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CN-121975132-A - Histamine functionalized dual-ligand ZIFs material and preparation method and application thereof

CN121975132ACN 121975132 ACN121975132 ACN 121975132ACN-121975132-A

Abstract

The invention relates to a histamine functionalized double-ligand ZIFs material and a preparation method and application thereof, belonging to the technical field of nano material preparation and water environment treatment. The method comprises four steps of ligand dissolution, metal coordination, pH adjustment, crystallization and post-treatment. The material has ultrahigh adsorption capacity, has the maximum saturated adsorption capacity of Congo red up to 2001.09mg/g and the adsorption capacity of tetracycline up to 943.39mg/g, is far superior to the existing ZIF-8 and most similar adsorbents, is simple and efficient to synthesize, adopts a one-pot method for co-assembly, avoids complicated post-modification steps, realizes uniform doping of functional groups, maintains high specific surface area, has high selectivity, has extremely high selective removal capacity for Congo red in a mixed dye system, and is easy to popularize and apply.

Inventors

  • ZHANG XUFENG
  • JIANG PEIRONG
  • SHEN JING
  • FENG XIYUN
  • WANG JUN
  • DUAN LIANGFEI

Assignees

  • 云南师范大学

Dates

Publication Date
20260505
Application Date
20260115

Claims (10)

  1. 1. The preparation method of the histamine functionalized dual-ligand ZIFs material is characterized by comprising the following steps of: Step (1), ligand dissolution, namely dissolving a main ligand and a functional ligand in a mixed solvent according to a molar ratio of 2.9-3.1:1 to obtain a clear ligand solution; The main ligand is 2-methylimidazole; The functional ligand is histamine or hydrochloride thereof; The mixed solvent is a mixed solvent of deionized water and methanol, and the volume ratio of the deionized water to the methanol is 19-21:9-10; step (2), metal coordination, namely adding zinc salt into the clarified ligand solution obtained in the step (1) under the stirring condition; wherein the molar ratio of the molar sum of the main ligand and the functional ligand to the zinc salt is 7.8-8.2:1; step (3), pH adjustment and crystallization, namely adjusting the pH value to 8.0-9.0 by using alkali liquor, stirring at room temperature for reaction, and standing for aging after the reaction is finished; And (4) post-treatment, namely centrifuging to collect white precipitate, repeatedly washing the precipitate with deionized water until the supernatant is neutral, and freeze-drying to obtain the histamine functionalized ZIFs material.
  2. 2. The process for the preparation of histamine-functionalized dual ligand ZIFs material according to claim 1, wherein in step (1), the molar ratio of primary ligand to functional ligand is 3:1; The volume ratio of deionized water to methanol is 21:9; The functional ligand is histamine dihydrochloride.
  3. 3. The method for preparing a histamine-functionalized dual-ligand ZIFs material according to claim 1, wherein in the step (1), the dosage ratio of the main ligand to the mixed solvent is 4mmoL:9-11mL.
  4. 4. The method for preparing the histamine-functionalized dual-ligand ZIFs material according to claim 1, wherein in the step (2), the zinc salt is zinc chloride, and the molar ratio of the molar sum of the main ligand and the functional ligand to the zinc salt is 8:1.
  5. 5. The method for preparing the histamine-functionalized dual-ligand ZIFs material according to claim 1, wherein in the step (3), the alkali solution is an aqueous NaOH solution with the concentration of 0.1M.
  6. 6. The method for preparing the histamine-functionalized dual-ligand ZIFs material according to claim 1, wherein in the step (3), stirring reaction is carried out for 6-8 hours, and standing and aging are carried out for 12 hours.
  7. 7. The method for preparing a histamine-functionalized dual ligand ZIFs material according to claim 1, wherein in step (4), the centrifugation parameter is 6000rpm; Washing with deionized water for more than 3 times; the freeze drying time is 48 hours, and the temperature is 30 ℃ below zero to 50 ℃ below zero.
  8. 8. The histamine-functionalized dual-ligand ZIFs material prepared by the preparation method of any one of claims 1 to 7.
  9. 9. Use of a histamine-functionalized dual ligand ZIFs material according to claim 8 as a preparation of an adsorbent.
  10. 10. The use of a histamine-functionalized dual-ligand ZIFs material according to claim 9 as a preparation adsorbent for removing organic dye or antibiotic contaminant from a body of water, wherein the organic dye is congo red and the antibiotic is tetracycline.

