CN110935322B - High-flux alpha-C-containing3N4/Ag3PO4Forward osmosis membrane of composite material and preparation method thereof - Google Patents
High-flux alpha-C-containing3N4/Ag3PO4Forward osmosis membrane of composite material and preparation method thereof Download PDFInfo
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Abstract
The invention relates to a high-flux alpha-C-containing material3N4/Ag3PO4The invention relates to a forward osmosis membrane of composite material and a preparation method thereof3N4The Ag3PO4 composite material is successfully embedded into a polyamide layer generated by the reaction of m-phenylenediamine and trimesoyl chloride, and a novel TFC membrane is prepared. Compared with the traditional TFC membrane, the CNT shortens the water molecule transfer path, reduces the water quality transfer resistance, promotes the rapid transportation of water molecules, and the a-C3N4The a-C3N4 in the/Ag 3PO4 composite material can provide additional nano channels, so that the water permeation rate of the forward osmosis membrane is improved, the separation performance of the forward osmosis membrane is obviously improved, and the composite material has abundant negative charges, so that the electronegativity of the surface of the membrane is increased. The surface of the membrane is not easy to adsorb pollutants, and the anti-fouling performance of the membrane is greatly improved.
Description
Technical Field
The invention relates to a high-flux alpha-C-containing material3N4/Ag3PO4A forward osmosis membrane made of composite material and a preparation method thereof belong to the technical field of forward osmosis membranes.
Background
With the development of society and the continuous increase of population, fresh water resources are increasingly reduced, the problem of water pollution is gradually serious, and in order to solve the problem, obtaining high-quality fresh water through seawater desalination is an effective method.
The thin film composite forward osmosis membrane (TFCFO) prepared by interfacial polymerization reaction is widely applied due to the characteristics of low energy consumption, high flux, simple operation and the like. However, in the actual operation process, the development of the forward osmosis membrane is restricted by the problems of the upper limit balance between water flux and salt interception, membrane pollution and the like. Compared with the traditional TFC membrane, the nano material is added into the polyamide layer, so that the thin film composite membrane has better separation performance and excellent bacteriostatic and resistant performances.
Carbon nanotubes are a novel nano material, have excellent physical stability, mechanical and chemical properties and are widely applied to various fields. The carbon nano tube is utilized to construct the middle layer in the traditional supporting layer, and the interfacial polymerization process is regulated and optimized by regulating and controlling the middle layer, so that the water quality transfer resistance is reduced, and the forward osmosis membrane with high flux and good salt interception performance is prepared.
g-C3N4Due to the two-dimensional graphene-shaped structure, regularly distributed triangular nano-pores and structural defects on a layered network, the a-C-shaped nano-porous membrane shows excellent performance in the aspect of preparing high-performance membranes, and is subjected to acidification treatment3N4Can overcome g-C3N4Poor dispersibility, and is better applied to the membrane preparation process. According to literature reports, the antibacterial performance of the film can be obviously improved by adding the silver nanoparticles into the film. A to C3N4And Ag3PO4The synthesis is carried out under certain conditions and then embedded into the PA layer by interfacial polymerization, thereby increasing the antimicrobial properties of the film.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides a high-flux alpha-C-containing material3N4/Ag3PO4A forward osmosis membrane of composite material and a preparation method thereof.
The invention is realized by the following technical scheme:
high-flux alpha-C-containing3N4/Ag3PO4The forward osmosis membrane of the composite material comprises a carbon nanotube CNT (carbon nanotube) -containing base membrane and a polyamide membrane layer positioned on the carbon nanotube CNT-containing base membrane, wherein functional components are uniformly distributed in the polyamide membrane layer, and the functional components are a-C3N4/Ag3PO4Composite materials, a-C3N4/Ag3PO4The nano Ag particles in the composite material are uniformly dispersed in a-C3N4And (4) nano-chips.
