CN114950154B - Polydopamine modified carbon nanotube-graphene oxide film and preparation method and application thereof - Google Patents

Polydopamine modified carbon nanotube-graphene oxide film and preparation method and application thereof Download PDF

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CN114950154B
CN114950154B CN202210516180.3A CN202210516180A CN114950154B CN 114950154 B CN114950154 B CN 114950154B CN 202210516180 A CN202210516180 A CN 202210516180A CN 114950154 B CN114950154 B CN 114950154B
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CN114950154A (en
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郭谨
盖晓莉
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Beijing University of Technology
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
    • B01D69/12—Composite membranes; Ultra-thin membranes
    • B01D69/125—In situ manufacturing by polymerisation, polycondensation, cross-linking or chemical reaction
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    • B01D67/0081—After-treatment of organic or inorganic membranes
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    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
    • B01D69/02—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor characterised by their properties
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    • B01D71/66—Polymers having sulfur in the main chain, with or without nitrogen, oxygen or carbon only
    • B01D71/68—Polysulfones; Polyethersulfones
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/44—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis
    • C02F1/442—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis by nanofiltration
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    • B—PERFORMING OPERATIONS; TRANSPORTING
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Abstract

The invention belongs to the technical field of membrane separation, and particularly relates to a polydopamine modified carbon nanotube-graphene oxide membrane, and a preparation method and application thereof. According to the polydopamine modified carbon nanotube-graphene oxide film provided by the invention, graphene oxides have a layered structure and are mutually stacked, a interception and screening effect is exerted on the bottom layer, the carbon nanotubes have extremely high specific surface area and good adsorption performance, a pre-adsorption effect is exerted on the surface layer, and the pollution-receiving capability of the polydopamine modified carbon nanotube-graphene oxide film is enhanced; the polydopamine is wrapped on the surface of the carbon nano tube, and the hydrophilia of the carbon nano tube can be improved due to the polydopamine having a plurality of hydrophilic groups, so that the dopamine-modified carbon nano tube membrane can form a hydrophilic layer with the preferential action of water molecules, pollutants are effectively prevented from entering membrane holes, irreversible pollution can be effectively reduced, and the anti-pollution effect of the polydopamine-modified carbon nano tube-graphene oxide membrane is improved.

Description

Polydopamine modified carbon nanotube-graphene oxide film and preparation method and application thereof
Technical Field
The invention belongs to the technical field of membrane separation, and particularly relates to a polydopamine modified carbon nanotube-graphene oxide membrane, and a preparation method and application thereof.
Background
The membrane separation technology has become one of the most development potential technologies in the water treatment field in recent years because of the advantages of low energy consumption, no secondary pollution, flexible and convenient operation, environmental friendliness and the like. The film is classified into an organic film and an inorganic film according to the material of the film. The organic film is also called a polymer film and is formed by processing an organic polymer material, such as PVDF, PES, PAN. The conventional polymer nanofiltration membrane structure consists of a porous supporting layer and a compact cortex, wherein the supporting layer at the bottom layer plays a supporting role, and the cortex at the surface plays a screening role.
Graphene Oxide (GO) contains rich oxygen-containing functional groups (such as hydroxyl, carboxyl, carbonyl and epoxy groups), GO is highly accumulated on the surface of the support membrane to form a compact layered structure, and nano channels between GO sheets only allow water molecules to pass through and entrap other pollutants larger than interlayer spacing, so that the carbon nano material nanofiltration membrane is novel. However, the GO membrane has a compact structure, so that pollutants are easily accumulated on the surface of the membrane to pollute a cake layer. Carbon Nanotubes (CNTs) have a very high specific surface area, and are ideal adsorption materials. The carbon nano tube can remove pollutants in water through Van der Waals force, hydrogen bond, pi-pi bond and the like, and can be applied as an inorganic film. Research shows that the carbon nanotube film prepared by vacuum filtering the carbon nanotubes on the film surface improves the removal of plugging pollutants in water, but the irreversible pollution of the carbon nanotube film is further increased due to the hydrophobic nature of the carbon nanotubes.
Disclosure of Invention
In view of the above, the invention aims to provide a polydopamine modified carbon nanotube-graphene oxide film, and a preparation method and application thereof.
