CN114904400A - Preparation method and application of TCPP @ HPAMAM @ PA/PVDF bifunctional composite membrane - Google Patents
Preparation method and application of TCPP @ HPAMAM @ PA/PVDF bifunctional composite membrane Download PDFInfo
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- RBTBFTRPCNLSDE-UHFFFAOYSA-N 3,7-bis(dimethylamino)phenothiazin-5-ium Chemical compound C1=CC(N(C)C)=CC2=[S+]C3=CC(N(C)C)=CC=C3N=C21 RBTBFTRPCNLSDE-UHFFFAOYSA-N 0.000 description 5
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Images
Classifications
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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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/06—Organic material
- B01D71/30—Polyalkenyl halides
- B01D71/32—Polyalkenyl halides containing fluorine atoms
- B01D71/34—Polyvinylidene fluoride
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/30—Treatment of water, waste water, or sewage by irradiation
-
- 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
- C02F1/40—Devices for separating or removing fatty or oily substances or similar floating material
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/308—Dyes; Colorants; Fluorescent agents
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A20/00—Water conservation; Efficient water supply; Efficient water use
- Y02A20/124—Water desalination
- Y02A20/131—Reverse-osmosis
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- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- Toxicology (AREA)
- Analytical Chemistry (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
Abstract
The invention belongs to the technical field of preparation of environment functional materials, and particularly relates to a preparation method and application of a TCPP @ HPAMAM @ PA/PVDF bifunctional composite membrane. The invention adopts a one-step method to prepare HPAMAM, and assembles HPAMAM, TCPP and PA to form a polyelectrolyte compound through electrostatic interaction; and depositing the polyelectrolyte compound on the PVDF membrane with excellent mechanical property by a self-assembly method to prepare the bifunctional composite membrane with super oleophobic property and catalytic degradation property. The oil-water emulsion is efficiently separated, and meanwhile, the oil-water emulsion has excellent degradation capability on various dyes; the method is applied to separation of oil-water emulsion and degradation of dye. Is a novel pollution-resistant and environment-friendly membrane material. Meanwhile, the preparation method has good anti-fouling performance and recycling performance, and the preparation method provided by the invention has the advantages of simple process, convenience in operation, low energy consumption, no chemical pollution and accordance with green chemical concept.
Description
Technical Field
The invention belongs to the technical field of preparation of environment functional materials, and particularly relates to a preparation method and application of a TCPP @ HPAMAM @ PA/PVDF bifunctional composite membrane.
Background
With the development of human industry, industries such as food processing, petrochemical industry, textile, metal smelting and the like generate a large amount of oily wastewater, wherein the oily wastewater not only contains stable emulsified oil, but also contains smaller organic dye molecules, so that the oily wastewater causes great pollution and damage to the environment and an ecological system, and the oily wastewater is still a great problem in the treatment of wastewater with complex components. At present, the methods for treating the oily sewage mainly comprise: the oil-water density difference is utilized to carry out gravity separation, centrifugal separation, filtration and adsorption and the like, but the separation methods have low separation efficiency and are easy to cause secondary pollution, thereby limiting the application of the separation methods. Membrane separation technology has become an effective method in the field of water purification and wastewater treatment due to its excellent separation performance.
The oily wastewater usually contains soluble dye pollutants, and is not easily degraded in nature, so that the oily wastewater has higher requirements on membrane separation materials. The bifunctional membrane material which can separate oil from water and degrade dyes becomes a hot point of research at present. Recent researches show that the photocatalysis technology has a remarkable effect on the degradation of the dye, so that the membrane separation technology and the photocatalysis technology are combined to prepare the dual-functional membrane which can separate the emulsion and degrade the dye, and has an important significance on the treatment of the oily wastewater. The introduction of the nano particles with catalytic performance into the separation membrane is a powerful method for realizing the combination of separation and photocatalysis, but the compatibility between the nano material and the membrane material is poor, so that the dispersibility of the nano particles is poor, the catalytic performance of the membrane is reduced, and therefore, a material with better compatibility with a membrane substrate is required to prepare a high-performance degradable composite membrane.
