CN114682100A - Preparation method of magnetic graphene-based MOFs hybrid membrane - Google Patents
Preparation method of magnetic graphene-based MOFs hybrid membrane Download PDFInfo
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 119
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- ISPYQTSUDJAMAB-UHFFFAOYSA-N 2-chlorophenol Chemical compound OC1=CC=CC=C1Cl ISPYQTSUDJAMAB-UHFFFAOYSA-N 0.000 description 1
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
- B01D67/0079—Manufacture of membranes comprising organic and inorganic components
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
- B01D69/02—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor characterised by their properties
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
- B01D69/14—Dynamic membranes
- B01D69/141—Heterogeneous membranes, e.g. containing dispersed material; Mixed matrix membranes
- B01D69/148—Organic/inorganic mixed matrix membranes
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/02—Inorganic material
- B01D71/021—Carbon
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
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- B01D71/06—Organic material
- B01D71/76—Macromolecular material not specifically provided for in a single one of groups B01D71/08 - B01D71/74
- B01D71/82—Macromolecular material not specifically provided for in a single one of groups B01D71/08 - B01D71/74 characterised by the presence of specified groups, e.g. introduced by chemical after-treatment
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/28—Treatment of water, waste water, or sewage by sorption
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/44—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01D2325/00—Details relating to properties of membranes
- B01D2325/46—Magnetic properties
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/305—Endocrine disruptive agents
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/34—Organic compounds containing oxygen
- C02F2101/345—Phenols
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Abstract
A preparation method of a magnetic graphene-based MOFs hybrid film comprises the steps of firstly preparing a magnetic graphene material by a hydrothermal reduction method, then loading ZnO on the surface of the magnetic graphene material, and synthesizing the magnetic graphene-based MOFs hybrid film by in-situ growth by taking the ZnO as a metal source. The prepared magnetic graphene-based MOFs hybrid membrane can be used for efficiently adsorbing and removing phenol endocrine disruptors in tap water. The invention has the advantages that: the preparation method of the magnetic graphene-based MOFs hybrid membrane is reasonable in process and easy to implement; when the material is used for removing endocrine disruptors, the material has good chemical stability and reusability, and is easy to actively adsorb, identify and separate the phenolic endocrine disruptors; the preparation method has strong magnetic responsiveness, presettability and practicability, greatly improves the use efficiency of the MOFs hybrid membrane, and widens the application range of the MOFs material.
Description
Technical Field
The invention relates to preparation of MOFs hybrid membranes, in particular to a preparation method of a magnetic graphene-based MOFs hybrid membrane.
Background
With the wide application of Phenolic fine chemical raw materials, pesticides, preservatives, antioxidants and the like in industrial and agricultural production, the pollution problem of Phenolic Endocrine Disrupting Chemicals (pEDCs) in water environment is becoming more and more serious. The pEDCs mainly comprise Alkylphenol (APs), bisphenol A (BPA) and Chlorophenol (CPs), and have attracted extensive attention for their environmental persistence, bioaccumulation, high toxicity and estrogen-like activity. BPA is ubiquitous in human daily life, mineral water bottles, medical instruments and food packages have 'miniature', and long-term use of BPA causes non-negligible BPA pollution in the environment. Especially, the problem of BPA pollution in water environment is closely related to the safety of drinking water, and ultra-trace BPA in water quality can possibly interfere the endocrine function of human or animals to cause various diseases such as cancer, hematopathy, diabetes, birth defects and the like, thereby having certain potential threat to the ecological environment and human health.
Graphene materials have generally attracted attention in the fields of environmental, chemical and biomedical applications due to their properties of dispersibility, hydrophilicity, polymer compatibility, and the like. The preparation of the functionalized graphene composite material can be designed into various ways according to the target functionality, and at present, the preparation mainly focuses on two aspects of preparation by taking functional nanoparticles as precursors and direct coordination assembly preparation of the functional nanoparticles and graphene. The functionalized graphene composite material is an important research direction in the application field of graphene, shows excellent performance in the fields of energy storage, liquid crystal devices, electronic devices, biological materials, sensing materials, catalyst carriers and the like, and has a wide application prospect.
