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CN-122011412-A - Six-fold-interpenetration anion metal organic framework material with monocrystal structure, and preparation method and application thereof

CN122011412ACN 122011412 ACN122011412 ACN 122011412ACN-122011412-A

Abstract

The invention discloses a six-fold-insertion anion metal organic frame material with a single crystal structure, a preparation method and application thereof, wherein the six-fold-insertion anion metal organic frame material with the single crystal structure is formed by coordination of ligands taking triphenylene as a main body and zinc ions under solvothermal conditions; in the presence of a regulator, six groups of structures with the same coordination mode are formed by interpenetration in different interpenetration modes, so that the structure has good crystallinity and stability, and the anionic framework attribute ensures that the framework material has a promoting effect on the adsorption of cationic organic dyes in drinking water, so that the cationic organic dyes in the water can be effectively removed.

Inventors

  • HE JUN
  • PENG XIANG
  • HU JIEYING

Assignees

  • 广东工业大学

Dates

Publication Date
20260512
Application Date
20260210

Claims (10)

  1. 1. The preparation method of the six-fold-insertion anion metal organic framework material with the single crystal structure is characterized by comprising the following steps of: The ratio of the ligand with the structure shown in the formula I to the precursor of the divalent zinc ion is 1 (4.5-5.5) according to the molar weight, and the solvothermal reaction is carried out in the presence of 1-ethyl-3-methylimidazole tetrafluoroborate, so that the six-fold interpenetration anion metal organic framework material with the single crystal structure is obtained; ; Wherein R is N is 0,1 or 2.
  2. 2. The method for producing a six-fold-interposed anionic metal organic framework material having a single-crystal structure according to claim 1, characterized in that, The divalent zinc ion precursor is acetic acid, hydrochloric acid, sulfuric acid or nitric acid compound of divalent zinc ion and hydrate thereof.
  3. 3. The method for producing a six-fold-interposed anionic metal organic framework material having a single-crystal structure according to claim 1, characterized in that, The addition amount of the 1-ethyl-3-methylimidazole tetrafluoroborate is 1-5% of the volume of the solvent.
  4. 4. The method for producing a six-fold-interposed anionic metal organic framework material having a single-crystal structure according to claim 1, characterized in that, The solvent for the reaction is a mixed solvent of NaOH methanol solution and ethylenediamine, and the volume ratio of the NaOH methanol solution to the ethylenediamine is 1 (0.5-2); The mass concentration of NaOH in the NaOH methanol solution is 200-278 mmol L –1 .
  5. 5. The method for producing a six-fold-interposed anionic metal organic framework material having a single-crystal structure according to claim 1, characterized in that, The solvothermal reaction conditions were: The volume ratio of the monomer with the structure shown in the formula I to the solvent is (1.5-3) mu mol to 1mL; the reaction temperature is 110-130 ℃, and the reaction time is 12-96h.
  6. 6. The method for producing a six-fold-interposed anionic metal organic framework material having a single-crystal structure according to claim 1, characterized in that, The reaction comprises a separation and washing process, and after separation, methanol is used for washing the solid, and vacuum drying is carried out to obtain the six-fold alternate anion metal organic framework material with the monocrystal structure.
  7. 7. A six-fold-interpenetration anion metal organic framework material with a single crystal structure is characterized in that, Is prepared by the preparation method of the six-fold-inserted anionic metal organic framework material with the single crystal structure in any one of claims 1-6.
  8. 8. The six-fold, interpenetrating anionic metal organic framework material having a single crystal structure according to claim 7, wherein six groups of structures of the same coordination mode in the six-fold, interpenetrating anionic metal organic framework material having a single crystal structure are interpenetrated by different interpenetration modes.
  9. 9. The six-fold-interposed anionic metal organic framework material having a single-crystal structure of claim 7, The crystal system of the six-fold interpenetration anion metal organic framework material with a single crystal structure is a triclinic system, the space group is P-1, the lattice parameter is a=20.81 a, b=24.22 a, c=31.07 a, alpha= 112.14 degrees, beta= 92.16 degrees and gamma= 91.90 degrees.
  10. 10. Use of a six-fold-interlude anionic metal organic framework material having a monocrystalline structure according to any one of claims 1-9 for adsorbing cationic organic dyes in drinking water.

