CN114592197A - Two-dimensional g-C3N4Nano-sheet membrane, electrochemical preparation method thereof and application thereof in ion separation - Google Patents
Two-dimensional g-C3N4Nano-sheet membrane, electrochemical preparation method thereof and application thereof in ion separation Download PDFInfo
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- 239000012528 membrane Substances 0.000 title claims abstract description 83
- 238000002360 preparation method Methods 0.000 title claims abstract description 22
- 238000000926 separation method Methods 0.000 title claims description 23
- 239000002135 nanosheet Substances 0.000 claims abstract description 69
- 150000002500 ions Chemical class 0.000 claims abstract description 32
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 25
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 21
- 239000000758 substrate Substances 0.000 claims abstract description 21
- 239000002064 nanoplatelet Substances 0.000 claims abstract description 20
- 229910021642 ultra pure water Inorganic materials 0.000 claims abstract description 16
- 239000012498 ultrapure water Substances 0.000 claims abstract description 16
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000003792 electrolyte Substances 0.000 claims abstract description 13
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 11
- 238000001652 electrophoretic deposition Methods 0.000 claims abstract description 11
- 229920000877 Melamine resin Polymers 0.000 claims abstract description 7
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 7
- 238000001035 drying Methods 0.000 claims abstract description 7
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims abstract description 7
- 229910052697 platinum Inorganic materials 0.000 claims abstract description 7
- 238000000151 deposition Methods 0.000 claims abstract description 3
- 230000008021 deposition Effects 0.000 claims abstract description 3
- 238000004519 manufacturing process Methods 0.000 claims abstract 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 12
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 claims description 8
- 150000008040 ionic compounds Chemical class 0.000 claims description 7
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 claims description 6
- 238000000502 dialysis Methods 0.000 claims description 6
- 239000011780 sodium chloride Substances 0.000 claims description 6
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims description 4
- 238000005119 centrifugation Methods 0.000 claims description 4
- 229910001629 magnesium chloride Inorganic materials 0.000 claims description 4
- 239000001110 calcium chloride Substances 0.000 claims description 3
- 229910001628 calcium chloride Inorganic materials 0.000 claims description 3
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 claims description 2
- 229910000369 cadmium(II) sulfate Inorganic materials 0.000 claims description 2
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 claims description 2
- 229910000366 copper(II) sulfate Inorganic materials 0.000 claims description 2
- 229910000357 manganese(II) sulfate Inorganic materials 0.000 claims description 2
- 238000006243 chemical reaction Methods 0.000 abstract description 5
- 230000000694 effects Effects 0.000 abstract description 3
- 239000000243 solution Substances 0.000 description 35
- 238000000034 method Methods 0.000 description 12
- 230000005540 biological transmission Effects 0.000 description 8
- 230000008859 change Effects 0.000 description 8
- 238000003756 stirring Methods 0.000 description 8
- 238000001291 vacuum drying Methods 0.000 description 8
- 239000002994 raw material Substances 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- 230000008569 process Effects 0.000 description 5
- 239000000919 ceramic Substances 0.000 description 4
- 238000001514 detection method Methods 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 229910021389 graphene Inorganic materials 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000013535 sea water Substances 0.000 description 3
- 238000010612 desalination reaction Methods 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000009776 industrial production Methods 0.000 description 2
- 238000001000 micrograph Methods 0.000 description 2
- 239000002120 nanofilm Substances 0.000 description 2
- 239000002055 nanoplate Substances 0.000 description 2
- JMANVNJQNLATNU-UHFFFAOYSA-N oxalonitrile Chemical compound N#CC#N JMANVNJQNLATNU-UHFFFAOYSA-N 0.000 description 2
- 229920005597 polymer membrane Polymers 0.000 description 2
- 238000004626 scanning electron microscopy Methods 0.000 description 2
- 230000001133 acceleration Effects 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000005422 blasting Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000011033 desalting Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000002848 electrochemical method Methods 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 230000004907 flux Effects 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 239000012466 permeate Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000000967 suction filtration Methods 0.000 description 1
- 238000012719 thermal polymerization Methods 0.000 description 1
- 238000003911 water pollution Methods 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B1/00—Electrolytic production of inorganic compounds or non-metals
- C25B1/01—Products
-
- 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
- B01D67/0039—Inorganic membrane manufacture
