CN107308826A - A kind of preparation method and application of graphene oxide seperation film - Google Patents
A kind of preparation method and application of graphene oxide seperation film Download PDFInfo
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- CN107308826A CN107308826A CN201710547411.6A CN201710547411A CN107308826A CN 107308826 A CN107308826 A CN 107308826A CN 201710547411 A CN201710547411 A CN 201710547411A CN 107308826 A CN107308826 A CN 107308826A
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- graphene oxide
- seperation film
- preparation
- film
- oxide seperation
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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
-
- 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
- B01D67/0081—After-treatment of organic or inorganic 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
- B01D71/024—Oxides
- B01D71/025—Aluminium oxide
-
- 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
- B01D71/48—Polyesters
Abstract
It is the invention discloses a kind of preparation method of graphene oxide seperation film, graphene oxide powder is scattered in deionized water, the graphene oxide seperation film with high stability is prepared by cross-flow method.By controlling the consumption of graphene oxide, cross-flow separation membrance casting condition and effective film forming area, the controllable seperation film of thickness can be obtained.Of the invention innovative prepares ultra-thin graphene oxide seperation film using cross-flow method, and enhances stability of the graphene oxide seperation film in aqueous phase by this film-forming process.Using the separation selectivity of graphene oxide seperation film, efficiently separating for mixed dye is realized.A kind of this graphene oxide seperation film filming technology for being that technique is simple, cost is low, being produced on a large scale.Instant invention overcomes too thick etc. deficiency of the structural instability of graphene oxide seperation film and film thickness, and excellent separating property is shown in dye separation, industrial prospect is huge.
Description
Technical field
The present invention relates to a kind of preparation method and applications of graphene oxide seperation film, more particularly to thickness is adjustable, steady
Qualitative graphene oxide separation membrane preparation method that is high, being suitable for large-scale production, and the application in mixed dye separation.
Background technology
Graphene oxide, as a kind of derivative of carbon, discovery is exactly the research heat of academia and industrial quarters always so far
Point, prominent performance is suffered from various fields.Due to its special two-dimensional layered structure, very strong mechanical performance and
Excellent film forming, graphene oxide is a kind of preferable separation membrane material, is led in gas separating-purifying, desalinization, ion
The field such as road research and DNA detections has potential application prospect.
At present, the traditional preparation methods of graphene oxide seperation film have the modes such as suction method, spin coating, self assembly.Suction method
In the presence of the deficiencies such as time-consuming, efficiency is low and film forming thickness is thicker are film-made, industrial-scale production is not suitable for.In addition, traditional
Graphene oxide seperation film structural stability prepared by method is poor.Due to the architectural characteristic of graphene oxide in itself, abundant contains
Oxygen functional group and hydrophily, membrane structure stability is poor in aqueous phase, easily occurs selfdecomposition, is scattered in again in solvent, so as to lead
Its separating property is caused to degenerate.By subsequent treatments such as thermal reduction, high molecular crosslinks, the steady of graphene oxide seperation film can be improved
It is qualitative, but it is complicated not enough with the undesirable grade of separating property to there is modified technique.
The content of the invention
The present invention devises one for currently preparing deficiency and problem that the various methods of graphene oxide seperation film are present
Kind of thickness is adjustable, stability is high, be suitable for large-scale production ultra-thin graphite oxide seperation film quick film-forming method.
The technical scheme is that：One is that, by cross-flow method, the microstructure to graphene oxide is adjusted, so that
Improve the stability of graphene oxide seperation film；Two be the consumption and cross-flow parameter (time, pressure, stream by graphene oxide
Speed, area, substrate etc.) control, obtain different-thickness, the preparation of the graphene oxide seperation film of area；Three be to utilize oxidation
The selectivity of graphene seperation film, realizes the separation of mixed dye.
The present invention concrete technical scheme be：A kind of preparation method and applications of graphene oxide seperation film, its is specific
Step is：
Graphene oxide dispersion is added in cross-flow devices container, makes graphene oxide dispersion parallel to basilar memebrane
Surface current is moved, in basement membrane surface formation graphene oxide seperation film under the driving of pressure differential.
