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CN-121972218-A - Application of ionic liquid functionalized copper compound nano-catalyst in degradation of antibiotics

CN121972218ACN 121972218 ACN121972218 ACN 121972218ACN-121972218-A

Abstract

The invention discloses an application of an ionic liquid functionalized copper compound nano catalyst in degrading antibiotics, which comprises the following steps of (1) carrying out alkylation reaction on raw materials comprising 2-mercapto-1-methylimidazole and long-chain halogenated alkane, (2) carrying out ion exchange reaction on a product obtained in the step (1) and lithium bis (trifluoromethanesulfonyl) imide to obtain a mercapto functionalized ionic liquid, (3) fully mixing a copper acetate aqueous solution with the mercapto functionalized ionic liquid prepared in the step (2), separating to obtain an oil phase containing copper ions, and then carrying out precipitation reaction on the oil phase and a strong alkali aqueous solution to obtain the ionic liquid functionalized copper compound nano catalyst. The ionic liquid functionalized copper compound nano catalyst disclosed by the invention is novel in structure, and when antibiotics are degraded, the addition amount of the photocatalyst is lower, the degradation efficiency of more than 90% can be realized only by 5min, and the excellent catalytic activity and the circulation stability are shown.

Inventors

  • ZHU HAIBAO
  • PAN JI
  • RUAN ZHENG
  • LIU DANHUA
  • XU CHENGMIN
  • CHEN JUNQIANG

Assignees

  • 杭州医学院

Dates

Publication Date
20260505
Application Date
20251219

Claims (10)

  1. 1. The application of the ionic liquid functionalized copper compound nano-catalyst in degrading antibiotics is characterized in that the preparation method of the ionic liquid functionalized copper compound nano-catalyst comprises the following steps: (1) Alkylation reaction is carried out on raw materials comprising 2-mercapto-1-methylimidazole and long-chain halogenated alkane; (2) Carrying out ion exchange reaction on the product obtained in the step (1) and lithium bis (trifluoromethanesulfonyl) imide to obtain a sulfhydryl functional ionic liquid; (3) Fully mixing the copper acetate aqueous solution with the mercapto-functionalized ionic liquid prepared in the step (2), separating to obtain an oil phase containing copper ions, and carrying out precipitation reaction with an aqueous solution of strong alkali to obtain the ionic liquid functionalized copper compound nano catalyst; And the precipitation reaction is carried out at a temperature of 40-90 ℃.
  2. 2. The use of the ionic liquid functionalized copper compound nanocatalyst according to claim 1 for degrading antibiotics, wherein in step (1): The carbon number of the long-chain halogenated alkane is 10-15; Equimolar addition of 2-mercapto-1-methylimidazole and long-chain haloalkane; The alkylation reaction is carried out at a temperature of 60-80 ℃.
  3. 3. The use of the ionic liquid functionalized copper compound nanocatalyst according to claim 1 for degrading antibiotics, characterized in that in step (2): equimolar addition of the product of step (1) and lithium bis (trifluoromethanesulfonyl) imide; The ion exchange reaction is carried out at room temperature.
  4. 4. The use of the ionic liquid functionalized copper compound nanocatalyst according to claim 1 for degrading antibiotics, characterized in that in step (3): The concentration of the copper acetate aqueous solution is 0.1-1.0 mol/L; the volume ratio of the copper acetate aqueous solution to the mercapto-functional ionic liquid is (2-8): 1.
  5. 5. The use of the ionic liquid functionalized copper compound nanocatalyst according to claim 1 for degrading antibiotics, characterized in that in step (3): the strong alkaline water solution is selected from one or more of sodium hydroxide water solution, potassium hydroxide water solution and lithium hydroxide water solution; the concentration of the strong alkaline aqueous solution is 1.0-2.0 mol/L; The volume ratio of the oil phase containing copper ions to the aqueous solution of strong alkali is 1 (2-8).
  6. 6. The application of the ionic liquid functionalized copper compound nano catalyst in degrading antibiotics according to claim 1, wherein in the step (3), the precipitation reaction is carried out at a temperature of 65-90 ℃.
  7. 7. The use of the ionic liquid functionalized copper compound nanocatalyst according to claim 1, wherein in step (3), the precipitation reaction is at a temperature of 65 ℃.
  8. 8. The use of the ionic liquid functionalized copper compound nano-catalyst according to claim 1 for degrading antibiotics, characterized by comprising the following specific steps: the photocatalysis system comprising the ionic liquid functionalized copper compound nano catalyst and potassium hydrogen peroxymonosulfate is added into wastewater containing antibiotics, and catalytic degradation is carried out under visible light.
  9. 9. The use of the ionic liquid functionalized copper compound nanocatalyst according to claim 8 for degrading antibiotics, characterized in that: the mass ratio of the ionic liquid functionalized copper compound nano catalyst to the potassium hydrogen peroxymonosulfate is 1 (1-15); the concentration of the ionic liquid functionalized copper compound nano catalyst added into the wastewater is not lower than 0.02 g.L < -1 >.
  10. 10. The use of the ionic liquid functionalized copper compound nanocatalyst according to claim 8 for degrading antibiotics, characterized in that: the antibiotic is selected from tetracyclines; The concentration of antibiotics in the wastewater is 1-50mg.L < -1 >.

