CN114849497A - Fibril-like self-repairing anti-pollution ZnO/MXene base membrane and preparation method and application thereof - Google Patents
Fibril-like self-repairing anti-pollution ZnO/MXene base membrane and preparation method and application thereof Download PDFInfo
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Abstract
The invention discloses a fibrous self-repairing anti-pollution ZnO/MXene base film, a preparation method and application thereofThe application is. Dissolving nano ZnO in water to prepare a ZnO seed solution, diluting, performing vacuum filtration to deposit ZnO seeds on a porous base film, and drying; suspending the obtained porous basement membrane in a stirred ZnO solution, washing and drying; suspending the obtained porous basement membrane in an aqueous solution of zinc nitrate hexahydrate and hexamethylenetetramine, reacting, washing and drying; and immersing the obtained porous basement membrane into MXene solution for reaction, washing and dehydrating. The membrane prepared by the invention has the permeation flux of 3.93 kg.m ‑2 ·h ‑1 The salt rejection rate is more than 99.9 percent; the membrane has stronger hydrophilic pollution resistance due to super hydrophobicity and rough surface. The ultraviolet light irradiation realizes the reversible conversion of hydrophobicity and hydrophilicity and the self-repair of the membrane, and has sustainable seawater desalination application prospect.
Description
Technical Field
The invention belongs to the technical field of membrane separation, and particularly relates to a fibrous-root-like self-repairing anti-pollution ZnO/MXene base membrane as well as a preparation method and application thereof.
Background
Fresh water is an essential component of many lives on earth, and its importance is self-evident; however, shortage of fresh water resources is further aggravated due to economic development and pollution of water resources. Current global demand cannot be met by 'throttling' alone, and 'open source' is necessary, and seawater desalination is a potential way to solve the problem. Membrane-based humidification-dehumidification desalination (MHDD) combined with solar, geothermal or waste heat resources provides a low cost thermally driven desalination technology; however, fouling and fouling of membranes remains a major obstacle to their industrial application. Superhydrophobic modification of the membrane surface has been shown to significantly reduce the formation of scale, with the hydrophobic layer acting as a buffer scale-inhibiting layer, primarily by reducing surface nucleation and particle adhesion. At present, superhydrophobic modification is mainly achieved by increasing surface roughness while decreasing surface energy. However, superhydrophobic surfaces readily adsorb hydrophobic contaminants in seawater, such as Humic Acid (HA) and proteins. Membrane cleaning can further increase the effective run time of the membrane. Cleaning of the contaminated membrane with chemicals such as chlorine or acid is believed to be effective in restoring the permeability of the membrane, but it can disrupt the membrane structure or further reduce the water quality, thereby increasing the cost of the process. Physical cleaning can avoid these problems, but is less effective and energy intensive. Therefore, there is a great need to find an effective and economically viable membrane cleaning process.
Generally, superhydrophobic surfaces are resistant to hydrophilic contaminants; whereas hydrophilic surfaces are less susceptible to hydrophobic contaminants. From this point of view, an ideal membrane should be both superhydrophobic and superhydrophilic. Since when the membrane is superhydrophobic it is a hydrophilic contaminant barrier when it switches to superhydrophilicWith water, the hydrophobic substance is easily washed. Although the manufacture of such a membrane is a very difficult task, a membrane with a reversible hydrophilic-hydrophobic transition may help to achieve this goal. Feng et al (Feng, x.j., Feng, l., Jin, m.h., Zhai, j., Jiang, l.and Zhu, d.b.2004.reversible super-hydrophilic to super-hydrophilic transition of aligned ZnO nano-rods.j.am.chem.soc.126 (1),62-63) achieve a reversible transition from superhydrophobic to superhydrophilic of oriented ZnO nanorod films by alternating between uv illumination and dark storage states. However, in the actual production process, unreacted Zn (OH) 2 Always remain on the surface of ZnO, and make ZnO crystal hydrophilic. Therefore, in practical cases, it is difficult to achieve a reversible hydrophobic-hydrophilic conversion directly using ZnO. To utilize the reversible hydrophobic and hydrophilic properties of ZnO, it needs to be hydrophobically modified first.