According to the invention, a high-throughput alpha-C-containing material3N4/Ag3PO4The preparation method of the forward osmosis membrane of the composite material comprises the following steps:
(1) preparation of carbon nanotube dispersion
Adding carbon nano tubes and sodium dodecyl benzene sulfonate into deionized water, ultrasonically mixing uniformly, then ultrasonically crushing by using an ultrasonic cell crusher, centrifuging the mixed solution, and taking supernatant to dilute by using pure water to obtain a diluent; then adding dopamine into the diluent under heating and stirring, uniformly mixing, adding Tris-HCl buffer solution into the system, heating and stirring for reaction for 20-24 hours, and centrifuging the reacted dispersion liquid to remove insoluble substances to obtain carbon nanotube dispersion liquid;
(2)a-C3N4/Ag3PO4preparation of composite materials
Taking AgNO3Dissolving in deionized water, adding ammonia water under stirring, and adding Na2HPO4And finally adding a-C3N4Stirring for 20-24h at normal temperature; suction filtering and drying to obtain alpha-C3N4/Ag3PO4A composite material;
(3) preparation of aqueous solutions
A to C3N4/Ag3PO4Dispersing the composite material in water, adding polyamine, and mixing and stirring uniformly to obtain a water phase solution;
(4) preparation of oil phase solution
Dissolving polyacyl chloride in an organic solvent to prepare an oil phase solution;
(5) CNT-containing base film preparation
Taking the carbon nano tube dispersion liquid in the step (1), loading carbon nano tube CNT on a base film in a suction filtration mode, and drying to obtain a carbon nano tube CNT-containing base film;
(6) interfacial polymerization
Pouring the aqueous phase solution on a CNT (carbon nano tube) -containing basement membrane, keeping the aqueous phase solution for 30-180 s, removing the redundant aqueous phase solution, naturally drying the aqueous phase solution, then pouring the oil phase solution, keeping the aqueous phase solution for 30-80 s, removing the redundant oil phase solution after reaction, and drying the oil phase solution to obtain the alpha-C-containing basement membrane with high permeability3N4/Ag3PO4A forward osmosis membrane of composite material.
Preferably, in the preparation method, in the step (1), the mass ratio of the carbon nanotube to the sodium dodecylbenzenesulfonate is: 1: 8-15.
Preferably, in the preparation method, in the step (1), the mass-to-volume ratio of the sodium dodecyl benzene sulfonate to the deionized water is as follows: (1-5): 1, unit, mg/mL.
Preferably, in the step (1), the ultrasonic homogenization time is 20-30min, and the power is 250-350W.
In the preparation method, preferably, in the step (1), the ultrasonic crushing power is 270W, and the ultrasonic crushing time is 8-10 h.
In the above production method, preferably, in the step (1), the dilution ratio of the supernatant is 1 to 3 times.
In the above preparation method, preferably, in the step (1), 8 to 12mg of dopamine is added to 150mL of the diluent, 8 to 15mL of Tris-HCl buffer solution is added to 150mL of the diluent, the concentration of the Tris-HCl buffer solution is 0.1mol/L, and the pH is 8.5.
In the preparation method, the heating and stirring temperature in the step (1) is preferably constant at 30-50 DEG C
In the above production method, preferably, in the step (1), the rotation speed of the centrifugal treatment is 10000 rmp.
In the preparation process of the carbon nano tube homogeneous dispersion liquid, the ultrasonic cell cleaning machine enables the carbon nano tube and the sodium dodecyl benzene sulfonate to be uniformly dispersed in deionized water, and the ultrasonic cell crusher crushes the carbon nano tube into smaller size so as to be uniformly dispersed in the solution. Dopamine enables amide bonds to be combined with carbon nanotubes with hydrophobic surfaces, so that the carbon nanotubes can be dispersed in a solution more stably. The Tris-HCl buffer solution maintained the reaction at a constant pH.
