CN114832836A - Micro-plastic catalyst, preparation method thereof and method for degrading micro-plastic - Google Patents

Micro-plastic catalyst, preparation method thereof and method for degrading micro-plastic Download PDF

Info

Publication number
CN114832836A
CN114832836A CN202210530272.7A CN202210530272A CN114832836A CN 114832836 A CN114832836 A CN 114832836A CN 202210530272 A CN202210530272 A CN 202210530272A CN 114832836 A CN114832836 A CN 114832836A
Authority
CN
China
Prior art keywords
fes
nano
micro
mixing
plastic
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
CN202210530272.7A
Other languages
Chinese (zh)
Inventor
何念新
黄在银
蓝芝文
张筱雨
欧阳惠婕
王肇域
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Guangxi University for Nationalities
Original Assignee
Guangxi University for Nationalities
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Guangxi University for Nationalities filed Critical Guangxi University for Nationalities
Priority to CN202210530272.7A priority Critical patent/CN114832836A/en
Publication of CN114832836A publication Critical patent/CN114832836A/en
Pending legal-status Critical Current

Links

Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • B01J27/02—Sulfur, selenium or tellurium; Compounds thereof
    • B01J27/04—Sulfides
    • B01J27/047—Sulfides with chromium, molybdenum, tungsten or polonium
    • B01J27/051—Molybdenum
    • B01J27/0515—Molybdenum with iron group metals or platinum group metals
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • B01J27/02—Sulfur, selenium or tellurium; Compounds thereof
    • B01J27/04—Sulfides
    • B01J27/043—Sulfides with iron group metals or platinum group metals
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • B01J27/02—Sulfur, selenium or tellurium; Compounds thereof
    • B01J27/04—Sulfides
    • B01J27/047—Sulfides with chromium, molybdenum, tungsten or polonium
    • B01J27/049—Sulfides with chromium, molybdenum, tungsten or polonium with iron group metals or platinum group metals
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J11/00—Recovery or working-up of waste materials
    • C08J11/04—Recovery or working-up of waste materials of polymers
    • C08J11/10—Recovery or working-up of waste materials of polymers by chemically breaking down the molecular chains of polymers or breaking of crosslinks, e.g. devulcanisation
    • C08J11/16—Recovery or working-up of waste materials of polymers by chemically breaking down the molecular chains of polymers or breaking of crosslinks, e.g. devulcanisation by treatment with inorganic material
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
    • Y02W30/00—Technologies for solid waste management
    • Y02W30/50—Reuse, recycling or recovery technologies
    • Y02W30/62—Plastics recycling; Rubber recycling

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Sustainable Development (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Catalysts (AREA)

Abstract

The invention provides a micro-plastic catalyst, a preparation method thereof and a method for degrading micro-plastic, and relates to the technical field of environmental remediation. The preparation method of the micro plastic catalyst provided by the invention comprises the following steps: FeS is prepared 2 Modifying the nanosheets to obtain a micro plastic catalyst; said modification comprising subjecting said FeS to 2 Sequentially carrying out surface oxidation treatment and reduction treatment on the nano-sheets, or carrying out surface oxidation treatment and reduction treatment on the FeS 2 Nanosheets and nano-CoS 2 Mixing the materials, or mixing the FeS 2 Mixing the nano-sheet and nano CoS material, or mixing the FeS 2 Nanosheet and nano MoS 2 Mixing the materials, or mixing the FeS 2 Nanosheets and nanoparticlesWS 2 And mixing the materials to obtain the micro plastic catalyst. The micro plastic catalyst provided by the invention is used for degrading micro plastic, the degradation efficiency is high, the energy utilization rate is high, and the whole micro plastic treatment process cannot cause secondary pollution.