A new family of two-dimensional materials, MXenes, was created by transformation from M n+1 AX n Etching an "A" layer, wherein M represents a transition metal, A represents a main group element (mainly IIIA or IVA), and X is C or N. Molecular formula M of MXenes n+1 X n T x (wherein T is x are-O, -OH and-F) have excellent antibacterial properties, excellent mechanical stability, antifouling properties and tunable surface chemistry, making them powerful candidates for water treatment applications. Previous studies have shown that MXene-based membranes have higher flux and excellent durability in seawater desalination. In addition, MXene is inherently hydrophilic (Chen, W.Y., Lai, S.N., Yen, C.C., Jiang, X.F., Perulis, D.and Stanciu, L.A.2020.surface function of Ti 3 C 2 T X MXene with high purity removable super-hydrophilic protection for volatile organic compounds sensing. ACS Nano 14(9),11490-11501), but due to its surface functional groups is susceptible to hydrophobic modification. Most importantly, MXene with end groups of-F and-OH is a semiconductor with a small bandgap. Therefore, the combination of MXene and ZnO is expected to achieve superhydrophobicity without hindering the hydrophobic-hydrophilic reversible transformation. To our knowledge, this is the first application of a reversible transition between hydrophilicity and hydrophobicity in the field of membrane distillation antifouling.
Disclosure of Invention
In order to solve the pollution problem faced by the current membrane seawater desalination, the invention aims to provide a preparation method of a self-repairing anti-pollution ZnO/MXene base membrane. The ZnO/MXene base film prepared by the method has the capability of resisting hydrophilic pollution and repairing hydrophobic pollution, and can stably run for a long time under the real seawater desalination condition.
The purpose of the invention is realized by the following technical scheme.
A preparation method of a fibrous self-repairing anti-pollution ZnO/MXene base film comprises the following steps:
(1) preparing a ZnO seed solution: dissolving nano ZnO in water to prepare ZnO seed solution;
(2) diluting the ZnO seed solution prepared in the step (1), performing vacuum filtration to deposit ZnO seeds on a porous base film, and drying;
(3) suspending the porous base membrane obtained in the step (2) in a stirred ZnO solution, washing the surface with deionized water, and drying; and adsorbing the ZnO seeds on the surface of the basement membrane through interaction, such as electrostatic adsorption or hydrogen bond.
(4) Suspending the porous base membrane obtained in the step (3) in an aqueous solution of zinc nitrate hexahydrate and hexamethylenetetramine, reacting, washing with deionized water and drying; the ZnO which is similar to fireworks is generated on the surface of the substrate.
(5) And (4) immersing the porous basement membrane obtained in the step (4) into MXene solution for reaction, washing and dehydrating. Unreacted Zn (OH) on MXene and ZnO surface 2 Dehydration reaction occurs to grow on the surface of ZnO.
Preferably, in the step (1), the particle size of the nano ZnO is 10-50 nm;
preferably, the concentration of the ZnO seed solution in the step (1) is 10-50 wt%.
Preferably, the dilution factor in step (2) is 1000-100000 times. The dilution is to make the ZnO seeds better dispersed on the surface of the film.
Preferably, the porous base membrane in step (2) is a polyvinylidene fluoride (PVDF) membrane, a Cellulose Acetate (CA) membrane, a Nylon, a polypropylene (PP) membrane, a Polytetrafluoroethylene (PTFE) membrane, a polyether sulfone (PES) filter membrane, or a mixture thereofOne or more of fiber MCE filter membranes; the aperture of the porous base membrane is 0.1-0.5 mu m; the volume of the diluted ZnO seed solution used for vacuum filtration and the area of the porous base membrane are in a ratio of (1-5) mL: (4 to 100) cm 2 (ii) a The drying temperature is 20-150 ℃, and the drying time is 2-10 h.
Preferably, the mass fraction of the ZnO solution in the step (3) is 0.1-10 wt%, and the particle size of the ZnO is 10-50 nm; the suspension time is 10-60min, and the stirring speed is 10-100r min -1 The drying temperature is 20-150 ℃, and the drying time is 2-10 h.
