WO2023197423A1 - Blocky metal organic framework material, and preparation method therefor and use thereof - Google Patents

Blocky metal organic framework material, and preparation method therefor and use thereof 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
    • B01J35/617—
    • 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.

Abstract

A blocky metal organic framework material, and a preparation method therefor and the use thereof. The preparation method for the blocky metal organic framework material comprises: mixing raw materials comprising metal oxide nanoparticles, part of a ligand compound and water to obtain a nanoparticle dispersion liquid; mixing the nanoparticle dispersion liquid with cyclohexane, and shearing and homogenizing the resulting mixture to obtain a high internal phase emulsion; mixing the high internal phase emulsion with the residual amount of the ligand compound for reaction; and sequentially carrying out liquid nitrogen freezing and freeze drying on the reaction product, and then heating and activating same to obtain a blocky metal organic framework material. The method belongs to a high internal phase emulsion template in-situ growth method, has a short method flow and simple and convenient operation, and is easy for industrial production. The blocky metal organic framework material belongs to a hierarchical pore MOF blocky material, and the pore size thereof covers the range of both macropores and small pores, such that all characteristics of a powder material are retained and high mechanical properties are ensured. In addition, the blocky metal organic framework material can be used as a catalyst.

Description

块状金属有机框架材料及其制备方法和应用Bulk metal-organic framework materials and preparation methods and applications thereof
相关申请的交叉引用Cross-references to related applications
本公开要求于2022年04月12日提交中国专利局的申请号为CN 202210379018.1、名称为“块状金属有机框架材料及其制备方法和应用”的中国专利申请的优先权，其全部内容通过引用结合在本公开中。This disclosure claims priority to the Chinese patent application with application number CN 202210379018.1 and titled "Bulk Metal Organic Framework Materials and Preparation Methods and Applications" submitted to the China Patent Office on April 12, 2022, the entire content of which is incorporated by reference. incorporated in this disclosure.
技术领域Technical field
本公开涉及材料领域，尤其涉及一种块状金属有机框架材料及其制备方法和应用。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.
背景技术Background technique
金属有机框架材料(Metal organic framework,MOF)是由金属离子(簇)和有机配体通过配位键自组装形成的一类多孔晶体纳米材料，因为具有比表面积大、孔结构可调和热稳定性高等优点，一直备受学界关注，被认为是最具潜力的纳米材料之一。在大多数情况下，MOF是通过溶剂热法合成的粉末状纳米颗粒，粒子尺寸和工业应用的填料尺寸相差巨大，直接使用粉末会导致设备压降过大且容易产生短路，增大操作难度，同时纳米粒子的团聚堆积会增加客体分子到达MOF表面的阻力，降低传质效率。但是由于MOF不溶不熔的特性，难以加工成型，所以需要通过一些特殊的手段，如冲压或3D打印等加工工艺以及模板法、溶胶凝胶法(Sol-gel)等纳米材料加工技术将MOF加工成块状材料。但这些方法都存在设备昂贵、制备过程复杂、复合材料结构不可控等问题。Metal organic framework (MOF) 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. At the same time, the agglomeration and accumulation of nanoparticles will increase the resistance of guest molecules to reach the MOF surface and reduce the mass transfer efficiency. However, due to the insoluble and infusible characteristics of MOF, it is difficult to process and shape it. Therefore, MOF needs to be processed through some special means, such as stamping or 3D printing and other processing techniques, as well as nanomaterial processing technologies such as template method and sol-gel method (Sol-gel). Material in bulk. However, these methods have problems such as expensive equipment, complex preparation processes, and uncontrollable composite material structures.
高内相乳液(HIPE)模板法是近年来新兴的制备MOF块材的方法。由HIPE模板制备的块状材料poly-HIPE具有低密度，孔隙结构高度可控的优点。其大孔结构由高度相互连接的“孔腔(Void)”和“孔喉(Window)”组成，使得客体分子能够迅速与MOF的活性位点接触。一般来说，MOF/poly-HIPE的结合大多通过两种方法实现。(1)首先从HIPE中制备Poly-HIPE，然后将其作为原位合成MOF的支架；(2)首先将MOF分散在HIPE中(在连续相中或在油/水界面)，然后引发HIPE聚合形成MOF/poly-HIPE块状材料。就现阶段而言，HIPE模板制备MOF块材仍然存在许多问题。首先，需要使用大量的聚合物将分散的MOF粒子粘连并提供必要的机械强度，然而此举会不可避免地导致MOF负载量降低；其次这些聚合物还会导致MOF被聚合物基体包埋甚至微孔堵塞，使得块材的比表面积下降，总体性能表现欠佳。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. Generally speaking, the combination of MOF/poly-HIPE is mostly achieved through two methods. (1) 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. However, this will inevitably lead to a reduction in the MOF loading; secondly, these polymers will also cause the MOF to be embedded in the polymer matrix or even microscopically The holes are clogged, causing the specific surface area of the block to decrease and the overall performance to be poor.
发明内容Contents of the invention
本公开提供一种块状金属有机框架材料的制备方法，包括：The present disclosure provides a method for preparing bulk metal organic framework materials, including:
将包括金属氧化物纳米粒子、部分量的配体化合物和水在内的原料混合得到纳米粒子分散液；Mix raw materials including metal oxide nanoparticles, a partial amount of a ligand compound and water to obtain a nanoparticle dispersion;
将所述纳米粒子分散液和环己烷混合，剪切均质得到高内相乳液；Mix the nanoparticle dispersion and cyclohexane and shear and homogenize to obtain a high internal phase emulsion;
将所述高内相乳液和剩余量的配体化合物混合，进行反应；Mix the high internal phase emulsion and the remaining amount of the ligand compound to react;
将反应产物依次进行液氮冷冻和冷冻干燥，然后加热活化，得到所述块状金属有机框架材料。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.
在一些实施方式中，所述原料还包括添加剂，所述添加剂包括聚乙烯醇。In some embodiments, the feedstock further includes additives including polyvinyl alcohol.
