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CN-122006811-A - Difunctional copper-based coordination polymer photocatalyst, preparation method and application

CN122006811ACN 122006811 ACN122006811 ACN 122006811ACN-122006811-A

Abstract

The invention relates to the technical field of environmental remediation, and particularly provides a difunctional copper-based coordination polymer photocatalyst, a preparation method and application thereof, wherein copper chloride dihydrate and 4,4' -bis (3-pyridine formamide) diphenyl ether are adopted, benzoic acid is used as main raw materials, and the difunctional copper-based coordination polymer photocatalyst { [ Cu 2 (3-padpe) 2 Cl 2 ]·H 2 O} n ] is generated by reaction in a hydrothermal kettle through adjustment of reaction parameters. The invention has the characteristics of simple process, low cost, high catalyst activity, good stability, repeated use and the like, has good application potential in repairing organic matters and heavy metal polluted water and soil, and provides new research ideas and insights for the development of novel multifunctional environment repairing agents.

Inventors

  • LI YEXIA
  • LUAN JIAN
  • ZHANG LILI
  • DUAN WENLONG
  • ZHANG LEI
  • LI WENZE

Assignees

  • 沈阳化工大学

Dates

Publication Date
20260512
Application Date
20260104

Claims (9)

  1. 1. A bifunctional copper-based coordination polymer photocatalyst, wherein the molecular formula of the copper-based coordination polymer photocatalyst is { [ Cu 2 (3-padpe) 2 Cl 2 ]·H 2 O} n , wherein 3-padpe is 4,4' -bis (3-pyridinecarboxamide) diphenyl ether, and the structural formula of a single structural unit of the copper-based coordination polymer photocatalyst is: 。
  2. 2. the dual function copper-based coordination polymer photocatalyst of claim 1, wherein the crystal form belongs to monoclinic system and the space group is Pc.
  3. 3. The dual function copper-based coordination polymer photocatalyst of claim 1, wherein a single structural unit of the copper-based coordination polymer photocatalyst consists of two Cu (I) ions, three 3-padpe ligands and one chloride anion, the Cu (I) ions adopting three coordination modes, exhibiting a triangular pyramid geometry, wherein two nitrogen atoms are from two 3-padpe ligands and one chloride anion, and the 3-padpe ligands join the Cu (I) ions to form a 1D chain, which then form a 3D supramolecular configuration by hydrogen bonding.
  4. 4. The dual function copper-based coordination polymer photocatalyst of claim 1, wherein the bond length of Cu (1) -N (1) is 1.890 (3) a, the bond length of Cu (1) -Cl (1) is 2.2439 (11) a, the bond angle of N (1) -Cu (1) -Cl (1) is 112.57 (9) o , and the bond angle of N (2) -Cu (2) -Cl (2) is 119.58 (9) o .
  5. 5. A method for preparing the bifunctional copper-based coordination polymer photocatalyst of any one of claims 1-4, comprising the steps of: Step 1, weighing copper chloride dihydrate, 4' -bis (3-pyridine carboxamide) diphenyl ether and benzoic acid according to a molar ratio, and adding the components into a reaction kettle; step 2, measuring a certain volume of deionized water and sodium hydroxide solution, and adding the deionized water and sodium hydroxide solution into a reaction kettle; And 3, sealing the reaction kettle, reacting for a certain time in an oven at constant temperature, naturally cooling to obtain yellow crystals, washing the yellow crystals with deionized water, filtering and drying to obtain the difunctional copper-based coordination polymer photocatalyst.
  6. 6. The method for preparing a bifunctional copper-based coordination polymer photocatalyst as recited in claim 5, wherein in the step 1, the molar ratio of copper chloride dihydrate, benzoic acid, 4' -bis (3-pyridinecarboxamide) diphenylether is 1-3:1:1-3.
  7. 7. The method for preparing a dual-function copper-based coordination polymer photocatalyst according to claim 5, wherein in the step 2, the volume ratio of deionized water to sodium hydroxide solution is 6:1, and the concentration of sodium hydroxide solution is 0.1 mol/L.
  8. 8. The method for preparing a dual-function copper-based coordination polymer photocatalyst according to claim 5, wherein in the step 3, the temperature of an oven is 120-140 o C, and the reaction time is 3-5 days.
  9. 9. Use of the bifunctional copper-based coordination polymer photocatalyst of any one of claims 1-4, for remediation of water and soil contaminated with oxytetracycline and hexavalent chromium heavy metals.

