CN117339403A - Antibacterial nanofiltration membrane based on nickel ion doped carbon dots, preparation method thereof and CrO in water removal 42- Application to - Google Patents
Antibacterial nanofiltration membrane based on nickel ion doped carbon dots, preparation method thereof and CrO in water removal 42- Application to Download PDFInfo
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- CN117339403A CN117339403A CN202311307193.0A CN202311307193A CN117339403A CN 117339403 A CN117339403 A CN 117339403A CN 202311307193 A CN202311307193 A CN 202311307193A CN 117339403 A CN117339403 A CN 117339403A
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- 239000012528 membrane Substances 0.000 title claims abstract description 209
- 238000001728 nano-filtration Methods 0.000 title claims abstract description 86
- 229910001453 nickel ion Inorganic materials 0.000 title claims abstract description 72
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 68
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 title claims abstract description 64
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 title claims abstract description 60
- 230000000844 anti-bacterial effect Effects 0.000 title claims abstract description 54
- 238000002360 preparation method Methods 0.000 title claims abstract description 28
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 53
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 52
- 239000008346 aqueous phase Substances 0.000 claims abstract description 41
- UWCPYKQBIPYOLX-UHFFFAOYSA-N benzene-1,3,5-tricarbonyl chloride Chemical compound ClC(=O)C1=CC(C(Cl)=O)=CC(C(Cl)=O)=C1 UWCPYKQBIPYOLX-UHFFFAOYSA-N 0.000 claims abstract description 38
- 238000000034 method Methods 0.000 claims abstract description 32
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- 238000012695 Interfacial polymerization Methods 0.000 claims abstract description 14
- CQSUOFIQGRWWDH-UHFFFAOYSA-N [Ni].N1CCNCC1 Chemical compound [Ni].N1CCNCC1 CQSUOFIQGRWWDH-UHFFFAOYSA-N 0.000 claims abstract description 9
- GLUUGHFHXGJENI-UHFFFAOYSA-N Piperazine Chemical compound C1CNCCN1 GLUUGHFHXGJENI-UHFFFAOYSA-N 0.000 claims description 54
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- MHABMANUFPZXEB-UHFFFAOYSA-N O-demethyl-aloesaponarin I Natural products O=C1C2=CC=CC(O)=C2C(=O)C2=C1C=C(O)C(C(O)=O)=C2C MHABMANUFPZXEB-UHFFFAOYSA-N 0.000 description 2
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- WZCQRUWWHSTZEM-UHFFFAOYSA-N 1,3-phenylenediamine Chemical compound NC1=CC=CC(N)=C1 WZCQRUWWHSTZEM-UHFFFAOYSA-N 0.000 description 1
- 229920012266 Poly(ether sulfone) PES Polymers 0.000 description 1
- 229920001273 Polyhydroxy acid Polymers 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
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Classifications
-
- 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
- B01D71/56—Polyamides, e.g. polyester-amides
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
- B01D67/0079—Manufacture of membranes comprising organic and inorganic components
-
- 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
- B01D69/02—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor characterised by their properties
-
- 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
- B01D71/02—Inorganic material
-
- 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
- B01D71/02—Inorganic material
- B01D71/021—Carbon
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/44—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis
- C02F1/442—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis by nanofiltration
-
- 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
- C02F2101/10—Inorganic compounds
- C02F2101/20—Heavy metals or heavy metal compounds
- C02F2101/22—Chromium or chromium compounds, e.g. chromates
-
- 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)
- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Nanotechnology (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Organic Chemistry (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
Abstract
The invention relates to the technical field of nanofiltration membrane modification, in particular to an antibacterial nanofiltration membrane based on nickel ion doped carbon dots, a preparation method thereof and CrO in water removal 4 2‑ Application to the above. The preparation method comprises the following steps: (1) preparing nickel ion doped carbon dots; (2) preparing piperazine-nickel ion doped carbon dot aqueous phase solution; (3) preparing trimesic acid chloride organic phase solution; (4) Letting piperazine-nickel leaveAnd carrying out interfacial polymerization on the aqueous phase solution of the sub-doped carbon points and the organic phase solution of the trimesoyl chloride on the surface of the polyether sulfone membrane to form a polyamide modified layer, thereby obtaining the antibacterial nanofiltration membrane based on the nickel ion doped carbon points. The antibacterial nanofiltration membrane based on the nickel ion doped carbon dots prepared by the method has good salt rejection rate and higher membrane flux, and has stronger antibacterial performance. At the same time, the nanofiltration membrane is specific to the micro-pollutant CrO 4 2‑ Exhibits fluorescence response properties and has great potential in monitoring the presence or absence of such ions in wastewater.
Description
Technical field:
the invention relates to the technical field of nanofiltration membrane modification, in particular to an antibacterial nanofiltration membrane based on nickel ion doped carbon dots, a preparation method thereof and CrO in water removal 4 2- Application to the above.
Technical background:
the membrane method is a current high-efficiency and promising water treatment method, and has the characteristics of economy, low energy consumption, expandability, easy manufacture, ecological friendliness and the like. Membrane processes include Reverse Osmosis (RO), forward Osmosis (FO), nanofiltration (NF), ultrafiltration (UF), and the like. Nanofiltration is a pressure driven membrane separation process between reverse osmosis and ultrafiltration, mainly for separating substances of small molecular weight. Nanofiltration has advantages of high permeate flux, low pressure driving, relatively high rejection rate, and low relative cost, compared to other filtration membranes, so that it is of great interest in various scientific fields of application, especially in the field of water treatment.
Membrane fouling is one of the biggest obstacles to the development of membrane separation. Membrane fouling is divided into biological and non-biological fouling. Non-biological contamination can be alleviated and addressed by physical means, such as rinsing and shaking, etc., while biological contamination is much more troublesome. During operation of the membrane module, microorganisms can deposit, adhere and grow on the inner and outer surfaces of the membrane, thereby causing biological contamination. Bacteria accumulate on the membrane surface, which not only affects water permeability, but also aggravates other types of contamination due to strong adhesion of bacteria. This biological contamination is irreversible, which can make the membrane less and less water purifying and separating, affecting the process of membrane operation.