在一些实施方式中，所述部分量的配体化合物与所述金属氧化物纳米粒子的摩尔量之比为(0.15-1)：1；In some embodiments, the molar ratio of the partial amount of the ligand compound to the metal oxide nanoparticles is (0.15-1): 1;
在一些实施方式中，所述部分量的配体化合物和所述剩余量的配体化合物的总摩尔量与所述金属氧化物纳米粒子的摩尔量之比为(2-6)：1。In some embodiments, 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.
在一些实施方式中，所述纳米粒子分散液和所述环己烷的体积比为1：(3-9)，所述剪切均质的剪切速率为3000-15000rpm。In some embodiments, 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.
在一些实施方式中，所述反应的温度为室温，时间为12-24h。In some embodiments, the reaction temperature is room temperature and the reaction time is 12-24 h.
在一些实施方式中，所述冷冻干燥的时间为12-24h。In some embodiments, the freeze-drying time is 12-24 hours.
在一些实施方式中，所述加热活化的温度为130-170℃，时间为9-27h。In some embodiments, the heating activation temperature is 130-170°C and the time is 9-27 hours.
在一些实施方式中，所述金属氧化物纳米粒子包括纳米氧化锌；In some embodiments, the metal oxide nanoparticles include nanozinc oxide;
在一些实施方式中，所述配体化合物包括咪唑、2-甲基咪唑、2-乙基咪唑、苯并咪唑、2-咪唑甲醛中的一种或多种。In some embodiments, the ligand compound includes one or more of imidazole, 2-methylimidazole, 2-ethylimidazole, benzimidazole, and 2-imidazolecarboxaldehyde.
本公开还提供一种块状金属有机框架材料，使用所述的块状金属有机框架材料的制备方法制得。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.
本公开还提供一种所述块状金属有机框架材料的应用，用作催化剂。The present disclosure also provides an application of the bulk metal organic framework material as a catalyst.
在一些实施方式中，所述催化剂包括光学催化剂、电学催化剂、齐聚催化剂、共聚催化剂。In some embodiments, the catalyst includes optical catalysts, electrical catalysts, oligomerization catalysts, and copolymerization catalysts.
本公开还提供所述块状金属有机框架材料在气体的储存和分离、传感器、过滤材料、光学材料、电学材料和磁学材料中的用途。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.
附图说明Description of the drawings
为了更清楚地说明本公开实施例的技术方案，下面将对实施例中所需要使用的附图作简单地介绍，应当理解，以下附图仅示出了本公开的某些实施例，因此不应被看作是对本公开范围的限定。In order to explain the technical solutions of the embodiments of the present disclosure more clearly, the drawings needed to be used in the embodiments will be briefly introduced below. It should be understood that the following drawings only show some embodiments of the present disclosure and therefore do not should be considered as limitations on the scope of this disclosure.
图1为本公开提供的块状金属有机框架材料的制备方法的原理示意图；Figure 1 is a schematic diagram of the principle of the preparation method of bulk metal organic framework materials provided by the present disclosure;
图2为实施例4所得材料置于花朵上的照片；Figure 2 is a photo of the material obtained in Example 4 placed on flowers;
图3为实施例4所得材料置于200g砝码下的照片；Figure 3 is a photo of the material obtained in Example 4 placed under a 200g weight;
图4为实施例4所得材料的断面SEM图；Figure 4 is a cross-sectional SEM image of the material obtained in Example 4;
图5为实施例4所得材料的断面局部放大SEM图；Figure 5 is a partially enlarged SEM image of the cross-section of the material obtained in Example 4;
图6为实施例4块状ZIF-8材料的N 2吸脱附曲线； Figure 6 is the N 2 adsorption and desorption curve of the bulk ZIF-8 material in Example 4;
图7为实施例4块状ZIF-8材料的DFT孔径分析曲线；Figure 7 is the DFT pore size analysis curve of the bulk ZIF-8 material in Example 4;
图8为实施例4块状ZIF-8材料与对照样的TGA曲线。Figure 8 is the TGA curve of the bulk ZIF-8 material and the control sample in Example 4.
具体实施方式Detailed ways
如本文所用之术语：As used in this article:
“由……制备”与“包含”同义。本文中所用的术语“包含”、“包括”、“具有”、“含有”或其任何其它变形，意在覆盖非排它性的包括。例如，包含所列要素的组合物、步骤、方法、制品或装置不必仅限于那些要素，而是可以包括未明确列出的其它要素或此种组合物、步骤、方法、制品或装置所固有的要素。"Prepared from" is synonymous with "comprising". As used herein, the terms "includes," "includes," "has," "contains," or any other variation thereof, are intended to cover a non-exclusive inclusion. For example, a composition, 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.
连接词“由……组成”排除任何未指出的要素、步骤或组分。如果用于权利要求中，此短语将使权利要求为封闭式，使其不包含除那些描述的材料以外的材料，但与其相关的常规杂质除外。当短语“由……组成”出现在权利要求主体的子句中而不是紧接在主题之后时，其仅限定在该子句中描述的要素；其它要素并不被排除在作为整体的所述权利要求之外。The conjunction "consisting of" excludes any unspecified elements, steps or components. If used in a claim, this phrase will close the claim so that it does not contain materials other than those described except for the usual impurities associated therewith. When the phrase "consisting of" appears in a clause of the body of a claim rather than immediately following the subject matter, it is limited only to the elements described in that clause; other elements are not excluded from the statement as a whole beyond the rights requirements.
当量、浓度、或者其它值或参数以范围、优选范围、或一系列上限优选值和下限优选值限定的范围表示时，这应当被理解为具体公开了由任何范围上限或优选值与任何范围下限或优选值的任一配对所形成的所有范围，而不论该范围是否单独公开了。例如，当公开了范围“1～5”时，所描述的范围应被解释为包括范围“1～4”、“1～3”、“1～2”、“1～2和4～5”、“1～3和5”等。当数值范围在本文中被描述时，除非另外说明，否则该范围意图包括其端值和在该范围内的所有整数和分数。When an amount, concentration, or other value or parameter is expressed in terms of a range, a preferred range, or a range defined by a series of upper preferred values and lower preferred values, this should be understood to specifically disclose any upper range limit or preferred value and any lower range limit. or any pairing of preferred values, whether or not that range is individually disclosed. For example, when the range "1 to 5" is disclosed, the described range should be interpreted to include the ranges "1 to 4", "1 to 3", "1 to 2", "1 to 2 and 4 to 5" , "1～3 and 5" etc. When a numerical range is described herein, unless otherwise stated, the range is intended to include the endpoints thereof and all integers and fractions within the range.
