CN109772183B - Anionic compound intercalation g-C3N4Preparation method and application of composite membrane - Google Patents

Anionic compound intercalation g-C3N4Preparation method and application of composite membrane Download PDF

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CN109772183B
CN109772183B CN201910206629.4A CN201910206629A CN109772183B CN 109772183 B CN109772183 B CN 109772183B CN 201910206629 A CN201910206629 A CN 201910206629A CN 109772183 B CN109772183 B CN 109772183B
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冉瑾
潘婷
储成全
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Hefei University of Technology
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Abstract

The invention discloses an anionic compound intercalation g-C3N4A process for preparing composite membrane includes such steps as thermal polymerizing to obtain bulk phase g-C3N4(ii) a Then the product is physically stripped to obtain g-C3N4A nanosheet dispersion; finally, mixing the anionic compound with g-C3N4Mixing and depositing the nano-sheet dispersion liquid on a porous base membrane to obtain the anionic compound intercalation g-C3N4A composite membrane. Compared with the prior art, the anionic compound intercalated g-C prepared by the invention3N4The composite membrane has higher water flux and more excellent selectivity.

Description

Anionic compound intercalation g-C3N4Preparation method and application of composite membrane
Technical Field
The invention relates to a preparation method of a two-dimensional film, in particular to an anionic compound intercalated g-C3N4A method for preparing a composite membrane and its use.
Background
With the rapid development of economy, the problems of environmental pollution and resource shortage are increasingly raised. The messy discharge of various industrial and domestic sewage places a heavier burden on countries that are otherwise in resource shortage. Membrane separation techniques are widely used for wastewater treatment due to their advantages of simple process and low energy consumption. In recent years, two-dimensional materials such as graphene oxide, transition metal disulfides, covalent organic compounds, metal organic compounds, layered double hydroxides and the like have become substrates for two-dimensional film preparation due to advantages of monoatomic thickness, porous or non-porous structure, stable chemical properties, thermal stability and the like. However, the existing two-dimensional film has the defects that the graphene oxide two-dimensional film is complex in preparation method and easy to swell in water.
Journal of Membrane Science and technology (Journal of Membrane Science,2015,490,72-83) reports that g-C3N4The nano-sheet is doped into a polymer matrix to prepare the high-selectivity hybrid membrane. By mixing a certain amount of g-C3N4The nanosheet powder was dispersed in water and sonicated, and then Sodium Alginate (SA) was dissolved in the above dispersion and stirred at 30 ℃ for 5 h. Spin coating the membrane solution on a substrate film Polyacrylonitrile (PAN), and then coating the membrane solution on a substrate film of 0.5mol/LCaCl2Immersing the aqueous solution for 10min to crosslink the film, and washing with water to remove uncrosslinked CaCl2. Although the prepared hybrid membrane has a certain improvement on the SA membrane with relatively pure flux and selectivity, the process is complex, the membrane controllability is poor, and the mass production is not facilitated.
Chinese patent CN105214512 discloses a preparation method of a graphene oxide film on the surface of a carrier, which comprises the steps of firstly introducing an amino active group on the surface of the carrier, and then uniformly loading graphene oxide on the surface of the carrier to obtain the graphene oxide film. The preparation method enhances the acting force between the carrier and the graphene oxide membrane, improves the retention rate of dye molecules, but also increases transmembrane resistance, so that the flux is only 5 L.h-1·m-2·bar-1And the process is complicated.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provides an anionic compound intercalated g-C3N4A method for preparing a composite membrane and its use. The composite membrane has higher water flux and more excellent selectivity.
The anionic compound intercalation g-C of the invention3N4The composite membrane is prepared by first obtaining a bulk phase g-C by a thermal polymerization process3N4(ii) a Then the product is physically stripped to obtain g-C3N4A nanosheet dispersion; finally, mixing the anionic compound with g-C3N4Mixing and depositing the nano-sheet dispersion liquid on a porous base membrane to obtain the anionic compound intercalation g-C3N4A composite membrane.
