CN109731482A - A kind of seperation film and preparation method thereof based on graphene oxide - Google Patents
A kind of seperation film and preparation method thereof based on graphene oxide Download PDFInfo
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- CN109731482A CN109731482A CN201910180434.7A CN201910180434A CN109731482A CN 109731482 A CN109731482 A CN 109731482A CN 201910180434 A CN201910180434 A CN 201910180434A CN 109731482 A CN109731482 A CN 109731482A
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Abstract
The present invention relates to a kind of seperation films based on graphene oxide, are made of separating layer and supporting layer, and the graphene oxide of small organic molecule intercalation is as separating layer, and polymeric ultrafiltration membranes are as supporting layer；The separating layer with a thickness of 30 ± 2nm, be made of graphene oxide and small organic molecule, wherein small organic molecule and graphene oxide mass ratio are 1-10%.The present invention is chemically modified graphene oxide using small organic molecule, one layer of graphene oxide is equably deposited in supporting body surface by the way that film-forming method is simply and easily filtered by vacuum, obtains flawless graphene oxide seperation film after thermally treated crosslinking drying.The seperation film utilizes the layer structure of graphene oxide composite material, and its covalent reaction between small organic molecule, the chemical structure and physical structure for adjusting graphene oxide composite material inter-layer passages simultaneously show good Pervaporation Separation applied to the Selective Separation of water in mixed system.The method of the present invention simple process economy, has a wide range of application, and is suitable for prepare with scale.
Description
Technical field
The seperation film and preparation method thereof based on graphene oxide that the present invention relates to a kind of, prepared film can be used for mixing
The preferential separation of water in dicyandiamide solution.
Background technique
In industrial processes, one of the committed step that the water in organic solvent is various applications is removed, such as high-purity
The production of solvent, solvent recovery and esterification are strengthened.Compared with traditional separating technology such as rectifying and molecular sieve are adsorbed, vapour is permeated
Be turned to important one of membrane separation technique, have low energy consumption, at low cost, occupied area is small, advantages of environment protection.
Derivative one of of the graphene oxide (GO) as graphene, thickness and micron-sized cross with monoatomic layer
To size, is conducive to stack in film construction process and self assembly goes out orderly two-dimentional inter-layer passages.Simultaneous oxidation graphene film
Layer surface has a large amount of oxygen-containing functional group, is conducive to be chemically modified it.However, graphene oxide membrane is separated in liquid
Mechanical performance is poor in environment, and stability is lower, and current method is difficult to realize mention while flux, selectivity and stability
It is high.
According to " solution-diffusion " mechanism, using small organic molecule chemical modification graphene oxide composite material vacuum filtration film
Method can regulate and control the physical structure and chemical structure in graphene oxide channel simultaneously, have easy to operate, repeatability, stability
The advantages such as good, are a kind of effective solution approach.
Summary of the invention
The object of the present invention is to provide a kind of seperation films based on graphene oxide composite material, and it is another object of the present invention to mention
For the preparation method of above-mentioned seperation film.The composite membrane prepared in this approach has good separation for separating alcohol-water mixture
Effect.Preparation method is simple for this, environmentally protective.
The technical solution of the present invention is as follows: a kind of seperation film based on graphene oxide, it is characterised in that: by separating layer and branch
It supports layer to constitute, the graphene oxide of small organic molecule intercalation is as separating layer, and polymeric ultrafiltration membranes are as supporting layer；It is described organic
The graphene oxide separating layer of small molecule intercalation with a thickness of 30 ± 2nm, be made of graphene oxide and small organic molecule, wherein
Small organic molecule and graphene oxide mass ratio are 1-10%.
The present invention also provides the preparation methods of above-mentioned seperation film, the specific steps of which are as follows:
A) graphene oxide composite material is added in solvent, is dispersed by stirring and ultrasound, is configured to 0.1-
The dispersion liquid of 0.3mg/ml；
B) organic small molecule material is added in aqueous slkali, dispersion is dissolved by stirring, is configured to 0.001-
The small organic molecule solution of 0.005M；
C) small organic molecule solution blending in the step A) dispersion liquid being configured to and step B) is diluted, by stirring and surpassing
Sound is uniformly dispersed, and is configured to mixed solution；
D step C)) is configured to mixed solution, is uniformly dispersed on polymer supports by the method for vacuum filtration,
Keep 10-14h；
E the film that D) is prepared) is handled 2-5h to be chemically crosslinked at 25 DEG C~65 DEG C, then vacuum drying obtains
Seperation film based on graphene oxide.
Preferred steps A) described in mixing speed be 500-1000rpm, mixing time 60-120min；Ultrasonic power
For 600-900W, ultrasonic time 30-60min；Step B) described in mixing speed be 800-1000rpm, mixing time is
10-30min；Step C) described in mixing speed be 800-1000rpm, mixing time 20-40min；Ultrasonic power is
600-900W, ultrasonic time 20-40min；Step E) in vacuum drying temperature be 25 DEG C~65 DEG C, time 12-24h.
Preferred steps A) described in solvent be water.Preferred steps B) described in organic small molecule material be at least benzene two
One of amine, diamino benzene sulfonic acid or benzidine disulfonic acid.Preferred steps B) described in aqueous slkali be sodium hydroxide or hydrogen-oxygen
Change one of potassium；The concentration of aqueous slkali is 0.001-0.005M.Preferred steps D) described in polymer supports material extremely
It is less one of polyacrylonitrile, polycarbonate or Kynoar.
Preferred steps E) small organic molecule and graphene oxide mass ratio are 1-10% in the seperation film that is prepared.
The utility model has the advantages that
The present invention is chemically modified graphene oxide composite material by small organic molecule, compensates for graphene oxide composite material
The disadvantages of mechanical performance of direct formation of film at surface is low, stability is poor controls the thickness of film by adjusting the related preparation condition for doing film
And structure, the Pervaporation Separation of Effective Regulation film, to adapt to different separation requirements.The method of the present invention simple process warp
Ji, it is applied widely.
Detailed description of the invention
Fig. 1 is the section scanning electron microscope photo that film is made in embodiment 2.
Specific embodiment
Comparative example 1
1) graphene oxide composite material is added to the water, by stirring (500rpm, 120min) and ultrasound (600W,
30min) dispersed, is configured to the dispersion liquid of 0.2mg/ml.
2) graphene oxide composite material dispersion liquid in 1ml step 1) is added in 200ml deionized water, by stirring
(800rpm, 20min) and ultrasonic (600W, 20min) is uniformly dispersed so that graphene oxide is fully dispersed in water.
3) it by dispersion liquid in step 2), is uniformly dispersed, is kept on polymer supports by the method for vacuum filtration
10h。
4) film being prepared is obtained into the seperation film based on graphene oxide composite material in 25 DEG C of vacuum drying 12h.Measurement
Film made from this example for butanol/water system separating property, when temperature be 40 DEG C, feed side water content be 10% when, film
Flux is 2080g/m2H, separation factor 110.
Embodiment 1
1) graphene oxide composite material is added to the water, by stirring (500rpm, 60min) and ultrasound (900W, 60min)
Dispersed, is configured to the dispersion liquid of 0.1mg/ml.
2) diamino benzene sulfonic acid is added in the sodium hydroxide solution of 0.001M, by stirring (1000rpm, 30min)
Dispersion is dissolved, the solution that diamino benzene sulfonic acid concentration is 0.001M is configured to.
3) small organic molecule solution in graphene oxide composite material dispersion liquid in 2ml step 1) and 1ml step 2) is added
In 200ml deionized water, it is uniformly dispersed by stirring (1000rpm, 30min) and ultrasonic (900W, 20min), is configured to mix
Solution.
4) it by dispersion liquid in step 3), is uniformly dispersed, is kept on polyacrylonitrile supporter by the method for vacuum filtration
10h。
5) film being prepared is handled 3h to be chemically crosslinked at 65 DEG C, is then dried in vacuo at 25 DEG C and obtains for 24 hours
To the seperation film based on graphene oxide composite material, film thickness 28nm.
Obtained film is the graphene oxide of small organic molecule intercalation as separating layer, and polymeric ultrafiltration membranes are as support
Layer；It is characterized through XPS, it was demonstrated that separating layer is the graphene oxide of small organic molecule intercalation, small organic molecule and graphite oxide in film
The mass ratio of alkene is 1%.Measure this example made from film for butanol/water system separating property, when temperature be 40 DEG C, feed side
When water content is 10%, the flux of film is 2113g/m2H, separation factor 379.
Embodiment 2
1) graphene oxide composite material is added to the water, by stirring (500rpm, 120min) and ultrasound (900W,
60min) dispersed, is configured to the dispersion liquid of 0.1mg/ml.
2) diamino benzene sulfonic acid is added in the sodium hydroxide solution of 0.002M, it will by stirring (800rpm, 30min)
It dissolves dispersion, is configured to the solution of 0.002M.
3) small organic molecule solution in graphene oxide composite material dispersion liquid in 2ml step 1) and 3ml step 2) is added
In 200ml deionized water, it is uniformly dispersed by stirring (1000rpm, 40min) and ultrasonic (600W, 40min), is configured to mix
Solution.
4) it by dispersion liquid in step 3), is uniformly dispersed, is kept on polyacrylonitrile supporter by the method for vacuum filtration
10h。
5) film being prepared is handled 3h to be chemically crosslinked at 65 DEG C, is then obtained in 65 DEG C of vacuum drying 12h
Seperation film based on graphene oxide composite material, film thickness 30nm.
Obtained film section SEM is as shown in Figure 1, can be seen from the chart that the graphene oxide of small organic molecule intercalation is made
For separating layer, polymeric ultrafiltration membranes are as supporting layer；It is characterized through XPS, it was demonstrated that separating layer is the oxidation stone of small organic molecule intercalation
Black alkene, the mass ratio of small organic molecule and graphene oxide is 9% in film.Film made from this example is measured for butanol/water system
Separating property, when temperature is 40 DEG C, and feed side water content is 10%, the flux of film is 2880g/m2H, separation factor are
1336。
Embodiment 3
1) graphene oxide composite material is added to the water, by stirring (500rpm, 120min) and ultrasound (900W,
60min) dispersed, is configured to the dispersion liquid of 0.2mg/ml.
2) diamino benzene sulfonic acid is added in the potassium hydroxide solution of 0.005M, it will by stirring (800rpm, 30min)
It dissolves dispersion, is configured to the solution that diamino benzene sulfonic acid concentration is 0.005M.
3) small organic molecule solution in graphene oxide composite material dispersion liquid in 1ml step 1) and 4ml step 2) is added
In 200ml deionized water, it is uniformly dispersed by stirring (1000rpm, 20min) and ultrasonic (900W, 20min), is configured to mix
Solution.
4) it by dispersion liquid in step 3), is uniformly dispersed, is kept on polycarbonate supporter by the method for vacuum filtration
12h。
5) film being prepared is handled 5h to be chemically crosslinked at 45 DEG C, is then obtained for 24 hours in 45 DEG C of vacuum drying
Seperation film based on graphene oxide composite material, film thickness 32nm.
Obtained film is the graphene oxide of small organic molecule intercalation as separating layer, and polymeric ultrafiltration membranes are as support
Layer；It is characterized through XPS, it was demonstrated that separating layer is the graphene oxide of small organic molecule intercalation, small organic molecule and graphite oxide in film
The mass ratio of alkene is 10%.Measure this example made from film for butanol/water system separating property, when temperature be 40 DEG C, raw material
When side water content is 10%, the flux of film is 2564g/m2H, separation factor 507.
Embodiment 4
1) graphene oxide composite material is added to the water, by stirring (500rpm, 120min) and ultrasound (900W,
60min) dispersed, is configured to the dispersion liquid of 0.3mg/ml.
2) phenylenediamine is added in the potassium hydroxide solution of 0.002M, is dissolved by stirring (800rpm, 30min)
Dispersion is configured to the solution that phenylenediamine concentration is 0.002M.
3) small organic molecule solution in graphene oxide composite material dispersion liquid in 1.5ml step 1) and 2ml step 2) is added
In 200ml deionized water, it is uniformly dispersed by stirring (900rpm, 20min) and ultrasonic (900W, 20min), is configured to mix molten
Liquid.
4) it by dispersion liquid in step 3), is uniformly dispersed, is protected on Kynoar supporter by the method for vacuum filtration
Hold 10h.
5) film being prepared is handled 5h to be chemically crosslinked at 25 DEG C, is then obtained in 25 DEG C of vacuum drying 12h
Seperation film based on graphene oxide composite material, film thickness 30nm.
Obtained film is the graphene oxide of small organic molecule intercalation as separating layer, and polymeric ultrafiltration membranes are as support
Layer；It is characterized through XPS, it was demonstrated that separating layer is the graphene oxide of small organic molecule intercalation, small organic molecule and graphite oxide in film
The mass ratio of alkene is 8%.Measure this example made from film for butanol/water system separating property, when temperature be 40 DEG C, feed side
When water content is 10%, the flux of film is 2761g/m2H, separation factor 664.
Embodiment 5
1) graphene oxide composite material is added to the water, by stirring (1000rpm, 120min) and ultrasound (600W,
30min) dispersed, is configured to the dispersion liquid of 0.3mg/ml.
2) biphenyl disulfonic acid is added in the potassium hydroxide solution of 0.002M, by stirring (800rpm, 30min) by its
Dissolution dispersion is configured to the solution that biphenyl disulfonic acid concentration is 0.002M.
3) small organic molecule solution in graphene oxide composite material dispersion liquid in 1.5ml step 1) and 2ml step 2) is added
In 200ml deionized water, it is uniformly dispersed by stirring (1000rpm, 30min) and ultrasonic (30min), is configured to mixed solution.
4) it by dispersion liquid in step 3), is uniformly dispersed, is kept on polycarbonate supporter by the method for vacuum filtration
10h。
5) film being prepared is handled 5h to be chemically crosslinked at 25 DEG C, is then obtained in 25 DEG C of vacuum drying 12h
Seperation film based on graphene oxide composite material, film thickness 30nm.
Obtained film is the graphene oxide of small organic molecule intercalation as separating layer, and polymeric ultrafiltration membranes are as support
Layer；It is characterized through XPS, it was demonstrated that separating layer is the graphene oxide of small organic molecule intercalation, small organic molecule and graphite oxide in film
The mass ratio of alkene is 10%.Measure this example made from film for butanol/water system separating property, when temperature be 40 DEG C, raw material
When side water content is 10%, the flux of film is 2985g/m2H, separation factor 946.
Claims (8)
1. a kind of seperation film based on graphene oxide, it is characterised in that: be made of separating layer and supporting layer, small organic molecule is inserted
The graphene oxide of layer is as separating layer, and polymeric ultrafiltration membranes are as supporting layer；The graphite oxide of the small organic molecule intercalation
Alkene separating layer with a thickness of 30 ± 2nm, be made of graphene oxide and small organic molecule, wherein small organic molecule and graphite oxide
Alkene mass ratio is 1-10%.
2. a kind of method for preparing seperation film as described in claim 1, the specific steps of which are as follows:
A) graphene oxide composite material is added in solvent, is dispersed by stirring and ultrasound, is configured to 0.1-0.3mg/ml
Dispersion liquid；
B) organic small molecule material is added in aqueous slkali, dispersion is dissolved by stirring, is configured to 0.001-0.005M
Small organic molecule solution；
C) small organic molecule solution blending in the step A) dispersion liquid being configured to and step B) is diluted, by stirring and ultrasound point
It dissipates uniformly, is configured to mixed solution；
D step C)) is configured to mixed solution, is uniformly dispersed on polymer supports by the method for vacuum filtration, is kept
10-14h；
E the film that D) is prepared) is handled 2-5h to be chemically crosslinked at 25 DEG C~65 DEG C, then vacuum drying is based on
The seperation film of graphene oxide.
