CN112374586A - Method for removing organic matters in water by improving plasma-Fenton reaction - Google Patents
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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
- C02F1/48—Treatment of water, waste water, or sewage with magnetic or electric fields
-
- 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
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/18—Carbon
-
- 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/74—Iron group metals
- B01J23/745—Iron
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/39—Photocatalytic 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
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/30—Treatment of water, waste water, or sewage by irradiation
- C02F1/32—Treatment of water, waste water, or sewage by irradiation with ultraviolet light
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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
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/722—Oxidation by peroxides
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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
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/725—Treatment of water, waste water, or sewage by oxidation by catalytic oxidation
-
- 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
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- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
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Abstract
The invention discloses a method for removing organic matters in water by improving a plasma-Fenton reaction, which comprises the following steps: placing the prepared solution into a reactor of an experimental system, and then adding the prepared rGO/Fe3O4Nano-particles, turning on power supply, applying voltage and generating plasma, ultraviolet light and H accompanied by plasma in generation process2O2For activating rGO/Fe3O4Generating a Fenton reactionThen, OH is generated, and the generated OH is used for oxidizing organic matters in the water body; by applying a magnet, rGO/Fe3O4rGO-Fe prepared by rapid separation from water3O4The composite catalyst realizes the simultaneous photocatalysis and Fenton reaction in the pulse discharge plasma, improves the generation amount of OH, promotes the degradation and mineralization of intermediate products, and is Fe3O4The magnetic separation of the catalyst is realized by the load, and the catalyst is convenient to recover and reuse.
Description
Technical Field
The invention relates to the technical field of water treatment, in particular to a method for removing organic matters in water by improving a plasma-Fenton reaction.
Background
1. Low temperature Plasma (Non-thermal Plasma, NTP) among advanced oxidation technologies has been widely used in water treatment in recent years. During NTP discharge, the high voltage applied between the electrodes induces gas ionization, producing many physical and chemical effects. Physical effects include high-energy electrons, light, ultrasound, electric fields, shock waves, etc., and chemical effects include some oxidizing substances: free radicals (. OH,. O,. H, etc.) and molecules (H)2O2,O3Etc.). Due to the high oxidation potential and non-selective oxidation characteristics, OH generated during the discharge process is believed to play a key role in the process of degrading organic substances. Accordingly, the active material (H) having a low oxidation potential2O2、O3Etc.) can not fully react with organic matters, resulting in low utilization rate of active substances in NTP. In addition, ultraviolet light, ultrasonic waves, heat energy and the like are directly emitted without being fully utilized in the discharging process, and energy loss is also caused. Therefore, how to further increase the amount of OH generated by utilizing the physical and chemical effects generated during the discharge process is an important direction in the development of this technology.
2. In order to solve the problem, related researches add iron ions to an NTP system to form a Fenton reaction and decompose H2O2OH is produced. However, the homogeneous Fenton reaction requires acidic conditions (pH)<3) The process is carried out. And secondly, the addition of iron ions inevitably causes secondary pollution to the water body, and is also not beneficial to the reutilization of the catalyst. In recent years heterogeneous Fenton reaction research has been promoted, the process can be carried out in a wider pH range, and the catalyst can be easily recovered. The heterogeneous Fenton process is assisted by ultraviolet light, and the catalytic reaction rate can be further improved. Meanwhile, the heterogeneous photo-Fenton catalyst can obviously reduce the residual concentration of iron ions in the solution. Magnetic nano Fe3O4The particles are used as a main catalyst of heterogeneous Fenton reaction and have high catalytic activity. However, Fe alone3O4Easy agglomeration in the preparation process, and poor dispersibility in aqueous solution, thereby limiting wide application. Due to excellent electronic properties, chemical stability and large specific surface area, graphene has received much attention as a metal oxide support. Research shows that graphene is used as a carrier and Fe3O4The binding may be through a synergistic effect, preventing Fe3O4The catalytic performance of the catalyst is improved.
Based on this, the invention designs a method for improving the plasma-Fenton reaction for removing organic matters in water so as to solve the above-mentioned problems.
Disclosure of Invention
The invention aims to provide a method for removing organic matters in water by improving plasma-Fenton reaction, and provides graphene-Fe3O4Introducing NTP system to make full use of light and H in NTP2O2And the light-Fenton reaction is formed to promote the generation of OH, and the magnetism given by the catalyst is beneficial to separating from the aqueous solution, so that the secondary pollution of the water body is avoided. .