The problem of exceeding the standard of heavy metal ions in wastewater is widely concerned, and the problem of exceeding the standard of heavy metal ions in wastewater has posed a serious threat to human health and ecosystems. CrO (CrO) 4 2- Is very toxic and is liable to cause serious diseases, resulting in environmental deterioration, but CrO 4 2- Still widely used in industry and agriculture. Thus, crO dissolved in water is detected and removed 4 2- Is of vital importance. To date, technology has tended to mature p-CrO 4 2- There are many monitoring methods, including electrochemical monitoring methods, mass spectrometry, atomic absorption spectrometry, and chromatography. Although the detection processes have good effect, the detection processes are not suitable for CrO in the field of water treatment 4 2- And (5) rapidly monitoring the concentration in real time. For many years, industry has also adopted various conventional methods to remove CrO from wastewater 4 2- Such as adsorption, chemical precipitation, redox, reverse osmosis, etc. The method does play the purpose of removing hexavalent chromium, but has the defects of high cost, low efficiency, complex operation steps, poor stability and selectivity, secondary pollution and the like, and is not suitable for the current application environment. Nanofiltration is capable of intercepting high valence ions and has been applied to the removal of many ions at present. Thus, nanofiltration is applied to CrO 4 2- The removal field of (3) is undoubtedly wide in application prospect.
Grafting, surface coating, incorporation of nanomaterials into polymers, and the like are some known methods of film modification. In the prior patent CN115090126A, molybdenum dioxide and copper are used for modifying an NF membrane, the method comprises the steps of respectively doping the molybdenum dioxide and the copper into an m-phenylenediamine aqueous phase solution and a trimesic acid chloride organic phase solution, then carrying out interfacial polymerization on the surface of a polyethersulfone membrane through the two solutions, combining the molybdenum dioxide and the copper on the membrane, and fixing the Cu on the surface of the membrane by utilizing the coordination and adsorption of S atoms to the Cu, so that the membrane has an antibacterial function. And molybdenum dioxide also has stronger hydrophilic property and contributes to the increase of the flux of the membrane to a certain extent. However, the membrane prepared by the method has the problems that the antibacterial capability is not very outstanding, copper ions on the surface of the membrane still easily leak, the antibacterial efficiency is weakened, the copper ions easily enter the permeate, and the permeate is influenced to a certain extent. Patent CN114345152B discloses a high-flux anti-pollution composite nanofiltration membrane and a preparation method thereof. The separation layer of the nanofiltration membrane is prepared by interfacial polymerization reaction between a water phase containing polyamine and an organic phase containing polybasic acyl chloride and side chain double-end epoxy modified silicone oil. The epoxy modified silicone oil directly participates in interfacial polymerization, an effective water channel is constructed on a polyamide network, the membrane flux can be effectively improved, unreacted epoxy groups react with carboxyl generated by hydrolysis of acyl chloride and carboxyl of polyhydroxy acid, the whole membrane tends to be electrically neutral, the hydrophilicity is effectively improved, and the anti-pollution capability of the nanofiltration membrane can be obviously improved. However, the preparation method is complex, the types of the reactants are various, the controllability is poor, and the sustainability of the membrane cannot be ensured. Patent CN102008908A discloses a preparation method of an ultrafiltration membrane with the use of modified carbon nanotubes to enhance antibacterial properties. In the method, the problem of agglomeration of the carbon nanotubes is solved, but the array orientation of the carbon nanotubes is very difficult to control, and the preparation process is complex. At the same time, the swelling problem of carbon nanotubes is also a difficult problem to ignore.
The invention comprises the following steps:
the invention aims to provide an antibacterial nanofiltration membrane based on nickel ion doped carbon dots and a preparation method thereof. Meanwhile, the modified nanofiltration membrane is coated on CrO 4 2- Has great potential in the removal and sensing detection of (C).
The technical scheme adopted by the invention is as follows:
performing interfacial polymerization on the surface of the polyether sulfone membrane by using a piperazine aqueous phase solution and a trimesoyl chloride organic phase solution to form a polyamide layer; adding nickel ion doped carbon points into the piperazine water phase for modification, wherein the specific steps are as follows:
step one: preparing piperazine aqueous phase solution, and doping nickel ion doped carbon points into the aqueous phase solution to obtain PIP-Ni-C-dots aqueous phase solution;
step two: preparing trimesic acid chloride organic phase solution;
step three: blowing the polyethersulfone membrane, pouring piperazine-nickel ion doped carbon dot aqueous phase solution on the front surface of the membrane, soaking for 3min, removing surface liquid drops at room temperature, pouring trimesoyl chloride organic phase solution on the surface of the membrane, and soaking for 2min to obtain a nanofiltration membrane after interfacial polymerization;
step four: and (3) placing the prepared nanofiltration membrane into a drying oven and drying at 60 ℃ for 8min to obtain the modified antibacterial nanofiltration membrane based on the nickel ion doped carbon dots.
Preferably, in the first step, the solute of the aqueous solution is piperazine and nickel ion doped carbon dots, and the solvent is deionized water;
preferably, the preparation of the piperazine-nickel ion doped carbon dot aqueous solution in the first step comprises the following steps:
weighing the anhydrous piperazine and the nickel ion doped carbon dots obtained by calculation in a beaker;
and II, adding deionized water into the beaker, and performing ultrasonic treatment for 30min to obtain PIP-Ni-C-dots aqueous phase solution.