在这些实施例中，除非另有指明，所述的份和百分比均按质量计。In these examples, parts and percentages are by mass unless otherwise indicated.
“质量份”指表示多个组分的质量比例关系的基本计量单位，1份可表示任意的单位质量，如可以表示为1g，也可表示2.689g等。假如我们说A组分的质量份为a份，B组分的质量份为b份，则表示A组分的质量和B组分的质量之比a：b。或者，表示A组分的质量为aK，B组分的质量为bK(K为任意数，表示倍数因子)。不可误解的是，与质量份数不同的是，所有组分的质量份之和并不受限于100份之限制。"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.
“和/或”用于表示所说明的情况的一者或两者均可能发生，例如，A和/或B包括(A和B)和(A或B)。"And/or" is used to indicate that one or both of the stated circumstances may occur, for example, A and/or B includes (A and B) and (A or B).
本公开一实施方式提供一种块状金属有机框架材料的制备方法，包括：One embodiment of the present disclosure provides a method for preparing bulk metal organic framework materials, including:
将包括金属氧化物纳米粒子、部分量的配体化合物和水在内的原料混合得到纳米粒子分散液；Mix raw materials including metal oxide nanoparticles, a partial amount of a ligand compound and water to obtain a nanoparticle dispersion;
将纳米粒子分散液和环己烷混合，剪切均质得到高内相乳液；Mix the nanoparticle dispersion and cyclohexane and shear and homogenize to obtain a high internal phase emulsion;
将高内相乳液和剩余量的配体化合物混合，进行反应；Mix the high internal phase emulsion and the remaining amount of the ligand compound to react;
将反应产物依次进行液氮冷冻和冷冻干燥，然后加热活化，得到块状金属有机框架材料。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.
在一种可选的实施方式中，原料还包括添加剂，添加剂包括但不限于聚乙烯醇。In an optional embodiment, the raw materials also include additives, including but not limited to polyvinyl alcohol.
聚乙烯醇作为添加剂，用于调节MOF结晶。Polyvinyl alcohol is used as an additive to adjust MOF crystallization.
在一种可选的实施方式中，部分量的配体化合物与金属氧化物纳米粒子的摩尔量之比为(0.15-1)：1。In an optional embodiment, the molar ratio of the partial amount of the ligand compound to the metal oxide nanoparticles is (0.15-1):1.
在一种可选的实施方式中，部分量的配体化合物和剩余量的配体化合物的总摩尔量与金属氧化物纳米粒子的摩尔量之比为(2-6)：1。In an optional embodiment, 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.
在一种可选的实施方式中，纳米粒子分散液和环己烷的体积比为1：(3-9)，剪切均质的剪切速率为3000-15000rpm。In an optional embodiment, 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.
可选的，部分量的配体化合物与金属氧化物纳米粒子的摩尔量之比可以为例如还可以为(0.2-0.95)：1、(0.25-0.85)：1或(0.35-0.75)：1，诸如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、0.75：1、0.80：1、0.85：1、0.90：1、0.95：1、1：1或者(0.15-1)：1之间任意一值。可选的，部分量的配体化合物和剩余量的配体化合物的总摩尔量与金属氧化物纳米粒子的摩尔量之比可以为2：1、3：1、4：1、5：1、6：1或者(2-6)：1之间任意一值。可选地，纳米粒子分散液和环己烷的体积比可以为例如1：(3.5-8.5)、1： (4-8)或1：(4.5-7.5)，诸如1：3、1：4、1：5、1：6、1：7、1：8、1：9或者1：(3-9)之间的任一值。可选地，剪切均质的剪切速率可以为例如4000-12000rpm、5000-10000rpm或6000-9000rpm，诸如3000rpm、5000rpm、10000rpm、15000rpm或者3000-15000rpm之间的任一值。Optionally, 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. Optionally, 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. Alternatively, 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). Alternatively, 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.
在一种可选的实施方式中，反应的温度为室温，时间为12-24h。In an optional embodiment, the reaction temperature is room temperature and the reaction time is 12-24 h.
可选的，反应的时间可以为例如14-22h、15-20h或16-19h，诸如12h、14h、16h、18h、20h、22h、24h或者12-24h之间的任一值。Alternatively, the 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.
需要说明的是，本公开所指的室温为20-25℃。It should be noted that the room temperature referred to in this disclosure is 20-25°C.
在一种可选的实施方式中，冷冻干燥的时间为12-24h。In an optional embodiment, the freeze-drying time is 12-24 hours.
冷冻干燥的目的是为了去除水和环己烷。The purpose of freeze-drying is to remove water and cyclohexane.
可选的，冷冻干燥的时间可以为例如14-22h、15-20h或16-19h，12h、14h、16h、18h、20h、22h、24h或者12-24h之间的任一值。Alternatively, the 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.
在一种可选的实施方式中，加热活化的温度为130-170℃，时间为9-27h。In an optional embodiment, the heating activation temperature is 130-170°C and the time is 9-27 hours.
可选的，加热活化的温度可以为例如130-170℃、130-170℃或130-170℃，诸如130℃、140℃、150℃、160℃、170℃或者130-170℃之间的任一值。可选的，加热活化的时间可以为例如12-25h、14-21h或16-18h，诸如9h、10h、12h、14h、16h、18h、20h、22h、24h、26h、27h或者9-27h之间的任一值。Alternatively, 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. One value. Alternatively, 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.
在一种可选的实施方式中，金属氧化物纳米粒子包括但不限于纳米氧化锌。In an alternative embodiment, the metal oxide nanoparticles include but are not limited to zinc oxide nanoparticles.
在一种可选的实施方式中，配体化合物包括但不限于咪唑、2-甲基咪唑、2-乙基咪唑、苯并咪唑、2-咪唑甲醛中的一种或多种。In an optional embodiment, the ligand compound includes, but is not limited to, one or more of imidazole, 2-methylimidazole, 2-ethylimidazole, benzimidazole, and 2-imidazolecarboxaldehyde.
