CN110252154A - A kind of graphene oxide/graphite phase carbon nitride composite membrane preparation method of glycine modification - Google Patents
A kind of graphene oxide/graphite phase carbon nitride composite membrane preparation method of glycine modification Download PDFInfo
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- CN110252154A CN110252154A CN201910639971.3A CN201910639971A CN110252154A CN 110252154 A CN110252154 A CN 110252154A CN 201910639971 A CN201910639971 A CN 201910639971A CN 110252154 A CN110252154 A CN 110252154A
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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
- B01D61/027—Nanofiltration
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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
- B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
- B01D67/0081—After-treatment of organic or inorganic membranes
- B01D67/0093—Chemical modification
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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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Abstract
The invention discloses a kind of graphene oxide/g-C of glycine modification3N4The preparation method of composite membrane is covalently attached using glycine as modification small molecule with graphene oxide with amido bond, and graphite phase carbon nitride (g-C is then added3N4) ultrasonic disperse formation uniform dispersion, assembling film forming is filtered under certain vacuum degree.The film certain time length then is impregnated with hyperbranched polyethyleneimine solution, its surface charge is modified.Modified glycine is modified into graphene oxide/g-C3N4Composite membrane carries out UF membrane application to waste water from dyestuff, it is found that it has good penetrating power and excellent cutoff performance to dyestuff/aqueous systems.
Description
Technical field
The present invention relates to technical field of membrane separation, and in particular to be that a kind of small molecule compound modification graphene oxide is multiple
Close the preparation method and applications of film.
Background technique
In recent years, due to mankind's activity and industrial development, it is discharged into a large amount of organic pollutants into water, causes serious water dirty
Dye, while life to the mankind and health also result in threat.At present in Water warfare field, carried out using nanofiltration useless
Extensive attention of the water process by researcher.But during preparing nanofiltration membrane, membrane material is most of all using organic high
Molecular material or metal oxide are raw material, are had certain problems in practical applications, such as rejection is low, fouling membrane is tight
Again etc..
And graphene oxide is as a kind of nanofiltration membrane material applied in field of waste water treatment, it is abundant due to containing
Hydroxyl and the oxygen groups such as carboxyl, have that unique two-dimensional nano chip architecture, large specific surface area, mechanical property be good, hydrophily
The features such as strong, receives the extensive concern of people.
However, be easy to decompose in water environment since pure zirconia graphene film has the oxygen-containing group of highly-hydrophilic, so
In order to improve the stability of graphene oxide membrane in water, need to modify graphene oxide.The modification of graphene oxide
Non-covalent bond and covalent bond can be generally taken to modify two ways.Non-covalent bond modification is made by π-π interaction, electrostatic
With, the noncovalent interactions power such as Van der Waals force, hydrogen bond by dressing agent in conjunction with graphene oxide.Therefore, common polymer, metal oxygen
Compound and other nano materials carry out non-covalent bond modification to graphene oxide, to improve the stability of graphene oxide membrane.
In addition to this, since surface of graphene oxide contains a large amount of active groups such as a large amount of carboxyl, hydroxyl, epoxy group, it is possible to
Group by introducing dressing agent and surface of graphene oxide chemically reacts, to form the graphite oxide of covalent bond modification
Alkene.And because decorating molecule enters in the thin layer of graphene oxide, the nano-pore of certain size, the layer of adjusting film can be constructed
Between structure (Grossman.J.C.Nano Lett., 2012,12:3602-3608), so as to regulate and control the nanofiltration performance of film.This
Outside, the graphene oxide chemical property after covalent bond modification is stablized, long service life.
Summary of the invention
It is an object of the invention to the surface functional groups by modification graphene oxide, change graphene oxide/graphite
The interlamellar spacing of phase carbon nitride composite membrane two-dimensional channel is developed a kind of with excellent with improving the infiltration and rejection of composite membrane
Graphene oxide/graphite phase carbon nitride composite membrane preparation method of the glycine modification of separating property.
In order to achieve the above objectives, technical scheme is as follows:
A kind of graphene oxide/g-C of glycine modification3N4The preparation method of composite membrane, comprising the following steps:
Step 1, certain volume concentration be 100~500ppm graphene oxide solution be added to the water, stir evenly,
Ultrasonic wave dissolution, obtains the graphene oxide water solution of even concentration；
Step is added to being completely dissolved in step 2, the water that a certain amount of carboxyl activator is dissolved in 10~20mL, stirring
(1) graphene oxide water solution obtained continues to be stirred to react 15~30min, to the first reaction solution；
Step 3 weighs glycine and is dissolved in water, and stirs to being completely dissolved, obtains glycine solution, glycine solution
Concentration be 0.5~2g/mL；
The glycine solution that step (3) obtains is added in the first reaction solution of step (2) by step 4, continues to stir
12~for 24 hours, obtain the second reaction solution, wherein glycine solution and the volume proportion of the graphene oxide solution in step (1) are
(0.3~1): 1；
Step 5, the g-C for measuring certain volume3N4Dispersion liquid instills step (4) resulting second reaction solution, ultrasonic disperse
1h obtains graphene oxide/g-C of glycine modification3N4Mixed dispersion liquid, wherein g-C3N4The concentration of dispersion liquid be 100~
250ppm, and graphene oxide water solution volume proportion (0.5~1): 1；
Graphene oxide/g-C that step 6, the glycine for obtaining step (5) are modified3N4Mixed dispersion liquid is in certain vacuum
Degree is lower to be filtered, and is deposited on cellulose basement membrane, is formed graphene oxide/g-C of glycine modification3N4Composite membrane；
Obtained composite membrane is carried out surface modification treatment with hyperbranched polyethyleneimine solution to get modification is arrived by step 7
Glycine modification graphene oxide/g-C3N4Composite membrane.