In the above production method, preferably, in the step (2), AgNO3The mass volume ratio of the added amount of the (1) to the deionized water is (1.1-1.5): (140-200), units, g/mL; the mass fraction of ammonia water is 8-15%, the volume ratio of the addition amount of ammonia water to deionized water is 15-20:150, and Na2HPO4The mass volume ratio of the added amount of the (C) to the deionized water is (0.05-0.1): (140-200), unit, g/mL.
In the above preparation method, preferably, in the step (2), the amount of a-C3N4 added is equal to AgNO3The mass ratio of (0.6-0.8): (1.1-1.5).
In the above production process, preferably, in the step (2), a to C3N4Is composed of g-C3N4The preparation method comprises the following steps: take 4g g-C3N4Adding the mixture into 52g of concentrated sulfuric acid, heating and stirring the mixture for 2 hours at the temperature of 140 ℃ in an oil bath kettle, and then heating and stirring the mixture for 3 hours continuously when the temperature is raised to 170 ℃; naturally cooling the solution obtained by the reaction, transferring the solution to distilled water with the temperature of 75 ℃ and the volume of 800mL, adding 85.58g of ammonium chloride, stirring for 2h, standing for 1h, carrying out hot filtration, placing the obtained liquid in a water bath kettle for ice bath for 1.5h, filtering, drying the obtained solid to obtain a-C3N4。
In the above preparation method, preferably, in the step (2), the drying temperature is constant at 30 to 50 ℃.
The silver nano material is uniformly loaded on the alpha-C3N4Thereby endowing the composite material with excellent sterilization capability.
In the above production process, it is preferable that, in the step (3), a to C in the aqueous solution3N4/Ag3PO4The concentration of the composite material is 0.1g-0.5g/L, preferably, a-C in aqueous phase solution3N4/Ag3PO4The concentration of the composite material was 0.5 g/L.
In the above production method, preferably, in the step (3), the mass concentration of the polyamine in the aqueous phase solution is 1 to 3%.
In the above preparation method, preferably, in the step (3), the polyamine is one of o-phenylenediamine, p-phenylenediamine, m-phenylenediamine and piperazine, and preferably, the polyamine is m-phenylenediamine.
In the above preparation method, preferably, in the step (4), the polybasic acyl chloride is one of trimesoyl chloride, m-trimesoyl chloride, cyclohexanetriacyl chloride, cyclopentanetriacyl chloride, propanetriacyl chloride or pentatriacyl chloride; the organic solvent is one of n-hexane, n-heptane, dodecane or tetradecane,
in the preparation method, preferably, in the step (4), the mass concentration of the polybasic acyl chloride in the oil phase solution is 0.02-0.2%
In the above preparation method, preferably, in the step (5), the base film is polysulfone, polyethersulfone, polyethylene, polyamideimide, polypropylene or polyacrylonitrile.
In the above production method, preferably, in the step (5), the base film is a circular film having a diameter of 5 cm.
In the above production method, the volume of the CNT dispersion used in step (5) is preferably 6 mL.
Preferably, in the step (5), the drying temperature is 50-70 ℃ and the drying time is 10 min.
In the above preparation method, preferably, in the step (6), after the aqueous phase solution is poured, the retention time is 120s, and the oil phase solution is poured, and the reaction time is 60 s.
Preferably, in the step (6), the drying temperature is 70-90 ℃ and the drying time is 4-8 min.
