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CN-121972166-A - Carbon-based fiber-supported MOF-derived Co3O4Preparation method and application of catalytic material

CN121972166ACN 121972166 ACN121972166 ACN 121972166ACN-121972166-A

Abstract

Preparation method and application of carbon-based fiber supported MOF derived Co 3 O 4 catalytic material. The preparation method comprises the steps of pretreating a carbon-based fiber substrate material, growing a MOF precursor on the surface of the pretreated carbon-based fiber in situ, and performing heat treatment in an inert atmosphere to convert the MOF precursor into Co 3 O 4 to obtain the carbon-based fiber supported Co 3 O 4 composite catalytic material. By controlling the heat treatment temperature, the grain size of Co 3 O 4 and the interface bonding state of Co 3 O 4 and carbon-based fiber can be controlled. Co 3 O 4 in the material is uniformly loaded on the surface of the carbon-based fiber, and the interface combination is firm, so that the problems of difficult recovery and easy agglomeration of the powder catalyst are avoided. The material is used for activating the peroxymonosulfate to degrade antibiotic pollutants, and has excellent catalytic activity and stability.

Inventors

  • QIU ZUMIN
  • LIAO YUFANG
  • ZHANG JIAN
  • YANG YUTING
  • SUN WEIKUN

Assignees

  • 南昌大学

Dates

Publication Date
20260505
Application Date
20260331

Claims (9)

  1. 1. The preparation method of the carbon-based fiber-supported MOF-derived Co 3 O 4 composite catalytic material is characterized by comprising the following steps of: (1) Pretreating a carbon-based fiber substrate material to obtain pretreated carbon-based fibers; (2) Placing the pretreated carbon-based fiber in a reaction system containing a metal source and an organic ligand, so that MOF precursors are generated on the surface of the carbon-based fiber in situ, and obtaining the carbon-based fiber loaded MOF precursor composite material; (3) And placing the carbon-based fiber supported MOF precursor composite material in an inert atmosphere, and calcining at 400-800 ℃ to convert the MOF precursor into Co 3 O 4 , so as to obtain the carbon-based fiber supported Co 3 O 4 composite catalytic material.
  2. 2. The method according to claim 1, wherein the carbon-based fiber base material in step (1) is carbon cloth, carbon fiber fabric, carbon fiber felt, or carbon fiber paper.
  3. 3. The method of claim 1, wherein the MOF precursor in step (2) is ZIF-67.
  4. 4. The method according to claim 4, wherein the calcination temperature is 600 ℃.
  5. 5. A carbon-based fiber-supported MOF-derived Co 3 O 4 composite catalytic material, characterized by being prepared by the preparation method of any one of claims 1 to 5.
  6. 6. The carbon-based fiber supported MOF-derived Co 3 O 4 composite catalytic material of claim 5, wherein the Co 3 O 4 is supported on the surface of the carbon-based fiber and forms an interface bond with the carbon-based fiber.
  7. 7. The use of the carbon-based fiber-supported MOF-derived Co 3 O 4 composite catalytic material of claim 5 or 6 for activating peroxymonosulfate to degrade organic pollutants.
  8. 8. The use according to claim 7, wherein the organic contaminant is an antibiotic.
  9. 9. The use according to claim 8, wherein the antibiotic is levofloxacin.

Description

Preparation method and application of carbon-based fiber supported MOF derived Co 3O4 catalytic material Technical Field The invention belongs to the technical field of environmental catalytic materials and advanced oxidation, and in particular relates to a carbon-based fiber supported Co 3O4 composite catalytic material obtained by taking carbon-based fibers as a carrier and metal-organic framework (MOF) as a precursor and performing calcination and conversion, a preparation method thereof and application thereof in activating and degrading antibiotic pollutants by using peroxymonosulfate, belonging to the field of advanced oxidation. Background In recent years, advanced oxidation technology has become an important direction for removing refractory organic pollutants due to the ability to generate highly active free radicals or non-free radical active species in situ. Among them, the oxidation system based on peroxymonosulfate is receiving attention because of its strong oxidizing ability, wide applicable pH range, and efficient activation by transition metal catalyst. In the activation process of the peroxymonosulfate, active species such as sulfate radical, hydroxyl radical, singlet oxygen and the like can be induced on the surface of the catalyst, so that the rapid degradation of antibiotic pollutants such as levofloxacin and the like is realized. However, most of the traditional peroxymonosulfate activated catalysts are powdery materials, and have the defects that firstly, the powdery catalysts are difficult to separate and recycle quickly in a water treatment system, the recycling performance is poor, secondly, the powdery materials are easy to agglomerate in the actual reaction process, so that the effective active sites are not exposed enough, thirdly, the powdery catalysts are easily influenced by inorganic ions, organic coexisting matters and natural organic matters in a complex water environment, the activity attenuation is faster, and fourthly, the powdery materials need additional carriers, adhesives or immobilization processes in an engineering device, so that the assembly difficulty is increased, and the mass transfer resistance is possibly increased. In order to solve the problems of the powder catalyst in practical application, it is important to develop a morphological catalytic material with high activity, high stability, easy assembly and good mass transfer capability. The carbon-based fiber is used as a flexible carbon-based conductive substrate, has a three-dimensional interwoven fiber network structure, good mechanical strength, excellent conductivity and larger specific surface area, and the surface of the carbon-based fiber generally contains a certain number of oxygen-containing functional groups, so that the anchoring and the growth of metal or metal oxide are facilitated. Therefore, the carbon-based fiber can be used as an excellent catalyst carrier or skeleton for constructing an integrated, recyclable, easily-cut and assembled morphological catalytic material. On the other hand, metal-organic framework Materials (MOFs) have the advantages of adjustable pore structure, uniform metal site distribution, large specific surface area, designable chemical composition and the like, and are widely focused in the fields of catalysis, separation, energy storage and the like. Particularly, a MOF precursor constructed by metal ions and organic ligands can be converted into metal oxide, metal/carbon composite material or porous derivative through pyrolysis, calcination or carbonization and the like, so that the MOF precursor has designability and stability and activity of derivative materials. The ZIF-67 is used as a typical cobalt-containing MOF material, and is widely used for constructing cobalt-based functional materials because of stable crystal structure, mild synthesis conditions and easy in-situ growth on the surface of carbon-based fibers, and cobalt-based oxides such as Co 3O4 can be formed after thermal conversion. However, reports of re-heating and converting a MOF precursor and a carbon-based fiber into cobalt oxide after combining in the prior art still have a plurality of defects, namely firstly, the growth uniformity and the adhesion strength of the MOF precursor on the carbon-based fiber are limited, so that the active phase after subsequent calcination is unevenly distributed, secondly, the influence of different calcination temperatures on the grain size, pore structure, interface combination and active site exposure of the material is lack of system regulation, thirdly, the existing material usually only focuses on single temperature point or single performance evaluation, and the coupling relation of 'temperature-structure-performance' is lack of deep design, and fourthly, the existing system still has the problems of insufficient activity, poor structural stability or quicker performance attenuation when continuously degrading antibiotic pollutants such as levofloxacin.