Description

Difunctional copper-based coordination polymer photocatalyst, preparation method and application Technical Field The invention relates to the technical field of environmental remediation, and particularly provides a difunctional copper-based coordination polymer photocatalyst, a preparation method and application thereof. Background With the rapid advancement of global industrialization, the concentration of antibiotics and heavy metals in surface water and soil is far beyond the standard range, and this phenomenon has attracted a great deal of attention. The environmental emissions of Oxytetracycline (OTC) and the heavy metal hexavalent chromium (Cr (VI)) can directly affect aquatic organisms and ecosystems, changing the physicochemical properties of the soil and the microbial community. If these contaminants and continue to accumulate, they pose a threat to human health. Therefore, restoring and improving the environmental quality of water and soil is critical to ensure sustainable utilization of natural resources and to achieve sustainable development. The photocatalysis technology is regarded as an effective means for water and soil restoration due to the characteristics of simple operation, environmental friendliness and the like. Therefore, the development of efficient photocatalysts is of great importance. Coordination Polymers (CPs) are highly crystalline materials assembled by coordinating metal nodes with organic linkers. Compared with traditional photocatalysts, CPs have rich active sites, adjustable structures and good stability, and therefore, have attracted extensive attention. Notably, despite significant advances in Cu-CP based photocatalysts, these high performance Cu-CP photocatalysts have been achieved primarily by integrating semiconductor materials with a photo-response. The preparation of these complex copper-based photocatalysts undoubtedly increases cost, process flow and energy consumption. Therefore, the Cu-CP-based photocatalyst with high catalytic activity is synthesized through reasonable ligand functional group design and precise reaction parameter adjustment, so that the dependence on additional photosensitive materials is eliminated and deserving deep research. Coordination polymer based catalysts with open metal sites are reported to exhibit excellent catalytic performance. However, in most cases, the metal center is completely coordinated by the organic ligand with few open metal sites. The coordination polymer can be synthesized by hydrothermal method, solvothermal method, microwave method, etc. To obtain coordination polymers with open metal sites, techniques such as ligand modulation, solvent exchange, chemical activation, and photothermal activation may be used to remove the coordinated solvent molecules on the metal atoms, thereby obtaining open metal centers. In summary, the construction of coordination polymers with open metal sites by rational ligand modulation is a viable approach to achieve high efficiency photocatalytic activity. Disclosure of Invention In order to solve the technical problems, the invention provides the difunctional copper-based coordination polymer photocatalyst, the preparation method and the application thereof, and the catalyst can simultaneously realize high-efficiency degradation of organic pollutants terramycin and reduction of heavy metal hexavalent chromium under the irradiation of sunlight, has the advantages of good stability and reusability, and is expected to become a repairing agent with excellent environmental field for treating polluted water quality and soil. The invention is realized by the way, and provides a difunctional copper-based coordination polymer photocatalyst, the molecular formula of the copper-based coordination polymer photocatalyst is { [ Cu 2(3-padpe)2Cl2]·H2O}n ], wherein 3-padpe is 4,4' -bis (3-pyridine formamide) diphenyl ether, and the structural formula of a single structural unit of the copper-based coordination polymer photocatalyst is as follows: 。 Preferably, the crystal form of the difunctional copper-based coordination polymer photocatalyst belongs to a monoclinic system, and the space group is Pc. Preferably, the single structural unit of the copper-based coordination polymer photocatalyst consists of two Cu (I) ions, three 3-padpe ligands and one chloride anion, the Cu (I) ions adopt three coordination modes and show a triangular pyramid geometry, wherein two nitrogen atoms come from two 3-padpe ligands and one chloride anion, and the 3-padpe ligands are connected with the Cu (I) ions to form a 1D chain, and then the 3D supermolecular configuration is generated through hydrogen bonding. Preferably, in the bifunctional copper-based coordination polymer photocatalyst, the bond length of Cu (1) -N (1) is 1.890 (3) A, the bond length of Cu (1) -Cl (1) is 2.2439 (11) A, the bond angle of N (1) -Cu (1) -Cl (1) is 112.57 (9) o, and the bond angle of N (2) -Cu (2) -Cl (2) is 119.58 (9) o. The preparation me