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CN-122006671-A - Halogen coordination copper-based MOF material and preparation method and application thereof

CN122006671ACN 122006671 ACN122006671 ACN 122006671ACN-122006671-A

Abstract

The invention relates to the technical field of functional materials and water treatment, in particular to a halogen coordination copper-based MOF material and a preparation method and application thereof. The invention dissolves cupric salt, organic ligand containing nitrogen, alkali and chloride in deionized water, and after hydrothermal reaction, separates, washes and dries to obtain the halogen coordination copper-based MOF material. The method is synthesized by adopting one-step hydrothermal reaction, has low raw material cost and simple preparation process, and the prepared halogen coordination copper-based MOF material has Cu (I) redox activity, can realize high adsorption and excellent selectivity to Ag + , and has important significance for efficient recovery of Ag + in complex water.

Inventors

  • FU KAIXING
  • QIN JIALONG
  • LUO SHENGLIAN
  • YIN KAI

Assignees

  • 湖南大学

Dates

Publication Date
20260512
Application Date
20260313

Claims (10)

  1. 1. A preparation method of a halogen coordination copper-based MOF material is characterized by comprising the steps of dissolving a cupric salt, a nitrogenous organic ligand, alkali and chloride in deionized water, carrying out hydrothermal reaction, and then separating, washing and drying to obtain the halogen coordination copper-based MOF material.
  2. 2. The method of claim 1, wherein the divalent copper salt is copper chloride, copper sulfate, or copper nitrate.
  3. 3. The method of claim 1, wherein the nitrogen-containing organic ligand is isonicotinic acid, pyrazine, or 4,4' -bipyridine.
  4. 4. The method of claim 1, wherein the base is potassium hydroxide or sodium hydroxide.
  5. 5. The method of claim 1, wherein the chloride is potassium chloride or sodium chloride.
  6. 6. The preparation method according to claim 1, wherein the molar ratio of Cu (II), the nitrogen-containing organic ligand, the base and chlorine in the chloride in the cupric salt is (0.8-1.5): 0.8-1.5.
  7. 7. The method of claim 1, wherein the hydrothermal reaction is carried out at a temperature of 160-200 ℃ for a time of 20-50 hours.
  8. 8. The halogen-coordinated copper-based MOF material prepared by the preparation method according to any one of claims 1 to 7, wherein the basic structural unit of the MOF material is a Cu-Cl-Cu ring structure formed by chloride ion bridging.
  9. 9. Use of a halogen-coordinated copper-based MOF material according to claim 8 for the adsorption and/or recovery of Ag + in water.
  10. 10. The use according to claim 9, wherein the halogen-coordinated copper-based MOF material is adsorbed by redox reaction of Cu (I) in its backbone with Ag + .

Description

Halogen coordination copper-based MOF material and preparation method and application thereof Technical Field The invention relates to the technical field of functional materials and water treatment, in particular to a halogen coordination copper-based MOF material and a preparation method and application thereof. Background Silver is an important noble metal, and is widely applied in the fields of electronics, electroplating, photography, medicine and the like, and a large amount of silver-containing wastewater can be generated in the production and use processes of the silver-containing wastewater, so that resource waste and environmental pollution are caused. Therefore, the efficient recovery of silver from wastewater has important economic and environmental significance. At present, the methods for recovering Ag + include a precipitation method, an ion exchange method, an electrolysis method and the like, but the methods generally have the problems of poor selectivity, high energy consumption, easiness in generating secondary pollution, poor recovery effect on low-concentration Ag + and the like. Adsorption shows great potential due to its simple operation and low cost, but developing an adsorbent with high selectivity, high adsorption capacity and good regeneration performance is a key challenge. Metal organic framework Materials (MOFs) are receiving a great deal of attention in the field of adsorptive separation due to their high specific surface area, controllable pore structure and chemical properties. Conventional MOF materials combine with targets mainly by physical adsorption or Lewis acid-base action, however, the adsorption effect is poor in water systems with complex components. When there are large amounts of co-existing cations in water, they can undergo competitive adsorption with the target Ag +, resulting in a significant decrease in the selective adsorption capacity and binding efficiency of the material to Ag +. Therefore, the material which can utilize the oxidation-reduction activity of Cu (I) to realize high-selectivity and high-capacity capture of Ag + is developed, and has important significance for high-efficiency recovery of Ag + in complex water bodies. Disclosure of Invention The invention provides a halogen coordination copper-based MOF material, and a preparation method and application thereof. The invention dissolves cupric salt, organic ligand containing nitrogen, alkali and chloride in deionized water, and after hydrothermal reaction, separates, washes and dries to obtain the halogen coordination copper-based MOF material. The method is synthesized by adopting one-step hydrothermal reaction, has low raw material cost and simple preparation process, and the prepared halogen coordination copper-based MOF material has Cu (I) redox activity, can realize high adsorption and excellent selectivity to Ag +, and has important significance for efficient recovery of Ag + in complex water. In order to achieve the above object, the present invention provides the following technical solutions: The invention provides a preparation method of a halogen coordination copper-based MOF material, which comprises the steps of dissolving cupric salt, nitrogenous organic ligand, alkali and chloride in deionized water, separating, washing and drying after hydrothermal reaction, and obtaining the halogen coordination copper-based MOF material. Preferably, the cupric salt is cupric chloride, cupric sulfate or cupric nitrate. Preferably, the nitrogen-containing organic ligand is isonicotinic acid, pyrazine or 4,4' -bipyridine. Preferably, the base is potassium hydroxide or sodium hydroxide. Preferably, the chloride is potassium chloride or sodium chloride. Preferably, the molar ratio of Cu (II), the nitrogen-containing organic ligand, the alkali and the chloride in the cupric salt is (0.8-1.5): (0.8-1.5). Preferably, the temperature of the hydrothermal reaction is 160-200 ℃, and the time of the hydrothermal reaction is 20-50h. The invention also provides the halogen coordination copper-based MOF material prepared by the preparation method, and the basic structural unit of the MOF material is a Cu-Cl-Cu annular structure formed by bridging chloride ions. The halogen coordination copper-based MOF material provided by the invention has rich pore canal structures, cu (I) in the material and Ag + in the wastewater undergo oxidation-reduction reaction to generate metallic silver simple substances which are fixed in the pore canal, and meanwhile, cu (I) in the material is oxidized into Cu (II). The process can be expressed as: MOF-Cu(I) + Ag+→ MOF-Cu(II) + Ag0↓。 Experimental results show that even if a large amount of coexisting cations (such as Na (I), zn (II), cu (II), fe (III), al (III) and the like) exist in a water body, the recovery rate of the material to Ag + is still higher than 99.5%, and the recovery selectivity coefficient calculated by the partition coefficient (Kd) exceeds 3X 10 6 mL/g, so that