CN111569829A - Method for removing micro-plastic in water based on graphene material - Google Patents
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Abstract
The invention provides a method for removing micro-plastic in water based on a graphene material, belonging to the technical field of environmental pollution research, and comprising the steps of adding a magnetic porous graphene material into a sample containing the micro-plastic, stirring and mixing for 3-6min, and then absorbing the magnetic porous graphene by using a magnet. The invention also provides the magnetic porous graphene and a preparation method thereof, and the method can increase the surface hydrophobic degree of the magnetic porous graphene and can increase the electronegativity of particles; the alkali activation effect on graphene can be enhanced, adsorption sites on nonpolar organic molecules are increased, and the adsorption quantity on the micro-plastic is increased, so that the removal rate of the micro-plastic is improved.
Description
Technical Field
The invention belongs to the technical field of environmental pollution research, and particularly relates to a method for removing micro-plastic in water based on a graphene material.
Background
The concept of micro-plastics was first proposed in 2004, and plastic particles with a particle size of less than 5mm were generally called micro-plastics, which have a wide range of micro-plastics contamination and were detectable in both soil and water, the small micro-plastic particles provide the possibility for phagocytosis, are ideal carriers for numerous hydrophobic organic pollutants and heavy metals, increase the possibility of release of plastic additives or chemical substances adsorbed on the micro-plastics in ingested organisms6t increased to 3.48 × 10 in 20178t, the products become potential sources of micro plastics after use, the recycling of waste plastics is an important measure for saving primary resources and reducing plastic pollution, and the recycling amount of waste plastics in our country is about 1.693 × 10 in 20177t, the import quantity of waste plastics is about 5.83 × 106t. Most of plastic fragments generated in the waste plastic regeneration process are utilized, and a small amount of fragments enter an enterprise sewage treatment plant along with workshop production wastewater. At present, sewage treatment plants are mainly aimed at COD in waterCr、BOD5The removal of TN, TP and the like does not have a link aiming at the treatment of the micro-plastics, so that the micro-plastics are not completely removed, and the micro-plastics enter rivers and oceans along with the discharge of sewage treatment plants.
Graphene-based materials have many advantages for application as adsorbents in water treatment: firstly, a single-layer graphene material has two basic surfaces for fully adsorbing pollutants; secondly, by using a simple method and simple equipment, graphite is easily oxidized and stripped to prepare graphene oxide, reduced graphene oxide and other graphene-based materials, so that the use cost is reduced; finally, the graphene-based material can be modified according to the requirements of actual engineering. Numerous researches show that the graphene-based material has large specific surface area, high-degree porous structure, strong mechanical property and stability, and can be used as an adsorbent and effectively adsorb and remove inorganic and organic pollutants in water. Graphene is often used for compounding with inorganic nanoparticles by virtue of large specific surface area and chemical stability to prepare graphene-based composite materials. The compounding of graphene with magnetic nanoparticles is of great interest because of the combination of the large specific surface area of graphene and the magnetically recoverable nature of magnetic particles.
Disclosure of Invention
The invention aims to provide magnetic porous graphene and a preparation method thereof, wherein the method increases the surface hydrophobicity of the magnetic porous graphene and can increase the electronegativity of particles; the alkali activation effect on graphene can be enhanced, adsorption sites on nonpolar organic molecules are increased, and the adsorption quantity on the micro-plastic is increased, so that the removal rate of the micro-plastic is improved.
The technical scheme adopted by the invention for realizing the purpose is as follows:
the preparation method of the magnetic porous graphene comprises the following steps:
s1, preparing graphene oxide;
s2, modifying graphene oxide;
s3, preparing magnetic porous graphene;
the method for modifying graphene oxide in step S2 specifically includes: placing graphene oxide in ultrapure water for ultrasonic dispersion for 20-30min, adding an activating agent glycine ethyl ester hydrochloride, activating for 30-40min at normal temperature, adding 1-methyl-3-phenylpropylamine, stirring and reacting at 65-75 ℃ for 60-80min, adding an ethanol solution, standing for 20-30min, removing supernatant, adding ethanol, performing centrifugal filtration, adding distilled water, performing centrifugal filtration, and drying at 55-60 ℃. The method is characterized in that glycine ethyl ester hydrochloride is used as an activating agent, 1-methyl-3-phenylpropylamine is used for modifying graphene oxide, amino groups of the 1-methyl-3-phenylpropylamine react with carboxyl groups on the surface of the graphene oxide to form amide, and a hydrophobic benzene ring and an alkyl chain are introduced, so that the surface hydrophobicity of the prepared magnetic porous graphene is increased, the hydrophobic interaction with the micro-plastic can be enhanced, the electronegativity of the surface of the magnetic porous graphene can be increased, the uniform dispersibility is enhanced, the adsorption effect on the micro-plastic is further increased, and the removal rate is increased.