The preparation method of the invention firstly prepares g-C3N4By acidification to a-C3N4Then a-C is added3N4To prepare a-C3N4/Ag3PO4 composite material. g-C3N4The two-dimensional network terminal was peeled to a-C3N4 with smaller size, higher water dispersibility, and more defects. g-C3N4a-C3N4, which decreases from μm to hundreds of nm, forms more nanocapillaries between adjacent a-C3N4 nanoplates. The a-C3N4 has excellent dispersing performance, aggregation of nanosheets is inhibited, after the a-C3N4 and Ag3PO4 are compounded, nano Ag particles are uniformly dispersed on the a-C3N4 nanosheets, the composite material is endowed with excellent bactericidal performance, the a-C3N4 can provide additional nano channels, water permeability can be improved, and a topological structure with rich a-C3N4 defects provides a short path for rapid diffusion of water. Dissolving the a-C3N4/Ag3PO4 composite material into an aqueous phase solution, and successfully embedding the a-C3N4/Ag3PO4 attapulgite-silver nanoparticle composite material into a polyamide layer generated by the reaction of m-phenylenediamine and trimesoyl chloride along with the generation of interfacial polymerization reaction. The a-C3N4/Ag3PO4 composite material has negative charges, so that the composite membrane has stronger anti-fouling capability to conventional pollutants. The composite membrane adopts CNT as a substrate, reduces the water quality transfer resistance, greatly improves the water flux compared with the prior TFC membrane, maintains the interception effect of NaCl at a higher level, and has the anti-fouling capabilityExcellent sterilizing capability and can be widely applied to the fields of seawater desalination, industrial wastewater recovery and the like.
The invention has the technical characteristics and advantages that:
1. the invention takes a CNT (carbon nano tube) base membrane containing carbon nano tubes as a substrate, and successfully embeds a-C3N4/Ag3PO4 composite material into a polyamide layer generated by the reaction of m-phenylenediamine and trimesoyl chloride through interfacial polymerization reaction between polyamine and polyacyl chloride to prepare the novel TFC membrane. Compared with the traditional TFC membrane, the CNT shortens the transfer path of water molecules, reduces the transfer resistance of water quality, promotes the rapid transportation of the water molecules, and the a-C3N4 in the a-C3N4/Ag3PO4 composite material can provide an additional nano channel, so that the water permeation rate of the forward osmosis membrane is improved, and the separation performance of the forward osmosis membrane is obviously improved.
2. The a-C3N4/Ag3PO4 composite material on the forward osmosis membrane is simple in preparation process, Ag can be attached to the surface of the a-C3N4 nanosheet, and the composite material has abundant negative charges, so that the electronegativity of the surface of the membrane is increased. Because the conventional pollutants have abundant negative charges, the surfaces of the membranes are not easy to adsorb the pollutants, and the antifouling performance of the membranes is greatly improved.
3. The silver nanoparticles in the a-C3N4/Ag3PO4 composite material on the forward osmosis membrane have bactericidal performance, so that the prepared TFC membrane has excellent antibacterial performance, and Ag ions can influence the normal life activities of bacteria, thereby inhibiting the growth and reproduction of the bacteria and prolonging the service life of the membrane.
4. The forward osmosis membrane has high water flux and strong bactericidal performance, has obvious separation performance, reduces the growth of bacteria on the surface of the membrane, has stable and durable effect and prolongs the service life of the membrane.
Drawings
FIG. 1 shows a-C on a forward osmosis membrane prepared in example 1 of the present invention3N4/Ag3PO4Electron microscopy of the composite.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
High-flux alpha-C-containing3N4/Ag3PO4The method for preparing a forward osmosis membrane of (1), comprising the steps of:
(1) preparation of CNT dispersion: 10mg of carbon nano tube and 100mg of sodium dodecyl benzene sulfonate are added into 100ml of deionized water, and the mixture is treated by ultrasonic for 30min by a 300W power ultrasonic cleaner, so that the solute is uniformly dispersed in the solution. Then ultrasonic treatment is carried out for 10h by an ultrasonic cell crusher. Centrifuging the mixed solution for 30min, and diluting the supernatant with pure water by 1 time to obtain a diluted solution; then adding dopamine into the diluent under heating and stirring, adding 10mg of dopamine into each 150mL of the diluent, continuously stirring for 1h at 40 ℃, adding Tris-HCl buffer (pH 8.5) into the system, continuously stirring for 24h at 40 ℃, adding 10mL of Tris-HCl buffer into each 150mL of the diluent, centrifuging the reacted dispersion for 30min, and taking the centrifuged supernatant to obtain a carbon nanotube dispersion; refrigerating in a constant temperature refrigerator at 4 deg.C.