本公开一实施方式还提供一种块状金属有机框架材料，使用的块状金属有机框架材料的制备方法制得。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.
本公开一实施方式还提供一种的块状金属有机框架材料的应用，用作催化剂。An embodiment of the present disclosure also provides an application of a bulk metal organic framework material for use as a catalyst.
在一些可选的实施方式中，催化剂包括光学催化剂、电学催化剂、齐聚催化剂、共聚催化剂。In some optional embodiments, catalysts include optical catalysts, electrical catalysts, oligomerization catalysts, and copolymerization catalysts.
本公开一实施方式还提供所述块状金属有机框架材料在气体的储存和分离、传感器、过滤材料、光学材料、电学材料和磁学材料中的用途。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.
本公开提供的块状金属有机框架材料的制备方法，是从HIPE的油水界面通过原位生长法制备MOF块状材料。通过HIPE模板，以金属氧化物纳米粒子作为稳定剂和金 属源在界面处自组装，引入配体对金属氧化物纳米粒子进行后修饰，且在较宽的配体/金属比下都可以实现HIPE稳定，形成稳定的三维界面网络，为MOF合成提供了稳定的模板；在此基础上，通过补加配体将界面处金属源原位转化为三维结构的MOF块材；冻干后块材呈现微孔-介孔-大孔的多级孔结构，通过进一步活化可以将比表面积提高至961.3m 2·g -1。 The preparation method of bulk metal-organic framework materials provided by the present disclosure is to prepare MOF bulk materials from the oil-water interface of HIPE through an in-situ growth method. Through the HIPE template, 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.
该方法仅涉及溶解、乳化、冷冻干燥、加热活化四种常用且发展成熟的化工单元操作。和现有的方法相比，不涉及对精细改性、洗涤等操作，内相环己烷可以回收重复使用，制备成本低廉，环境污染小；流程短，操作简便，易于工业化生产，在制备低密度、高比表面积、高MOF含量的MOF复合材料上具有显著优势。该块状金属有机框架材料的制备方法可广泛应用于制备ZIF系列。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.
本公开提供的块状金属有机框架材料，属于多级孔低密度MOF块状材料，同时涵盖大孔和微孔范围，由MOF多晶组成高度规整的骨架结构，保留了全部粉体MOF材料的性能，宏观上复合材料具有非常低的密度和良好的力学性能，易于后加工和工业操作；微观上MOF颗粒相互连接，规整地组装成结构稳定的三维网络，MOF质量百分比为93.2-99.9％，块状材料密度约80mg·cm -3，材料强度为3-40kPa，比表面积为900-961.3m 2/g。 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.
本公开提供的块状金属有机框架材料，用于催化Knoevenagel缩合反应，块材在长时间催化后未出现明显结构变化与催化剂失活，且有利于简化回收过程。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.
实施例Example
下面将结合具体实施例对本公开的实施方案进行详细描述，但是本领域技术人员将会理解，下列实施例仅用于说明本公开，而不应视为限制本公开的范围。实施例中未注明具体条件者，按照常规条件或制造商建议的条件进行。所用试剂或仪器未注明生产厂商者，均为可以通过市售购买获得的常规产品。The embodiments of the present disclosure will be described in detail below with reference to specific examples, but those skilled in the art will understand that the following examples are only used to illustrate the present disclosure and should not be regarded as limiting the scope of the present disclosure. If the specific conditions are not specified in the examples, the conditions should be carried out according to the conventional conditions or the conditions recommended by the manufacturer. If the manufacturer of the reagents or instruments used is not indicated, they are all conventional products that can be purchased commercially.
实施例1Example 1
如图1所示，本实施例提供一种块状金属有机框架材料，其制备方法如下：As shown in Figure 1, this embodiment provides a bulk metal organic framework material, and its preparation method is as follows:
(1)准确称量0.5g纳米氧化锌分散液，30mg 2-甲基咪唑，0.5g去离子水，2mg PVA，将四者搅拌混合均匀制备成均匀的分散液，随后加入4ml环己烷，在3,000rpm搅拌下得到均匀的HIPE。(1) Accurately weigh 0.5g nano zinc oxide dispersion, 30mg 2-methylimidazole, 0.5g deionized water, 2mg PVA, stir and mix the four to prepare a uniform dispersion, and then add 4ml cyclohexane. A uniform HIPE was obtained with stirring at 3,000 rpm.
(2)精确称量200mg 2-甲基咪唑，与(1)中制备的HIPE混合。将HIPE置于任意模具中，室温反应12-24小时。(2) Accurately weigh 200mg 2-methylimidazole and mix it with the HIPE prepared in (1). Place HIPE in any mold and react at room temperature for 12-24 hours.
(3)待(2)中的HIPE完全固化后，将HIPE经液氮冰冻后冷冻干燥，除去复合材料中的水和残留溶剂，冷冻干燥后块状材料从模具中脱落。(3) After the HIPE in (2) is completely solidified, freeze the HIPE in liquid nitrogen and then freeze-dry to remove the water and residual solvent in the composite material. After freeze-drying, the block material will fall off the mold.
(4)将(3)中的块状材料置于130℃烘箱活化27小时，最终得到多级孔ZIF-8块状材料。(4) Place the block material in (3) for activation in an oven at 130°C for 27 hours, and finally obtain a multi-stage porous ZIF-8 block material.
实施例2Example 2
本实施例提供一种块状金属有机框架材料，其制备方法如下：This embodiment provides a bulk metal organic framework material, and its preparation method is as follows:
(1)准确称量0.5g纳米氧化锌分散液，30mg 2-甲基咪唑，0.5g去离子水，5mg PVA，将四者搅拌混合均匀制备成均匀的分散液，随后加入4ml环己烷，在3,000rpm搅拌下得到均匀的HIPE。(1) Accurately weigh 0.5g nano zinc oxide dispersion, 30mg 2-methylimidazole, 0.5g deionized water, 5mg PVA, stir and mix the four to prepare a uniform dispersion, and then add 4ml cyclohexane. A uniform HIPE was obtained with stirring at 3,000 rpm.
