CN111318176A - Graphene-based conductive filter membrane and preparation method thereof - Google Patents
Graphene-based conductive filter membrane and preparation method thereof Download PDFInfo
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01D69/12—Composite membranes; Ultra-thin membranes
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- B01D39/20—Other self-supporting filtering material ; Other filtering material of inorganic material, e.g. asbestos paper, metallic filtering material of non-woven wires
- B01D39/2003—Glass or glassy material
- B01D39/2017—Glass or glassy material the material being filamentary or fibrous
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- B01D46/00—Filters or filtering processes specially modified for separating dispersed particles from gases or vapours
- B01D46/54—Particle separators, e.g. dust precipitators, using ultra-fine filter sheets or diaphragms
- B01D46/543—Particle separators, e.g. dust precipitators, using ultra-fine filter sheets or diaphragms using membranes
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Abstract
The invention discloses a graphene-based conductive filter membrane and a preparation method thereof, wherein the preparation method comprises the following steps: placing a base film in a filter cup of a vacuum filtration device, then adding the graphene oxide dispersion liquid into the filter cup, turning on a vacuum pump of the vacuum filtration device, controlling the filtration pressure, carrying out vacuum filtration, and placing the prepared graphene oxide loaded base film in a vacuum oven for drying; placing the graphene oxide-loaded base membrane on a culture dish, dropwise adding a hydrazine hydrate solution into the culture dish, fumigating the hydrazine hydrate solution in an oven, and taking out the fumigated product to obtain the graphene-based conductive filter membrane. The graphene-based conductive filter membrane can realize uniform loading of graphene on a base membrane, and the high-efficiency reduction of the graphene can be realized in a hydrazine hydrate steam fumigation reduction process. The conductivity of the graphene-based conductive filter membrane is 0.0004-0.0006 s/cm, and the filtering efficiency of the graphene-based conductive filter membrane on particles with the particle size of 0.1-0.5 mu m is 96-99%. The graphene-based conductive filter membrane disclosed by the invention is low in raw material price, simple in operation process and expected to realize industrialization.
Description
Technical Field
The invention belongs to the technical field of filter membrane preparation, and particularly relates to a graphene-based conductive filter membrane and a preparation method thereof.
Background
With the continuous development of industry and science technology, the emission of atmospheric pollutants, such as various polluting aerosols, is gradually increased by the combustion of various industrial fossil fuels, the exhaust emission in transportation processes, the infection and the spread of epidemic diseases, and the like, and the pollutants in the atmosphere seriously threaten the inhabitation environment and the health of human beings. At present, the air pollution treatment becomes a research hotspot of the current times, and the center of gravity of the research on filtration, collection, detection, treatment and prevention is realized. Electrostatic adsorption deposition is a common mode in aerosol collection technology, and the basic principle is to charge particles in air aerosol by using a high-voltage electric field, and then the charged particles are adsorbed and collected on an electrode under the action of electric field force. Therefore, the effective way for realizing the electrostatic adsorption filtration membrane collection technology is to design a conductive nano-porous composite filtration membrane based on the traditional filtration membrane, and simultaneously has the functions of electrode and filtration, thereby improving the collection efficiency, the detection sensitivity and the reliability.
Disclosure of Invention
An object of the present invention is to solve at least the above problems and/or disadvantages and to provide at least the advantages described hereinafter.
To achieve these objects and other advantages in accordance with the present invention, there is provided a method for preparing a graphene-based conductive filter membrane, comprising the steps of:
placing a base film in a filter cup of a vacuum filtration device, then adding the graphene oxide dispersion liquid into the filter cup, starting a vacuum pump of the vacuum filtration device, controlling the filtration pressure to be between 0.008 and 0.020MPa, carrying out vacuum filtration, and drying the prepared graphene oxide loaded base film in a vacuum oven at 65-75 ℃;
and step two, placing the graphene oxide-loaded base membrane on a culture dish, dropwise adding a hydrazine hydrate solution into the culture dish, fumigating the culture dish in an oven at the temperature of 65-75 ℃ for 15-45 min, and taking out the culture dish to obtain the graphene-based conductive filter membrane.