In order to achieve the above object, the present invention provides the following technical solutions:
the invention provides a polydopamine modified carbon nanotube-graphene oxide film, which comprises a polyether sulfone base film, a graphene oxide layer bonded on the polyether sulfone base film and a polydopamine modified carbon nanotube layer attached to the surface of the graphene oxide layer.
Preferably, the ratio of the mass of the graphene oxide layer to the area of the polyethersulfone membrane is (0.03-0.1) mg:28.27 cm 2 The method comprises the steps of carrying out a first treatment on the surface of the The ratio of the mass of the polydopamine modified carbon nano tube to the area of the polyethersulfone membrane is (20-60) mg:28.27 cm 2 。
The invention also provides a preparation method of the polydopamine modified carbon nanotube-graphene oxide membrane, which comprises the following steps:
after the graphene oxide dispersion liquid and the polyethersulfone membrane are first compounded, modifying to obtain a graphene oxide modified membrane;
mixing carbon nanotubes, an organic solvent, dopamine and a buffer solution, and performing polymerization reaction to obtain polydopamine modified carbon nanotube dispersion;
and carrying out second compounding on the polydopamine modified carbon nanotube dispersion liquid and the graphene oxide modified membrane, and then carrying out loading to obtain the polydopamine modified carbon nanotube-graphene oxide membrane.
Preferably, the first compounding and the second compounding are both positive pressure filtration; the pressure of the positive pressure filtration is independently 0.1-0.2 MPa.
Preferably, the concentration of the graphene oxide dispersion liquid is 0.2g/L; the ratio of the volume of the graphene oxide dispersion liquid to the area of the polyethersulfone membrane is (0.15-0.5) mL:28.27 cm 2 。
Preferably, the pore diameter of the polyethersulfone-based membrane is 100kDa; the effective filtration area of the polyethersulfone-based membrane is 28.27cm 2 。
Preferably, the mass ratio of the carbon nano tube to the dopamine is (10-30) to (10-30); the concentration of the dopamine solution is 1-2 g/L; the concentration of the polydopamine modified carbon nano tube dispersion liquid is 0.33-0.92 g/L; the ratio of the volume of the polydopamine modified carbon nanotube dispersion liquid to the area of the graphene oxide modified polyether sulfone membrane is (55-80) mL:28.27 cm 2 。
Preferably, the buffer solution is a tris buffer solution; the concentration of the buffer solution is 10-50 mmol/L; the pH value of the buffer solution is 8.5-10.
Preferably, the carbon nanotubes are multiwall carbon nanotubes; the outer diameter of the carbon nano tube is 10-20 nm.
The invention also provides an application of the polydopamine modified carbon nano tube-graphene oxide membrane prepared by the technical scheme or the polydopamine modified carbon nano tube-graphene oxide membrane prepared by the preparation method in sewage treatment.
The invention provides a polydopamine modified carbon nanotube-graphene oxide film, which comprises a polyether sulfone base film, a graphene oxide layer bonded on the polyether sulfone base film and a polydopamine modified carbon nanotube layer attached to the surface of the graphene oxide layer. The polydopamine modified carbon nanotube-graphene oxide film provided by the invention has a structure that an upper layer is loose and a lower layer is compact, graphene oxides in the lower layer are stacked mutually, the size distribution of the graphene oxides in the lower layer is very narrow, the interception and screening functions are exerted on the lower layer, the polydopamine modified carbon nanotube in the upper layer is loose in structure, the carbon nanotubes have extremely high specific surface area and good adsorption performance, and the pre-adsorption function is exerted on the surface layer, so that the pollution-receiving capacity of the polydopamine modified carbon nanotube-graphene oxide film is enhanced; after the Polydopamine (PDA) is used for modifying the carbon nano tube, as the PDA has a plurality of hydrophilic groups such as amino and hydroxyl, the hydrophilicity of the carbon nano tube can be improved, so that the polydopamine modified carbon nano tube film can preferentially act with water molecules to form a hydrophilic layer, pollutants are effectively prevented from entering into a film hole, irreversible pollution can be effectively reduced, the anti-pollution effect of the polydopamine modified carbon nano tube-graphene oxide film is improved, and the polydopamine modified carbon nano tube-graphene oxide film provided by the invention has high pollutant receiving capacity and good anti-pollution effect.