Porphyrin and derivatives thereof are aromatic macrocyclic conjugated compounds, the unique 18 pi electron structure is beneficial to electron transfer in porphyrin, so that the porphyrin has excellent oxidation-reduction property and photosensitivity, and is often used as a photocatalyst for degrading pollutants in water. At present, most researches endow the membrane with catalytic degradation performance by doping porphyrin nanoparticles in the membrane and obtain a better effect, but the direct blending membrane forming mode can lead a part of reaction active sites to be embedded in the membrane, so that the photocatalytic degradation efficiency is reduced, and an organic solvent is needed in the preparation process of the blending membrane, so that the requirements of green chemical development are not met, and therefore, a method which is environment-friendly, simple in preparation method and surface modified is needed to better exert the characteristics of a functional material.
Disclosure of Invention
In view of the above, the invention provides a TCPP @ HPAMAM @ PA/PVDF bifunctional composite membrane aiming at the defects in the prior art. Porphyrin, hyperbranched polyamide-amine and phytic acid are loaded on PVDF after being compounded, so that the dual-function combination of oil-water separation and dye degradation is realized, and the separation efficiency is greatly improved.
In order to achieve the purpose, the invention adopts the following technical scheme:
in a specific embodiment, the invention provides a preparation method of a TCPP @ HPAMAM @ PA/PVDF bifunctional composite membrane, which specifically comprises the following steps:
(1) adding a tetra (4-carboxyphenyl) porphyrin (TCPP) aqueous solution into a hyperbranched polyamide-amine (HPAMAM) aqueous solution, stirring at normal temperature, dripping Phytic Acid (PA), and continuously stirring to obtain a TCPP @ HPAMAM @ PA polyelectrolyte compound;
(2) fixing the cleaned PVDF membrane on a sand core filter cup of a filter flask, pouring the TCPP @ HPAMAM @ PA polyelectrolyte compound obtained in the step (1) into the filter cup, and depositing the polyelectrolyte compound on the PVDF membrane under pressure to obtain the TCPP @ HPAMAM @ PA/PVDF membrane.
Preferably, the preparation method of the hyperbranched polyamide-amine in the step (1) comprises the steps of placing N, N-methylene bisacrylamide and ethylenediamine in a flask, adding deionized water, sealing, then carrying out magnetic stirring for 4-6 hours at 60-80 ℃ under an inert atmosphere, purifying the product, and carrying out vacuum drying to obtain the hyperbranched polyamide-amine.
Further, the molar ratio of the N, N-methylene bisacrylamide to the ethylenediamine is 4-6: 7, and the mass of the deionized water is 2-3 times that of the N, N-methylene bisacrylamide.
The concentration of the HPAMAM aqueous solution in the step (1) is 1-3 mg/mL; the concentration of the TCPP aqueous solution is 2 mg/mL; the volume ratio of HPAMAM to TCPP is 2: 1.
the concentration of the phytic acid in the step (1) is 2 mg/mL; the volume ratio of TCPP to phytic acid is 1: 1; and the continuous stirring is to stir for 1 hour, then add water to dilute to 5-10 times of the volume, and then stir for 2 hours.
And (3) in the step (2), the PVDF membrane is firstly soaked and washed by ethanol and then is washed by deionized water.
The pressure in step (2) was 0.095 MPa.
In a specific embodiment, the invention also provides the bifunctional composite membrane prepared by the preparation method.
In a specific embodiment, the invention also provides application of the prepared bifunctional composite membrane in the fields of catalytic degradation of dyes and/or oil-water emulsion separation.
Compared with the prior art, the invention has the beneficial effects that:
the invention adopts a one-step method to prepare HPAMAM, and assembles HPAMAM, TCPP and PA to form a polyelectrolyte compound through electrostatic interaction; and the polyelectrolyte compound is deposited on the PVDF membrane with excellent mechanical property by a self-assembly method to prepare the difunctional composite membrane with super oleophobic and catalytic degradation properties. The oil-water emulsion is efficiently separated, and meanwhile, the oil-water emulsion has excellent degradation capability on various dyes; the method is applied to separation of oil-water emulsion and degradation of dye. Is a novel pollution-resistant and environment-friendly membrane material. Meanwhile, the preparation method has good anti-fouling performance and recycling performance, and the preparation method provided by the invention has the advantages of simple process, convenience in operation, low energy consumption, no chemical pollution and accordance with green chemical concept.