Preferably, the concentration of the graphene oxide dispersion liquid is 1-6 mg/L; the thickness of the base film is 0.5-3 mm.
Preferably, the ratio of the amount of the graphene oxide dispersion to the surface area of the base film is: 1mL of 3-4 cm2。
Preferably, the concentration of the hydrazine hydrate solution is 60-80 wt%; the volume ratio of the hydrazine hydrate solution to the graphene oxide dispersion liquid is 1: 30-60.
Preferably, the base membrane is any one of a glass fiber membrane, a polypropylene membrane, a polyacrylonitrile membrane, a nylon membrane, a polylactic acid membrane and a polystyrene membrane.
Preferably, the glass fiber membrane is a borosilicate glass fiber membrane.
Preferably, the base film is a polycarbonate-polycaprolactone composite film, and the preparation method comprises the following steps: dissolving polycarbonate and polycaprolactone in a mass ratio of 3-5: 1 in a mixed solvent of chloroform and DMF to obtain a polycarbonate-polycaprolactone mixed solution with a mass fraction of 5-8%, namely a shell solution, wherein the volume ratio of chloroform to DMF is (4-6): 1; dissolving polyoxyethylene in water to obtain a polyoxyethylene solution with the mass fraction of 3-5%, namely a nuclear layer solution, respectively injecting the shell layer solution and the nuclear layer solution into an outer layer and an inner layer of a stainless steel coaxial nozzle in an electrostatic spinning machine, applying voltage between the stainless steel coaxial nozzle and a receiving flat plate, paving tin foil paper on the receiving flat plate, then spraying the shell layer solution and the nuclear layer solution onto the tin foil paper of the receiving flat plate under a high-voltage electrostatic spraying condition to form a fiber membrane, drying the fiber membrane, adding the dried fiber membrane into the water, and ultrasonically soaking for 12 hours, wherein the ultrasonic frequency is 35-45 kHz; fishing out the fiber film and drying; obtaining the polycarbonate-polycaprolactone composite film.
Preferably, the high-voltage electrostatic spraying conditions are as follows: the environment temperature in the electrostatic spinning machine is 40-55 ℃, the output voltage of a high-voltage power supply is 15-20 kV, the distance between a receiving flat plate and a stainless steel coaxial nozzle spinning nozzle is 5-10cm, the flow rate of a nuclear layer solution is 5-10 mL/h, and the flow rate ratio of the nuclear layer solution to a shell layer solution is 1: 2; the inner diameter of the inner needle head of the stainless steel coaxial nozzle is 0.5-0.8 mm, and the inner diameter of the outer needle head is 1.2-1.6 mm.
Preferably, the obtained polycarbonate-polycaprolactone composite film is reprocessed, and the process comprises the following steps: and (3) treating the surface of the polycarbonate-polycaprolactone composite film for 0.5-0.6 s by using femtosecond laser under the conditions of a wavelength of 800nm, a pulse width of 50-80 fs and a repetition frequency of 2-3 KHz.
The invention also provides the graphene-based conductive filter membrane prepared by the preparation method of the graphene-based conductive filter membrane, wherein the conductivity of the graphene-based conductive filter membrane is 0.0004-0.0006 s/cm, and the average filtration efficiency of the graphene-based conductive filter membrane on particles of 0.1-0.5 mu m is 96-98%.
The invention at least comprises the following beneficial effects: the graphene-based conductive filter membrane can realize uniform loading of graphene on a base membrane, and the high-efficiency reduction of the graphene can be realized in a hydrazine hydrate steam fumigation reduction process. The conductivity of the graphene-based conductive filter membrane is 0.0004-0.0006 s/cm, and the average filtering efficiency of the graphene-based conductive filter membrane on particles with the particle size of 0.1-0.5 mu m is 96-99%. The graphene-based conductive filter membrane disclosed by the invention is low in raw material price, simple in operation process and expected to realize industrialization.
Additional advantages, objects, and features of the invention will be set forth in part in the description which follows and in part will become apparent to those having ordinary skill in the art upon examination of the following or may be learned from practice of the invention.
