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CN-121992443-A - MOF-74 derived bimetallic oxide material, preparation method and application thereof in ultrafast sterilization and dye degradation

CN121992443ACN 121992443 ACN121992443 ACN 121992443ACN-121992443-A

Abstract

The invention provides a MOF-74 derived bimetallic oxide material, a preparation method and application thereof in ultrafast sterilization and dye degradation, belonging to the technical field of material science, electrochemical catalysis and water treatment environment protection cross. The bimetallic oxide material is MgO/CuO bimetallic oxide material prepared by taking Mg/Cu-MOF-74 as a template through a pyrolysis method. The preparation method comprises the steps of mixing MgCl 2 ·6H 2 O、Cu(NO 3 ) 2 ·3H 2 O and 2, 5-dihydroxyterephthalic acid, dissolving in a mixed solution of N, N-dimethylformamide, ethanol and water, reacting, cooling a reaction system after the reaction is finished, centrifuging, washing and soaking a product, finally standing to obtain Mg/Cu-MOF-74, and calcining the Mg/Cu-MOF-74 at a high temperature to obtain the MgO/CuO bimetallic oxide material. The MgO/CuO bimetallic oxide material prepared by the invention has higher hydrogen peroxide selectivity and yield, can be used for killing pseudomonas aeruginosa in situ, has better sterilization effect, and can be used for rapidly degrading methylene blue dye in wastewater by electrocatalytic synergistic Fenton reaction, thereby improving degradation efficiency.

Inventors

  • WANG NAN
  • DUAN JIZHOU
  • HOU BAORONG

Assignees

  • 中国科学院海洋研究所

Dates

Publication Date
20260508
Application Date
20260225

Claims (10)

  1. 1. The MOF-74 derived bimetallic oxide material is characterized in that the bimetallic oxide material is MgO/CuO bimetallic oxide material prepared by taking Mg/Cu-MOF-74 as a template through a pyrolysis method.
  2. 2. A method of preparing a MOF-74 derived bimetallic oxide material as claimed in claim 1, comprising the steps of: (1) Mixing MgCl 2 ·6H 2 O、Cu(NO 3 ) 2 ·3H 2 O and 2, 5-dihydroxyterephthalic acid, dissolving in a mixed solution of N, N-dimethylformamide, ethanol and water, reacting, cooling a reaction system after the reaction is finished, centrifuging, washing and soaking a reaction product, and finally standing to obtain the Mg/Cu-MOF-74; (2) And heating and preserving the heat of the Mg/Cu-MOF-74, and cooling to obtain the MgO/CuO bimetallic oxide material.
  3. 3. The process according to claim 2, wherein the ratio of MgCl 2 ·6H 2 O、Cu(NO 3 ) 2 ·3H 2 O to 2, 5-dihydroxyterephthalic acid used in step (1) is 1.7:2.0:1.0; The volume ratio of the N, N-dimethylformamide to the ethanol to the water is 1.5:1:1; The mass ratio of the 2, 5-dihydroxyterephthalic acid to the N, N-dimethylformamide is 1:182-183.
  4. 4. The method according to claim 2, wherein the reaction in step (1) is carried out at a temperature of 120 to 160 ℃ for 16 to 24 hours.
  5. 5. The preparation method according to claim 2, wherein the rotational speed of the centrifugation in the step (1) is 7000 to 8000 rpm for 5 to 10 minutes; the washing is to wash the centrifuged solid 3-5 times by adopting N, N-dimethylformamide; The soaking is to soak the washed product in methanol for 3d times, and the methanol is replaced every 12: 12 h times; the standing is 12 h in vacuum at 60 ℃.
  6. 6. The method according to claim 2, wherein the heating and maintaining in step (2) is performed by raising the temperature to 800 ℃ at a heating rate of 5 ℃ per minute, and then maintaining at 1h in an argon atmosphere at 800 ℃.
  7. 7. A method for preparing hydrogen peroxide, wherein the hydrogen peroxide is prepared by performing an electrocatalytic oxidation-reduction reaction using the MOF-74 derived bimetallic oxide material as set forth in claim 1.
  8. 8. The method for sterilizing pseudomonas aeruginosa is characterized in that the MOF-74 derived bimetallic oxide material as defined in claim 1 is used as a catalyst to perform electrocatalytic oxidation-reduction reaction to generate hydrogen peroxide, and the hydrogen peroxide acts on the pseudomonas aeruginosa in situ to sterilize.
  9. 9. A method for rapidly degrading dye in water is characterized in that the MOF-74 derived bimetallic oxide material as defined in claim 1 is adopted as a catalyst to perform electrocatalytic oxidation-reduction reaction to generate hydrogen peroxide, and ferrous ions are added into water to construct an electrocatalytic-Fenton reaction system to complete degradation of dye in water.
  10. 10. The method of rapidly degrading a dye in water according to claim 9, wherein the dye is a methylene blue dye; the degradation time is 5-30 min.

