CN109173730A - A kind of method that MOFs@f-GO hybridized film is prepared in situ in Freeze Drying Technique - Google Patents

A kind of method that MOFs@f-GO hybridized film is prepared in situ in Freeze Drying Technique Download PDF

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CN109173730A
CN109173730A CN201811076605.3A CN201811076605A CN109173730A CN 109173730 A CN109173730 A CN 109173730A CN 201811076605 A CN201811076605 A CN 201811076605A CN 109173730 A CN109173730 A CN 109173730A
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CN109173730B (en
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安全福
张文海
王乃鑫
殷明杰
纪树兰
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Beijing University of Technology
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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
    • B01D61/025—Reverse osmosis; Hyperfiltration
    • 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
    • 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
    • B01D67/0095—Drying
    • 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
    • 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

A kind of method that MOFs@f-GO hybridized film is prepared in situ in Freeze Drying Technique, belongs to nanofiltration membrane separation field.The following steps are included: preparation GO dispersion liquid, a certain amount of metal complex ion or organic ligand are added in GO dispersion liquid；In the way of suction filtration deposition, GO base dispersion liquid is assembled to porous membrane surface, prepares hygrometric state GO group compound film；Resulting hygrometric state GO group compound film is prepared to the GO group compound film of open structure using Freeze Drying Technique；Obtained composite membrane corresponding immerse is subjected to the growth of MOFs in-situ hybridization in organic ligand solution or metal complex ion solution, prepares metal organic framework@graphene oxide (MOFs@f-GO) hydridization nanofiltration membrane.Such film can be used for the separation of dyestuff in water, high price salt and organic phase small molecular.

Description

A kind of method that MOFs@f-GO hybridized film is prepared in situ in Freeze Drying Technique
Technical field
It is miscellaneous for metal organic framework@graphene oxide that the present invention relates to a kind of Freeze Drying Techniques and growth in situ coordinate system Change the method for film (MOFs@f-GO), such film can be used for the separation of dyestuff in water, high price salt and organic phase small molecular, belong to Nanofiltration membrane separation field.
Background technique
Nanofiltration because its have many advantages, such as it is easy to operate, energy-efficient and without secondary pollution, it is considered to be a kind of liquid phase High price salt and small organic molecule efficiently separate means in system, and nanofiltration membrane is the key that nanofiltration.Currently, all nanofiltrations In membrane material, polymer film is most widely used, simple mainly due to its preparation process, high mechanical strength and convenient for being assembled into Integrated membrane module, is easy to large-scale use.However, polymer nano filter membrane still have chemical stability and thermal stability compared with The disadvantages such as poor, the easy to pollute and service life is low.
Graphene oxide (GO) as the oxidized derivatives of graphene not only maintain part graphene superior function and It is easy to large scale preparation.In addition, GO can be by simply filtering or spin-coating method is assembled into and possesses abundant two-dimensional nano duct net Macroscopical membrane material of network, therefore it is considered that there is boundless application potential [E.N.Wang and in UF membrane field R.Karnik,Nature Nanotechnology.,2012,7,552.].However, the mass transfer of GO film relies primarily on interlayer spacing, This greatly prolongs mass transfer path, reduces infiltration rate, to limit the application of GO film.Furthermore it recent studies have shown that GO In the process of running, there are microstructure densification to cause flux substantially to decay and dissociate phenomenon in water for film, greatly limits Industrial application [Wei Y, Zhang Y, Gao X, the et al.Carbon, 2016,108:568-575 of GO film；Chong J Y, Wang B,Mattevi C,et al.Journal of Membrane Science,2017,549.].For this purpose, a series of improvement Method is suggested.
At present in research, the mode of GO membrane flux and stability is improved mainly to include: a. chemical crosslinking, is such as selected more The molecules such as first amine, polynary acyl chlorides and lamella are chemically crosslinked；B, using nano particle filling technique, realize that GO interlayer nanometer passes The building in matter channel.The above method can play support, firm and regulation interlamellar spacing.But two ways also has itself Deficiency, as small-molecule chemical crosslinking is little for the contribution for improving permeation flux；Nano particle is introduced in a manner of physical blending The filling hydridization of (template) is difficult to realize the controllable building of nanometer transmission channel and particle agglomeration is easy to generate defect reduction point Problem from selectivity.For this purpose, a kind of method for developing porous material in-situ hybridization is the key that solve the above problems.