In order to achieve the purpose, the invention provides the following technical scheme: a method for improving a plasma-Fenton reaction for removing organic matters in water comprises the following steps: placing the prepared solution into a reactor of an experimental system, and then adding the prepared rGO/Fe3O4Nano-particles, turning on power supply, applying voltage and generating plasma, ultraviolet light and H accompanied by plasma in generation process2O2For activating rGO/Fe3O4Generating Fenton reaction, and then generating OH, wherein the generated OH is used for oxidizing organic matters in the water body; by applying a magnet, rGO/Fe3O4Quickly separated from water.
Preferably, the experimental system mainly comprises a pulse power supply, a reactor, an electrical detection system and a spectrum detection system, wherein the pulse power supply comprises a direct current power supply, an energy storage capacitor, a forming capacitor and a rotary spark gap switch, the reactor comprises a reaction cavity and an aeration cavity, gas is provided with an air pump, is blown into the aeration cavity of the reactor through a flowmeter and is further blown into the reaction cavity through a stainless steel injector needle head, the electrical monitoring system comprises an oscilloscope, a voltage probe and a current probe, the voltage probe and the current probe are used for detecting voltage and current applied to the reactor and outputting images and numerical values through the oscilloscope, and the spectrum detection system comprises a spectrometer and a computer.
Preferably, the peak voltage of the pulse power supply is adjustable between 0-40kV, the frequency is adjustable between 0-150Hz, the rise time is 20-100us, and the pulse width is 100-500 ns.
Preferably, the bottom of reactor is equipped with high voltage electrode, high voltage electrode is connected in parallel by seven 17# stainless steel syringe needles and is constituteed, and six stainless steel syringe needles wherein are located the top of chamber of exposing to the sun, and a stainless steel syringe needle is located the center of chamber of exposing to the sun, the distance of central point to summit is 30mm, the internal diameter of stainless steel syringe needle is 1.12mm, and the wall thickness is 0.18mm, reactor connection is by earthing electrode, earthing electrode is the stainless steel board, and its radius and thickness are 30mm and 2mm respectively.
Preferably, the fiber-optic probe of the spectrometer is horizontally aligned with the tip of the stainless steel syringe needle.
Preferably, said rGO/Fe3O4The preparation steps of the nano-particles are as follows:
firstly adding graphite powder with the particle size of 1-2 mu m and sodium nitrate into concentrated sulfuric acid, stirring in ice bath for 1h, and then slowly adding KMnO4Continuously stirring for 1 hour; then heating to 30 ℃ and maintaining for 30min to obtain a mixed solution; adding deionized water into the mixed solution, heating to 90 ℃ and maintaining for 2 hours; then deionized water is added and then 30 percent of H is slowly added2O2(ii) a Filtering the mixed solution, washing with 5% HCl, and washing with warm water until the pH is neutral; performing ultrasonic treatment on the remained dispersion liquid in water for 30min, centrifuging to remove large particles, and performing freeze drying on the obtained GO of the brownish yellow supernatant; adding freeze-dried GO into ethylene glycol, performing ultrasonic treatment until the GO is completely dispersed, and adding F at normal temperatureeCl3·6H2O and anhydrous sodium acetate, and stirring for 1 h; then transferring the stirred solution into a 100mL polytetrafluoroethylene high-pressure reaction kettle, and reacting for 6h at 200 ℃; after the reaction kettle is naturally cooled to room temperature, carrying out magnetic separation, and alternately and repeatedly washing the obtained black solid by using deionized water and ethanol; finally, drying for 24h at 50 ℃ in a vacuum drying oven to obtain rGO/Fe3O4And storing in a dryer for use.
Preferably, by regulating GO and Fe3O4Preparing rGO/Fe with different graphene doping amounts according to the mass ratio3O4The different graphene doping amounts comprise 6 wt%, 12 wt%, 18 wt% and 24 wt%, and the rGO/Fe is doped according to different graphene doping amounts3O4The markers are rGFe-6, rGFe-12, rGFe-18, rGFe-24.
