Search

KR-20260065197-A - COMPOSITION FOR FORMING METAL-ORGANIC FRAMEWORK BASED XEROGEL MONOLITH, MANUFACTURING METHOD FOR METAL-ORGANIC FRAMEWORK BASED XEROGEL MONOLITH, METAL-ORGANIC FRAMEWORK BASED XEROGEL MONOLITH AND CATALYST

KR20260065197AKR 20260065197 AKR20260065197 AKR 20260065197AKR-20260065197-A

Abstract

The present invention relates to a metal-organic framework-based zero-gel monolith capable of stably capturing an active ingredient, a method for manufacturing the same, a composition for forming a metal-organic framework-based zero-gel monolith, and a catalyst.

Inventors

  • 김진수
  • 탁 응옥 투
  • 장근옥

Assignees

  • 경희대학교 산학협력단
  • 한국수력원자력 주식회사

Dates

Publication Date
20260508
Application Date
20241101

Claims (18)

  1. Metal precursor compound; Ligand compounds; and A composition for forming a metal-organic framework-based zero-gel monolith comprising a modifier represented by the following chemical formula 1: [Chemical Formula 1] In the above chemical formula 1, R1 is hydrogen; or a substituted or unsubstituted straight-chain or branched-chain alkyl group having 1 to 5 carbon atoms, and The substituent of the substituted alkyl group is a halogen element.
  2. In paragraph 1, A composition for forming a metal-organic framework-based zero-gel monolith, wherein the metal precursor compound comprises at least one metal ion selected from Zr, V, Al, Fe, Cr, Ti, Hf, Cu, Zn, Ni, Ce, U, and Th.
  3. In paragraph 1, The above-mentioned ligand compound is a metal-organic framework comprising at least one of terephthalic acid, 1-methylimidazole, 2-methylimidazole, 1-benzylimidazole, 1-butyl-3-methylimidazolium, 1,3,5-tricarboxybenzene, 1,3,5-tris(4-carboxyphenyl)benzene, benzene dicarboxylate, aminobenzene dicarboxylate, 1,4-dicarboxybenzene, 9,10-anthracene dicarboxylic acid, 5-cyano-1,3-benzenedicarboxylic acid, 4,4'-biphenyldicarboxylic acid, 2,5-dihydroxybenzene carboxylic acid, 2,5-dihydroxy-1,4-benzenedicarboxylic acid, p-terphenyl-4,4'-dicarboxylic acid, and 2-(diphenylphosphino)terephthalic acid. Composition for forming a base zero-gel monolith.
  4. In paragraph 1, A composition for forming a metal-organic framework-based zero-gel monolith, wherein the molar ratio of the metal precursor compound to the modifier is 1:15 to 1:85.
  5. In paragraph 1, A composition for forming a metal-organic framework-based zero-gel monolith, wherein the molar ratio of the metal precursor compound to the ligand compound is 1:1.5 to 1:3.
  6. In paragraph 1, A composition for forming a metal-organic framework-based zero-gel monolith, wherein the molar ratio of the ligand compound to the modifier is 1:10 to 1:50.
  7. In paragraph 1, A composition for forming a metal-organic framework-based zero-gel monolith, further comprising a polar solvent.
  8. A step of preparing a composition for forming a metal-organic framework-based zero-gel monolith according to claim 1; A step of heat-treating the above composition to produce a first product in the form of a gel; A step of preparing a second product by mixing the first product with an exchange solvent containing an alcohol-based solvent; and A method for manufacturing a metal-organic framework-based zero-gel monolith, comprising the step of aging and drying the second product to produce a metal-organic framework-based zero-gel monolith.
  9. In paragraph 8, The step of manufacturing the first product above is, A method for manufacturing a metal-organic framework-based zero-gel monolith, comprising heat-treating the above composition at a temperature of 100°C or higher and 200°C or lower for a period of 12 hours or more and 24 hours or less.
  10. In Paragraph 9, The step of manufacturing the first product above is, A method for manufacturing a metal-organic framework-based zero-gel monolith, comprising centrifuging a heat-treated material at a rotational speed of 5,000 rpm or more and 10,000 rpm or less to obtain the first product.
  11. In paragraph 8, A method for manufacturing a metal-organic framework-based zero-gel monolith, wherein the second product is aged under conditions of centrifugation at a rotational speed of 11,000 rpm or more and 15,000 rpm or less at a temperature of 5 ℃ or more and 20 ℃ or less.
  12. A metal-organic framework-based zero-gel monolith comprising a reaction product of a composition for forming a metal-organic framework-based zero-gel monolith according to claim 1.
  13. In Paragraph 12, Metal-organic framework-based zero-gel monoliths with a particle size of 50 nm or less.
  14. In Paragraph 13, A metal-organic framework-based zero-gel monolith with a pore size of 25 nm or less.
  15. In Paragraph 13, A metal-organic framework-based zero-gel monolith with a specific surface area of 1,000 m² /g or more.
  16. Metal-organic framework-based zero-gel monolith according to claim 12; and A catalyst containing an active ingredient.
  17. In Paragraph 16, The catalyst in which the above active ingredient is captured in the metal-organic framework-based zero-gel monolith in the form of a ship-in-a-bottle.
  18. In Paragraph 16, The above catalyst is a catalyst comprising at least a catalyst for hydrogen generation.

