WO2023197423A1 - Matériau de structure organométallique en blocs, procédé de préparation s'y rapportant et son utilisation - Google Patents

Matériau de structure organométallique en blocs, procédé de préparation s'y rapportant et son utilisation Download PDF

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WO2023197423A1
WO2023197423A1 PCT/CN2022/096692 CN2022096692W WO2023197423A1 WO 2023197423 A1 WO2023197423 A1 WO 2023197423A1 CN 2022096692 W CN2022096692 W CN 2022096692W WO 2023197423 A1 WO2023197423 A1 WO 2023197423A1
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organic framework
bulk metal
framework material
materials
metal organic
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PCT/CN2022/096692
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Chinese (zh)
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朱世平
王捷睿
朱贺
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香港中文大学（深圳）
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G83/00—Macromolecular compounds not provided for in groups C08G2/00 - C08G81/00
    • C08G83/008—Supramolecular polymers
    • 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
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • B01J31/1691—Coordination polymers, e.g. metal-organic frameworks [MOF]
    • 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
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • B01J31/18—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms
    • B01J31/1805—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms the ligands containing nitrogen
    • B01J31/181—Cyclic ligands, including e.g. non-condensed polycyclic ligands, comprising at least one complexing nitrogen atom as ring member, e.g. pyridine
    • B01J31/1815—Cyclic ligands, including e.g. non-condensed polycyclic ligands, comprising at least one complexing nitrogen atom as ring member, e.g. pyridine with more than one complexing nitrogen atom, e.g. bipyridyl, 2-aminopyridine
    • 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
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J35/61—Surface area
    • B01J35/617—500-1000 m2/g
    • 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
    • B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
    • B01J2531/20—Complexes comprising metals of Group II (IIA or IIB) as the central metal
    • B01J2531/26—Zinc
    • 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 disclosure relates to the field of materials, and in particular to a bulk metal organic framework material and its preparation method and application.
  • Metal organic framework is a type of porous crystalline nanomaterial formed by the self-assembly of metal ions (clusters) and organic ligands through coordination bonds. It has a large specific surface area, adjustable pore structure and thermal stability. Due to its advanced advantages, it has always attracted much attention from the academic community and is considered to be one of the most promising nanomaterials. In most cases, MOF is powdered nanoparticles synthesized by solvothermal method. The particle size is very different from the filler size for industrial applications. Direct use of powder will cause excessive pressure drop of the equipment and is prone to short circuit, increasing the difficulty of operation.
  • MOF metal-organic chemical vapor deposition
  • the high internal phase emulsion (HIPE) template method is an emerging method for preparing MOF blocks in recent years.
  • Poly-HIPE a bulk material prepared from HIPE templates, has the advantages of low density and highly controllable pore structure. Its macroporous structure consists of highly interconnected "voids” and “pore throats (Window)", allowing guest molecules to quickly contact the active sites of MOF.
  • Window pore throats
  • Poly-HIPE is first prepared from HIPE and then used as a scaffold for in-situ synthesis of MOF; (2) MOF is first dispersed in HIPE (in the continuous phase or at the oil/water interface), and then HIPE polymerization is initiated Form MOF/poly-HIPE bulk material. At this stage, there are still many problems in preparing MOF blocks using HIPE templates. First, a large amount of polymer is needed to adhere the dispersed MOF particles and provide the necessary mechanical strength.
  • the present disclosure provides a method for preparing bulk metal organic framework materials, including:
  • the reaction product is sequentially subjected to liquid nitrogen freezing and freeze-drying, and then is heated and activated to obtain the massive metal-organic framework material.
  • the feedstock further includes additives including polyvinyl alcohol.
  • the molar ratio of the partial amount of the ligand compound to the metal oxide nanoparticles is (0.15-1): 1;
  • the ratio of the total molar amount of the partial amount of the ligand compound and the remaining amount of the ligand compound to the molar amount of the metal oxide nanoparticles is (2-6):1.