Description

Micro-plastic catalyst, preparation method thereof and method for degrading micro-plastic
Technical Field
The invention relates to the technical field of environmental remediation, in particular to a micro-plastic catalyst, a preparation method thereof and a method for degrading micro-plastic.
Background
In recent years, micro plastics have become an environmental problem of high interest to international society. The micro plastic not only causes white pollution of the environment, but also destroys the development of marine biodiversity and even endangers the health of people. Of these, there are about millions of seabirds each year, 10 tens of thousands of marine mammals die from micro-plastic contamination, and humans ingest an average of 86000 plastic particles each year, whereas natural degradation of PE micro-plastic takes 200 years. The environment of the united nations can greatly equate the problems of marine plastic wastes and micro-plastics to global major environmental problems such as global climate change and the like. And the plastic is produced by 3 hundred million tons every year in the world, and the micro plastic pollution is a serious concern of the environmental protection all over the world.
Biological methods and advanced oxidation methods are the mainstream means for degrading micro-plastics at present. However, both biological and advanced oxidation processes have certain disadvantages: the biological method has the biggest defect that the degradation treatment period is long, the PE plastic degradation time needs at least 2 months in the prior biological method, and the corresponding degradation mechanism of different types of micro-plastics is not clear, so that the popularization and the application of the micro-plastics are restricted; the traditional advanced oxidation method also has certain disadvantages, which are mainly represented by the problems of low degradation efficiency, low energy utilization rate, secondary pollution and the like.
Disclosure of Invention
The invention aims to provide a micro-plastic catalyst, a preparation method thereof and a method for degrading micro-plastic.
In order to achieve the above object, the present invention provides the following technical solutions:
the invention provides a preparation method of a micro-plastic catalyst, which comprises the following steps:
FeS is prepared 2 Modifying the nanosheets to obtain a micro plastic catalyst;
the modification comprises any one of steps (1) to (5);
(1) subjecting the FeS to 2 Sequentially carrying out surface oxidation treatment and reduction treatment on the nanosheets to obtain a micro-plastic catalyst;
(2) subjecting the FeS to 2 Nanosheets and nano-CoS 2 Mixing the materials to obtain a micro plastic catalyst;
(3) subjecting the FeS to 2 Mixing the nanosheets and the nano CoS material to obtain a micro plastic catalyst;
(4) subjecting the FeS to 2 Nanosheet and nano MoS 2 Mixing the materials to obtain a micro plastic catalyst;
(5) subjecting the FeS to 2 Nanosheets and nano-WS 2 And mixing the materials to obtain the micro plastic catalyst.
Preferably, the FeS 2 The preparation method of the nano-sheet comprises the following steps: FeSO (ferric oxide) is added 4 、Na 2 S 2 O 3 Grinding and mixing the sulfur powder and elemental sulfur to obtain mixed powder; mixing the mixed powder with water and oleic acid, and carrying out hydrothermal reaction to obtain FeS 2 Nanosheets.
Preferably, the temperature of the hydrothermal reaction is 220-250 ℃; the heat preservation time is 24-28 h.
Preferably, the surface oxidation treatment comprises: in an air atmosphere, the FeS is added 2 And calcining the nanosheets.
Preferably, the reduction treatment is a hydrogen reduction treatment.
Preferably, FeS is used in the steps (2), (3), (4) and (5) 2 Before the nano-sheet is modified, defect treatment is also independently carried out;
the FeS 2 Defect treatment of the nanoplatelets comprises: FeS is prepared 2 Mixing the nanosheets and aqueous hydrogen peroxide solution, and carrying out oxidation reaction to obtain FeS with defects 2 Nanosheets.
Preferably, the nano CoS material in the step (3) is mixed with FeS 2 Defect treatment is also included before the nano sheets are mixed; the nano CoS Defect handling of materials includes:
and mixing the nano CoS material with ethanol, and carrying out solvothermal reaction to obtain the defective nano CoS material.
Preferably, the nano MoS in the step (4) 2 Material in and FeS 2 Defect treatment is also included before the nano sheets are mixed; the nano MoS 2 The defect treatment of the material comprises the following steps:
mixing the nano MoS 2 Mixing the material with ethanol, and carrying out solvothermal reaction to obtain defect nano MoS 2 A material.
The invention provides the micro plastic catalyst prepared by the preparation method in the technical scheme.
The invention provides a method for degrading micro-plastic, which comprises the following steps:
the micro plastic, the micro plastic catalyst and the hydrogen peroxide solution are mixed, and hydrothermal reaction is carried out under an acidic condition to degrade the micro plastic.
The invention provides a preparation method of a micro plastic catalyst, and Fe in the micro plastic catalyst is used for degrading micro plastic in a hydrogen peroxide solution 2+ Promoting the decomposition of hydrogen peroxide to generate a large amount of OH with strong oxidizing property to oxidize and decompose micro-plastics, wherein the main decomposition process comprises the following steps: OH attacks a carbon-carbon single bond in the micro plastic, the carbon-carbon single bond is broken and substituted by two hydroxyl groups, OH continuously attacks the hydroxyl groups and is oxidized into carbonyl and carboxyl in sequence, and finally at a certain high temperature, the carboxyl group is continuously attacked to generate decarboxylation and is finally degraded into CO 2 And H 2 And O. Besides promoting the decomposition of hydrogen peroxide to form OH, the micro-plastic catalyst can adsorb sulfur vacancy defects to a certain extent, so that the micro-plastic and the OH react almost at zero distance, and the degradation efficiency is greatly improved. S dropped after introduction of sulfur vacancy 2- Changing a small amount of free oxygen in water into O by electron donating 2- O having strong reducibility 2- Promoting Fe on the surface of the catalyst 3+ To Fe 2+ And conversion is carried out, so that the aim of circulation is fulfilled, and secondary pollution cannot be caused in the whole micro-plastic treatment process. Moreover, the present invention is adoptedThe micro-plastic catalyst provided by the invention is used for degrading micro-plastic, the process flow is simple and convenient, the operation is easy, the preprocessing of the degraded micro-plastic is not needed, the degradation cost is low, and the micro-plastic catalyst is suitable for large-scale application.
Detailed Description
The invention provides a preparation method of a micro-plastic catalyst, which comprises the following steps:
FeS is prepared 2 Modifying the nanosheets to obtain a micro plastic catalyst;
the modification comprises any one of steps (1) to (5);
(1) subjecting the FeS to 2 Sequentially carrying out surface oxidation treatment and reduction treatment on the nanosheets to obtain a micro-plastic catalyst;
(2) subjecting the FeS to 2 Nanosheets and nano-CoS 2 Mixing the materials to obtain a micro plastic catalyst;
(3) subjecting the FeS to 2 Mixing the nanosheets and the nano CoS material to obtain a micro plastic catalyst;
(4) subjecting the FeS to 2 Nanosheet and nano MoS 2 Mixing the materials to obtain a micro plastic catalyst;
(5) subjecting the FeS to 2 Nanosheets and nano-WS 2 And mixing the materials to obtain the micro plastic catalyst.
The invention leads FeS to be 2 And modifying the nano sheet to obtain the micro plastic catalyst. In the present invention, the FeS 2 The preparation method of the nanoplatelets preferably comprises the following steps: FeSO (ferric oxide) is added 4 、Na 2 S 2 O 3 Grinding and mixing the sulfur powder and elemental sulfur to obtain mixed powder; mixing the mixed powder with water and oleic acid, and carrying out hydrothermal reaction to obtain FeS 2 Nanosheets.
FeSO is preferably prepared by the method 4 、Na 2 S 2 O 3 And grinding and mixing the sulfur and the elemental sulfur to obtain mixed powder. In the present invention, the FeSO 4 、Na 2 S 2 O 3 And the mass ratio of the elemental sulfur to the elemental sulfur is preferably 0.8305-3218: 1.5811-4.7433: 0.3200-0.6400, more preferably 1.6609-3.0382: 1622: 0.6400. in the present invention, the grinding and mixingThe time of (a) is preferably 15 to 40min, more preferably 15 to 30 min.
After mixed powder is obtained, the mixed powder is mixed with water and oleic acid for hydrothermal reaction to obtain FeS 2 Nanosheets; in the invention, the mass ratio of the mixed powder to water is preferably 2.7316-8.7051: 30-60, more preferably 5.4631-6.8404: 30-60; the mass ratio of the mixed powder to the oleic acid is preferably 2.7316-8.7051: 10, and more preferably 5.4631-6.8404: 10. In the present invention, the mixing is preferably performed at room temperature; the mixing is preferably carried out under stirring conditions, more preferably magnetic stirring; the mixing time is preferably 20-45 min, and more preferably 30 min.
In the invention, the temperature of the hydrothermal reaction is preferably 200-220 ℃; the incubation time is preferably 24 h.
In the present invention, it is preferable that the hydrothermal reaction further comprises: carrying out solid-liquid separation on the obtained reaction system to obtain a solid substance; the solid material is washed and dried in sequence. In the present invention, the method of solid-liquid separation is preferably centrifugation; the centrifugal rotating speed is preferably 10000-12000 r/min; the time for centrifugation is preferably 5-6 min. In the present invention, the washing preferably includes water washing, carbon tetrachloride washing and absolute ethanol washing, which are sequentially performed. In the present invention, the water washing is preferably distilled water washing; the number of times of water washing is preferably 8-10; the number of times of washing with carbon tetrachloride is preferably 8-10 times; the number of times of washing with absolute ethyl alcohol is preferably 8-10. The present invention preferably performs centrifugation after each wash. In the invention, the drying temperature is preferably 60-70 ℃; the drying time is preferably 6-10 h; the drying is preferably vacuum drying.
To obtain FeS 2 After the nano-sheets are prepared, the FeS2 nano-sheets are modified to obtain a micro-plastic catalyst; the modification comprises any one of steps (1) to (5); (1) subjecting the FeS to 2 Sequentially carrying out surface oxidation treatment and reduction treatment on the nanosheets to obtain a micro-plastic catalyst; (2) subjecting the FeS to 2 Nanosheets and nano-CoS 2 Mixing the materials to obtain the micro plastic catalyst(ii) a (3) Subjecting the FeS to 2 Mixing the nanosheets and the nano CoS material to obtain a micro plastic catalyst; (4) subjecting the FeS to 2 Nanosheet and nano MoS 2 Mixing the materials to obtain a micro plastic catalyst; (5) subjecting the FeS to 2 Nanosheets and nano-WS 2 And mixing the materials to obtain the micro plastic catalyst. Following FeS 2 The methods of modifying the nanosheets will be described in detail.
(1) Subjecting the FeS to 2 And sequentially carrying out surface oxidation treatment and reduction treatment on the nanosheets to obtain the micro-plastic catalyst. In the present invention, the surface oxidation treatment preferably includes: in an air atmosphere, the FeS is added 2 And calcining the nanosheets. In the present invention, the temperature of the calcination is preferably 400 ℃; the calcination time is preferably 2 h. In the calcining process, the surface of the ferrous disulfide is oxidized to form ferric oxide.
In the present invention, the reduction treatment is preferably a hydrogen reduction treatment. The invention utilizes hydrogen reduction treatment to form sulfur vacancy defects and oxygen defects on the surface of ferrous disulfide.
In the present invention, Fe generating sulfur and oxygen vacancies in the microplastic catalyst 2+ The double active sites promote the decomposition of hydrogen peroxide to generate a large amount of OH with strong oxidizing property to oxidize and decompose micro plastic, and the main decomposition process is as follows: OH attacks a carbon-carbon single bond in the micro plastic, the carbon-carbon single bond is broken and substituted by two hydroxyl groups, OH continuously attacks the hydroxyl groups and is oxidized into carbonyl and carboxyl in sequence, and finally at a certain high temperature, the carboxyl group is continuously attacked to generate decarboxylation and is finally degraded into CO 2 And H 2 And O. Besides promoting the decomposition of hydrogen peroxide to form OH, the micro-plastic catalyst can adsorb the sulfur vacancy defects to a certain extent, so that the micro-plastic reacts with the OH almost at zero distance, and the degradation efficiency is greatly improved. S dropped after introduction of sulfur vacancy 2- Changing a small amount of free oxygen in water into O by electron donating 2- O having strong reducibility 2- Capable of reducing Fe 3+ Is Fe 2+ And the purpose of self-repairing active sites is achieved.