Preferably, the mass ratio of the graphene oxide to the 1-methyl-3-phenylpropylamine in the step S2 is 2-3: 1.
Preferably, the preparation method of the magnetic porous graphene comprises the following steps:
a. mixing the modified graphene oxide and KOH, heating to 800 ℃ at the speed of 5-8 ℃/min, keeping the temperature for 55-75min, introducing nitrogen during the heating, cooling, respectively washing with 0.1-0.15mol/L hydrochloric acid solution and deionized water for 2-3, freeze-drying for 12-14h, and taking out to obtain porous graphene oxide;
b. dissolving porous graphene oxide in ethylene glycol, performing ultrasonic dispersion for 30-45min to obtain a solution R1, weighing ferric trichloride and sodium acetate, dissolving the ferric trichloride and the sodium acetate in the ethylene glycol, performing ultrasonic dispersion for 30-45min to obtain a solution R2, mixing and stirring the solutions R1 and R2 for 50-75min, heating to 190 ℃ with temperature, and performing a closed reaction for 11-13 h;
c. after the reaction is finished, cooling to room temperature, collecting the product by a strong magnet, washing for 2-3 times by ethanol and water respectively, and freeze-drying.
Preferably, 6-benzyladenine is further added when the modified graphene oxide in the step a is mixed with KOH. The graphene is treated by utilizing 6-benzyladenine, so that the alkali activation effect can be enhanced, the surface wrinkles of the graphene are increased, the pore structure is increased, the specific surface area is increased, the adsorption sites for nonpolar organic molecules are increased, the adsorption content for the micro-plastic is increased, and the removal rate is improved.
Preferably, the mass ratio of the modified graphene oxide, KOH and 6-benzyladenine in the step a is as follows: 2-3:5-6:1-2.
Preferably, the mass ratio of the porous graphene oxide, the ferric trichloride and the sodium acetate in the step b is 1:1-2: 9-10.
The magnetic porous graphene is prepared by the preparation method of the magnetic porous graphene.
The method for removing the micro-plastic in the water body is provided, the magnetic porous graphene material is added into a sample containing the micro-plastic, stirred and mixed for 3-6min, and then the magnetic porous graphene is absorbed by a magnet.
Provides application of magnetic porous graphene in removing organic pollutants in water.
The invention has the beneficial effects that:
1) according to the method, glycine ethyl ester hydrochloride is used as an activating agent, 1-methyl-3-phenylpropylamine is used for modifying graphene oxide, amino groups of the 1-methyl-3-phenylpropylamine react with carboxyl groups on the surface of the graphene oxide to form amide, and a hydrophobic benzene ring and an alkyl chain are introduced, so that the surface hydrophobicity of the prepared magnetic porous graphene is increased, the hydrophobic interaction with micro-plastics can be enhanced, the electronegativity of the surface of the magnetic porous graphene can be increased, the uniform dispersibility is enhanced, the adsorption effect on the micro-plastics is further increased, and the removal rate is increased;
2) according to the invention, the graphene is treated by utilizing 6-benzyladenine, so that the alkali activation effect can be enhanced, the wrinkles on the surface of the graphene are increased, the pore structure is increased, the specific surface area is increased, the adsorption sites for nonpolar organic molecules are increased, the adsorption content for micro-plastics is increased, and the removal rate is improved;
3) the magnetic porous graphene prepared by the method is used for removing micro-plastics in water, and has the advantages of simplicity and convenience in operation, low cost, high removal rate, reusability, and environmental friendliness.