  • the volume ratio of the nanoparticle dispersion liquid and the cyclohexane is 1: (3-9), and the shear rate of the shear homogenization is 3000-15000 rpm.
  • the reaction temperature is room temperature and the reaction time is 12-24 h.
  • the freeze-drying time is 12-24 hours.
  • the heating activation temperature is 130-170°C and the time is 9-27 hours.
  • the metal oxide nanoparticles include nanozinc oxide
  • the ligand compound includes one or more of imidazole, 2-methylimidazole, 2-ethylimidazole, benzimidazole, and 2-imidazolecarboxaldehyde.
  • the present disclosure also provides a bulk metal organic framework material, which is prepared using the preparation method of the bulk metal organic framework material.
  • the present disclosure also provides an application of the bulk metal organic framework material as a catalyst.
  • the catalyst includes optical catalysts, electrical catalysts, oligomerization catalysts, and copolymerization catalysts.
  • the present disclosure also provides uses of the bulk metal-organic framework materials in gas storage and separation, sensors, filter materials, optical materials, electrical materials and magnetic materials.
  • Figure 1 is a schematic diagram of the principle of the preparation method of bulk metal organic framework materials provided by the present disclosure
  • Figure 2 is a photo of the material obtained in Example 4 placed on flowers
  • Figure 3 is a photo of the material obtained in Example 4 placed under a 200g weight
  • Figure 4 is a cross-sectional SEM image of the material obtained in Example 4.
  • Figure 5 is a partially enlarged SEM image of the cross-section of the material obtained in Example 4.
  • Figure 6 is the N 2 adsorption and desorption curve of the bulk ZIF-8 material in Example 4.
  • Figure 7 is the DFT pore size analysis curve of the bulk ZIF-8 material in Example 4.
  • Figure 8 is the TGA curve of the bulk ZIF-8 material and the control sample in Example 4.
  • compositions, step, method, article, or device that includes listed elements need not be limited to those elements, but may include other elements not expressly listed or inherent to such composition, step, method, article, or device. elements.
  • Part by mass refers to the basic measurement unit that expresses the mass proportion relationship of multiple components.
  • One part can represent any unit mass, such as 1g, 2.689g, etc. If we say that the mass part of component A is part a and the mass part of component B is part b, it means that the ratio of the mass of component A to the mass of component B is a:b. Or, it means that the mass of component A is aK and the mass of component B is bK (K is an arbitrary number, indicating a multiple factor). It should not be misunderstood that, unlike mass parts, the sum of mass parts of all components is not limited to 100 parts.
  • a and/or B includes (A and B) and (A or B).
  • One embodiment of the present disclosure provides a method for preparing bulk metal organic framework materials, including:
  • the reaction product is sequentially frozen in liquid nitrogen and freeze-dried, and then activated by heating to obtain a massive metal-organic framework material.
  • the raw materials also include additives, including but not limited to polyvinyl alcohol.
  • Polyvinyl alcohol is used as an additive to adjust MOF crystallization.
  • the molar ratio of the partial amount of the ligand compound to the metal oxide nanoparticles is (0.15-1):1.
  • the ratio of the total molar amount of part of the ligand compound and the remaining amount of the ligand compound to the molar amount of the metal oxide nanoparticles is (2-6):1.
  • the volume ratio of the nanoparticle dispersion liquid and cyclohexane is 1: (3-9), and the shear rate for shear homogenization is 3000-15000 rpm.
  • the molar ratio of the partial amount of the ligand compound to the metal oxide nanoparticles can be, for example, (0.2-0.95):1, (0.25-0.85):1 or (0.35-0.75):1. , such as 0.15:1, 0.20:1, 0.25:1, 0.30:1, 0.35:1, 0.40:1, 0.45:1, 0.50:1, 0.55:1, 0.60:1, 0.65:1, 0.70:1, Any value between 0.75:1, 0.80:1, 0.85:1, 0.90:1, 0.95:1, 1:1 or (0.15-1):1.