Preferably, the content of the zinc nitrate hexahydrate and the hexamethylene tetramine in the aqueous solution of the zinc nitrate hexahydrate and the hexamethylene tetramine in the step (4) is 10-100mM, and the content of the hexamethylene tetramine is 10-100 mM; the reaction temperature is 20-150 ℃, and the reaction time is 2-10 h; the drying temperature is 20-150 ℃, and the drying time is 2-10 h;
preferably, the reaction temperature in the step (5) is 0-20 ℃, and the reaction time is 2-50 h;
preferably, the dehydration in the step (5) is two-step dehydration; the temperature of the first step of dehydration is 60-100 ℃, and the time is 2-10 h; the temperature of the second step of dehydration is 100-.
Preferably, the preparation of the MXene solution in the step (5) comprises the following steps: etching the three-dimensional layered MAX by using a mixed solution of LiF and HCl, washing, adding water, and ultrasonically dispersing to obtain a two-dimensional layered MXene suspension; the mol ratio of LiF to HCl is (1-3): (1-20), wherein the molar ratio of MAX to LiF is (1-5): (5-150); the etching temperature is 20-50 ℃, and the etching time is 10-80 h. (MXene solution preparation reference CN 2021101910589)
The fibrous-root-like self-repairing anti-pollution ZnO/MXene base film prepared by the preparation method.
Preferably, the shape of the whisker-like self-repairing anti-pollution ZnO/MXene base film is whisker-like, the contact angle is 150-165 degrees, and the roughness is 1-3 μm;
preferably, the fibrous-root-like self-repairing anti-pollution ZnO/MXene base membrane has hydrophilic-hydrophobic reversible conversion capability, the wettability of the membrane surface can be changed into hydrophilic under ultraviolet irradiation, and then the membrane surface gradually returns to a hydrophobic state under a dark condition.
The application of the fibrous-root-like self-repairing anti-pollution ZnO/MXene base membrane in seawater desalination has the salt barrier property of more than 99.9% under the real seawater condition and the water yield of 1.5-4 kg m -2 h -1 The operation can be continued for more than 120 h; the membrane can recover more than 90% of permeation flux after being polluted, and simultaneously, the salt rejection rate is kept more than 99.9%, so that the self-repairing of the membrane is realized.
The invention has the beneficial effects that:
(1) the invention prepares a fibrous-root-like super-hydrophobic membrane with a rough surface.
(2) The invention prepares a membrane with super-hydrophobicity and hydrophilicity reversible conversion.
(3) The film prepared by the invention can realize self-repair by simply switching between ultraviolet irradiation and dark air storage. The adsorbed hydrophobic contaminants can be desorbed from the membrane surface under ultraviolet irradiation, so that the surface wettability is changed into hydrophilicity, and the hydrophobic contamination resistance is shown. Subsequently, in dark conditions, the membrane surface returns to the hydrophobic state again. The membrane can recover 90% of permeation flux, and simultaneously, 99.9% of salt rejection rate is kept, so that self-repairing of the membrane is realized.
(4) The membrane prepared by the invention has general antifouling performance. The membrane has stronger hydrophilic pollution resistance due to super hydrophobicity and rough surface.
(5) The ZM base film prepared by the invention has sustainable seawater desalination application prospect, and has very high moisture permeability and excellent salt rejection rate (more than 99.9%) under real seawater conditions.
Drawings
FIG. 1a is a scanning electron micrograph of the porous substrate PVDF used in example 1;
FIG. 1b is a scanning electron microscope image of the self-repairing anti-contamination ZnO/MXene base membrane with fibrous root shape prepared in example 1;
FIG. 1c shows the roughness of the ZnO/MXene-based film prepared in example 1;
FIG. 2 is a diagram showing the bouncing process of water droplets on the fibril-like self-healing anti-fouling ZnO/MXene base film prepared in example 2;
FIG. 3a is a photograph showing a contact angle of the ZnO-based film prepared in step (4) of example 3;
FIG. 3b is a photograph of the initial Contact Angle (CA) of the whisker-like self-repairing anti-fouling ZnO/MXene base film prepared in example 3 (left), the contact angle after UV irradiation (middle) and dark storage at 60 ℃ for 3 days (right);
FIG. 4 shows the water yield and salt rejection rate of the fibrous-root-like self-repairing anti-pollution ZnO/MXene base membrane and polyvinylidene fluoride PVDF porous base membrane prepared in example 4 under real seawater conditions for long-term operation;
FIG. 5 is a normalized flux comparison graph of the whisker-like self-repairing anti-fouling ZnO/MXene base membrane prepared in example 5 after being respectively polluted by Bovine Serum Albumin (BSA) and Humic Acid (HA) and after being subjected to ultraviolet repairing;
FIG. 6 is a self-repairing schematic diagram of the whisker-like self-repairing anti-pollution ZnO/MXene base film prepared by the method.