Description

Six-fold-interpenetration anion metal organic framework material with monocrystal structure, and preparation method and application thereof Technical Field The invention belongs to the technical field of metal organic frame functional materials, and particularly relates to a six-fold alternate anion metal organic frame material with a single crystal structure, and a preparation method and application thereof. Background Conventional adsorption materials have a long-term dominant role in the removal of organic dyes from drinking water, mainly comprising ‌ activated carbon, zeolite, clay minerals and biochar ‌, and the technical basis is based on physical adsorption and surface chemistry. Conventional adsorbents rely primarily on physical or simple chemical action, with inherent bottlenecks in performance. For example, activated carbon ‌ adsorbs organic matters by pi-pi stacking ‌ and ‌ micropore filling ‌, has good effect on nonpolar dyes, but has limited specific surface area, usually less than 1500m 2/g, lower adsorption capacity of 20-80mg/g, high regeneration energy consumption and poor selectivity on polar dyes. Zeolite ‌ is adsorbed by ‌ ion exchange ‌ and ‌ electrostatic action ‌, has a fixed pore size, is generally smaller than 1.2nm, is difficult to adsorb macromolecular dyes such as congo red, and has a low capacity of 15-60 mg/g. Clay mineral ‌ relies on ‌ cation exchange ‌ and surface adsorption, has very low specific surface area and adsorption capacity, has adsorption capacity of 10-40mg/g, and is easily interfered by coexisting ions. Biochar ‌ has various adsorption mechanisms including hydrogen bond, static electricity, pi-pi and the like, but has slow dynamics, easy collapse of structure and capacity of generally less than 200mg/g. The method has the common limitations of low adsorption capacity, slow dynamics, insufficient selectivity and poor regeneration performance, and is difficult to meet the requirement of high-efficiency deep purification. Organic dyes (such as methyl orange, rhodamine B, methylene blue and the like) widely exist in printing and dyeing, pharmaceutical and paper industry wastewater, and have the characteristics of ‌ high toxicity, difficult biodegradation, strong color development ‌ and the like, and even low concentration can destroy the ecology of water and threaten the health of human bodies. Traditional adsorbents (such as activated carbon) have the bottlenecks of low adsorption capacity, difficult regeneration, poor selectivity and the like. The metal organic frame material (‌ Metal Organic Frameworks, MOFs ‌) is a porous crystal material formed by self-assembling metal ions or clusters and organic ligands through coordination bonds, has a ‌ ultrahigh specific surface area ‌, can reach more than 7000m 2/g, has ‌ adjustable aperture ‌ (3-100A), and ‌ functionalized surface sites ‌ and ‌ structural designability ‌, and is an ideal adsorbent for efficiently removing organic dyes in drinking water. MOFs can be efficiently adsorbed by (1) electrostatic action, strong coulomb attraction is formed between the surface of the positively charged MOF (such as UiO-66-NH 2) and an anionic dye (such as Congo red), pi-pi accumulation ‌ is realized, aromatic ligands and the conjugated structure of dye molecules are subjected to non-covalent interaction, hydrogen bonding action ‌, functional groups such as NH 2 and COOH and the like form a hydrogen bonding network with-OH and N=N in the dye, and pore channel domain limiting effect ‌ is realized, and nano pore channels smaller than 2nm generate size screening and concentration effects on dye molecules. The research shows that MOFs has highest adsorption efficiency on anionic dye within the pH range of ‌ and 7-9 ‌, and partial materials (such as PSP-MIL-53) can realize the seawater desalination and the synchronous dye removal within ‌ min ‌, so that the WHO drinking water standard is met. Disclosure of Invention For the above reasons, in order to achieve further purification of drinking water, a first object of the present invention is to provide a preparation method of a six-fold-insertion anion metal organic framework material having a single crystal structure, wherein under solvothermal reaction conditions, insertion of a coordination structure is achieved by controlling the addition amount of a zinc ion precursor and using a specific regulator, and the six-fold-insertion anion metal organic framework material is obtained. The second object of the present invention is to provide a six-fold-interpenetration anionic metal organic framework material with a single crystal structure, wherein six groups of structures with the same coordination mode are interpenetrated by different interpenetration modes, and the six groups of structures have good crystallinity and stability. The third object of the invention is to provide an application of the six-fold-insertion anion metal organic framework material with a single crystal structure in