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CN-118851398-B - Fenton-like catalytic membrane based on block copolymer and preparation method and application thereof

CN118851398BCN 118851398 BCN118851398 BCN 118851398BCN-118851398-B

Abstract

The invention belongs to the technical field of wastewater pollutant treatment, and relates to a Fenton-like catalytic membrane based on a block copolymer, and a preparation method and application thereof, wherein the preparation method is that a nano porous block copolymer membrane is immersed in a mixed solution containing metal ions and an organic ligand A for reaction, the nano porous block copolymer membrane contains an organic ligand B, and the metal ions simultaneously form coordination bonds with the organic ligand A and the organic ligand B, so that MOF is synthesized on the surface and in holes of the nano porous block copolymer membrane; the finally prepared Fenton-like catalytic membrane based on the block copolymer is used for removing the dye in the wastewater, and after the block copolymer-like catalytic membrane is used for a period of time, the permeability and the dye removal rate of the Fenton-like catalytic membrane based on the block copolymer are both high, so that the industrial application requirements can be met.

Inventors

  • GUO LEIMING
  • XU JINGJING
  • LI FAXUE
  • YU JIANYONG

Assignees

  • 东华大学

Dates

Publication Date
20260512
Application Date
20240701

Claims (9)

  1. 1. A preparation method of a Fenton-like catalytic membrane based on a block copolymer is characterized in that a nano-porous block copolymer membrane is immersed in a mixed solution containing metal ions and an organic ligand A for reaction, the nano-porous block copolymer membrane contains an organic ligand B, and the metal ions form coordination bonds with the organic ligand A and the organic ligand B at the same time, so that MOF is synthesized on the surface and in holes of the nano-porous block copolymer membrane, and the Fenton-like catalytic membrane based on the block copolymer is obtained; The metal ion is at least one of cobalt ion, iron ion and copper ion, the organic ligand A is at least one of 2-methylimidazole, 1,3, 5-benzene tricarboxylic acid and 2-amino terephthalic acid, and the organic ligand B is pyridyl, amino, carboxyl, ester, siloxy or alkoxy.
  2. 2. The method for preparing a Fenton-like catalytic membrane based on a block copolymer according to claim 1, wherein the reaction temperature is 25 ℃ and the reaction time is 1h.
  3. 3. The preparation method of the Fenton-like catalytic membrane based on the block copolymer according to claim 1, wherein the concentration of metal ions in the mixed solution is 0.01-0.06mol/L, and the concentration of organic ligand A in the mixed solution is 0.01-0.4mol/L.
  4. 4. The method for preparing a Fenton-like catalytic membrane based on a block copolymer according to claim 1, wherein the nanoporous block copolymer membrane is obtained by: (1) Adding the block copolymer solution onto a microfiltration membrane, rotating the microfiltration membrane through a spin coater to uniformly coat the block copolymer solution on the surface of the microfiltration membrane, and drying to obtain a composite membrane; (2) Immersing the composite membrane in a mixed solvent containing a good solvent and a poor solvent, and transferring the composite membrane into the poor solvent to obtain the nano porous segmented copolymer membrane.
  5. 5. The preparation method of the Fenton-like catalytic membrane based on the block copolymer according to claim 4, wherein in the step (1), the block copolymer in the block copolymer solution consists of a block a and a block b, wherein the block a is polystyrene, polysulfone, polyethylene or polycyclohexene carbonate, the block b is poly (2-vinylpyridine), polyethylene oxide, poly (4-vinylpyridine), polymethyl methacrylate, polymethyl N, N-dimethylaminoethyl ester, polyethylene glycol or polylactic acid, the volume of the block b accounts for 1-60% of the total volume of the block a and the block b, and the molecular weight of the block copolymer is 5-800kg/mol.
  6. 6. The method for preparing a Fenton-like catalytic membrane based on a block copolymer according to claim 5, wherein in the step (1), the block copolymer solution is obtained by dissolving at least one of the block copolymers in an organic solvent, the organic solvent is at least one of acetone and chloroform, and the block copolymer content in the block copolymer solution is 1-5wt%.
  7. 7. The method for preparing a Fenton-like catalytic membrane based on a block copolymer according to claim 4, wherein in the step (2), the good solvent is at least one of acetone, chloroform, tetrahydrofuran, toluene, 1, 2-dichlorobenzene and cyclohexane, the poor solvent is at least one of methanol, ethanol, 2-propanol, acetic acid and n-hexadecane, the volume ratio of the good solvent to the poor solvent is 1/9-5/5, the soaking time is 1-60s, and the soaking temperature is 25 ℃.
  8. 8. A block copolymer-based Fenton-like catalytic membrane, obtained by a preparation method according to any one of claims 1-7.
  9. 9. The use of a block copolymer based Fenton-like catalytic membrane according to claim 8, wherein the membrane is used for removing dye from wastewater, wherein the permeability of the block copolymer based Fenton-like catalytic membrane is 736-3070L/(m 2 .h.bar) after a period of use, the dye removal rate is 89.6-100%, and the membrane is filtered for 2h at 0.1bar and 25 ℃ after a period of use.