Detailed Description
The present invention is further illustrated by, but is not limited to, the following examples.
The method for preparing MXene solution used in the examples comprises the following steps:
etching the three-dimensional layered MAX by using a mixed solution of LiF and HCl, washing, adding water, and ultrasonically dispersing to obtain a two-dimensional layered MXene suspension; the mixed solution etches the A layer of the three-dimensional laminar MAX, the removed A is replaced by-F, -OH and-O functional groups, and the A and the F are adsorbed on the surface of MXene to form a terminal group; the mol ratio of LiF to HCl is 1: 2, the molar ratio of MAX to LiF is 1: 10; the etching temperature is 35 ℃, and the etching time is 24 hours.
The "contact angle" in the present invention is a "water contact angle".
Example 1
A preparation method of a fibrous self-repairing anti-pollution ZnO/MXene base film comprises the following steps:
(1) preparing a ZnO seed solution: dissolving ZnO with particle size of 20nm in a certain amount of water to prepare 25 wt% of ZnO seed solution;
(2) measuring 5 mu L of the seed solution prepared in the step (1) in 100mL of deionized water, and carrying out vacuum filtration to deposit the seeds on a polyvinylidene fluoride (PVDF) porous substrate membrane with the pore diameter of 0.45 mu m, wherein the ratio of the volume of the solution to the area of the porous substrate membrane is 2 mL: 5cm 2 Drying at room temperature for 6 h;
(3) suspending the film obtained in the step (2) in a ZnO (particle size of 20nm) solution with the mass fraction of 1 wt%, and performing vacuum evaporation for 20r min -1 Stirring for 30min at the rotating speed, washing the surface with deionized water, and drying for 10h at room temperature;
(4) suspending the membrane obtained in the step (3) in an aqueous solution containing zinc nitrate hexahydrate (50mM) and hexamethylenetetramine (50mM), reacting for 4 hours at 150 ℃, washing with deionized water and drying for 5 hours at 60 ℃;
(5) the membrane was immersed in MXene solution for 24h at 5 ℃ and washed and dehydrated for 2h at 80 ℃ and 120 ℃ respectively.
FIG. 1a is a scanning electron micrograph of the porous substrate PVDF used in example 1; FIG. 1b is a scanning electron microscope image of the whisker-like ZnO/MXene film prepared in example 1. As can be seen from the figure, the prepared ZnO/MXene rod has a diameter of 200-260nm and a length of 2.5-3.3 μm.
The contact angle of the ZnO/MXene base film obtained in this example was 158 ℃ and the roughness was 1.955 μm. (FIG. 1c)
Example 2
A preparation method of a fibrous self-repairing anti-pollution ZnO/MXene base film comprises the following steps:
(1) preparing a ZnO seed solution: dissolving ZnO with the particle size of 50nm in a certain amount of water to prepare 15 wt% of ZnO seed solution;
(2) weighing 3 mu L of the seed solution prepared in the step (1) in 50mL of deionized water, and carrying out vacuum filtration to deposit the seeds on a Polytetrafluoroethylene (PTFE) porous substrate membrane with the pore diameter of 0.22 mu m, wherein the ratio of the volume of the solution to the area of the porous substrate membrane is 5 mL: 20cm 2 Drying at room temperature for 10 h;
(3) suspending the film obtained in the step (2) in ZnO (particle size of 50nm) solution with mass fraction of 0.5 wt%, and treating for 40r min -1 Stirring for 20min at the rotating speed, washing the surface with deionized water, and drying for 5h at 40 ℃;
(4) suspending the membrane obtained in the step (3) in a solution (20mM) containing zinc nitrate hexahydrate aqueous solution (20mM) and hexamethylenetetramine, reacting for 8 hours at 90 ℃, washing with deionized water and drying for 6 hours at 80 ℃;
(5) the membrane was immersed in MXene solution for reaction at 7 ℃ for 36h, rinsed and dehydrated at 60 ℃ and 100 ℃ for 4h, respectively.