- B01D67/0069—Inorganic membrane manufacture by deposition from the liquid phase, e.g. electrochemical deposition
-
- 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
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/44—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B1/00—Electrolytic production of inorganic compounds or non-metals
- C25B1/50—Processes
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D13/00—Electrophoretic coating characterised by the process
- C25D13/02—Electrophoretic coating characterised by the process with inorganic material
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
- C02F2103/08—Seawater, e.g. for desalination
-
- 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
Abstract
The invention discloses a two-dimensional g-C3N4Nanoplane membrane and method of making sameAn electrochemical preparation method. The preparation method comprises the following steps: (1) melamine, sodium hydroxide and water are mixed according to the mass volume ratio of (1-3) g: (0.5-1) g: (50-100) mL of the electrolyte is uniformly mixed to serve as electrolyte; taking a platinum sheet as an electrode, electrifying a direct current power supply with the voltage of 3-10V for reaction for 1-3 h, centrifuging and dialyzing the reacted electrolyte to obtain g-C3N4A nanosheet solution; (2) fixing the processed porous substrate in the middle of a U-shaped groove, inserting carbon plates at two ends as electrodes, and adding g-C at one side of the U-shaped groove3N4Adding ultrapure water into the other side of the nanosheet solution, electrifying for electrophoretic deposition, taking out the substrate after deposition is finished, and drying to obtain two-dimensional g-C3N4A nanoplatelet film. The two-dimensional g-C3N4The nano-sheet membrane has a higher interception effect on ions.
Description
Technical Field
The invention belongs to the technical field of ion separation membranes, and particularly relates to a two-dimensional g-C3N4A nano-sheet membrane, an electrochemical preparation method thereof and application thereof in ion separation.
Background
With the excessive growth of population and the acceleration of industrialization, the problem of water pollution is becoming more serious, and how to obtain clean water becomes a crucial problem. Almost 97% of the water on earth is brackish and sea water, and desalination of sea water and brackish water has become an important alternative source of clean water. Compared with the traditional desalination technology, the membrane separation technology has received much attention due to the advantages of small occupied area, low cost, convenient operation, etc.
In the membrane separation process, the most central problem is the development of membrane materials. At present, most polymer membranes and ceramic membranes are used, but the polymer membranes have the problems of easy pollution, low flux and the like, and the ceramic membranes have the defects of high cost and the like, so that the application of the ceramic membranes is greatly limited. Therefore, an ideal membrane having both the easy preparation of an organic membrane and the thermal stability of a ceramic membrane can meet the needs of industrial applications.
In recent years, two-dimensional materials have been present in the field of vision and are used in the field of membrane separation, the most representative of which is a graphene oxide membrane. However, the graphene oxide film is unstable in an aqueous solution and tends to swell. There is an urgent need to develop another two-dimensional material film for water treatment process. And two-dimensional graphite phase carbon nitride (g-C)3N4) Compared with a graphene oxide film, the nano-sheet film is simpler to prepare, higher in stability and shown in the separation fieldHas industrial application potential.
In general, the properties of two-dimensional nanoplatelets films are related to the quality of the nanoplatelets on the one hand and to the method of preparation of the film on the other hand. Among these, the quality of the nanosheets determines the stability of the membrane, while the method of preparing the membrane determines to a large extent the integrity of the membrane, thereby affecting its separation performance. At present, g-C3N4The nanosheets are typically prepared by thermal polymerization to give the bulk g-C3N4Then peeling off to obtain g-C3N4The nano-sheet, however, the process involves more steps and requires conditions such as high temperature, which easily causes g-C3N4The structure of the nanosheet is destroyed; two dimensional g-C3N4The preparation of the nano-sheet film is generally to stack the nano-sheets into a film in a suction filtration mode, but the process is long in time and low in efficiency. Therefore, if a high quality g-C can be produced by a simple process3N4Nanosheets and two-dimensional g-C3N4The nanosheet membrane, and exhibiting excellent separation performance, is of great significance to the development of industry.
Disclosure of Invention
To overcome the disadvantages and shortcomings of the prior art, it is a primary object of the present invention to provide a two-dimensional g-C3N4The electrochemical preparation method of the nanosheet membrane has the advantages of simple process, low energy consumption, less required raw materials, low cost, high repeatability and wide applicability, and is suitable for industrial production.
The second purpose of the invention is to provide the two-dimensional g-C prepared by the preparation method3N4The nanosheet membrane has a high ion interception effect.