(2) Subjecting the FeS to 2 Nanosheets and nano-CoS 2 And mixing the materials to obtain the micro plastic catalyst. In the invention, the nano CoS 2 The method of preparing the material preferably comprises: adding divalent cobalt salt and Na 2 Mixing S and glycol, and carrying out solvothermal reaction to obtain nano CoS 2 A material. In the present invention, the divalent cobalt salt is preferably CoCl 2 . In the present invention, the temperature of the solvothermal reaction is preferably 180 ℃; the solvothermal reaction time is preferably 24 h. In the present invention, the solvothermal reaction preferably further comprises: carrying out solid-liquid separation on the obtained reaction system to obtain a solid substance; the solid material is washed and dried in sequence. In the present invention, the method of solid-liquid separation is preferably centrifugation; the centrifugal rotating speed is preferably 10000-12000 r/min; the time for centrifugation is preferably 5-6 min. In the present invention, the washing preferably includes water washing and absolute ethanol washing performed in this order. In the present invention, the water washing is preferably distilled water washing. The present invention preferably performs centrifugation after each wash. In the present invention, the temperature of the drying is preferably 80 ℃; the drying is preferably vacuum drying.
In the present invention, the FeS 2 Nanosheets and nano-CoS 2 The mass ratio of the materials is preferably 5: 1. In the present invention, the FeS 2 Nanosheets and nano-CoS 2 The material mixing is preferably carried out in a ball mill; the rotating speed of the ball mill is preferably 400 r/min; the mixing time is preferably 2 h.
In the present invention, Fe is contained in the microplastic catalyst 2+ The active sites promote the decomposition of hydrogen peroxide to generate a large amount of OH with strong oxidizing property to oxidize and decompose micro plastics, and the main decomposition process is as follows: OH attacks a carbon-carbon single bond in the micro plastic, the carbon-carbon single bond is broken and substituted by two hydroxyl groups, OH continuously attacks the hydroxyl groups and is oxidized into carbonyl and carboxyl in sequence, and finally at a certain high temperature, the carboxyl group is continuously attacked to generate decarboxylation and is finally degraded into CO 2 And H 2 And O. Besides promoting the decomposition of hydrogen peroxide to form OH, the micro-plastic catalyst can adsorb the sulfur vacancy defects to a certain extent, so that the micro-plastic reacts with the OH almost at zero distance, and the degradation efficiency is greatly improved. Introduction of sulfur voidsS dropped after position 2- Changing a small amount of free oxygen in water into O by electron donating 2- O having strong reducibility 2- Reducible Fe 3+ Is Fe 2+ The purpose of self-repairing is achieved; meanwhile, on the basis of self-repair, CoS 2 At H 2 O 2 Large amount of Co exposed after formation of sulfur vacancy defects in the solution 3+ Promoting Fe on the surface of the catalyst by taking Co-Fe bond as a channel for transferring electrons 3+ To Fe 2+ And conversion is carried out, so that the aim of circulation is fulfilled, and secondary pollution cannot be caused in the whole micro-plastic treatment process.
In the present invention, the FeS 2 Nanosheets in and nano CoS 2 Before the materials are mixed, defect treatment is preferably also included. In the present invention, the FeS 2 The defect treatment of the nanoplatelets preferably comprises: FeS is prepared 2 Mixing the nanosheets and aqueous hydrogen peroxide solution, and carrying out oxidation reaction to obtain FeS with defects 2 Nanosheets. In the present invention, the concentration of the aqueous hydrogen peroxide solution is preferably 0.0979 mol/L; the FeS 2 The dosage ratio of the nano sheet to the aqueous hydrogen peroxide solution is preferably 0.1500-1.5000 g: 100mL, more preferably 0.2000: 100 mL. In the invention, the temperature of the oxidation reaction is preferably room temperature, and particularly preferably 18-25 ℃; the oxidation reaction is preferably carried out under stirring conditions, and the rotation speed of the stirring is preferably 1000 rpm; the time of the oxidation reaction is preferably 1-2 h.
In the present invention, it is preferable that the oxidation reaction further comprises: carrying out solid-liquid separation on the obtained reaction system to obtain a solid substance; drying the solid matter. In the present invention, the method of solid-liquid separation is preferably centrifugation; the centrifugal rotating speed is preferably 10000-12000 r/min; the time for centrifugation is preferably 5-6 min. In the present invention, the temperature of the drying is preferably 60 ℃; the drying time is preferably 6-10 h; the drying is preferably vacuum drying.
In the present invention, FeS 2 The nano sheets are subjected to defect treatment, so that active sites can be further increased, the decomposition of hydrogen peroxide is promoted, and the decomposition efficiency of the micro plastic is improved.
(3) Subjecting the FeS to 2 And mixing the nanosheets and the nano CoS material to obtain the micro plastic catalyst. In the present invention, the FeS 2 Before the nano sheet is mixed with the nano CoS material, preferably, defect treatment is also included; the FeS 2 The defect processing method of the nanosheet is consistent with that described above, and is not described herein again.
In the present invention, the preparation method of the nano CoS material preferably includes: mixing divalent cobalt salt and oleic acid to obtain a cobalt salt solution; and mixing the cobalt salt solution and thioacetamide, and carrying out solvothermal reaction to obtain the nano CoS material. In the present invention, the divalent cobalt salt preferably includes cobalt nitrate. In the present invention, the concentration of the cobalt salt solution is preferably 0.00679 g/mL. In the present invention, the temperature of the solvothermal reaction is preferably 180 ℃; the solvothermal reaction time is preferably 12 h. In the present invention, the solvothermal reaction preferably further comprises: carrying out solid-liquid separation on the obtained reaction system to obtain a solid substance; the solid material is washed and dried in sequence. In the present invention, the method of solid-liquid separation is preferably centrifugation; the centrifugal rotating speed is preferably 10000-12000 r/min; the time for centrifugation is preferably 5-6 min. In the present invention, the washing preferably includes water washing and absolute ethanol washing sequentially performed. In the present invention, the water washing is preferably distilled water washing. The present invention preferably performs centrifugation after each wash. In the present invention, the temperature of the drying is preferably 60 ℃; the drying time is preferably 6 h; the drying is preferably vacuum drying.
In the invention, the nano CoS material is mixed with FeS 2 The nanosheet preferably further comprises a defect treatment prior to mixing; the defect treatment method of the nano CoS material preferably comprises the following steps: and mixing the nano CoS material with ethanol, and carrying out solvothermal reaction to obtain the defective nano CoS material. In the present invention, the dosage ratio of the nano CoS material and ethanol is preferably 0.01g: 40 mL. In the present invention, the mixing is preferably ultrasonic mixing; the time of the ultrasonic mixing is preferably 3 hours. In the present invention, the temperature of the solvothermal reaction is preferably 220 ℃; the solvothermal reaction time is preferably 6 h. In the present invention, the solutionAfter the agent thermal reaction, the agent thermal reaction also preferably comprises: and washing and drying the obtained solid product in sequence to obtain the defective nano CoS material. In the present invention, the washing liquid is preferably absolute ethanol; the temperature of the drying is preferably 60 ℃; the drying is preferably vacuum drying.
In the present invention, the FeS 2 The mass ratio of the nanosheets to the nano-CoS material is preferably 5: 1. In the present invention, the FeS 2 Mixing the nano-sheets and the nano CoS material is preferably carried out in a ball mill; the rotating speed of the ball mill is preferably 400 r/min; the mixing time is preferably 2 h.
In the present invention, Fe is contained in the microplastic catalyst 2+ The active sites promote the decomposition of hydrogen peroxide to generate a large amount of OH with strong oxidizing property to oxidize and decompose micro plastics, and the main decomposition process is as follows: OH attacks a carbon-carbon single bond in the micro plastic, the carbon-carbon single bond is broken and substituted by two hydroxyl groups, OH continuously attacks the hydroxyl groups and is oxidized into carbonyl and carboxyl in sequence, and finally at a certain high temperature, the carboxyl group is continuously attacked to generate decarboxylation and is finally degraded into CO 2 And H 2 And O. Besides promoting the decomposition of hydrogen peroxide to form OH, the micro-plastic catalyst can adsorb the sulfur vacancy defects to a certain extent, so that the micro-plastic reacts with the OH almost at zero distance, and the degradation efficiency is greatly improved. S dropped after introduction of sulfur vacancy 2- Changing a small amount of free oxygen in water into O by electron donating 2- O having strong reducibility 2- Reducible Fe 3+ Is Fe 2+ The purpose of self-repairing is achieved; meanwhile, CoS is in H on the basis of self-repair 2 O 2 After sulfur vacancy defect is formed in the solution, a large amount of exposed free cobalt ions are used as a channel for transferring electrons through Co-Fe bonds to promote Fe on the surface of the catalyst 3+ To Fe 2+ And conversion is carried out, so that the aim of circulation is fulfilled, and secondary pollution cannot be caused in the whole micro-plastic treatment process.
(4) Subjecting the FeS to 2 Nanosheet and nano MoS 2 And mixing the materials to obtain the micro plastic catalyst. In the present invention, the FeS 2 Nano sheet and nano MoS 2 Before the materials are mixed, defect treatment is preferably further included; what is needed isThe FeS 2 The defect processing method of the nanosheet is consistent with that described above, and is not described herein again.
In the present invention, the nano MoS 2 The method of preparing the material preferably comprises: mixing Na 2 MoO 4 Mixing with water, and adjusting the pH value to 6.5 to obtain a Mo salt solution; mixing the Mo salt solution, L-cysteine and polyvinylpyrrolidone (PVP) to perform hydrothermal reaction to obtain nano MoS 2 A material. In the present invention, the mass ratio of L-cysteine to PVP is preferably 3: 2. In the present invention, the temperature of the hydrothermal reaction is preferably 180 ℃; the time of the hydrothermal reaction is preferably 48 h. In the present invention, it is preferable that the hydrothermal reaction further comprises: carrying out solid-liquid separation on the obtained reaction system to obtain a solid substance; the solid material is washed and dried in sequence. In the present invention, the method of solid-liquid separation is preferably centrifugation; the rotating speed of the centrifugation is preferably 18000 r/min; the time for centrifugation is preferably 5-6 min. In the present invention, the washing preferably includes water washing and absolute ethanol washing performed in this order. In the present invention, the water washing is preferably distilled water washing. The present invention preferably performs centrifugation after each wash. In the present invention, the temperature of the drying is preferably 80 ℃; the drying time is preferably 12 h; the drying is preferably vacuum drying.
In the present invention, the FeS 2 Nanosheet and nano MoS 2 The mass ratio of the materials is preferably 5: 1. In the present invention, the FeS 2 Nanosheet and nano MoS 2 The material mixing is preferably carried out in a ball mill; the rotating speed of the ball mill is preferably 400 r/min; the mixing time is preferably 2-3 h.
In the present invention, Fe is contained in the microplastic catalyst 2+ The active sites promote the decomposition of hydrogen peroxide to generate a large amount of OH with strong oxidizing property to oxidize and decompose micro plastics, and the main decomposition process is as follows: OH attacks a carbon-carbon single bond in the micro plastic, the carbon-carbon single bond is broken and substituted by two hydroxyl groups, OH continuously attacks the hydroxyl groups and is oxidized into carbonyl and carboxyl in sequence, and finally at a certain high temperature, the carboxyl group is continuously attacked to generate decarboxylation and is finally degraded into CO 2 And H 2 And O. Besides promoting the decomposition of hydrogen peroxide to form OH, the micro-plastic catalyst can adsorb the micro-plastic to a certain extent by sulfur vacancy defects and layered molybdenum disulfide, so that the micro-plastic reacts with the OH at almost zero distance, and the degradation efficiency is greatly improved. S dropped after introduction of sulfur vacancy 2- Changing a small amount of free oxygen in water into O by electron donating 2- O having strong reducibility 2- Reducible Fe 3+ Is Fe 2+ The purpose of self-repairing is achieved; meanwhile, on the basis of self-repairing, MoS 2 At H 2 O 2 A large amount of Mo exposed after sulfur vacancy defect is formed in the solution 3+ Promoting Fe on the surface of the catalyst by taking Mo-Fe bond as a channel for transferring electrons 3+ To Fe 2+ And conversion is carried out, so that the aim of circulation is fulfilled, and secondary pollution cannot be caused in the whole micro-plastic treatment process.
In the present invention, the nano MoS 2 Material in and FeS 2 The defect treatment is preferably further included before the mixing of the nanosheets; the nano MoS 2 The defect management of the material preferably comprises: mixing the nano MoS 2 Mixing the material with ethanol, and carrying out solvothermal reaction to obtain defect nano MoS 2 A material. In the present invention, the nano MoS 2 The ratio of the amount of material to ethanol is preferably 0.1 g: 60 mL. In the present invention, the mixing is preferably ultrasonic mixing; the time of the ultrasonic mixing is preferably 3 hours. In the present invention, the temperature of the solvothermal reaction is preferably 220 ℃; the solvothermal reaction time is preferably 12 h. In the present invention, the solvothermal reaction preferably further comprises: washing and drying the obtained solid product in sequence to obtain the defect nano MoS 2 A material. In the present invention, the washing liquid is preferably absolute ethanol; the temperature of the drying is preferably 80 ℃; the drying time is preferably 12 h; the drying is preferably vacuum drying.