(2)a-C3N4/Ag3PO4Preparation of composite Material 1.3512g of AgNO was taken3Dissolving in 150mL deionized water, stirring for 30min, adding 18mL 10% ammonia water, adding 0.3744g Na2HPO4Dissolving in 30mL deionized water, adding into the system, stirring for 30min, and adding 0.0777g of a-C3N4Stirring for 24 hours at normal temperature; suction filtering and drying to obtain alpha-C3N4/Ag3PO4A composite material; a-C3N4/Ag3PO4The electron micrograph of the composite material is shown in FIG. 1, and it can be seen from FIG. 1 that the nano Ag particles are uniformly dispersed in the a-C3N4And (4) nano-chips.
(3) Preparation of aqueous phase solution: a to C3N4/Ag3PO4Dispersing the composite material in water, adding m-phenylenediamine, mixing and stirring uniformly to obtain an aqueous phase solution, wherein a-C in the aqueous phase solution3N4/Ag3PO4The concentration of the composite material is 0.5g/L, and the mass concentration of m-phenylenediamine is 2%.
(4) Preparation of oil phase solution: dissolving trimesoyl chloride in n-hexane to obtain an oil phase solution with the mass fraction of 0.1%, and uniformly mixing the oil phase solution by ultrasonic waves to obtain an oil phase solution;
(5) CNT-containing base film preparation
Taking 6mL of the carbon nanotube dispersion liquid obtained in the step (1), loading carbon nanotube CNT on a base film in a suction filtration mode, and drying to obtain a carbon nanotube CNT-containing base film;
(6) interfacial polymerization
Pouring the water phase solution on a CNT (carbon nanotube) -containing CNT-based film, keeping for 120s, removing the redundant water phase solution, naturally drying, pouring the oil phase solution, contacting with the oil phase solution for 60s, removing the redundant oil phase solution on the surface, naturally drying, and oven drying at 80 deg.C for 5min to obtain the high-flux a-C-containing CNT-based film3N4/Ag3PO4A forward osmosis membrane of composite material.
Example 2
High throughput a-C containing samples as described in example 13N4/Ag3PO4The forward osmosis membrane of (1), except that,
in step (3), a-C in the aqueous solution3N4/Ag3PO4The concentration of the composite material was 0.3 g/L.
Example 3
High throughput a-C containing samples as described in example 13N4/Ag3PO4The forward osmosis membrane of (1), except that,
in step (3), a-C in the aqueous solution3N4/Ag3PO4The concentration of the composite material was 0.4 g/L.
Comparative example 1
High throughput a-C containing samples as described in example 13N4/Ag3PO4The forward osmosis membrane of (1), except that,
in step (3), a-C in the aqueous solution3N4/Ag3PO4The concentration of the composite material was 0.6 g/L.
Comparative example 2
High throughput a-C containing samples as described in example 13N4/Ag3PO4The forward osmosis membrane of (1), except that,
in step (3), a-C in the aqueous solution3N4/Ag3PO4The concentration of the composite material was 0.7 g/L.
Comparative example 3
A preparation method of a PES-PA forward osmosis membrane comprises the following steps:
(1) preparation of aqueous phase solution: adding m-phenylenediamine into water to obtain an aqueous phase solution with the mass concentration of the m-phenylenediamine of 2 percent,
(2) preparation of oil phase solution: dissolving trimesoyl chloride in n-hexane to obtain an oil phase solution with the mass fraction of 0.1%, and uniformly mixing the oil phase solution by ultrasonic waves to obtain an oil phase solution;
(3) interfacial polymerization
Pouring the water phase solution on a PES basement membrane, keeping the PES basement membrane for 120s, removing the redundant water phase solution, naturally drying, then pouring the oil phase solution, removing the redundant oil phase solution on the surface after contacting 60s, naturally drying, and then putting the dried solution into an 80-degree oven for drying for 5min to obtain the PES-PA forward osmosis membrane.
