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CN-122011421-A - Porous metal organic framework gel material and preparation method and application thereof

CN122011421ACN 122011421 ACN122011421 ACN 122011421ACN-122011421-A

Abstract

The invention discloses a porous metal organic framework gel material { [ Cu 4 (TTPE)(μ 4 -O)(μ 3 -OH)]·4H 2 O} n @ H (n = infinity) and a preparation method and application thereof, and belongs to the technical field of flexible sensing materials. According to the invention, the friction nano generator (TENG) is assembled by using { [ Cu 4 (TTPE)(μ 4 -O)(μ 3 -OH)]·4H 2 O} n @ H (n = infinity), meanwhile, the influence of different doping ratios on the TENG output performance is explored, a flexible sensor system for ultra-sensitively monitoring the recovery progress after knee injury is constructed by using the material, self-power supply is realized by pressing the sensor through bending at the knee, and then the output signals are compared, so that the quantification of the movement state and the stress condition of the knee joint is realized, and the knee state is evaluated.

Inventors

  • LIU JING
  • WANG DANDAN
  • HUANG CHAO
  • ZHANG YINGYING
  • CUI JIAXING
  • HUANG ZIBIN
  • LI SHANQING

Assignees

  • 中原工学院

Dates

Publication Date
20260512
Application Date
20260319

Claims (10)

  1. 1. The preparation method of the porous metal organic framework gel material is characterized by comprising the following steps of: (1) Dissolving CuCl and C 26 H 22 O 4 in a solvent, and stirring to obtain a mixed solution I, wherein C 26 H 22 O 4 is 1, 2-tetra (4- (2H-tetrazol-5-yl) phenyl) ethane; (2) Respectively dissolving MBA and APS in deionized water to obtain MBA solution and APS solution, and then adding the MBA solution and the APS solution into a mixed solution of water, AM and NaCl at the same time to obtain a mixed solution II; (3) And (3) uniformly stirring and mixing the mixed solution I obtained in the step (1) and the mixed solution II obtained in the step (2), sealing, heating for reaction, and cooling after the reaction is finished to obtain the porous metal organic framework gel material.
  2. 2. The preparation method of the aqueous solution of CuCl and C 26 H 22 O 4 as set forth in claim 1, wherein the mass ratio of CuCl to C 26 H 22 O 4 in the step (1) is 1-20:2-36, and the solvent is a mixed solvent of N, N-dimethylformamide, absolute ethyl alcohol, triethylamine and ammonia water.
  3. 3. The method according to claim 2, wherein the volume ratio of N, N-dimethylformamide, absolute ethyl alcohol, triethylamine and aqueous ammonia in the step (1) is 1-30:1-30:2-48:2-60.
  4. 4. The preparation method of claim 3, wherein the MBA solution in the step (2) is 1-5% by weight, the APS solution is 10-50% by weight, and the mass ratio of MBA, APS, AM to NaCl in the mixed solution II is 0.01-1:0.1-10:50-120:2-15.
  5. 5. The method according to claim 4, wherein the mass ratio of the mixed solution I to the mixed solution II in the step (3) is 1-50:3-150, and the stirring time is 5-50min.
  6. 6. The process according to claim 5, wherein the reaction in step (3) is carried out at a temperature of 60 to 100℃for a period of 20 to 90 hours.
  7. 7. A porous metal-organic framework gel material prepared by the preparation method of any one of claims 1 to 6.
  8. 8. Use of the porous metal-organic framework gel material of claim 7 for the preparation of flexible electronics and wearable sensors.
  9. 9. A porous metal-organic framework gel TENG device comprises a positive plate and a negative plate, and is characterized in that the positive plate comprises the porous metal-organic framework gel material of claim 7.
  10. 10. Use of the porous metal-organic framework gel TENG device of claim 9 in the manufacture of a medical detection device for monitoring the progress of knee joint recovery.