The anionic compound intercalation g-C of the invention3N4Preparation of composite membranesThe method specifically comprises the following steps:
step 1: weighing 1-5g of melamine or urea, placing the melamine or urea in a mortar for grinding for 10-20min, and then placing the melamine or urea in a muffle furnace for calcining at the temperature of 500-600 ℃ for 8-12h to obtain a bulk phase g-C3N4；
Step 2: subjecting the bulk phase g-C obtained in step 13N4Grinding into powder to prepare g-C3N4Heating and ultrasonic treating the suspension, centrifuging at 8000rpm for 20min, centrifuging for three times, and collecting supernatant to obtain stably dispersed g-C3N4A nanosheet dispersion;
and step 3: g-C obtained in step 23N4Mixing the nano-sheet dispersion liquid and the anionic compound solution, heating and ultrasonically treating for 10-20min to uniformly mix the nano-sheet dispersion liquid and the anionic compound solution, and loading the mixed membrane liquid on the pretreated porous base membrane by using a nano-sheet assembly technology to obtain the anionic compound intercalation g-C3N4And (5) compounding the film, and drying to remove the redundant solvent.
In step 2, g-C3N4The concentration of the suspension is 3-6 mg/mL; the heating and ultrasonic treatment temperature is 80-120 deg.C, and the ultrasonic treatment time is 10-18 h.
In the step 3, the anionic compound solution is sulfonated polyphenylene ether (SPPO) solution, Evans Blue (EB) solution or Methyl Blue (MB) solution, and the concentration of the anionic compound solution is 1 mg/mL.
In step 3, g-C3N4The mass ratio of the nanosheet dispersion to the anionic compound solution is 1:0.5-1: 10.
In the step 3, the porous base membrane comprises one of a polyether sulfone membrane, a polyvinylidene fluoride membrane, a polycarbonate membrane, an anodic aluminum oxide membrane, a polyacrylonitrile membrane and the like, and the aperture of the porous carrier is 100-450 nm. The pretreatment of the porous basement membrane refers to that the porous basement membrane is placed in deionized water to be soaked for 1-3 days to obtain the pretreated porous basement membrane.
In the step 3, the nanosheet assembly technology comprises vacuum filtration, layer-by-layer self-assembly, electrostatic spinning, spin coating and the like.
In the step 3, the drying is carried out for 8-15h at the temperature of 40-80 ℃.
The anionic compound intercalation g-C prepared by the invention3N4The thickness of the composite film is 200nm-1 μm.
Among anionic compounds, sulfonated polyphenylene ether (SPPO) has the following structural formula:
Figure BDA0001999179880000021
in the anionic compounds, the structural formula of Evans Blue (EB) is as follows:
Figure BDA0001999179880000022
among the anionic compounds, Methyl Blue (MB) has the following structural formula:
Figure BDA0001999179880000031
the anionic compound intercalation g-C prepared by the invention3N4The composite membrane is fixed on a nanofiltration device and used for intercepting nano particles with different sizes and charges.
The nano particles comprise methylene blue, methyl blue, rhodamine B, Evans blue, methyl orange, Congo red and the like.
The principle of the invention is as follows: g-C3N4Is a structure similar to graphene, but g-C in an aqueous environment3N4The interlayer spacing of the film can be kept constant, and g-C3N4The natural triangular nanopore structure and structural defects enable the graphene oxide to have one more molecular transportation way than graphene oxide. Nevertheless, the water flux is not high due to the interlayer spacing and pore size of only around 0.3 nm. The invention is achieved by3N4Anionic compounds with different sizes are intercalated among the nano sheets to increase the interlayer spacing of the membrane so as to achieve the aim of improving the water flux, and meanwhile, the high retention rate can be kept.