Metal organic framework (MOFs) is a kind of novel porous materials developed in the recent period, because of its special pore property, Be widely used in the preparation of seperation film, and have more excellent separating property [CN106823854A, CN104209022A, CN104209021A].However current hydridization method is mostly direct physical blending, causes dispersion uneven and when additive amount is higher It is easy to reunite.And in-situ hybridization is a kind of very strong solution, however pure GO film accumulates comparatively dense, hardly possible because of interlayer To carry out growth in situ, and the premise of in-situ hybridization growth is building particle growth space.And freeze-drying, also known as ice Mould plate technique, be grow up in the recent period one kind it is very effective prepare porous material method [CN107200583A, CN106084302A, CN107185500A], the present invention is by combining Freeze Drying Technique and in-situ hybridization growth pathway thus Standby metal organic framework@graphene oxide (MOFs@f-GO) the hydridization nanofiltration membrane with double split tunnels of coordinate system, passes through the party Method effectively improves membrane mass transfer rate, while also maintaining higher separation selectivity, and preparation process is simple, reproducible, There is very big potential application foreground in liquid phase separation field.
Summary of the invention
The purpose of the present invention is had using the collaboration building of Freeze Drying Technique and in-situ hybridization growth pathway pair separate it is logical Metal organic framework@graphene oxide (MOFs@f-GOm) the hydridization nanofiltration membrane in road.The f-GO obtained by freeze-drying process Film simultaneously carries out direct in-situ hydridization.Composite membrane using this method preparation has good separating property for nanofiltration separation field And stability.
Method includes the following steps:
(1) porous basement membrane is pre-processed, removes its surface organic matter, inorganic matter and microorganism；
(2) in deionized water by the dispersion of GO powder, in the way of ultrasound centrifugation, GO dispersion liquid is configured；
(3) a certain amount of metal complex ion or organic ligand are added in GO dispersion liquid；
(4) in the way of suction filtration deposition, GO base dispersion liquid is assembled to porous membrane surface, it is compound to prepare hygrometric state GO base Film；
(5) the resulting hygrometric state GO group compound film of step (4) is prepared to the GO base of open structure using Freeze Drying Technique Composite membrane；
(6) corresponding immerse in organic ligand solution or metal complex ion solution of composite membrane obtained in (5) is carried out The growth of MOFs in-situ hybridization, prepares metal organic framework@graphene oxide (MOFs@f-GO) hydridization nanofiltration membrane.
Be used to prepare in the present invention polyelectrolyte composite membrane substrate can for business tubular membrane or plate membrane it is inorganic Perforated membrane, membrane material are aluminium oxide, silica, zirconium oxide, and the porous membrane aperture is 0.1~1.0 μm；
GO dispersion liquid mass percent concentration in step (2) for assembling is 0.001~0.5%；Step (3) GO dispersion The concentration of metal complex ion or organic ligand is 0.01~1mol/L in liquid.
In step (4), the pressure limit for filtering deposition is 0.01~0.1MPa, and deposition time ranges are 0.1~10min；
Freeze Drying Technique in step (5) is that first Decompression Sublimation, cryogenic temperature are -10~-50 DEG C to freezing ice crystalization again, Ice crystallization time is 0.5~3h, and the pressure of Decompression Sublimation is 1~10Pa, and the lyophilization time is 1~10h；
Reaction temperature in step (6) is 20~60 DEG C, and the reaction time is 1~36h；Corresponding organic ligand solution is matched The molar concentration of position metal ion solution is 0.01-10mol/L.
The principle of technical solution of the present invention is: prepare the GO group compound film of hygrometric state first using the method for filtering deposition, and Freezing processing is carried out by low temperature, when being lower than solvent freezing point, solvent solidifies, and generates the solvent nucleus of nano-scale, then The method for carrying out negative pressure distillation removes solvent, to construct the space of special microcellular structure, carries out MOFs's with this space basis In-situ hybridization growth.The method also maintains high while the structural stability and mass transfer rate for increasing substantially GO film Separation selectivity.
Technical advantage
The present invention has the MOFs@f-GO hydridization nanofiltration membrane of double split tunnels using Freeze Drying Technique building, is improving Rejection is also maintained while membrane structure stability and permeation flux；This method is typical in-situ hybridization technology, operation letter List and stable structure have commercial introduction potentiality.Using the MOFs f-GO hydridization nanofiltration UF membrane of technology preparation for separating The methyl blue water solution system of 0.1g/L, the eriochrome black T water solution system of 0.1g/L, 0.1g/L aqueous sodium sulfate liquid system, with And the Evans blue methanol solution system of 0.1g/L, when operating pressure is 0.1MPa, flux is respectively 30.9L/m2h bar、 29.2L/m2h bar、38.6L/m2H bar and 34.2L/m2h bar；Rejection is followed successively by 99.8%, 99.0%, 66.2% and 90.2%.