The MOFs material has the advantages of large specific surface area, high catalytic activity, capability of performing chemical modification according to needs and the like, and has become a research hotspot in many fields. The characteristics of the MOFs material such as high specific surface area, high catalytic activity and the like can obviously improve the enrichment efficiency of the sensitive material on target molecules and sense detection signals. The design and synthesis of the magnetic graphene-based MOFs hybrid membrane is a composite membrane material obtained by selecting magnetic graphene as a substrate and growing the MOFs membrane on the surface in situ. The magnetic graphene-based MOFs hybrid membrane has the advantages that the structure is a two-dimensional thin-film structure, the MOFs film grown in situ in the structure is thin and compact, most catalytic active sites are exposed on the surface of the composite membrane, the stability between the catalytic active sites and the magnetic graphene is good, and the preparation and application research of the magnetic graphene-based MOFs hybrid membrane is a brand new direction in the research field of MOFs materials.
Disclosure of Invention
The invention aims to overcome the defects of uneven MOFs doping amount, weaker combination stability with a supporting matrix and the like in the structure of a conventional massive and granular MOFs composite material, provides a preparation method of a magnetic graphene-based MOFs hybrid membrane, and applies the magnetic graphene-based MOFs hybrid membrane to the adsorption and removal of trace phenol secretion interferents in a water environment.
The technical scheme of the invention is as follows:
a preparation method of a magnetic graphene-based MOFs hybrid film comprises the steps of firstly preparing a magnetic graphene material by a hydrothermal reduction method, then loading ZnO on the surface of the magnetic graphene material, and synthesizing the magnetic graphene-based MOFs hybrid film by in-situ growth by taking the ZnO as a metal source.
Further, the magnetic graphene material is obtained by the following method that ferric chloride hexahydrate is dissolved in a mixed solution of ethylene glycol and diethylene glycol, graphene oxide is added after ultrasonic treatment and is uniformly mixed, sodium citrate and anhydrous sodium acetate are added for ultrasonic dissolution, and the mixed solution is subjected to high-temperature reaction, washing and drying.
Further, the ZnO modified magnetic graphene is obtained by respectively dissolving a magnetic graphene material and zinc oxide in absolute ethyl alcohol, dropping the zinc oxide into absolute ethyl alcohol dispersion liquid of the magnetic graphene material after ultrasonic treatment, and performing ultrasonic treatment, washing, magnetic separation on a product and drying.
Further, the magnetic graphene-based MOFs hybrid membrane is obtained by dissolving ZnO modified magnetic graphene and dimethyl imidazole in DMF and H2And in the mixed solution of O, reacting the mixed solution after ultrasonic treatment to obtain a product, washing and drying to obtain the magnetic graphene-based MOFs hybrid membrane.
A preparation method of a magnetic graphene-based MOFs hybrid membrane comprises the following steps:
1) preparation of magnetic graphene material
Dissolving 1.62g of ferric chloride hexahydrate in 40mL of a mixed solution of ethylene glycol and diethylene glycol, performing ultrasonic treatment for 10min, adding 50-200 mg of graphene oxide into the uniformly mixed solution, uniformly mixing the graphene oxide and the uniformly mixed solution, adding 0.3529g of sodium citrate and 4.32g of anhydrous sodium acetate, performing ultrasonic dissolution, simultaneously performing magnetic stirring for 30min, putting the mixed solution into a reaction kettle, reacting for 12h at 200 ℃, naturally cooling, taking out, washing a product obtained by the reaction with anhydrous ethanol for 5 times, and performing vacuum drying at 60 ℃ to obtain magnetic graphene;
2) preparation of ZnO modified magnetic graphene
Respectively dissolving 50-100 mg of magnetic graphene material and 20-50 mg of zinc oxide in absolute ethyl alcohol, carrying out ultrasonic treatment for 120min, slowly dropping the zinc oxide subjected to ultrasonic treatment into the absolute ethyl alcohol dispersion liquid of the magnetic graphene material, carrying out ultrasonic treatment for 60min, washing the product for 5 times with absolute ethyl alcohol, carrying out magnetic separation on the product, and carrying out vacuum drying at 60 ℃ to obtain ZnO modified magnetic graphene;
3) preparation of magnetic graphene-based MOFs hybrid membrane
10-30 mg of ZnO modified magnetic graphene and 50-100 mg of diMethylimidazole dissolved in 13.5mL DMF and 2.5mL H2And (3) carrying out ultrasonic treatment in the mixed solution in the O for 60min, putting the mixed solution after ultrasonic treatment into a polytetrafluoroethylene reaction kettle, reacting for 120min at 60 ℃, washing a product obtained by the reaction with absolute ethyl alcohol for 5 times, and carrying out vacuum drying at 60 ℃ to obtain the magnetic graphene-based MOFs hybrid membrane.