Compared with the prior art, the invention has the beneficial effects that:
1. the invention adopts anionic compound (SPPO, EB, MB) and two-dimensional g-C3N4A method for assembling nano sheets in a homogeneous phase to prepare a novel porous anionic compound intercalation g-C3N4A composite membrane material. SA/g-C reported in Journal of Membrane Science and technology (2015, 490,72-83)3N4Compared with the preparation method of the composite membrane, the preparation method has the advantages of cheap raw materials, simple process, easily controlled reaction conditions and easy large-scale production.
2. Compared with the preparation method of the graphene oxide film on the surface of the carrier disclosed in the Chinese patent CN105214512, the preparation method of the graphene oxide film on the surface of the carrier has the advantage that the anionic compound is intercalated into g-C3N4The composite membrane has simple process and stable chemical property and mechanical property, and due to the stable interlayer structure, the water flux can be increased by 500 times in nanofiltration application, and the retention rate can also keep a numerical value of about 90%.
Drawings
FIG. 1 is examples 1g-C3N4Atomic Force Microscopy (AFM) images of two-dimensional nanoplatelets.
FIG. 2 is example 2SPPO/g-C3N4Scanning Electron Microscopy (SEM) images of the composite film surface.
FIG. 3 is SPPO/g-C of example 23N4Scanning Electron Microscopy (SEM) image of cross section of composite membrane.
Detailed Description
The invention will now be further described with reference to specific examples, but the scope of the invention is not limited to the following examples.
Example 1:
1. weighing 1g of melamine, grinding the melamine in a mortar for 10min, calcining the melamine in a muffle furnace at 500 ℃ for 8h to obtain bulk g-C3N4。
2. The obtained bulk phase g-C3N4Grinding into powder to prepare 3mg/mL g-C3N4Heating and ultrasonic treating the suspension at 80 deg.C for 10h, centrifuging at 8000rpm for 20min, centrifuging for three times, and collecting supernatant to obtain stably dispersed g-C3N4A nanosheet dispersion. The concentration of the nanosheets was 0.08mg/mL as measured with an ultraviolet-visible spectrophotometer.
3. The anionic compound, sulfonated polyphenylene ether (SPPO), was prepared at a concentration of 1 mg/mL.
4. G to C3N4Mixing the nano-sheet dispersion liquid and the SPPO solution according to the mass ratio of 1:1, heating and ultrasonically treating for 10min to uniformly mix the nano-sheet dispersion liquid and the SPPO solution, soaking a polyvinylidene fluoride (PVDF) basement membrane loaded with the mixed membrane liquid with the aperture of 0.22 mu m for 1 day by using a vacuum filtration method to obtain the SPPO/g-C3N4A composite membrane. Drying at 40 ℃ for 8h to remove the excess solvent.
Example g-C obtained in step 23N4The nanoplatelets were subjected to Atomic Force Microscopy (AFM) testing, as shown in FIG. 1, from which it can be seen that the nanoplatelets are about 1nm thick and about 1.5 μm in size, indicating a monoatomic thickness.
5. SPPO/g-C of this example3N4The application of the composite membrane in nanofiltration: the above PVDF-supported SPPO/g-C3N4The composite membrane is fixed in a filtering device, the concentration of the composite membrane is 15 mu mol/L of positively charged MLB (methylene blue) aqueous solution, and the water flux of the composite membrane is 3245 L.h-1·m-2·bar-1The retention rate for methylene blue is 100%; MB (methyl blue) water solution with the concentration of 50 mu mol/L and the water flux of 2783 L.h-1·m-2·bar-1The rejection rate for methyl blue was 100%.
Example 2:
1. weighing 1g of melamine, grinding the melamine in a mortar for 10min, putting the ground melamine in a muffle furnace for calcining at 510 ℃ for 9h to obtain bulk phase g-C3N4。
2. The obtained bulk phase g-C3N4Grinding into powder to prepare 3mg/mL g-C3N4Heating and ultrasonic treating the suspension at 80 deg.C for 10h, centrifuging at 8000rpm for 20min, centrifuging for three times, and collecting supernatant to obtain stably dispersed g-C3N4A nanosheet dispersion. The concentration of the nanosheets was 0.08mg/mL as measured with an ultraviolet-visible spectrophotometer.