FIG. 2 shows the bouncing process of water droplets on the whisker-like ZnO/MXene film prepared in example 2. As can be seen from the figure, the water droplets completely bounce off after falling on the surface of the film from a certain position, demonstrating the superhydrophobicity of the prepared film.
Example 3
A preparation method of a fibrous self-repairing anti-pollution ZnO/MXene base film comprises the following steps:
(1) preparing a ZnO seed solution: dissolving ZnO with particle size of 30nm in a certain amount of water to prepare 35 wt% ZnO seed solution;
(2) measuring 1 mu L of the seed solution prepared in the step (1) in 30mL of deionized water, and carrying out vacuum filtration to deposit the seeds on a polyether sulfone (PES) porous base membrane with the pore diameter of 0.22 mu m, wherein the ratio of the volume of the solution to the area of the porous base membrane is 3 mL: 50cm 2 Drying at 60 ℃ for 4 h;
(3) suspending the film obtained in the step (2) in ZnO (particle size of 30nm) solution with the mass fraction of 5 wt% for 35r min -1 Stirring for 50min at the rotating speed, washing the surface with deionized water, and drying for 2h at the temperature of 80 ℃;
(4) suspending the membrane obtained in the step (3) in a solution (60mM) containing zinc nitrate hexahydrate aqueous solution (60mM) and hexamethylenetetramine, reacting for 5 hours at 100 ℃, washing with deionized water and drying for 10 hours at room temperature;
(5) the membrane was immersed in MXene solution for reaction at 8 ℃ for 48h, rinsed and dehydrated at 80 ℃ and 110 ℃ for 6h, respectively.
Fig. 3a is a contact angle photograph of the ZnO based film prepared in step (4) of example 3, the contact angle being 64.4 °. Fig. 3b is a photograph of the initial Contact Angle (CA) of the film prepared in example 3 (left), a photograph of the contact angle after uv irradiation (middle) and dark storage at 60 ℃ for 3 days (right). As can be seen, the CA of the prepared membrane changed from the initial 158.5 ° to 34 ° after uv irradiation for 30min, indicating the transition of the membrane from the hydrophobic state to the hydrophilic state. After 3 days of dark air storage at 60 ℃, the membrane returned to the hydrophobic state (CA 152.2 °). The prepared membrane is proved to have hydrophilic-hydrophobic reversible conversion capability.
Example 4
A preparation method of a fibrous self-repairing anti-pollution ZnO/MXene base film comprises the following steps:
(1) preparing a ZnO seed solution: ZnO with the grain diameter of 40nm is dissolved in a certain amount of water to prepare 45 wt% of ZnO seed solution;
(2) measuring 10 mu L of the seed solution prepared in the step (1) into 200mL of deionized water, and carrying out vacuum filtration to deposit the seeds on a polyvinylidene fluoride (PVDF) porous substrate membrane with the pore diameter of 0.45 mu m, wherein the ratio of the volume of the solution to the area of the porous substrate membrane is 4 mL: 60cm 2 Drying at 40 ℃ for 8 h;
(3) suspending the film obtained in the step (2) in ZnO (particle size of 40nm) solution with the mass fraction of 8 wt%, and performing treatment for 50r min -1 Stirring for 10min at the rotating speed, washing the surface with deionized water, and drying for 6h at 60 ℃;
(4) suspending the membrane obtained in the step (3) in a solution (80mM) containing zinc nitrate hexahydrate aqueous solution (80mM) and hexamethylenetetramine, reacting for 7 hours at 120 ℃, washing with deionized water and drying for 8 hours at 80 ℃;
(5) the membrane was immersed in MXene solution for 12h at 10 ℃ and washed and dehydrated for 8h at 60 ℃ and 120 ℃ respectively.
FIG. 4 is a comparison graph of water yield and salt rejection rate of long-time running of a fibrous self-repairing anti-pollution ZnO/MXene base film and a base film (the base film is a PVDF film) manufactured under real seawater conditions; it can be seen that the prepared hydrophobic membrane has a permeation flux of 3.93 kg.m -2 ·h -1 The salt rejection rate is more than 99.9 percent; the difference between the water yield of the prepared hydrophobic membrane and the basal membrane is not large, and in the process of continuously treating real seawater for 120h,the water production flux and the salt barrier rate are not reduced, and the durability is excellent.