The application of the prepared magnetic graphene-based MOFs hybrid membrane is used for adsorbing and removing trace phenolic endocrine disruptors in a water environment, and the specific method comprises the following steps: preparing a phenolic endocrine disruptor water sample with the pH value of 7, adding the magnetic graphene-based MOFs hybrid membrane into the water sample for oscillation adsorption, enriching with an external magnet in the process, and evaluating the adsorption efficiency of the hybrid membrane material on the basis of considering temperature, adsorption time, substrate concentration influence factors and repeated utilization rate.
The invention has the advantages that: the preparation method of the magnetic graphene-based MOFs hybrid membrane provided by the invention has the advantages of reasonable process and easiness in implementation; the magnetic graphene-based MOFs hybrid membrane prepared by the method has good chemical stability and reusability when being used for removing endocrine disruptors, has strong magnetic responsiveness in a magnetic field, and can be easily separated under the action of an external magnetic field after the 'active' adsorption and identification of phenolic endocrine disruptors are completed, so that the purposes of active identification and convenient separation are achieved; the preparation method has strong magnetic responsiveness, presettability, identifiability and practicability, brings great convenience to the removal of the phenolic endocrine disruptors, greatly improves the use efficiency of the MOFs hybrid membrane, and widens the application range of the MOFs hybrid membrane.
Drawings
Fig. 1 is an electron microscope image of a magnetic graphene material.
Fig. 2 is an electron microscope image of ZnO-modified magnetic graphene.
FIG. 3 is an electron microscope image of a magnetic graphene-based MOFs hybrid film.
Fig. 4 is an adsorption time curve of the magnetic graphene-based MOFs hybrid film.
Detailed Description
Example (b):
a preparation method of a magnetic graphene-based MOFs hybrid film comprises the following steps of firstly preparing a magnetic graphene material by a hydrothermal reduction method, then loading ZnO on the surface of the magnetic graphene material, and synthesizing the magnetic graphene-based MOFs hybrid film by in-situ growth by taking the ZnO as a metal source, wherein the preparation method comprises the following steps:
1) preparation of magnetic graphene material
The method for synthesizing the magnetic graphene material by adopting a hydrothermal method comprises the following specific steps: dissolving 1.62g of ferric chloride hexahydrate in 40mL of mixed solution of ethylene glycol and diethylene glycol, performing ultrasonic treatment for 10min, adding 100mg of graphene oxide into the uniformly mixed solution, uniformly mixing the graphene oxide and the uniformly mixed solution, then adding 0.3529g of sodium citrate and 4.32g of anhydrous sodium acetate, performing ultrasonic treatment for dissolving, and performing magnetic stirring for 30 min. And (4) putting the mixed solution into a reaction kettle, and reacting for 12 hours at 200 ℃ (taking out after natural cooling). Washing the product obtained by the reaction with absolute ethyl alcohol for 5 times, and then drying in vacuum at 60 ℃ to obtain the magnetic graphene.
Fig. 1 is an electron microscope image of a magnetic graphene material. The figure shows that: the graphene has a uniform sheet-like structure and has good light transmittance. The surface of the flaky structure is loaded with a large amount of Fe3O4The magnetic microsphere has uniform particle size of about 300 nm.
2) Preparation of ZnO modified magnetic graphene
Respectively dissolving 50mg of magnetic graphene and zinc oxide in 30mL of absolute ethyl alcohol and 20mL of absolute ethyl alcohol, performing ultrasonic treatment for 120min, slowly dropping the zinc oxide subjected to ultrasonic treatment into the absolute ethyl alcohol dispersion liquid of the magnetic graphene, performing ultrasonic treatment for 60min, washing the product for 5 times with the absolute ethyl alcohol, performing magnetic separation on the product, and performing vacuum drying at 60 ℃ to obtain the ZnO modified magnetic graphene.
