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Directionally assembled flexible MOF hydrogel, and preparation method and proton conduction application thereof

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  • Publication Date:
    March 25, 2025
  • Additional Information
    • Patent Number:
      12258,361
    • Appl. No:
      18/654004
    • Application Filed:
      May 03, 2024
    • Abstract:
      Provided are a directionally assembled flexible MOF hydrogel, a preparation method and a proton conduction application thereof. The prepared method includes: mixing a transition metal salt and L-Glu to prepare a mixed aqueous solution; putting the mixed aqueous solution into a reaction kettle to react at a constant reaction temperature in a range from 80° C. to 200° C. for a reaction period of 1-5 hours, to thereby obtain a reacted aqueous solution; cooling the reacted aqueous solution to room temperature; and washing the reacted aqueous solution after the cooling with deionized water and absolute ethanol, to thereby obtain the directionally assembled flexible MOF hydrogel, L-Glu-M (M═Zr, Fe, or Co), for sealing and storing. The preparation method is simpler and easier to operate, and the directionally assembled flexible MOF hydrogel has great prospects in the field of proton conducting technologies.
    • Inventors:
      Zhejiang University of Technology. (Hangzhou, CN); Eco-Environmental Science Research & Design Institute of Zhejiang Province. (Hangzhou, CN)
    • Assignees:
      Zhejiang University of Technology (Hangzhou, CN), Eco-Environmental Science Research & Design Institute of Zhejiang Province (Hangzhou, CN)
    • Claim:
      1. A preparation method of a directionally assembled flexible metal-organic framework (MOF) hydrogel, comprising: mixing a transition metal salt and L-Glutamic acid (L-Glu) to prepare a mixed aqueous solution; putting the mixed aqueous solution into a reaction kettle to react at a constant reaction temperature in a range from 80° C. to 200° C. for a reaction period of 1-5 hours, to thereby obtain a reacted aqueous solution after the reacting is completed; cooling the reacted aqueous solution to room temperature; and washing the reacted aqueous solution after the cooling with deionized water and absolute ethanol, to thereby obtain the directionally assembled flexible MOF hydrogel for sealing and storing; and making the directionally assembled flexible MOF hydrogel into a cylinder and measuring a conductivity of the cylinder under an environment temperature, wherein the conductivity of the cylinder increases with an increase of the environment temperature; wherein a molar ratio of the L-Glu to the transition metal salt is 1:2, and the transition metal salt is one selected from the group consisting of a zirconium salt, an iron salt, and a cobalt salt.
    • Claim:
      2. The preparation method of the directionally assembled flexible MOF hydrogel as claimed in claim 1 , wherein the zirconium salt is zirconium sulfate, the iron salt is ferric chloride, and the cobalt salt is cobalt nitrate.
    • Claim:
      3. The preparation method of the directionally assembled flexible MOF hydrogel as claimed in claim 1 , wherein a concentration of the transition metal salt in the mixed aqueous solution is in a range from 1 mole per liter (mol/L) to 6 mol/L.
    • Claim:
      4. The preparation method of the directionally assembled flexible MOF hydrogel as claimed in claim 1 , wherein the constant reaction temperature is 150° C., and the reaction period is 2 hours.
    • Claim:
      5. The preparation method of the directionally assembled flexible MOF hydrogel as claimed in claim 1 , wherein the transition metal salt is the zirconium salt, and a conductivity of the directionally assembled flexible MOF hydrogel prepared at the constant reaction temperature of 180° C. is less than a conductivity of the directionally assembled flexible MOF hydrogel prepared at the constant reaction temperature of 150° C., and greater than a conductivity of the directionally assembled flexible MOF hydrogel prepared at the constant reaction temperature of 120° C.
    • Claim:
      6. The preparation method of the directionally assembled flexible MOF hydrogel as claimed in claim 1 , wherein the transition metal salt is the zirconium salt, and a conductivity of the directionally assembled flexible MOF hydrogel prepared with the zirconium salt at a concentration of 3 mol/L is less than a conductivity of the directionally assembled flexible MOF hydrogel prepared with the zirconium salt at a concentration of 4 mol/L, and greater than a conductivity of the directionally assembled flexible MOF hydrogel prepared with the zirconium salt at a concentration of 5 mol/L.
    • Claim:
      7. The preparation method of the directionally assembled flexible MOF hydrogel as claimed in claim 1 , wherein the environment temperature is in a range from 20° C. to 90° C.
    • Claim:
      8. The preparation method of the directionally assembled flexible MOF hydrogel as claimed in claim 1 , wherein the cylinder is with a radius of 1 centimeter and a height of 2 millimeters.
    • Patent References Cited:
      2015/0150981 June 2015 Gref
      111389235 July 2020

    • Other References:
      Sun et al., “Advances in metal-organic framework-based hydrogel materials: preparation, properties, and applications” , Journal of Materials Chermistry A, 11, pp. 2092-2127. (Year: 2023). cited by examiner
      Machine translation of CN-111389235-A, 16 pages. (Year: 2020). cited by examiner
    • Assistant Examiner:
      Edmondson, Lynne
    • Primary Examiner:
      Hoban, Matthew E.
    • Accession Number:
      edspgr.12258361