3-9H 2 O), 0.596 g of trimethyl-1,3,5-benzenetricarboxylate, 4.4 ml. of nitric acid (1 M HNO3) and 16 ml of water placed in a Teflon cell with a volume of 125 ml and a Parr brand steel trademark autoclave (trademark).
  • the reaction takes place at 210 ° C. for 3h30 in an oven (temperature rise 1 h). 0.55 g of MIL-100 (Al) is obtained.
  • the pH of the reaction is 1.8.
  • a second preparation can be carried out starting from a mixture of 7.485 g of aluminum nitrate (Al (NO 3 ) 3-9H 2 O), 3.39 g of trimethyl-1,3,5-benzenetricarboxylate, 25 ml nitric acid (1 M HNO3) and 91.29 ml of water placed in a Teflon cell with a volume of 500 ml and then a steel autoclave of trademark type Parr (registered trademark). The reaction takes place at 210 ° C. for 3h30 in an oven (temperature rise 1 h). 3.45 g of MIL-100 (Al) is obtained. The pH of the reaction is 1.8. The resulting products consist of a homogeneous yellow powder which is filtered and washed with deionized water at room temperature.
  • the activation of this product is as follows: one gram of MIL-100 (Al) and 40 ml of DMF (N, N'-dimethylformamide) are placed in a 125 ml hydrothermal chamber and heated at 150 ° C. for 4 hours. . After filtration, the white compound is washed with distilled water under reflux at 100 ° C for 12 hours and then filtered again at room temperature.
  • the measured BET surface is 2150 m 2 .g- 1 and the Langmuir surface is
  • Thermogravimetric analysis indicates that the MIL-100 (Al) material is stable up to 350 ° C. (FIG. 3).
  • TRAPDOR is performed [29].
  • the TRAPDOR experiment is designed to measure dipolar interactions between two different spins under Magic Angle Spinning (MAS).
  • MAS Magic Angle Spinning
  • the first measurement is a control experiment, wherein a synchronized rotor 1 H spin-echo sequence (90 ° -fr180 ° -Q is applied with Detant a rotor period.
  • the second experience is the same spin-echo as the first experiment except that during the first half of the echo (Q on the spins 1H observed spins 27 AI are continuously irradiated.
  • the high-power, continuous radiofrequency irradiation of 27 AI spins in Magic Angle Spinning (MAS) rotation conditions affects the echo intensity of 1 H spins if an aluminum is in close proximity, such as a coupled dipole
  • the TRAPDOR difference spectrum ( Figure 19b) is obtained by subtracting the TRAPDOR spectrum from the control spectrum, and indicates the dipolar coupling
  • the signal remaining in the difference spectrum shows that only the signal water is significantly affected due to the proximity of its protons to 27 AI nuclei
  • the binding of water to aluminum indicates the Bronsted acidity of these sites.
  • Figure 20 shows the spectrum 27 Al MAS NMR MIL-100 successive heating times in different forms dehydrated, fully hydrated ( Figure 20a) partially dried ( Figures 2b-c), and after a subsequent re-hydration ( Figure 2d).
  • Figure 2d After 4h at 130 0 C, an additional signal appears on the spectrum 27 AI around 37 ppm isotropic chemical shifts compatible with penta-coordinated species of AI. By increasing the processing temperature, the signal increases.
  • MIL-I OO (AI)
  • MIL-IO on the same Al 3 trimer, a site may have both a Bronsted acidity and a Lewis-type acidity.
  • Dehydration which results in the appearance of a penta-coordinated aluminum in MIL-I O (AI) is different from that of its chromium and iron counterparts.
  • MIL-I O one in three aluminum changes coordination instead of two out of three described for its corresponding to chromium or iron.
  • MIL-96 AI
  • MIL-110 Al
  • MIL-100 Al
  • MIL-100 Al
  • porosity and pore accessibility are radically different from MIL-I O (AI)
  • the dehydration of the reactive sites in MIL-96 (Al) is blocked by the water present in its pores.
  • MIL-110 (Al) its thermal stability is much lower than that of MIL-100 (Al).
  • MIL-100 combines, the maximum porosity, diffusion paths (the possibility of communication between the pores) allowing the entry and exit of large molecules, and an activation of its sites by dehydration at low temperature (as per example 130-150 0 C) and selective sites.
  • MIL-I O AI
  • MIL-IO AI in the form of a mixture of phases, such as, for example, with MIL-96 (AI) and / or MIL-110 (Al)
  • MIL-100_as (as synthesized) showing that the activated form of MIL-100 (with empty pores) is stable and the 3D structure is maintained during the activation process.
  • the last diagram in Fig. 22 is a diagram computed from atomic data of a single crystal of MIL-100. This shows that the X-ray diffractogram of MIL-100 is in very good agreement with that calculated, reflecting the high purity of the MIL-100 product obtained.
  • Example 2 Preparation of MIL-120 (Al)
  • the compound MIL-120 (Al) is obtained from a mixture of 3.2 g of aluminum nitrate (Al (NO 3 ) 3-9H 2 O), 0.5 g of 1,2,4,5-benzenetetracarboxylic acid, 3.2 ml of sodium hydroxide (4 M NaOH) and 20 ml of water placed in a Teflon cell with a volume of 125 ml and then inserted into a a Parr brand steel trademark autoclave (registered trademark). The reaction takes place at 210 ° C. for 24 hours in an oven. 0.68 g of MIL-120 (Al) is obtained. The pH of the reaction is 1.85. The product is washed by heating under reflux in distilled water overnight, and is filtered at room temperature. It is activated by heating at 200 ° C. overnight.
  • Thermogravimetric analysis indicates that the MIL-120 (Al) material is stable up to 290 ° C ( Figure 7).
  • the combination of these different characterization analyzes shows that it is a very well identified material with a very high crystalline purity.
  • the compound MIL-121 (Al) is obtained from a mixture of 9.6 g of aluminum nitrate (Al (NO 3 ) 3-9H 2 O), 3.2 g of acid 1, 2, 4,5-benzenetetracarboxylic and
  • the BET surface area is 173 m 2 .g -1 and the Langmuir surface is 258 m 2 .g -1 (FIG. 10).
  • Thermogravimetric analysis indicates that the MIL-121 (Al) material is stable up to 430 ° C ( Figure 11).

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JP2013144284A (ja) * 2012-01-16 2013-07-25 Toyobo Co Ltd 多孔性複合材料とその製造方法、及び硫化水素ガス除去材
WO2017152240A1 (en) 2016-03-11 2017-09-14 Commonwealth Scientific And Industrial Research Organisation Polymeric agents and compositions for inhibiting corrosion
WO2018167078A1 (en) 2017-03-16 2018-09-20 Universidad De Zaragoza Organic - inorganic porous hybrid material, method for obtaining it and use thereof
EP3932540A2 (en) 2020-07-01 2022-01-05 Indian Oil Corporation Limited Zinc based metal organic frameworks (zit) with mixed ligands for hydrogen storage
US11607666B2 (en) 2020-07-01 2023-03-21 Indian Oil Corporation Limited Zinc based metal organic frameworks (ZIT) with mixed ligands for hydrogen storage

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EP2376503B1 (fr) 2018-07-04
JP2016155879A (ja) 2016-09-01
US8658562B2 (en) 2014-02-25
JP6004650B2 (ja) 2016-10-12
US20120055880A1 (en) 2012-03-08

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