Description of the drawings:
fig. 1 is an SEM image of the graphene-based conductive filter membrane prepared in example 7 of the present invention;
fig. 2 is a diagram of a graphene-based conductive filter membrane prepared in example 7 of the present invention;
FIG. 3 is an atomic force microscope image of graphene oxide employed in the present invention;
FIG. 4 is an X-ray diffraction pattern of graphene oxide employed in the present invention;
fig. 5 is a schematic diagram of a double-filter membrane filtration efficiency test sample according to the present invention.
The specific implementation mode is as follows:
the present invention is further described in detail below with reference to the attached drawings so that those skilled in the art can implement the invention by referring to the description text.
It will be understood that terms such as "having," "including," and "comprising," as used herein, do not preclude the presence or addition of one or more other elements or groups thereof.
Example 1:
a preparation method of a graphene-based conductive filter membrane comprises the following steps:
putting a borosilicate glass fiber membrane into a filter cup of a vacuum filtration device, then adding 5mL of graphene oxide dispersion liquid with the concentration of 2mg/L into the filter cup, starting a vacuum pump of the vacuum filtration device, controlling the filtration pressure to be 0.008-0.020 MPa, carrying out vacuum filtration, and drying the prepared graphene oxide-loaded base membrane in a vacuum oven at 70 ℃; the borosilicate glass fiber film has the thickness of 1mm, the diameter of 50mm and the area pi r2＝19.625cm2；
Placing the borosilicate glass fiber membrane loaded with the graphene oxide on a culture dish, dropwise adding 100 mu L of hydrazine hydrate solution into the culture dish, fumigating the culture dish in an oven at 70 ℃ for 15min, and taking out the culture dish to obtain the graphene-based conductive filter membrane; the concentration of the hydrazine hydrate solution is 80 wt%; the conductivity of the filter membrane is 0.000448s/cm, and the filtration efficiency of the filter membrane on particles with the particle size of 0.1-0.5 mu m is 96.2%.
Example 2:
a preparation method of a graphene-based conductive filter membrane comprises the following steps:
step one, a borosilicate glass fiber membrane is placed in a filter cup of a vacuum filtration device, then 5mL of graphene oxide dispersion liquid with the concentration of 3mg/L is added into the filter cup, a vacuum pump of the vacuum filtration device is started, the filtration pressure is controlled to be 0.008-0.020 MPa, and vacuum filtration is carried outPerforming suction filtration, namely placing the prepared graphene oxide loaded base film in a vacuum oven at 70 ℃ for drying; the borosilicate glass fiber film has the thickness of 1mm, the diameter of 50mm and the area pi r2＝19.625cm2；
Placing the borosilicate glass fiber membrane loaded with the graphene oxide on a culture dish, dropwise adding 100 mu L of hydrazine hydrate solution into the culture dish, fumigating the culture dish in an oven at 70 ℃ for 30min, and taking out the culture dish to obtain the graphene-based conductive filter membrane; the concentration of the hydrazine hydrate solution is 80 wt%; the conductivity of the filter membrane is 0.000459s/cm, and the filtration efficiency of the filter membrane on 0.1-0.5 mu m particles is 97.1%.
Example 3:
a preparation method of a graphene-based conductive filter membrane comprises the following steps:
putting a borosilicate glass fiber membrane into a filter cup of a vacuum filtration device, then adding 5mL of graphene oxide dispersion liquid with the concentration of 5mg/L into the filter cup, starting a vacuum pump of the vacuum filtration device, controlling the filtration pressure to be 0.008-0.020 MPa, carrying out vacuum filtration, and drying the prepared graphene oxide-loaded base membrane in a vacuum oven at 70 ℃; the borosilicate glass fiber film has the thickness of 1mm, the diameter of 50mm and the area pi r2＝19.625cm2；
Placing the borosilicate glass fiber membrane loaded with the graphene oxide on a culture dish, dropwise adding 100 mu L of hydrazine hydrate solution into the culture dish, fumigating the culture dish in an oven at 70 ℃ for 45min, and taking out the culture dish to obtain the graphene-based conductive filter membrane; the concentration of the hydrazine hydrate solution is 80 wt%; the conductivity of the filter membrane is 0.000625s/cm, and the filtration efficiency of the filter membrane on particles with the particle size of 0.1-0.5 mu m is 97.5%.