Preferably, carboxyl activator described in step (2) is 1- (3- dimethylamino-propyl) -3- ethyl carbodiimide salt
Hydrochlorate/n-hydroxysuccinimide catalyst system, 1- (3- dimethylamino-propyl) -3- ethyl-carbodiimide hydrochloride/1- hydroxyl
Benzotriazole catalyst system or 1- (3- dimethylamino-propyl) -3- ethyl-carbodiimide hydrochloride/N- hydroxyl -7- azo benzo
Triazole catalyst system.
Preferably, cellulose basement membrane described in step (6) is cellulose acetate film, nitrocellulose filter or composite fibre
Plain film, the cellulose mixture film are mixed by cellulose acetate film and nitrocellulose filter 1:1 in mass ratio.
Preferably, in step (6), cellulose basement membrane is cellulose microporosity filter membrane, and aperture is 0.22 μm~0.45 μm.
Preferably, surface modification treatment described in step (7) refers to the graphene oxide/g-C for modifying glycine3N4
Composite membrane, which is placed in hyperbranched polyethyleneimine solution, impregnates 30min.
Preferably, hyperbranched polyethyleneimine solution concentration is 1wt%, wherein the molecular weight of hyperbranched polyethyleneimine
It is 600~20000.
After adopting the above technical scheme, a kind of graphene oxide/g-C of glycine modification of the present invention3N4The preparation of composite membrane
Method is modification small molecule based on glycine, is covalently keyed with graphene oxide with amido bond, g-C is added3N4Ultrasonic disperse
Uniform dispersion is formed, assembling forms glycine modification graphene oxide/g-C under a certain pressure3N4Composite membrane.And pass through table
The modified glycine modification graphene oxide/g-C for obtaining excellent nanofiltration performance in face3N4Composite membrane.Synthetic method is simple, can be obvious
Improve the nanofiltration performance of conventional oxidation graphene film.Glycine modifies graphene oxide/g-C3N4Composite membrane has excellent nanofiltration
Performance, the composite membrane can be applied to the fields such as environmental protection, wastewater treatment.During the separation of dyestuff/water, infiltration capacity is big,
Rejection is high, with excellent solute/solvent selectivity, has a extensive future, has very high value in terms of industrial application.
Detailed description of the invention
Fig. 1 is the comparison infrared spectroscopy of the graphene oxide and pure zirconia graphene of glycine modification in present example 1
Scheme (FTIR)；
Fig. 2 is graphene oxide/graphite phase carbon nitride composite membrane scanning electron microscope of glycine modification in present example 1
Scheme (SEM).
The sample that " GO " is marked in Fig. 1 is the infrared absorpting light spectra of pure zirconia graphene；It is marked in figure " Gly/GO "
Sample is the infrared absorpting light spectra of the graphene oxide after the modification of small molecule glycine；
Fig. 2 medium scale is 2 microns, 2000 times of amplification factor.
Specific embodiment
In order to further explain the technical solution of the present invention, being explained in detail below by specific embodiment the present invention
It states.Those skilled in the art can various modifications may be made or change to the present invention, these various changes or change of equal value should all regard
Not depart from patent category of the invention.
Embodiment 1
Using glycine as dressing agent, graphene oxide is reactant, and 1- (3- dimethylamino-propyl) -3- ethyl carbon two is sub-
Amine hydrochlorate (EDCI)/n-hydroxysuccinimide (NHS) is carboxyl activator.
Wherein, the preparation of glycine solution are as follows: the glycine solid for taking 50mg is added in the deionized water of 50mL, is surpassed
Sound wave dissolution, obtains the glycine solution of 1mg/mL.
The preparation of EDCI solution are as follows: take 10mg EDCI solid, be added in 10mL deionized water, ultrasonic wave dissolution is now matched
It is current.
NHS solution is prepared as, and 10mgNHS solid is dissolved in the deionized water of 20mL, ultrasonic wave dissolution, now with existing
With.