It is a third object of the present invention to provide a two-dimensional g-C3N4The application of the nanosheet membrane is particularly applied to the field of ion separation.
The primary purpose of the invention is realized by the following technical scheme:
two-dimensional g-C3N4The electrochemical preparation method of the nanosheet membrane comprises the following steps:
(1) melamine, sodium hydroxide and water are mixed according to the mass volume ratio of (1-3) g: (0.5-1) g: (50-100) mL of the electrolyte is uniformly mixed to serve as electrolyte; taking a platinum sheet as an electrode, using a direct current power supply with the voltage of 3-10V, electrifying for 1-3 h, centrifuging the reacted electrolyte, and dialyzing to obtain g-C3N4A nanosheet solution;
(2) fixing the processed porous substrate in the middle of a U-shaped groove, inserting carbon plates at two ends as electrodes, and adding g-C at one side of the U-shaped groove3N4Adding ultrapure water into the other side of the nanosheet solution, electrifying for electrophoretic deposition, taking out the substrate after deposition is finished, and drying to obtain two-dimensional g-C3N4A nanoplatelet film.
Preferably, the rotation speed of the centrifugation in the step (1) is 5000-10000 rpm; the centrifugation time is 30-60 min.
Preferably, the molecular weight of a dialysis bag used in the dialysis in the step (1) is 1000-5000 Da; the dialysis time is 3-5 days.
Preferably, the conditions of the electrophoretic deposition in step (2): the voltage is 15-30V and the time is 30-60 min.
Preferably, said g-C in step (2)3N4The thickness of the two-dimensional nanosheet film is 350-630 nm.
The second purpose of the invention is realized by the following technical scheme:
two-dimensional g-C3N4The nanosheet membrane is prepared by the preparation method.
The third purpose of the invention is realized by the following technical scheme:
two-dimensional g-C3N4Use of a nanoplatelets membrane in ion separation.
In particular, the two dimensions g-C3N4The application of the nanosheet membrane in ion separation comprises the following steps:
two dimensions g-C3N4The nano-sheet membrane is arranged in an ion interception device, one side of the membrane is added with ionic compound solution, and the other side of the membrane is added with water, thereby realizing the ion interception。
Preferably, the concentration of the ionic compound solution is 0.01-2 mol/L.
Preferably, the concentration of the ionic compound solution is 0.1-0.2 mol/L.
Preferably, the ionic compound is NaCl, LiCl, CaCl2，MgCl2，AlCl3，CuSO4，CdSO4Or MnSO4One kind of (1).
Preferably, the water is ultrapure water or deionized water.
Compared with the prior art, the invention has the following advantages and beneficial effects:
(1) electrochemical method for preparing two-dimensional g-C in the invention3N4The nano-sheet film process is simple, the energy consumption is low, the required raw materials are few, the cost is low, the repeatability is high, the applicability is wide, and the method is suitable for industrial production;
(2) the invention relates to a two-dimensional g-C prepared by an electrophoretic deposition method3N4The nano-sheet membrane has the advantages of good stability, strong pollution resistance and the like;
(3) the invention relates to two-dimensional g-C prepared by an electrophoretic deposition method3N4When the nano sheet membrane is used for ion interception, the nano sheet membrane has a higher interception effect on ions.
(4) g-C prepared by the invention patent3N4The nanosheet membrane is mainly used for ion separation and mainly used for desalting seawater and brackish water.
Drawings
FIG. 1 is a two-dimensional g-C3N4A schematic diagram of the preparation of the nanoplatelets film;
FIG. 2 is the two dimensions g-C of example 13N4Nanoplate Scanning Electron Microscopy (SEM) images;
FIG. 3 is the two dimensions g-C of example 13N4Surface Scanning Electron Microscope (SEM) images of nanoplatelet films;
FIG. 4 shows two dimensions g-C of example 13N4Cross-sectional Scanning Electron Microscope (SEM) images of nanoplatelet films;
FIG. 5 is two-dimensional g-C of example 13N4Nanoplatelets filmsPermeation test plots for 0.2mol/L NaCl solution with the ordinate being the permeate side solution conductivity and the abscissa being time.
Detailed Description
The technical solution of the present invention is further described in detail with reference to the following examples, but the embodiments and the protection scope of the present invention are not limited thereto.
The treated porous substrate referred to in this example means that the substrate is first subjected to a gold-blasting treatment.