Example 4:
a preparation method of a graphene-based conductive filter membrane comprises the following steps:
step one, placing a polypropylene film in a filter cup of a vacuum filtration device, then adding 5mL of graphene oxide dispersion liquid with the concentration of 2mg/L into the filter cup, starting a vacuum pump of the vacuum filtration device, controlling the filtration pressure to be 0.008-0.020 MPa, carrying out vacuum filtration, and preparing the graphene oxide dispersion liquidThe base film loaded with the graphene oxide is placed in a vacuum oven at 70 ℃ for drying; the polypropylene film has a thickness of 1mm, a diameter of 50mm and an area pi r2＝19.625cm2；
Placing the graphene oxide-loaded polypropylene membrane on a culture dish, dropwise adding 100 mu L of hydrazine hydrate solution into the culture dish, fumigating the culture dish in an oven at 70 ℃ for 15min, and taking out the culture dish to obtain the graphene-based conductive filter membrane; the concentration of the hydrazine hydrate solution is 80 wt%; the conductivity of the filter membrane is 0.000436s/cm, and the filtration efficiency of the filter membrane on particles with the particle size of 0.1-0.5 mu m is 94.5%.
Example 5:
a preparation method of a graphene-based conductive filter membrane comprises the following steps:
putting a polycarbonate film into a filter cup of a vacuum filtration device, then adding 5mL of graphene oxide dispersion liquid with the concentration of 2mg/L into the filter cup, starting a vacuum pump of the vacuum filtration device, controlling the filtration pressure to be 0.008-0.020 MPa, carrying out vacuum filtration, and drying the prepared graphene oxide-loaded base film in a vacuum oven at 70 ℃; the polycarbonate film has a thickness of 1mm, a diameter of 50mm and an area of pi r2＝19.625cm2(ii) a The preparation method of the polycarbonate membrane comprises the following steps: dissolving polycarbonate in a mixed solvent of chloroform and DMF to obtain a polycarbonate solution with the mass fraction of 6%, namely a shell solution, wherein the volume ratio of chloroform to DMF is 5: 1; dissolving polyoxyethylene in water to obtain a polyoxyethylene solution with the mass fraction of 4%, namely a nuclear layer solution, respectively injecting the shell layer solution and the nuclear layer solution into an outer layer and an inner layer of a stainless steel coaxial nozzle in an electrostatic spinning machine, applying voltage between the stainless steel coaxial nozzle and a receiving flat plate, paving tin foil paper on the receiving flat plate, then spraying the shell layer solution and the nuclear layer solution onto the tin foil paper of the receiving flat plate under the condition of high-voltage electrostatic spraying to form a fiber membrane, drying the fiber membrane, adding the dried fiber membrane into the water, and ultrasonically soaking for 12 hours at the ultrasonic frequency of 40 kHz; fishing out the fiber film and drying; obtaining a polycarbonate film; the high-voltage electrostatic spraying conditions are as follows: the environment temperature of the electrostatic spinning machine is 45 ℃, and the output voltage of the high-voltage power supply is 18kVThe distance between the receiving flat plate and a spinneret orifice of the stainless steel coaxial nozzle is 8cm, the flow rate of the nuclear layer solution is 6mL/h, and the flow rate ratio of the nuclear layer solution to the shell layer solution is 1: 2; the inner diameter of an inner needle head of the stainless steel coaxial nozzle is 0.6mm, and the inner diameter of an outer needle head of the stainless steel coaxial nozzle is 1.2 mm;
placing the polycarbonate membrane loaded with the graphene oxide on a culture dish, dropwise adding 100 mu L of hydrazine hydrate solution into the culture dish, fumigating the culture dish in an oven at 70 ℃ for 15min, and taking out the culture dish to obtain the graphene-based conductive filter membrane; the concentration of the hydrazine hydrate solution is 80 wt%; the conductivity of the filter membrane is 0.000441s/cm, and the filtration efficiency of the filter membrane on particles with the particle size of 0.1-0.5 mu m is 95.3%.
