CN109224888A - A kind of graphene oxide framework modified polyamide reverse osmose membrane and its application - Google Patents
A kind of graphene oxide framework modified polyamide reverse osmose membrane and its application Download PDFInfo
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- CN109224888A CN109224888A CN201710554728.2A CN201710554728A CN109224888A CN 109224888 A CN109224888 A CN 109224888A CN 201710554728 A CN201710554728 A CN 201710554728A CN 109224888 A CN109224888 A CN 109224888A
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- 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
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D61/00—Processes of separation using semi-permeable membranes, e.g. dialysis, osmosis or ultrafiltration; Apparatus, accessories or auxiliary operations specially adapted therefor
- B01D61/02—Reverse osmosis; Hyperfiltration ; Nanofiltration
- B01D61/025—Reverse osmosis; Hyperfiltration
-
- 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
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- 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
- B01D2325/00—Details relating to properties of membranes
- B01D2325/36—Hydrophilic membranes
Abstract
The invention discloses the preparations and application of a kind of graphene oxide framework modified polyamide reverse osmose membrane, belong to membrane for water treatment preparation technical field.Present invention solves the technical problem that being that existing polyamide reverse osmose membrane hydrophily is poor, problem of permeance property difference.The technical scheme is that a kind of building graphene oxide frame is proposed, and the separating property for improving reverse osmosis membrane, its specific method includes: (1) prepares graphene oxide by Hummer；(2) graphene oxide reacts building graphene oxide frame with polyamine；(3) it carries out interfacial polymerization and prepares graphene oxide framework modified polyamide reverse osmose membrane.The present invention has the graphene oxide framework modified polyamide reverse osmose membrane of nanometer aquaporin, effectively raises the hydrophily and permeance property of polyamide reverse osmose membrane, has good prospects for commercial application.
Description
Technical field
The invention belongs to the preparations of membrane for water treatment technical field more particularly to graphene oxide framework modified PA reverse osmosis membrane
And its application.
Background technique
Since the mankind are during rapid economic development, the protection to existing water resource is ignored, so that existing water provides
Source water quality is also greatly reduced, and eventually leads to the demand that existing water resource is much unable to satisfy social development.Due to seawater abundant
Resource obtains freshwater resources, i.e. seawater fresh water from seawater, it has also become a kind of very important method for obtaining fresh water.According to point
From principle, desalination technology can be divided into thermal method and embrane method two major classes.Technology based on thermal method have multistage flash distillation (MSF),
Multiple-effect evaporation (MED) and gas compression distillation (CVD)；Desalination technology based on embrane method has reverse osmosis (RO), nanofiltration (NF), electric osmose
Analyse (EDI) and some new technology such as ion exchanges.Compared with thermal method desalting technology, not with the reverse osmosis membrane technology for representative
It is related to phase transformation, therefore low energy consumption.Meanwhile reverse osmosis technology is with easy to operate, occupied area is small, the chemicals of needs is few, can
The advantages that normal-temperature operation, it is considered to be one of water treatment technology most with prospects.Currently, most widely used reverse osmosis in the market
Film is the PA composite membrane prepared by interfacial polymerization.But the hydrophily of film is poor so that pollutant be readily adsorbed in film surface or
Inside fenestra, the performance of film is caused sharply to decline；Meanwhile the permeation flux of film is small, so that required impressed pressure is larger.Cause
This, is badly in need of a kind of effective mode to improve the hydrophily and permeance property of film.
Graphene is as a kind of novel material, with many excellent performances.Graphene oxide is that graphene is most heavy
A kind of growth wanted, its structure and graphene are substantially the same, and are that one layer of carbon atom composition two-dimensional space infinitely extends
Structure.It is that graphene oxide has many oxygen-containing functional groups with the maximum difference of graphene in structure, is respectively as follows:
It is distributed in the hydroxyl and epoxy group of graphene oxide on piece；It is distributed in the carboxyl and carbonyl at graphene oxide sheet edge.2012
When Massachusetts Institute Technology has registered porous graphene film for sea water desalination, compared with traditional PA reverse osmosis membrane, water is logical
Amount improves 100~1000 times.Therefore, graphene film has showed wide application prospect in field of seawater desalination.Currently,
Graphene oxide is used to prepare reverse osmosis membrane and is mainly the following measure: LBL self-assembly, insertion PA active layer in and polyethers
Sulfone or polysulfones are blended, are covalently connected to reverse osmosis membrane surface etc., these methods do not make full use of the structure of graphene oxide special
Point (quickly without friction aquaporin).Therefore, graphene frame is constructed, so that the nanometer aquaporin of graphene is made full use of, with this
To improve the performance of PA reverse osmosis membrane.