Compared with the prior art, the invention has the beneficial effects that: the invention provides a prepared rGO-Fe3O4The composite catalyst realizes the simultaneous photocatalysis and Fenton reaction in the pulse discharge plasma, improves the generation amount of OH, promotes the degradation and mineralization of intermediate products, and is Fe3O4The magnetic separation of the catalyst is realized by the load, and the catalyst is convenient to recover and reuse.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings used in the description of the embodiments will be briefly introduced below, and it is obvious that the drawings in the following description are only some embodiments of the present invention, and it is obvious for those skilled in the art that other drawings can be obtained according to the drawings without creative efforts.
FIG. 1 is a schematic diagram of an experimental system according to the present invention;
FIG. 2 is a scanning electron micrograph of the present invention wherein (a) and (c) are Fe3O4Scanning electron micrographs, wherein (b) and (d) are rGO-Fe3O4Scanning an electron microscope image;
FIG. 3 shows Fe of the present invention3O4And the hysteresis loop plot of rGFe-18;
FIG. 4 is a graph showing the effect of plasma-Fenton on treating ofloxacin in water.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. 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.
The invention provides a technical scheme that: a method for improving plasma-Fenton reaction for removing organic matters in water comprises the following steps: placing the prepared solution into a reactor of an experimental system, and then adding the prepared rGO/Fe3O4Nano-particles, turning on power supply, applying voltage and generating plasma, ultraviolet light and H accompanied by plasma in generation process2O2For activating rGO/Fe3O4Generating Fenton reaction, and then generating OH, wherein the generated OH is used for oxidizing organic matters in the water body; by applying a magnet, rGO/Fe3O4Quickly separated from water.
The experimental system mainly comprises a pulse power supply, a reactor, an electrical detection system and a spectrum detection system, wherein the pulse power supply is independently developed by the institute of electrostatic and special power supply of university of technology and mainly comprises a direct-current power supply 1, an energy storage capacitor 2(Ce, 100 muF), a forming capacitor 3(Cp, 2nF) and a rotary spark gap switch 4, the peak voltage of the pulse power supply is adjustable between 0 and 40kV, the frequency is adjustable between 0 and 150Hz, the rise time is 20 to 100us, and the pulse width is 100-500 ns.
The reactor comprises reaction chamber 5 and aeration chamber 6, the bottom of reactor is equipped with high-voltage electrode, high-voltage electrode is parallelly connected by seven 17# stainless steel syringe needles and is constituteed, wherein six stainless steel syringe needles are located the top of aeration chamber 6, a stainless steel syringe needle is located the center of aeration chamber 6, the distance of central point to summit is 30mm, the internal diameter of stainless steel syringe needle is 1.12mm, the wall thickness is 0.18mm, the reactor is connected by telluric electricity field, the ground electrode is stainless steel plate, its radius and thickness are 30mm and 2mm respectively.
The gas supply air pump 7 is blown into the aeration cavity 6 of the reactor through the flowmeter 8 and further blown into the reaction cavity 5 through a stainless steel syringe needle, the electrical monitoring system is composed of an oscilloscope 9, a voltage probe 10 and a current probe 11, the voltage probe 10 and the current probe 11 are used for detecting the voltage and the current applied to the reactor and outputting images and numerical values through the oscilloscope 9, and the spectrum detection system is composed of a spectrometer 12 and a computer 13. During the measurement, the fiber optic probe of the spectrometer 12 is horizontally aligned with the tip of the stainless steel syringe needle.
Wherein, rGO/Fe3O4The preparation steps of the nano-particles are as follows:
firstly adding graphite powder with the particle size of 1-2 mu m and sodium nitrate into concentrated sulfuric acid, stirring in ice bath for 1h, and then slowly adding KMnO4Continuously stirring for 1 hour; then heating to 30 ℃ and maintaining for 30min to obtain a mixed solution; adding deionized water into the mixed solution, heating to 90 ℃ and maintaining for 2 hours; then deionized water is added and then 30 percent of H is slowly added2O2(ii) a Filtering the mixed solution, washing with 5% HCl, and washing with warm water until the pH is neutral; performing ultrasonic treatment on the remained dispersion liquid in water for 30min, centrifuging to remove large particles, and performing freeze drying on the obtained GO of the brownish yellow supernatant; adding freeze-dried GO into ethylene glycol, performing ultrasonic treatment until the GO is completely dispersed, and adding FeCl at normal temperature3·6H2O and anhydrous sodium acetate, and stirring for 1 h; then transferring the stirred solution into a 100mL polytetrafluoroethylene high-pressure reaction kettle, and reacting for 6h at 200 ℃; after the reaction kettle is naturally cooled to room temperature, carrying out magnetic separation, and alternately and repeatedly washing the obtained black solid by using deionized water and ethanol; finally, drying for 24h at 50 ℃ in a vacuum drying oven to obtain rGO/Fe3O4And storing in a dryer for use. By regulating GO and Fe3O4Preparing rGO/Fe with different graphene doping amounts according to the mass ratio3O4The different doping amounts of the graphene comprise 6 wt%, 12 wt%, 18 wt% and 24 wt%, and the rGO/Fe is doped according to different doping amounts of the graphene3O4The markers are rGFe-6, rGFe-12, rGFe-18, rGFe-24.