Drawings
Fig. 1 is an infrared spectrum of magnetic porous graphene prepared in examples 1 and 4 of the present invention;
FIG. 2 is a graph showing the results of the measurement of the graft ratio in example 7 of the present invention;
FIG. 3 shows the results of the contact angle test in example 7 of the present invention;
FIG. 4 shows the results of measurement of Zeta potential in example 7 of the present invention;
fig. 5 is SEM images of porous graphene oxide prepared in examples 4 and 6 of the present invention;
FIG. 6 is the result of the measurement of specific surface area in example 7 of the present invention;
FIG. 7 shows the results of the measurement of the adsorption amount in example 7 of the present invention;
FIG. 8 shows the results of measurement of the removal rate of the micro plastic in example 7 of the present invention.
Detailed Description
Unless otherwise indicated, all publications, patent applications, patents, and other references mentioned herein are incorporated by reference in their entirety as if set forth in their entirety.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. In case of conflict, the present specification, including definitions, will control.
When an amount, concentration, or other value or parameter is given as either a range, preferred range, or a list of upper preferable values and lower preferable values, this is to be understood as specifically disclosing all ranges formed from any pair of any larger range limit or preferred value and any smaller range limit or preferred value, regardless of whether ranges are separately disclosed. For example, when a range of "1 to 5" is described, the described range should be construed as including ranges of "1 to 4", "1 to 3", "1 to 2 and 4 to 5", "1 to 3 and 5", and the like. Where numerical ranges are described herein, unless otherwise stated, the stated ranges are intended to include the endpoints of the ranges and all integers and fractions within the ranges.
In addition, the words "a" and "an" preceding an element or component of the invention are intended to mean no limitation on the number of times that the element or component appears (i.e., occurs). Thus, "a" or "an" should be understood to include one or at least one and the singular forms of an element or component also include the plural unless the singular is explicitly stated.
Embodiments of the present invention, including embodiments of the invention described in the summary section and any other embodiments described herein below, can be combined arbitrarily.
The invention is described in detail below:
the preparation method of the magnetic porous graphene comprises the following steps:
s1, preparing graphene oxide: respectively weighing 2-4g of crystalline flake graphite and 10-14g of potassium permanganate, uniformly mixing, pouring into a 200mL reaction kettle liner, and then putting the reaction kettle liner into a stainless steel reaction kettle jacket; quickly adding 90-100mL of concentrated sulfuric acid into the liner, quickly covering the liner cover, and tightly covering the stainless steel reaction kettle cover in a rotating manner; the reaction kettle is stored for 3 to 4 hours at the temperature of 0 to 4 ℃; after the reaction is finished, the reaction kettle is quickly placed into a drying oven with the temperature of 100-; after the reaction is finished, taking the reaction kettle out of the oven, cooling to room temperature, and opening; diluting the reactant by using 300-400mL deionized water, dropwise adding 45-55mL 30% hydrogen peroxide after cooling again, and fully stirring until the solution is golden yellow; washing the obtained mixed solution with 4.5-5% hydrochloric acid for three times, and then washing with deionized water until the pH value of the graphene oxide solution is 6.8-7.5; after cleaning, carrying out freeze drying on the graphene oxide for 10-12 h;
s2, modifying graphene oxide;
s3, preparing magnetic porous graphene;
the method for modifying graphene oxide in step S2 specifically includes: placing graphene oxide in ultrapure water for ultrasonic dispersion for 20-30min, adding an activating agent glycine ethyl ester hydrochloride, activating for 30-40min at normal temperature, adding 1-methyl-3-phenylpropylamine, stirring and reacting at 65-75 ℃ for 60-80min, adding an ethanol solution, standing for 20-30min, removing supernatant, adding ethanol, performing centrifugal filtration, adding distilled water, performing centrifugal filtration, and drying at 55-60 ℃. The method is characterized in that glycine ethyl ester hydrochloride is used as an activating agent, 1-methyl-3-phenylpropylamine is used for modifying graphene oxide, amino groups of the 1-methyl-3-phenylpropylamine react with carboxyl groups on the surface of the graphene oxide to form amide, and a hydrophobic benzene ring and an alkyl chain are introduced, so that the surface hydrophobicity of the prepared magnetic porous graphene is increased, the hydrophobic interaction with the micro-plastic can be enhanced, the electronegativity of the surface of the magnetic porous graphene can be increased, the uniform dispersibility is enhanced, the adsorption effect on the micro-plastic is further increased, and the removal rate is increased.
Preferably, the mass ratio of the graphene oxide to the 1-methyl-3-phenylpropylamine in the step S2 is 2-3: 1.
Preferably, the mass ratio of 1-methyl-3-phenylpropylamine to glycine ethyl ester hydrochloride in step S2 is 3-5: 1.