Description

Histamine functionalized dual-ligand ZIFs material and preparation method and application thereof Technical Field The invention belongs to the technical field of nano material preparation and water environment treatment, and particularly relates to a histamine functionalized dual-ligand ZIFs material, and a preparation method and application thereof. Background Along with the acceleration of the industrialization process, the water pollution problem is increasingly serious. In particular, synthetic dyes (e.g., congo red CR) and antibiotics (e.g., tetracycline TC) pose a great threat to the ecological environment due to their persistence and toxicity. Metal Organic Frameworks (MOFs) are widely used for water remediation due to high specific surface area and porosity, with ZIF-8 being a typical representative. Although the traditional ZIF-8 has stable structure, the traditional ZIF-8 lacks a specific strong adsorption active site, so that the adsorption efficiency of complex organic pollutants is limited. The current mainstream method of improving its performance is Post-synthesis modification (Post-SYNTHETIC MODIFICATION, PSM). However, the PSM method has significant drawbacks: (1) The process is complex, involves multi-step operation, and is time-consuming and labor-consuming; (2) Uneven distribution, namely functional groups are difficult to uniformly distribute in the framework; (3) The structural damage is that the pore canal is easy to be blocked, even the integrity of the framework is damaged, and the specific surface area is greatly reduced. At present, a direct and simple one-pot strategy is lacking, and high-density amino active sites can be uniformly implanted into a framework (zeolite imidazole framework) while the high crystallinity of ZIFs is maintained, so that high-efficiency cooperative adsorption of pollutants is realized. How to overcome the defects of the prior art is a problem to be solved in the prior art. Disclosure of Invention The invention aims to solve the defects of the prior art and provides a histamine functionalized dual-ligand ZIFs material and a preparation method and application thereof. In order to achieve the above purpose, the technical scheme adopted by the invention is as follows: a preparation method of a histamine functionalized dual-ligand ZIFs material comprises the following steps: Step (1), ligand dissolution, namely dissolving a main ligand and a functional ligand in a mixed solvent according to a molar ratio of 2.9-3.1:1 to obtain a clear ligand solution; The main ligand is 2-methylimidazole; The functional ligand is histamine or hydrochloride thereof; The mixed solvent is a mixed solvent of deionized water and methanol, and the volume ratio of the deionized water to the methanol is 19-21:9-10; step (2), metal coordination, namely adding zinc salt into the clarified ligand solution obtained in the step (1) under the stirring condition; wherein the molar ratio of the molar sum of the main ligand and the functional ligand to the zinc salt is 7.8-8.2:1; step (3), pH adjustment and crystallization, namely adjusting the pH value to 8.0-9.0 by using alkali liquor, stirring at room temperature for reaction, and standing for aging after the reaction is finished; And (4) post-treatment, namely centrifuging to collect white precipitate, repeatedly washing the precipitate with deionized water until the supernatant is neutral, and freeze-drying to obtain the histamine functionalized ZIFs material. Further, it is preferred that in step (1), the molar ratio of the primary ligand to the functional ligand is 3:1; The volume ratio of deionized water to methanol is 21:9; The functional ligand is histamine dihydrochloride. Further, it is preferable that in the step (1), the amount ratio of the main ligand to the mixed solvent is 4mmoL:9-11mL. Further, it is preferable that in the step (2), the zinc salt is zinc chloride, and the molar sum of the main ligand and the functional ligand and the zinc salt is 8:1. Further, it is preferable that in the step (3), the alkali solution is an aqueous NaOH solution at a concentration of 0.1M. Further, it is preferable that in the step (3), the reaction is stirred for 6 to 8 hours and then left to stand and age for 12 hours. Further, it is preferable that in the step (4), the centrifugation parameter is 6000rpm; Washing with deionized water for more than 3 times; the freeze drying time is 48 hours, and the temperature is 30 ℃ below zero to 50 ℃ below zero. The invention also provides the histamine functionalized double-ligand ZIFs material prepared by the preparation method of the histamine functionalized double-ligand ZIFs material. The invention also provides application of the histamine functionalized dual-ligand ZIFs material in preparing an adsorbent. Further, it is preferable that the adsorbent is used for removing organic dye or antibiotic pollutant in water, the organic dye is congo red, and the antibiotic is tetracycline. The invention