Example 5
A preparation method of a fibrous self-repairing anti-pollution ZnO/MXene base film comprises the following steps:
(1) preparing a ZnO seed solution: dissolving ZnO with particle size of 10nm in a certain amount of water to prepare 50 wt% ZnO seed solution;
(2) weighing 20 mu L of the seed solution prepared in the step (1) into 500mL of deionized water, and carrying out vacuum filtration to deposit the seeds on a polyvinylidene fluoride (PVDF) porous basement membrane with the pore diameter of 0.22 mu m, wherein the ratio of the volume of the solution to the area of the porous basement membrane is 5 mL: 100cm 2 Drying at 60 ℃ for 10 h;
(3) suspending the film obtained in the step (2) in ZnO (particle size of 10nm) solution with the mass fraction of 10 wt% for 60r min -1 Stirring for 50min at the rotating speed, washing the surface with deionized water, and drying for 8h at 50 ℃;
(4) suspending the membrane obtained in the step (3) in a solution (60mM) containing zinc nitrate hexahydrate aqueous solution (60mM) and hexamethylenetetramine, reacting for 10 hours at 100 ℃, washing with deionized water and drying for 6 hours at 90 ℃;
(5) the membrane was immersed in MXene solution for reaction at 15 ℃ for 48h, rinsed and dehydrated at 80 ℃ and 100 ℃ for 10h, respectively.
FIG. 6 is a self-repairing schematic diagram of the whisker-like self-repairing anti-pollution ZnO/MXene base film prepared by the method.
FIG. 5 is a normalized flux comparison graph of the prepared ZnO/MXene base membrane after being respectively polluted by Bovine Serum Albumin (BSA) and Humic Acid (HA) and after being subjected to ultraviolet repair; it can be seen that, after bovine serum albumin contamination, the membrane flux decreased to 69.3% of the original membrane, and recovered to 93.4% after ultraviolet irradiation. The air permeability after humic acid contamination was reduced to 83.6% of the initial value and recovered to 97.9% after UV irradiation. Notably, the salt rejection of all films was 99.9%, indicating the anti-wetting properties of the films. Therefore, the reversible transformation of the surfaces of the hydrophilic and hydrophobic PVDF-ZM membranes can effectively reduce pollution and realize self-repair of the membranes.
The above embodiments are preferred embodiments of the present invention, but the technical implementation of the present invention is not limited to the above embodiments, and any other simplification, change, substitution, modification and combination made under the principle and spirit of the present invention should be equivalent substitution ways, and all are included in the protection scope of the present invention.
Claims (10)
1. A preparation method of a fibrous self-repairing anti-pollution ZnO/MXene base film is characterized by comprising the following steps:
(1) preparing a ZnO seed solution: dissolving nano ZnO in water to prepare ZnO seed solution;
(2) diluting the ZnO seed solution prepared in the step (1), performing vacuum filtration to deposit ZnO seeds on a porous base film, and drying;
(3) suspending the porous base membrane obtained in the step (2) in a stirred ZnO solution, washing the surface with deionized water, and drying;
(4) suspending the porous base membrane obtained in the step (3) in an aqueous solution of zinc nitrate hexahydrate and hexamethylenetetramine, reacting, washing with deionized water and drying;
(5) and (4) immersing the porous basement membrane obtained in the step (4) into MXene solution for reaction, washing and dehydrating.
2. The method for preparing the fibril-like self-repairing anti-pollution ZnO/MXene-based membrane as claimed in claim 1, wherein in step (1), the particle size of nano ZnO is 10-50 nm;
the concentration of the ZnO seed solution in the step (1) is 10-50 wt%.
3. The method for preparing the fibril-like self-repairing anti-pollution ZnO/MXene-based membrane as claimed in claim 1, wherein the dilution factor in step (2) is 1000-100000 times.