Comparative example 4
A PES-CNT-PA forward osmosis membrane was prepared in the same manner as in comparative example 3, except that,
and (4) the basement membrane in the step (3) is a carbon nanotube CNT basement membrane, and the PES-CNT-PA forward osmosis membrane is obtained after the preparation is finished.
Comparative example 5
PES-a-C3N4The process for the preparation of a forward osmosis membrane was carried out according to the process of comparative example 4, except that,
step (1) reacting a to C3N4Dispersing in water, adding m-phenylenediamine, mixing and stirring to obtainTo aqueous solution, a-C in aqueous solution3N4The concentration of (A) is 0.5g/L, and the mass concentration of m-phenylenediamine is 2%; after the preparation is finished, PES-a-C is obtained3N4A forward osmosis membrane.
Application test example:
1. five different forward osmosis membranes of examples 1 to 3 and comparative examples 1 to 2 were placed in a forward osmosis membrane module for testing the separation performance thereof.
The separation performance is carried out by adopting a forward osmosis testing device which is an independent membrane component, and the effective testing area of the membrane component is 3cm2The drawing liquid is a 1mol/L NaCl solution, the mass counting is carried out on the side of the drawing liquid by an electronic balance, the stock solution is deionized water, and the reverse salt flux is measured by a conductivity meter for the stock solution measurement. The gear pump and cross flow operation mode are adopted, and the flow rate is controlled to be cm/s. Fixing the forward osmosis membrane on a membrane component, opening a gear pump, running for 10-15min, starting counting by using an electronic balance, and measuring the conductivity of the stock solution every two minutes. The water flux as well as the reverse salt flux of the forward osmosis membrane was calculated from the added mass of the balance and the measured conductivity. Containing a-C3N4/Ag3PO4The water flux and reverse salt flux of the composite forward osmosis membrane are shown in table 1:
TABLE 1 Water flux and reverse salt flux of Forward osmosis membranes
| Example 1 | Example 2 | Example 3 | Comparative example 1 | Comparative example 2 | |
| Water flux (LMH) | 69.7 | 46 | 50.7 | 49.3 | 40 |
| Reverse salt flux (gMH) | 2.67 | 2 | 2.44 | 2.33 | 2 |
As can be seen from Table 1, as the amount of material added increases, the water flux begins to increase due to a-C in the composite material3N4More channels are provided for water molecule transmission, the water flux of the forward osmosis membrane reaches the maximum when the adding amount is 0.5g/L, and the water flux of the forward osmosis membrane begins to decrease along with the increase of the adding amount, because the excessive material causes the blockage of membrane pores, so that the water flux of the forward osmosis membrane is reduced.
2. For example 1 containing a to C3N4/Ag3PO4Composite forward osmosis membrane, PES-PA forward osmosis membrane of comparative example 3, PES-CNT-PA forward osmosis membrane of comparative example 4, PES-a-C of comparative example 53N4The forward osmosis membrane of (2) was subjected to an anti-fouling test to compare the anti-fouling effect to the control.
Anti-fouling experiment: humic acid and bovine serum albumin respectively represent common natural organic matters and protein pollutants, and a cross flow mode is used for pollution-cleaning-recovery test. Fixing a forward osmosis membrane in a membrane pool, firstly using 1mol of NaCl as an extraction liquid and deionized water as a stock solution to carry out membrane initial flux measurement, after the operation is stable, converting the stock solution into humic acid or bovine serum albumin, carrying out an item pollution test for 24h
Followed by a 15min membrane rinse with deionized water. And then, replacing the drawing liquid side with new 1mol of NaCl drawing liquid, replacing the stock solution side with deionized water, and carrying out membrane recovery flux measurement for 5 hours. The antifouling properties of the forward osmosis membrane are the flux recovery (FRR,%) and the total fouling rate (R%tAnd,%) as shown in Table 2,
TABLE 2 forward osmosis membrane anti-fouling Performance test
| Humic acid | PES-PA | PES-CNT-PA | PES-a-C3N4 | Example 1 |
| FRR(％) | 59.15 | 70 | 80 | 81.25 |
| Rt(％) | 62 | 47 | 50 | 49 |
| Bovine serum albumin | PES-PA | PES-CNT-PA | PES-a-C3N4 | Example 1 |
| FRR(％) | 25 | 35 | 38.5 | 61.7 |
| Rt(％) | 86 | 78 | 67 | 63 |
The data show that the forward osmosis membrane has better anti-fouling performance to humic acid, because bovine serum albumin is micromolecular protein and is easier to attach to the forward osmosis surface, so that the flux of the forward osmosis membrane is reduced more quickly. And the forward osmosis membrane added with the composite material has the optimal membrane anti-fouling performance through a parallel control group.