3. The anionic compound, sulfonated polyphenylene ether (SPPO), was prepared at a concentration of 1 mg/mL.
4. G to C3N4Mixing the nano-sheet dispersion liquid and the SPPO solution according to the mass ratio of 1:1, heating and ultrasonically treating for 15min to uniformly mix the nano-sheet dispersion liquid and the SPPO solution, soaking a polyvinylidene fluoride (PVDF) basement membrane loaded with the mixed membrane liquid with the aperture of 0.22 mu m for 1 day by using a vacuum filtration method to obtain the SPPO/g-C3N4A composite membrane. Drying at 40 ℃ for 8h to remove the excess solvent.
SPPO/g-C obtained in step 4 of this example3N4The Scanning Electron Microscope (SEM) test of the composite film showed that the surface and cross section of the composite film are as shown in fig. 2 and 3, and it can be seen from the figure that the surface of the film is relatively smooth and free of defects, and the thickness of the film is about 250 nm.
5. SPPO/g-C of this example3N4Application in nanofiltration: the above PVDF-supported SPPO/g-C3N4The composite membrane is fixed in a filtering device, the concentration of the composite membrane is 10 mu mol/L of positive RB (rhodamine B) water solution, and the water flux of the composite membrane is 1638 L.h-1·m-2·bar-1The retention rate of rhodamine B is 94.9%.
Example 3:
1. weighing 2g of melamine, grinding the melamine in a mortar for 15min, putting the ground melamine in a muffle furnace for calcining at 510 ℃ for 9h to obtain bulk phase g-C3N4。
2. The obtained bulk phase g-C3N4Grinding into powder to prepare 4mg/mL g-C3N4Heating and ultrasonic treating the suspension at 90 deg.C for 12h, centrifuging at 8000rpm for 20min, centrifuging for three times, and collecting supernatant to obtain stably dispersed g-C3N4A nanosheet dispersion. The concentration of the nanosheets was 0.10mg/mL as measured with an ultraviolet-visible spectrophotometer.
3. The anionic compound, sulfonated polyphenylene ether (SPPO), was prepared at a concentration of 1 mg/mL.
4. G to C3N4Mixing the nano-sheet dispersion liquid and the SPPO solution according to the mass ratio of 1:5, heating and ultrasonically treating for 15min to uniformly mix, soaking the nano-sheet dispersion liquid and the SPPO solution in deionized water for 2 days by a vacuum filtration method, wherein the pore diameter of the nano-sheet dispersion liquid is 0.22 mu mLoading mixed membrane liquid on polyvinylidene fluoride (PVDF) basement membrane to obtain SPPO/g-C3N4A composite membrane. Drying at 60 ℃ for 10h to remove the excess solvent.
5. SPPO/g-C of this example3N4Application in nanofiltration: the above PVDF-supported SPPO/g-C3N4The composite membrane is fixed in a filtering device, the concentration of the composite membrane is 15 mu mol/L of positively charged MLB (methylene blue) aqueous solution, and the water flux of the composite membrane is 2481 L.h-1·m-2·bar-1The retention rate for methylene blue is 98.9%; MB (methyl blue) water solution with the concentration of 50 mu mol/L and the water flux of 2791 L.h-1·m-2·bar-1The rejection rate for methyl blue was 100%.
Example 4:
1. weighing 3g of melamine, grinding the melamine in a mortar for 20min, calcining the melamine in a muffle furnace at 530 ℃ for 9h to obtain bulk phase g-C3N4。
2. The obtained bulk phase g-C3N4Grinding into powder to prepare 6mg/mL g-C3N4Heating and ultrasonic treating the suspension at 100 deg.C for 14h, centrifuging at 8000rpm for 20min, centrifuging for three times, and collecting supernatant to obtain stably dispersed g-C3N4A nanosheet dispersion. The concentration of the nanosheets was 0.25mg/mL as measured with an ultraviolet-visible spectrophotometer.