The graphene oxide solution that 2mL concentration is 100ppm is added in the water of 14mL, is stirred evenly, ultrasonic dissolved
Solution, obtains the graphene oxide water solution of even concentration, then in graphene oxide water solution, is successively added 300 μ L's
The NHS solution of EDCI and 300 μ L react 15 minutes, obtain the first reaction solution；
2mL glycine solution is added dropwise again, continues to be stirred to react 12 hours, to after reaction, obtain the second reaction solution.
The g-C that 2mL concentration is 200ppm is added dropwise3N4(graphite phase carbon nitride) dispersion liquid is in the second reaction solution, 1 hour of ultrasonic disperse,
Obtain graphene oxide/g-C of glycine modification3N4Mixed dispersion liquid.
Graphene oxide/g-C that glycine is modified3N4Mixed dispersion liquid is placed in Suction filtration device, under the pressure of 1bar
It is filtered, graphene oxide/g-C that glycine is modified3N4Complex deposits form glycine and repair on cellulose basement membrane
Graphene oxide/g-C of decorations3N4Composite membrane, cellulose basement membrane are preferably that (cellulose nitrate and acetic acid are fine for composite fibre miillpore filter
The ratio of dimension is 1:1,0.22 μm of aperture；Film diameter 47mm), obtained composite membrane is then subjected to surface modification treatment, specifically
Then 10 are washed by composite membrane at hyperbranched polyethyleneimine (molecular weight 10000) aqueous solution soaking 30 minutes of 1wt% in ground
Second, obtain modified composite membrane.
Composite membrane (i.e. modified composite membrane) after surface modification treatment is applied into the film mistake in dyestuff methylene blue and water
In filter separation, the infiltration capacity for as a result obtaining film is 26Lh-1·m-2·bar-1, the rejection to solute is 87%.Without sweet
Graphene oxide/g-C of propylhomoserin modification3N4Rejection variation after modifying compound film surface is little, but infiltration capacity only has 4Lh-1·m-2·bar-1。
Characterizing for graphene oxide is modified to glycine by Fourier Transform Infrared Spectrometer.FTIR characterization test
Instrument is U.S. Thermo Nicolet iS50 type Fourier Transform Infrared Spectrometer.As seen from Figure 1, by with pure oxygen fossil
The comparison of black alkene, we can be found that the relative intensity of the infrared absorption peak of the graphene oxide of glycine modification changes,
This is because caused by glycine is connected with graphene oxide with amido bond.Therefore, the composite membrane after glycine modification is added, changes
The interlayer structure for having become film forms the two-dimensional nano channel of specific film, is conducive to passing through for solvent, to improve infiltration
Amount.The film surface is flat and smooth as seen from Figure 2, zero defect, is conducive to be subsequently applied to dyestuff/water UF membrane system.
It should be noted that the concentration of (1) graphene oxide is 100~500ppm (preferably 100ppm) in the present invention；
(2)g-C3N4The concentration of dispersion liquid is 100~250ppm (preferably 200ppm)；(3)g-C3N4Dispersion liquid is molten with graphene oxide
Liquid volume proportion (0.5~1): 1；(4) acetate fiber also can be used other than using above-mentioned cellulose mixture film in cellulose basement membrane
Plain film or nitrocellulose filter, the aperture of film are 0.22 μm or 0.45 μm；(4) molecular weight of hyperbranched polyethyleneimine is
600-20000；(5) carboxyl activator is in addition to using above-mentioned 1- (3- dimethylamino-propyl) -3- ethyl-carbodiimide hydrochloride
(EDCI) outside the catalyst system of/n-hydroxysuccinimide (NHS), 1- (3- dimethylamino-propyl) -3- ethyl carbon also can be used
Diimmonium salt hydrochlorate (EDCI)/I-hydroxybenzotriazole (HOBT) catalyst system or 1- (3- dimethylamino-propyl) -3- ethyl
Carbodiimide hydrochloride (EDCI)/N- hydroxyl -7- azo benzotriazole (HOAT) catalyst system；(6) glycine solution is dense
Degree is 0.5~2g/mL (preferably 1mg/mL)
A kind of graphene oxide/g-C of glycine modification of the present invention3N4The preparation method of composite membrane is to repair based on glycine
Small molecule is adornd, is covalently keyed with graphene oxide with amido bond, g-C is added3N4Ultrasonic disperse forms uniform dispersion, one
Assembling forms glycine modification graphene oxide/g-C under constant-pressure3N4Composite membrane.And excellent nanofiltration is obtained by surface modification
The glycine of energy modifies graphene oxide/g-C3N4Composite membrane.Synthetic method is simple, can significantly improve conventional oxidation graphene film
Nanofiltration performance.Glycine modifies graphene oxide/g-C3N4Composite membrane has excellent nanofiltration performance, separates in dyestuff/water
Cheng Zhong, infiltration capacity is big, rejection is high, with excellent solute/solvent selectivity, has a extensive future, in terms of industrial application
With very high value.