Example 6:
a preparation method of a graphene-based conductive filter membrane comprises the following steps:
step one, putting a polycaprolactone film into a filter cup of a vacuum filtration device, then adding 5mL of graphene oxide dispersion liquid with the concentration of 2mg/L into the filter cup, starting a vacuum pump of the vacuum filtration device, controlling the filtration pressure to be 0.008-0.020 MPa, carrying out vacuum filtration, and drying the prepared graphene oxide loaded base film in a vacuum oven at 70 ℃; the thickness of the polycaprolactone film is 1mm, the diameter of the polycaprolactone film is 50mm, and the area pi r of the polycaprolactone film2＝19.625cm2(ii) a Dissolving polycaprolactone in a mixed solvent of chloroform and DMF to obtain a polycaprolactone solution with the mass fraction of 6%, namely a shell solution, wherein the volume ratio of chloroform to DMF is 5: 1; dissolving polyoxyethylene in water to obtain a polyoxyethylene solution with the mass fraction of 4%, namely a nuclear layer solution, respectively injecting the shell layer solution and the nuclear layer solution into an outer layer and an inner layer of a stainless steel coaxial nozzle in an electrostatic spinning machine, applying voltage between the stainless steel coaxial nozzle and a receiving flat plate, paving tin foil paper on the receiving flat plate, then spraying the shell layer solution and the nuclear layer solution onto the tin foil paper of the receiving flat plate under the condition of high-voltage electrostatic spraying to form a fiber membrane, drying the fiber membrane, adding the dried fiber membrane into the water, and ultrasonically soaking for 12 hours at the ultrasonic frequency of 40 kHz; fishing out the fiber film and drying; obtaining a polycaprolactone film; the high-voltage electrostatic spraying conditions are as follows: the ambient temperature in the electrostatic spinning machine is 45 ℃, and the high pressure isThe output voltage of the power supply is 18kV, the distance between the receiving flat plate and a spinneret orifice of the stainless steel coaxial nozzle is 8cm, the flow rate of the nuclear layer solution is 6mL/h, and the flow rate ratio of the nuclear layer solution to the shell layer solution is 1: 2; the inner diameter of an inner needle head of the stainless steel coaxial nozzle is 0.6mm, and the inner diameter of an outer needle head of the stainless steel coaxial nozzle is 1.2 mm;
placing the graphene oxide-loaded polycaprolactone membrane on a culture dish, dropwise adding 100 mu L of hydrazine hydrate solution into the culture dish, fumigating the culture dish in an oven at 70 ℃ for 15min, and taking out the culture dish to obtain the graphene-based conductive filter membrane; the concentration of the hydrazine hydrate solution is 80 wt%; the conductivity of the filter membrane is 0.000439s/cm, and the filtration efficiency of the filter membrane on particles with the particle size of 0.1-0.5 mu m is 95.0%.
Example 7:
a preparation method of a graphene-based conductive filter membrane comprises the following steps:
putting a polycarbonate-polycaprolactone composite film into a filter cup of a vacuum filtration device, then adding 5mL of graphene oxide dispersion liquid with the concentration of 2mg/L into the filter cup, starting a vacuum pump of the vacuum filtration device, controlling the filtration pressure to be 0.008-0.020 MPa, carrying out vacuum filtration, and drying the prepared graphene oxide-loaded base film in a vacuum oven at 70 ℃; the thickness of the polycarbonate-polycaprolactone composite membrane is 1mm, the diameter is 50mm, and the area pi r2＝19.625cm2(ii) a The preparation method of the polycarbonate-polycaprolactone composite film comprises the following steps: dissolving polycarbonate and polycaprolactone in a mass ratio of 4:1 in a mixed solvent of chloroform and DMF to obtain a polycarbonate-polycaprolactone mixed solution with a mass fraction of 6%, namely a shell solution, wherein the volume ratio of chloroform to DMF is 5: 1; dissolving polyoxyethylene in water to obtain a polyoxyethylene solution with the mass fraction of 4%, namely a nuclear layer solution, respectively injecting the shell layer solution and the nuclear layer solution into an outer layer and an inner layer of a stainless steel coaxial nozzle in an electrostatic spinning machine, applying voltage between the stainless steel coaxial nozzle and a receiving flat plate, paving tin foil paper on the receiving flat plate, then spraying the shell layer solution and the nuclear layer solution on the tin foil paper of the receiving flat plate under the condition of high-voltage electrostatic spraying to form a fiber membrane, drying the fiber membrane, adding the dried fiber membrane into the water for ultra-treatmentSoaking for 12h by sound to dissolve the polycaprolactone fiber of the inner layer in water to form a