  • the ratio of the total molar amount of the partial amount of the ligand compound and the remaining amount of the ligand compound to the molar amount of the metal oxide nanoparticles can be 2:1, 3:1, 4:1, 5:1, Any value between 6:1 or (2-6):1.
  • the volume ratio of the nanoparticle dispersion and cyclohexane can be, for example, 1: (3.5-8.5), 1: (4-8) or 1: (4.5-7.5), such as 1:3, 1:4 , 1:5, 1:6, 1:7, 1:8, 1:9 or any value between 1: (3-9).
  • the shear rate for shear homogenization may be, for example, 4000-12000rpm, 5000-10000rpm or 6000-9000rpm, such as 3000rpm, 5000rpm, 10000rpm, 15000rpm or any value between 3000-15000rpm.
  • the reaction temperature is room temperature and the reaction time is 12-24 h.
  • reaction time may be, for example, 14-22h, 15-20h or 16-19h, such as 12h, 14h, 16h, 18h, 20h, 22h, 24h or any value between 12-24h.
  • room temperature referred to in this disclosure is 20-25°C.
  • the freeze-drying time is 12-24 hours.
  • freeze-drying is to remove water and cyclohexane.
  • freeze-drying time can be, for example, 14-22h, 15-20h or 16-19h, 12h, 14h, 16h, 18h, 20h, 22h, 24h or any value between 12-24h.
  • the heating activation temperature is 130-170°C and the time is 9-27 hours.
  • the temperature for heat activation may be, for example, 130-170°C, 130-170°C, or 130-170°C, such as 130°C, 140°C, 150°C, 160°C, 170°C, or anywhere between 130-170°C.
  • the heating activation time may be, for example, 12-25h, 14-21h or 16-18h, such as 9h, 10h, 12h, 14h, 16h, 18h, 20h, 22h, 24h, 26h, 27h or 9-27h. any value between.
  • the metal oxide nanoparticles include but are not limited to zinc oxide nanoparticles.
  • the ligand compound includes, but is not limited to, one or more of imidazole, 2-methylimidazole, 2-ethylimidazole, benzimidazole, and 2-imidazolecarboxaldehyde.
  • An embodiment of the present disclosure also provides a bulk metal-organic framework material, which is prepared using a method for preparing a bulk metal-organic framework material.
  • An embodiment of the present disclosure also provides an application of a bulk metal organic framework material for use as a catalyst.
  • catalysts include optical catalysts, electrical catalysts, oligomerization catalysts, and copolymerization catalysts.
  • An embodiment of the present disclosure also provides the use of the bulk metal organic framework material in gas storage and separation, sensors, filter materials, optical materials, electrical materials and magnetic materials.
  • the preparation method of bulk metal-organic framework materials is to prepare MOF bulk materials from the oil-water interface of HIPE through an in-situ growth method.
  • metal oxide nanoparticles are used as stabilizers and metal sources to self-assemble at the interface, and ligands are introduced to post-modify the metal oxide nanoparticles, and HIPE can be achieved under a wide ligand/metal ratio.
  • Stable forming a stable three-dimensional interface network, providing a stable template for MOF synthesis; on this basis, the metal source at the interface is converted in situ into a three-dimensional structured MOF block by adding ligands; the block appears after freeze-drying
  • the hierarchical pore structure of micropores, mesopores and macropores can increase the specific surface area to 961.3m 2 ⁇ g -1 through further activation.
  • This method only involves four commonly used and well-developed chemical unit operations: dissolution, emulsification, freeze-drying, and heating activation. Compared with the existing methods, it does not involve fine modification, washing and other operations. The internal phase cyclohexane can be recycled and reused. The preparation cost is low and the environmental pollution is small. The process is short, the operation is simple, easy to industrialize production, and the preparation cost is low. MOF composite materials with high density, high specific surface area and high MOF content have significant advantages. The preparation method of bulk metal-organic framework materials can be widely used to prepare ZIF series.