Preferably, the concentration of anhydrous piperazine in step one is 1.00wt%; the concentration of the nickel ion doped carbon point is 0.25 to 1.00 weight percent;
preferably, in the trimesic acid chloride organic phase solution in the second step, the solute is trimesic acid chloride (TMC), and the solvent is n-hexane;
preferably, the TMC concentration in the trimesic acid chloride organic phase solution in step two is 0.15wt%;
preferably, the preparation of Ni-C-dots in step one is as follows:
s1: 0.17g of NiCl was taken 2 ·6H 2 O,0.56g EDTA and 0.32g PIP in a beaker;
s2: adding 30mL of deionized water into a beaker, and performing ultrasonic treatment for 30min to completely dissolve the solute in the water; s3: transferring the obtained solution into a polytetrafluoroethylene liner high-pressure reaction kettle for heating;
s4: heating at 180deg.C at a rate of 5deg.C/min for 360min, and naturally cooling to room temperature after the reaction;
s5: subpackaging the obtained solution into a centrifuge tube, centrifuging at a rotating speed of 12000r/min, and retaining supernatant after centrifuging;
s6: dialyzing the obtained supernatant to remove unreacted molecules, ions and the like in the solution;
s7: and performing treatments such as rotary evaporation, freeze drying and vacuum drying on the carbon dot solution to obtain dried carbon dot powder.
The antibacterial nanofiltration membrane prepared by the method of the invention removes CrO in water 4 2- Application to the above.
The invention has the beneficial effects that:
1、Ni 2+ takes part in the reaction of the carbon point and is firmly combined with other reactants through chemical bonds to form a part of the carbon point. During interfacial polymerization, nickel ions are fixed on the surface of the membrane along with carbon dots, thus ensuring that nickel ions cannot leak in long-term operation of the membrane. Thus, the stability of the membrane is ensured, and meanwhile, the pollution to the permeate liquid is avoided.
2. The carbon dots prepared by the method have a large number of hydrophilic groups such as amino groups, imino groups, carboxyl groups and the like, and when the carbon dots are uniformly distributed on the membrane, the hydrophilicity of the membrane can be increased, and the flux of the nanofiltration membrane can be improved.
3. The nickel ion doped carbon point prepared by the invention can generate Reactive Oxygen Species (ROS) under the irradiation of specific wavelength, and the ROS can attack protein structures such as cell membranes and cytoplasm of bacteria, so that the aim of inactivating the bacteria is fulfilled, and the wavelength corresponding to the dual-wavelength effect of the carbon point in the invention is just positioned in the range of an incandescent lamp, so that a light source is cheaper, and the antibiosis can be completed under the irradiation of the incandescent lamp, which is a good message for nanofiltration membrane antibiosis. Furthermore, ni 2+ The antibacterial agent also has antibacterial property, and can exert antibacterial effect after being dispersed on the film along with carbon dots. Under the double antibacterial conditions, the nanofiltration membrane has the super antibacterial effect.
4. The nickel ion doped carbon dot nanofiltration membrane prepared by the method is modified by doping carbon dots into PIP aqueous phase solution and performing interfacial polymerization reaction. Compared with unmodified membranes, the nanofiltration membrane prepared by the method has flux improved between 40.98 and 71.25 percent, and the rejection rate reduction of magnesium sulfate, magnesium chloride, sodium sulfate and sodium chloride is also within an acceptable range under the pressure of 3.5 bar.
5. The nickel ion doped carbon point nanofiltration membrane prepared by the invention is CrO in the membrane 4 2- In the trapping experiments of (2)For CrO under alkaline condition 4 2- The retention rate of the catalyst can reach more than 99 percent, and shows good CrO 4 2- Retention properties. In addition, the nanofiltration membrane prepared by the method also shows good CrO 4 2- Sensing properties, useful as probes for such trace contaminants.
6. The preparation method of the nickel ion doped carbon point super-antibacterial nanofiltration membrane provided by the invention has the advantages of simple process, safety and environmental protection, can effectively reduce the chemical cleaning frequency of the nanofiltration membrane, prolong the service life of the nanofiltration membrane, remarkably increase the economic benefit, and has the potential of being applied to the actual production industries such as water treatment, medicines and the like.
In a word, the nickel ion doped carbon point nanofiltration membrane prepared by the method has the super-antibacterial capability, improves the water flux and simultaneously controls the salt interception rate within an acceptable range. At the same time, at CrO 4 2- The method has great application potential in aspects of removal and sensing.
Description of the drawings:
in order that the invention may be more clearly understood, a detailed description of the invention will be rendered by reference to specific embodiments thereof which are illustrated in the appended drawings.
Fig. 1 is a TEM image of nickel ion doped carbon dots.
Fig. 2 is a FTIR plot of nickel ion doped carbon dots.
Fig. 3 is an XRD and Zeta potential plot of nickel ion doped carbon dots.
Fig. 4 is a water contact angle for the comparative example and the example. From top to bottom are comparative example, example 1, example 2, example 3, example 4, respectively.
Fig. 5 is an AFM (atomic force microscope) of comparative example and example. Comparative example, example 1, example 2, example 3, example 4.
FIG. 6 is a graph showing the flux of pure water in the comparative examples and examples.
FIG. 7 is a graph of comparative and example versus NaCl, na 2 SO 4 ，MgCl 2 ，MgSO 4 Is a graph of the retention ratio.
FIG. 8 shows the acid nature of the acid,Respectively for Na under neutral and alkaline conditions 2 SO 4 ，MgSO 4 Is a graph of the retention ratio versus the transmission coefficient.
FIG. 9 is a schematic diagram showing the antibacterial effect against E.coli of the comparative example and the example. From left to right, from top to bottom are comparative example, example 1, example 2, example 3, example 4, respectively.
FIG. 10 is a diagram for explaining a chemical method of carbon dot antibacterial mechanism.
FIG. 11 is a graph showing the retention rate of CrO 42-in water by the nanofiltration membranes prepared in comparative examples 1 to 4.
FIG. 12 is a graph of Ni-C-dots sensing CrO 42-.
FIG. 13 shows the CrO 42-sensing by the nanofiltration membranes prepared in examples 1-4.
FIG. 14 is a graph showing the effect of anions on fluorescence spectra of Ni-C-dots aqueous solutions.