Drawings
FIG. 1 is a SEM comparison of a PVDF-based membrane and a TCPP @ HPAMAM @ PA/PVDF membrane; in the figure, (a) is a PVDF-based film, and (b) is a TCPP @ HPAMAM @ PA/PVDF film;
FIG. 2 is a graph of contact angle of TCPP @ HPAMAM @ PA/PVDF film; in the figure, (a) is the water-in-air contact angle of the film and (b) is the underwater oil contact angle of the film;
FIG. 3 is a graph of an underwater dynamic oil pick-up test for TCPP @ HPAMAM @ PA/PVDF film;
FIG. 4 is a graph of the separability efficiency of TCPP @ HPAMAM @ PA/PVDF membrane for an oil-water emulsion;
FIG. 5 is a graph of the cyclic separation performance of TCPP @ HPAMAM @ PA/PVDF membrane for an oil-water emulsion;
FIG. 6 is a graph of the efficiency of degradation of TCPP @ HPAMAM @ PA/PVDF films on RhB; in the figure, a and b are respectively a degradation efficiency curve and a change curve of absorbance;
FIG. 7 is a graph of the degradation efficiency of TCPP @ HPAMAM @ PA/PVDF films on MB; in the figure, a and b are respectively a degradation efficiency curve and a change curve of absorbance.
Detailed description of the preferred embodiment
The present invention will be further described by the following examples, however, the scope of the present invention is not limited to the following examples. The present invention has been described generally and/or specifically with respect to materials used in testing and testing methods. The following examples are examples of experimental methods not indicating specific conditions, and the detection is usually carried out according to conventional conditions or according to the conditions recommended by the manufacturers. Reagents, biomaterials, etc. used in the following examples are commercially available unless otherwise specified.
Hyperbranched Polyamidoamines (HPAMAM) are ideally monodisperse macromolecules with regular, highly branched three-dimensional polymers having a greater degree of branching than conventional branched polymers and less than dendritic polymers. Compared with dendritic polymers, the dendritic polymer has no strictly regular geometric configuration, but has the characteristics of simple synthesis method, high yield and easy industrialization, so that the dendritic polymer has more excellent characteristics. As HPAMAM has a unique molecular structure and a large number of terminal amino functional groups, the HPAMAM and porphyrin and natural compound phytic acid form an environment-friendly polyelectrolyte compound through electrostatic interaction. The composite material has good compatibility, is deposited on a PVDF film with excellent mechanical property by a one-step self-assembly method, solves the key problems of chemical pollution, complicated preparation process, poor compatibility among materials and the like, and the prepared film has good cyclicity and pollution resistance, realizes double combination of oil-water separation and catalytic degradation, and has great application potential.
Example 1
(1) Synthesis of hyperbranched polyamide-amine: 2.31 g (15 mmoL) of N, N-methylene bisacrylamide and 1.052 g (17.5 mmoL) of ethylenediamine are weighed and placed in a flask, 6.72 mL of deionized water is added, then a rubber plug is used for sealing, vacuumizing and nitrogen gas introduction are carried out for three times, magnetic stirring is carried out for 6 hours at 60 ℃, a polymer solution is obtained after the reaction is finished, acetone with 10 times volume is used for precipitating and washing the polymer solution, and the obtained sticky matter is dried in vacuum for 48 hours at 40 ℃ to obtain the light yellow sticky polymer HPAMAM.
(2) Preparation of polyelectrolyte Complex: dispersing 20 mg of HPAMAM prepared in the step (1) in 10 mL of water to obtain an HPAMAM aqueous solution; and further, ultrasonically dispersing 10 mg of tetra (4-carboxyphenyl) porphyrin (TCPP) in 5 mL of water, adding the water into the HPAMAM aqueous solution, stirring for 2 hours at normal temperature, dropwise adding 5 mL of Phytic Acid (PA) solution with the concentration of 2 mg/mL, stirring for 1 hour, adding 100mL of deionized water for dilution, and stirring for 2 hours to obtain the TCPP @ HPAMAM @ PA polyelectrolyte compound.