  • the bulk metal-organic framework material provided by this disclosure is a multi-level porous low-density MOF bulk material, covering both macropore and micropore ranges. It is composed of MOF polycrystals and has a highly regular skeleton structure, retaining all the characteristics of powder MOF materials. Performance: Macroscopically, composite materials have very low density and good mechanical properties, and are easy to post-process and industrial operations; microscopically, MOF particles are connected to each other and regularly assembled into a three-dimensional network with stable structure. The MOF mass percentage is 93.2-99.9%.
  • the density of the bulk material is about 80 mg ⁇ cm -3 , the material strength is 3-40kPa, and the specific surface area is 900-961.3m 2 /g.
  • the bulk metal-organic framework material provided by the present disclosure is used to catalyze the Knoevenagel condensation reaction.
  • the block material does not show obvious structural changes and catalyst deactivation after long-term catalysis, and is conducive to simplifying the recycling process.
  • this embodiment provides a bulk metal organic framework material, and its preparation method is as follows:
  • This embodiment provides a bulk metal organic framework material, and its preparation method is as follows:
  • This embodiment provides a bulk metal organic framework material, and its preparation method is as follows:
  • This embodiment provides a bulk metal organic framework material, and its preparation method is as follows:
  • FIG. 2 A photo of the material obtained in Example 4 placed on a flower is shown in Figure 2. It can be seen from Figure 2 that the material obtained has low density characteristics.
  • Figure 6 shows the N 2 adsorption and desorption curve of the material obtained in Example 4.
  • the adsorption amount in the low pressure region increases rapidly, which is a type I isotherm.
  • the BET specific surface area is 961.3m 2 /g, indicating that the obtained material has excellent adsorption performance.
  • Figure 7 is the DFT pore size analysis curve of the material obtained in Example 4, which shows that the obtained material covers the macropore and micropore range.
  • Example 4 only takes Example 4 as an example to characterize the characteristics of the materials obtained in this disclosure.
  • the metal organic framework materials prepared in Examples 1-3 and 5 of this disclosure also have low density, mechanical properties similar to those in Example 4. Excellent performance, the material has porous characteristics, excellent adsorption performance, and the material covers the significant characteristics of macropores and micropores.
  • This embodiment provides a bulk metal organic framework material, and its preparation method is as follows:
  • the resulting material contains no ZIF-8, is shapeless, and has almost no strength.
  • the resulting bulk material has an unstable structure and almost no strength.
  • the resulting block material has a collapsed structure and a porosity of less than 20%.
  • the obtained bulk material has low crystallinity, a large amount of zinc oxide is not converted, and the specific surface area is only 323.3m 2 /g.
  • N 2 adsorption and desorption curve The N 2 adsorption and desorption curve was measured using the gas adsorption instrument (AUTOSORB-IQ2-MP) of the American QUANTACHROME Instrument Company, and vacuum degassing at 100°C for 24 hours before measurement.
  • gas adsorption instrument AUTOSORB-IQ2-MP
  • Specific surface area S BET and pore size distribution Use the software ASiQwin to calculate the specific surface area and pore size distribution of the bulk material.
  • the specific surface area is calculated using the Brunauer–Emmett–Teller (BET) method, and the pore size is calculated using the Density Functional Theory (DFT) method. .
  • BET Brunauer–Emmett–Teller
  • DFT Density Functional Theory
  • Porosity and macropore diameter Characterized by mercury porosimeter (MIP, AutoPore IV 9510) from McMurray Instruments Company of the United States.
  • X-ray diffraction PXRD Characterized by the X-pert Powder X-ray diffractometer of PANalytical Company of the Netherlands, with a scanning range of 5-50°.
  • the bulk metal organic framework material obtained by the present disclosure has the characteristics of low density, high specific surface area and high porosity.
  • the material obtained in Example 4 and the control sample material for Material obtained in proportion 2
  • the TGA test atmosphere is air
  • the flow rate is set to 20mL/min
  • the heating speed is 10°C/min
  • the temperature range is 100-680°C.
  • the TGA residues of the control sample and the experimental sample are both ZnO.