Summary of the invention
Primary and foremost purpose of the invention is to provide a kind of hydrophilic method for effectively improving reverse osmosis membrane, provides one kind and changes
Property PA reverse osmosis membrane and preparation method thereof, the effective solution problem.
PA reverse osmosis membrane in the present invention, including high-molecular porous supporting layer and PA active layer, which is characterized in that aoxidize stone
Black alkene frame is modifying agent, is added in the aqueous phase solution of polyamine, then successively contacts high-molecular porous supporting layer oxygen-containing
The PA of the polyamine aqueous phase solution of graphite alkene frame and the oil-phase solution of polynary acyl chlorides, preparation insertion graphene oxide frame is anti-
Permeable membrane.
The invention adopts the following technical scheme:
A kind of graphene oxide framework modified reverse osmosis membrane, is prepared as follows to obtain:
(1) high-molecular porous supporting layer preparation: by high molecular material stirring and dissolving in nonpolarity or polar organic solvent,
Standing and defoaming forms the casting solution of stable uniform, on a glass by casting solution blade coating, through deionized water coagulating bath, phase occurs
Conversion film forming is then stored in the further exchange of solvent of 12~48h progress in deionized water and is obtained with removing remaining solvent
The high-molecular porous supporting layer；The high molecular material is selected from polyether sulfone, polysulfones, polyimides, polyethylene oxide, polyethers
At least one of acid imide, polypropylene or carbonic ester；
(2) preparation of graphene oxide frame: will be existed by the graphite oxide of modified Hummer method preparation by ultrasonic disperse
In solvent, polynary amine monomers are then added, carries out solvent reaction, is centrifugally separating to obtain the graphene oxide frame after washing several times
Frame, re-dry are stand-by；The polynary amine monomers are hydrazine hydrate, propane diamine, hexamethylene diamine, diethylenetriamine, triethylene tetramine, adjacent benzene
At least one of diamines, m-phenylene diamine (MPD), p-phenylenediamine or polyethyleneimine
(3) graphene oxide frame prepared by step (2) preparation of PA active layer: is distributed to the more members of 0.1~1w/v%
In amine aqueous phase solution, graphene oxide frame is 500~2000ppm in polyamine aqueous phase solution concentration, then step (1) is made
High-molecular porous supporting layer immerse 1~4min in above-mentioned polyamine aqueous phase solution, high-molecular porous supporting layer is removed after taking-up
The moisture on surface, then 1~4min into the more first acyl chlorides oil-phase solutions of 0.01~0.05w/v% is immersed, removal film surface oil mixes
After liquid, 5~20min is then handled at 65~85 DEG C, the graphene oxide framework modified reverse osmosis membrane is prepared.
Further, step (1) the of the present invention nonpolarity or polar solvent are benzene, carbon tetrachloride, dichloroethanes, N, N- bis-
At least one of methylformamide, n,N-dimethylacetamide or N-Methyl pyrrolidone.
Further, high molecular material mass content 10~30% described in step (1) the of the present invention casting solution, it is described non-
Polarity or polar organic solvent mass content 70~90%.
Further, step (2) the of the present invention solvent is water, methanol, ethyl alcohol, n,N-Dimethylformamide, N, N- diformazan
At least one of yl acetamide or N-Methyl pyrrolidone.
Further, the content of step (2) the of the present invention graphite oxide in a solvent is 300~800ppm.
Further, content is 0.2~0.8mol/L to step (2) the polynary amine monomers of the present invention in a solvent.