Example 1
Two-dimensional g-C3N4The electrochemical preparation method of the nanosheet membrane specifically comprises the following steps:
(1) dissolving 1g of melamine and 1g of sodium hydroxide in 50mL of water as electrolyte, taking a platinum sheet as an electrode, applying a voltage of 5V to two ends of the electrode by using a direct current power supply, reacting for 1h, centrifuging the obtained product solution at 8000 rpm for 30min, and dialyzing for 3 days to obtain two-dimensional g-C3N4A nanosheet solution;
(2) fixing the processed porous substrate in the middle of a U-shaped groove, inserting carbon plates at two ends as electrodes, and adding g-C at one side of the U-shaped groove3N4Adding ultrapure water into the other side of the nanosheet solution, electrifying for electrophoretic deposition at a constant voltage of 30V for 30min, pouring out the solution, taking out the substrate, and putting the substrate into a vacuum drying tank for vacuum drying to obtain two-dimensional g-C3N4Nano sheet film, its electrophoretic deposition method for preparing two-dimensional g-C3N4A schematic of the nanoplatelets film is shown in fig. 1.
Drying the two-dimensional g-C3N4And (3) placing the nanosheet membrane into a U-shaped groove, fixing the nanosheet membrane in the middle, adding the raw material liquid into one side of the membrane, adding ultrapure water into the other side of the membrane, adding stirrers into two sides of the membrane, stirring, measuring the change of the conductivity of the pure water measuring solution along with time, and obtaining the permeation quantities of different ions through conversion.
g-C obtained in this example3N4The shape of the nano-sheet is shown in figure 2, and the two-dimensional g-C is loaded on the anodic aluminum oxide film3N4Surface electron microscope image and cross-sectional electron microscope image of nanoplate filmAs shown in FIGS. 4 and 3, respectively, it can be seen from FIG. 4 that the two-dimensional g-C prepared in this example3N4The thickness of the nanoplatelets film is about 450 nm.
Two-dimensional g-C prepared in this example3N4The application of the nanosheet membrane in ion separation:
mixing the two-dimensional g-C prepared above3N4The nano-film is fixed in the middle channel of the ion transmission testing U-shaped groove device by a gasket, and 0.2mol/L of NaCl, LiCl and CaCl is respectively added into one side of the U-shaped groove2Or MgCl2A solution; 50mL of ultrapure water is added into the permeation side, stirrers are added into two sides for stirring, the rotating speed is 400rpm, and the conductivity change of water on the permeation side under different solutions is detected by using a conductivity meter at room temperature. After 4h of detection, two-dimensional g-C is found3N4Nano-film on NaCl, LiCl and CaCl2Or MgCl2The molar transmission rates of (A) are on average 2.63X 10, respectively-2mol/m2/h、1.86×10-2mol/m2/h、7.43×10-2mol/m2/h、3.59×10-2mol/m2H, 1mol/m in comparison with the permeation rate2The substrate has obvious interception function.
FIG. 4 is a graph showing permeation test of 0.2mol/L NaCl solution in practical example 1 of the present invention, with the ordinate representing the conductivity of the solution on the permeation side and the abscissa representing time.
Example 2
Two-dimensional g-C3N4The electrochemical preparation method of the nanosheet membrane specifically comprises the following steps: :
(1) dissolving 0.8g of melamine and 0.5g of sodium hydroxide in 80mL of water to be used as electrolyte, using a platinum sheet as an electrode, applying a voltage of 3V to two ends of the electrode by using a direct current power supply, reacting for 2 hours, centrifuging the obtained product solution at the rotating speed of 5000rpm for 60min, and dialyzing for 4 days to obtain two-dimensional g-C3N4A nanosheet solution;
(2) fixing the processed porous substrate in the middle of a U-shaped groove, inserting carbon plates at two ends as electrodes, and adding g-C at one side of the U-shaped groove3N4Adding ultrapure water into the other side of the nanosheet solution, electrifying for electrophoretic precipitationAccumulating; constant voltage is 30V, and time is 60 min; after pouring out the solution, the substrate was taken out and placed in a vacuum drying tank for vacuum drying to obtain two-dimensional g-C3N4A nanoplatelet film;
drying the two-dimensional g-C3N4And (3) placing the nanosheet membrane into a U-shaped groove, fixing the nanosheet membrane in the middle, adding the raw material liquid into one side of the membrane, adding ultrapure water into the other side of the membrane, adding stirrers into two sides of the membrane, stirring, measuring the change of the conductivity of the pure water measuring solution along with time, and obtaining the permeation quantities of different ions through conversion.