Preferably, the preparation method of the magnetic porous graphene comprises the following steps:
a. mixing the modified graphene oxide and KOH, heating to 800 ℃ at the speed of 5-8 ℃/min, keeping the temperature for 55-75min, introducing nitrogen during the heating, cooling, respectively washing with 0.1-0.15mol/L hydrochloric acid solution and deionized water for 2-3, freeze-drying for 12-14h, and taking out to obtain porous graphene oxide;
b. dissolving porous graphene oxide in ethylene glycol, performing ultrasonic dispersion for 30-45min to obtain a solution R1, weighing ferric trichloride and sodium acetate, dissolving the ferric trichloride and the sodium acetate in the ethylene glycol, performing ultrasonic dispersion for 30-45min to obtain a solution R2, mixing and stirring the solutions R1 and R2 for 50-75min, heating to 190 ℃ with temperature, and performing a closed reaction for 11-13 h;
c. after the reaction is finished, cooling to room temperature, collecting the product by a strong magnet, washing for 2-3 times by ethanol and water respectively, and freeze-drying.
Preferably, 6-benzyladenine is further added when the modified graphene oxide in the step a is mixed with KOH. The graphene is treated by utilizing 6-benzyladenine, so that the alkali activation effect can be enhanced, the surface wrinkles of the graphene are improved, the pore structure is increased, the specific surface area is increased, the adsorption sites for nonpolar organic molecules are increased, the adsorption content for the micro-plastic is increased, and the removal rate is improved.
Preferably, the mass ratio of the modified graphene oxide, KOH and 6-benzyladenine in the step a is as follows: 2-3:5-6:1-2.
Preferably, the mass ratio of the porous graphene oxide, the ferric trichloride and the sodium acetate in the step b is 1:1-2: 9-10.
The magnetic porous graphene is prepared by the preparation method of the magnetic porous graphene.
The method for removing the micro-plastic in the water body is provided, the magnetic porous graphene material is added into a sample containing the micro-plastic, stirred and mixed for 3-6min, and then the magnetic porous graphene is absorbed by a magnet.
Provides application of magnetic porous graphene in removing organic pollutants in water.
The present invention is further described in detail with reference to the following examples:
example 1:
a preparation method of magnetic porous graphene comprises the following steps:
s1, preparing graphene oxide: respectively weighing 3g of crystalline flake graphite and 12g of potassium permanganate, uniformly mixing, pouring into a 200mL reaction kettle liner, and then putting the reaction kettle liner into a stainless steel reaction kettle jacket; quickly adding 100mL of concentrated sulfuric acid into the liner, quickly covering the liner cover, and tightly covering the stainless steel reaction kettle cover in a rotating manner; the reaction kettle is stored for 4 hours at the temperature of 4 ℃; after the reaction is finished, quickly putting the reaction kettle into a 100 ℃ oven for heating, and quickly carrying out oxidation reaction for 1.5 h; after the reaction is finished, taking the reaction kettle out of the oven, cooling to room temperature, and opening; diluting the reactant by using 300mL of deionized water, dropwise adding 55mL of 30% hydrogen peroxide after cooling again, and fully stirring until the solution is golden yellow; washing the obtained mixed solution with 5% hydrochloric acid for three times, and then washing with deionized water until the pH value of the graphene oxide solution is 6.8; after washing, the graphene oxide was freeze-dried for 10 h.
S2, modification of graphene oxide: placing 3g of graphene oxide in ultrapure water, performing ultrasonic dispersion for 30min, adding 0.5g of activating agent glycine ethyl ester hydrochloride, activating for 30min at normal temperature, adding 1.5g of 1-methyl-3-phenylpropylamine, stirring at 70 ℃ for reaction for 70min, adding an ethanol solution, standing for 20min, removing supernatant, adding ethanol, performing centrifugal filtration, adding distilled water, performing centrifugal filtration, and drying at 55 ℃.