Description

Composition for forming a metal-organic framework-based xerogel monolith, method for manufacturing a metal-organic framework-based xerogel monolith, metal-organic framework-based xerogel monolith and catalyst The present invention relates to a composition for forming a metal-organic framework-based zero-gel monolith, a method for manufacturing a metal-organic framework-based zero-gel monolith, a metal-organic framework-based zero-gel monolith, and a catalyst. A metal-organic framework (MOF) is a type of porous material assembled from inorganic metal clusters and organic linkers containing chelation groups through strong coordination bonds. By controlling the pore size, shape, and surface polarity of MOFs through these principles, they are being utilized in various fields such as catalysis, proton conduction, chemical sensors, and gas adsorption and separation. Recently, there has been increasing interest in technologies for capturing large molecules using MOFs. These materials exhibit interesting properties in catalysis and drug delivery. In particular, MOFs with large pore sizes are being utilized to adsorb large molecules. However, in practice, it is not easy to apply MOFs due to issues such as structural collapse during the solvent removal process, difficulties in designing sophisticated structures, and the release of guest molecules under undesirable conditions. Therefore, there is a need to develop MOF utilization technologies capable of stably capturing large molecules. Figure 1 is a schematic diagram illustrating a method for manufacturing an MOF-based zero-gel monolith in Example 1 of the present invention. FIG. 2 shows the PXRD pattern of the first product in gel form prepared in Examples 1-1 to 1-4 of the present invention. Figure 3 is a photograph of a metal-organic framework-based zero-gel monolith prepared in Examples 1-1 to 1-4 of the present invention. Figure 4 shows the SEM images and particle size analysis results of the metal-organic framework-based zero-gel monoliths prepared in Examples 1-1 to 1-4 of the present invention and the metal-organic framework powder prepared in Comparative Example 1. FIG. 5 shows the N2 desorption isotherms of metal-organic framework-based zero-gel monoliths prepared in Examples 1-1 to 1-4 of the present invention and the BJH plot obtained using them. Figure 6 shows the FT-IR analysis results of the metal-organic framework-based zero-gel monoliths prepared in Examples 1-1 to 1-4 of the present invention and the metal-organic framework powder prepared in Comparative Example 1. FIG. 7 shows the PXRD patterns of the catalysts prepared in Examples 2-1 to 2-4 of the present invention. Figure 8 shows the FT-IR analysis results of the catalysts prepared in Examples 2-1 to 2-4 of the present invention. FIG. 9 shows the adsorption capacity of vitamin B12 for the metal-organic framework-based zero-gel monoliths prepared in Examples 1-1 to 1-4 of the present invention and the metal-organic framework powder prepared in Comparative Example 1. Figure 10 shows the N2 desorption isotherm of the catalyst prepared in Example 2-1 of the present invention. Figure 11 shows the results of the adsorption stability evaluation for the active component of the catalyst prepared in Example 2-1 of the present invention. Figure 12 shows the results of evaluating the electrochemical catalytic properties of the catalyst prepared in Example 2-1 of the present invention. Throughout this specification, when a part is described as "comprising" a certain component, this means that, unless specifically stated otherwise, it does not exclude other components but may include additional components. Throughout this specification, when a component is described as being located "on" another component, this includes not only cases where a component is in contact with another component, but also cases where another component exists between the two components. Throughout this specification, terms including ordinal numbers, such as “first” and “second,” are used for the purpose of distinguishing one component from another and are not limited by said ordinal numbers. For example, within the scope of the invention, the first component may also be named the second component, and similarly, the second component may be named the first component. The present specification will be described in more detail below. One embodiment of the present invention provides a composition for forming a metal-organic framework-based zero-gel monolith comprising: a metal precursor compound; a ligand compound; and a modifier represented by the following formula 1: [Chemical Formula 1] In the above chemical formula 1, R1 is hydrogen; or a substituted or unsubstituted straight-chain or branched-chain alkyl group having 1 to 5 carbon atoms, and the substituent of the substituted alkyl group is a halogen element. A composition for forming a metal-organic framework-based zero-gel monolith according to one embodiment of the present invent