Further, polyamine is p-phenylenediamine, o-phenylenediamine or equal in step (3) the polyamine aqueous phase solution of the present invention
At least one of benzene triamine.
Further, polynary acyl chlorides is o-phthaloyl chloride, isophthalic in step (3) the of the present invention polynary acyl chlorides oil-phase solution
At least one of dimethyl chloride or paraphthaloyl chloride.
Further, oil is mutually normal octane, hexamethylene, normal heptane in step (3) the of the present invention polynary acyl chlorides oil-phase solution
Or at least one of mixing isoparaffin.
In addition, the present invention also provides graphene oxide framework modified reverse osmosis membrane the answering in water process described in one kind
With.The application is particularly for Industrial Wastewater Treatment and sea water desalination.
Compared with the prior art, the advantages of the present invention are as follows: it is anti-using the open loop addition between polyamine and graphene oxide
It answers or condensation reaction constructs the graphene oxide frame with nanometer aquaporin；Using the graphene oxide with nanometer aquaporin
Frame shows good hydrophily, and it is uneven, easy to reunite to solve the problems, such as that graphene oxide disperses in aqueous phase solution solution；
Graphene oxide frame is uniformly scattered in aqueous phase solution as filler, and graphene oxide may be implemented in polyamide activity
It is evenly dispersed in layer；The frame structure of simultaneous oxidation graphene provides good aquaporin, can polyamide reverse osmose membrane significantly
Hydrophily is poor, the low problem of permeation flux.Used method is simple, easy to operate, is suitable for large-scale production.
Detailed description of the invention
Fig. 1 is the schematic diagram of the diethylenetriamine-GO/PA reverse osmosis membrane prepared in embodiment 1.
1 in figure: polyamide active layer；2: polymeric backing layer；3: graphene frame.
Fig. 2 is the scanning electron microscope (SEM) photograph on the surface of the diethylenetriamine-GO/PA reverse osmosis membrane prepared in embodiment 1.
Fig. 3 is the water contact angle figure of the diethylenetriamine-GO/PA reverse osmosis membrane prepared in embodiment 1.
Specific embodiment
Combined with specific embodiments below, the present invention is described further, but the present invention is not limited to the following embodiments,
It is not departing from the content of present invention and range, change all should be comprising within the technical scope of the present invention.
It is reverse osmosis that embodiment 1 prepares diethylenetriamine-GO/PA
(1) 3.87g Kynoar is added in 20mL n,N-Dimethylformamide, stirring and dissolving, standing and defoaming,
Form the casting solution of stable uniform.Casting solution is scratched on a glass using scraper, is put into rapidly in deionized water coagulating bath,
After inversion of phases is complete, Kynoar supporting layer is transferred in new deionized water and continues exchange of solvent for 24 hours.
(2) it using crystalline flake graphite as raw material, using the concentrated sulfuric acid, potassium permanganate as oxidant, is prepared into modified Hummers method
To graphite oxide.It is prepared as follows: 1g crystalline flake graphite and 1g sodium nitrate is added in the 40mL concentrated sulfuric acid, under condition of ice bath,
3gKMnO is added4.Then 1h is kept at room temperature, 90mL deionized water is then added, and is then reacted 40min at 98 DEG C and is obtained
Bright yellow solution.Then 2.5mLH is added2O2.Then graphite oxide is washed till neutrality with deionized water, is dried at 65 DEG C standby
With.
(3) 0.03g graphite oxide is added in 100mL deionized water, ultrasound removing obtains GO suspension, 2mL is added
Diethylenetriamine solution, is reacted, and products therefrom is centrifuged after reaction, is then washed with deionized water, and is done at room temperature
It is dry, obtain black oxidation graphene frame.
(4) Kynoar supporting layer is immersed to equal benzene triamine (0.2w/v%) the solution 2min of the frame containing graphene oxide
In, graphene oxide frame concentration is respectively 500ppm and 2000ppm；It is then immersed in m-phthaloyl chloride-normal octane (0.02w/
V%) in solution 2min, interface polymerization reaction occurs and generates the ultra-thin dense separation layers of PA, then 80 DEG C of processing 15min；It takes out into
Film saves stand-by in deionized water.
It (5) is 2000mg/LNaCl solution testing gained 500ppm graphene oxide frame with concentration at 20 DEG C, 1.5MPa
The water flux of the modified PA reverse osmosis membrane of frame is 3.2L/ (m2Hbar), salt-stopping rate 96.4%；2000ppm graphite oxide
The water flux of the PA reverse osmosis membrane of alkene framework modified is 2.0L/ (m2Hbar), salt-stopping rate 97.4%
Embodiment 2 prepares p-phenylenediamine-GO/PA composite membrane
(1) 2.28g polyetherimide is added in 20mL N-Methyl pyrrolidone, stirring and dissolving, standing and defoaming, shape
At the casting solution of stable uniform.Casting solution is scratched on a glass using scraper, is put into rapidly in deionized water coagulating bath, to
After inversion of phases is complete, Kynoar supporting layer is transferred in new deionized water and continues exchange of solvent 12h.
(2) it using crystalline flake graphite as raw material, using the concentrated sulfuric acid, potassium permanganate as oxidant, is prepared into modified Hummers method
To graphite oxide.
(3) 0.08g graphite oxide is added in 100mL ethyl alcohol, ultrasound removing obtains GO suspension, is added 8.65g pairs
Phenylenediamine is reacted, and products therefrom is centrifuged after reaction, is then washed with deionized water, and is dried at room temperature, is obtained black
Color graphene oxide frame.
(4) polyetherimide supporting layer is immersed to o-phenylenediamine (1w/v%) the solution 1min of the frame containing graphene oxide
In, graphene oxide frame concentration is 500ppm, 2000ppm；It is then immersed in m-phthaloyl chloride-mixing isoparaffin
In (0.05w/v%) solution 1min, interface polymerization reaction occurs and generates the ultra-thin dense separation layers of PA, then 65 DEG C of processing 5min；
Film forming is taken out, is saved in deionized water stand-by.
It (5) is 2000mg/L NaCl solution test gained 500ppm graphene oxide with concentration at 50 DEG C, 1.5MPa
The water flux of the PA reverse osmosis membrane of framework modified is 2.6L/ (m2Hbar), salt-stopping rate 97.5%；2000ppm graphite oxide
The water flux of the PA reverse osmosis membrane of alkene framework modified is 1.8L/ (m2Hbar), salt-stopping rate 98.0%
Embodiment 3 prepares polyethyleneimine-GO/PA composite membrane
(1) 11.36g polyethylene oxide is added in 20mL dichloroethanes, stirring and dissolving, standing and defoaming, is formed and is stablized
Uniform casting solution.Casting solution is scratched on a glass using scraper, is put into rapidly in deionized water coagulating bath, to inversion of phases
After completely, polyethylene oxide supporting layer is transferred in new deionized water and continues exchange of solvent 48h.
(2) it using crystalline flake graphite as raw material, using the concentrated sulfuric acid, potassium permanganate as oxidant, is prepared into modified Hummers method
To graphite oxide.
(3) 0.06g graphite oxide being added in 100mL N-Methyl pyrrolidone, ultrasound removing obtains GO suspension,
11.65mL polyethyleneimine (molecular weight: 600Da) solution is added, is reacted, products therefrom is centrifuged after reaction,
Then it is washed with deionized water, dries at room temperature, obtain black oxidation graphene frame.
(4) polyethylene oxide supporting layer is immersed to equal benzene triamine (1w/v%) the solution 4min of the frame containing graphene oxide
In, graphene oxide frame concentration is 500ppm, 2000ppm；It is then immersed in m-phthaloyl chloride-normal octane (0.01w/v%)
In solution 4min, interface polymerization reaction occurs and generates the ultra-thin dense separation layers of PA, then 85 DEG C of processing 20min；Film forming is taken out,
It is saved in deionized water stand-by.
It (5) is 2000mg/L NaCl solution test gained 500ppm graphene oxide with concentration at 20 DEG C, 1.5MPa
The water flux of the PA reverse osmosis membrane of framework modified is 3.0L/ (m2Hbar), salt-stopping rate 97.0%；2000ppm aoxidizes stone
The water flux of the PA reverse osmosis membrane of black alkene framework modified is 2.3L/ (m2Hbar), salt-stopping rate 97.9%.