In preparation process, can by control the amount of film forming graphene oxide, film formation time, film forming substrate, film forming area,
Film pressure and film forming flow velocity, obtain the ultra-thin graphene oxide seperation film of different-thickness.
Preferably, step 2) in, the concentration of described graphene oxide dispersion is 2.5 × 10-4~2.5 × 10-2g/
L。
Preferably, described film formation time is 1-30min.
Preferably, step 3) in, described basilar memebrane is the seperation film that any aperture is 10nm~1.0 μm, is preferably
The alumina ceramic membrane in 200nm apertures or the polycarbonate membrane in 200nm apertures.
Preferably, step 3) in, described effective area is any size.
Preferably, step 3) in, described film pressure is 0.1~5.0bar.
Preferably, step 3) in, described film forming flow velocity is 0.1~2.0LHM.
Another object of the present invention is to provide a kind of graphene oxide seperation film prepared by above-mentioned preparation method.
Another object of the present invention is to provide it is a kind of by above-mentioned graphene oxide seperation film in one-component dyestuff or many
Application in the separation of component dye.Separated dyestuff be azovan blue, rhodamine B, Bengal rose red in one kind or
A variety of solution.
Instant invention overcomes the deficiency of other preparation methods, belong to a kind of quick, low cost preparation method, be suitable for rule
Modelling is produced, with fabulous economic results in society and value.Film thickness prepared by the present invention, area are controllable, and thickness can be controlled
System arrives several micrometer ranges at tens nanometers, solves the traditional thickness for preparing graphene oxide seperation film thickness, stability difference etc.
Technical barrier, with great commercial value.In addition, graphene oxide seperation film is also used for similar structure dyestuff by the present invention
Separation, as a result shows that it has very high selectivity.
Brief description of the drawings
Fig. 1 is the section SEM photograph of graphene oxide seperation film prepared by embodiment 2；
Fig. 2 is the surface SEM photograph of graphene oxide seperation film prepared by embodiment 2.
Embodiment
The present invention is further elaborated and illustrated with reference to the accompanying drawings and detailed description.
Graphene oxide dispersion can be prepared using prior art in the present invention, be given below in the present invention follow-up
A kind of preparation method of embodiment, it is to be noted that this method only aids in understanding for those skilled in the art, is not intended as
The restriction of the present invention.
Realized in subsequent embodiment using graphene oxide powder by ultrasonic disperse in deionized water, aoxidize stone
The preparation method of black alkene is as follows：
By the 30ml concentrated sulfuric acids as in dry three-necked flask, stirred in ice-water bath, while being put inside three-necked flask
Put the temperature change of mixing liquid in a thermometer, moment monitoring flask.After concentrated sulfuric acid temperature is down to 0 DEG C, pre- oxygen is added
Fossil ink powder, after stirring, obtains black mixing liquid.It is slowly added to 3.75g KMnO4Powder, and moment monitoring thermometer
Change, it is ensured that mixture temperature of reaction system is maintained at less than 20 DEG C.Treat KMnO4After powder whole addition is finished, continue to stir
15min, makes mixture reaction system be sufficiently mixed uniformly.Then, three-necked flask is placed in 35 DEG C of waters bath with thermostatic control and reacts 2h.Treat
After reaction terminates, three-necked flask is taken out, is placed in ice bath and cools down.Mixture liquid after cooling is more using glass bar incorporation way
It is secondary to be slowly transferred in the beaker containing 62.5ml deionized waters on a small quantity.In whole transfer process, beaker is placed in ice-water bath all the time
Middle cooling is simultaneously stirred, to ensure that dilute solution system temperature is less than 50 DEG C.Mixture after dilution is transferred back to three-necked flask again
In, it is placed in 35 DEG C of waters bath with thermostatic control and reacts 2h again.After question response terminates, mixture is transferred to dilute in 175ml deionized water
Release.Solution to be diluted is cooled to room temperature, adds the H that 5ml mass fractions are 30%2O2Solution.Now, produced in mixing liquid big
Bubble is measured, solution colour is changed into golden yellow from dark-brown.Add 2.5ml mass fractions and be 5% HCl solution, and continue stirring
15min.Afterwards, golden solution is stood into 24h at ambient temperature.Thing layering to be mixed, golden yellow precipitate is sunken to burning substantially
Behind cup bottom, beaker supernatant liquor is slowly removed with liquid-transfering gun.Put the precipitate in 4 50ml centrifuge tubes, under 7000rpm from
Heart 5min, removes supernatant liquor.Solvent is added, under ultrasonication, centrifugation sample in pipe is uniformly dispersed again, again
It is placed in centrifuge 10,000rpm centrifugations 10min.So operate 8 times, 3 times washed with watery hydrochloric acid repeatedly, use deionization latter 5 times
Water washing.Finally graphene oxide (GO) sample obtained after abundant washing is placed in 60 DEG C of air dry ovens, 24h is dried,
Obtain the graphene oxide sample of paper-like.
