CN105964151A - Preparation method and use of graphene composite film with interlayer MOFs - Google Patents
Preparation method and use of graphene composite film with interlayer MOFs Download PDFInfo
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- CN105964151A CN105964151A CN201610292722.8A CN201610292722A CN105964151A CN 105964151 A CN105964151 A CN 105964151A CN 201610292722 A CN201610292722 A CN 201610292722A CN 105964151 A CN105964151 A CN 105964151A
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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
- B01D61/00—Processes of separation using semi-permeable membranes, e.g. dialysis, osmosis or ultrafiltration; Apparatus, accessories or auxiliary operations specially adapted therefor
- B01D61/36—Pervaporation; Membrane distillation; Liquid permeation
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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
- B01D67/0002—Organic membrane manufacture
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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
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Abstract
The invention discloses a preparation method and use of a graphene composite film with interlayer MOFs. The preparation method comprises immersing a graphene film in a metal salt solution so that metal ions enters the gap between the graphene layers, wherein the graphene film is a graphene oxide film or a reduced graphene oxide film, putting the immersed film in a corresponding ligand solution, carrying out hydrothermal crystallization, and carrying out cooling and drying to obtain the graphene composite film with the interlayer MOFs. The graphene composite film with the interlayer MOFs completely changes impermeability of the traditional graphene film and has very high organic solvent permeability. The graphene composite film with the interlayer MOFs can be used in alcohol-water separation.
Description
Technical field
The preparation method and the graphite alkenes prepared by the method that the present invention relates to graphite alkenes composite membrane are combined
Film and the application of this composite membrane, the preparation side of a kind of graphene composite film with interlayer MOFs
Method and by the method prepare the graphene composite film with interlayer MOFs and application.
Background technology
As a kind of two dimension monoatomic layer material, Graphene has the chemical machinery stability of excellence.Due to it
Fixing interlamellar spacing and reliably self-defect, from the Ruoff research group in 2007 method by sucking filtration
Since successfully preparing graphene oxide film, graphite alkenes material is by the substantial amounts of preparation for separating film.Stone
The separating mechanism of ink alkenes separation film mainly has two kinds.For ultra-thin graphite alkenes separation film, (thickness is 10
Below nm) for, owing to the number of plies of Graphene is few, the separation function of film depends on graphite alkenes and receives
The internal flaw of rice sheet itself.But there is spreadability problem in ultra-thin graphite alkenes film and prepared by difficult scale
Problem.The separation of micron-sized graphite alkenes film relies primarily on Graphene interlamellar spacing between layers and carries out point
From.But the graphene oxide of reduction or graphene film have non-permeable.Although graphene oxide membrane energy
Selective through water, but it has non-permeable to other steam or gas.Therefore prepare and pass through
The graphite alkenes film of property has important science and using value.
Metal-organic framework materials (MOFs) has specific surface area height, duct is adjustable, hydrophilic and hydrophobic is adjustable
Feature.Being different from and prepare Graphene from graphite stripping, MOFs is generally prepared from by little molecule crystallization.Therefore
MOFs can be grown between graphene layer to prepare the Graphene of porous by the way of growth in situ by we
Class composite membrane.Thus obtain the graphite alkenes thin film can with selective penetrated property, to solve micron order Graphene
Class separation film can only be permeable problem.
Summary of the invention
The primary and foremost purpose of the present invention is to provide stone simple to operate, that a kind of interlayer that is that be suitable for amplifying has MOFs
Ink alkene composite membrane preparation method, by the way of at the interlayer growth in situ MOFs of graphite alkenes thin film with
Improve the porosity of graphite alkenes film and change the through performance of graphite oxide alkenes film.
Second purpose of the present invention is to provide a kind of interlayer and has the graphene composite film of MOFs, changes completely
The impermeability of conventional graphite alkenes film, has high organic solvent permeability.
Third object of the present invention is to provide described interlayer and has the graphene composite film of MOFs at alcohol moisture
Application in from.
Below technical scheme is illustrated.
The preparation method of a kind of graphene composite film with interlayer MOFs, comprises the following steps:
Graphite alkenes film is placed in metal salt solution immersion so that metal ion enters between graphene layer,
Described graphite alkenes film is graphene oxide membrane or redox graphene film, and the film after then soaking is put
In corresponding ligand solution, carry out hydrothermal crystallizing, more cooled, be dried to obtain the stone with interlayer MOFs
Ink alkene composite membrane.