Comparative example 1 prepares PA composite membrane
(1) 3.87g Kynoar is added in 20mL n,N-Dimethylformamide, stirring and dissolving, standing and defoaming,
Form the casting solution of stable uniform.Casting solution is scratched on a glass using scraper, is put into rapidly in deionized water coagulating bath,
After inversion of phases is complete, Kynoar supporting layer is transferred in new deionized water and continues exchange of solvent for 24 hours.
(2) Kynoar supporting layer is immersed in equal benzene triamine (0.1w/v%) solution 2min；It is then immersed in isophthalic two
In formyl chloro- normal octane (0.02w/v%) solution 2min, interface polymerization reaction occurs and generates the ultra-thin dense separation layers of PA, then
80 DEG C of processing 15min；Film forming is taken out, is saved in deionized water stand-by.
It (3) is the water flux of 2000mg/LNaCl solution testing gained PA reverse osmosis membrane with concentration at 20 DEG C, 1.5MPa
For 1.5L/ (m2Hbar), salt-stopping rate 98.3%.
Comparative example 2 prepares PA composite membrane
(1) 2.28g polyetherimide is added in 20mL N-Methyl pyrrolidone, stirring and dissolving, standing and defoaming, shape
At the casting solution of stable uniform.Casting solution is scratched on a glass using scraper, is put into rapidly in deionized water coagulating bath, to
After inversion of phases is complete, Kynoar supporting layer is transferred in new deionized water and continues exchange of solvent 12h.
(2) polyetherimide supporting layer is immersed in equal benzene triamine (1w/v%) solution 1min；It is then immersed in isophthalic diformazan
In acyl chlorides-mixing isoparaffin (0.05w/v%) solution 1min, interface polymerization reaction occurs and generates the ultra-thin dense separation layers of PA,
Then 65 DEG C of processing 5min；Film forming is taken out, is saved in deionized water stand-by.
It (3) is the water flux of 2000mg/LNaCl solution testing gained PA reverse osmosis membrane with concentration at 20 DEG C, 1.5MPa
For 1.8L/ (m2Hbar), salt-stopping rate 95.3%.
Comparative example 3 prepares PA composite membrane
(1) 11.36g polyethylene oxide is added in 20mL dichloroethanes, stirring and dissolving, standing and defoaming, is formed and is stablized
Uniform casting solution.Casting solution is scratched on a glass using scraper, is put into rapidly in deionized water coagulating bath, to inversion of phases
After completely, Kynoar supporting layer is transferred in new deionized water and continues exchange of solvent 48h.
(2) polyethylene oxide supporting layer is immersed in equal benzene triamine (1w/v%) solution 4min；It is then immersed in isophthalic diformazan
In acyl chlorides-mixing isoparaffin (0.01w/v%) solution 4min, interface polymerization reaction occurs and generates the ultra-thin dense separation layers of PA,
Then 85 DEG C of processing 20min；Film forming is taken out, is saved in deionized water stand-by.
It (3) is the water flux of 2000mg/LNaCl solution testing gained PA reverse osmosis membrane with concentration at 20 DEG C, 1.5MPa
For 1.3L/ (m2Hbar), salt-stopping rate 98.3%.