Description

MOF-74 derived bimetallic oxide material, preparation method and application thereof in ultrafast sterilization and dye degradation Technical Field The invention belongs to the technical fields of material science, electrochemical catalysis and water treatment environmental protection and cross, and particularly relates to a MOF-74 derived bimetallic oxide material, a preparation method and application thereof in ultrafast sterilization and dye degradation. Background Meanwhile, with the rapid development of industries such as textile, cosmetics, food, pharmacy and the like, the pollution problem of dye wastewater is increasingly prominent, and dyes contained in the wastewater have high toxicity, carcinogenicity and mutagenicity, and are a great hazard to natural ecosystems and human health. Therefore, developing efficient, safe, economical and environmentally friendly sterilization and dye degradation technologies has become a vital and urgent challenge in the field of environmental engineering. The existing sterilization and disinfection processes such as Ultraviolet (UV) irradiation, chlorination, ozonization, pulsed electric field treatment and the like inevitably have the defects of generating carcinogenic disinfection byproducts, excessively consuming energy and the like in the application process. The existing dye degradation methods comprise a physical method and a chemical method, wherein the physical method (such as ultrasonic, adsorption and membrane filtration) can only realize the transfer of dye, but the dye is essentially adsorbed, the dye is not really degraded, and the chemical method has the problems of high treatment efficiency, high cost and easy generation of secondary pollution such as toxic sludge, halogenated byproducts and the like. Photodegradation is a research hotspot for dye degradation, but most synthetic dyes have high chemical stability, photodegradation resistance and biodegradation resistance, making them persistent pollutants in the environment. Advanced oxidation techniques (AOPs) can thoroughly mineralize dye molecules by generating strongly oxidative free radicals (e.g., OH), but require high catalyst and oxidant costs, which are not conducive to scale-up applications. Hydrogen peroxide (H 2O2) is used as an environment-friendly oxidant and an energy carrier, the reaction products are only water and oxygen, no secondary pollution is generated, and the hydrogen peroxide is widely applied to the scenes of wound sterilization, water treatment and the like, has remarkable advantages when being used for in-situ sterilization and synergistic Fenton reaction degradation of dyes, and is an important direction of the next-generation environment-friendly sterilization and dye degradation technology. However, the main stream production method of H 2O2 in industry is anthraquinone method, which has the defects of large scale of infrastructure, complex operation, large amount of dangerous waste, and the like, and H 2O2 is easy to decompose and has strong corrosiveness, so that the storage and transportation costs are high, the safety risk is high, and the popularization and application of the method in the scene of on-site disinfection and dye degradation are severely limited. In order to solve the problems, the technology of generating H 2O2 in situ by using O 2 as a raw material through electrochemical two-electron redox reaction (2 e - ORR) has the advantages of mild reaction conditions, simple operation and environmental friendliness, can directly prepare H 2O2 on the application site and realize in situ sterilization or synergistic Fenton degradation of dye, does not need additional storage and transportation links, and is considered as an ideal scheme for replacing an anthraquinone method. The key to the success of the 2e - ORR technique, however, is to design a highly efficient electrocatalyst that ensures that the catalyst can selectively reduce O 2 to H 2O2, rather than forming H 2 O via the competitive four-electron redox pathway (4 e - ORR). Currently, the catalyst materials for 2e - ORR mainly include noble metals and their alloys, carbon materials, single-atom catalysts, transition metal compounds, metal-organic frameworks (MOFs), and the like. The noble metal catalyst has excellent performance, high selectivity and small overpotential, but scarcity and high cost prevent large-scale application, the carbon-based material has high abundance and low cost, the activity of the noble metal catalyst is from defect engineering and heteroatom doping, but the specific structural design of atomic precision is difficult to realize, the active site of the transition metal compound is easy to identify and control, the specific surface area is small and the porosity is poor due to easy agglomeration, the utilization rate of the internal active site is limited, the isolated site of the single-atom catalyst can obviously improve the atomic utilization rate and the 2e - ORR selectivity,