Embodiment 2
Using glycine as dressing agent, graphene oxide is reactant, and 1- (3- dimethylamino-propyl) -3- ethyl carbon two is sub-
Amine hydrochlorate (EDCI)/n-hydroxysuccinimide (NHS) is catalyst.Wherein, the preparation of glycine, EDCI and NHS solution
It is same as Example 1.
The graphene oxide solution that 2mL concentration is 100ppm is added in the water of 14mL, stirs evenly, is successively added
The NHS solution of the EDCI of 300 μ L and 300 μ L react 15 minutes, then 0.6mL glycine solution are added dropwise, and continue to be stirred to react 12
Hour.To which the g-C that 2mL concentration is 200ppm after reaction, is added dropwise3N4Dispersion liquid, ultrasonic 1 hour obtain glycine modification
Graphene oxide/g-C3N4Mixed dispersion liquid.
Glycine is modified into graphene oxide/g-C3N4Mixed dispersion liquid is placed in Suction filtration device, under the pressure of 1bar into
Row filters, graphene oxide/g-C that glycine is modified3N4Complex deposits (0.22 μ of aperture on composite fibre miillpore filter
m；Film diameter 47mm) on, form graphene oxide/g-C of glycine modification3N4Then composite membrane carries out obtained composite membrane
Surface modification treatment, specifically, hyperbranched polyethyleneimine (molecular weight 10000) solution by composite membrane in 1wt% are impregnated
30 minutes, then wash 10 seconds, obtain modified composite membrane.
Composite membrane (i.e. modified composite membrane) after surface modification treatment is applied into the film mistake in dyestuff methylene blue and water
It filters in separation, as the result is shown the infiltration capacity 10Lh of film-1·m-2·bar-1, relatively it is not added with the infiltration capacity of the composite membrane of glycine
Slightly rise, but corresponding rejection then drops to 78%.
Embodiment 3
Using glycine as dressing agent, graphene oxide is reactant, and 1- (3- dimethylamino-propyl) -3- ethyl carbon two is sub-
Amine hydrochlorate (EDCI)/n-hydroxysuccinimide (NHS) is catalyst.Wherein, the preparation of glycine, EDCI and NHS solution
It is same as Example 1.
The graphene oxide solution that 2mL concentration is 100ppm is added in the water of 14mL, stirs evenly, is successively added
The NHS solution of the EDCI of 300 μ L and 300 μ L react 15 minutes, then 0.8mL glycine solution are added dropwise, and continue to be stirred to react 12
Hour.To which the g-C that 2mL concentration is 200ppm after reaction, is added dropwise3N4Dispersion liquid, ultrasonic 1 hour obtain glycine modification
Graphene oxide/g-C3N4Mixed dispersion liquid.
Glycine is modified into graphene oxide/g-C3N4Mixed dispersion liquid is placed in Suction filtration device, under the pressure of 1bar into
Row filters, graphene oxide/g-C that glycine is modified3N4Complex deposits are in composite fibre miillpore filter (0.22 μm of aperture；
Film diameter 47mm) on, form graphene oxide/g-C of glycine modification3N4Composite membrane, then by obtained composite membrane carry out table
Composite membrane is specifically impregnated 30 points in 1% hyperbranched polyethyleneimine (molecular weight 10000) solution by face modification
Clock, then wash 10 seconds, obtain modified composite membrane.
Composite membrane (i.e. modified composite membrane) after surface modification treatment is applied into the film mistake in dyestuff methylene blue and water
In filter separation, the infiltration capacity for as a result obtaining film is 14Lh-1·m-2·bar-1, the rejection to solute is 56%.
Embodiment 4
Using glycine as dressing agent, graphene oxide is reactant, and 1- (3- dimethylamino-propyl) -3- ethyl carbon two is sub-
Amine hydrochlorate (EDCI)/n-hydroxysuccinimide (NHS) is catalyst.Wherein, the preparation of glycine, EDCI and NHS solution
It is same as Example 1.
It is that 100ppm graphene oxide solution is added in the water of 14mL by 2mL concentration, stirs evenly, 300 μ are successively added
The NHS solution of the EDCI of L and 300 μ L react 15 minutes, then 1mL glycine solution are added dropwise, and continue to be stirred to react 12 hours.
To which the g-C that 2mL concentration is 200ppm after reaction, is added dropwise3N4Dispersion liquid, ultrasonic 1 hour obtain glycine modification oxidation
Graphene/g-C3N4Mixed dispersion liquid.
Glycine is modified into graphene oxide/g-C3N4Mixed dispersion liquid is placed in Suction filtration device, under the pressure of 1bar into
Row filters, i.e., the graphene oxide/g-C modified glycine3N4Complex deposits are in composite fibre miillpore filter (0.22 μ of aperture
m；Film diameter 47mm) on, form graphene oxide/g-C of glycine modification3N4Then composite membrane carries out obtained composite membrane
Surface modification treatment, specifically, hyperbranched polyethyleneimine (molecular weight 10000) solution by composite membrane in 1wt% are impregnated
30 minutes, then wash 10 seconds, obtain modified composite membrane.