(2)精确称量200mg 2-甲基咪唑，与(1)中制备的HIPE混合。将HIPE置于任意模具中，室温反应12-24小时。(2) Accurately weigh 200mg 2-methylimidazole and mix it with the HIPE prepared in (1). Place HIPE in any mold and react at room temperature for 12-24 hours.
(3)待(2)中的HIPE完全固化后，将HIPE经液氮冰冻后冷冻干燥，除去复合材料中的水和残留溶剂，冷冻干燥后块状材料从模具中脱落。(3) After the HIPE in (2) is completely solidified, freeze the HIPE in liquid nitrogen and then freeze-dry to remove the water and residual solvent in the composite material. After freeze-drying, the block material will fall off the mold.
(4)将(3)中的块状材料置于130℃烘箱活化27小时，最终得到多级孔ZIF-8块状材料。(4) Place the block material in (3) for activation in an oven at 130°C for 27 hours, and finally obtain a multi-stage porous ZIF-8 block material.
实施例3Example 3
本实施例提供一种块状金属有机框架材料，其制备方法如下：This embodiment provides a bulk metal organic framework material, and its preparation method is as follows:
(1)准确称量0.5g纳米氧化锌分散液，30mg 2-甲基咪唑，0.5g去离子水，10mg PVA，将四者搅拌混合均匀制备成均匀的分散液，随后加入4ml环己烷，在3,000rpm搅拌下得到均匀的HIPE。(1) Accurately weigh 0.5g nano zinc oxide dispersion, 30mg 2-methylimidazole, 0.5g deionized water, 10mg PVA, stir and mix the four to prepare a uniform dispersion, and then add 4ml cyclohexane. A uniform HIPE was obtained with stirring at 3,000 rpm.
(2)精确称量200mg 2-甲基咪唑，与(1)中制备的HIPE混合。将HIPE置于任意模具中，室温反应12-24小时。(2) Accurately weigh 200mg 2-methylimidazole and mix it with the HIPE prepared in (1). Place HIPE in any mold and react at room temperature for 12-24 hours.
(3)待(2)中的HIPE完全固化后，将HIPE经液氮冰冻后冷冻干燥，除去复合材料中的水和残留溶剂，冷冻干燥后块状材料从模具中脱落。(3) After the HIPE in (2) is completely solidified, freeze the HIPE in liquid nitrogen and then freeze-dry to remove the water and residual solvent in the composite material. After freeze-drying, the block material will fall off the mold.
(4)将(3)中的块状材料置于130℃烘箱活化27小时，最终得到多级孔ZIF-8块状材料。(4) Place the block material in (3) for activation in an oven at 130°C for 27 hours, and finally obtain a multi-stage porous ZIF-8 block material.
实施例4Example 4
本实施例提供一种块状金属有机框架材料，其制备方法如下：This embodiment provides a bulk metal organic framework material, and its preparation method is as follows:
(1)准确称量0.5g纳米氧化锌分散液，30mg 2-甲基咪唑，0.5g去离子水，20mg PVA，将四者搅拌混合均匀制备成均匀的分散液，随后加入4ml环己烷，在3,000rpm 搅拌下得到均匀的HIPE。(1) Accurately weigh 0.5g nano zinc oxide dispersion, 30mg 2-methylimidazole, 0.5g deionized water, 20mg PVA, stir and mix the four to prepare a uniform dispersion, and then add 4ml cyclohexane. A uniform HIPE was obtained under stirring at 3,000 rpm.
(2)精确称量200mg 2-甲基咪唑，与(1)中制备的HIPE混合。将HIPE置于任意模具中，室温反应12-24小时。(2) Accurately weigh 200mg 2-methylimidazole and mix it with the HIPE prepared in (1). Place HIPE in any mold and react at room temperature for 12-24 hours.
(3)待(2)中的HIPE完全固化后，将HIPE经液氮冰冻后冷冻干燥，除去复合材料中的水和残留溶剂，冷冻干燥后块状材料从模具中脱落。(3) After the HIPE in (2) is completely solidified, freeze the HIPE in liquid nitrogen and then freeze-dry to remove the water and residual solvent in the composite material. After freeze-drying, the block material will fall off the mold.
(4)将(3)中的块状材料置于130℃烘箱活化27小时，最终得到多级孔ZIF-8块状材料。(4) Place the block material in (3) for activation in an oven at 130°C for 27 hours, and finally obtain a multi-stage porous ZIF-8 block material.
实施例4所得材料置于花朵上的照片如图2所示，由图2可知，所得材料具有低密度特征。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.
实施例4所得材料73.5mg置于200g砝码下的照片如图3所示，由图3可知，所得材料具有优异的力学性能。A photo of 73.5 mg of the material obtained in Example 4 placed under a 200g weight is shown in Figure 3. It can be seen from Figure 3 that the obtained material has excellent mechanical properties.
实施例4所得材料的断面SEM图如图4所示，实施例4所得材料的断面局部放大SEM图如图5所示，由图4和图5可知，所得材料具有多孔特征。The cross-sectional SEM picture of the material obtained in Example 4 is shown in Figure 4, and the partially enlarged SEM picture of the cross-section of the material obtained in Example 4 is shown in Figure 5. It can be seen from Figures 4 and 5 that the obtained material has porous characteristics.
图6为实施例4所得材料的N 2吸脱附曲线，低压区吸附量快速增加，为I型等温线，BET比表面积为961.3m 2/g，表明所得材料具有优异的吸附性能。 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.
图7为实施例4所得材料的DFT孔径分析曲线，其表明所得材料涵盖大孔和微孔范围。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.
需要说明的是，本公开仅以实施例4为例表征本公开所得材料的特征，本公开实施例1-3以及5所制备的金属有机框架材料同样具有与实施例4相近的低密度、力学性能优异、材料具有多孔特征、吸附性能优异以及材料涵盖大孔和微孔范围的显著特性。It should be noted that this disclosure 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.
实施例5Example 5
本实施例提供一种块状金属有机框架材料，其制备方法如下：This embodiment provides a bulk metal organic framework material, and its preparation method is as follows:
(1)准确称量0.5g纳米氧化锌分散液，35.5mg 2-乙基咪唑，0.5g去离子水，20mg PVA，将四者搅拌混合均匀制备成均匀的分散液，随后加入4ml环己烷，在3,000rpm搅拌下得到均匀的HIPE。(1) Accurately weigh 0.5g nano zinc oxide dispersion, 35.5mg 2-ethylimidazole, 0.5g deionized water, 20mg PVA, stir and mix the four to prepare a uniform dispersion, and then add 4ml cyclohexane , obtain uniform HIPE under stirring at 3,000 rpm.