3. The anionic compound, sulfonated polyphenylene ether (SPPO), was prepared at a concentration of 1 mg/mL.
4. G to C3N4Mixing the nano-sheet dispersion liquid and the SPPO solution according to the mass ratio of 1:10, heating and ultrasonically treating for 20min to uniformly mix the nano-sheet dispersion liquid and the SPPO solution, soaking a polyvinylidene fluoride (PVDF) basement membrane loaded with the mixed membrane liquid for 3 days by using deionized water through a vacuum filtration method to obtain the SPPO/g-C3N4A composite membrane. Drying at 80 ℃ for 10h to remove the excess solvent.
5. SPPO/g-C of this example3N4Application in nanofiltration: the above PVDF-supported SPPO/g-C3N4The composite membrane is fixed in a filtering device, the concentration of the composite membrane is 15 mu mol/L of positive MLB (methylene blue) water solution, and the water flux of the composite membrane is1701 L·h-1·m-2·bar-1The retention rate for methylene blue is 95.5%; EB (Evans blue) water solution with the concentration of 10 mu mol/L and negative electricity, and the water flux of the EB (Evans blue) water solution is 716 L.h-1·m-2·bar-1The evans blue retention was 100%.
Example 5:
1. weighing 5g of melamine, putting the melamine into a mortar for grinding for 20min, putting the ground melamine into a muffle furnace for calcining at 550 ℃ for 10h to obtain bulk phase g-C3N4。
2. The obtained bulk phase g-C3N4Grinding into powder to prepare 6mg/mL g-C3N4Heating and ultrasonic treating the suspension at 90 deg.C for 12h, centrifuging at 8000rpm for 20min, centrifuging for three times, and collecting supernatant to obtain stably dispersed g-C3N4A nanosheet dispersion. The concentration of the nanosheets was 0.15mg/mL as measured with an ultraviolet-visible spectrophotometer.
3. The anionic compound, Evans Blue (EB), was prepared at a concentration of 1 mg/mL.
4. G to C3N4Mixing the nano-sheet dispersion liquid and the EB solution according to the mass ratio of 1:0.5, heating and ultrasonically treating for 20min to uniformly mix the nano-sheet dispersion liquid and the EB solution, soaking a polyvinylidene fluoride (PVDF) basement membrane loaded with the mixed membrane liquid for 3 days by using deionized water through a vacuum filtration method to obtain EB/g-C3N4A composite membrane. Drying at 60 ℃ for 12h to remove the excess solvent.
5. EB/g-C of this example3N4The application of the composite membrane in nanofiltration: EB/g-C obtained by supporting the above-mentioned PVDF in the above-mentioned solvent3N4The composite membrane is fixed in a filtering device, the concentration of the composite membrane is 10 mu mol/L of positive charged RB (rhodamine B) aqueous solution, and the water flux of the composite membrane is 1081 L.h-1·m-2·bar-1The retention rate of rhodamine B is 91.5 percent; MB (methyl blue) water solution with the concentration of 50 mu mol/L and the water flux of 1670 L.h-1·m-2·bar-1The methyl blue retention was 88.0%.
Example 6:
1. weighing 5g of melamine, grinding in a mortar for 20min, placing in a muffle furnace at 550 DEG CCalcining for 11h to obtain a bulk phase g-C3N4。
2. The obtained bulk phase g-C3N4Grinding into powder to prepare 6mg/mL g-C3N4Heating and ultrasonic treating the suspension at 100 deg.C for 18h, centrifuging at 8000rpm for 20min, centrifuging for three times, and collecting supernatant to obtain stably dispersed g-C3N4A nanosheet dispersion. The concentration of the nanosheets was 0.40mg/mL as measured with an ultraviolet-visible spectrophotometer.
