Search

CN-121972182-A - Cobalt-loaded magnesium-manganese composite oxide material and preparation method and application thereof

CN121972182ACN 121972182 ACN121972182 ACN 121972182ACN-121972182-A

Abstract

The invention discloses a cobalt-loaded magnesium-manganese composite oxide material and a preparation method thereof, wherein the preparation method comprises the following steps of (1) synthesizing MgMn-MOF precursor by adopting solvothermal reaction; and (2) dipping a soluble cobalt salt solution on the MgMn-MOF precursor, drying, and calcining at 500-800 ℃ under an inert atmosphere for 2-3-h to obtain the cobalt-loaded magnesium-manganese composite oxide material Co-MgMn-C. The cobalt-loaded magnesium-manganese composite oxide material can catalyze ozone to decompose into active free radicals more efficiently, and has excellent stability. The invention also discloses application of the cobalt-loaded magnesium-manganese composite oxide material in catalyzing ozone oxidation to degrade organic pollutants in water.

Inventors

  • TONG SHAOPING
  • WANG YIDA

Assignees

  • 浙江工业大学

Dates

Publication Date
20260505
Application Date
20260202

Claims (10)

  1. 1. The preparation method of the cobalt-loaded magnesium-manganese composite oxide material is characterized by comprising the following steps of: (1) Synthesizing MgMn-MOF precursor by adopting solvothermal reaction; (2) And (3) dipping the soluble cobalt salt solution on the MgMn-MOF precursor, drying, and calcining at 500-800 ℃ under inert atmosphere for 2-3 h to obtain the cobalt-loaded magnesium-manganese composite oxide material Co-MgMn-C.
  2. 2. The method for preparing the cobalt-loaded magnesium-manganese composite oxide material according to claim 1, wherein the step (1) comprises the steps of dissolving magnesium salt, manganese salt and organic ligand in an organic solvent to form a mixed solution, carrying out solvothermal reaction on the mixed solution in a reaction kettle, and separating, washing, drying and grinding the obtained reaction product to obtain the MgMn-MOF precursor.
  3. 3. The method for preparing a cobalt-loaded magnesium-manganese composite oxide material according to claim 2, wherein the molar ratio of magnesium salt to manganese salt is 1-2:1.
  4. 4. The method for preparing a cobalt-loaded magnesium-manganese composite oxide material according to claim 2, wherein the molar ratio of the total amount of magnesium salt and manganese salt to the organic ligand is 1-2:1.
  5. 5. The method for producing a cobalt-supported magnesium-manganese composite oxide material according to claim 1, wherein in the step (2), a soluble cobalt salt solution is impregnated onto a MgMn-MOF precursor in an equal volume, and the doping amount of cobalt element is 3 to 10%.
  6. 6. The method for producing a cobalt-supported magnesium manganese composite oxide material according to claim 1, wherein in the step (2), the calcination is performed under an inert atmosphere, and the temperature is raised to 500 to 800 ℃ at a rate of 3 to 7 ℃ per minute, and 2 to 3h is maintained.
  7. 7. A cobalt-loaded magnesium-manganese composite oxide material prepared by the preparation method according to any one of claims 1 to 6.
  8. 8. The cobalt-supported magnesium-manganese composite oxide material according to claim 7, wherein Mg and Mn are present as oxides and Co is present as a simple substance in the cobalt-supported magnesium-manganese composite oxide material.
  9. 9. The cobalt-loaded magnesium manganese composite oxide material according to claim 7 or 8, wherein the X-ray diffraction pattern of the cobalt-loaded magnesium manganese composite oxide material has characteristic diffraction peaks at 35.8 °, 42.0 °, 44.2 °, 51.5 °, 61.4 °, 75.8 ° in 2Θ.
  10. 10. Use of a cobalt-loaded magnesium manganese composite oxide material according to any one of claims 7 to 9 for catalytic ozonation degradation of organic contaminants in water.