(3) Fixing the cleaned PVDF membrane on a sand core filter cup of a filter flask, pouring the TCPP @ HPAMAM @ PA polyelectrolyte compound obtained in the step (2) into the filter cup, filtering by using the pressure of 0.095 MPa, depositing the polyelectrolyte compound on the hydrophobic PVDF membrane by a one-step self-assembly method, washing with deionized water, and drying to obtain the TCPP @ HPAMAM @ PA/PVDF membrane.
And evaluating the anti-fouling performance of different TCPP @ HPAMAM @ PA/PVDF films through a dynamic underwater viscous oil experiment. The oil droplets were pressed against the membrane surface using an oil needle, then gently peeled off the membrane surface and the course of the experiment was recorded by a contact angle meter.
FIG. 1 is a SEM comparison of a PVDF-based membrane and a TCPP @ HPAMAM @ PA/PVDF membrane; in the figure, (a) is a PVDF basement membrane, (b) is TCPP @ HPAMAM @ PA/PVDF membrane; as can be seen in FIG. 1, the prepared TCPP @ HPAMAM @ PA/PVDF membrane has a rough surface and a small membrane pore size; after the TCPP @ HPAMAM @ PA polyelectrolyte compound is deposited on the surface of the PVDF membrane, the appearance of the membrane surface is changed, so that the membrane surface is rough, and the membrane pore size is reduced.
The prepared TCPP @ HPAMAM @ PA/PVDF film was subjected to a wettability test, and FIG. 2 is a contact angle graph of the TCPP @ HPAMAM @ PA/PVDF film; in the figure, (a) is the water-in-air contact angle of the film and (b) is the underwater oil contact angle of the film; as can be seen from FIG. 2, the contact angle of the membrane in air is 0 degrees, the contact angle of the underwater oil is 152 degrees, and the membrane has super-hydrophilic/underwater super-oleophobic performance.
Respectively taking Toluene (Toluene) and Dichloroethane (Dichloroethane) as oil phases to carry out an underwater dynamic oil sticking experiment to determine the adhesion of the surface of the prepared TCPP @ HPAMAM @ PA/PVDF film; FIG. 3 is a graph of an underwater dynamic oil pick-up test for TCPP @ HPAMAM @ PA/PVDF film; as can be seen from figure 3, oil drops can be separated from the surface of the membrane, and the oil drops are not deformed, which shows that the prepared membrane has extremely small adhesion to the oil drops underwater, is an underwater super-oleophobic material and has excellent anti-fouling performance.
Example 2:
(1) synthesis of hyperbranched polyamide-amine: weighing 1.155 g (7.5 mmoL) of N, N-Methylene Bisacrylamide (MBA) and 0.526 g (8.75 mmoL) of Ethylenediamine (EDA) in a flask, adding 3.465 mL of deionized water, sealing by a rubber plug, vacuumizing, introducing nitrogen, circulating for three times, magnetically stirring at 80 ℃ for 4 hours to obtain a polymer solution after the reaction is finished, and using a certain volume of acetone (V) Acetone (II) :V Reaction solvent =10: 1) precipitating and washing the polymer solution; the product was dried under vacuum at 40 ℃ for 48 hours to give a pale yellow viscous polymer Hyperbranched Polyamidoamine (HPAMAM).
(2) Preparation of polyelectrolyte complex: dispersing 10 mg of HPAMAM prepared in the step (1) in 10 mL of water to obtain an HPAMAM aqueous solution; dispersing 10 mg of tetra (4-carboxyphenyl) porphyrin (TCPP) in 5 mL of water by ultrasonic waves uniformly, adding the mixture into HPAMAM aqueous solution, stirring for 2 hours at normal temperature, and filtering by using a filter head with the diameter of 0.22 mu m after stirring; 5 mL of Phytic Acid (PA) solution with the concentration of 2 mg/mL is dripped into the filtrate, 200mL of deionized water is added for dilution after stirring for 1 hour, and the mixture is stirred for 2 hours to obtain the TCPP @ HPAMAM @ PA polyelectrolyte compound.
(3) And (2) cleaning the PVDF membrane, fixing the PVDF membrane on a sand core filter cup of a filter bottle, pouring the TCPP @ HPAMAM @ PA polyelectrolyte compound obtained in the step (2) into the filter cup, filtering by using the pressure of 0.095 MPa, depositing the polyelectrolyte compound on the hydrophobic PVDF membrane by a one-step self-assembly method, washing with deionized water, and drying to obtain the TCPP @ HPAMAM @ PA/PVDF membrane.