Carrying out bacteriostasis test on the positive osmosis membrane, and selecting four groups of parallel control groups: PES-PA, PES-CNT-PA, PES-a-C, respectively3N4PES-complex, as detailed below: coli (strain ATCC25922) was added to sterilized 250mL LB broth and cultured on a constant temperature shaker at 37 ℃ for 24 hours. Centrifuging the cultured Escherichia coli at 10000rpm for 5min, and diluting with normal saline to a concentration of about 1.0 × 106cfu/mL. The membrane was then added to the flask containing the bacterial suspension and incubated for 2h in a 37 ℃ constant temperature shaker. Thereafter, the membrane was washed with 5ml of physiological saline to collect the large intestine on the surface thereofA bacillus. 0.1ml of the bacterial suspension collected by washing was spread on LB agar medium, spread evenly with a spreading bar, and cultured at 37 ℃ for 24 hours. The medium was removed, the number of colonies was obtained by plate counting and the bacteriostatic rate was calculated, and the results are shown in table 3.
TABLE 3 forward osmosis membrane bacteriostatic performance test
| PES-PA | PES-CNT-PA | PES-a-C3N4 | Example 1 | |
| Bacteriostatic ratio (%) | 0 | 2.3 | 13 | 99 |
As can be seen from Table 3, the forward osmosis membrane added with the composite material in example 1 has 99% of bacteriostasis rate and the best bacteriostasis effect.
Claims (10)
1. High-flux alpha-C-containing3N4/Ag3PO4The forward osmosis membrane of the composite material comprises a carbon nanotube CNT (carbon nanotube) -containing base membrane and a polyamide membrane layer positioned on the carbon nanotube CNT-containing base membrane, wherein functional components are uniformly distributed in the polyamide membrane layer, and the functional components are a-C3N4/Ag3PO4Composite materials, a-C3N4/Ag3PO4Nano Ag in composite material3PO4Is uniformly dispersed in a-C3N4And (4) nano-chips.
2. High-flux alpha-C-containing3N4/Ag3PO4The preparation method of the forward osmosis membrane of the composite material comprises the following steps:
(1) preparation of carbon nanotube dispersion
Adding carbon nano tubes and sodium dodecyl benzene sulfonate into deionized water, ultrasonically mixing uniformly, then ultrasonically crushing by using an ultrasonic cell crusher, centrifuging the mixed solution, and taking supernatant to dilute by using pure water to obtain a diluent; then adding dopamine into the diluent under heating and stirring, uniformly mixing, adding Tris-HCl buffer solution into the system, heating and stirring for reaction for 20-24 hours, and centrifuging the reacted dispersion liquid to remove insoluble substances to obtain carbon nanotube dispersion liquid;
（2）a-C3N4/Ag3PO4preparation of composite materials
Taking AgNO3Dissolving in deionized water, adding ammonia water under stirring, and adding Na2HPO4And finally adding a-C3N4Stirring for 20-24h at normal temperature; suction filtering and drying to obtain alpha-C3N4/Ag3PO4A composite material;
(3) preparation of aqueous solutions
A to C3N4/Ag3PO4Dispersing the composite material in water, adding polyamine, and mixing and stirring uniformly to obtain a water phase solution;
(4) preparation of oil phase solution
Dissolving polyacyl chloride in an organic solvent to prepare an oil phase solution;
(5) CNT-containing base film preparation
Taking the carbon nano tube dispersion liquid in the step (1), loading carbon nano tube CNT on a base film in a suction filtration mode, and drying to obtain a carbon nano tube CNT-containing base film;
(6) interfacial polymerization
Pouring the aqueous phase solution on a CNT (carbon nano tube) -containing basement membrane, keeping the aqueous phase solution for 30-180 s, removing the redundant aqueous phase solution, naturally drying the aqueous phase solution, then pouring the oil phase solution, keeping the aqueous phase solution for 30-80 s, removing the redundant oil phase solution after reaction, and drying the oil phase solution to obtain the alpha-C-containing basement membrane with high permeability3N4/Ag3PO4A forward osmosis membrane of composite material.