hollow polycarbonate-polycaprolactone composite membrane; the frequency of the ultrasound is 40 kHz; fishing out the fiber film and drying; obtaining a polycarbonate-polycaprolactone composite film; the high-voltage electrostatic spraying conditions are as follows: the environment temperature in the electrostatic spinning machine is 45 ℃, the output voltage of a high-voltage power supply is 18kV, the distance between a receiving flat plate and a stainless steel coaxial nozzle spinning nozzle is 8cm, the flow rate of a nuclear layer solution is 6mL/h, and the flow rate ratio of the nuclear layer solution to a shell layer solution is 1: 2; the inner diameter of an inner needle head of the stainless steel coaxial nozzle is 0.6mm, and the inner diameter of an outer needle head of the stainless steel coaxial nozzle is 1.2 mm;
placing the graphene oxide-loaded base membrane on a culture dish, dropwise adding 100 mu L of hydrazine hydrate solution into the culture dish, fumigating the culture dish in an oven at 70 ℃ for 15min, and taking out the fumigated product to obtain the graphene-based conductive filter membrane; the concentration of the hydrazine hydrate solution is 80 wt%; the conductivity of the filter membrane is 0.000658s/cm, and the filtration efficiency of the filter membrane on particles with the particle size of 0.1-0.5 mu m is 98.5%.
Example 8:
a preparation method of a graphene-based conductive filter membrane comprises the following steps:
putting a polycarbonate-polycaprolactone composite film into a filter cup of a vacuum filtration device, then adding 5mL of graphene oxide dispersion liquid with the concentration of 2mg/L into the filter cup, starting a vacuum pump of the vacuum filtration device, controlling the filtration pressure to be 0.008-0.020 MPa, carrying out vacuum filtration, and drying the prepared graphene oxide-loaded base film in a vacuum oven at 70 ℃; the thickness of the polycarbonate-polycaprolactone composite membrane is 1mm, the diameter is 50mm, and the area pi r2＝19.625cm2(ii) a The preparation method of the polycarbonate-polycaprolactone composite film comprises the following steps: dissolving polycarbonate and polycaprolactone in a mass ratio of 4:1 in a mixed solvent of chloroform and DMF to obtain a polycarbonate-polycaprolactone mixed solution with a mass fraction of 6%, namely a shell solution, wherein the volume ratio of chloroform to DMF is 5: 1; dissolving polyoxyethylene in water to obtain a polyoxyethylene solution with the mass fraction of 4%, namely a nuclear layer solution, and respectively injecting the shell layer solution and the nuclear layer solution into the outer layer of a stainless steel coaxial nozzle in an electrostatic spinning machineThe inner layer is applied with voltage between the stainless steel coaxial spray head and the receiving flat plate, the receiving flat plate is paved with tin foil paper, then the shell layer solution and the nuclear layer solution are sprayed on the tin foil paper of the receiving flat plate under the high-voltage electrostatic spraying condition to form a fiber film, the fiber film is dried, the dried fiber film is added into water for ultrasonic soaking for 12 hours, and the ultrasonic frequency is 40 kHz; fishing out the fiber film and drying; the polycarbonate-polycaprolactone composite membrane is obtained, under the conditions of the wavelength of 800nm, the pulse width of 80fs and the repetition frequency of 2KHz, the surface of the polycarbonate-polycaprolactone composite membrane is treated for 0.5s by using femtosecond laser, and the surface appearance of the polycarbonate-polycaprolactone composite membrane is changed by using the femtosecond laser treatment, so that the loading of graphene oxide is facilitated; the high-voltage electrostatic spraying conditions are as follows: the environment temperature in the electrostatic spinning machine is 45 ℃, the output voltage of a high-voltage power supply is 18kV, the distance between a receiving flat plate and a stainless steel coaxial nozzle spinning nozzle is 8cm, the flow rate of a nuclear layer solution is 6mL/h, and the flow rate ratio of the nuclear layer solution to a shell layer solution is 1: 2; the inner diameter of an inner needle head of the stainless steel coaxial nozzle is 0.6mm, and the inner diameter of an outer needle head of the stainless steel coaxial nozzle is 1.2 mm;
placing the graphene oxide-loaded base membrane on a culture dish, dropwise adding 100 mu L of hydrazine hydrate solution into the culture dish, fumigating the culture dish in an oven at 70 ℃ for 15min, and taking out the fumigated product to obtain the graphene-based conductive filter membrane; the concentration of the hydrazine hydrate solution is 80 wt%; the conductivity of the filter membrane is 0.000714s/cm, and the filtration efficiency of the filter membrane on particles with the particle size of 0.1-0.5 mu m is 99.5%.