3. according to the method described in claim 1, it is characterized in that step A) described in mixing speed be 500-1000rpm,
Mixing time is 60-120min；Ultrasonic power is 600-900W, ultrasonic time 30-60min；Step B) described in stirring
Speed is 800-1000rpm, mixing time 10-30min；Step C) described in mixing speed be 800-1000rpm, stirring
Time is 20-40min；Ultrasonic power is 600-900W, ultrasonic time 20-40min；Step E) in vacuum drying temperature be 25
DEG C~65 DEG C, time 12-24h.
4. according to the method described in claim 2, it is characterized in that step A) described in solvent be water.
5. according to the method described in claim 2, it is characterized in that step B) described in organic small molecule material be at least benzene
One of diamines, diamino benzene sulfonic acid or benzidine disulfonic acid.
6. according to the method described in claim 2, it is characterized in that step B) described in aqueous slkali be sodium hydroxide or hydroxide
One of potassium；The concentration of aqueous slkali is 0.001-0.005M.
7. according to the method described in claim 1, it is characterized in that step D) described in the materials of polymer supports be at least
One of polyacrylonitrile, polycarbonate or Kynoar.
8. according to the method described in claim 2, it is characterized in that step E) in the seperation film that is prepared small organic molecule with
Graphene oxide mass ratio is 1-10%.
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| 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 |
| CN110787652A (en) * | 2019-10-29 | 2020-02-14 | 南京工业大学 | Method for enhancing water stability of graphene oxide composite film |
| CN110860215A (en) * | 2019-10-12 | 2020-03-06 | 浙江大学 | Graphene oxide film with tent-like structure and preparation method and application thereof |
| CN111346517A (en) * | 2020-03-17 | 2020-06-30 | 北京理工大学 | Composite crosslinked graphene oxide membrane, preparation method and application thereof |
| CN111589307A (en) * | 2020-06-10 | 2020-08-28 | 杨晓飞 | Composite nanofiltration membrane and preparation method thereof |
| CN112023718A (en) * | 2020-07-31 | 2020-12-04 | 南京工业大学 | Zwitter-ion pervaporation separation membrane and preparation method thereof |
| CN113522059A (en) * | 2021-07-02 | 2021-10-22 | 五邑大学 | Folded graphene oxide film and preparation method thereof |
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| CN110787652B (en) * | 2019-10-29 | 2021-10-29 | 南京工业大学 | Method for enhancing water stability of graphene oxide composite film |
| CN110787652A (en) * | 2019-10-29 | 2020-02-14 | 南京工业大学 | Method for enhancing water stability of graphene oxide composite film |
| CN111346517B (en) * | 2020-03-17 | 2021-06-11 | 北京理工大学 | Composite crosslinked graphene oxide membrane, preparation method and application thereof |
| CN111346517A (en) * | 2020-03-17 | 2020-06-30 | 北京理工大学 | Composite crosslinked graphene oxide membrane, preparation method and application thereof |
| CN111589307A (en) * | 2020-06-10 | 2020-08-28 | 杨晓飞 | Composite nanofiltration membrane and preparation method thereof |
| CN111589307B (en) * | 2020-06-10 | 2022-06-14 | 东莞市逸轩环保科技有限公司 | Composite nanofiltration membrane and preparation method thereof |
| CN112023718A (en) * | 2020-07-31 | 2020-12-04 | 南京工业大学 | Zwitter-ion pervaporation separation membrane and preparation method thereof |
| CN113522059A (en) * | 2021-07-02 | 2021-10-22 | 五邑大学 | Folded graphene oxide film and preparation method thereof |
| CN113522059B (en) * | 2021-07-02 | 2023-02-17 | 五邑大学 | Folded graphene oxide film and preparation method thereof |
| CN114618583A (en) * | 2022-03-24 | 2022-06-14 | 中国科学院理化技术研究所 | Membrane catalytic material for catalyzing Knoevenagel condensation reaction at room temperature at high speed and high conversion rate |
| CN114618583B (en) * | 2022-03-24 | 2023-07-21 | 中国科学院理化技术研究所 | Membrane catalytic material for catalyzing Knoevenagel condensation reaction at room temperature with high conversion rate |
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Application publication date: 20190510 |