Composite membrane (i.e. modified composite membrane) after surface modification treatment is applied into the film mistake in dyestuff methylene blue and water
In filter separation, for the performance of film is compared with the compound film properties of 0.8mL glycine modification are added as the result is shown, infiltration capacity does not have more
Big variation, in 14Lh-1·m-2·bar-1Left and right, and rejection slightly promotes (for 60%).
Embodiment 5
Using glycine as dressing agent, graphene oxide is reactant, and 1- (3- dimethylamino-propyl) -3- ethyl carbon two is sub-
Amine hydrochlorate (EDCI)/n-hydroxysuccinimide (NHS) is catalyst.Wherein, the preparation of glycine, EDCI and NHS solution
It is same as Example 1.
The graphene oxide solution that 2mL concentration is 100ppm is added in the water of 14mL, stirs evenly, is successively added
The NHS solution of the EDCI of 300 μ L and 300 μ L react 15 minutes, then 2mL glycine solution are added dropwise, and continue to be stirred to react 12 small
When.To which the g-C that 2mL concentration is 200ppm after reaction, is added dropwise3N4Dispersion liquid, ultrasonic 1 hour obtain glycine modification oxygen
Graphite alkene/g-C3N4Mixed dispersion liquid.
Glycine is modified into graphene oxide/g-C3N4Mixed dispersion liquid is placed in Suction filtration device, under the pressure of 1bar into
Row filters, graphene oxide/g-C that glycine is modified3N4Complex deposits are in composite fibre miillpore filter (0.22 μm of aperture；
Film diameter 47mm), form graphene oxide/g-C of glycine modification3N4Composite membrane.
Then obtained composite membrane (composite membrane does not carry out surface modification treatment) is directly applied to dyestuff methylene blue
In being separated by filtration with the film of water.Composite membrane changes graphene oxide/g-C due to glycine3N4The interlamellar spacing of composite membrane is formed
Specific two-dimensional nano channel, so be conducive to passing through for water, so that the infiltration capacity of composite membrane has reached 110Lh-1·m-2·bar-1.Further, since lacking, surface is modified, and after glycine is added, solute is also easier to through film, therefore the retention of composite membrane
Rate is only 25%, and this also illustrates composite membrane is no to the separation of solute and solvent apparent selective during the filtration process.
Embodiment 6
Using glycine as dressing agent, graphene oxide is reactant, and 1- (3- dimethylamino-propyl) -3- ethyl carbon two is sub-
Amine hydrochlorate (EDCI)/n-hydroxysuccinimide (NHS) is catalyst.Wherein, the preparation of glycine, EDCI and NHS solution
It is same as Example 1.
The graphene oxide solution that 2mL concentration is 100ppm is added in the water of 14mL, stirs evenly, is successively added
The NHS solution of the EDCI of 300 μ L and 300 μ L react 15 minutes, then 2mL glycine solution are added dropwise, and continue to be stirred to react 12 small
When.To which the g-C that 2mL concentration is 200ppm after reaction, is added dropwise3N4Dispersion liquid, ultrasonic 1 hour obtain glycine modification oxygen
Graphite alkene/g-C3N4Mixed dispersion liquid.
Glycine is modified into graphene oxide/g-C3N4Mixed dispersion liquid is placed in Suction filtration device, under the pressure of 1bar into
Row filters, graphene oxide/g-C that glycine is modified3N4Complex deposits are in composite fibre miillpore filter (0.22 μm of aperture；
Film diameter 47mm) on, form graphene oxide/g-C of glycine modification3N4Composite membrane, then by obtained composite membrane in 1wt
Hyperbranched polyethyleneimine (molecular weight 600) solution impregnate 30 minutes, then wash 10 seconds, obtain modified composite membrane.
Composite membrane (i.e. modified composite membrane) after surface modification treatment is applied into the film mistake in dyestuff methylene blue and water
In filter separation.Since the molecular weight of hyperbranched polyethyleneimine is smaller, modified result is not obvious.It is repaired with 2mL glycine is added
Graphene oxide/g-C of decorations3N4Composite membrane is compared, and infiltration capacity is close, is 108Lh-1·m-2·bar-1, rejection then from
25% is promoted to 36%.
Embodiment 7
Using glycine as dressing agent, graphene oxide is reactant, and 1- (3- dimethylamino-propyl) -3- ethyl carbon two is sub-
Amine hydrochlorate (EDCI)/n-hydroxysuccinimide (NHS) is catalyst.Wherein, the preparation of glycine, EDCI and NHS solution
It is same as Example 1.