Description

Cobalt-loaded magnesium-manganese composite oxide material and preparation method and application thereof Technical Field The invention relates to the technical field of water treatment, in particular to a cobalt-loaded magnesium-manganese composite oxide material and a preparation method and application thereof. Background In recent years, advanced oxidation technologies (AOPs) have been increasingly studied to degrade organic contaminants in water. The advanced oxidation technology mainly comprises an ozone oxidation method, a photocatalytic oxidation method, an electrochemical oxidation method, a Fenton oxidation method, an ultrasonic oxidation method, a wet oxidation method and the like. Wherein, the ozone has the advantages of strong oxidizing property, excellent sterilization and decoloration effects, no secondary pollution and the like. However, ozone oxidation alone has problems of low mineralization efficiency for organic pollutants, high reaction selectivity, high operation cost, possibility of generating toxic intermediate products and the like. In order to overcome the defects, the catalytic ozone oxidation technology has been developed, ozone molecules are activated by introducing a catalyst, and the ozone molecules are converted into active oxygen species with stronger oxidizing ability (such as hydroxyl radical, OH, super oxygen radical, O 2-, singlet oxygen 1O2 and the like), so that the efficient degradation and mineralization of pollutants are realized. Heterogeneous catalytic ozonation can significantly improve ozone oxidation efficiency, wherein metal oxides are of interest for their high efficiency and ease of operation. Research on the application of metal oxides, metal supported catalysts, carbon materials, and the like as catalysts to ozone oxidation of organic matters has been widely reported. Chinese patent publication No. CN116037209a discloses an ozone oxidation catalyst, in which Mn element is doped into a metal-organic framework Mg-MOF by an isovolumetric impregnation method, and calcined to obtain a magnesium-manganese binary metal-organic framework catalyst. The Chinese patent document with publication number CN102161526A discloses the application of a magnesium oxide loaded cobalt-iron metal magnetic nano material, which is particularly used for degrading organic pollutant orange II in wastewater. The two catalysts have limited degradation capability on organic matters. In systems for adsorption-catalytic ozonation of catalysts, the adsorption capacity of the catalyst is often in competing relationship with the catalytically active sites. High adsorption can enrich organic matters on the surface of the catalyst and shorten the free radical transmission distance, but excessive adsorption can cause the occupation of active sites or the blockage of pore channels, so that the contact with ozone and the initiation of subsequent chain reactions are inhibited. Thus, the removal of contaminants by the system can be enhanced by increasing the catalytic activity of the catalyst. This requires that we have modified the surface of the catalyst using various methods to achieve enhanced removal of contaminants from the water. According to the heterogeneous catalytic ozone oxidation mechanism and the characteristics required by heterogeneous catalysts, the invention provides a cobalt-loaded magnesium-manganese composite oxide material and a preparation method thereof. The doping of the main catalyst by introducing metallic cobalt element is an effective means for regulating and controlling the electronic structure, increasing defect sites and improving oxidation-reduction capability. Cobalt as a transition metal with a strong Co 2+/Co3+ redox couple, the doping of which proved to significantly enhance the ozone activation performance of the catalyst. Disclosure of Invention The invention provides a cobalt-loaded magnesium-manganese composite oxide material and a preparation method thereof, and the material can catalyze ozone to decompose into active free radicals more efficiently and has excellent stability. The technical scheme of the invention is as follows: the preparation method of the cobalt-loaded magnesium-manganese composite oxide material comprises the following steps: (1) Synthesizing MgMn-MOF precursor by adopting solvothermal reaction; (2) And (3) dipping the soluble cobalt salt solution on the MgMn-MOF precursor, drying, and calcining at 500-800 ℃ under inert atmosphere for 2-3 h to obtain the cobalt-loaded magnesium-manganese composite oxide material Co-MgMn-C. In the Co-MgMn-C material, mg and Mn exist in the form of oxides, and Co exists in the form of simple substances. MgO can provide stable alkaline environment and structural support, mnO 2 provides main ozonolysis active sites and multivalent redox pairs, and Co introduction can modify the electronic structure of manganese oxide, further promote electron transfer, strengthen the coupling between Co 2+/Co3+ and Mn 3+/Mn4