(5) Subjecting the FeS to 2 Nanosheets and nano-WS 2 And mixing the materials to obtain the micro plastic catalyst. In the present invention, the FeS 2 Nano sheet and nano MoS 2 Before the materials are mixed, defect treatment is preferably further included; the FeS 2 Of nanosheetsThe defect processing method is consistent with the foregoing description, and is not repeated here.
In the present invention, the nano WS 2 The method of preparing the material preferably comprises: mixing sodium tungstate dihydrate, thiourea, hydroxylamine hydrochloride, Cetyl Trimethyl Ammonium Bromide (CTAB) and water, and carrying out hydrothermal reaction to obtain nano WS 2 A material. In the present invention, the mass ratio of the thiourea to the hydroxylamine hydrochloride is preferably 1.5224: 0.6949. in the present invention, the mass ratio of thiourea to CTAB is preferably 1.5224: 0.2400. in the present invention, the mass ratio of thiourea to water is preferably 1.5224: 30 mL. In the present invention, the mixing is preferably performed under stirring conditions; the mixing is preferably carried out at room temperature, and particularly preferably at 25 ℃; the stirring time is preferably 1 hour. In the present invention, the temperature of the hydrothermal reaction is preferably 180 ℃; the hydrothermal reaction time is preferably 24 hours. In the present invention, it is preferable that the hydrothermal reaction further comprises: carrying out solid-liquid separation on the obtained reaction system to obtain a solid substance; the solid material is washed and dried in sequence. In the present invention, the method of solid-liquid separation is preferably centrifugation; the rotating speed of the centrifugation is preferably 12000 r/min; the time for centrifugation is preferably 5-6 min. In the present invention, the washing preferably includes water washing, ethanol washing, and acetone washing, which are sequentially performed. In the present invention, the water washing is preferably distilled water washing. In the present invention, the number of times of the water washing is preferably 5 times; the number of the ethanol washing is preferably 5; the number of acetone washes is preferably 5. The present invention preferably performs centrifugation after each wash. In the present invention, the temperature of the drying is preferably 40 ℃; the drying time is preferably 8 h; the drying is preferably vacuum drying.
In the present invention, the FeS 2 Nanosheets and nano-WS 2 The mass ratio of the materials is preferably 4: 1. In the present invention, the FeS 2 Nanosheets and nano-WS 2 The material mixing is preferably carried out in a ball mill; the rotating speed of the ball mill is preferably 400 r/min; the mixing time is preferably 2-3 h.
In the present invention, Fe is contained in the microplastic catalyst 2+ The active sites promote the decomposition of hydrogen peroxide to generate a large amount of OH with strong oxidizing property to oxidize and decompose micro plastics, and the main decomposition process is as follows: OH attacks a carbon-carbon single bond in the micro plastic, the carbon-carbon single bond is broken and substituted by two hydroxyl groups, OH continuously attacks the hydroxyl groups and is oxidized into carbonyl and carboxyl in sequence, and finally at a certain high temperature, the carboxyl group is continuously attacked to generate decarboxylation and is finally degraded into CO 2 And H 2 And O. Besides promoting the decomposition of hydrogen peroxide to form OH, the micro-plastic catalyst can adsorb the micro-plastic to a certain extent by sulfur vacancy defects and layered tungsten disulfide, so that the micro-plastic reacts with the OH at almost zero distance, and the degradation efficiency is greatly improved. S dropped after introduction of sulfur vacancy 2- Changing a small amount of free oxygen in water into O by electron donating 2- O having strong reducibility 2- Reducible Fe 3+ Is Fe 2+ The purpose of self-repairing is achieved; at the same time, based on self-repair, WS 2 At H 2 O 2 A large amount of W exposed after formation of sulfur vacancy defects in the solution 3+ Promoting Fe on the surface of the catalyst by taking W-Fe bond as a channel for transferring electrons 3+ To Fe 2+ And conversion is carried out, so that the aim of circulation is fulfilled, and secondary pollution cannot be caused in the whole micro-plastic treatment process.
The invention provides the micro plastic catalyst prepared by the preparation method in the technical scheme.
The invention also provides a method for degrading the micro-plastic, which comprises the following steps:
the micro plastic, the micro plastic catalyst and the hydrogen peroxide solution are mixed, and hydrothermal reaction is carried out under an acidic condition to degrade the micro plastic.
The method provided by the invention can be used for degrading the micro-plastic by using a thermal Fenton oxidation method, so that the degradation efficiency of the catalyst can be improved, the resource utilization rate can be improved, and the treatment cost of the micro-plastic can be reduced.
In the present invention, the component of the micro plastic preferably comprises one or more of polyethylene, polypropylene, polyvinyl chloride and polystyrene. In a specific embodiment of the present invention, the micro plastic is a mixture of polyethylene, polypropylene, polyvinyl chloride and polystyrene; the mass ratio of the polyethylene to the polypropylene to the polyvinyl chloride to the polystyrene is preferably 2: 1: 1: 1. in the present invention, before the micro plastic is degraded, the method preferably further comprises mixing the micro plastic with water to obtain an aqueous dispersion of the micro plastic. In the invention, the mass ratio of the micro plastic to the water is preferably 0.01: 40-50. In the present invention, the water is preferably ultrapure water. In the present invention, the mixing of the micro-plastic and water is preferably carried out under stirring conditions, the stirring speed is preferably 1500 rpm; the stirring time is preferably 10 min.
In the present invention, the concentration of the hydrogen peroxide solution is preferably 2 mol/L. In the present invention, the mass ratio of the micro plastic to the micro plastic catalyst is preferably 0.01: 0.05; the dosage ratio of the micro plastic to the hydrogen peroxide solution is preferably 0.01g to 10 mL. In the present invention, the mixing of the micro plastic, the micro plastic catalyst and the hydrogen peroxide solution preferably comprises: mixing the micro plastic and the micro plastic catalyst, and adding the hydrogen peroxide solution for ultrasonic stirring. In the invention, the time of ultrasonic stirring is preferably 5-15 min, and more preferably 10 min.
In the invention, the temperature of the hydrothermal reaction is preferably 140-160 ℃, and more preferably 150 ℃; the time of the hydrothermal reaction is preferably 8-16 h. In the present invention, the hydrothermal reaction is carried out under acidic conditions; the concentration of hydrogen ions in the hydrothermal reaction system is preferably 0.24 mol/L.
In the present invention, it is preferable that the hydrothermal reaction further comprises: carrying out solid-liquid separation on the obtained reaction system to obtain a solid substance; drying the solid matter. In the present invention, the method of solid-liquid separation is preferably centrifugation; the centrifugal rotating speed is preferably 10000-12000 r/min; the time for centrifugation is preferably 5-6 min. In the invention, the drying time is preferably 36-48 h; the drying is preferably vacuum drying.
In the invention, the degradation rate of the micro plastic is preferably 40-90%.
The technical solution of the present invention will be clearly and completely described below with reference to the embodiments of the present invention. It is to be understood that the described embodiments are merely exemplary of the invention, and not restrictive of the full scope of the invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
FeS 2 Preparing a nanosheet:
(1) 3.18g of FeSO were weighed out separately 4 、4.7433g Na 2 S 2 O 3 0.6400g of elemental sulfur, adding the substances into a mortar, and manually grinding for 30 min;
(2) putting the solid obtained by grinding in the step (1) into a beaker, adding 60mL of deionized water and 10mL of oleic acid, and magnetically stirring for 45min at room temperature until the solid is completely dissolved;
(3) transferring the solution stirred and dissolved in the step (2) to a high-pressure reaction kettle with a polytetrafluoroethylene lining;
(4) putting the reaction kettle into an electric heating constant-temperature air-blowing drying oven, and heating for 24 hours at 220 ℃ to perform reaction;
(5) taking out the high-pressure reaction kettle after the reaction is finished, cooling the high-pressure reaction kettle to room temperature, opening the reaction kettle, and pouring substances in the reaction kettle into a centrifugal tube;
(6) placing the centrifugal tube in a centrifuge to centrifuge for 6min at the rotating speed of 12000 r/min;
(7) centrifuging, pouring out the clear liquid, keeping the precipitate, and washing the precipitate with distilled water for 10 times, carbon tetrachloride for 8 times and absolute ethyl alcohol for 10 times respectively. During the process, the sample is centrifugally separated every time;
(8) dispersing the centrifuged product by using absolute ethyl alcohol after centrifugation, transferring the dispersed product into a watch glass, and vacuumizing and drying the product for 8 hours in a vacuum drying oven with the set temperature of 60 ℃;
(9) taking out the product after drying to obtain FeS 2 Nanosheets.
Preparation of a micro plastic catalyst:
(1) 5g of the FeS prepared above are weighed 2 Nano sheets, which are laid in a box specially made by a tube furnace;
(2) transferring the box into a tubular furnace, adjusting the calcining temperature to 400 ℃, and setting the calcining time to 2 hours; then reducing by hydrogen;
(3) and after the temperature is cooled, taking out the product to obtain the micro plastic catalyst.
Example 2
FeS 2 Preparing a nanosheet:
(1) 0.8305g of FeSO were weighed out separately 4 、1.5811g Na 2 S 2 O 3 0.3200g of elemental sulfur, adding the substances into a mortar, and manually grinding for 15 min;
(2) putting the solid obtained by grinding in the step (1) into a beaker, adding 30mL of deionized water and 10mL of oleic acid, and magnetically stirring for 20min at room temperature until the solid is completely dissolved;
(3) transferring the solution stirred and dissolved in the step (2) to a high-pressure reaction kettle with a polytetrafluoroethylene lining;
(4) putting the reaction kettle into a muffle furnace, and heating for 24 hours at 220 ℃ to perform reaction;
(5) taking out the high-pressure reaction kettle after the reaction is finished, cooling the high-pressure reaction kettle to room temperature, opening the reaction kettle, and pouring substances in the reaction kettle into a centrifugal tube;
(6) placing the centrifugal tube in a centrifugal machine, and centrifuging for 6min at the rotating speed of 10000 r/min;
(7) centrifuging, pouring out the clear liquid, keeping the precipitate, and washing the precipitate with distilled water for 10 times, carbon tetrachloride for 8 times and absolute ethyl alcohol for 10 times respectively. During the process, the sample is centrifugally separated every time;
(8) dispersing the centrifuged product by using absolute ethyl alcohol after centrifugation, transferring the dispersed product into a watch glass, and vacuumizing and drying the product for 8 hours in a vacuum drying oven with the set temperature of 60 ℃;
(9) taking out the product after drying to obtain FeS 2 Nanosheets.
Nano CoS 2 Preparing materials:
(1) 1.1897g CoCl were weighed out 2 ·6H 2 O、2.6419g Na 2 S·9H 2 O, putting the substances into a beaker, and adding 50mL of glycol for ultrasonic dissolution;
(2) after dissolving, transferring the mixture into a high-pressure reaction kettle with a polytetrafluoroethylene lining by using ethanol;
(3) putting the reaction kettle into an electric heating constant-temperature air-blast drying oven, and heating for 24 hours at 180 ℃ to perform reaction;
(4) taking out the high-pressure reaction kettle after the reaction is finished, opening the reaction kettle after the high-pressure reaction kettle is cooled to room temperature, and pouring the reaction kettle into a centrifugal tube;
(5) placing the centrifugal tube in the step (4) in a centrifugal machine to centrifuge for 6min at the rotating speed of 10000 r/min;
(6) after the centrifugation is finished, pouring out supernatant in the centrifuge tube, reserving precipitate, and respectively cleaning the precipitate with distilled water and absolute ethyl alcohol, wherein the centrifugation is carried out each time;
(7) dispersing the centrifuged product by using absolute ethyl alcohol after centrifugation, transferring the product into a watch glass, drying the product in vacuum at 80 ℃ to obtain black powder, grinding the black powder after complete drying to prepare a sample to obtain the nano CoS 2 A material.
Preparation of a micro-plastic catalyst:
subjecting the FeS to 2 Nanosheets and nano-CoS 2 The materials are mixed according to the mass ratio of 5:1, the mixture is placed in a ball mill, and the mixture is ground for 2 hours at the rotating speed of 400r/min, so that the micro plastic catalyst is obtained.
Example 3
FeS 2 Preparing a nanosheet:
(1) 1.6609g of FeSO were weighed out separately 4 、1.5811g Na 2 S 2 O 3 0.6400g of elemental sulfur, adding the substances into a mortar, and manually grinding for 40 min;
(2) putting the solid obtained by grinding in the step (1) into a beaker, adding 60mL of deionized water and 10mL of oleic acid, and magnetically stirring for 30min at room temperature until the solid is completely dissolved;
(3) transferring the solution stirred and dissolved in the step (2) to a high-pressure reaction kettle with a polytetrafluoroethylene lining;
(4) putting the reaction kettle into an electric heating constant-temperature air-blowing drying box, and heating for 24 hours at the temperature of 200 ℃ to perform reaction;
(5) taking out the high-pressure reaction kettle after the reaction is finished, cooling the high-pressure reaction kettle to room temperature, opening the reaction kettle, and pouring substances in the reaction kettle into a centrifugal tube;
(6) placing the centrifugal tube in a centrifugal machine, and centrifuging for 5min at the rotating speed of 10000 r/min;
(7) centrifuging, pouring out the clear liquid, keeping the precipitate, and washing the precipitate with distilled water for 8 times, carbon tetrachloride for 8 times and absolute ethyl alcohol for 8 times respectively. During the process, the sample is centrifugally separated every time;
(8) dispersing the centrifuged product by using absolute ethyl alcohol after centrifugation, transferring the dispersed product into a watch glass, and vacuumizing and drying the product for 10 hours in a vacuum drying oven with the set temperature of 60 ℃;
(9) taking out the product after drying to obtain FeS 2 Nanosheets.
Defect FeS 2 Preparing a nano sheet:
(1) measuring 10mL of 30 wt% hydrogen peroxide solution, putting the hydrogen peroxide solution into a beaker, adding a proper amount of deionized water for dilution, transferring the solution into a 1000mL capacity bottle, and carrying out volume fixing on the solution by using the deionized water to obtain 0.0979mol/L hydrogen peroxide solution;
(2) 0.1500g of the prepared FeS is weighed 2 Placing the nanosheets into a beaker, adding 100mL (1) of prepared hydrogen peroxide solution into the beaker, uniformly stirring by using a glass rod, sealing the beaker, and stirring for 2 hours on a magnetic stirrer at the room temperature of 25 ℃;
(3) transferring the reacted sample into a centrifuge tube, centrifuging for 5min at the rotating speed of 10000r/min, pouring out excessive liquid, dispersing the centrifugal product into a watch glass by using absolute ethyl alcohol, transferring the centrifugal product into a vacuum drying oven, setting the temperature to be 60 ℃, drying for 10h, and obtaining the FeS defect after drying 2 Nanosheets.
Nano CoS 2 Preparing materials:
(1) 2.3793g CoCl were weighed out 2 ·6H 2 O、5.28374g Na 2 S·9H 2 O, putting the substances into a beaker, and adding 50mL of glycol for ultrasonic dissolution;
(2) after dissolving, transferring the mixture into a high-pressure reaction kettle with a polytetrafluoroethylene lining by using ethanol;
(3) putting the reaction kettle into an electric heating constant-temperature air-blast drying oven, and heating for 24 hours at 180 ℃ to perform reaction;
(4) taking out the high-pressure reaction kettle after the reaction is finished, opening the reaction kettle after the high-pressure reaction kettle is cooled to room temperature, and pouring the reaction kettle into a centrifugal tube;
(5) placing the centrifugal tube in the step (4) in a centrifugal machine to centrifuge for 5min at the rotating speed of 10000 r/min;
(6) after the centrifugation is finished, pouring out supernatant in the centrifuge tube, reserving precipitate, and respectively cleaning the precipitate with distilled water and absolute ethyl alcohol, wherein the centrifugation is carried out each time;
(7) dispersing the centrifuged product by using absolute ethyl alcohol after centrifugation, transferring the product into a watch glass, drying the product in vacuum at 80 ℃ to obtain black powder, grinding the black powder after complete drying to prepare a sample to obtain the nano CoS 2 A material.
Preparation of a micro-plastic catalyst:
FeS the defect 2 Nanosheets and nano-CoS 2 The materials are mixed according to the mass ratio of 5:1, the mixture is placed in a ball mill, and the mixture is ground for 2 hours at the rotating speed of 400r/min, so that the micro plastic catalyst is obtained.
Example 4
FeS 2 Preparing a nanosheet:
(1) 3.0382g of FeSO were weighed out separately 4 、3.1622g Na 2 S 2 O 3 0.6400g of elemental sulfur, adding the substances into a mortar, and manually grinding for 30 min;
(2) putting the solid obtained by grinding in the step (1) into a beaker, adding 60mL of deionized water and 10mL of oleic acid, and magnetically stirring for 30min at room temperature until the solid is completely dissolved;
(3) transferring the solution stirred and dissolved in the step (2) to a high-pressure reaction kettle with a polytetrafluoroethylene lining;
(4) putting the reaction kettle into an electric heating constant-temperature air-blowing drying box, and heating for 24 hours at the temperature of 200 ℃ to perform reaction;
(5) taking out the high-pressure reaction kettle after the reaction is finished, cooling the high-pressure reaction kettle to room temperature, opening the reaction kettle, and pouring substances in the reaction kettle into a centrifugal tube;
(6) placing the centrifugal tube in a centrifuge to centrifuge for 6min at the rotating speed of 12000 r/min;
(7) centrifuging, pouring out the clear liquid, keeping the precipitate, and washing the precipitate with distilled water for 10 times, carbon tetrachloride for 8 times and absolute ethyl alcohol for 10 times respectively. During the process, the sample is centrifugally separated every time;
(8) dispersing the centrifuged product by using absolute ethyl alcohol after centrifugation, transferring the dispersed product into a watch glass, and vacuumizing and drying the product for 6 hours in a vacuum drying oven with the set temperature of 60 ℃;
(9) taking out the product after drying to obtain FeS 2 Nanosheets.
Defect FeS 2 Preparing a nano sheet:
(1) measuring 10mL of 30 wt% hydrogen peroxide solution, putting the hydrogen peroxide solution into a beaker, adding a proper amount of deionized water for dilution, transferring the solution into a 1000mL capacity bottle, and carrying out volume fixing on the solution by using the deionized water to obtain 0.0979mol/L hydrogen peroxide solution;
(2) 1.5000g of the prepared FeS was weighed 2 Placing the nanosheets into a beaker, adding 100mL (1) of prepared hydrogen peroxide solution into the beaker, uniformly stirring by using a glass rod, sealing the beaker, placing the beaker on a magnetic stirrer at the room temperature of 25 ℃, and stirring for 1h at the rotating speed of 1000 rpm;
(3) transferring the reacted sample into a centrifuge tube, centrifuging for 6min at the rotating speed of 12000r/min, pouring out excessive liquid, dispersing the centrifugal product into a watch glass by using absolute ethyl alcohol, transferring the centrifugal product into a vacuum drying oven, setting the temperature to be 60 ℃, drying for 6h, and obtaining the FeS with the defect after drying 2 Nanosheets.
Preparation of nano CoS material:
(1) 0.4075g of cobalt nitrate (Co (NO) was weighed out 3 ) 2 ) Putting the mixture into a beaker, grinding the mixture by using a glass rod, adding 60mL of oleic acid, and dissolving cobalt nitrate by using an ultrasonic cleaning machine in an ultrasonic manner;
(2) 0.1229g of Thioacetamide (TAA) is added into the dissolved cobalt nitrate for ultrasonic dissolution, and then the beaker is stirred for 1 hour at normal temperature by using a magnetic stirrer;
(3) transferring the solution in the step (2) to a high-pressure reaction kettle with a polytetrafluoroethylene lining for reaction at 180 ℃ for 12 hours;
(4) taking out the high-pressure reaction kettle after the reaction is finished, cooling to room temperature, opening the reaction kettle, and pouring into a centrifugal tube;
(5) washing the precipitate with distilled water and anhydrous ethanol for 5 times, wherein the centrifugation is performed each time;
(6) and after the centrifugation is finished, dispersing the centrifuged product into a watch glass by using absolute ethyl alcohol, carrying out vacuum drying for 6h in a vacuum drying oven with the set temperature of 60 ℃, and taking out the product to obtain the nano CoS material.
Preparation of a defective nano CoS material:
(1) pouring 40mL of absolute ethyl alcohol into a beaker, adding 0.0100g of the nano CoS material, and dispersing the nano CoS material in the absolute ethyl alcohol by using a glass rod;
(2) carrying out ultrasonic treatment for 3h by using an ultrasonic cleaning machine;
(3) transferring the mixture to a polytetrafluoroethylene reaction kettle for heating treatment for 6 hours at the temperature of 220 ℃;
(4) and naturally cooling the reaction kettle, filtering and collecting black precipitate, washing with absolute ethyl alcohol, and drying in a vacuum drying oven at 60 ℃ to obtain the defective nano CoS material.
Preparation of a micro-plastic catalyst:
FeS the defect 2 Mixing the nanosheets and the defective nano CoS material in a mass ratio of 5:1, placing the mixture in a ball mill, and grinding for 2 hours at a rotating speed of 400r/min to obtain the micro plastic catalyst.
Example 5
FeS 2 Preparing a nanosheet:
(1) 1.6609g of FeSO were weighed out separately 4 、1.5811g Na 2 S 2 O 3 0.6400g of elemental sulfur, adding the substances into a mortar, and manually grinding for 30 min;
(2) putting the solid obtained by grinding in the step (1) into a beaker, adding 30mL of deionized water and 10mL of oleic acid, and magnetically stirring for 30min at room temperature until the solid is completely dissolved;
(3) transferring the solution stirred and dissolved in the step (2) into a high-pressure reaction kettle with a polytetrafluoroethylene lining;
(4) putting the reaction kettle into an electric heating constant-temperature air-blowing drying box, and heating for 24 hours at the temperature of 200 ℃ to perform reaction;
(5) taking out the high-pressure reaction kettle after the reaction is finished, cooling the high-pressure reaction kettle to room temperature, opening the reaction kettle, and pouring substances in the reaction kettle into a centrifugal tube;
(6) placing the centrifugal tube in a centrifuge to centrifuge for 6min at the rotating speed of 12000 r/min;
(7) centrifuging, pouring out the clear liquid, keeping the precipitate, and washing the precipitate with distilled water for 10 times, carbon tetrachloride for 8 times and absolute ethyl alcohol for 10 times respectively. During the process, the sample is centrifugally separated every time;
(8) dispersing the centrifuged product by using absolute ethyl alcohol after centrifugation, transferring the dispersed product into a watch glass, and vacuumizing and drying the product for 6 hours in a vacuum drying oven with the set temperature of 60 ℃;
(9) taking out the product after drying to obtain FeS 2 Nanosheets.
Defect FeS 2 Preparing a nano sheet:
(1) measuring 10mL of 30 wt% hydrogen peroxide solution, putting the hydrogen peroxide solution into a beaker, adding a proper amount of deionized water for dilution, transferring the solution into a 1000mL capacity bottle, and carrying out volume fixing on the solution by using the deionized water to obtain 0.0979mol/L hydrogen peroxide solution;
(2) 1.5000g of the prepared FeS was weighed 2 Placing the nanosheets into a beaker, adding 100mL (1) of prepared hydrogen peroxide solution into the beaker, uniformly stirring by using a glass rod, sealing the beaker, and stirring for 2 hours on a magnetic stirrer at the room temperature of 25 ℃;
(3) transferring the reacted sample into a centrifuge tube, centrifuging for 6min at the rotating speed of 12000r/min, pouring out excessive liquid, dispersing the centrifugal product into a watch glass by using absolute ethyl alcohol, transferring the centrifugal product into a vacuum drying oven, setting the temperature to be 60 ℃, drying for 6h, and obtaining the FeS with the defect after drying 2 Nanosheets.
Nano MoS 2 Preparation of the material:
(1) 0.200g of Na 2 MoO 4 ·2H 2 Putting the O solid in a beaker, adding 80mL of deionized water, ultrasonically stirring for 10min for dissolving, and adjusting the pH of the solution to 6.5 by using 0.1mol/L NaOH solution;
(2) adding 0.3000g L-cysteine and 0.2000g PVP into the solution in the step (1), and manually stirring the mixture for 5 minutes until the mixture is completely dissolved;
(3) transferring the solution stirred in the step (2) into a polytetrafluoroethylene lining high-pressure kettle, and sealing;
(4) putting the reaction kettle into an electric heating constant-temperature air blast drying box, reacting for 48 hours at 180 ℃, taking out the high-pressure reaction kettle after the reaction is finished, placing the high-pressure reaction kettle in a room, cooling to room temperature, opening the reaction kettle, and pouring substances in the reaction kettle into a centrifugal tube;
(5) placing the centrifugal tube into a high-speed centrifuge, centrifuging for 6min at the rotating speed of 18000r/min, taking out the centrifugal tube, pouring out clear liquid, and keeping precipitate;
(6) washing the precipitate with water and anhydrous ethanol respectively for 10 times, and centrifuging each time;
(7) after the centrifugation is finished, the centrifuged precipitate product is dispersed and transferred to a watch glass by using absolute ethyl alcohol, the mixture is vacuumized and dried for 12 hours in a vacuum drying oven with the set temperature of 80 ℃, and the product is taken out to obtain the nano MoS 2 A material.
Preparation of a micro-plastic catalyst:
FeS the defect 2 Nanosheet and nano MoS 2 The materials are mixed according to the mass ratio of 5:1, the mixture is placed in a ball mill, and the mixture is ground for 2 hours at the rotating speed of 400r/min, so that the micro plastic catalyst is obtained.