The specific embodiment is as follows:
in order that the invention may be more clearly set forth, a detailed description of the invention will be rendered by reference to specific embodiments thereof which are illustrated in the appended drawings. The examples are not intended to limit the scope of the invention but are merely illustrative of the invention and any modifications within the scope of the claims remain within the scope of the invention.
The following examples and comparative examples each used a self-made PES-based membrane. The specific process of the laboratory homemade PES base film is as follows:
polyether sulfone PES, N-methyl pyrrolidone DMAC and N-N-dimethylacetamide NMP are prepared according to the following mass ratio: n-methylpyrrolidone DMAC: N-N-dimethylacetamide NMP:12:44:44, obtaining a casting solution, pouring the prepared casting solution on a glass plate which is cleaned in advance, and casting by using a casting knife with the thickness of 120 mu m. The casting solution was exposed to the air atmosphere for 1min, and then immersed in an aqueous coagulation bath at room temperature, and the solution was immediately subjected to phase inversion to form a base film. The prepared film was stored in deionized water, and water was changed every 6 hours for two days to remove the residual solvent.
The test methods and results for each type of relevant performance parameters in examples and comparative examples are shown below:
both membrane flux and salt rejection tests were performed in a dead-end filtration device with magnetic stirring.
During flux test of the membrane, the membrane passing pressure is set to 3.5bar, the pure water volume passing through the membrane is tested, and the pure water flux calculation formula is as follows:
in J W (in L/m2.h) is the flux of pure water in the membrane, and As (in m 2 ) DeltaV (in L) is the change in permeate volume over the test time Deltat (in h) for the effective membrane area.
When the salt interception rate of the membrane is tested, the membrane passing pressure is set to be 3.5bar, the solution rough preparation concentration is 1000ppm, the accurate conductivity of the solution before passing through the membrane and the conductivity of the permeate after passing through the membrane are tested, and the salt interception rate is calculated according to the formula:
wherein Rs (% of units) is the salt rejection rate, C p And C f The concentration of the solution after permeation and the initial feed solution concentration are given in ppm, respectively.
The water contact angle test of the film was performed at room temperature.
The static antibacterial test of nanofiltration membranes is as follows:
the antibacterial activity of the membranes was determined using colony counting. The film (effective area 2.54 cm. Times.7.62 cm) was sterilized with ultraviolet light for 10min and placed on a slide. Then, under the irradiation of incandescent lamp light, 75 mu L of 10 3 The CFU/mL bacterial suspension contacted the active side of the membrane and then covered the membrane with a glass slide at 37 c with an incandescent light source power of 40W, 15cm from the membrane, for a light exposure time of 3h. After illumination, transferring the membrane into normal saline for ultrasonic treatment for 5min, and removing bacteria deposited on the surface of the membrane. Finally, the bacterial suspension is placed on a nutrient agar plate, incubated for 12 hours at 37 ℃, and the colony count is counted. The antibacterial activity is calculated as follows:
where Nb and Nm are the colony numbers corresponding to the comparative example and the example, respectively.
CrO of film 4 2- When the interception test is carried out, the pressure of the passing film is set to be 3.5bar, the concentration of the solution is roughly prepared to be 500ppm, the ultraviolet spectroscopic spectra of the solution before passing through the film and the penetrating liquid after passing through the film are tested, the concentration is calculated according to a standard curve, and the interception rate calculation formula is as follows:
wherein R is s Rejection rate (in%) C p And C f The concentration of the solution after permeation and the initial feed solution concentration are given in ppm, respectively.
CrO with nickel ion doped carbon dots 4 2- In the sensing test, crO is added 4 2- And testing fluorescence spectrums of different target concentrations by the solution to obtain a sensing effect graph.
CrO of film 4 2- In the sensing test, crO with different target concentrations is added 4 2- And (3) testing the fluorescence spectrum of the film added with different target concentrations on the film to obtain a sensing effect graph.
Comparative example:
a nanofiltration membrane preparation, comprising the steps of:
step one: preparing 100g of piperazine aqueous phase solution, wherein the solute is PIP, the solvent is deionized water, the concentration of PIP is 1.00wt%, and carrying out ultrasonic treatment for 30min;
step two: preparing 100g of trimesic acid chloride organic phase solution, wherein the solute is TMC, the solvent is n-hexane, the concentration of TMC is 0.15wt%, and carrying out ultrasonic treatment for 30min;
step three: taking a piece of PES (polyether sulfone) basal membrane which is self-made in a laboratory and is subjected to solvent removal, washing the surface of the membrane by deionized water, drying the PES basal membrane in a drying box at 60 ℃, taking out the basal membrane after the drying is finished, and naturally cooling to room temperature;
step four: fixing the base film on a laboratory film making device, and enabling the smooth surface of the base film to face upwards;
step five: pouring piperazine aqueous phase solution subjected to ultrasonic treatment on the front surface of a membrane, soaking for 3min, taking down the membrane, removing surface liquid drops at room temperature, fixing the membrane on a self-made membrane device in a laboratory again, pouring trimesoyl chloride organic phase solution on the surface of the membrane, soaking for 2min, and taking down the membrane to obtain a nanofiltration membrane subjected to interfacial polymerization;
step six: and (3) putting the prepared membrane into a drying oven, drying at 60 ℃ for 8min to obtain a nanofiltration membrane, cooling to room temperature, and then putting the nanofiltration membrane into deionized water for storage.
Example 1:
the preparation of the antibacterial nanofiltration membrane based on the nickel ion doped carbon dots comprises the following steps:
step one, preparing nickel ion doped carbon dots: 0.17g of NiCl was taken 2 ·6H 2 O,0.56g EDTA and 0.32g PIP were stirred ultrasonically in a beaker containing 30mL deionized water until completely dissolved. Carrying out a hydrothermal reaction for 360min under the conditions of 180 ℃ and a heating speed of 5 ℃/min, and naturally cooling to room temperature after the reaction is finished; and (3) centrifuging the obtained solution at the rotating speed of 12000r/min for 30min, dialyzing and purifying the supernatant, and spin-evaporating and freeze-drying to obtain dry blue carbon dot powder.