Description

Fenton-like catalytic membrane based on block copolymer and preparation method and application thereof Technical Field The invention belongs to the technical field of wastewater pollutant treatment, and particularly relates to a Fenton-like catalytic membrane based on a block copolymer, and a preparation method and application thereof. Background The main challenges faced by the existing wastewater treatment plants are the increasing number of refractory compounds in wastewater, such as surfactants, dyes, personal care products, and pharmaceuticals. Conventional treatment techniques have not been effective in removing these refractory organics from the wastewater, which are inevitably released into the environment, causing serious adverse effects not only on aquatic organisms but also on human health. To solve this problem, advanced oxidation technologies (Advanced Oxidation Processes, AOPs) have become a promising wastewater treatment technology. Common AOPs are largely classified into Fenton technology, ozone oxidation technology, persulfate oxidation technology, wet oxidation technology, and supercritical water oxidation technology. The Fenton oxidation technology system is mature, can rapidly generate hydroxyl free radicals with strong oxidability, and is an effective method for treating refractory organic matters in wastewater. However, the traditional homogeneous Fenton technology has the defects of narrow optimal pH value range of catalytic reaction, difficult recovery and separation of catalyst active components, secondary pollution caused by generated iron and the like, and greatly limits the popularization and application of the technology. The heterogeneous Fenton technology is wide in applicable pH value range, chemical sludge is not generated, and the problems that active free radicals are easy to self-quench in water, the life cycle is extremely short and the like cannot be avoided. Therefore, it is important to study how to improve the Fenton technology. The membrane separation technology is an advanced technology which has wider application and can continuously carry out water treatment, has the advantages of simplicity, high efficiency, small occupied area and the like, but is easy to be polluted in the use process. The Fenton-like catalyst is anchored on the surface of the membrane or inside the membrane hole to prepare the Fenton-like catalytic membrane, so that the mass transfer path of Reactive Oxygen Species (ROS) can be shortened, and pollutants in water can be continuously and efficiently catalyzed in the membrane separation process, so that the catalytic efficiency is greatly improved. However, during the process of combining the Fenton-like catalyst with the membrane, the active site of the Fenton-like catalyst is covered or the membrane pores are blocked by the catalyst, so that the Fenton-like catalytic membrane is low in pollutant degradation efficiency or poor in permeability of the catalytic membrane. Document (Overcoming the permeability-selectivity challenge in water purification using two-dimensional cobalt-functionalized vermiculite membrane.Nature Communications,2024,15:391.) discloses a two-dimensional cobalt-functionalized vermiculite membrane with a permeability of 122.4L/(m 2 h·bar) and a pollutant removal rate of 100%. Document (Angstrom-confined catalytic water purification within Co-TiOx laminar membrane nanochannel.Nature Communications,2022,13:4010.) discloses a two-dimensional laminated film assembled from single-layer cobalt-doped titania nanoplates with a permeability of 131L/(m 2 h·bar) and a contaminant removal rate of 100%. Document (Inert magnesium-doped Co3O4 spinel assembling catalytic membrane for instantaneous peroxymonosulfate activation and contaminants elimination.Chemical Engineering Journal,2023,477:146987.) discloses that the permeability of MCO@PES film produced by vacuum filtration deposition of inert magnesium doped Co 3O4 (MCO) on the PES substrate film surface is 315L/(m 2.h.bar), and the contaminant removal rate is 99.5%. Document (Honeycomb-like holey Co3O4 membrane triggered peroxymonosulfate activation for rapid degradation of organic contaminants.Science of the Total Environment,2022,814:152698.) discloses a honeycomb porous Co 3O4 membrane with a permeability of 176L/(m 2 ·h·bar) and a contaminant removal of 100%. Document (Confining Free Radicals in Close Vicinity to Contaminants Enables Ultrafast Fenton-like Processes in the Interspacing of MoS2Membranes.Angewandte Chemie International Edition,2019,58(24):8134-8138.) discloses a laminated film made of a 2D MoS 2 stack with a permeability of 152.9L/(m 2 h·bar) and a contaminant removal of 90%. Document (Laminar membranes assembled by ultrathin cobalt-copper oxide nanosheets for nanoconfined catalytic degradation of contaminants.Chemical Engineering Journal,2022,449:137811.) discloses a Fenton membrane prepared by depositing ultra-thin cobalt-copper oxide nanoplatelets (Co-Cu ONS) on t