Fig. 2 is an electron microscope image of ZnO-modified magnetic graphene. The following are shown in the figure: compared with the graph in fig. 1, a layer of relatively uniform nano-particles with the size of about 20nm zno is uniformly dispersed on the surface of the magnetic graphene material through electrostatic deposition in the experimental process.
3) Preparation of magnetic graphene-based MOFs hybrid membrane
10mg of ZnO-modified magnetic graphene and 80mg of dimethylimidazole were dissolved in 13.5mL of DMF and 2.5mL of H2And (4) carrying out ultrasonic treatment on the mixed solution in the O for 1 h. Putting the mixed solution after ultrasonic treatment intoAnd (3) reacting for 2 hours at the temperature of 60 ℃ in a polytetrafluoroethylene reaction kettle. Washing the product obtained by the reaction with absolute ethyl alcohol for 5 times, and then carrying out vacuum drying at 60 ℃ to obtain the magnetic graphene-based MOFs hybrid membrane.
FIG. 3 is an electron microscope image of a magnetic graphene-based MOFs hybrid film. The figure shows that: by using dimethyl imidazole and benzimidazole as etching agents, ZnO nanoparticles on the surface of ZnO modified magnetic graphene grow in situ and are converted into a layer of MOFs film, and the MOFs film is uniformly coated on the surface of microspheres in the magnetic graphene structure.
The prepared magnetic graphene-based MOFs hybrid membrane is applied to adsorption and removal of trace phenolic endocrine disruptors in a water environment, bisphenol A is taken as a target molecule, and the magnetic graphene-based MOFs hybrid membrane is used for carrying out an adsorption performance experiment on the bisphenol A:
preparing bisphenol A solution with concentration of 0.01-0.15mmol/L, adjusting pH to 7.0, respectively taking 5ml of bisphenol A solution with different concentrations, adding 5mg of magnetic graphene-based MOFs hybrid membrane, oscillating in a shaking table for 40min, separating with external magnet, respectively taking supernatant and bisphenol A solution before adsorption, and measuring absorbance value at 286nm with an ultraviolet spectrophotometer. The detection result shows that: after the magnetic graphene-based MOFs hybrid membrane material is adsorbed, the absorbance value of the supernatant at 286nm is greatly reduced compared with that of the bisphenol A solution before adsorption, and is less than 20% of that of the bisphenol A solution before adsorption, and the adsorption efficiency of the magnetic graphene-based MOFs hybrid membrane on the bisphenol A can reach 93%.
Detection of bisphenol a in tap water:
the method is to inject 5mL of 2mol/L bisphenol A solution into a 100mL volumetric flask and add tap water to obtain an actual water sample of bisphenol A. Taking 5mL of an actual water sample, adding 5mg of a magnetic graphene-based MOFs hybrid membrane, oscillating and adsorbing for 40min, separating by an external magnet, and respectively taking a supernatant and a bisphenol A solution before adsorption at 286nm and measuring the absorbance value of the solution by using an ultraviolet spectrophotometer. The detection result shows that: the adsorption efficiency of the magnetic graphene-based MOFs hybrid membrane on bisphenol A in an actual water sample can reach 72%.
FIG. 4 is a graph of the adsorption time of the magnetic graphene-based MOFs hybrid film. The figure shows that: the adsorption efficiency of the magnetic graphene-based MOFs hybrid membrane on bisphenol A is obviously higher than that of magnetic graphene, the adsorption efficiency is rapidly increased in the first 15min, and the adsorption gradually tends to be balanced after 15 min.
Claims (7)
1. The preparation method of the magnetic graphene-based MOFs hybrid membrane is characterized by comprising the following steps of: firstly, loading Fe on the surface of graphene by a hydrothermal method3O4And (2) magnetic microspheres, then loading ZnO on the surface of the magnetic microspheres by taking the magnetic graphene as a carrier to obtain ZnO modified magnetic graphene, and synthesizing the magnetic graphene-based MOFs hybrid film by utilizing a solvent etching effect and taking the ZnO as a metal source through in-situ growth.