Example 3:
(1) synthesis of hyperbranched polyamide-amine: 3.465 g (22.5 mmoL) of N, N-methylene bisacrylamide and 1.578 g (26.25 mmoL) of ethylenediamine are weighed and placed in a flask, 6.93 mL of deionized water is added, then a rubber plug is used for sealing, then vacuumizing and nitrogen gas introduction are carried out for three times, the mixture is magnetically stirred for 6 hours at 60 ℃, a polymer solution is obtained after the reaction is finished, the polymer solution is precipitated and washed by 10 times of volume of acetone, and the obtained sticky matter is dried for 48 hours at 40 ℃ in vacuum, so that the light yellow sticky polymer HPAMAM is obtained.
(2) Preparation of polyelectrolyte complex: dispersing 30 mg of HPAMAM prepared in the step (1) in 10 mL of water to obtain an HPAMAM aqueous solution; and further, ultrasonically dispersing 10 mg of tetra (4-carboxyphenyl) porphyrin (TCPP) in 5 mL of water, adding the water into the HPAMAM aqueous solution, stirring for 2 hours at normal temperature, dropwise adding 5 mL of Phytic Acid (PA) solution with the concentration of 2 mg/mL, stirring for 1 hour, adding 100mL of deionized water for dilution, and stirring for 2 hours to obtain the TCPP @ HPAMAM @ PA polyelectrolyte compound.
(3) Fixing the cleaned PVDF membrane on a sand core filter cup of a filter flask, pouring the TCPP @ HPAMAM @ PA polyelectrolyte compound obtained in the step (2) into the filter cup, filtering by using the pressure of 0.095 MPa, depositing the polyelectrolyte compound on the hydrophobic PVDF membrane by a one-step self-assembly method, washing with deionized water, and drying to obtain the TCPP @ HPAMAM @ PA/PVDF membrane.
Example 4:
the separation experiment of oil-water emulsion was performed on the TCPP @ HPAMAM @ PA/PVDF membrane prepared in example 1 by preparing different kinds of oil-water emulsion with Hexane (Hexane), Petroleum ether (Petroleum ether), Diesel oil (Diesel), Toluene (Toluene) and Dichloroethane (dichlorethane) as oil phase. Fixing the membrane to be tested in a sand core suction filtration device, respectively pouring the oil/water emulsion into a glass tube at the upper part of the device, separating the oil/water emulsion under the pressure of 0.9 bar, and then measuring the oil content by using an ultraviolet visible spectrophotometer so as to calculate the separation efficiency. And the circulation performance of the oil-water emulsion is analyzed by adopting a film to separate the oil-water emulsion for multiple times.
FIG. 4 is a graph of the separability efficiency of TCPP @ HPAMAM @ PA/PVDF membrane for an oil-water emulsion; as can be seen from FIG. 4, the TCPP @ HPAMAM @ PA/PVDF membrane has the separation efficiency of more than 98.5 percent for different types of oil-water emulsions and has good separation performance; FIG. 5 is a graph of the cyclic separation performance of TCPP @ HPAMAM @ PA/PVDF membrane for an oil-water emulsion; as can be seen from FIG. 5, after the TCPP @ HPAMAM @ PA/PVDF membrane is used for repeatedly and circularly separating the oil-water emulsion, the separation efficiency is still over 98 percent, which indicates that the membrane has excellent circulating performance.
Example 5:
the TCPP @ HPAMAM @ PA/PVDF film prepared in example 1 was subjected to a degradation experiment with dyes. The degradation performance of the TCPP @ HPAMAM @ PA/PVDF membrane is inspected through a batch photocatalytic degradation experiment, a constant-temperature photocatalytic device at 25 ℃ is adopted for the experiment, condensed water is externally connected to a double-layer jacket beaker, the double-layer jacket beaker is placed on a magnetic stirrer, a xenon lamp light source is positioned above the beaker, a prepared rhodamine B (RhB) solution or a prepared Methylene Blue (MB) solution is poured into the jacket beaker, and the prepared TCPP @ HPAMAM @ PA/PVDF membrane is added. Firstly carrying out dark adsorption for 30 min to saturate the physical adsorption of the membrane, then turning on a light source to carry out batch degradation, taking supernate at intervals, and testing the characteristic absorbance of the supernate by an ultraviolet visible-spectrophotometer so as to calculate the degradation efficiency.