S3, preparing magnetic porous graphene: 1) mixing 3g of modified graphene oxide, 5g of KOH and 1g of 6-benzyladenine, heating to 800 ℃ at a speed of 8 ℃/min, keeping for 60min, introducing nitrogen during the heating, cooling, respectively washing 3% by using 0.15mol/L hydrochloric acid solution and deionized water, freeze-drying for 14h, and taking out to obtain porous graphene oxide;
2) dissolving 3g of porous graphene oxide in 1L of ethylene glycol, performing ultrasonic dispersion for 30min to obtain a solution R1, weighing 3g of ferric trichloride and 27g of sodium acetate, dissolving in 800mL of ethylene glycol, performing ultrasonic dispersion for 30min to obtain a solution R2, mixing and stirring the solutions R1 and R2 for 60min, then heating to 180 ℃, and performing closed reaction for 12 h;
3) after the reaction, the reaction mixture was cooled to room temperature, and the product was collected by a strong magnet, washed 3 times with ethanol and water, respectively, and freeze-dried.
Example 2:
the glycine ethyl ester hydrochloride was not added when modifying graphene oxide, and the remaining part was completely the same as in example 1.
Example 3:
the graphene oxide was modified without adding 1-methyl-3-phenylpropylamine, and the remainder was completely the same as in example 1.
Example 4:
graphene oxide was not modified, and the remainder was completely the same as in example 1.
Example 5:
6-benzyladenine was not added in the preparation of magnetic porous graphene, and the rest was completely the same as in example 1.
Example 6:
6-benzyladenine was not added in the preparation of magnetic porous graphene, and the rest was completely the same as in example 4.
Example 7:
1. sample characterization:
1.1 Fourier transform infrared spectroscopy: an external spectrometer of the 8900-FTIR type was used, equipped with a deuterated triglycine sulfate (DTGS) detector and a KBr electron beam splitter. Before testing, the sample is mixed with KBr, ground and tabletted, and the mass concentration of the sample is about 1%. The processed sample is placed in a sample cell for scanning, and the scanning wavelength range is 4000--1. The infrared spectra of the magnetic porous graphene prepared in example 1 and example 4 are shown in fig. 1. The grafting ratio of 1-methyl-3-phenylpropylamine on the surface of the magnetic porous graphene in example 1, example 2, example 3 and example 4 was measured by infrared spectroscopy, and the measurement result of the grafting ratio is shown in fig. 2.
As can be seen from fig. 1, compared to example 4,EXAMPLE 1 Infrared Spectrum 1603cm-1The absorption peak of C ═ O in the carboxyl group was reduced to 1673cm-1The C ═ O stretching vibration peak of the amide appears at the position, 3250--1The peak of stretching vibration of CH of benzene ring is 2923cm-1At 2876cm-1In the presence of-CH2Expansion peak, 1560--1The C ═ C vibration peak of benzene ring skeleton appears at 1230cm-1The bending vibration peak in the CH plane of the benzene ring is 772cm-1And an out-of-plane bending vibration peak of a benzene ring CH appears, which indicates that the amino group of the 1-methyl-3-phenylpropylamine in the example 1 reacts with the carboxyl group on the surface of the graphene oxide to form an amide, a hydrophobic benzene ring and an alkyl chain are introduced, and the 1-methyl-3-phenylpropylamine is successfully grafted to the surface of the graphene oxide.
As can be seen from fig. 2, compared with example 1, the grafting ratio of example 2 is significantly lower, and the grafting ratios of examples 3 and 4 are 0, which indicates that the surface of graphene oxide can be modified at a higher grafting ratio by using 1-methyl-3-phenylpropylamine and glycine ethyl ester hydrochloride as an activating agent.
1.2 contact Angle test: the magnetic porous graphene was tested on a Data physics Instruments Gmb OCA30 goniometer. The contact angle test results are shown in FIG. 3.
1.3Zeta potential analysis; zeta potential measurement is carried out on the magnetic porous graphene by adopting a Zeta-Meter System model 3.0 potentiometric instrument. The results of the Zeta potential measurements are shown in FIG. 4.
As can be seen from fig. 3, the contact angles of the magnetic porous graphene prepared in examples 1 and 5 are significantly larger than those of examples 2, 4 and 6, and as can be seen from fig. 4, the electronegativity of examples 1 and 5 is stronger, and under most pH conditions, the absolute value of Zeta potential of the magnetic porous graphene prepared in examples 1 and 5 is significantly higher, which indicates that 1-methyl-3-phenylpropylamine modifies the surface of graphene oxide with a higher grafting ratio, so that the surface hydrophobicity of the prepared magnetic porous graphene is increased, and the electronegativity of the surface of the magnetic porous graphene can be increased, and the uniform dispersibility is enhanced.