2. The preparation method of the magnetic graphene-based MOFs hybrid film according to claim 1, wherein: the magnetic graphene material is obtained by the following method that ferric chloride hexahydrate is dissolved in a mixed solution of ethylene glycol and diethylene glycol, graphene oxide is added and uniformly mixed after ultrasonic treatment, sodium citrate and anhydrous sodium acetate are added for ultrasonic dissolution, and the mixed solution is subjected to high-temperature reaction, washing and drying.
3. The preparation method of the magnetic graphene-based MOFs hybrid film according to claim 1, wherein: the ZnO modified magnetic graphene is obtained by the following method that a magnetic graphene material and zinc oxide are respectively dissolved in absolute ethyl alcohol, the zinc oxide is dripped into absolute ethyl alcohol dispersion liquid of the magnetic graphene material after ultrasonic treatment, and the magnetic graphene material is obtained by ultrasonic treatment, washing, magnetic separation of a product and drying.
4. The preparation method of the magnetic graphene-based MOFs hybrid film according to claim 1, wherein: the magnetic graphene-based MOFs hybrid membrane is obtained by dissolving ZnO-modified magnetic graphene and dimethyl imidazole in DMF (dimethyl formamide) and H (hydrogen peroxide)2And in the mixed solution of O, reacting the mixed solution after ultrasonic treatment to obtain a product, washing and drying to obtain the magnetic graphene-based MOFs hybrid membrane.
5. The preparation method of the magnetic graphene-based MOFs hybrid film according to claim 1, wherein: the method comprises the following steps:
1) preparation of magnetic graphene material
Dissolving 1.62g of ferric chloride hexahydrate in 40mL of a mixed solution of ethylene glycol and diethylene glycol, performing ultrasonic treatment for 10min, adding 50-200 mg of graphene oxide into the uniformly mixed solution, uniformly mixing the graphene oxide and the uniformly mixed solution, adding 0.3529g of sodium citrate and 4.32g of anhydrous sodium acetate, performing ultrasonic dissolution, simultaneously performing magnetic stirring for 30min, putting the mixed solution into a reaction kettle, reacting for 12h at 200 ℃, naturally cooling, taking out, washing a product obtained by the reaction with anhydrous ethanol for 5 times, and performing vacuum drying at 60 ℃ to obtain magnetic graphene;
2) preparation of ZnO modified magnetic graphene
Respectively dissolving 50-100 mg of magnetic graphene material and 20-50 mg of zinc oxide in absolute ethyl alcohol, carrying out ultrasonic treatment for 120min, slowly dropping the zinc oxide subjected to ultrasonic treatment into the absolute ethyl alcohol dispersion liquid of the magnetic graphene material, carrying out ultrasonic treatment for 60min, washing the product for 5 times with absolute ethyl alcohol, carrying out magnetic separation on the product, and carrying out vacuum drying at 60 ℃ to obtain ZnO modified magnetic graphene;
3) preparation of magnetic graphene-based MOFs hybrid membrane
Dissolving 10-30 mg of ZnO modified magnetic graphene and 50-100 mg of dimethyl imidazole in 13.5mL of DMF and 2.5mL of H2And (3) carrying out ultrasonic treatment on the mixed solution in the O for 60min, putting the mixed solution after ultrasonic treatment into a polytetrafluoroethylene reaction kettle, reacting for 120min at 60 ℃, washing a product obtained by the reaction with absolute ethyl alcohol for 5 times, and carrying out vacuum drying at 60 ℃ to obtain the magnetic graphene-based MOFs hybrid membrane.
6. Use of a magnetic graphene-based MOFs hybrid film prepared by any one of the methods of claims 1-5, characterized in that: the method is used for adsorbing and removing trace phenolic endocrine disruptors in the water environment.
7. The use of the magnetic graphene-based MOFs hybrid film according to claim 6, wherein: preparing a practical water sample of the phenol endocrine disruptors with the pH value of 7, adding the magnetic graphene-based MOFs hybrid membrane into the water sample for oscillation and adsorption, enriching the external magnet in the process, and evaluating the adsorption efficiency of the magnetic graphene-based MOFs hybrid membrane on the basis of considering temperature, adsorption time, substrate concentration influence factors and repeated utilization rate.
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