FIG. 6 is a graph of the degradation efficiency of TCPP @ HPAMAM @ PA/PVDF membrane for RhB; in the figure, a and b are respectively a degradation efficiency curve and a change curve of absorbance, and FIG. 7 is a graph of the degradation efficiency of TCPP @ HPAMAM @ PA/PVDF film to MB; in the figure, a and b are respectively a degradation efficiency curve and a change curve of absorbance; as can be seen from FIGS. 6 and 7, the TCPP @ HPAMAM @ PA/PVDF film has excellent catalytic degradation performance on rhodamine B and methylene blue dyes.
While embodiments of the invention have been shown and described above, it is to be understood that the above embodiments are exemplary and not to be construed as limiting the invention, and that various embodiments or examples and features of various embodiments or examples described in this specification are capable of being combined and brought together by those skilled in the art without thereby conflicting with each other.
Claims (10)
1. A preparation method of a TCPP @ HPAMAM @ PA/PVDF bifunctional composite membrane is characterized by comprising the following steps:
(1) adding the TCPP aqueous solution into the HPAMAM aqueous solution, stirring at normal temperature, dripping PA, and continuously stirring to obtain a TCPP @ HPAMAM @ PA polyelectrolyte compound;
(2) fixing the cleaned PVDF membrane on a sand core filter cup of a filter flask, pouring the TCPP @ HPAMAM @ PA polyelectrolyte compound obtained in the step (1) into the filter cup, and depositing the polyelectrolyte compound on the PVDF membrane under pressure to obtain the TCPP @ HPAMAM @ PA/PVDF membrane.
2. The preparation method of claim 1, wherein the hyperbranched polyamidoamine in step (1) is prepared by placing N, N-methylenebisacrylamide and ethylenediamine in a flask, adding deionized water, sealing, magnetically stirring at 60-80 ℃ under an inert atmosphere for 4-6 h, purifying the product, and vacuum drying to obtain the hyperbranched polyamidoamine.
3. The preparation method according to claim 2, wherein the molar ratio of the N, N-methylene bisacrylamide to the ethylenediamine is 4-6: 7, and the mass of the deionized water is 2-3 times that of the N, N-methylene bisacrylamide.
4. The preparation method according to claim 1, wherein the concentration of the HPAMAM aqueous solution in the step (1) is 1-3 mg/mL; the concentration of the TCPP aqueous solution is 2 mg/mL; the volume ratio of HPAMAM to TCPP is 2: 1.
5. the method according to claim 1, wherein the concentration of phytic acid in step (1) is 2 mg/mL; the volume ratio of TCPP to phytic acid is 1: 1.
6. the preparation method according to claim 1, wherein the continuous stirring is performed for 1 hour, and then the mixture is diluted to 5-10 times of the volume by adding water and stirred for 2 hours.
7. The method according to claim 1, wherein the cleaning in step (2) is performed by soaking and washing the PVDF membrane with ethanol and then washing with deionized water.
8. The production method according to claim 1, wherein the pressure in step (2) is 0.095 MPa.
9. The TCPP @ HPAMAM @ PA/PVDF bifunctional composite membrane prepared by the preparation method according to any one of claims 1-8.
10. The application of the bifunctional composite membrane according to claim 9 in the fields of catalytic degradation of dyes and/or oil-water emulsion separation.
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| CN114031803A (en) * | 2021-10-25 | 2022-02-11 | 江苏大学 | Method for preparing polyamide-amine gel composite membrane based on click chemistry and application |
| US20220072483A1 (en) * | 2018-12-21 | 2022-03-10 | G20 Water Technologies Limited | Membrane and method of producing the same |
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| US20220072483A1 (en) * | 2018-12-21 | 2022-03-10 | G20 Water Technologies Limited | Membrane and method of producing the same |
| CN114031803A (en) * | 2021-10-25 | 2022-02-11 | 江苏大学 | Method for preparing polyamide-amine gel composite membrane based on click chemistry and application |
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