In the present invention, the kind of described slaine according to required for the difference of metallic organic framework that obtains and
Different.Mainly there are the salt of zinc, the salt of copper, the salt of cobalt, the salt of ferrum, the salt of aluminum, the salt of chromium
Class, the salt etc. of zirconium.The solvent species of described metal salt solution according to required for the organic bone of metal that obtains
The difference of frame and different, predominantly water, methanol, ethanol, isopropanol, glycerol, butanol, the tert-butyl alcohol,
Ketopyrrolidine, N, N-diethylformamide, oxolane, dioxane or dimethyl sulfoxide etc..Described
The concentration of metal salt solution between 20mmol/L to 800mmol/L, preferably 50～200mmol/L it
Between.
In the present invention, the kind of described part according to required for the difference of metallic organic framework that obtains and not
With, predominantly Carboxylic acid ligand or imidazole ligands.The concentration of described ligand solution is the most saturated at 20mmol/L
Between concentration, preferably between 50～200mmol/L.
In the present invention, hydrothermal crystallizing condition is: temperature is at 60～200 DEG C, and the time is 2～48 hours.This area
Technical staff can set suitable condition according to the needs of concrete MOFs synthesis.
In the present invention, described graphite alkenes film can be graphene oxide membrane or redox graphene film,
It is preferably redox graphene film.Described graphite alkenes film can be prepared by a conventional method, and such as may be used
To prepare graphene oxide membrane by conventional pressure filtration method.The graphene oxide membrane of gained is again by routine
Method of reducing i.e. can get redox graphene film.
The present invention preferably prepares redox graphene film by hydro-thermal method, specifically includes:
(1) basement membrane is carried out amino modified, described basement membrane can be ceramic membrane can also be polymeric film,
Such as pvdf membrane；
(2) preparation graphene oxide suspension；
(3) basement membrane after amino modified it is immersed in graphene oxide suspension and keeps vertical, being transferred to
In water heating kettle, directly graphene oxide is reduced by hydro-thermal and be deposited on the membrane surface after amino modified with
Obtain redox graphene film.
Further, the amino modified method of the basement membrane described in step (1) is as follows: basement membrane is placed in ethylenediamine water
Carrying out heat treated in solution, treatment temperature is 100～200 DEG C, and the process time is 10～48 hours, after amination
Basement membrane ethanol and deionized water clean to remove unreacted ethylenediamine, the most at room temperature respectively fully
Natural drying.
Further, described graphene oxide suspension concentration is between 0.1mg/mL to 10mg/mL.
Further, the temperature of hydrothermal reduction is between 60 DEG C to 200 DEG C, and the time is between 2 to 48 hours.
The present invention has prepared the graphene composite film with interlayer MOFs, and this composite membrane has high organic
Solvent permeability.
There is the graphene composite film of interlayer MOFs at alcohol water especially first alcohol and water described in the invention provides
Application in separation.
Compared with prior art, the beneficial effects of the present invention is:
(1) method employed in the present invention has fabulous universality, simple to operate, easily amplifies.
(2) present invention can use one-step method to prepare redox graphene film, has abandoned traditional deposition-reduction
Two-step preparation.
(3) the graphite alkenes composite membrane that prepared by the present invention changes being not through of conventional graphite alkenes film completely
Property, there is high organic solvent permeability.
Accompanying drawing explanation
Fig. 1 is the Electronic Speculum figure of cellulose acetate membrane employed in the embodiment of the present invention 1.
Fig. 2 is the Electronic Speculum figure of ZIF-8/rGO synthesized in the embodiment of the present invention 2.
Fig. 3 is the Electronic Speculum figure of CuBTC/rGO synthesized in the embodiment of the present invention 3.
Detailed description of the invention
Below by embodiment, technical scheme is described further, but the protection model of the present invention
Enclose and be not limited to this.