Catalyst characterization:
FIG. 2a shows Fe3O4SEM picture of (1), Fe can be seen3O4It is in the state of nanometer particle, and the particle diameter is about 75 nm. As can be seen from FIG. 2b, Fe3O4Can successfully load on rGO, the surface of the rGO presents an obvious graphite layer tilting phenomenon and conforms to a typical rGO shape. Nano Fe3O4Distributed on the surface of the rGO or wrapped in the rGO, and the particle size of the nano particles is about 50 nm. Relative to Fe3O4, rGO-Fe3O4The reduction in particle size indicates that rGO has a role in limiting domain growth during nanoparticle formation. As can be seen from TEM, Fe3O4There appear spherical-like solid particles with rough surfaces (fig. 2 c). As can be seen in FIG. 2d, the rGO surface is wrinkled, Fe3O4The particles are supported on the graphene flakes.
FIG. 3 shows Fe3O4And rGFe-18 hysteresis loop at room temperature (300K). Fe can be observed3O4The magnetization hysteresis loops of the rGFe-18 and the rGFe-18 are S-shaped, the initial magnetization curves of all samples are basically superposed with the demagnetization curves, and no hysteresis loop appears, which indicates that Fe3O4And rGFe-18 has a strong paramagnetism. Fe3O4And rGFe-18 had magnetic strengths of 71.99emu/g and 66.05emu/g, respectively. Relative to Fe3O4rGFe-18 has a low magnetic strength, which is Fe3O4Non-magnetic rGO attached to the surface of the particles. It can also be seen from fig. 3 that when an external magnet is applied, rGFe-18 can be separated from the solution, facilitating catalyst recovery for reuse.
Organic matter take-out effect:
to evaluate the catalytic performance, first, rGO/Fe was investigated3O4The adsorption performance and the results are shown in FIG. 4. It can be seen that the adsorption rate of rGFe-18 to OFX after 60min was 21%, because rGFe-18 has magnetism and can adsorb OFX molecules on its surface. Meanwhile, after the treatment for 60min, the degradation rate of the independent NTP to the OFX is shown to be65.0 percent. Addition of Fe3O4After that, the OFX degradation rate can be improved to 89.6%. Relative to Fe3O4,rGO/Fe3O4So that the degradation rate of OFX is further improved. And with the increase of the doping amount of the graphene, the OFX degradation rate is increased firstly and then reduced. When the doping amount of the graphene is 18%, the OFX degradation rate can reach the maximum value and can reach 99.9%.
In the description herein, references to the description of "one embodiment," "an example," "a specific example" or the like are intended to mean that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the invention. In this specification, the schematic representations of the terms used above do not necessarily refer to the same embodiment or example. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples.
The preferred embodiments of the invention disclosed above are intended to be illustrative only. The preferred embodiments are not intended to be exhaustive or to limit the invention to the precise embodiments disclosed. Obviously, many modifications and variations are possible in light of the above teaching. The embodiments were chosen and described in order to best explain the principles of the invention and the practical application, to thereby enable others skilled in the art to best utilize the invention. The invention is limited only by the claims and their full scope and equivalents.
Claims (7)
1. A method for improving plasma-Fenton reaction for removing organic matters in water is characterized by comprising the following steps: the method comprises the following steps: placing the prepared solution into a reactor of an experimental system, and then adding the prepared rGO/Fe3O4Nano-particles, turning on power supply, applying voltage and generating plasma, ultraviolet light and H accompanied by plasma in generation process2O2For activating rGO/Fe3O4Generating Fenton reaction, and then generating OH, wherein the generated OH is used for oxidizing organic matters in the water body; by applyingAdding magnet to mix rGO/Fe3O4Quickly separated from water.