Example 6
FeS 2 Preparing a nanosheet:
(1) 3.0382g of FeSO were weighed out separately 4 、3.1622g Na 2 S 2 O 3 0.6400g of elemental sulfur, adding the substances into a mortar, and manually grinding for 30 min;
(2) putting the solid obtained by grinding in the step (1) into a beaker, adding 60mL of deionized water and 10mL of oleic acid, and magnetically stirring for 30min at room temperature until the solid is completely dissolved;
(3) transferring the solution stirred and dissolved in the step (2) to a high-pressure reaction kettle with a polytetrafluoroethylene lining;
(4) putting the reaction kettle into an electric heating constant-temperature air-blowing drying box, and heating for 24 hours at the temperature of 200 ℃ to perform reaction;
(5) taking out the high-pressure reaction kettle after the reaction is finished, cooling the high-pressure reaction kettle to room temperature, opening the reaction kettle, and pouring substances in the reaction kettle into a centrifugal tube;
(6) placing the centrifugal tube in a centrifuge to centrifuge for 6min at the rotating speed of 12000 r/min;
(7) centrifuging, pouring out the clear liquid, keeping the precipitate, and washing the precipitate with distilled water for 10 times, carbon tetrachloride for 8 times and absolute ethyl alcohol for 10 times respectively. During the process, the sample is centrifugally separated every time;
(8) dispersing the centrifuged product by using absolute ethyl alcohol after centrifugation, transferring the dispersed product into a watch glass, and vacuumizing and drying the product for 6 hours in a vacuum drying oven with the set temperature of 60 ℃;
(9) taking out the product after drying to obtain FeS 2 Nanosheets.
Defect FeS 2 Preparing a nano sheet:
(1) measuring 10mL of 30 wt% hydrogen peroxide solution, putting the hydrogen peroxide solution into a beaker, adding a proper amount of deionized water for dilution, transferring the solution into a 1000mL capacity bottle, and carrying out volume fixing on the solution by using the deionized water to obtain 0.0979mol/L hydrogen peroxide solution;
(2) 1.5000g of the prepared FeS was weighed 2 Placing the nanosheets into a beaker, adding 100mL (1) of prepared hydrogen peroxide solution into the beaker, uniformly stirring by using a glass rod, sealing the beaker, placing the beaker on a magnetic stirrer at the room temperature of 25 ℃, and stirring for 1h at the rotating speed of 1000 rpm;
(3) transferring the reacted sample into a centrifuge tube, centrifuging for 6min at the rotating speed of 12000r/min, pouring out excessive liquid, dispersing the centrifugal product into a watch glass by using absolute ethyl alcohol, transferring the centrifugal product into a vacuum drying oven, setting the temperature to be 60 ℃, drying for 6h, and obtaining the FeS with the defect after drying 2 Nanosheets.
Nano MoS 2 Preparation of the material:
(1) 0.200g of Na 2 MoO 4 ·2H 2 Putting the O solid in a beaker, adding 80mL of deionized water, ultrasonically stirring for 10min for dissolving, and adjusting the pH of the solution to 6.5 by using 0.1mol/L NaOH solution;
(2) adding 0.3000g L-cysteine and 0.2000g PVP into the solution in the step (1), and manually stirring the mixture for 5 minutes until the mixture is completely dissolved;
(3) transferring the solution stirred in the step (2) into a polytetrafluoroethylene lining high-pressure kettle, and sealing;
(4) putting the reaction kettle into an electric heating constant-temperature air blast drying box, reacting for 48 hours at 180 ℃, taking out the high-pressure reaction kettle after the reaction is finished, placing the high-pressure reaction kettle in a room, cooling to room temperature, opening the reaction kettle, and pouring substances in the reaction kettle into a centrifugal tube;
(5) placing the centrifugal tube into a high-speed centrifuge, centrifuging for 6min at the rotating speed of 18000r/min, taking out the centrifugal tube, pouring out clear liquid, and keeping precipitate;
(6) washing the precipitate with water and anhydrous ethanol respectively for 10 times, and centrifuging each time;
(7) after the centrifugation is finished, the centrifuged precipitate product is dispersed and transferred to a watch glass by using absolute ethyl alcohol, the mixture is vacuumized and dried for 12 hours in a vacuum drying oven with the set temperature of 80 ℃, and the product is taken out to obtain the nano MoS 2 A material.
Defective nano MoS 2 Preparation of the material:
(1) 0.1000g of nano MoS 2 Placing the material in a beaker, dispersing in 60mL of absolute ethyl alcohol, and carrying out ultrasonic treatment for 3h by using an ultrasonic cleaner;
(2) after ultrasonic treatment, transferring the mixture into a polytetrafluoroethylene reaction kettle, and heating the mixture for 12 hours at 220 ℃;
(3) the treated nano MoS 2 Washing with anhydrous alcohol for 5 times, and centrifuging each time;
(4) pouring out supernatant of the sample after the last centrifugation, transferring the sample into a vacuum drying oven at 80 ℃ by using absolute ethyl alcohol, and performing vacuum drying for 12 hours to obtain the defect nano MoS 2 A material.
Preparation of a micro-plastic catalyst:
subjecting the defect FeS2 nanosheets and defect nano MoS 2 The materials are mixed according to the mass ratio of 5:1, the mixture is placed in a ball mill, and the mixture is ground for 3 hours at the rotating speed of 400r/min, so that the micro plastic catalyst is obtained.
Example 7
FeS 2 Preparing a nanosheet:
(1) 2.4914g of FeSO were weighed out separately 4 、4.7433g Na 2 S 2 O 3 0.9600g of elemental sulfur, adding the substances into a mortar, and manually grinding for 30 min;
(2) putting the solid obtained by grinding in the step (1) into a beaker, adding 50mL of deionized water and 10mL of oleic acid, and magnetically stirring for 30min at room temperature until the solid is completely dissolved;
(3) transferring the solution stirred and dissolved in the step (2) to a high-pressure reaction kettle with a polytetrafluoroethylene lining;
(4) putting the reaction kettle into an electric heating constant-temperature air-blowing drying box, and heating for 24 hours at the temperature of 200 ℃ to perform reaction;
(5) taking out the high-pressure reaction kettle after the reaction is finished, cooling the high-pressure reaction kettle to room temperature, opening the reaction kettle, and pouring substances in the reaction kettle into a centrifugal tube;
(6) placing the centrifugal tube in a centrifuge to centrifuge for 6min at the rotating speed of 12000 r/min;
(7) centrifuging, pouring out the clear liquid, keeping the precipitate, and washing the precipitate with distilled water for 9 times, carbon tetrachloride for 8 times and absolute ethyl alcohol for 10 times respectively. During the process, the sample is centrifugally separated every time;
(8) dispersing the centrifuged product by using absolute ethyl alcohol after centrifugation, transferring the dispersed product into a watch glass, and vacuumizing and drying the product for 10 hours in a vacuum drying oven with the set temperature of 70 ℃;
(9) taking out the product after drying to obtain FeS 2 Nanosheets.
Defect FeS 2 Preparing a nano sheet:
(1) measuring 10mL of 30 wt% hydrogen peroxide solution, putting the hydrogen peroxide solution into a beaker, adding a proper amount of deionized water for dilution, transferring the solution into a 1000mL capacity bottle, and carrying out volume fixing on the solution by using the deionized water to obtain 0.0979mol/L hydrogen peroxide solution;
(2) 0.2000g of the prepared FeS is weighed 2 Placing the nanosheets into a beaker, adding 100mL (1) of prepared hydrogen peroxide solution into the beaker, uniformly stirring by using a glass rod, sealing the beaker, and stirring for 2 hours on a magnetic stirrer at the temperature of 18 ℃;
(3) transferring the reacted sample into a centrifuge tube, centrifuging for 5min at the rotating speed of 12000r/min, pouring out excessive liquid, and usingDispersing the centrifugal product into a surface dish by using water and ethanol, putting the surface dish into a vacuum drying oven, setting the temperature to be 60 ℃, drying for 6 hours, and obtaining the FeS with the defects after the drying is finished 2 Nanosheets.
Nano WS 2 Preparation of the material:
(1) respectively weighing 1.6492g of sodium tungstate dihydrate, 1.5224g of thiourea, 0.6949g of hydroxylamine hydrochloride and 0.2400g of CTAB, putting the materials into a beaker, weighing 30mL of deionized water, adding the deionized water into the beaker, uniformly stirring the materials by using a glass rod, adding a magnet, sealing the beaker, putting the beaker on a magnetic stirrer at the room temperature of 25 ℃, and continuously stirring and reacting for 1 hour;
(2) after the reaction is finished, a white precipitate is formed, and the pH value of the solution is measured to be 6.15;
(3) transferring the mixture obtained in the step (2) into a Teflon coating high-pressure autoclave, putting the high-pressure autoclave into an electric heating constant-temperature air blast drying box, and heating for 24 hours at 180 ℃ for reaction;
(4) taking out the high-pressure autoclave after the reaction is finished, placing the high-pressure autoclave in a shade place to be cooled to room temperature, opening the reaction kettle, pouring all substances in the autoclave into a centrifugal tube, and centrifuging the centrifugal tube in a centrifuge at the rotating speed of 12000r/min for 6 min;
(5) after the centrifugation is finished, pouring out the supernatant, keeping the precipitate, washing for 5 times by using distilled water, washing for 5 times by using ethanol and washing for 5 times by using acetone respectively, and performing centrifugation operation once in the sample washing process;
(6) dispersing the centrifuged product by using absolute ethyl alcohol, transferring the product into a watch glass, vacuumizing the watch glass in a vacuum drying oven at the set temperature of 40 ℃ for drying for 8 hours to obtain the nano WS 2 A material.
Preparation of a micro-plastic catalyst:
FeS the defect 2 Nanosheets and nano-WS 2 The materials are mixed according to the mass ratio of 4:1, and the mixture is placed in a ball mill and ground for 3 hours at the rotating speed of 400r/min, so that the micro plastic catalyst is obtained.
Test example
(1) 0.0100g of the microplastic mixture (0.004 g, 0.002g and 0.002g of polyethylene, polypropylene, polyvinyl chloride and polystyrene, respectively, in mass) was weighed out, placed in a beaker, and 40mL of ultrapure water was added.
(2) The beaker was placed on a magnetic stirrer and vigorously stirred at 1500rpm for 10 min.
(3) After the stirring, 0.0500g of the micro plastic catalyst prepared in the example was weighed and placed in the beaker of (2), 1mL of concentrated hydrochloric acid with a concentration of 12mol/L was added, and the micro plastic catalyst was dispersed in the solution by ultrasonic stirring for 10min, followed by the addition of 10mL of hydrogen peroxide solution with a concentration of 2 mol/L.
(4) Transferring the solution obtained in the step (3) after ultrasonic stirring into a polytetrafluoroethylene lining high-pressure kettle, putting the reaction kettle into an electric heating constant-temperature air blowing drying oven, heating for different times at 160 ℃ for reaction, and calculating the degradation rate of the micro plastic in different heating times; the heating time is respectively 8h, 10h, 12h, 14h and 16 h.
(5) And (4) taking out the high-pressure reaction kettle after the heating reaction is finished, cooling the high-pressure reaction kettle to room temperature, opening the reaction kettle, and pouring the substances in the kettle into a centrifugal tube.
(6) Placing the centrifugal tube in a centrifuge, centrifuging for 6min at the rotating speed of 12000r/min, retaining insoluble solids after centrifugation, and pouring out clear liquid.
(7) Insoluble solids were collected, placed in a vacuum oven and dried under vacuum at 60 ℃ for 48 h.
(8) The dried solid was placed on a digital analytical balance and the weighing data recorded.
Data processing:
the degradation rate of the micro-plastic by different heating time is expressed by weight loss (%);
the weight of the undegraded microplastic mixture is recorded as W 0 In units of g;
the mass of the centrifugally dried solid mixture was recorded as W m In units of g;
the weight of the degraded micro-plastic is recorded as W t In units of g;
wherein W t ＝W m -mass of the micro-plastic catalyst in g;
weight loss(％)＝(W 0 -W t )/W 0 ×100％。
TABLE 1 degradation rate of microplastic catalyst from example 1
Heating time/h Weight loss/％
8 42.56
10 60.23
12 71.46
14 79.36
16 82.97
TABLE 2 Microplastic degradation rate of the microplastic catalyst prepared in example 2
Heating time/h Weight loss/％
8 40.53
10 53.24
12 77.85
14 85.09
16 89.51
TABLE 3 degradation rate of microplastic catalyst from example 3
Figure BDA0003645923880000231
Figure BDA0003645923880000241
TABLE 4 rate of microplastic degradation by microplastic catalyst prepared in example 4
Heating time/h Weight loss/％
8 50.52
10 59.23
12 75.46
14 88.13
16 92.47
TABLE 5 degradation rate of microplastic catalyst from example 5
Heating time/h Weight loss/％
8 60.56
10 72.73
12 80.86
14 88.63
16 90.42
TABLE 6 degradation of microplastics by the microplastic catalysts prepared in example 6
Heating time/h Weight loss/％
8 62.62
10 73.83
12 83.96
14 90.63
16 91.42
TABLE 7 degradation rate of microplastic catalyst from example 7
Figure BDA0003645923880000242
Figure BDA0003645923880000251
The test results in tables 1-7 show that the micro-plastic catalyst prepared by the invention has good degradation effect on micro-plastic at 160 ℃, and the degradation rate of the micro-plastic is gradually increased along with the increase of the reaction time, and the degradation rate reaches 91% at most.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.