Embodiment 1:
ZIF-8/GO film
(1) prepared by graphite oxide: prepare graphite oxide by hummer method.The amount of weighing 2g graphite powder and
1g sodium nitrate joins in the concentrated sulphuric acid of 46mL under ice-water bath, is then joined by 6g potassium permanganate
In the solution in face.Above-mentioned solution is kept in the case of 25 DEG C of effects 30min, then adds 92mL
Deionized water, then solution temperature is risen to 98 DEG C, and keeps 40min to obtain bright orange solution.Add 6
The hydrogen peroxide of mL.Afterwards with deionized water repeated multiple times cleaning graphite oxide, it is subsequently placed in the baking oven of 50 DEG C
Interior vacuum drying is standby.
(2) GO film: configuration graphite oxide aqueous solution (0.2mg/mL), after being stirred for 2h, ultrasonic place
Reason obtains GO suspension.Afterwards this suspension is deposited on cellulose acetate membrane by the way of sucking filtration
Surface, and cleaning-drying.
(3) ZIF-8/GO film: prepared GO film is placed in the Zn (NO of 100mmol/L3)2·6H2O
Aqueous solution soaks and makes Zn2+Can sufficiently enter into GO interlayer, be dried afterwards and clean.Configuration 100
The 2-methylimidazole aqueous solution of mmol/L, the film obtained afterwards is immersed in 2-methylimidazole aqueous solution,
Abundant crystallization 12h in the case of 60 DEG C.ZIF-8/GO film, drying for standby is obtained after natural cooling.Obtain
Film to the permeability of water less than 1.2 × 10-2mol m-2s-1.And the flux of methanol is 0.22mol m-2s-1。
Embodiment 2:
ZIF-8/rGO film
(1) pvdf membrane is modified: is spent by polyvinylidene fluoride film and is carried out from water and is dried, after cleaning
Film volumetric concentration 25v/v% that is placed in 100mL ethylenediamine solution in carry out heat treated, process temperature
Degree is 160 DEG C, and the process time is 20 hours.Film ethanol after processing and deionized water, dry under room temperature
Dry obtain amination hollow-fibre membrane.
(2) prepared by graphite oxide: with embodiment 1.
(3) rGO/PVDF film: configuration graphite oxide aqueous solution (1mg/mL), after being stirred for 2h,
Supersound process obtains GO suspension.Afterwards modified pvdf membrane is fixed on support holding vertical,
And be immersed in suspension, it is transferred in water heating kettle, hydrothermal treatment consists 8h in the case of 150 DEG C.The coldest
Obtain rGO/PVDF film, and cleaning-drying the most afterwards.
(4) ZIF-8/rGO film: rGO/PVDF film is placed in the Zn (NO of 50mmol/L3)2·6H2O water
Solution soaks and makes Zn2+Can sufficiently enter into rGO interlayer, be dried afterwards and clean.Configuration 50mmol/L
2-methylimidazole aqueous solution, it is vertical that rGO/PVDF film is fixed on support holding afterwards, and is immersed in
In 2-methylimidazole aqueous solution, it is transferred in water heating kettle, abundant crystallization 6h in the case of 110 DEG C.Natural
ZIF-8/rGO film, drying for standby is obtained after cooling.The film obtained is less than 4.5 × 10 to the permeability of water-6mol
m-2s-1.And the flux of methanol is 2.5 × 10-2mol m-2s-1。
Embodiment 3:
CuBTC/rGO film
Pvdf membrane is modified: embodiment 2 simultaneously.
Prepared by graphite oxide: embodiment 1 simultaneously.
RGO/PVDF film: embodiment 2 simultaneously.
CuBTC/rGO film: rGO/PVDF film is placed in the Cu (NO of 200mmol/L3)2·3H2O is water-soluble
Liquid soaks and makes Cu2+Can sufficiently enter into rGO interlayer, be dried afterwards and clean.Configuration 200mmol/L
Trimesic acid ethanol solution, is fixed on rGO/PVDF film on support holding afterwards vertically, and is immersed in
In trimesic acid ethanol solution, it is transferred in water heating kettle, abundant crystallization 6h in the case of 110 DEG C.From
So obtain CuBTC/rGO film, drying for standby after cooling.The film obtained is less than 1 × 10 to the permeability of water-3mol
m-2s-1.And the flux of methanol is 0.21mol m-2s-1。
Embodiment 4:
ZIF-8/rGO film
Pvdf membrane is modified: embodiment 2 simultaneously.