In examples 1 to 8, the method for testing the average filtering efficiency of the graphene-based conductive filter membrane on particles of 0.1 to 0.5 μm is as follows:
1. test conditions
And (3) specification of filter paper: 50mm 1mm (diameter thickness); and (3) testing flow: 60L/min (3.6 m)2H); effective collecting area for test of 15.90cm2；
2. Test method and process
2.1 test methods
And testing by adopting a double-filter membrane method.
2.2 test procedure
The experimental method of membrane filtration sampling is shown in fig. 5. Placing two pieces of filter paper, namely a test filter paper and a high-efficiency filter paper (the filter efficiency is more than 99%), in the sampling box, placing the test filter paper at the top and the high-efficiency filter paper at the bottom; radon daughter aerosol particles in the air are taken as a sampling object.
Starting the air pump, adjusting the sampling flow (mass flow) to the testing flow, keeping constant-flow sampling, taking off two filter papers after proper sampling time, and respectively carrying out α counting measurement on the filter papers, wherein the characteristic of the natural radon aerosol particle size is generally regarded as AMAD (American society of Industrial science) 0.1-0.5 (mum), sigma and the likegThe radon daughter aerosol is 1.5-2.5, so the method for testing the filtration efficiency of the filter membrane taking the radon daughter aerosol as a sampling object is feasible.
The activity counts on the two filters after sampling were measured several times at equal time intervals by an α (or β) counting meter.
In the formula, E (f)1) To test the filtration efficiency of the filter paper, N (f)1) And N (f)0) The α activity count rates were tested for filter paper and high efficiency filter paper, respectively.
3. Test results
According to the above method, after sampling and counting measurement of the provided filter membrane sample, it is also necessary to correct inequivalence of the counting measurement result due to decay on the filter paper in data processing. After data correction, the filter paper filtration efficiency results were obtained as follows:
TABLE 1 filtration efficiency test results
| Examples | N(f1)*T | N(f0)*T | Efficiency of |
| 1 | 2152 | 85 | 96.2％ |
| 2 | 2411 | 72 | 97.1％ |
| 3 | 2301 | 59 | 97.5％ |
| 4 | 1203 | 70 | 94.5％ |
| 5 | 1176 | 58 | 95.3％ |
| 6 | 1425 | 75 | 95.0％ |
| 7 | 3612 | 55 | 98.5％ |
| 8 | 5970 | 30 | 99.5％ |
While embodiments of the invention have been described above, it is not limited to the applications set forth in the description and the embodiments, which are fully applicable in various fields of endeavor to which the invention pertains, and further modifications may readily be made by those skilled in the art, it being understood that the invention is not limited to the details shown and described herein without departing from the general concept defined by the appended claims and their equivalents.
Claims (10)
1. A preparation method of a graphene-based conductive filter membrane is characterized by comprising the following steps:
placing a base film in a filter cup of a vacuum filtration device, then adding the graphene oxide dispersion liquid into the filter cup, starting a vacuum pump of the vacuum filtration device, controlling the filtration pressure to be between 0.008 and 0.020MPa, carrying out vacuum filtration, and drying the prepared graphene oxide loaded base film in a vacuum oven at 65-75 ℃;
and step two, placing the graphene oxide-loaded base membrane on a culture dish, dropwise adding a hydrazine hydrate solution into the culture dish, fumigating the culture dish in an oven at the temperature of 65-75 ℃ for 15-45 min, and taking out the culture dish to obtain the graphene-based conductive filter membrane.