Two-dimensional g-C prepared in this example3N4The thickness of the nanoplatelets film is about 630 nm.
Two-dimensional g-C prepared in this example3N4The application of the nanosheet membrane in ion separation:
two-dimensional g-C to be prepared3N4The nano-sheet membrane is fixed on the middle channel of the ion transmission testing U-shaped groove device by a gasket, and 0.2mol/L MgCl is added to one side of the U-shaped groove2A solution; 50mL of ultrapure water is added to the permeation side, a stirrer is added to the two sides for stirring, the rotating speed is 400rpm, and the conductivity change of water on the permeation side is detected by using a conductivity meter at room temperature. After 4h detection, the membrane pair MgCl is found2The molar transmission rate of (A) is 2.35X 10 on average-2mol/m2H, 1mol/m in comparison with the permeation rate2The substrate has obvious interception function.
Example 3
Two-dimensional g-C3N4The electrochemical preparation method of the nanosheet membrane specifically comprises the following steps: (1) dissolving 3g of melamine and 1g of sodium hydroxide in 100mL of water as electrolyte, taking a platinum sheet as an electrode, applying a voltage of 10V to two ends of the electrode by using a direct current power supply, reacting for 3h, centrifuging the obtained product solution at 10000rpm for 40min, and dialyzing for 5 days to obtain two-dimensional g-C3N4A nanosheet solution;
(2) fixing the processed porous substrate in the middle of a U-shaped groove, inserting carbon plates at two ends as electrodes, and adding g-C at one side of the U-shaped groove3N4Adding ultrapure water into the other side of the nanosheet solution, and electrifyingAnd (4) performing line electrophoretic deposition. Constant voltage is 30V, and time is 30 min; after pouring out the solution, the substrate was taken out and placed in a vacuum drying tank for vacuum drying to obtain two-dimensional g-C3N4A nanoplatelet film;
drying the two-dimensional g-C3N4And (3) placing the nanosheet membrane into a U-shaped groove, fixing the nanosheet membrane in the middle, adding the raw material liquid into one side of the membrane, adding ultrapure water into the other side of the membrane, adding stirrers into two sides of the membrane, stirring, measuring the change of the conductivity of the pure water measuring solution along with time, and obtaining the permeation quantities of different ions through conversion.
Two-dimensional g-C prepared in this example3N4The thickness of the nanoplatelets film is about 450 nm.
Two-dimensional g-C prepared in this example3N4The application of the nanosheet membrane in ion separation:
two-dimensional g-C to be prepared3N4The nano-sheet membrane is fixed on the middle channel of the ion transmission testing U-shaped groove device by a gasket, and 1mol/L MgCl is added to one side of the U-shaped groove2A solution; 50mL of ultrapure water is added to the permeation side, a stirrer is added to the two sides for stirring, the rotating speed is 400rpm, and the conductivity change of water on the permeation side is detected by using a conductivity meter at room temperature. After 4h detection, the membrane pair MgCl is found2The molar transmission rate of (A) is 6.23X 10 on average-2mol/m2H, as compared to a permeation rate of 8mol/m2The substrate has obvious interception function.
Example 4
Two-dimensional g-C3N4The electrochemical preparation method of the nanosheet membrane specifically comprises the following steps:
(1) dissolving 1.5g of melamine and 0.7g of sodium hydroxide in 60mL of water to be used as electrolyte, using a platinum sheet as an electrode, applying a voltage of 9V to two ends of the electrode by using a direct current power supply, reacting for 2 hours, centrifuging the obtained product solution at a rotating speed of 6000rpm for 60min, and dialyzing for 4 days to obtain two-dimensional g-C3N4A nanosheet solution;
(2) fixing the processed porous substrate in the middle of a U-shaped groove, inserting carbon plates at two ends as electrodes, and adding g-C at one side of the U-shaped groove3N4Nano-sheetAdding ultrapure water into the solution on the other side, and electrifying for electrophoretic deposition; constant voltage is 30V, and time is 30 min; after pouring out the solution, the substrate was taken out and placed in a vacuum drying tank for vacuum drying to obtain two-dimensional g-C3N4A nanoplatelet film.