Description

Application of ionic liquid functionalized copper compound nano-catalyst in degradation of antibiotics Technical Field The invention relates to the technical field of photocatalysts, in particular to application of an ionic liquid functionalized copper compound nanocatalyst in degradation of antibiotics. Background Antibiotics are widely used for their remarkable bactericidal and anti-inflammatory effects, however, overuse and incomplete metabolism result in frequent detection in wastewater and are typical emerging pollutants due to their difficulty in degradation and their strong toxicity. The residues not only destroy the water ecosystem, but also accelerate the generation and the transmission of drug-resistant strains, and threaten public health and social economic safety. In order to solve the difficult problem of antibiotic wastewater treatment, advanced oxidation technologies such as electrochemical oxidation, fenton oxidation and ozone oxidation are widely studied, but the defects of high energy consumption, harsh conditions, byproduct generation and the like are common. Photocatalysis is considered as one of degradation methods with the most application prospect due to the advantages of high efficiency, environmental friendliness, low cost and the like. Currently, various materials such as metal oxides and graphite phase carbon nitride (g-C 3N4) are widely used as photocatalysts for antibiotic removal. However, most pure photocatalysts suffer from the problem of rapid recombination of the photogenerated electron (e −) -hole (h +) pairs, thus exhibiting lower photocatalytic activity. In order to solve the bottleneck, researchers put forward strategies such as heterojunction construction, doping and defect regulation, and part of new materials show good performance in antibiotic degradation, but still have the problems of high cost, limited resources or harsh preparation conditions. In recent years, bismuth (Bi) based and g-C 3N4 based catalysts have received attention for good visible light response. For example, MIL-101/BiOBr heterogeneous photo-Fenton catalyst can remove 94.3% tetracycline hydrochloride within 60 minutes, and CuO/g-C 3N4 heterojunction system realizes 99.87% degradation within 10 minutes through PMS activation. However, bi is very low in abundance in the crust, and is difficult to support for large-scale application, while the high-temperature calcination preparation process of CuO/g-C 3N4 is excessively energy-consuming, so that the green sustainability of the CuO/g-C 3N4 is limited. The high efficiency of CuO/g-C 3N4 is known to be mainly due to its special structure that facilitates electron-hole pair separation, but how to maintain and even improve performance while avoiding high temperature calcination remains a challenge to be broken through. Therefore, the shortages of the existing photocatalysts highlight the necessity of developing novel functionalized materials with rich resources, low energy consumption and excellent performance. Disclosure of Invention Aiming at the problems in the prior art, the invention discloses application of an ionic liquid functionalized copper compound nano catalyst in degrading antibiotics, the ionic liquid functionalized copper compound nano catalyst is novel in structure, the addition amount of the photocatalyst is lower when the antibiotics are degraded, the degradation efficiency of more than 90% can be realized only in 5min, and excellent catalytic activity and cycle stability are shown. The specific technical scheme is as follows: The application of the ionic liquid functionalized copper compound nano-catalyst in degrading antibiotics is provided, and the preparation method of the ionic liquid functionalized copper compound nano-catalyst comprises the following steps: (1) Alkylation reaction is carried out on raw materials comprising 2-mercapto-1-methylimidazole and long-chain halogenated alkane; (2) Carrying out ion exchange reaction on the product obtained in the step (1) and lithium bis (trifluoromethanesulfonyl) imide to obtain a sulfhydryl functional ionic liquid; (3) Fully mixing the copper acetate aqueous solution with the mercapto-functionalized ionic liquid prepared in the step (2), separating to obtain an oil phase containing copper ions, and carrying out precipitation reaction with an aqueous solution of strong alkali to obtain the ionic liquid functionalized copper compound nano catalyst; And the precipitation reaction is carried out at a temperature of 40-90 ℃. The invention discloses an application of an ionic liquid functionalized copper compound nano catalyst with a novel structure in degrading antibiotics, which is synthesized in situ under mild conditions by utilizing a specific type of IL medium, avoids the traditional high-temperature calcination process, reduces energy consumption and structural defects, and constructs a sustainable material preparation route. Experiments show that the ionic liquid functionalized copp