Embodiment 1
1) preparation of graphene oxide dispersion：
The foregoing graphene oxide powder prepared is scattered in deionized water, ultrasonic disperse is made into 0.1g/L's
Graphene oxide dispersion
2) preparation of graphene oxide seperation film
The μ l of graphene oxide dispersion 5 are taken to be added in 400ml deionized water, in cross-flow pressure 1bar, cross-flow flow velocity
0.35LPM, effective membrane area 3.14cm2, 200nm apertures PC films, cross-flow film forming 15min prepares ultra-thin graphene oxide
Seperation film.
Embodiment 2
1) preparation of graphene oxide dispersion：
The foregoing graphene oxide powder prepared is scattered in deionized water, ultrasonic disperse is made into 0.4g/L's
Graphene oxide dispersion；
2) preparation of graphene oxide seperation film：
The μ l of graphene oxide dispersion 5 are taken to be added in 400ml deionized water, in cross-flow pressure 1bar, cross-flow flow velocity
0.35LPM, effective membrane area 3.14cm2, 200nm apertures PC films, cross-flow membrane formation process 30min prepares ultra-thin graphite oxide
Alkene seperation film.As illustrated in fig. 1 and 2, the thickness of the GO seperation films is 10nm.
Embodiment 3
1) preparation of graphene oxide dispersion：
The foregoing graphene oxide powder prepared is scattered in deionized water, ultrasonic disperse is made into 0.4g/L's
Graphene oxide dispersion；
3) preparation of graphene oxide seperation film：
The μ l of graphene oxide dispersion 500 are taken to be added in 400ml deionized water, in cross-flow pressure 1bar, cross-flow stream
Fast 0.35LPM, effective membrane area 3.14cm2, 200nm apertures PC films, cross-flow membrane formation process 5min prepares ultra-thin graphite oxide
Alkene seperation film.
Embodiment 4
1) preparation of graphene oxide dispersion：
The foregoing graphene oxide powder prepared is scattered in deionized water, ultrasonic disperse is made into 0.4g/L's
Graphene oxide dispersion；
3) preparation of graphene oxide seperation film：
The μ l of graphene oxide dispersion 20 are taken to be added in 400ml deionized water, in cross-flow pressure 1bar, cross-flow flow velocity
0.35LPM, effective membrane area 12.56cm2, 200nm apertures PC films, cross-flow membrane formation process 30min prepares ultra-thin graphite oxide
Alkene seperation film.
Embodiment 5
1) preparation of graphene oxide dispersion：
The foregoing graphene oxide powder prepared is scattered in deionized water, ultrasonic disperse is made into 0.4g/L's
Graphene oxide dispersion；
3) preparation of graphene oxide seperation film：
The μ l of graphene oxide dispersion 5 are taken to be added in 400ml deionized water, in cross-flow pressure 3bar, cross-flow flow velocity
0.35LPM, effective membrane area 3.14cm2, 200nm apertures PC films, cross-flow membrane formation process 30min prepares ultra-thin graphite oxide
Alkene seperation film.