1.4 field emission Scanning Electron Microscopy (SEM): and dissolving porous graphene oxide in an ethanol solution, performing ultrasonic treatment for 10min, diluting, dripping the porous graphene oxide solution on the silicon wafer and the copper mesh, naturally drying, and testing an SEM (scanning electron microscope) with the SEM magnification of 10000 times. SEM images of the porous graphene oxide prepared in example 4 and example 6 are shown in fig. 5.
1.5 specific surface area test: and (3) determining the specific surface area of the magnetic porous graphene sample by using a Quantachrome NOVA-2000E specific surface area analyzer. The samples were first dried under vacuum at 105 ℃ for 12h and then N-dried in a liquid nitrogen environment (77K)2(0.162nm2) Adsorption-desorption experiments. And calculating the specific surface area of the magnetic porous graphene sample by adopting a multipoint BET method. The results of the specific surface area test are shown in FIG. 6.
As can be seen from fig. 5, the wrinkles on the surface of the porous graphene oxide prepared in example 4 are significantly greater than those of example 6, and as can be seen from fig. 6, the specific surface areas of the magnetic porous graphene prepared in examples 1, 2 and 4 are significantly greater than those of examples 5 and 6, which indicates that the alkali activation effect can be enhanced, the wrinkles on the surface of the graphene can be increased, the pore structure can be increased, and the specific surface area can be increased by treating the graphene with 6-benzyladenine.
2. And (3) performance testing:
testing of adsorption amount: adding ABS, PP and PE 3 micro-plastics with the same mass and different particle sizes (the particle size ranges include 0.10-0.25mm, 0.25-0.50mm and 0.5-5.0mm) into a water body to prepare a water sample with the micro-plastic concentration of 0.2 mg/L. Taking 50mL of water sample, adjusting the pH value of the wastewater to 7.8, adding 2mg of magnetic porous graphene, stirring for 300s at 100r/min, absorbing the magnetic porous graphene by using a magnet, collecting the water samples at 0, 5, 10, 20, 30, 60, 120 and 300s respectively, pouring the water samples into a screen which is stacked according to the pore size (5, 2, 1, 0.5, 0.25 and 0.1mm), drying, weighing, and calculating the adsorption capacity of the magnetic porous graphene to the micro-plastic. The results of the adsorption amount test are shown in FIG. 7.
As can be seen from FIG. 7, the adsorption amount of the magnetic porous graphene prepared in example 1 to the micro plastic is significantly larger than that of the magnetic porous graphene prepared in example 2,
Example 4, example 5, example 6; example 5 had a significantly greater adsorption than example 6; the results show that the 1-methyl-3-phenylpropylamine modifies the surface of graphene oxide at a high grafting rate, so that the hydrophobic interaction between the prepared magnetic porous graphene and the micro plastic can be enhanced, and the colloid can keep suspension stability, thereby increasing the adsorption effect on the micro plastic; the adsorption capacity of the embodiment 2 and the embodiment 4 is obviously greater than that of the embodiment 6, which shows that the alkali activation effect can be enhanced, the adsorption sites for nonpolar organic molecules can be increased, and the adsorption capacity for micro-plastics can be increased by treating the graphene with 6-benzyladenine.
Example 8:
a method for removing micro-plastic in a water body, comprising:
3 kinds of micro plastic particles PP (polypropylene), ABS (acrylonitrile-butadiene-styrene) and PE (polyethylene) with different colors are prepared in a test, wherein the density of the ABS is 1.05g/cm3PP having a density of 0.94g/cm3The density of PE was 0.92g/cm3(ii) a The sludge is obtained from a sewage treatment plant of a large waste plastic regeneration enterprise. In order to avoid the influence of micro-plastics in the sludge on the test, the sludge is sieved by a standard sieve with 0.075 mm. Adding ABS, PP and PE 3 micro-plastics with the same mass and different particle sizes (the particle size ranges include 0.10-0.25mm, 0.25-0.50mm and 0.5-5.0mm) to prepare the simulated micro-plastic-containing wastewater with the micro-plastic concentration of 0.15mg/L and the water temperature of 27 ℃.