The graphene oxide solution that 2mL concentration is 100ppm is added in the water of 14mL, stirs evenly, is successively added
The NHS solution of the EDCI of 300 μ L and 300 μ L react 15 minutes, then 2mL glycine solution are added dropwise, and continue to be stirred to react 12 small
When.To which the g-C that 2mL concentration is 200ppm after reaction, is added dropwise3N4Dispersion liquid, ultrasonic 1 hour obtain glycine modification oxygen
Graphite alkene/g-C3N4Mixed dispersion liquid.
Glycine is modified into graphene oxide/g-C3N4Mixed dispersion liquid is placed in Suction filtration device, under the pressure of 1bar into
Row filters, graphene oxide/g-C that glycine is modified3N4Complex deposits are in composite fibre miillpore filter (0.22 μm of aperture；
Film diameter 47mm) on, form graphene oxide/g-C of glycine modification3N4Composite membrane, then by obtained composite membrane carry out table
Face modification, specifically, hyperbranched polyethyleneimine (molecular weight 1800) solution by composite membrane in 1wt% impregnate 30 points
Clock, then wash 10 seconds, obtain modified composite membrane.
Composite membrane (i.e. modified composite membrane) after surface modification treatment is applied into the film mistake in dyestuff methylene blue and water
In filter separation.The infiltration capacity of composite membrane is 75Lh as the result is shown-1·m-2·bar-1, still much larger than not plus glycine modification
Composite membrane.In addition to this, the rejection of film improves, and can reach 44% or so.
Embodiment 8
Using glycine as dressing agent, graphene oxide is reactant, and 1- (3- dimethylamino-propyl) -3- ethyl carbon two is sub-
Amine hydrochlorate (EDCI)/n-hydroxysuccinimide (NHS) is catalyst.Wherein, the preparation of glycine, EDCI and NHS solution
It is same as Example 1.
The graphene oxide solution that 2mL concentration is 100ppm is added in the water of 14mL, stirs evenly, is successively added
The NHS solution of the EDCI of 600 μ L and 600 μ L react 15 minutes, then 2mL glycine solution are added dropwise, and continue to be stirred to react 12 small
When.To which the g-C that 2mL concentration is 200ppm after reaction, is added dropwise3N4Dispersion liquid, ultrasonic 1 hour obtain glycine modification oxygen
Graphite alkene/g-C3N4Mixed dispersion liquid.
Glycine is modified into graphene oxide/g-C3N4Mixed dispersion liquid is placed in Suction filtration device, under the pressure of 1bar into
Row filters, graphene oxide/g-C that glycine is modified3N4Complex deposits are in composite fibre miillpore filter (0.22 μm of aperture；
Film diameter 47mm) on, form graphene oxide/g-C of glycine modification3N4Composite membrane.Then by composite membrane, (composite membrane is not
Carry out surface modification treatment) it is directly applied to dyestuff methylene blue and the film of water is separated by filtration.It was found that with being urged in preparation process
Agent dosage increases, and the interconnection of glycine and graphene oxide is also more easier.Simultaneously with 300 μ L EDCI/NHS of addition
And not no graphene oxide/g-C of surface modification treatment3N4Composite membrane is compared, the not big variation of the nanofiltration performance of the film, right
The selectivity of water and dye molecule is not high.
Embodiment 9
Using glycine as dressing agent, graphene oxide is reactant, and 1- (3- dimethylamino-propyl) -3- ethyl carbon two is sub-
Amine hydrochlorate (EDCI)/n-hydroxysuccinimide (NHS) is catalyst.Wherein, the preparation of glycine, EDCI and NHS solution
It is same as Example 1.
The graphene oxide solution that 2mL concentration is 100ppm is added in the water of 14mL, stirs evenly, is successively added
The NHS solution of the EDCI of 600 μ L and 600 μ L react 15 minutes, then 2mL glycine solution are added dropwise, and continue to be stirred to react 12 small
When.To which the g-C that 2mL concentration is 200ppm after reaction, is added dropwise3N4Dispersion liquid, ultrasonic 1 hour obtain glycine modification oxygen
Graphite alkene/g-C3N4Mixed dispersion liquid.
Glycine is modified into graphene oxide/g-C3N4Mixed dispersion liquid is placed in Suction filtration device, under the pressure of 1bar into
Row filters, graphene oxide/g-C that glycine is modified3N4Complex deposits are in composite fibre miillpore filter (0.22 μm of aperture；
Film diameter 47mm) on, form graphene oxide/g-C of glycine modification3N4Then composite membrane exists obtained composite membrane
Hyperbranched polyethyleneimine (molecular weight 10000) solution of 1wt% impregnates 30 minutes, then washs 10 seconds, obtains modified answer
Close film.