Step two, preparing PIP-Ni-C-dots aqueous phase solution: preparing 100g of piperazine aqueous phase solution, wherein the solute is PIP, the solvent is deionized water, the concentration of PIP is 1.00wt%, nickel ion doped carbon dots are doped into the aqueous phase solution to obtain PIP-Ni-C-dots aqueous phase solution, the concentration of Ni-C-dots is 0.25wt%, and carrying out ultrasonic treatment for 30min;
step three, preparing trimesic acid chloride organic phase solution: preparing 100g of trimesic acid chloride organic phase solution, wherein the solute is TMC, the solvent is n-hexane, the concentration of TMC is 0.15wt%, and carrying out ultrasonic treatment for 30min;
step four, taking a piece of PES (polyether sulfone) basal membrane which is self-made in a laboratory and is subjected to solvent removal, flushing the surface of the membrane by deionized water, drying the PES basal membrane in a drying box at 60 ℃, taking out the basal membrane after the drying is finished, and naturally cooling to room temperature;
fixing the base film on a self-made film making device in a laboratory so that the smooth surface of the base film faces upwards;
pouring the PIP-Ni-C-dots aqueous phase solution subjected to ultrasonic treatment on the front surface of the membrane, soaking for 3min, taking down the membrane, removing surface liquid drops at room temperature, fixing the membrane on a self-made membrane preparation device in a laboratory again, pouring the trimesoyl chloride organic phase solution on the surface of the membrane, soaking for 2min, and taking down the membrane to obtain the nanofiltration membrane subjected to interfacial polymerization;
and seventhly, drying the prepared membrane in a drying oven at 60 ℃ for 8min to obtain the antibacterial nanofiltration membrane based on the nickel ion doped carbon dots, cooling to room temperature, and then placing in deionized water for preservation. The nanofiltration membrane prepared by the embodiment has the advantages of antibiosis and high efficiency for removing CrO in water body 4 2- Simultaneously, crO in the water body can be monitored in real time 4 2 Ion content.
Example 2:
the preparation of the antibacterial nanofiltration membrane based on the nickel ion doped carbon dots comprises the following steps:
step one: 0.17g of NiCl was taken 2 ·6H 2 O,0.56g EDTA and 0.32g PIP were stirred ultrasonically in a beaker containing 30mL deionized water until completely dissolved. Carrying out a hydrothermal reaction for 360min under the conditions of 180 ℃ and a heating speed of 5 ℃/min, and naturally cooling to room temperature after the reaction is finished; and (3) centrifuging the obtained solution at the rotating speed of 12000r/min for 30min, dialyzing and purifying the supernatant, and spin-evaporating and freeze-drying to obtain dry blue carbon dot powder.
Step two: preparing 100g of piperazine aqueous phase solution, wherein the solute is PIP, the solvent is deionized water, the concentration of PIP is 1.00wt%, nickel ion doped carbon dots are doped into the aqueous phase solution to obtain PIP-Ni-C-dots aqueous phase solution, the concentration of Ni-C-dots is 0.50wt%, and carrying out ultrasonic treatment for 30min;
step three: preparing 100g of trimesic acid chloride organic phase solution, wherein the solute is TMC, the solvent is n-hexane, the concentration of TMC is 0.15wt%, and carrying out ultrasonic treatment for 30min;
step four: taking a piece of PES (polyether sulfone) basal membrane which is self-made in a laboratory and is subjected to solvent removal, washing the surface of the membrane by deionized water, drying the PES basal membrane in a drying box at 60 ℃, taking out the basal membrane after the drying is finished, and naturally cooling to room temperature;
step five: fixing the base film on a self-made film making device in a laboratory so that the smooth surface of the base film faces upwards;
step six: pouring PIP-Ni-C-dots aqueous phase solution subjected to ultrasonic treatment on the front surface of a membrane, soaking for 3min, taking down the membrane, removing surface liquid drops at room temperature, fixing the membrane on a self-made membrane preparation device in a laboratory again, pouring trimesoyl chloride organic phase solution on the surface of the membrane, soaking for 2min, and taking down the membrane to obtain a nanofiltration membrane subjected to interfacial polymerization;
step seven: and (3) putting the prepared membrane into a drying oven, drying at 60 ℃ for 8min to obtain the antibacterial nanofiltration membrane based on nickel ion doped carbon dots, cooling to room temperature, and then putting into deionized water for preservation. The nanofiltration membrane prepared by the embodiment has the advantages of antibiosis and high efficiency for removing CrO in water body 4 2- Simultaneously, crO in the water body can be monitored in real time 4 2 Ion content.
Example 3:
the preparation of the antibacterial nanofiltration membrane based on the nickel ion doped carbon dots comprises the following steps:
step one: 0.17g of NiCl was taken 2 ·6H 2 O,0.56g EDTA and 0.32g PIP were stirred ultrasonically in a beaker containing 30mL deionized water until completely dissolved. Carrying out a hydrothermal reaction for 360min under the conditions of 180 ℃ and a heating speed of 5 ℃/min, and naturally cooling to room temperature after the reaction is finished; and (3) centrifuging the obtained solution at the rotating speed of 12000r/min for 30min, dialyzing and purifying the supernatant, and spin-evaporating and freeze-drying to obtain dry blue carbon dot powder.