Claims (10)

1. A preparation method of a micro-plastic catalyst comprises the following steps:
FeS is prepared 2 Modifying the nanosheets to obtain a micro plastic catalyst;
the modification comprises any one of steps (1) to (5);
(1) subjecting the FeS to 2 Sequentially carrying out surface oxidation treatment and reduction treatment on the nanosheets to obtain a micro-plastic catalyst;
(2) subjecting the FeS to 2 Nanosheets and nano-CoS 2 Mixing the materials to obtain a micro plastic catalyst;
(3) subjecting the FeS to 2 Mixing the nanosheets and the nano CoS material to obtain a micro plastic catalyst;
(4) subjecting the FeS to 2 Nanosheet and nano MoS 2 Mixing the materials to obtain a micro plastic catalyst;
(5) subjecting the FeS to 2 Nanosheets and nano-WS 2 And mixing the materials to obtain the micro plastic catalyst.
2. The method of claim 1, wherein the FeS is prepared by 2 The preparation method of the nano-sheet comprises the following steps: FeSO (ferric oxide) is added 4 、Na 2 S 2 O 3 Grinding and mixing the sulfur powder and elemental sulfur to obtain mixed powder; mixing the mixed powder with water and oleic acid, and carrying out hydrothermal reaction to obtain FeS 2 A nanosheet.
3. The preparation method according to claim 2, wherein the temperature of the hydrothermal reaction is 220-250 ℃; the heat preservation time is 24-28 h.
4. According to claimThe production method according to claim 1, wherein the surface oxidation treatment comprises: in an air atmosphere, the FeS is added 2 And calcining the nanosheets.
5. The production method according to claim 1, wherein the reduction treatment is a hydrogen reduction treatment.
6. The method according to claim 1, wherein FeS is used in the steps (2), (3), (4) and (5) 2 Before the nano-sheet is modified, defect treatment is also independently carried out;
the FeS 2 Defect treatment of the nanoplatelets comprises: FeS is prepared 2 Mixing the nanosheets and aqueous hydrogen peroxide solution, and carrying out oxidation reaction to obtain FeS with defects 2 Nanosheets.
7. The preparation method according to claim 1, wherein the step (3) is carried out by mixing the nano CoS material with FeS 2 Defect treatment is also included before mixing the nano sheets; the defect treatment of the nano CoS material comprises the following steps:
and mixing the nano CoS material with ethanol, and carrying out solvothermal reaction to obtain the defective nano CoS material.
8. The method according to claim 1, wherein the step (4) is performed by nano MoS 2 Material in and FeS 2 Defect treatment is also included before the nano sheets are mixed; the nano MoS 2 The defect treatment of the material comprises the following steps:
mixing the nano MoS 2 Mixing the material with ethanol, and carrying out solvothermal reaction to obtain defect nano MoS 2 A material.
9. A micro plastic catalyst prepared by the preparation method of any one of claims 1 to 8.
10. A method of degrading a micro-plastic comprising the steps of:
mixing the micro plastic, the micro plastic catalyst of claim 9 and a hydrogen peroxide solution, and carrying out hydrothermal reaction under an acidic condition to degrade the micro plastic.
CN202210530272.7A 2022-05-16 2022-05-16 Micro-plastic catalyst, preparation method thereof and method for degrading micro-plastic Pending CN114832836A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202210530272.7A CN114832836A (en) 2022-05-16 2022-05-16 Micro-plastic catalyst, preparation method thereof and method for degrading micro-plastic