Drawings
Fig. 1 is a schematic structural diagram of a polydopamine modified carbon nanotube-graphene oxide film provided by the application;
FIG. 2 is a XPS contrast plot of the carbon nanotubes and polydopamine modified carbon nanotubes of example 1;
fig. 3 is a graph showing contact angle comparison of the carbon nanotube and polydopamine-modified carbon nanotube film of example 1.
Fig. 4 is a graph of pure water flux of the polydopamine-modified carbon nanotube-graphene oxide membrane, graphene oxide-modified membrane, polydopamine-modified carbon nanotube membrane, and polyethersulfone-based membrane of example 1 under different pressures;
FIG. 5 is a graph showing the removal rate of humic acid from the polydopamine-modified carbon nanotube-graphene oxide film, graphene oxide-modified film, polydopamine-modified carbon nanotube film, and polyethersulfone-based film in example 1;
FIG. 6 is a three-dimensional fluorescence plot of membrane-filtered water after 4h of humic acid filtration by polydopamine-modified carbon nanotube-graphene oxide membrane, graphene oxide-modified membrane, polydopamine-modified carbon nanotube membrane, polyethersulfone-based membrane in example 1;
fig. 7 is a graph showing the specific fluxes of the polydopamine-modified carbon nanotube-graphene oxide membrane, the graphene oxide-modified membrane, the polydopamine-modified carbon nanotube membrane, and the polyethersulfone membrane in example 1.
Detailed Description
The invention provides a polydopamine modified carbon nanotube-graphene oxide film, which comprises a polyether sulfone base film, a graphene oxide layer bonded on the polyether sulfone base film and a polydopamine modified carbon nanotube layer attached to the surface of the graphene oxide layer.
In the present invention, the ratio of the mass of the graphene oxide layer to the area of the polyethersulfone-based membrane is preferably (0.03 to 0.1) mg:28.27 cm 2 More preferably 0.03 mg/28.27 cm 2 The method comprises the steps of carrying out a first treatment on the surface of the The ratio of the mass of the polydopamine modified carbon nano tube and the area of the polyethersulfone membrane is preferably (20-60) mg:28.27 cm 2 More preferably 20 mg:28.27 cm 2 。
Fig. 1 is a schematic structural diagram of a polydopamine modified carbon nanotube-graphene oxide membrane provided by the application. As shown in fig. 1, the polydopamine modified carbon nanotube-graphene oxide film provided by the application is characterized in that a polyethersulfone membrane is used as a bottom, a graphene oxide layer is bonded on the polyethersulfone membrane, and a polydopamine modified carbon nanotube layer is attached on the graphene oxide layer, so that an upper loose and lower compact structure is formed.
The invention also provides a preparation method of the polydopamine modified carbon nanotube-graphene oxide membrane, which comprises the following steps:
after the graphene oxide dispersion liquid and the polyethersulfone membrane are first compounded, modifying to obtain a graphene oxide modified membrane;
mixing carbon nanotubes, an organic solvent, dopamine and a buffer solution, and performing polymerization reaction to obtain polydopamine modified carbon nanotube dispersion;
and carrying out second recombination on the polydopamine modified carbon nanotube dispersion liquid and the graphene oxide modified polyether sulfone membrane, and then carrying out loading to obtain the polydopamine modified carbon nanotube-graphene oxide membrane.
The present invention is not limited to the specific source of the raw materials used, and may be commercially available products known to those skilled in the art, unless otherwise specified.
According to the invention, after the graphene oxide dispersion liquid and the polyether sulfone membrane are first compounded, modification is carried out.
In the preparation process of the graphene oxide dispersion liquid, preferably, graphene oxide powder and water are mixed, ultrasonic treatment and centrifugation are sequentially carried out, then graphene oxide aggregates are removed, and supernatant liquid is removed to obtain the graphene oxide dispersion liquid; the power of the ultrasound is preferably 300W; the ultrasonic mode is preferably water bath ultrasonic; the time of the ultrasonic treatment is preferably 60 minutes; the rate of centrifugation is preferably 11000rpm; the time of the centrifugation is preferably 15min.
In the present invention, the pore diameter of the polyethersulfone-based membrane is preferably 100kDa; the effective filtration area of the polyethersulfone-based membrane is preferably 28.27cm 2 。
In the present invention, the concentration of the graphene oxide dispersion is preferably 0.2g/L; the ratio of the volume of the graphene oxide dispersion liquid to the area of the polyethersulfone membrane is preferably (0.15-0.5) mL:28.27 cm 2 More preferably 0.15 mL:28.27 cm 2 The method comprises the steps of carrying out a first treatment on the surface of the The first compounding mode is preferably positive pressure filtration; the positive pressure filtration is preferably performed by a positive pressure filtration device; the pressure of the positive pressure filtration is preferably 0.1 to 0.2MPa, more preferably 0.1MPa.
In the modification process, the hydrogen bond interaction between the carboxyl on the graphene oxide and the sulfonic acid group on the polyethersulfone membrane stabilizes the graphene oxide layer on the surface of the polyethersulfone membrane to form the graphene oxide membrane.
After the modification is completed, the modified film is preferably cleaned to obtain the graphene oxide modified film. In the invention, the solution used for cleaning is ultrapure water; in the present invention, it is preferable that the TOC value of the solution after the washing is equal to the TOC value of pure water in the washing step.
According to the invention, the carbon nano tube, the organic solvent, the dopamine and the buffer solution are mixed for polymerization reaction, so that the polydopamine modified carbon nano tube dispersion liquid is obtained.
In the present invention, the carbon nanotubes are preferably multiwall carbon nanotubes; the outer diameter of the carbon nano tube is preferably 10-20 nm; the organic solvent is preferably absolute ethanol.
In the present invention, the buffer solution is preferably a Tris buffer solution; the preparation process of the Tris buffer solution is preferably to dissolve Tris in water and then to adjust the pH with hydrochloric acid; the concentration of the buffer solution is preferably 10 to 50mmol/L, more preferably 10mmol/L; the ratio of the mass of the carbon nano tube to the volume of the buffer solution is preferably 10mg to 10mL; the pH of the buffer solution is preferably 8.5 to 10, more preferably 8.5.
In the invention, the mixing process of the carbon nano tube, the organic solvent, the dopamine and the buffer solution is preferably to mix the carbon nano tube and the organic solvent, carry out ultrasonic treatment, then add the dopamine to stir, and finally add the buffer solution; the ultrasound is preferably performed under ice bath conditions; the ultrasonic equipment is preferably an ultrasonic breaker; the power of the ultrasound is preferably 150W; the time of the ultrasonic treatment is preferably 15min; the stirring is preferably magnetic stirring.
In the invention, the mass ratio of the carbon nano tube to the dopamine is preferably (10-30) to (10-30), more preferably 10:10; the ratio of the mass of the carbon nanotubes to the volume of the organic solvent is preferably 10mg:50mL.
In the present invention, the temperature of the polymerization reaction is preferably 40 ℃; the polymerization reaction is preferably carried out under the condition of constant temperature water bath; the polymerization time is preferably 5 hours.
Because the polydopamine formed by self-polymerization of the dopamine has adhesiveness, the dopamine-modified carbon nanotube layer can be physically adsorbed on the graphene oxide layer, so that the structure of the whole formed composite membrane is stable. Dopamine is self-polymerized into Polydopamine (PDA) to wrap the surface of the carbon nano tube under the weak base condition, and the PDA has a plurality of hydrophilic groups such as amino and hydroxyl, so that the hydrophilicity of the carbon nano tube can be improved.
After the graphene oxide modified polyethersulfone-based membrane and the polydopamine modified carbon nanotube dispersion liquid are obtained, the polydopamine modified carbon nanotube dispersion liquid and the graphene oxide modified membrane are subjected to second compounding and then are loaded, so that the polydopamine modified carbon nanotube-graphene oxide membrane is obtained.
In the present invention, the concentration of the polydopamine-modified carbon nanotube dispersion is preferably 0.33 to 0.92g/L, more preferably 0.33g/L; the ratio of the volume of the polydopamine modified carbon nanotube dispersion liquid to the area of the graphene oxide modified polyether sulfone membrane is preferably (55-80) mL:28.27 cm 2 Preferably 60 mL:28.27 cm 2 。
In the present invention, the second compounding mode is preferably positive pressure filtration; the positive pressure filtration is preferably performed by a positive pressure filtration device; the pressure of the positive pressure filtration is preferably 0.1 to 0.2MPa, more preferably 0.1MPa.
After loading is completed, the membrane obtained by loading is preferably cleaned and dried to obtain the polydopamine modified carbon nano tube-graphene oxide membrane.
In the present invention, the solution for cleaning is preferably ultrapure water; in the present invention, it is preferable that the TOC value of the solution after washing is the same as the TOC value of pure water in the washing step; the drying is preferably vacuum drying; the temperature of the drying is preferably 50 ℃; the drying time is preferably 15 minutes.
The invention also provides an application of the polydopamine modified carbon nano tube-graphene oxide membrane prepared by the technical scheme or the polydopamine modified carbon nano tube-graphene oxide membrane prepared by the preparation method in sewage treatment.
In the invention, the pure water flux of the polydopamine modified carbon nano tube-graphene oxide membrane under 0.1Mpa is 15L/(m) 2 H), the polydopamine modified carbon nanotube-graphene oxide membrane provided by the invention is a nanofiltration membrane.
The application mode of the polydopamine modified carbon nanotube-graphene oxide membrane in sewage treatment is not particularly limited, and the application mode well known in the art can be adopted.
The technical solutions of the present invention will be clearly and completely described in the following in connection with the embodiments of the present invention.
Example 1
Weighing 10mg of graphene oxide powder, dissolving in 50mL of pure water, performing water bath ultrasonic treatment at 300W for 60min, centrifuging at 11000rpm for 15min, removing graphene oxide aggregates, and removing graphene oxide supernatant to obtain graphene oxide dispersion liquid;
a100 kDa molecular weight Polyethersulfone (PES) based membrane was placed in a positive pressure filtration apparatus and 0.15mL of the graphene oxide dispersion was pressure filtered to 28.27cm 2 The surface of the polyethersulfone membrane is applied with the pressure of 0.1MPa, and is cleaned by pure water after being filtered to obtain a graphene oxide modified membrane (GO membrane);
12.1mg of Tris is weighed and dissolved in 10mL of water, and the pH value is adjusted to 8.5 by hydrochloric acid to obtain a Tris buffer solution (10 mmol/L, pH=8.5);
weighing 10mg of carbon nano tube (with the outer diameter of 10-20 nm), dissolving in 50mL of absolute ethyl alcohol, carrying out ice bath ultrasonic treatment for 15min under 150W power by adopting an ultrasonic crusher, adding 0.1g of Dopamine (DA), magnetically stirring, adding 10mLTris buffer solution after 15min, and reacting for 5h under 40 ℃ constant-temperature water bath to obtain polydopamine modified carbon nano tube dispersion liquid (with the concentration of 0.33 g/L);
placing the graphene oxide modified polyether sulfone membrane into a positive pressure filter device, and filtering 60mL of the polydopamine modified carbon nanotube dispersion liquid to 28.27cm by adopting a pressure filtration mode 2 And (3) applying pressure of 0.1Mpa on the surface of the graphene oxide modified film, filtering, cleaning with pure water, and vacuum drying at 50 ℃ for 15min to obtain the polydopamine modified carbon nanotube-graphene oxide film (PDA/CNT-GO film).
Example 2
The difference from example 1 is that the mass of the carbon nanotubes was replaced with 30mg, which is consistent with that of example 1.
Comparative example 1
The polydopamine modified carbon nanotube dispersion liquid prepared in the embodiment 1 is subjected to positive pressure filtration to the surface of a polyethersulfone base membrane under the pressure of 0.1Mpa to prepare a polydopamine modified carbon nanotube membrane (PDA/CNT membrane), and then the graphene oxide modified membrane (GO membrane), the polydopamine modified carbon nanotube membrane-graphene oxide membrane (PDA/CNT-GO membrane) and the polyethersulfone base membrane (PES base membrane) in the embodiment 1 are taken as comparative examples.
Application example 1
A filtration removal experiment was performed on Humic Acid (HA) solution with a concentration of 10mgC/L for 4 hours using the PDA/CNT-GO membrane prepared in example 1.
Comparative application example 1
The PDA/CNT-GO film in application example 1 was replaced with the GO film, PDA/CNT film, PES-based film in comparative example.
Performance testing
1) The carbon nanotubes and polydopamine-modified carbon nanotubes of example 1 were tested using X-ray photoelectron spectroscopy and the results are shown in fig. 2.
As can be seen from fig. 2, the polydopamine-modified carbon nanotube film can be successfully prepared.
2) The CNT of example 1 was tested for contact with the PDA/CNT film and the results are shown in fig. 3.
As can be seen from fig. 3, the contact angle of the CNT is 101 °, the contact angle of the PDA/CNT film is 77 °, and the hydrophilicity of the PDA/CNT film is improved after modification by PDA.
3) The PDA/CNT-GO film, PDA/CNT film, PES base film prepared in example 1 were measured for film flux under the same conditions, and specific test steps were that a constant pressure filtration experimental apparatus was used to pre-press the film flux with pure water for 30min at a pressure of 0.1MPa to uniformly stabilize the film flux, and then the pressures of nitrogen cylinders were adjusted to 0.06, 0.1, 0.14, and 0.2MPa, respectively, and the film flux under four pressures was obtained by analyzing the quality and time interval of pure water recorded by a computer connected to an analytical balance, and further a pure water flux-transmembrane pressure graph was obtained, and the results are shown in fig. 4.
As can be seen from FIG. 4, the standard water flux of the PDA/CNT-GO film is 18.22L/(m) 2 H.bar) slightly less than the single layer PDA/CNT film (26.6L/(m) 2 H.bar)) and monolayer GO film (26.89L/(m) 2 H.bar)).
4) The removal rate of humic acid by the PDA/CNT-GO film, the PDA/CNT film and the PES film prepared in the example 1 is measured, and the specific test process is as follows: the membrane flux is uniformly stabilized by pre-pressing with pure water for 30min under the pressure of 0.1MPa by adopting a constant pressure filtration experimental device, then 10mgC/L HA solution is poured into the device, the membrane dynamic filtration experiment is carried out under the pressure of 0.1MPa, the whole experimental process lasts for 4h, the membrane is taken out every 10min to filter out water, the absorbance of HA is measured, and the relation curve between the removal rate and the filtration time of HA is obtained by analyzing the concentration of the water sample of the water to be filtered and the concentration of the water sample of the water to be fed, and the result is shown in figure 5.
As can be seen from fig. 5, the removal rate of HA after 4h was 65% for the PDA/CNT-GO film, which is superior to the removal effect of the single-layer PDA/CNT film (47%) and the single-layer GO film (52%).
5) The three-dimensional fluorescence (EEM) of the membrane-filtered water after 4 hours of humic acid solution was analyzed by a fluorescence spectrophotometer for the PDA/CNT-GO membrane, PDA/CNT membrane, PES-based membrane filtration prepared in example 1, and the results are shown in fig. 6.
The three-dimensional fluorescence spectrum analysis of fig. 6 can more intuitively show the removal effect of the film on HA, namely the removal effect of the PDA/CNT-GO film on HA, which is superior to the removal effect of the single-layer PDA/CNT film and the single-layer GO film.
6) And (3) prepressing the membrane with pure water for 30min under the pressure of 0.1MPa by adopting a constant-pressure filtration experimental device to ensure that the membrane flux is uniform and stable, and calculating the pure water flux of the membrane. The device is filled with 10mgC/L HA solution, the PDA/CNT-GO membrane, PDA/CNT membrane and PES membrane prepared in example 1 are subjected to membrane dynamic filtration experiments, the mass of membrane permeate is recorded by adopting an electronic balance-computer data acquisition system, flux in the membrane filtration process is obtained after conversion, and a specific flux-time graph is obtained after data analysis. The results are shown in FIG. 7.
As can be seen from fig. 7, the specific flux of the PDA/CNT-GO film after 2 hours is 0.85, which is greater than the specific fluxes of the single-layer PDA/CNT film (0.80) and the single-layer GO film (0.74) after 2 hours, indicating that the anti-pollution effect of the PDA/CNT-GO film is better than that of the single-layer PDA/CNT film and the single-layer GO film.