Step two: preparing 100g of piperazine aqueous phase solution, wherein the solute is PIP, the solvent is deionized water, the concentration of PIP is 1.00wt%, nickel ion doped carbon dots are doped into the aqueous phase solution to obtain PIP-Ni-C-dots aqueous phase solution, the concentration of Ni-C-dots is 0.75wt%, and carrying out ultrasonic treatment for 30min;
step three: preparing 100g of trimesic acid chloride organic phase solution, wherein the solute is TMC, the solvent is n-hexane, the concentration of TMC is 0.15wt%, and carrying out ultrasonic treatment for 30min;
step four: taking a piece of PES (polyether sulfone) basal membrane which is self-made in a laboratory and is subjected to solvent removal, washing the surface of the membrane by deionized water, drying the PES basal membrane in a drying box at 60 ℃, taking out the basal membrane after the drying is finished, and naturally cooling to room temperature;
step four: fixing the base film on a self-made film making device in a laboratory so that the smooth surface of the base film faces upwards;
step five: pouring PIP-Ni-C-dots aqueous phase solution subjected to ultrasonic treatment on the front surface of a membrane, soaking for 3min, taking down the membrane, removing surface liquid drops at room temperature, fixing the membrane on a self-made membrane preparation device in a laboratory again, pouring trimesoyl chloride organic phase solution on the surface of the membrane, soaking for 2min, and taking down the membrane to obtain a nanofiltration membrane subjected to interfacial polymerization;
step six: and (3) putting the prepared membrane into a drying oven, drying at 60 ℃ for 8min to obtain the antibacterial nanofiltration membrane based on nickel ion doped carbon dots, cooling to room temperature, and then putting into deionized water for preservation. The nanofiltration membrane prepared by the embodiment has the advantages of antibiosis and high efficiency for removing CrO in water body 4 2- Simultaneously, crO in the water body can be monitored in real time 4 2 Ion content.
Example 4:
the preparation of the antibacterial nanofiltration membrane based on the nickel ion doped carbon dots comprises the following steps:
step one: 0.17g of NiCl was taken 2 ·6H 2 O,0.56g EDTA and 0.32g PIP were stirred ultrasonically in a beaker containing 30mL deionized water until completely dissolved. Carrying out a hydrothermal reaction for 360min under the conditions of 180 ℃ and a heating speed of 5 ℃/min, and naturally cooling to room temperature after the reaction is finished; and (3) centrifuging the obtained solution at the rotating speed of 12000r/min for 30min, dialyzing and purifying the supernatant, and spin-evaporating and freeze-drying to obtain dry blue carbon dot powder.
Step two: preparing 100g of piperazine aqueous phase solution, wherein the solute is PIP, the solvent is deionized water, the concentration of PIP is 1.00wt%, nickel ion doped carbon dots are doped into the aqueous phase solution to obtain PIP-Ni-C-dots aqueous phase solution, the concentration of Ni-C-dots is 1.00wt%, and carrying out ultrasonic treatment for 30min;
step three: preparing 100g of trimesic acid chloride organic phase solution, wherein the solute is TMC, the solvent is n-hexane, the concentration of TMC is 0.15wt%, and carrying out ultrasonic treatment for 30min;
step four: taking a piece of PES (polyether sulfone) basal membrane which is self-made in a laboratory and is subjected to solvent removal, washing the surface of the membrane by deionized water, drying the PES basal membrane in a drying box at 60 ℃, taking out the basal membrane after the drying is finished, and naturally cooling to room temperature;
step five: fixing the base film on a self-made film making device in a laboratory so that the smooth surface of the base film faces upwards;
step six: pouring PIP-Ni-C-dots aqueous phase solution subjected to ultrasonic treatment on the front surface of a membrane, soaking for 3min, taking down the membrane, removing surface liquid drops at room temperature, fixing the membrane on a self-made membrane preparation device in a laboratory again, pouring trimesoyl chloride organic phase solution on the surface of the membrane, soaking for 2min, and taking down the membrane to obtain a nanofiltration membrane subjected to interfacial polymerization;
step seven: and (3) drying the prepared membrane in a drying oven at 60 ℃ for 8min to obtain the antibacterial nanofiltration membrane based on nickel ion doped carbon dots, cooling to room temperature, and then placing in deionized water for preservation. The nanofiltration membrane prepared by the embodiment has the advantages of antibiosis and high efficiency for removing CrO in water body 4 2- Simultaneously, crO in the water body can be monitored in real time 4 2 Ion content.
The following characterization was performed on the antibacterial nanofiltration membranes based on nickel ion doped carbon dots prepared in examples 1 to 4:
1. the nickel ion doped carbon points were characterized. As shown in fig. 1, successful synthesis of spherical carbon dots is evident from the TEM image of nickel ion doped carbon dots. And, by counting the particle size distribution thereof, it was found that it is a typical particle size distribution of carbon dots, and the average size of the carbon dots was 6.92nm.
2. Characterization of FTIR at carbon sites, as shown in FIG. 2, FIG. 2A can see that the carbon sites are located at 3262cm -1 The broad peak at the site is O-H,2959cm-1The broad peak at which belongs to the N-H stretching vibration. The intensity of these two peaks did not change much compared to the starting material. And at 1586cm -1 There is a peak of higher intensity, which is clearly a stretching vibration peak belonging to c=n/c=o. There is also a distinct peak in FIG. 2A, i.e., at 3262cm -1 The C-N/C-H stretching vibration peak. At 1320cm -1 There is also a more pronounced absorption peak, which is derived from the C-O stretching shock. It can be derived from this that-NH is present in the Ni-C-dots 2 and-COOH. Notably, for Ni-C-dots, see FIG. 2B, at 1107, 1000, and 974cm -1 The new absorption band at the site of the stretching vibration of the metal ligand bond further confirms Ni 2+ Synergistic effect with C-dots.
3. To analyze the state and surface charge of the Ni-C-dots, XRD and Zeta potential tests were performed on the Ni-C-dots, see FIG. 3, and FIG. 3A shows that after Ni doping, ni-C-dots have a diffraction peak and shoulder at 23.7 DEG and 41.6 DEG, respectively, corresponding to the (002) and (100) crystal planes of carbon, indicating that Ni-C-dots are amorphous structures. The Zeta potential measurement of FIG. 3B shows that the potential of Ni-C-dots is about-11.3 mV, which indicates that the Ni-C-dots surface has abundant hydrophilic groups-COOH, resulting in the Ni-C-dots surface having negative charges.