3. The preparation method according to claim 2, wherein in the step (1), the mass ratio of the carbon nanotubes to the sodium dodecylbenzenesulfonate is 1: 8-15 parts of; the mass volume ratio of the sodium dodecyl benzene sulfonate to the deionized water is (1-5): 1, unit, mg/mL.
4. The preparation method according to claim 2, wherein in the step (1), the ultrasonic homogenizing time is 20-30min, and the power is 250-350W; the ultrasonic crushing power is 270W, and the ultrasonic crushing time is 8-10 h; the dilution multiple of the supernatant is 1-3 times; 8-12mg of dopamine is added into each 150mL of diluent, 8-15mL of Tris-HCl buffer solution is added into each 150mL of diluent, the concentration of the Tris-HCl buffer solution is 0.1mol/L, and the pH = 8.5; the heating and stirring temperature is constant temperature of 30-50 ℃.
5. The method according to claim 2, wherein in the step (2), AgNO3The mass volume ratio of the added amount of the (1) to the deionized water is (1.1-1.5): (140-200), units, g/mL; the mass fraction of ammonia water is 8-15%, the volume ratio of the addition amount of ammonia water to deionized water is 15-20:150, and Na2HPO4The mass volume ratio of the added amount of the (C) to the deionized water is (0.05-0.1): (140-200), unit, g/mL.
6. The method according to claim 2, wherein the amount of a-C3N4 added in step (2) is equal to AgNO3The mass ratio of (0.6-0.8): (1.1-1.5).
7. According to claimThe process according to claim 2, wherein, in the step (2), a to C3N4Is composed of g-C3N4The preparation method comprises the following steps: take 4g g-C3N4Adding the mixture into 52g of concentrated sulfuric acid, heating and stirring the mixture for 2 hours at the temperature of 140 ℃ in an oil bath kettle, and then heating and stirring the mixture for 3 hours continuously when the temperature is raised to 170 ℃; naturally cooling the solution obtained by the reaction, transferring the solution to distilled water with the temperature of 75 ℃ and the volume of 800mL, adding 85.58g of ammonium chloride, stirring for 2h, standing for 1h, carrying out hot filtration, placing the obtained liquid in a water bath kettle for ice bath for 1.5h, filtering, drying the obtained solid to obtain a-C3N4。
8. The method according to claim 2, wherein in the step (3), a-C in the aqueous solution3N4/Ag3PO4The concentration of the composite material is 0.1g-0.5g/L, and the mass concentration of the polyamine in the aqueous phase solution is 1-3%.
9. The method according to claim 2, wherein in the step (4), the polybasic acid chloride is one of trimesoyl chloride, m-trimesoyl chloride, cyclohexanetriyl chloride, cyclopentanetriyl chloride, propanetriacyl chloride or pentatriacyl chloride; the organic solvent is one of n-hexane, n-heptane, dodecane or tetradecane, and the mass concentration of the polyacyl chloride in the oil phase solution is 0.02-0.2%.
10. The method according to claim 2, wherein in the step (6), after the aqueous phase solution is poured, the holding time is 120s, the oil phase solution is poured, and the reaction time is 60 s; the drying temperature is 70-90 deg.C, and the drying time is 4-8 min.
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