2. The method for removing organic matters in water by enhancing the plasma-Fenton reaction according to claim 1, wherein the method comprises the following steps: the experimental system mainly comprises a pulse power supply, a reactor, an electrical detection system and a spectrum detection system, wherein the pulse power supply comprises a direct-current power supply, an energy storage capacitor, a forming capacitor and a rotary spark gap switch, the reactor comprises a reaction cavity and an aeration cavity, gas is provided with an air pump and is blown into the aeration cavity of the reactor through a flowmeter, the gas is further blown into the reaction cavity through a stainless steel syringe needle head, the electrical monitoring system comprises an oscilloscope, a voltage probe and a current probe, the voltage probe and the current probe are used for detecting voltage and current applied to the reactor, images and numerical values are output through the oscilloscope, and the spectrum detection system comprises a spectrometer and a computer.
3. The method for removing organic matters in water by enhancing the plasma-Fenton reaction according to claim 2, wherein: the peak voltage of the pulse power supply is adjustable between 0kV and 40kV, the frequency is adjustable between 0Hz and 150Hz, the rise time is 20 us to 100us, and the pulse width is 100-500 ns.
4. The method for removing organic matters in water by enhancing the plasma-Fenton reaction according to claim 2, wherein: the reactor is characterized in that a high-voltage electrode is arranged at the bottom end of the reactor and consists of seven No. 17 stainless steel syringe needles which are connected in parallel, wherein six stainless steel syringe needles are positioned at the top end of an aeration cavity, one stainless steel syringe needle is positioned at the center of the aeration cavity, the distance from the center point to the vertex is 30mm, the inner diameter of each stainless steel syringe needle is 1.12mm, the wall thickness is 0.18mm, the reactor is connected with a grounding electrode, the grounding electrode is a stainless steel plate, and the radius and the thickness of the grounding electrode are respectively 30mm and 2 mm.
5. The method for removing organic matters in water by enhancing the plasma-Fenton reaction according to claim 2, wherein: the fiber-optic probe of the spectrometer is horizontally aligned with the top end of the stainless steel syringe needle.
6. The method for removing organic matters in water by enhancing the plasma-Fenton reaction according to claim 1, wherein the method comprises the following steps: the rGO/Fe3O4The preparation steps of the nano-particles are as follows:
firstly adding graphite powder with the particle size of 1-2 mu m and sodium nitrate into concentrated sulfuric acid, stirring in ice bath for 1h, and then slowly adding KMnO4Continuously stirring for 1 hour; then heating to 30 ℃ and maintaining for 30min to obtain a mixed solution; adding deionized water into the mixed solution, heating to 90 ℃ and maintaining for 2 hours; then deionized water is added and then 30 percent of H is slowly added2O2(ii) a Filtering the mixed solution, washing with 5% HCl, and washing with warm water until the pH is neutral; performing ultrasonic treatment on the remained dispersion liquid in water for 30min, centrifuging to remove large particles, and performing freeze drying on the obtained GO of the brownish yellow supernatant; adding freeze-dried GO into ethylene glycol, performing ultrasonic treatment until the GO is completely dispersed, and adding FeCl at normal temperature3·6H2O and anhydrous sodium acetate, and stirring for 1 h; then transferring the stirred solution into a 100mL polytetrafluoroethylene high-pressure reaction kettle, and reacting for 6h at 200 ℃; after the reaction kettle is naturally cooled to room temperature, carrying out magnetic separation, and alternately and repeatedly washing the obtained black solid by using deionized water and ethanol; finally, drying for 24h at 50 ℃ in a vacuum drying oven to obtain rGO/Fe3O4And storing in a dryer for use.
7. The method for removing organic matters in water by improving plasma-Fenton reaction according to claim 6, wherein: by regulating GO and Fe3O4Preparing rGO/Fe with different graphene doping amounts according to the mass ratio3O4The different graphene doping amounts comprise 6 wt%, 12 wt%, 18 wt% and 24 wt%, and the rGO/Fe is doped according to different graphene doping amounts3O4The markers are rGFe-6, rGFe-12, rGFe-18, rGFe-24.
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