Composite membrane (i.e. modified composite membrane) after surface modification treatment is applied into the film mistake in dyestuff methylene blue and water
In filter separation.The rejection of composite membrane has 85% as the result is shown, and infiltration capacity can also reach 21Lh-1·m-2·bar-1。
From above embodiments it can be found that graphene oxide/g-C of the glycine modification provided according to the present invention3N4It is compound
Membrane preparation method, it is modified through hyperbranched polyethyleneimine, in waste water from dyestuff separation process, have good infiltration capacity,
Excellent rejection and high solute selectivity.Preparation method provided by the invention simultaneously, it is simple process, environmentally protective, in reality
There is very high application value in.
Claims (6)
1. a kind of graphene oxide/g-C of glycine modification3N4The preparation method of composite membrane, it is characterised in that: including following step
It is rapid:
Step 1, certain volume concentration be 100~500ppm graphene oxide solution be added to the water, stir evenly, then
Ultrasonic wave dissolution, obtains the graphene oxide water solution of even concentration；
A certain amount of carboxyl activator is dissolved in water by step 2, and the oxidation that step (1) obtains is added to being completely dissolved in stirring
Graphene aqueous solution continues to be stirred to react 15~30min, to the first reaction solution；
Step 3 weighs glycine and is dissolved in water, and stirs to being completely dissolved, and obtains glycine solution, glycine solution it is dense
Degree is 0.5~2g/mL；
The glycine solution that step (3) obtains is added in the first reaction solution of step (2) by step 4, continue stirring 12~
For 24 hours, the second reaction solution is obtained, wherein the volume proportion of the graphene oxide solution in glycine solution and step (1) is (0.3
~1): 1；
Step 5, the g-C for measuring certain volume3N4Dispersion liquid instills step (4) resulting second reaction solution, after ultrasonic wave dispersion
Graphene oxide/the g-C modified to glycine3N4Mixed dispersion liquid, wherein g-C3N4The concentration of dispersion liquid is 100~250ppm,
With graphene oxide water solution volume proportion (0.5~1): 1；
Graphene oxide/g-C that step 6, the glycine for obtaining step (5) are modified3N4Mixed dispersion liquid is under certain vacuum degree
It filters, is deposited on cellulose basement membrane, form graphene oxide/g-C of glycine modification3N4Composite membrane；
Obtained composite membrane is carried out surface modification treatment with hyperbranched polyethyleneimine aqueous solution to get modification is arrived by step 7
Graphene oxide/g-C of glycine modification3N4Composite membrane.
2. a kind of graphene oxide/g-C of glycine modification according to claim 13N4The preparation method of composite membrane,
Be characterized in that: carboxyl activator described in step (2) be 1- (3- dimethylamino-propyl) -3- ethyl-carbodiimide hydrochloride/
N-hydroxysuccinimide catalyst system, 1- (3- dimethylamino-propyl) -3- ethyl-carbodiimide hydrochloride/1- hydroxy benzo three
Azoles catalyst system or 1- (3- dimethylamino-propyl) -3- ethyl-carbodiimide hydrochloride/N- hydroxyl -7- azo benzotriazole
Catalyst system.
3. a kind of graphene oxide/g-C of glycine modification according to claim 13N4The preparation method of composite membrane,
Be characterized in that: cellulose basement membrane described in step (6) be cellulose acetate film, nitrocellulose filter or cellulose mixture film,
The cellulose mixture film is mixed by cellulose acetate film and nitrocellulose filter 1:1 in mass ratio.
4. a kind of graphene oxide/g-C of glycine modification according to claim 13N4The preparation method of composite membrane,
Be characterized in that: in step (6), cellulose basement membrane is cellulose microporosity filter membrane, and pore diameter range is 0.22~0.45 μm.
5. a kind of graphene oxide/g-C of glycine modification according to claim 13N4The preparation method of composite membrane,
Be characterized in that: surface modification treatment described in step (7) refers to the graphene oxide/g-C for modifying glycine3N4Composite membrane
It is placed in hyperbranched polyethyleneimine solution and impregnates 30min.