5mg of the magnetic porous graphene prepared in the above examples 1, 2, 4, 5 and 6 was added to 25mL of simulated wastewater, stirred and mixed for 5min, and then the magnetic porous graphene was removed by magnet attraction, a water sample was collected, poured into a sieve stacked according to pore sizes (5, 2, 1, 0.5, 0.25 and 0.1mm), dried and weighed, and the removal rate of the micro-plastic in the wastewater was calculated. The results of the determination of the removal rate of the micro-plastics are shown in FIG. 8.
As can be seen from FIG. 8, the removal rate of the magnetic porous graphene prepared in example 1 to the micro plastic is obviously greater than that of the magnetic porous graphene prepared in example 2,
Example 4, example 5, example 6; the removal rate of the example 5 is obviously higher than that of the example 6, which shows that the 1-methyl-3-phenylpropylamine modifies the surface of the graphene oxide at a higher grafting rate, so that the adsorption effect of the prepared magnetic porous graphene on the micro-plastic can be enhanced, and the removal rate is improved; the removal rates of the examples 2 and 4 are obviously higher than those of the example 6, which shows that the adsorption amount of the micro plastic can be increased and the removal rate can be improved by treating the graphene with 6-benzyladenine.
Conventional techniques in the above embodiments are known to those skilled in the art, and therefore, will not be described in detail herein.
The above embodiments are merely illustrative, and not restrictive, and those skilled in the art can make various changes and modifications without departing from the spirit and scope of the invention. Therefore, all equivalent technical solutions also belong to the scope of the present invention, and the protection scope of the present invention should be defined by the claims.
Claims (9)
1. The preparation method of the magnetic porous graphene is characterized by comprising the following steps:
s1, preparing graphene oxide;
s2, modifying graphene oxide;
s3, preparing magnetic porous graphene;
the method for modifying graphene oxide in step S2 specifically includes: placing graphene oxide in ultrapure water for ultrasonic dispersion for 20-30min, adding an activating agent glycine ethyl ester hydrochloride, activating for 30-40min at normal temperature, adding 1-methyl-3-phenylpropylamine, stirring and reacting at 65-75 ℃ for 60-80min, adding an ethanol solution, standing for 20-30min, removing supernatant, adding ethanol, performing centrifugal filtration, adding distilled water, performing centrifugal filtration, and drying at 55-60 ℃.
2. The method of claim 1, wherein: the mass ratio of the graphene oxide to the 1-methyl-3-phenylpropylamine in the step S2 is 2-3: 1.
3. The method of claim 1, wherein: the preparation method of the magnetic porous graphene comprises the following steps:
a. mixing the modified graphene oxide and KOH, heating to 800 ℃ at the speed of 5-8 ℃/min, keeping the temperature for 55-75min, introducing nitrogen during the heating, cooling, respectively washing with 0.1-0.15mol/L hydrochloric acid solution and deionized water for 2-3, freeze-drying for 12-14h, and taking out to obtain porous graphene oxide;
b. dissolving porous graphene oxide in ethylene glycol, performing ultrasonic dispersion for 30-45min to obtain a solution R1, weighing ferric trichloride and sodium acetate, dissolving the ferric trichloride and the sodium acetate in the ethylene glycol, performing ultrasonic dispersion for 30-45min to obtain a solution R2, mixing and stirring the solutions R1 and R2 for 50-75min, heating to 190 ℃ with temperature, and performing a closed reaction for 11-13 h;
c. after the reaction is finished, cooling to room temperature, collecting the product by a strong magnet, washing for 2-3 times by ethanol and water respectively, and freeze-drying.
4. The method of claim 1, wherein: and b, adding 6-benzyladenine when the modified graphene oxide in the step a is mixed with KOH.
5. The production method according to claim 3, characterized in that: in the step b, the mass ratio of the porous graphene oxide to the ferric trichloride to the sodium acetate is 1:1-2: 9-10.
6. The method of claim 4, wherein: the mass ratio of the modified graphene oxide, KOH and 6-benzyladenine in the step a is as follows: 2-3:5-6:1-2.
7. A magnetic porous graphene characterized by: the magnetic porous graphene is prepared by the preparation method of any one of claims 1 to 6.
8. A method for removing micro-plastics in a water body is characterized by comprising the following steps: adding the magnetic porous graphene material of claim 7 into a sample containing the micro plastic, stirring and mixing for 3-6min, preferably 4-5min, and then absorbing the magnetic porous graphene by using a magnet.
9. Use of the magnetic porous graphene according to claim 7 for removing organic pollutants in a water body.
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