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202210530272.7A CN114832836A (en) 2022-05-16 2022-05-16 Micro-plastic catalyst, preparation method thereof and method for degrading micro-plastic

Publications (1)

Publication Number Publication Date
CN114832836A true CN114832836A (en) 2022-08-02

Family

ID=82571245

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202210530272.7A Pending CN114832836A (en) 2022-05-16 2022-05-16 Micro-plastic catalyst, preparation method thereof and method for degrading micro-plastic

Country Status (1)

Country Link
CN (1) CN114832836A (en)

Citations (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101851006A (en) * 2010-06-08 2010-10-06 南开大学 Method for preparing MoS2 microspheres by solvent hot method
CN104384171A (en) * 2014-10-17 2015-03-04 耿兆翔 Resource recycling method for pyritic cinders
CN106396074A (en) * 2016-09-30 2017-02-15 浙江工业大学 Fast organic pollutant removing method based on vulcanized zero-valence-iron-activated hydrogen peroxide
CN106984334A (en) * 2017-03-13 2017-07-28 同济大学 The synthetic method of cobalt disulfide nanobelt package assembly in a kind of titanium sheet substrate
US20190015818A1 (en) * 2017-07-13 2019-01-17 Board Of Trustees Of The University Of Arkansas Doped carbonaceous materials for photocatalytic removal of pollutants under visible light, making methods and applications of same
US20190366309A1 (en) * 2018-05-31 2019-12-05 Soochow University FUNCTIONALIZED HYBRID NANOTUBE C@MoS2/SnS2 AND PREPARATION METHOD AND APPLICATION THEREOF
CN110560092A (en) * 2019-08-02 2019-12-13 江苏大学 MoS2/BiVO4Preparation method and application of heterojunction composite photocatalyst
CN111068720A (en) * 2019-12-06 2020-04-28 南京邮电大学 Co-FeS2/CoS2Nano flower material, preparation method and method for regulating electrocatalytic performance thereof
CN111732181A (en) * 2020-07-06 2020-10-02 广西民族大学 Multiphase Fenton reagent and application thereof
CN112316956A (en) * 2020-11-16 2021-02-05 青岛科技大学 WS (WS)2Preparation method and application of/FeS nanosphere hybrid catalyst

Patent Citations (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101851006A (en) * 2010-06-08 2010-10-06 南开大学 Method for preparing MoS2 microspheres by solvent hot method
CN104384171A (en) * 2014-10-17 2015-03-04 耿兆翔 Resource recycling method for pyritic cinders
CN106396074A (en) * 2016-09-30 2017-02-15 浙江工业大学 Fast organic pollutant removing method based on vulcanized zero-valence-iron-activated hydrogen peroxide
CN106984334A (en) * 2017-03-13 2017-07-28 同济大学 The synthetic method of cobalt disulfide nanobelt package assembly in a kind of titanium sheet substrate
US20190015818A1 (en) * 2017-07-13 2019-01-17 Board Of Trustees Of The University Of Arkansas Doped carbonaceous materials for photocatalytic removal of pollutants under visible light, making methods and applications of same
US20190366309A1 (en) * 2018-05-31 2019-12-05 Soochow University FUNCTIONALIZED HYBRID NANOTUBE C@MoS2/SnS2 AND PREPARATION METHOD AND APPLICATION THEREOF
CN110560092A (en) * 2019-08-02 2019-12-13 江苏大学 MoS2/BiVO4Preparation method and application of heterojunction composite photocatalyst
CN111068720A (en) * 2019-12-06 2020-04-28 南京邮电大学 Co-FeS2/CoS2Nano flower material, preparation method and method for regulating electrocatalytic performance thereof
CN111732181A (en) * 2020-07-06 2020-10-02 广西民族大学 Multiphase Fenton reagent and application thereof
CN112316956A (en) * 2020-11-16 2021-02-05 青岛科技大学 WS (WS)2Preparation method and application of/FeS nanosphere hybrid catalyst

Non-Patent Citations (7)

* Cited by examiner, † Cited by third party
Title
吴小平: ""铁系非均相类Fenton催化剂的制备及催化性能研究"" *
安丽娜: ""Fe，Co，Ni纳米氧化物和硫化物的制备与表征"" *
崔雅红: ""酸性煤矸石堆场化学氧化产酸的实验研究"" *
梅秀锋等: ""水热法合成二硫化亚铁纳米片及性能研究"" *
沈舒宜: ""二硫化钼及其复合材料的制备及电化学性能研究"" *
王阳等: ""高活性复合金属化合物催化类Fenton降解染料废水"" *
陈庆安: ""硫化钴用作铝离子二次电池正极的探索与性能研究"" *

Similar Documents

Publication Publication Date Title
CN105289693B (en) A kind of Zn0.5Co0.5Fe2O4/g‑C3N4The preparation method of composite photo-catalyst
US10800689B2 (en) Magnetic nanoparticle microbial composite with core-shell structure, preparation method thereof, and its application in the treatment of azo dyes
CN107876006B (en) Preparation method and application of carbon nanofiber-hydrotalcite composite material adsorbent
CN106732688A (en) Composite magnetic visible light catalyst silver silver halide BiOX cobalt ferrite and preparation method thereof
CN104001474A (en) Carbon-coated ferroferric oxide core-shell nano particle and preparation method thereof
CN105032375B (en) Preparation method of magnetic graphite-based heavy metal adsorbing material
Guo et al. Efficient charge separation in sulfur doped AgFeO2 photocatalyst for enhanced photocatalytic U (VI) reduction: The role of doping and mechanism insights
CN109647349B (en) Modified ferroferric oxide nano compound for removing heavy metal ions and organic matters in industrial wastewater and preparation method thereof
CN111036249A (en) FexP/Mn0.3Cd0.7S composite photocatalyst and preparation method and application thereof
CN106064836B (en) A kind of modified green syt nano-sized iron oxide and its preparation method and application
CN107519897A (en) A kind of novel tertiary Z-type structure photochemical catalyst and its preparation method and application
CN107324401B (en) A kind of preparation method of high-purity nm ferroso-ferric oxide
CN114130408B (en) Z-type alpha-Fe 2 O 3 /ZnIn 2 S 4 Preparation method and application of composite photocatalyst
CN109437323A (en) A kind of preparation method of biology sympathy magnetic ferroferric oxide nano-particles
CN115121277A (en) Iodine-doped monoatomic nanoenzyme CoCNI and preparation method and application thereof
Feng et al. Acidithiobacillus ferrooxidans mediates morphology evolution of schwertmannite in the presence of Fe2+
CN114832836A (en) Micro-plastic catalyst, preparation method thereof and method for degrading micro-plastic
CN108927102A (en) A kind of preparation method and application of titania nanotube material
CN109482209A (en) Utilize the method for the double Z shaped photochemical catalyst catalytic elimination antibiotic of silver orthophosphate/bismuth sulfide/bismuth oxide
CN111686703A (en) Remove aquatic Cs+Composite microcapsule adsorbent and preparation method thereof
Fang et al. Transformation of iron in pure culture process of extremely acidophilic microorganisms
CN112121797A (en) Magnetic TiO2Preparation method of graphene oxide composite material
CN110064645A (en) A kind of synthesis hydrolysis charcoal-nano zero valence iron method and in-situ remediation method
CN111471859B (en) Method for leaching uranium from low-grade uranium ore by macro-particle reinforced aspergillus niger
CN109455790A (en) A method of utilizing two-dimentional black phosphorus material efficient degradation organic pollutant

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination