CN107252635A - A kind of high stability graphene oxide membrane synthetic method - Google Patents
A kind of high stability graphene oxide membrane synthetic method Download PDFInfo
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- CN107252635A CN107252635A CN201710621640.8A CN201710621640A CN107252635A CN 107252635 A CN107252635 A CN 107252635A CN 201710621640 A CN201710621640 A CN 201710621640A CN 107252635 A CN107252635 A CN 107252635A
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- graphene oxide
- oxide membrane
- synthetic method
- high stability
- film
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- 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
- B01D69/12—Composite membranes; Ultra-thin membranes
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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
- B01D71/02—Inorganic material
- B01D71/021—Carbon
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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
- B01D71/52—Polyethers
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- 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
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/101—Sulfur compounds
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/12—Halogens or halogen-containing compounds
Abstract
The invention discloses a kind of high stability graphene oxide membrane synthetic method, comprise the following steps：Prepare graphene oxide；Synthesize brominated polyphenylether film；Graphene oxide is mixed with crosslinking agent, then ultrasound is filled on brominated polyphenylether film, then hybrid films are placed in water-bath steam, graphene oxide membrane is obtained.This method substantially increases the stability of synthesized graphene oxide membrane, it is crosslinking between GO and BPPO matrix and between GO and EDA, graphene oxide membrane easily dispersible problem in water can preferably be solved, moreover it is possible to solve the problem of graphene oxide membrane synthetic method is complicated.This method is a kind of high stability graphene oxide membrane synthetic method, and gained graphene oxide membrane is applied to the processing of environmental pollution, and be particularly suitable for use in water process.
Description
Technical field
The invention belongs to materials science field, more particularly to a kind of graphene oxide membrane synthetic method, gained is high steady
Qualitative graphene oxide composite membrane is particularly suitable for use in water process.
Background technology
Graphene oxide has monoatomic layer thickness, laminated structure, and water without hindrance in the non-oxide region of graphene oxide
The inwardness such as the smooth migration of power, these inwardness cause graphene oxide to be more suitable for applying in field of membrane science.While by
Easily disperse in water in stannic oxide/graphene nano piece, this also oxidizing graphene film in water process using bringing new choose
War -- stability problem.
The content of the invention
The purpose of the present invention is to overcome weak point of the prior art to be closed there is provided a kind of high stability graphene oxide membrane
Into method, operating method is simple and the compound membrane stability of gained is higher.
To achieve the above object, the technical solution adopted by the present invention is：
A kind of high stability graphene oxide membrane synthetic method, comprises the following steps：
Step a, prepares graphene oxide；
Step b, synthesizes brominated polyphenylether film；
Step c, graphene oxide is mixed with crosslinking agent, ultrasound, is then filled on brominated polyphenylether film, then will be mixed
Close film to be placed in water-bath steam, obtain graphene oxide membrane.
It is preferred that, in the step a, graphene oxide is prepared using improved Hummers methods.
It is preferred that, in the step b, brominated polyphenylether film is synthesized with inversion process.
It is preferred that, in the step b, the thickness of the brominated polyphenylether film of synthesis is 50~80 μm.
It is preferred that, in the step c, crosslinking agent is ethylenediamine.
It is preferred that, in the step c, the mass ratio of graphene oxide and ethylenediamine is 1/1800~1/180.
It is preferred that, in the step c, ultrasound 30 minutes.
It is preferred that, in the step c, the mixed liquor of graphene oxide and crosslinking agent is filled on brominated polyphenylether film
Mode is vacuum filtration.
It is preferred that, in the step c, hybrid films are placed in 80 DEG C of water-bath steam 4 hours.
Beneficial effect：The present invention regulates and controls brominated polyphenylether BPPO and second by changing crosslinking agent ethylenediamine EDA content
Crosslinking between diamines EDA and between graphene oxide GO and ethylenediamine EDA, to prepare the graphene oxide of high stability
Film.This method substantially increases the stability of synthesized graphene oxide membrane, effectively solves graphene oxide membrane easy in water
Scattered the problem of, moreover it is possible to solve the problem of graphene oxide membrane synthetic method is complicated.Major advantage：
1. EDA crosslinking agents used in the present invention, can not only be such that GO is crosslinked with GO lamellas, GO also has friendship with BPPO matrix membranes
Connection, stability of the gained composite membrane in water treatment applications is higher.
2. pressure self assembly filter membrane of the present invention and heating water bath method, easy to operate simple.
Brief description of the drawings
Fig. 1 is synthetic method schematic diagram of the invention；
In figure：1- graphene oxides and crosslinking agent mixed liquor, 2- brominated polyphenylether films, 3- vacuum filtrations, 4- vapor, 5-
High stability graphene oxide membrane.
Embodiment
The present invention is further described below in conjunction with the accompanying drawings.
Embodiment 1
As shown in figure 1, a kind of high stability graphene oxide membrane synthetic method, comprises the following steps：
Step a, graphene oxide (GO) is prepared using improved Hummers methods；Concretely comprise the following steps：
The first step：2.5g graphite and 1.25g sodium nitrate are weighed, they are blended in 500mL wide mouth glass bottles with agitator
In, vial is placed in ice-water bath, is stirred 10 minutes；
Second step：60mL sulfuric acid is slowly added to vial along with being stirred vigorously, after 30 minutes, by 7.5g permanganic acid
Potassium is added in vial, is stirred 2 hours, is then removed ice-water bath, said mixture is stirred at room temperature 12 hours；
3rd step：135mL deionized waters and 25mL hydrogen peroxide are added, continues to stir, obtains pale yellow after mixed liquor is cooled down
Color liquid, is the graphene oxide (GO) tentatively obtained, is then cleaned with hydrochloric acid and deionized water.Through the GO after salt acid elution
Bag filter is put into, first water is changed within every 6 hours, then the product after dialysis is cleaned with centrifuge, 5000rpm is used before this
Centrifugation 20 minutes, remove top clear water and bottom black precipitation, obtain the GO of brown gummy, 8000rpm is used after washing 3 times
High speed centrifugation is cleaned.Dry GO samples are dried with freeze drier.
Step b, brominated polyphenylether (BPPO) film is synthesized with inversion process；
3g brominated polyphenylethers (BPPO) are dissolved in 17gN- methyl pyrrolidones (NMP), is stirred at room temperature 24 hours and obtains
Homogeneous mixed liquor, then stands 12 hours.The BPPO/NMP casting solutions configured are poured on clean glass plate, knifing is used
Knife (thickness is 250mm) scrapes liquid film in uniform thickness, and then this film is vertically placed in DI water coagulating baths at once.Stand 24
After hour, these films are transferred in new DI water and stored for future use.Gained BPPO film thicknesses are 60 μm.
Step c, by graphene oxide (GO) and ethylenediamine (EDA) according to mass ratio 1:1800 mixing, ultrasound 30 minutes, so
After be filtered by vacuum on brominated polyphenylether film, hybrid films are placed in 80 DEG C of water-bath steam 4 hours, obtain high stability oxygen
Graphite alkene composite membrane.
Embodiment 2
It is with the difference of embodiment 1：In step b, gained BPPO film thicknesses are 50 μm；In step c, stone will be aoxidized
Black alkene (GO) is with ethylenediamine (EDA) according to mass ratio 1:800 mixing；Other steps are same as Example 1.
Embodiment 3
It is with the difference of embodiment 1：In step b, gained BPPO film thicknesses are 80 μm；In step c, stone will be aoxidized
Black alkene (GO) is with ethylenediamine (EDA) according to mass ratio 1:180 mixing；Other steps are same as Example 1.
Embodiment 4
High stability graphene oxide membrane obtained by above-described embodiment 1-3 is used into brine waste to handle, NaCl in waste water,
Na2SO4And MgSO4Concentration be 2000ppm.Membrane flux is 3.14-284L/m2.h.bar, to NaCl, Na2SO4And MgSO4
Salt-stopping rate up to be 56.2%, 48% and 36.3%.
Described above is only the preferred embodiment of the present invention, it should be pointed out that：For the ordinary skill people of the art
For member, under the premise without departing from the principles of the invention, some improvements and modifications can also be made, these improvements and modifications also should
It is considered as protection scope of the present invention.
Claims (9)
1. a kind of high stability graphene oxide membrane synthetic method, it is characterised in that：Comprise the following steps：
Step a, prepares graphene oxide；
Step b, synthesizes brominated polyphenylether film；
Step c, graphene oxide is mixed with crosslinking agent, ultrasound, is then filled on brominated polyphenylether film, then by hybrid films
It is placed in water-bath steam, obtains graphene oxide membrane.
2. high stability graphene oxide membrane synthetic method according to claim 1, it is characterised in that：In the step a,
Graphene oxide is prepared using improved Hummers methods.
3. high stability graphene oxide membrane synthetic method according to claim 1, it is characterised in that：In the step b,
Brominated polyphenylether film is synthesized with inversion process.
4. high stability graphene oxide membrane synthetic method according to claim 1, it is characterised in that：In the step b,
The thickness of the brominated polyphenylether film of synthesis is 50~80 μm.
5. high stability graphene oxide membrane synthetic method according to claim 1, it is characterised in that：In the step c,
Crosslinking agent is ethylenediamine.
6. high stability graphene oxide membrane synthetic method according to claim 5, it is characterised in that：In the step c,
The mass ratio of graphene oxide and ethylenediamine is 1/1800~1/180.
7. high stability graphene oxide membrane synthetic method according to claim 1, it is characterised in that：In the step c,
Ultrasound 30 minutes.
8. high stability graphene oxide membrane synthetic method according to claim 1, it is characterised in that：In the step c,
It is vacuum filtration that the mixed liquor of graphene oxide and crosslinking agent is filled into the mode on brominated polyphenylether film.
9. high stability graphene oxide membrane synthetic method according to claim 1, it is characterised in that：In the step c,
Hybrid films are placed in 80 DEG C of water-bath steam 4 hours.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN109364774A (en) * | 2018-11-15 | 2019-02-22 | 合肥工业大学 | A kind of Ionomer and stannic oxide/graphene nano composite membrane and its preparation method and application |
| CN110354696A (en) * | 2018-04-09 | 2019-10-22 | 天津大学 | A kind of flexible high-pass graphene oxide/silica composite films and preparation method thereof |
| 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 |
| CN110508164A (en) * | 2019-08-07 | 2019-11-29 | 大连理工大学 | A kind of preparation method of the graphene oxide composite membrane of stable structure |
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Cited By (7)
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| CN110354696A (en) * | 2018-04-09 | 2019-10-22 | 天津大学 | A kind of flexible high-pass graphene oxide/silica composite films and preparation method thereof |
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| CN110508164A (en) * | 2019-08-07 | 2019-11-29 | 大连理工大学 | A kind of preparation method of the graphene oxide composite membrane of stable structure |
| 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 |
| CN110394070B (en) * | 2019-08-09 | 2021-12-03 | 中国海洋大学 | Multilayer crosslinked graphene oxide, and preparation method and application thereof |
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