(2)精确称量236mg 2-乙基咪唑，与(1)中制备的HIPE混合。将HIPE置于任意模具中，室温反应12-24小时。(2) Accurately weigh 236 mg of 2-ethylimidazole and mix it with the HIPE prepared in (1). Place HIPE in any mold and react at room temperature for 12-24 hours.
(3)待(2)中的HIPE完全固化后，将HIPE经液氮冰冻后冷冻干燥，除去复合材料中的水和残留溶剂，冷冻干燥后块状材料从模具中脱落。(3) After the HIPE in (2) is completely solidified, freeze the HIPE in liquid nitrogen and then freeze-dry to remove the water and residual solvent in the composite material. After freeze-drying, the block material will fall off the mold.
(4)将(3)中的块状材料置于130℃烘箱活化27小时，最终得到多级孔ZIF-14 块状材料。(4) Place the block material in (3) for activation in an oven at 130°C for 27 hours, and finally obtain the multi-stage porous ZIF-14 block material.
对比例1Comparative example 1
(1)准确称量0.5g纳米氧化锌分散液，30mg 2-甲基咪唑，0.5g去离子水，20mg PVA，将四者搅拌混合均匀制备成均匀的分散液，随后加入4ml环己烷，在3,000rpm搅拌下得到均匀的HIPE。(1) Accurately weigh 0.5g nano zinc oxide dispersion, 30mg 2-methylimidazole, 0.5g deionized water, 20mg PVA, stir and mix the four to prepare a uniform dispersion, and then add 4ml cyclohexane. A uniform HIPE was obtained with stirring at 3,000 rpm.
(2)待(1)中的HIPE完全固化后，将HIPE经液氮冰冻后冷冻干燥，除去复合材料中的水和残留溶剂，冷冻干燥后块状材料从模具中脱落。(2) After the HIPE in (1) is completely solidified, freeze the HIPE in liquid nitrogen and then freeze-dry to remove the water and residual solvent in the composite material. After freeze-drying, the block material will fall off the mold.
(3)将(1)中的块状材料置于130℃烘箱活化27小时，最终得到材料。(3) Place the block material in (1) for activation in an oven at 130°C for 27 hours to finally obtain the material.
得到的材料无ZIF-8生成，材料不成型，几乎无强度。The resulting material contains no ZIF-8, is shapeless, and has almost no strength.
对比例2Comparative example 2
(1)准确称量0.5g纳米氧化锌分散液，30mg 2-甲基咪唑，0.5g去离子水，将四者搅拌混合均匀制备成均匀的分散液，随后加入4ml环己烷，在3,000rpm搅拌下得到均匀的HIPE。(1) Accurately weigh 0.5g nano zinc oxide dispersion, 30mg 2-methylimidazole, and 0.5g deionized water. Stir and mix the four to prepare a uniform dispersion. Then add 4ml cyclohexane and stir at 3,000rpm. A uniform HIPE is obtained under stirring.
(2)精确称量200mg 2-甲基咪唑，与(1)中制备的HIPE混合。将HIPE置于任意模具中，室温反应12-24小时。(2) Accurately weigh 200mg 2-methylimidazole and mix it with the HIPE prepared in (1). Place HIPE in any mold and react at room temperature for 12-24 hours.
(3)待(2)中的HIPE完全固化后，将HIPE经液氮冰冻后冷冻干燥，除去复合材料中的水和残留溶剂，冷冻干燥后块状材料从模具中脱落。(3) After the HIPE in (2) is completely solidified, freeze the HIPE in liquid nitrogen and then freeze-dry to remove the water and residual solvent in the composite material. After freeze-drying, the block material will fall off the mold.
(4)将(3)中的块状材料置于130℃烘箱活化27小时，最终得到块状材料。(4) Place the block material in (3) for activation in an oven at 130°C for 27 hours to finally obtain the block material.
得到的块状材料结构不稳定，几乎无强度。The resulting bulk material has an unstable structure and almost no strength.
对比例3Comparative example 3
(1)准确称量0.5g纳米氧化锌分散液，30mg 2-甲基咪唑，0.5g去离子水，20mg PVA，将四者搅拌混合均匀制备成均匀的分散液，随后加入4ml环己烷，在3,000rpm搅拌下得到均匀的HIPE。(1) Accurately weigh 0.5g nano zinc oxide dispersion, 30mg 2-methylimidazole, 0.5g deionized water, 20mg PVA, stir and mix the four to prepare a uniform dispersion, and then add 4ml cyclohexane. A uniform HIPE was obtained with stirring at 3,000 rpm.
(2)精确称量200mg 2-甲基咪唑，与(1)中制备的HIPE混合。将HIPE置于任意模具中，室温反应12-24小时。(2) Accurately weigh 200mg 2-methylimidazole and mix it with the HIPE prepared in (1). Place HIPE in any mold and react at room temperature for 12-24 hours.
(3)待(2)中的HIPE完全固化后，将HIPE经真空干燥，除去复合材料中的水和残留溶剂，干燥后块状材料从模具中脱落。(3) After the HIPE in (2) is completely cured, dry the HIPE in a vacuum to remove the water and residual solvent in the composite material. After drying, the bulk material falls off the mold.
(4)将(3)中的块状材料置于130℃烘箱活化27小时，最终得到ZIF-8块状材料。(4) Place the block material in (3) for activation in an oven at 130°C for 27 hours, and finally obtain ZIF-8 block material.
得到的块状材料结构坍塌，孔隙率不足20％。The resulting block material has a collapsed structure and a porosity of less than 20%.
对比例4Comparative example 4
(1)准确称量0.5g纳米氧化锌分散液，30mg 2-甲基咪唑，0.5g去离子水，20mg PVA，将四者搅拌混合均匀制备成均匀的分散液，随后加入4ml环己烷，在3,000rpm搅拌下得到均匀的HIPE。(1) Accurately weigh 0.5g nano zinc oxide dispersion, 30mg 2-methylimidazole, 0.5g deionized water, 20mg PVA, stir and mix the four to prepare a uniform dispersion, and then add 4ml cyclohexane. A uniform HIPE was obtained with stirring at 3,000 rpm.