4. The method for preparing the fibril-like self-repairing anti-pollution ZnO/MXene base membrane as claimed in claim 1, wherein the porous base membrane of step (2) is polyvinylidene fluoride (PVDF) membrane or cellulose acetate fiberMore than one of a cellulose CA membrane, Nylon Nylon, a polypropylene PP membrane, a polytetrafluoroethylene PTFE membrane, a polyether sulfone PES filter membrane and a mixed fiber MCE filter membrane; the aperture of the porous base membrane is 0.1-0.5 mu m; the volume of the diluted ZnO seed solution used for vacuum filtration and the area of the porous base membrane are in a ratio of (1-5) mL: (4 to 100) cm 2 (ii) a The drying temperature is 20-150 ℃, and the drying time is 2-10 h.
5. The method for preparing the fibril-like self-repairing anti-pollution ZnO/MXene-based membrane as claimed in claim 1, wherein the mass fraction of the ZnO solution in step (3) is 0.1-10 wt%, and the particle size of the ZnO is 10-50 nm; the suspension time is 10-60min, and the stirring speed is 10-100r min -1 The drying temperature is 20-150 ℃, and the drying time is 2-10 h.
6. The method for preparing the fibril-like self-repairing anti-pollution ZnO/MXene base film according to claim 1, wherein the zinc nitrate hexahydrate comprises 10-100mM of zinc nitrate hexahydrate and the hexamethylenetetramine comprises 10-100mM of hexamethylenetetramine in the aqueous solution of zinc nitrate hexahydrate and hexamethylenetetramine in step (4); the reaction temperature is 20-150 ℃, and the reaction time is 2-10 h; the drying temperature is 20-150 ℃, and the drying time is 2-10 h;
the reaction temperature in the step (5) is 0-20 ℃, and the reaction time is 2-50 h;
the dehydration in the step (5) is two-step dehydration; the temperature of the first step of dehydration is 60-100 ℃, and the time is 2-10 h; the temperature of the second step of dehydration is 100-.
7. The method for preparing the fibril-like self-repairing anti-pollution ZnO/MXene-based membrane as claimed in claim 1, wherein the MXene solution preparation in step (5) comprises the following steps: etching the three-dimensional layered MAX by using a mixed solution of LiF and HCl, washing, adding water, and ultrasonically dispersing to obtain a two-dimensional layered MXene suspension; the mol ratio of LiF to HCl is (1-3): (1-20), wherein the molar ratio of MAX to LiF is (1-5): (5-150); the etching temperature is 20-50 ℃, and the etching time is 10-80 h.
8. The self-repairing anti-pollution ZnO/MXene base film with the fibrous root shape prepared by the preparation method of any one of claims 1-7.
9. The fibril-like self-repairing anti-pollution ZnO/MXene base membrane of claim 8, wherein the fibril-like self-repairing anti-pollution ZnO/MXene base membrane has a fibril-like shape with a contact angle of 150-165 ° and a roughness of 1-3 μm;
the fibrous-root-like self-repairing anti-pollution ZnO/MXene base membrane has the capability of hydrophilic-hydrophobic reversible conversion, the wettability of the surface of the membrane can be changed into hydrophilic property under the irradiation of ultraviolet rays, and then the surface of the membrane gradually recovers to a hydrophobic state under a dark condition.
10. The application of the fibril-like self-repairing anti-pollution ZnO/MXene base membrane in seawater desalination is characterized in that the barrier property to salt under the real seawater condition is more than 99.9%, and the water yield is 1.5-4 kg m -2 h -1 The operation can be continued for more than 120 h; the membrane can recover more than 90% of permeation flux after being polluted, and simultaneously, the salt rejection rate is kept more than 99.9%, so that the self-repairing of the membrane is realized.
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| PCT/CN2022/128474 WO2023197565A1 (en) | 2022-04-11 | 2022-10-31 | Fibrous root-like self-repairing and anti-pollution zno/mxene base membrane and preparation method therefor and application thereof |
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| WO2023197565A1 (en) * | 2022-04-11 | 2023-10-19 | 华南理工大学 | Fibrous root-like self-repairing and anti-pollution zno/mxene base membrane and preparation method therefor and application thereof |
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| CN117547984B (en) * | 2024-01-12 | 2024-04-12 | 无锡中源晟朝生态环境有限公司 | Water treatment membrane of MABR aeration bioreactor and preparation method thereof |
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