What is prepared in the various embodiments described above may be incorporated for the separation of one-component dyestuff or multi-component dyes, below with
Exemplified by graphene oxide seperation film in embodiment 2, its separating effect is illustrated.
Embodiment 6
The graphene oxide seperation film that embodiment 2 is prepared is used for the separation of one-component azovan blue dyestuff.By 10 μM
EB solution, in the container for pouring into cross-flow devices.During cross-flow, rejection of the graphene oxide seperation film for EB dyestuffs
For 96%, water flux is 1500LHM bar-1；Stream time is 300h.
Embodiment 7
The graphene oxide seperation film that embodiment 2 is prepared is used for the separation of azovan blue and rhodamine b mixed dyes.
By 5L azovan blue (EB, 10 μM) and rhodamine b (RhB, 10 μM) mixed solution, in the container for pouring into cross-flow devices.In mistake
During stream, graphene oxide seperation film is 25%, water for the rejection that the rejection of EB dyestuffs is 99.9%, RhB dyestuffs
Flux is 1500LHM bar-1, stream time is 300h.In filtrate, RhB and EB selectivity reach 80, with fine
Separating effect.
Embodiment 8
The graphene oxide seperation film that embodiment 2 is prepared is used for azovan blue and Bengal rose red mixed dye
Separation.By 5L azovan blue (EB, 10 μM) and Bengal rose red (RB, 10 μM) mixed solution, the appearance of cross-flow devices is poured into
In device.During cross-flow, graphene oxide seperation film is for the rejection that the rejection of EB dyestuffs is 99.9%, RB dyestuffs
95%, water flux is 1500LHM bar-1, stream time is 300h.
Comparative example
The preparation of graphene oxide seperation film：
1) preparation of graphene oxide dispersion：
Graphene oxide powder is scattered in deionized water, ultrasonic disperse, the graphene oxide for being made into 0.4g/L disperses
Liquid
3) preparation of graphene oxide seperation film
The μ l of solution 5 2) are taken to add in Vacuum filtration device, film pressure 1bar, effective membrane area 3.14cm2, 200nm
Aperture PC films, prepare graphene oxide seperation film.
Dye separation：
The graphene oxide seperation film that above-mentioned vacuum filtration method is prepared is transferred in cross-flow devices, passes through cross-flow method
Carry out dye separation experiment.During cross-flow, graphene oxide seperation film is for EB dyestuffs substantially without retention.This is due to table
Face souring, causes graphene oxide seperation film to crush, loses separating effect.
Embodiment described above is a kind of preferably scheme of the present invention, and so it is not intended to limiting the invention.Have
The those of ordinary skill for closing technical field, without departing from the spirit and scope of the present invention, can also make various changes
Change and modification.Therefore the technical scheme that all modes for taking equivalent substitution or equivalent transformation are obtained, all falls within the guarantor of the present invention
In the range of shield.
Claims (10)
1. a kind of preparation method of graphene oxide seperation film, it is characterised in that concretely comprise the following steps：
Graphene oxide dispersion is added in cross-flow devices container, makes graphene oxide dispersion parallel to basilar memebrane surface current
It is dynamic, in basement membrane surface formation graphene oxide seperation film under the driving of pressure differential.
2. the preparation method of graphene oxide seperation film according to claim 1, it is characterised in that：Step 2) in, it is described
Graphene oxide dispersion concentration be 2.5 × 10-4~2.5 × 10-2g/L。
3. the preparation method of graphene oxide seperation film according to claim 1, it is characterised in that：Step 3) in, it is described
Film formation time be 1-30min.
4. the preparation method of graphene oxide seperation film according to claim 1, it is characterised in that：Step 3) in, it is described
Basilar memebrane be seperation film that any aperture is 10nm~1 μm, the preferably alumina ceramic membrane in 200nm apertures or 200nm holes
The polycarbonate membrane in footpath.
5. the preparation method of graphene oxide seperation film according to claim 1, it is characterised in that：Step 3) in, it is described
Effective area be any size.