(2)精确称量200mg 2-甲基咪唑，与(1)中制备的HIPE混合。将HIPE置于任意模具中，室温反应12-24小时。(2) Accurately weigh 200mg 2-methylimidazole and mix it with the HIPE prepared in (1). Place HIPE in any mold and react at room temperature for 12-24 hours.
(3)待(2)中的HIPE完全固化后，将HIPE经液氮冰冻后冷冻干燥，除去复合材料中的水和残留溶剂，冷冻干燥后块状材料从模具中脱落。(3) After the HIPE in (2) is completely solidified, freeze the HIPE in liquid nitrogen and then freeze-dry to remove the water and residual solvent in the composite material. After freeze-drying, the block material will fall off the mold.
得到的块状材料结晶度低，且大量氧化锌未转化，比表面积仅323.3m 2/g。 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.
本公开实施例和对比例中所采用的测试分析方法如下：The test and analysis methods used in the embodiments and comparative examples of the present disclosure are as follows:
N 2吸脱附曲线：采用美国QUANTACHROME仪器公司的气体吸附仪(AUTOSORB-IQ2-MP)测定N 2吸脱附曲线，测量前100℃真空脱气24小时。 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.
比表面积S BET和孔径分布：使用软件ASiQwin计算块状材料的比表面积和孔径分布，其中，比表面积采用Brunauer–Emmett–Teller(BET)方法计算得到，孔径通过Density Functional Theory(DFT)方法计算得到。 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. .
孔隙率及大孔孔径：采用美国麦克默瑞提克仪器公司的压汞仪(MIP,AutoPore IV 9510)表征。Porosity and macropore diameter: Characterized by mercury porosimeter (MIP, AutoPore IV 9510) from McMurray Instruments Company of the United States.
表面形态结构：日本日立公司的SU-8010场发射扫描电子显微镜(FE-SEM)表征，在3kV加速电压下观察，观察前真空镀金120秒。Surface morphology and structure: Characterized by the SU-8010 field emission scanning electron microscope (FE-SEM) of Hitachi, Japan, observed at an accelerating voltage of 3kV, and vacuum gold-plated for 120 seconds before observation.
X射线衍射PXRD：采用荷兰PANalytical公司的PANalytical公司的X-pert Powder X射线衍射仪表征，扫描范围为5-50°。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°.
实施例1至实施例4得到的ZIF-8块状材料的性能参数如下表1所示：The performance parameters of the ZIF-8 bulk materials obtained from Examples 1 to 4 are as shown in Table 1 below:
表1性能参数Table 1 Performance parameters
Figure PCTCN2022096692-appb-000001
Figure PCTCN2022096692-appb-000001
Figure PCTCN2022096692-appb-000002
Figure PCTCN2022096692-appb-000002
由上表1可知，本公开获得的块状金属有机框架材料，具有低密度、高比表面积和高孔隙率的特征。为了检测MOF的含量，以本公开实施例1、2和4制备的材料为例，使用美国PE公司的PerkinElmer instrument Pyris 1热重分析仪(TGA)测定实施例4所得材料和对照样材料(对比例2所得材料)，结果如图8所示。TGA测试气氛为空气，流量设定为20mL/min，加热速度为10℃/min，温度范围为100-680℃。对照样和实验样的TGA残留物均为ZnO，对照样残重为34.953％，实施例4为32.624％，由此计算MOF含量为32.624/34.953＝93.3％，同时测定得出实施例1、2的MOF含量分别为99.8％和97.3％。As can be seen from Table 1 above, the bulk metal organic framework material obtained by the present disclosure has the characteristics of low density, high specific surface area and high porosity. In order to detect the content of MOF, taking the materials prepared in Examples 1, 2 and 4 of the present disclosure as an example, the material obtained in Example 4 and the control sample material (for Material obtained in proportion 2), the results are shown in Figure 8. The TGA test atmosphere is air, the flow rate is set to 20mL/min, the heating speed is 10°C/min, and the temperature range is 100-680°C. The TGA residues of the control sample and the experimental sample are both ZnO. The residual weight of the control sample is 34.953% and that of Example 4 is 32.624%. From this, the MOF content is calculated to be 32.624/34.953=93.3%. At the same time, it is measured that Examples 1 and 2 are obtained. The MOF contents are 99.8% and 97.3% respectively.
由此可知，实施例1、2和4所获得的材料，具有较高含量的MOF。需要说明的是，本公开仅以实施例1、2和4为例表征本公开所得材料的特征，本公开实施例3以及5所制备的金属有机框架材料同样具有与实施例1、2和4相近，均具有较高含量的MOF的显著特征。It can be seen that the materials obtained in 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.
最后应说明的是：以上各实施例仅用以说明本公开的技术方案，而非对其限制；尽管参照前述各实施例对本公开进行了详细的说明，本领域的普通技术人员应当理解：其依然可以对前述各实施例所记载的技术方案进行修改，或者对其中部分或者全部技术特征进行等同替换；而这些修改或者替换，并不使相应技术方案的本质脱离本公开各实施例技术方案的范围。Finally, it should be noted that the above embodiments are only used to illustrate the technical solution of the present disclosure, but not to limit it; although the present disclosure has been described in detail with reference to the foregoing embodiments, those of ordinary skill in the art should understand that: The technical solutions described in the foregoing embodiments can still be modified, or some or all of the technical features can be equivalently replaced; and these modifications or substitutions do not deviate from the essence of the corresponding technical solutions from the technical solutions of the embodiments of the present disclosure. scope.