Detailed description of the invention
Fig. 1 is the scanning electron microscope (SEM) photograph of the ZIF-8@f-GO hydridization nanofiltration membrane section of freeze-drying process in embodiment 1,
Fig. 2 is the scanning electron microscope (SEM) photograph of ZIF-8 f-GO hydridization nanofiltration film surface in embodiment 1.
Specific embodiment
Below in conjunction with specific embodiment, the present invention is described in detail, but the present invention is not limited to following embodiments.
Embodiment 1
Use commercialization perforated membrane for alumina material, form is tubular ultra-filtration membrane, and membrane aperture is 0.1 μm, and membrane area is 10cm2, selected GO dispersing agent is deionized water, and GO dispersion liquid concentration is 0.003g/L.
The preparation method of ZIF-8@f-GO hydridization nanofiltration membrane
(1) pellumina of a length of 5cm or so is rinsed pretreatment with deionized water, remove its surface organic matter, Then inorganic matter and microorganism are put in 50 DEG C of baking ovens and dry；
(2) in deionized water by the dispersion of a certain amount of GO powder, in the way of ultrasound centrifugation, configuration concentration ratio is The GO dispersion liquid of 0.003g/L and in 2-methylimidazole, concentration 1mol/L is wherein added；
(3) by the GO base dispersion liquid of (2) configuration aluminium oxide basement membrane that is assembled into that treated by way of filtering deposition, Suction filtration pressure is 0.1MPa, and the suction filtration time is 3min；
(4) the hygrometric state GO composite membrane prepared in (3) is directly introduced in freeze drying box, temperature is -50 DEG C, ice crystal Time is 3h；Then carry out lyophilization 10h；Final take out is put into 50 DEG C of baking ovens dry 12h；
(5) f-GO composite membrane obtained above is impregnated in 6h in the zinc nitrate hexahydrate solution of 0.01mol/L, taken out simultaneously Drying.When operating pressure is 0.1MPa, rejection and flux to sodium sulphate are respectively 66.2% and 38.6L/m2h bar。
Embodiment 2
Use commercialization perforated membrane for alumina material, form is tubular ultra-filtration membrane, and membrane aperture is 0.1 μm, and membrane area is 10cm2, selected GO dispersing agent is deionized water, and GO dispersion liquid concentration is 0.003g/L.
The preparation method of ZIF-8@f-GO hydridization nanofiltration membrane
(1) pellumina of a length of 5cm or so is rinsed pretreatment with deionized water, remove its surface organic matter, Then inorganic matter and microorganism are put in 50 DEG C of baking ovens and dry；
(2) in deionized water by the dispersion of a certain amount of GO powder, in the way of ultrasound centrifugation, configuration concentration ratio is The GO dispersion liquid of 0.003g/L and in 2-methylimidazole, concentration 1mol/L is wherein added；
(3) by the GO base dispersion liquid of (2) configuration aluminium oxide basement membrane that is assembled into that treated by way of filtering deposition, Suction filtration pressure is 0.1MPa, and the suction filtration time is 3min；
(4) the hygrometric state GO composite membrane prepared in (3) is directly introduced in freeze drying box, temperature is -50 DEG C, ice crystal Time is 3h；Then carry out lyophilization 10h；Final take out is put into 50 DEG C of baking ovens dry 12h；
(5) f-GO composite membrane obtained above is impregnated in 6h in the zinc nitrate hexahydrate solution of 0.01mol/L, taken out simultaneously Drying.When operating pressure is 0.1MPa, rejection and flux to methyl blue are respectively 99.8% and 30.9L/m2h bar。
Embodiment 3
Use commercialization perforated membrane for alumina material, form is tubular ultra-filtration membrane, and membrane aperture is 0.1 μm, and membrane area is 10cm2, selected GO dispersing agent is deionized water, and GO dispersion liquid concentration is 0.003g/L.