The results of comparing the pure water flux and the contact angle of the antibacterial nanofiltration membranes based on the nickel ion doped carbon dots of examples 1 to 4 with those of the conventional polyamide nanofiltration membranes of the comparative example are shown in table one:
table one:
from Table one can see that the nanofiltration membranes of examples 1-4 have a flux improvement between 40.98% and 71.25% compared to the nanofiltration membranes of the comparative examples at a pressure of 3.5bar, and the reason for the increase in water flux is analyzed in conjunction with FIGS. 4, 5 and 6: firstly, a large number of hydrophilic groups exist on carbon points, and the groups can form hydrogen bonds with water molecules, so that the transmission of the water molecules is accelerated; and secondly, as carbon points are dispersed on the surface of the nanofiltration membrane, the surface of the membrane becomes smooth, and the transport resistance of water molecules is reduced. However, as can be seen from examples 1-4, when the carbon dot concentration exceeds 0.75wt%, a decrease in membrane flux is caused when 1.00wt% is reached, which is probably due to agglomeration of carbon dots on the membrane surface, resulting in clogging of membrane pores, which is analyzed from a decrease in water flux without an increase in contact angle. From the experimental results, it was found that the membrane flux increase rate was maximized when the concentration of the nickel ion doped carbon dots was 0.75 wt%.
Examples 1-4 antibacterial nanofiltration membranes based on Nickel ion doped carbon dots were prepared with the same comparative conventional polyamide nanofiltration membranes against NaCl, na 2 SO 4 ，MgCl 2 ，MgSO 4 The retention rate of (2) was compared, and the results are shown in Table II.
And (II) table:
from the analysis of table one and table two, referring to fig. 6 and 7, it can be seen that as the concentration of carbon dots increases, the water flux increases to a concentration of 0.75wt% to peak, and the rejection rate of four salts also decreases to the lowest point at this time, and then as the concentration of carbon dots increases, the water flux of nanofiltration membranes decreases, and the rejection rate increases, because the carbon dots agglomerate on the membrane surface, blocking the membrane pores is caused, and ions do not easily pass through the membrane, thereby causing the rejection rate to increase.
As is clear from FIG. 7, the overall salt cut rate is ranked as NaCl<Na 2 SO 4 <MgCl 2 <MgSO 4 The reason for this is explained by the fact that the membrane surface is positively charged in an acidic environment, and the repulsive effect on divalent cations is stronger, whereas the charge repulsive effect comes from the negative charge on the surface in an alkaline condition, and thus the trapping capacity for the same divalent anions is similar. The experimental environment of the salt interception rate of the invention is mediumIs acidic or weakly acidic, thus leading to NaCl<Na 2 SO 4 <MgCl 2 <MgSO 4 Such a cut-off ordering is fully matched to the results of fig. 7 and 8.
The antibacterial ability of the antibacterial nanofiltration membranes of examples 1 to 4 based on nickel ion doped carbon dots was compared with that of the conventional polyamide nanofiltration membranes of comparative examples, and the results are shown in Table III.
Table three:
| sequence number | Comparative example | Example 1 | Example 2 | Example 3 | Example 4 |
| Antibacterial efficiency (%) | / | 98.81 | 100 | 100 | 100 |
From the comparison of examples 1-4 and comparative example, it can be seen that, with the increase of the concentration of the carbon dots doped with nickel ions, the bacterial inactivation rate of the modified membrane gradually increases, when the concentration of the carbon dots reaches 0.25wt%, the antibacterial rate reaches 98.81%, when the concentration of the carbon dots reaches 0.50wt%, the antibacterial rate reaches 100%, which indicates that the modified membrane has a super strong bactericidal effect on escherichia coli, and the inactivation rate of the modified polyamide nanofiltration membrane for two bacteria reaches 100% when the concentration of the carbon dots is continuously increased.
Such strong bactericidal power can be attributed to the following reasons: the nickel ion doped carbon point prepared by the invention can generate ROS under the irradiation of specific wavelength, in particular 1 O 2 As shown in FIG. 10, after TMB is added to the carbon dot solution, the solution turns blue under the irradiation of natural light, and the ultraviolet curve corresponding to the solution also shows a distinct characteristic peak at about 650nm, and the solution can be captured after the TMB is added 1 O 2 After tryptophan as a capturing agent of (C), the blue color of the solution disappeared, and the absorption peak of the ultraviolet curve of the solution at about 650nm was also substantially disappeared, indicating that the resultant 1 O 2 Has been captured by tryptophan. This experiment demonstrates that the ROS species generated by this carbon point are 1 O 2 . While 1 O 2 Can attack protein structures such as cell membranes and cytoplasm of bacteria, thereby achieving the purpose of inactivating the bacteria.
FIG. 11 shows the removal of CrO from Ni-C-dots-M at 500ppm concentration with pH=10 solution pH at an applied pressure of 3.5bar 4 2- Is effective in (1). Different from the monovalent and divalent interception conditions, the modified membrane has the following effect on CrO with the addition of the concentration of carbon points 4 2- The interception effect of the polymer is improved compared with that of an unmodified membrane, and the interception rate reaches 99.18 percent. With the increase of the carbon point adding proportion, the film pair CrO 4 2- The rejection rate of the catalyst is also reduced to a minimum point at 0.75wt% and the rejection effect is reduced to the minimum point at the time, and the salt rejection rate is increased back along with the subsequent increase of the concentration of the carbon dots, and the salt rejection rate is increased back due to the agglomeration phenomenon of the carbon dots on the surface of the membrane, so that the membrane pores are blocked, ions are not easy to pass through the membrane, and the salt rejection rate is increased back. This experiment demonstrates that Ni-C-dots-M has CrO removal 4 2- Is not limited by the potential of (a).
As shown in FIG. 12, ni-C-dots were used for CrO at a concentration ranging from 0.1 to 100. Mu.M 4 2- Has obvious quenching effect and concentrationThe larger the quenching effect is, the more remarkable. This shows that Ni-C-dots have good fluorescent probe function and can be used for CrO 4 2- And (5) sensing.
Further evaluation of CrO of Ni-C-dots-M 4 2- Is suitable for detection. As shown in FIG. 13, ni-C-dots-M remained specific to CrO over the 0-10 μm concentration range 4 2- Has obvious quenching effect and shows that the catalyst has a high quenching effect on CrO 4 2- Good sensing effect.