此外，本领域的技术人员能够理解，尽管在此的一些实施例包括其它实施例中所包括的某些特征而不是其它特征，但是不同实施例的特征的组合意味着处于本公开的范围之内并且形成不同的实施例。例如，在上面的权利要求书中，所要求保护的实施例的任意之一都可以以任意的组合方式来使用。公开于该背景技术部分的信息仅仅旨在加深对本公开的总体背景技术的理解，而不应当被视为承认或以任何形式暗示该信息构成已为本领域技术人员所公知的现有技术。Furthermore, those skilled in the art will understand that, although some embodiments herein include certain features included in other embodiments but not others, combinations of features of different embodiments are meant to be within the scope of the present disclosure. and form different embodiments. For example, in the claims above, any of the claimed embodiments may be used in any combination. The information disclosed in this Background section is merely intended to enhance an understanding of the general background of the present disclosure and should not be construed as an admission or in any way implying that the information constitutes prior art that is already known to those skilled in the art.
工业实用性Industrial applicability
本公开提供一种块状金属有机框架材料及其制备方法和应用，本公开的制备方法属于高内相乳液模板原位生长法，方法流程短，操作简便，易于工业化生产；由本公开制 备方法制备获得的块状金属有机框架材料，属于多级孔MOF块状材料，具有孔径尺寸同时覆盖大孔、小孔范围，保证高力学性能的同时保留了粉体材料的全部特性，具有优异的实用性能，可以广泛地应用于催化剂、传感器、过滤材料、光学材料、电学材料和磁学材料等领域。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.

Claims (12)

  1. 一种块状金属有机框架材料的制备方法，其特征在于，包括：A method for preparing bulk metal-organic framework materials, which is characterized by including:
    将包括金属氧化物纳米粒子、部分量的配体化合物和水在内的原料混合得到纳米粒子分散液；Mix raw materials including metal oxide nanoparticles, a partial amount of a ligand compound and water to obtain a nanoparticle dispersion;
    将所述纳米粒子分散液和环己烷混合，剪切均质得到高内相乳液；Mix the nanoparticle dispersion and cyclohexane and shear and homogenize to obtain a high internal phase emulsion;
    将所述高内相乳液和剩余量的配体化合物混合，进行反应；Mix the high internal phase emulsion and the remaining amount of the ligand compound to react;
    将反应产物依次进行液氮冷冻和冷冻干燥，然后加热活化，得到所述块状金属有机框架材料。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.
  2. 根据权利要求1所述的块状金属有机框架材料的制备方法，其特征在于，所述原料还包括添加剂，所述添加剂包括聚乙烯醇。The method for preparing bulk metal-organic framework materials according to claim 1, wherein the raw materials further include additives, and the additives include polyvinyl alcohol.
  3. 根据权利要求1或2所述的块状金属有机框架材料的制备方法，其特征在于，所述部分量的配体化合物与所述金属氧化物纳米粒子的摩尔量之比为(0.15-1)：1；The method for preparing bulk metal-organic framework materials according to claim 1 or 2, characterized in that the molar ratio of the partial amount of ligand compound to the metal oxide nanoparticles is (0.15-1) :1;
    优选地，所述部分量的配体化合物和所述剩余量的配体化合物的总摩尔量与所述金属氧化物纳米粒子的摩尔量之比为(2-6)：1。Preferably, 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.
  4. 根据权利要求1-3中任一项所述的块状金属有机框架材料的制备方法，其特征在于，所述纳米粒子分散液和所述环己烷的体积比为1：(3-9)，所述剪切均质的剪切速率为3000-15000rpm。The preparation method of bulk metal organic framework material according to any one of claims 1-3, characterized in that the volume ratio of the nanoparticle dispersion liquid and the cyclohexane is 1: (3-9) , the shear rate for shear homogeneity is 3000-15000 rpm.
  5. 根据权利要求1-4中任一项所述的块状金属有机框架材料的制备方法，其特征在于，所述反应的温度为室温，时间为12-24h。The method for preparing bulk metal-organic framework materials according to any one of claims 1 to 4, characterized in that the reaction temperature is room temperature and the reaction time is 12-24 hours.
  6. 根据权利要求1-5中任一项所述的块状金属有机框架材料的制备方法，其特征在于，所述冷冻干燥的时间为12-24h。The method for preparing bulk metal-organic framework materials according to any one of claims 1-5, characterized in that the freeze-drying time is 12-24 hours.
  7. 根据权利要求1-6中任一项所述的块状金属有机框架材料的制备方法，其特征在于，所述加热活化的温度为130-170℃，时间为9-27h。The method for preparing bulk metal organic framework materials according to any one of claims 1 to 6, characterized in that the heating activation temperature is 130-170°C and the time is 9-27 hours.
  8. 根据权利要求1-7任一项所述的块状金属有机框架材料的制备方法，其特征在于，所述金属氧化物纳米粒子包括纳米氧化锌；The method for preparing bulk metal organic framework materials according to any one of claims 1 to 7, wherein the metal oxide nanoparticles include nano zinc oxide;
    优选地，所述配体化合物包括咪唑、2-甲基咪唑、2-乙基咪唑、苯并咪唑、2-咪唑甲醛中的一种或多种。Preferably, the ligand compound includes one or more of imidazole, 2-methylimidazole, 2-ethylimidazole, benzimidazole, and 2-imidazolecarboxaldehyde.
  9. 一种块状金属有机框架材料，其特征在于，使用权利要求1-8任一项所述的块状金属有机框架材料的制备方法制得。A bulk metal-organic framework material, characterized in that it is prepared by using the preparation method of a bulk metal-organic framework material according to any one of claims 1 to 8.
  10. 一种权利要求9所述的块状金属有机框架材料的用途，其特征在于，用作催化剂。A use of the bulk metal organic framework material according to claim 9, characterized in that it is used as a catalyst.
  11. 根据权利要求10所述的用途，其特征在于，所述催化剂包括光学催化剂、电学催化剂、齐聚催化剂、共聚催化剂。The use according to claim 10, characterized in that the catalyst includes an optical catalyst, an electrical catalyst, an oligomerization catalyst, and a copolymerization catalyst.
  12. 一种权利要求9所述的块状金属有机框架材料在气体的储存和分离、传感器、过滤材料、光学材料、电学材料和磁学材料中用途。A bulk metal organic framework material according to claim 9 is used in gas storage and separation, sensors, filter materials, optical materials, electrical materials and magnetic materials.
PCT/CN2022/096692 2022-04-12 2022-06-01 Blocky metal organic framework material, and preparation method therefor and use thereof WO2023197423A1 (en)

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