2. The method for preparing the graphene-based conductive filter membrane according to claim 1, wherein the concentration of the graphene oxide dispersion liquid is 1-6 mg/L; the thickness of the base film is 0.5-3 mm.
3. The method for preparing the graphene-based conductive filter membrane according to claim 1, wherein the ratio of the amount of the graphene oxide dispersion liquid to the surface area of the base membrane is as follows: 1mL of 3-4 cm2。
4. The preparation method of the graphene-based conductive filter membrane according to claim 1, wherein the concentration of the hydrazine hydrate solution is 60-80 wt%; the volume ratio of the hydrazine hydrate solution to the graphene oxide dispersion liquid is 1: 30-60.
5. The method of claim 1, wherein the base membrane is any one of a glass fiber membrane, a polypropylene membrane, a polyacrylonitrile membrane, a nylon membrane, a polycarbonate membrane, and a polycaprolactone membrane.
6. The method of preparing a graphene-based conductive filter membrane according to claim 1, wherein the glass fiber membrane is a borosilicate glass fiber membrane.
7. The method for preparing the graphene-based conductive filter membrane according to claim 1, wherein the base membrane is a polycarbonate-polycaprolactone composite membrane, and the method for preparing the graphene-based conductive filter membrane comprises the following steps: dissolving polycarbonate and polycaprolactone in a mass ratio of 3-5: 1 in a mixed solvent of chloroform and DMF to obtain a polycarbonate-polycaprolactone mixed solution with a mass fraction of 5-8%, namely a shell solution, wherein the volume ratio of chloroform to DMF is (4-6): 1; dissolving polyoxyethylene in water to obtain a polyoxyethylene solution with the mass fraction of 3-5%, namely a nuclear layer solution, respectively injecting the shell layer solution and the nuclear layer solution into an outer layer and an inner layer of a stainless steel coaxial nozzle in an electrostatic spinning machine, applying voltage between the stainless steel coaxial nozzle and a receiving flat plate, paving tin foil paper on the receiving flat plate, then spraying the shell layer solution and the nuclear layer solution onto the tin foil paper of the receiving flat plate under a high-voltage electrostatic spraying condition to form a fiber membrane, drying the fiber membrane, adding the dried fiber membrane into the water, and ultrasonically soaking for 12 hours, wherein the ultrasonic frequency is 35-45 kHz; fishing out the fiber film and drying; obtaining the polycarbonate-polycaprolactone composite film.
8. The method for preparing the graphene-based conductive filter membrane according to claim 1, wherein the high-voltage electrostatic spraying conditions are as follows: the environment temperature in the electrostatic spinning machine is 40-55 ℃, the output voltage of a high-voltage power supply is 15-20 kV, the distance between a receiving flat plate and a stainless steel coaxial nozzle spinning nozzle is 5-10cm, the flow rate of a nuclear layer solution is 5-10 mL/h, and the flow rate ratio of the nuclear layer solution to a shell layer solution is 1: 2; the inner diameter of the inner needle head of the stainless steel coaxial nozzle is 0.5-0.8 mm, and the inner diameter of the outer needle head is 1.2-1.6 mm.
9. The method for preparing a graphene-based conductive filter membrane according to claim 7, wherein the obtained polycarbonate-polycaprolactone composite membrane is reprocessed, and the process is as follows: and (3) treating the surface of the polycarbonate-polycaprolactone composite film for 0.5-0.6 s by using femtosecond laser under the conditions of a wavelength of 800nm, a pulse width of 50-80 fs and a repetition frequency of 2-3 KHz.
10. The graphene-based conductive filter membrane prepared by the preparation method of the graphene-based conductive filter membrane according to any one of claims 1 to 9, wherein the conductivity of the graphene-based conductive filter membrane is 0.0004 to 0.0006s/cm, and the average filtration efficiency of the graphene-based conductive filter membrane on 0.1 to 0.5 μm particles is 96 to 98%.
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