Although the foregoing embodiments have been described in some, but not all, embodiments of the invention, according to which one can obtain other embodiments without inventiveness, these embodiments are all within the scope of the invention.

Claims (9)

1. The polydopamine modified carbon nanotube-graphene oxide film is characterized by comprising a polyether sulfone base film, a graphene oxide layer bonded on the polyether sulfone base film and a polydopamine modified carbon nanotube layer attached to the surface of the graphene oxide layer;
the ratio of the mass of the graphene oxide layer to the area of the polyethersulfone membrane is (0.03-0.1) mg:28.27 cm 2 The method comprises the steps of carrying out a first treatment on the surface of the The ratio of the mass of the polydopamine modified carbon nano tube layer to the area of the polyethersulfone membrane is (20-60) mg:28.27 cm 2 。
2. The method for preparing the polydopamine modified carbon nanotube-graphene oxide membrane according to claim 1, which is characterized by comprising the following steps:
after the graphene oxide dispersion liquid and the polyethersulfone membrane are first compounded, modifying to obtain a graphene oxide modified membrane;
mixing carbon nanotubes, an organic solvent, dopamine and a buffer solution, and performing polymerization reaction to obtain polydopamine modified carbon nanotube dispersion;
and carrying out second compounding on the polydopamine modified carbon nanotube dispersion liquid and the graphene oxide modified membrane, and then carrying out loading to obtain the polydopamine modified carbon nanotube-graphene oxide membrane.
3. The method of claim 2, wherein the first compounding and the second compounding are by positive pressure filtration; the pressure of the positive pressure filtration is independently 0.1-0.2 MPa.
4. The method according to claim 2, wherein the concentration of the graphene oxide dispersion is 0.2g/L; the ratio of the volume of the graphene oxide dispersion liquid to the area of the polyethersulfone membrane is (0.15-0.5) mL:28.27 cm 2 。
5. The method of preparation according to claim 2, wherein the polyethersulfoneThe pore size of the basal membrane is 100kDa; the effective filtration area of the polyethersulfone-based membrane is 28.27cm 2 。
6. The preparation method according to claim 2, wherein the mass ratio of the carbon nanotubes to the dopamine is (10-30) to (10-30); the concentration of the dopamine solution is 1-2 g/L; the concentration of the polydopamine modified carbon nano tube dispersion liquid is 0.33-0.92 g/L; the ratio of the volume of the polydopamine modified carbon nanotube dispersion liquid to the area of the graphene oxide modified polyether sulfone membrane is (55-80) mL:28.27 cm 2 。
7. The method of claim 2, wherein the buffer solution is a tris buffer solution; the concentration of the buffer solution is 10-50 mmol/L; the pH value of the buffer solution is 8.5-10.
8. The method of claim 2, wherein the carbon nanotubes are multi-walled carbon nanotubes; the outer diameter of the carbon nano tube is 10-20 nm.
9. The polydopamine modified carbon nanotube-graphene oxide membrane of claim 1 or the polydopamine modified carbon nanotube-graphene oxide membrane prepared by the preparation method of claims 2-8 is applied to sewage treatment.
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WO2011005258A1 (en) * 2009-07-09 2011-01-13 Board Of Regents, The University Of Texas System Polymer deposition and modification of membranes for fouling resistance
CN106621856A (en) * 2017-01-22 2017-05-10 河北工业大学 Stable-structure high-performance graphene oxide nanofiltration composite membrane and preparation method thereof
CN109433023A (en) * 2018-09-14 2019-03-08 浙江工业大学 The graphene oxide nanofiltration membrane and the preparation method and application thereof of one type graphitic nitralloy carbon intercalation

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2011005258A1 (en) * 2009-07-09 2011-01-13 Board Of Regents, The University Of Texas System Polymer deposition and modification of membranes for fouling resistance
CN106621856A (en) * 2017-01-22 2017-05-10 河北工业大学 Stable-structure high-performance graphene oxide nanofiltration composite membrane and preparation method thereof
CN109433023A (en) * 2018-09-14 2019-03-08 浙江工业大学 The graphene oxide nanofiltration membrane and the preparation method and application thereof of one type graphitic nitralloy carbon intercalation

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