The invention also researches the conventional anion pair CrO 4 2- The effect of the assay. As shown in FIG. 14, strongly reducing anions such as SO are not considered 3 2- 、S 2- And I - For the effects of containing 6mg mL -1 Ni-C-dots and 20. Mu.M CrO 4 2- 1mM Cl - ，SO 4 2- And NO 3 - 0.5. Mu.M AC - And CO 3 2- F at 0.5mM - And Br (Br) - ClO 0.1mM 4 - ，MnO 4 2- No significant interference is generated.
The previous description of the embodiments is provided to facilitate a person skilled in the art to make and use the present invention. The present invention is not limited to the above-described embodiments, and modifications and variations made by those skilled in the art in light of the present invention or within the scope of the present invention should be included in the scope of the present invention.
Claims (9)
1. The preparation method of the antibacterial nanofiltration membrane based on the nickel ion doped carbon dots is characterized by comprising the following steps of: performing interfacial polymerization on the surface of a polyether sulfone membrane by using piperazine-nickel ion doped carbon point aqueous phase solution and trimesoyl chloride TMC organic phase solution to form the antibacterial nanofiltration membrane based on nickel ion doped carbon points, wherein the specific steps are as follows:
(1) Preparing nickel ion doped carbon points;
(2) Preparing piperazine-nickel ion doped carbon dot aqueous phase solution: preparing a piperazine aqueous phase solution with a certain concentration, and then doping nickel ion doped carbon points into the piperazine aqueous phase solution to obtain a PIP-Ni-C-dots aqueous phase solution;
(3) Preparation of trimesoyl chloride organic phase solution: according to the concentration requirement, dissolving trimesic acid chloride TMC in normal hexane, and fully mixing and dissolving to obtain trimesic acid chloride organic phase solution;
(4) Fixing a dry polysulfone base membrane on a membrane preparation mould, then soaking the upper surface of the polysulfone base membrane in the piperazine-nickel ion doped carbon dot aqueous phase solution prepared in the step (2) for a few minutes, removing the surface aqueous phase solution at room temperature, soaking the upper surface of the polysulfone base membrane in the trimesoyl chloride organic phase solution prepared in the step (3) for a few minutes, and removing the surface organic phase solution at room temperature to obtain a modified nanofiltration membrane;
(5) And (3) placing the modified nanofiltration membrane prepared in the step (4) into a drying oven for drying treatment to obtain the antibacterial nanofiltration membrane based on the nickel ion doped carbon points.
2. The method for preparing the antibacterial nanofiltration membrane based on the nickel ion doped carbon dots, which is characterized by comprising the following steps of: the preparation method of the nickel ion doped carbon point in the step (1) comprises the following specific steps:
s1: respectively weighing a certain amount of NiCl according to a proportion 2 ·6H 2 O, EDTA and piperazine PIP are placed in a beaker, a proper amount of deionized water is added in the beaker, and ultrasonic stirring is carried out for 28-32min, so that solute is completely dissolved in water;
s2: transferring the solution obtained in the step S1 into a polytetrafluoroethylene liner high-pressure reaction kettle, heating a reaction system at a certain speed, after the temperature is raised to a set temperature, carrying out heat preservation reaction for 5-7h, naturally cooling to room temperature after the reaction is finished, centrifuging the reaction solution cooled to the room temperature, and reserving supernatant;
s3: dialyzing the obtained supernatant, and collecting the dialysate to obtain a carbon dot solution;
s4: and performing rotary evaporation and drying treatment on the carbon dot solution to obtain the dry nickel ion doped carbon dot Ni-C-dots powder.
3. The method for preparing the antibacterial nanofiltration membrane based on the nickel ion doped carbon dots, which is characterized by comprising the following steps of: the specific operation of the piperazine-nickel ion doped carbon dot aqueous phase solution preparation in the step (2) is as follows: weighing the anhydrous piperazine and nickel ion doped carbon point powder obtained by calculation according to the concentration requirement, adding deionized water into a beaker, and performing ultrasonic treatment for 28-32min to obtain PIP-Ni-C-dots aqueous phase solution.
4. The method for preparing the antibacterial nanofiltration membrane based on the nickel ion doped carbon dots, which is characterized by comprising the following steps of: the concentration of piperazine in the PIP-Ni-C-dots aqueous phase solution in the step (2) is 1.00 weight percent, and the concentration of nickel ion doped carbon points in the PIP-Ni-C-dots aqueous phase solution is 0.25-1.00 weight percent.
5. The method for preparing the antibacterial nanofiltration membrane based on the nickel ion doped carbon dots, which is characterized by comprising the following steps of: in the step (4), the upper surface of the dried polysulfone-based membrane is soaked in the piperazine-nickel ion doped carbon dot aqueous phase solution prepared in the step (2) for 3min; and (3) soaking the upper surface of the polysulfone base membrane soaked by the water phase in the step (4) in a trimesoyl chloride organic phase solution for 2 minutes.
6. The method for preparing the antibacterial nanofiltration membrane based on the nickel ion doped carbon dots, which is characterized by comprising the following steps of: niCl in step S1 2 ·6H 2 The mixing mass ratio of O, EDTA to piperazine PIP is 1 (3.2-3.3) (1.8-1.9).
7. The method for preparing the antibacterial nanofiltration membrane based on the nickel ion doped carbon dots, which is characterized by comprising the following steps of: and when the reaction system in the step S2 is heated, the heating speed is 5 ℃/min, and the set temperature is 180 ℃.
8. An antibacterial nanofiltration membrane prepared by the method for preparing an antibacterial nanofiltration membrane based on nickel ion doped carbon dots according to any one of claims 1 to 7.
9. According to the weightsThe method for preparing an antibacterial nanofiltration membrane based on nickel ion doped carbon dots of claim 8, wherein CrO in water is removed from the antibacterial nanofiltration membrane 4 2- Application to the above.
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