3. The anionic compound, Evans Blue (EB), was prepared at a concentration of 1 mg/mL.
4. G to C3N4Mixing the nano-sheet dispersion liquid and the EB solution according to the mass ratio of 1:1, heating and ultrasonically treating for 20min to uniformly mix the nano-sheet dispersion liquid and the EB solution, soaking a polyvinylidene fluoride (PVDF) basement membrane loaded with the mixed membrane liquid for 3 days by using deionized water through a vacuum filtration method to obtain EB/g-C3N4A composite membrane. Drying at 60 ℃ for 12h to remove the excess solvent.
5. EB/g-C of this example3N4The application of the composite membrane in nanofiltration: EB/g-C obtained by supporting the above-mentioned PVDF in the above-mentioned solvent3N4The composite membrane was fixed in a filtration apparatus at a concentration of 50. mu. mol/L of negatively charged MB (methyl blue) aqueous solution with a flux of 1908 L.h-1·m-2·bar-1The methyl blue retention rate is 91.2%; the water flux of a positively charged MLB (methylene blue) aqueous solution with a concentration of 15. mu. mol/L is 1988 L.h-1·m-2·bar-1The rejection rate for methylene blue was 98%.
Example 7:
1. weighing 5g of melamine, putting the melamine into a mortar for grinding for 20min, putting the ground melamine into a muffle furnace for calcining at 550 ℃ for 12h to obtain bulk phase g-C3N4。
2. The obtained bulk phase g-C3N4Grinding into powder to prepare 6mg/mL g-C3N4Heating and ultrasonic treating the suspension at 100 deg.C for 18h, centrifuging at 8000rpm for 20min, centrifuging for three times, and collecting supernatant to obtain stably dispersed g-C3N4A nanosheet dispersion. Measuring the nano-meter by an ultraviolet-visible spectrophotometerThe concentration of the rice flakes was 0.40 mg/mL.
3. The anionic compound, Evans Blue (EB), was prepared at a concentration of 1 mg/mL.
4. G to C3N4Mixing the nano-sheet dispersion liquid and the EB solution according to the mass ratio of 1:5, heating and ultrasonically treating for 20min to uniformly mix the nano-sheet dispersion liquid and the EB solution, soaking a polyvinylidene fluoride (PVDF) basement membrane loaded with the mixed membrane liquid for 3 days by using deionized water through a vacuum filtration method to obtain EB/g-C3N4A composite membrane. Drying at 60 ℃ for 12h to remove the excess solvent.
5. EB/g-C of this example3N4The application of the composite membrane in nanofiltration: EB/g-C obtained by supporting the above-mentioned PVDF in the above-mentioned solvent3N4The composite membrane is fixed in a filtering device, the concentration of the composite membrane is 50 mu mol/L of negatively charged MB (methyl blue) aqueous solution, and the water flux of the composite membrane is 2767 L.h-1·m-2·bar-1The methyl blue retention rate is 100%; the water flux of the positively charged MLB (methylene blue) aqueous solution with the concentration of 15 mu mol/L is 1463 L.h-1·m-2·bar-1The retention rate for methylene blue was 99.0%.
Example 8:
1. weighing 5g of melamine, putting the melamine into a mortar for grinding for 20min, putting the ground melamine into a muffle furnace for calcining at 550 ℃ for 10h to obtain bulk phase g-C3N4。
2. The obtained bulk phase g-C3N4Grinding into powder to prepare 6mg/mL g-C3N4Heating and ultrasonic treating the suspension at 100 deg.C for 18h, centrifuging at 8000rpm for 20min, centrifuging for three times, and collecting supernatant to obtain stably dispersed g-C3N4A nanosheet dispersion. The concentration of the nanosheets was 0.40mg/mL as measured with an ultraviolet-visible spectrophotometer.