Drying the two-dimensional g-C3N4And (3) placing the nanosheet membrane into a U-shaped groove, fixing the nanosheet membrane in the middle, adding the raw material liquid into one side of the membrane, adding ultrapure water into the other side of the membrane, adding stirrers into two sides of the membrane, stirring, measuring the change of the conductivity of the pure water measuring solution along with time, and obtaining the permeation quantities of different ions through conversion.
Two-dimensional g-C prepared in this example3N4The thickness of the nanoplatelets film is about 450 nm.
Two-dimensional g-C prepared in this example3N4The application of the nanosheet membrane in ion separation:
two-dimensional g-C to be prepared3N4The nano-sheet membrane is fixed on the middle channel of the ion transmission testing U-shaped groove device by a gasket, and 2mol/L MgCl is added to one side of the U-shaped groove2A solution; 50mL of ultrapure water is added to the permeation side, a stirrer is added to the two sides for stirring, the rotating speed is 400rpm, and the conductivity change of water on the permeation side is detected by using a conductivity meter at room temperature. After 4h detection, the membrane pair MgCl is found2The molar transmission rate of (A) is 8.75X 10 on average-2mol/m2Per h, permeation rate compared to the substrate of 12mol/m2The reaction time per hour is obvious.
The above embodiments are merely preferred embodiments of the present invention, which are intended to be illustrative and not limiting, and any changes, substitutions, combinations, simplifications, modifications, etc. made by those skilled in the art without departing from the spirit and principle of the present invention shall be included in the scope of the present invention.
Claims (10)
1. Two-dimensional g-C3N4The electrochemical preparation method of the nanosheet membrane is characterized by comprising the following steps of:
(1) melamine, sodium hydroxide and water are mixed according to the mass volume ratio of (1-3) g: (0.51) g: (50-100) mL of the electrolyte is uniformly mixed to serve as electrolyte; taking a platinum sheet as an electrode, using a direct current power supply with the voltage of 3-10V, electrifying for 1-3 h, centrifuging the reacted electrolyte, and dialyzing to obtain g-C3N4A nanosheet solution;
(2) fixing the processed porous substrate in the middle of a U-shaped groove, inserting carbon plates at two ends as electrodes, and adding g-C at one side of the U-shaped groove3N4Adding ultrapure water into the other side of the nanosheet solution, electrifying for electrophoretic deposition, taking out the substrate after deposition is finished, and drying to obtain two-dimensional g-C3N4A nanoplatelet film.
2. The two-dimensional g-C of claim 13N4The electrochemical preparation method of the nanosheet membrane is characterized in that the rotation speed of the centrifugation in the step (1) is 5000-10000 rpm; the centrifugation time is 30-60 min.
3. The two-dimensional g-C of claim 13N4The electrochemical preparation method of the nanosheet membrane is characterized in that the molecular weight of a dialysis bag used in the dialysis in the step (1) is 1000-5000 Da; the dialysis time is 3-5 days.
4. The two-dimensional g-C of claim 13N4The electrochemical preparation method of the nanosheet membrane is characterized in that the electrophoretic deposition conditions in the step (2) are as follows: the voltage is 15-30V and the time is 30-60 min.
5. Two dimensional g-C as in claim 13N4The electrochemical preparation method of the nanosheet membrane is characterized in that g-C in the step (2)3N4The thickness of the two-dimensional nanosheet film is 350-630 nm.
6. Two-dimensional g-C3N4Nanosheet membrane, characterized in being produced according to the production method of any one of claims 1 to 5.
7. Two-dimensional g-C3N4Use of a nanoplatelets membrane in ion separation.
8. The two-dimensional g-C of claim 73N4Use of a nanoplatelets membrane for ion separation, characterized in that the two-dimensional g-C3N4The application of the nanosheet membrane in ion separation comprises the following steps:
two dimensions g-C3N4The nano-sheet membrane is placed in an ion interception device, an ionic compound solution is added into one side of the membrane, and water is added into the other side of the membrane, so that ion interception is realized.
9. The two-dimensional g-C of claim 73N4The application of the nanosheet membrane in ion separation is characterized in that the concentration of the ionic compound solution is 0.01-2 mol/L.
10. The two-dimensional g-C of claim 73N4The application of the nano-sheet membrane in ion separation is characterized in that the ionic compound is NaCl, LiCl or CaCl2，MgCl2，AlCl3，CuSO4，CdSO4Or MnSO4One kind of (1).
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