  • the MOF contents are 99.8% and 97.3% respectively.
  • Examples 1, 2 and 4 have a relatively high content of MOF. It should be noted that this disclosure only takes Examples 1, 2 and 4 as examples to characterize the characteristics of the materials obtained in this disclosure.
  • the metal organic framework materials prepared in Examples 3 and 5 of this disclosure also have the same characteristics as those in Examples 1, 2 and 4. They are similar and both have the distinctive characteristics of higher content of MOF.
  • the present disclosure provides a bulk metal organic framework material and its preparation method and application.
  • the preparation method of the present disclosure belongs to the high internal phase emulsion template in-situ growth method.
  • the method has a short process flow, simple operation, and is easy for industrial production; it is prepared by the preparation method of the present disclosure.
  • the obtained bulk metal organic framework material is a hierarchical porous MOF bulk material, with a pore size that covers both large and small pores, ensuring high mechanical properties while retaining all the characteristics of the powder material, and has excellent practical performance. , can be widely used in catalysts, sensors, filter materials, optical materials, electrical materials and magnetic materials and other fields.

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Abstract

L'invention concerne un matériau de structure organométallique en blocs, un procédé de préparation s'y rapportant et son utilisation. Le procédé de préparation du matériau de structure organométallique en blocs comprend : le mélange de matières premières comprenant des nanoparticules d'oxyde métallique, une partie d'un composé ligand et de l'eau pour obtenir un liquide de dispersion de nanoparticules ; le mélange du liquide de dispersion de nanoparticules avec du cyclohexane, et le cisaillement et l'homogénéisation du mélange ainsi obtenu pour obtenir une émulsion à proportion de phase interne élevée ; le mélange de l'émulsion à proportion de phase interne élevée avec la quantité résiduelle du composé ligand pour réaction ; et la mise en œuvre séquentielle d'une congélation à l'azote liquide et d'une lyophilisation sur le produit de réaction, puis le chauffage et l'activation de celui-ci pour obtenir un matériau de structure organométallique en blocs. Le procédé est du type procédé de croissance in situ sur matrice d'émulsion à proportion de phase interne élevée, a un enchaînement des opérations court et un fonctionnement simple et pratique et est facile pour une production industrielle. Le matériau de structure organométallique en blocs est du type matériau en blocs de réseaux métallo-organiques (MOF) à pores hiérarchiques et la taille des pores de celui-ci couvre la plage à la fois des macropores et des petits pores, de telle sorte que toutes les caractéristiques d'un matériau en poudre sont conservées et que des propriétés mécaniques élevées sont assurées. De plus, le matériau de structure organométallique en blocs peut être utilisé en tant que catalyseur.
PCT/CN2022/096692 2022-04-12 2022-06-01 Matériau de structure organométallique en blocs, procédé de préparation s'y rapportant et son utilisation WO2023197423A1 (fr)

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CN116272896A (zh) * 2023-02-24 2023-06-23 中国人民解放军军事科学院防化研究院 一种多级孔mof-808宏观整体材料的制备方法

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CN113461959A (zh) * 2021-07-01 2021-10-01 南开大学 一种利用高压均质制备金属有机框架材料的方法
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CN109395779A (zh) * 2018-09-21 2019-03-01 江苏大学 一种基于乳液模板法的多功能固体催化剂的制备方法和用途
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CN107349964A (zh) * 2017-07-15 2017-11-17 北京化工大学 一种纳米颗粒@小尺寸金属有机框架材料的制备方法
CN110270315A (zh) * 2019-07-01 2019-09-24 香港中文大学（深圳） Mof-聚合物复合材料、其制备方法及应用
WO2021212533A1 (fr) * 2020-04-21 2021-10-28 苏州大学 Composé de réseau organométallique poreux et son application pour adsorber un gaz radioactif
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CN113461959A (zh) * 2021-07-01 2021-10-01 南开大学 一种利用高压均质制备金属有机框架材料的方法

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