3. The anionic compound Methyl Blue (MB) was prepared at a concentration of 1 mg/mL.
4. G to C3N4Mixing the nano-sheet dispersion liquid and the MB solution according to the mass ratio of 1:0.5, heating and ultrasonically treating for 20min to uniformly mix the nano-sheet dispersion liquid and the MB solution, soaking a polyvinylidene fluoride (PVDF) basement membrane with the aperture of 0.22 mu m for 3 days by using a vacuum filtration method to load the mixed membrane liquid, namelyObtaining MB/g-C3N4A composite membrane. Drying at 60 ℃ for 12h to remove the excess solvent.
5. MB/g-C of the present example3N4The application of the composite membrane in nanofiltration: the above PVDF-loaded MB/g-C3N4The composite membrane is fixed in a filtering device, the concentration is 10 mu mol/L of EB (Evans blue) water solution with negative electricity, and the water flux is 2545 L.h-1·m-2·bar-1The evans blue retention was 98.0%; the water flux of the positively charged MLB (methylene blue) aqueous solution with the concentration of 15 mu mol/L is 1280 L.h-1·m-2·bar-1The rejection rate for methylene blue was 98.0%.
Example 9:
1. weighing 5g of melamine, putting the melamine into a mortar for grinding for 20min, putting the ground melamine into a muffle furnace for calcining at 550 ℃ for 10h to obtain bulk phase g-C3N4。
2. The obtained bulk phase g-C3N4Grinding into powder to prepare 6mg/mL g-C3N4Heating and ultrasonic treating the suspension at 100 deg.C for 18h, centrifuging at 8000rpm for 20min, centrifuging for three times, and collecting supernatant to obtain stably dispersed g-C3N4A nanosheet dispersion. The concentration of the nanosheets was 0.40mg/mL as measured with an ultraviolet-visible spectrophotometer.
3. The anionic compound Methyl Blue (MB) was prepared at a concentration of 1 mg/mL.
4. G to C3N4Mixing the nano-sheet dispersion liquid and the MB solution according to the mass ratio of 1:1, heating and ultrasonically treating for 20min to uniformly mix the nano-sheet dispersion liquid and the MB solution, soaking a polyvinylidene fluoride (PVDF) basement membrane loaded with the mixed membrane liquid for 3 days by using deionized water through a vacuum filtration method to obtain the MB/g-C nano-sheet dispersion liquid3N4A composite membrane. Drying at 60 ℃ for 12h to remove the excess solvent.
5. MB/g-C of the present example3N4The application of the composite membrane in nanofiltration: the above PVDF-loaded MB/g-C3N4The composite membrane is fixed in a filtering device, the water flux of the composite membrane is 2226 L.h, and the concentration of the composite membrane is 10 mu mol/L of EB (Evans blue) water solution with negative electricity-1·m-2·bar-1The evans blue retention was 98.1%; the water flux of a negatively charged MB (methyl blue) aqueous solution with a concentration of 50. mu. mol/L is 1757 L.h-1·m-2·bar-1The methyl blue retention was 100%.
Example 10:
1. weighing 5g of melamine, putting the melamine into a mortar for grinding for 20min, putting the ground melamine into a muffle furnace for calcining at 550 ℃ for 10h to obtain bulk phase g-C3N4。
2. The obtained bulk phase g-C3N4Grinding into powder to prepare 6mg/mL g-C3N4Heating and ultrasonic treating the suspension at 100 deg.C for 18h, centrifuging at 8000rpm for 20min, centrifuging for three times, and collecting supernatant to obtain stably dispersed g-C3N4A nanosheet dispersion. The concentration of the nanosheets was 0.40mg/mL as measured with an ultraviolet-visible spectrophotometer.
3. The anionic compound Methyl Blue (MB) was prepared at a concentration of 1 mg/mL.
4. G to C3N4Mixing the nano-sheet dispersion liquid and the MB solution according to the mass ratio of 1:5, heating and ultrasonically treating for 20min to uniformly mix the nano-sheet dispersion liquid and the MB solution, soaking a polyvinylidene fluoride (PVDF) basement membrane loaded with the mixed membrane liquid for 3 days by using deionized water through a vacuum filtration method to obtain the MB/g-C nano-sheet dispersion liquid3N4A composite membrane. Drying at 60 ℃ for 12h to remove the excess solvent.