Description

Porous metal organic framework gel material and preparation method and application thereof Technical Field The invention belongs to the technical field of flexible sensing materials, and particularly relates to a sensor preparation technology based on a metal organic framework and hydrogel composite system and application thereof. Background As a crystalline porous material formed by self-assembling metal ions/clusters and organic ligands through coordination, the Metal Organic Frameworks (MOFs) have the advantages of adjustable structure, high specific surface area, ordered pore channel structure, sensitive physicochemical response and the like, and have great potential in the fields of sensing, catalysis, energy storage and the like. For example, the invention patent with publication number CN121181922A discloses a photosensitive Cu-MOF (copper metal organic framework) material, a composite xerogel material, a preparation method and application thereof, wherein the photosensitive Cu-MOF material with a specific crystal structure is synthesized by a solvothermal method, and is compounded with sodium carboxymethylcellulose (CMC)/polyvinyl alcohol (PVA) to prepare a xerogel material (Cu-MOF@XG), so that a friction nano generator (TENG) device is further constructed, the specific response to ultraviolet light and the self-powered sensing function are realized, and the effectiveness of the Cu-MOF in enhancing the functional characteristics of the composite material is verified. However, the Cu-MOF is prepared by the joint reaction of H 4 TTPE and triethylene diamine ligand, on one hand, the Cu-MOF skeleton is neutral and uncharged, and on the other hand, the triethylene diamine is used as a bridging ligand, so that the conjugation degree of the Cu-MOF structure is increased, the Cu-MOF structure has quick response to light of different wave bands, and further the application of the Cu-MOF in the actual environment is affected, however, when the Cu-MOF is compounded with xerogel, the mechanical property of the Cu-MOF is limited, and the Cu-MOF is not suitable for repeated detection movement of knee joints. The immobilization of MOFs to hydrogels can increase their flexibility and biocompatibility. However, the MOF-hydrogel composite material prepared by the traditional physical blending method often has the problems of weak bonding force between MOF particles and a polymer network interface, uneven dispersion, easy agglomeration, easy falling off from a matrix in the use process and the like, and especially under the environment of long-term or cyclic mechanical deformation (such as repeated stretching and bending), the interface problem easily causes the damage of the structural integrity of the composite material, the decline of the functional stability, and the reliability, the repeatability and the service life of a sensing device are severely restricted. Therefore, a novel metal organic framework composite hydrogel material is developed, and the tough and stable combination between MOF and hydrogel matrix is realized, so that the mechanical properties (such as toughness and fatigue resistance), sensing sensitivity, response stability and environmental durability of the composite material are cooperatively improved, and the metal organic framework composite hydrogel material has important research value and practical significance for pushing a wearable flexible sensor with high performance and long service life. Disclosure of Invention Aiming at the technical problems of poor structural stability, long-term repeatability and poor service life of the traditional hydrogel and MOF composite material, the invention provides a porous metal-organic framework gel material, a preparation method and application thereof, and solves the problems of MOF agglomeration and unstable structure by an in-situ synchronous synthesis technology, thereby realizing double breakthrough of material performance and application scene. In order to achieve the above object, the technical scheme of the present invention is as follows: in a first aspect, the invention provides a method for preparing a porous metal-organic framework gel material, comprising the following steps: (1) Dissolving CuCl and C 26H22O4 in a solvent, and stirring to obtain a mixed solution I, wherein C 26H22O4 is 1, 2-tetra (4- (2H-tetrazol-5-yl) phenyl) ethane; (2) Respectively dissolving N-N' methylene acrylamide (MBA) and Ammonium Persulfate (APS) in deionized water to obtain an MBA solution and an APS solution, and then adding the MBA solution and the APS solution into a mixed solution of water, acrylamide (AM) and NaCl at the same time to obtain a mixed solution II; (3) And (3) uniformly stirring and mixing the mixed solution I obtained in the step (1) and the mixed solution II obtained in the step (2), sealing, heating for reaction, and cooling after the reaction is finished to obtain the porous metal organic framework gel material. The mass ratio of the CuC