6. the preparation method of graphene oxide seperation film according to claim 1, it is characterised in that：Step 3) in, it is described
Film pressure be 0.1~5.0bar.
7. the preparation method of graphene oxide seperation film according to claim 1, it is characterised in that：Step 3) in, it is described
Film forming flow velocity be 0.1~2.0LHM.
8. a kind of graphene oxide seperation film prepared as preparation method described in claim 1.
9. a kind of graphene oxide seperation film as claimed in claim 8 is in the separation of one-component dyestuff or multi-component dyes
Using.
10. application according to claim 9, it is characterised in that：Separated dyestuff is azovan blue, rhodamine B, Meng Jia
Draw one or more solution in rose-red.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108854592A (en) * | 2018-06-14 | 2018-11-23 | 江苏大学 | Graphene oxide/isostearic acid composite separating film and its preparation method and application |
| CN110152494A (en) * | 2018-02-13 | 2019-08-23 | 中国科学院生态环境研究中心 | Control membrane fouling method based on graphene oxide directional separation film |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102671549A (en) * | 2012-04-10 | 2012-09-19 | 浙江大学 | Preparation method of graphene-based composite separation membrane device |
| CN102688701A (en) * | 2012-06-18 | 2012-09-26 | 中国海洋大学 | Preparation method of polyelectrolyte self-assembled composite nonafiltration membrane based on coordination |
| CN104393283A (en) * | 2014-10-20 | 2015-03-04 | 中国工程物理研究院化工材料研究所 | Nano crystalline CoO-graphene composite material as well as preparation and application thereof |
| CN104810426A (en) * | 2014-01-26 | 2015-07-29 | 中国科学院苏州纳米技术与纳米仿生研究所 | Self-driven light detector and preparation method thereof |
| CN106582318A (en) * | 2016-12-20 | 2017-04-26 | 南京工业大学 | Graphene oxide-modified organic solvent-resistant nanofiltration membrane, preparation method and application |
| CN106745463A (en) * | 2017-01-20 | 2017-05-31 | 华中科技大学 | A kind of sewage water treatment method of utilization reducing agent in-situ reducing graphene oxide |
-
2017
- 2017-07-06 CN CN201710547411.6A patent/CN107308826A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102671549A (en) * | 2012-04-10 | 2012-09-19 | 浙江大学 | Preparation method of graphene-based composite separation membrane device |
| CN102688701A (en) * | 2012-06-18 | 2012-09-26 | 中国海洋大学 | Preparation method of polyelectrolyte self-assembled composite nonafiltration membrane based on coordination |
| CN104810426A (en) * | 2014-01-26 | 2015-07-29 | 中国科学院苏州纳米技术与纳米仿生研究所 | Self-driven light detector and preparation method thereof |
| CN104393283A (en) * | 2014-10-20 | 2015-03-04 | 中国工程物理研究院化工材料研究所 | Nano crystalline CoO-graphene composite material as well as preparation and application thereof |
| CN106582318A (en) * | 2016-12-20 | 2017-04-26 | 南京工业大学 | Graphene oxide-modified organic solvent-resistant nanofiltration membrane, preparation method and application |
| CN106745463A (en) * | 2017-01-20 | 2017-05-31 | 华中科技大学 | A kind of sewage water treatment method of utilization reducing agent in-situ reducing graphene oxide |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110152494A (en) * | 2018-02-13 | 2019-08-23 | 中国科学院生态环境研究中心 | Control membrane fouling method based on graphene oxide directional separation film |
| CN110152494B (en) * | 2018-02-13 | 2021-04-16 | 中国科学院生态环境研究中心 | Membrane pollution control method based on graphene oxide directional separation membrane |
| CN108854592A (en) * | 2018-06-14 | 2018-11-23 | 江苏大学 | Graphene oxide/isostearic acid composite separating film and its preparation method and application |
| CN108854592B (en) * | 2018-06-14 | 2020-09-25 | 江苏大学 | Graphene oxide/isostearic acid composite separation membrane and preparation method and application thereof |
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