Prepared by graphite oxide: embodiment 1 simultaneously.
RGO/PVDF film: embodiment 2 simultaneously.
ZIF-8/rGO film: rGO/PVDF film is placed in the Zn (NO of 400mmol/L3)2·6H2O aqueous solution
Middle immersion makes Zn2+Can sufficiently enter into rGO interlayer, be dried afterwards and clean.Configuration 400mmol/L's
2-methylimidazole aqueous solution, is fixed on rGO/PVDF film on support holding afterwards vertically, and is immersed in 2-
In Methylimidazole. aqueous solution, it is transferred in water heating kettle, abundant crystallization 6h in the case of 200 DEG C.The coldest
Obtain ZIF-8/rGO film, drying for standby the most afterwards.The film obtained is less than 4.5 × 10 to the permeability of water-6mol m-2
s-1.And the flux of methanol is 1.3 × 10-1mol m-2s-1。
Claims (10)
1. there is a preparation method for the graphene composite film of interlayer MOFs, comprise the following steps:
Graphite alkenes film is placed in metal salt solution immersion so that metal ion enters between graphene layer,
Described graphite alkenes film is graphene oxide membrane or redox graphene film, and the film after then soaking is put
In corresponding ligand solution, carry out hydrothermal crystallizing, more cooled, be dried to obtain the stone with interlayer MOFs
Ink alkene composite membrane.
Having the preparation method of the graphene composite film of interlayer MOFs the most as claimed in claim 1, it is special
Levy and be: the concentration of described metal salt solution is between 20mmol/L to 800mmol/L, and described joins
The concentration of liquid solution is between 20mmol/L to saturated concentration.
Having the preparation method of the graphene composite film of interlayer MOFs the most as claimed in claim 1, it is special
Levy and be: the concentration of described metal salt solution is between 50mmol/L to 200mmol/L, and described joins
The concentration of liquid solution is between 50mmol/L to 200mmol/L.
4. the preparation method of the graphene composite film with interlayer MOFs as described in one of claims 1 to 3,
It is characterized in that: hydrothermal crystallizing condition is: temperature is at 60～200 DEG C, and the time is 2～48 hours.
5. the preparation method of the graphene composite film with interlayer MOFs as described in one of claims 1 to 3,
It is characterized in that: described redox graphene film is prepared by hydro-thermal method, specifically include following steps:
(1) basement membrane carrying out amino modified, described basement membrane is ceramic membrane or polymeric film；
(2) preparation graphene oxide suspension；
(3) basement membrane after amino modified it is immersed in graphene oxide suspension and keeps vertical, being transferred to
In water heating kettle, directly graphene oxide is reduced by hydro-thermal and be deposited on the membrane surface after amino modified with
Obtain redox graphene film.
Having the preparation method of the graphene composite film of interlayer MOFs the most as claimed in claim 5, it is special
Levy and be that the amino modified method of the basement membrane described in step (1) is as follows: basement membrane is placed in ethylenediamine solution
Carrying out heat treated, treatment temperature is 100～200 DEG C, and the process time is 10～48 hours, the basement membrane after amination
The most fully clean to remove unreacted ethylenediamine with ethanol and deionized water, the most dry
Dry.
Having the preparation method of the graphene composite film of interlayer MOFs the most as claimed in claim 5, it is special
Levy and be: described graphene oxide suspension concentration is between 0.1mg/mL to 10mg/mL.
Having the preparation method of the graphene composite film of interlayer MOFs the most as claimed in claim 5, it is special
Levying and be: the temperature of hydrothermal reduction is between 60 DEG C to 200 DEG C, the time is between 2 to 48 hours.
The graphene composite film with interlayer MOFs that the most according to claim 1, method prepares.
There is the graphene composite film of interlayer MOFs the most as claimed in claim 9 in alcohol-water separation
Application.
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| CN111389235B (en) * | 2020-04-20 | 2021-03-30 | 武汉理工大学 | Porous metal organic framework doped graphene oxide-based composite material and rapid preparation method and application thereof |
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| CN113304630A (en) * | 2021-06-04 | 2021-08-27 | 徐州禹慧环境科技研究院有限公司 | Preparation method of graphene oxide framework composite membrane |
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