6. a kind of graphene oxide/g-C of glycine modification according to claim 53N4The preparation method of composite membrane,
Be characterized in that: hyperbranched polyethyleneimine solution concentration be 1wt%, wherein the molecular weight of hyperbranched polyethyleneimine be 600~
20000。
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110649258A (en) * | 2019-10-08 | 2020-01-03 | 北京航空航天大学 | Preparation method of three-dimensional porous tin oxide graphene composite electrode material |
| CN112625776A (en) * | 2019-10-08 | 2021-04-09 | 中国石油化工股份有限公司 | Graphene compound for lubricating oil additive and preparation method and application thereof |
| CN112642291A (en) * | 2020-12-30 | 2021-04-13 | 陕西科技大学 | Amino acid bonded molybdenum disulfide reverse osmosis membrane and preparation method and application thereof |
| CN114016286A (en) * | 2021-12-15 | 2022-02-08 | 四川大学 | Method for modifying carbon fiber by functionalized graphene oxide electrophoretic deposition and carbon fiber composite material thereof |
| CN114591545A (en) * | 2022-01-22 | 2022-06-07 | 中北大学 | Forming method for preparing graphene master batch and long-life heavy vehicle load wheel tire by water phase synergistic coagulation process |
| CN114669199A (en) * | 2022-03-15 | 2022-06-28 | 山东大学 | Modified mica sheet-nanocellulose composite nanofiltration membrane and preparation method thereof |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104069752A (en) * | 2014-06-27 | 2014-10-01 | 天津大学 | Sulfonated polyether-ether-ketone-amino acid modified graphene oxide hybrid membrane and preparation and application thereof |
| CN105413494A (en) * | 2016-01-04 | 2016-03-23 | 福州大学 | High-performance lyophilic PVDF/GO-lysine composite membrane |
| KR20160061543A (en) * | 2014-11-21 | 2016-06-01 | 한양대학교 산학협력단 | Material for water treatment, and method of fabricating the same |
| CN105921031A (en) * | 2016-05-15 | 2016-09-07 | 高学理 | Carboxylic oxidized graphene and method for modifying organic release film by means of same |
| US20190039028A1 (en) * | 2017-07-24 | 2019-02-07 | Northeastern University | Porous Membranes Comprising Nanosheets and Fabrication Thereof |
| CN109433023A (en) * | 2018-09-14 | 2019-03-08 | 浙江工业大学 | The graphene oxide nanofiltration membrane and the preparation method and application thereof of one type graphitic nitralloy carbon intercalation |
-
2019
- 2019-07-16 CN CN201910639971.3A patent/CN110252154B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104069752A (en) * | 2014-06-27 | 2014-10-01 | 天津大学 | Sulfonated polyether-ether-ketone-amino acid modified graphene oxide hybrid membrane and preparation and application thereof |
| KR20160061543A (en) * | 2014-11-21 | 2016-06-01 | 한양대학교 산학협력단 | Material for water treatment, and method of fabricating the same |
| CN105413494A (en) * | 2016-01-04 | 2016-03-23 | 福州大学 | High-performance lyophilic PVDF/GO-lysine composite membrane |
| CN105921031A (en) * | 2016-05-15 | 2016-09-07 | 高学理 | Carboxylic oxidized graphene and method for modifying organic release film by means of same |
| US20190039028A1 (en) * | 2017-07-24 | 2019-02-07 | Northeastern University | Porous Membranes Comprising Nanosheets and Fabrication Thereof |
| CN109433023A (en) * | 2018-09-14 | 2019-03-08 | 浙江工业大学 | The graphene oxide nanofiltration membrane and the preparation method and application thereof of one type graphitic nitralloy carbon intercalation |
Non-Patent Citations (3)
| Title |
|---|
| ANEELA SABIR等: "Hyperbranched polyethyleneimine induced polycationic membranes for improved fouling resistance and high RO performance", 《EUROPEAN POLYMER JOURNAL》 * |
| 王双双: "基于氧化石墨烯及其复合物的聚合物分离膜改性和功能化", 《中国优秀硕士学位论文全文数据库 工程科技Ⅰ辑》 * |
| 邢毓成等: "还原氧化石墨烯/石墨相氮化碳复合膜的制备及其脱盐性能", 《青岛科技大学学报（自然科学版）》 * |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110649258A (en) * | 2019-10-08 | 2020-01-03 | 北京航空航天大学 | Preparation method of three-dimensional porous tin oxide graphene composite electrode material |
| CN112625776A (en) * | 2019-10-08 | 2021-04-09 | 中国石油化工股份有限公司 | Graphene compound for lubricating oil additive and preparation method and application thereof |
| CN110649258B (en) * | 2019-10-08 | 2021-05-04 | 北京航空航天大学 | Preparation method of three-dimensional porous tin oxide graphene composite electrode material |
| CN112642291A (en) * | 2020-12-30 | 2021-04-13 | 陕西科技大学 | Amino acid bonded molybdenum disulfide reverse osmosis membrane and preparation method and application thereof |
| CN114016286A (en) * | 2021-12-15 | 2022-02-08 | 四川大学 | Method for modifying carbon fiber by functionalized graphene oxide electrophoretic deposition and carbon fiber composite material thereof |
| CN114591545A (en) * | 2022-01-22 | 2022-06-07 | 中北大学 | Forming method for preparing graphene master batch and long-life heavy vehicle load wheel tire by water phase synergistic coagulation process |
| CN114591545B (en) * | 2022-01-22 | 2024-04-05 | 中北大学 | Forming method for preparing graphene masterbatch and long-service-life heavy vehicle road wheel tire through water phase cooperative coagulation process |
| CN114669199A (en) * | 2022-03-15 | 2022-06-28 | 山东大学 | Modified mica sheet-nanocellulose composite nanofiltration membrane and preparation method thereof |
| CN114669199B (en) * | 2022-03-15 | 2023-07-25 | 山东大学 | Modified mica sheet-nanocellulose composite nanofiltration membrane and preparation method thereof |
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