Claims (10)
1. a kind of graphene oxide framework modified reverse osmosis membrane, it is characterised in that the reverse osmosis membrane is prepared as follows
It arrives:
(1) it high-molecular porous supporting layer preparation: by high molecular material stirring and dissolving in nonpolarity or polar organic solvent, stands
Deaeration forms the casting solution of stable uniform, on a glass by casting solution blade coating, through deionized water coagulating bath, inversion of phases occurs
Film forming is then stored in 12~48h in deionized water and carries out further exchange of solvent, to remove remaining solvent, obtains described
High-molecular porous supporting layer；The high molecular material is selected from polyether sulfone, polysulfones, polyimides, polyethylene oxide, polyetherimide
At least one of amine, polypropylene or carbonic ester；
(2) preparation of graphene oxide frame: ultrasonic disperse will be passed through in solvent by the graphite oxide of modified Hummer method preparation
In, polynary amine monomers are then added, carries out solvent reaction, is centrifugally separating to obtain the graphene oxide frame after washing several times,
Re-dry is stand-by；The polynary amine monomers are hydrazine hydrate, propane diamine, hexamethylene diamine, diethylenetriamine, triethylene tetramine, adjacent benzene two
At least one of amine, m-phenylene diamine (MPD), p-phenylenediamine or polyethyleneimine
(3) graphene oxide frame prepared by step (2) preparation of PA active layer: is distributed to the more first aqueous amines of 0.1~1w/v%
In phase solution, graphene oxide frame is 500~2000ppm in polyamine aqueous phase solution concentration, then by height made from step (1)
Molecular porous supporting layer immerses 1~4min in above-mentioned polyamine aqueous phase solution, and high-molecular porous support layer surface is removed after taking-up
Moisture, then immerse 1~4min into the more first acyl chlorides oil-phase solutions of 0.01~0.05w/v%, after removing film surface oil-phase solution,
Then 5~20min is handled at 65~85 DEG C, and the graphene oxide framework modified reverse osmosis membrane is prepared.
2. graphene oxide framework modified reverse osmosis membrane according to claim 1, it is characterised in that: step (1) is described non-
Polarity or polar solvent are benzene, carbon tetrachloride, dichloroethanes, n,N-Dimethylformamide, n,N-dimethylacetamide or N- first
At least one of base pyrrolidones.
3. graphene oxide framework modified reverse osmosis membrane according to claim 1, it is characterised in that: step (1) described casting
High molecular material mass content described in film liquid 10~30%, the nonpolarity or polar organic solvent mass content 70~
90%.
4. graphene oxide framework modified reverse osmosis membrane according to claim 1, it is characterised in that: step (2) is described molten
Agent is at least one in water, methanol, ethyl alcohol, n,N-Dimethylformamide, n,N-dimethylacetamide or N-Methyl pyrrolidone
Kind.
5. graphene oxide framework modified reverse osmosis membrane according to claim 1, it is characterised in that: step (2) described oxygen
The content of graphite in a solvent is 300~800ppm.
6. graphene oxide framework modified reverse osmosis membrane according to claim 1, it is characterised in that: step (2) is described more
Content is 0.2~0.8mol/L to first amine monomers in a solvent.
7. graphene oxide framework modified reverse osmosis membrane according to claim 1, it is characterised in that: step (3) is described more
Polyamine is at least one of p-phenylenediamine, o-phenylenediamine or equal benzene triamine in first amine aqueous phase solution.
8. preparation method according to claim 1, it is characterised in that polynary acyl in step (3) the polynary acyl chlorides oil-phase solution
Chlorine is at least one of o-phthaloyl chloride, m-phthaloyl chloride or paraphthaloyl chloride.
9. preparation method according to claim 1, it is characterised in that oil is mutually in step (3) the polynary acyl chlorides oil-phase solution
At least one of normal octane, hexamethylene, normal heptane or mixing isoparaffin.
10. graphene oxide framework modified reverse osmosis membrane described in any right is in water process according to claim 1~9
Using.
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Cited By (5)
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| CN110180402A (en) * | 2019-07-08 | 2019-08-30 | 清华大学 | A method of loose nanofiltration membrane is prepared based on interfacial polymerization |
| CN110394070A (en) * | 2019-08-09 | 2019-11-01 | 中国海洋大学 | A kind of multilayer crosslinking-oxidization graphene, preparation method and application |
| CN110841487A (en) * | 2019-12-05 | 2020-02-28 | 中国石油大学(华东) | Preparation method of seawater desalination membrane |
| CN113897059A (en) * | 2021-09-28 | 2022-01-07 | 广州特种承压设备检测研究院 | Graphene @ silicon carbide core-shell composite polyimide permeable membrane and preparation method thereof |
| CN114437339A (en) * | 2020-11-03 | 2022-05-06 | 天津工业大学 | Preparation method and application of high-absorbance honeycomb polyamide membrane |
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