5. MB/g-C of the present example3N4The application of the composite membrane in nanofiltration: the above PVDF-loaded MB/g-C3N4The composite membrane is fixed in a filtering device, and the water flux of the composite membrane is 1828 L.h, wherein the concentration of the composite membrane is 10 mu mol/L of EB (Evans blue) water solution with negative electricity-1·m-2·bar-1The evans blue retention was 98.5%; the water flux of the positively charged RB (rhodamine B) aqueous solution with the concentration of 10 mu mol/L is 1312 L.h-1·m-2·bar-1The retention rate of rhodamine B is 88.0%.
The technical solution of the present invention is not limited to the limitations of the above specific embodiments, and all technical modifications made according to the technical solution of the present invention belong to the protection scope of the present invention.

Claims (6)

1. Anionic compound intercalation g-C3N4The preparation method of the composite membrane is characterized by comprising the following steps:
first of all, a bulk phase g-C is obtained by a thermal polymerization process3N4(ii) a Then the product is physically stripped to obtain g-C3N4A nanosheet dispersion; finally, mixing the anionic compound with g-C3N4Mixing and depositing the nano-sheet dispersion liquid on a porous base membrane to obtain the anionic compound intercalation g-C3N4Compounding film; the method comprises the following steps:
step 1: weighing 1-5g of melamine or urea, placing the melamine or urea in a mortar for grinding for 10-20min, and then placing the melamine or urea in a muffle furnace for calcining at the temperature of 500-600 ℃ for 8-12h to obtain a bulk phase g-C3N4；
Step 2: subjecting the bulk phase g-C obtained in step 13N4Grinding into powder to prepare g-C3N4Heating and ultrasonic treating the suspension, centrifuging at 8000rpm for 20min, centrifuging for three times, and collecting supernatant to obtain stably dispersed g-C3N4A nanosheet dispersion;
and step 3: g-C obtained in step 23N4Mixing the nano-sheet dispersion liquid and the anionic compound solution, heating and ultrasonically treating for 10-20min to uniformly mix the nano-sheet dispersion liquid and the anionic compound solution, and loading the mixed membrane liquid on the pretreated porous base membrane by using a nano-sheet assembly technology to obtain the anionic compound intercalation g-C3N4Drying the composite membrane to remove the redundant solvent;
in the step 3, the anionic compound solution is a sulfonated polyphenylene ether solution, an evans blue solution or a methyl blue solution; the concentration of the anionic compound solution is 1 mg/mL; g-C3N4The mass ratio of the nanosheet dispersion to the anionic compound solution is 1:0.5-1: 10.
2. The method of claim 1, wherein:
in step 2, g-C3N4The concentration of the suspension is 3-6 mg/mL; heating and ultrasonic treating at 80-120 deg.C for ultrasonic treatmentIs 10-18 h.
3. The method of claim 1, wherein:
in the step 3, the porous base membrane comprises one of a polyether sulfone membrane, a polyvinylidene fluoride membrane, a polycarbonate membrane, an anodic aluminum oxide membrane and a polyacrylonitrile membrane, and the aperture of the porous carrier is 100-450 nm.
4. The method of claim 1, wherein:
in the step 3, the drying is carried out for 8-15h at the temperature of 40-80 ℃.
5. The method of claim 1, wherein:
prepared anionic compound intercalation g-C3N4The thickness of the composite membrane is 200nm-1 mu m.
6. Anionic compound intercalated g-C prepared according to the process of any one of claims 1-53N4The application of the composite membrane is characterized in that: fixing the composite membrane on a nanofiltration device for intercepting nano particles with different sizes and charges; the nano particles comprise methylene blue, methyl blue, rhodamine B, Evans blue, methyl orange and Congo red.
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