The preparation method of ZIF-8@f-GO hydridization nanofiltration membrane
(1) pellumina of a length of 5cm or so is rinsed pretreatment with deionized water, remove its surface organic matter, Then inorganic matter and microorganism are put in 50 DEG C of baking ovens and dry；
(2) in deionized water by the dispersion of a certain amount of GO powder, in the way of ultrasound centrifugation, configuration concentration ratio is The GO dispersion liquid of 0.003g/L and in 2-methylimidazole, concentration 1mol/L is wherein added；
(3) by the GO base dispersion liquid of (2) configuration aluminium oxide basement membrane that is assembled into that treated by way of filtering deposition, Suction filtration pressure is 0.1MPa, and the suction filtration time is 3min；
(4) the hygrometric state GO composite membrane prepared in (3) is directly introduced in freeze drying box, temperature is -50 DEG C, ice crystal Time is 3h；Then carry out lyophilization 10h；Final take out is put into 50 DEG C of baking ovens dry 12h；
(5) f-GO composite membrane obtained above is impregnated in 6h in the zinc nitrate hexahydrate solution of 0.01mol/L, taken out simultaneously Drying.When operating pressure is 0.1MPa, rejection and flux to eriochrome black T are respectively 99.0% and 29.2L/m2h bar。
Embodiment 4
Use commercialization perforated membrane for alumina material, form is tubular ultra-filtration membrane, and membrane aperture is 0.1 μm, and membrane area is 10cm2, selected GO dispersing agent is deionized water, and GO dispersion liquid concentration is 0.003g/L.
The preparation method of ZIF-8@f-GO hydridization nanofiltration membrane
(1) pellumina of a length of 5cm or so is rinsed pretreatment with deionized water, remove its surface organic matter, Then inorganic matter and microorganism are put in 50 DEG C of baking ovens and dry；
(2) in deionized water by the dispersion of a certain amount of GO powder, in the way of ultrasound centrifugation, configuration concentration ratio is The GO dispersion liquid of 0.003g/L and in 2-methylimidazole, concentration 1mol/L is wherein added；
(3) by the GO base dispersion liquid of (2) configuration aluminium oxide basement membrane that is assembled into that treated by way of filtering deposition, Suction filtration pressure is 0.1MPa, and the suction filtration time is 3min；
(4) the hygrometric state GO composite membrane prepared in (3) is directly introduced in freeze drying box, temperature is -50 DEG C, ice crystal Time is 3h；Then carry out lyophilization 10h；Final take out is put into 50 DEG C of baking ovens dry 12h；
(5) f-GO composite membrane obtained above is impregnated in 6h in the zinc nitrate hexahydrate solution of 0.01mol/L, taken out simultaneously Drying.When operating pressure is 0.1MPa, rejection and flux to Evans blue are respectively 902% and 34.2L/m2h bar。
Embodiment 5
Use commercialization perforated membrane for alumina material, form is tubular ultra-filtration membrane, and membrane aperture is 0.1 μm, and membrane area is 10cm2, selected GO dispersing agent is deionized water, and GO dispersion liquid concentration is 0.003g/L.
The preparation method of ZIF-11@f-GO hydridization nanofiltration membrane
(1) pellumina of a length of 5cm or so is rinsed pretreatment with deionized water, remove its surface organic matter, Then inorganic matter and microorganism are put in 50 DEG C of baking ovens and dry；
(2) in deionized water by the dispersion of a certain amount of GO powder, in the way of ultrasound centrifugation, configuration concentration ratio is The GO dispersion liquid of 0.003g/L and in benzimidazole, concentration 1mol/L is wherein added；
(3) by the GO base dispersion liquid of (2) configuration aluminium oxide basement membrane that is assembled into that treated by way of filtering deposition, Suction filtration pressure is 0.1MPa, and the suction filtration time is 3min；
(4) the hygrometric state GO composite membrane prepared in (3) is directly introduced in freeze drying box, temperature is -50 DEG C, ice crystal Time is 3h；Then carry out lyophilization 10h；Final take out is put into 50 DEG C of baking ovens dry 12h；
(5) f-GO composite membrane obtained above is impregnated in 6h in the zinc nitrate hexahydrate solution of 0.01mol/L, taken out simultaneously Drying.When operating pressure is 0.1MPa, rejection and flux to methyl blue are respectively 99.8% and 25.9L/m2h bar。
Embodiment 6
Use commercialization perforated membrane for alumina material, form is tubular ultra-filtration membrane, and membrane aperture is 0.1 μm, and membrane area is 10cm2, selected GO dispersing agent is deionized water, and GO dispersion liquid concentration is 0.003g/L.
The preparation method of ZIF-90@f-GO hydridization nanofiltration membrane
(1) pellumina of a length of 5cm or so is rinsed pretreatment with deionized water, remove its surface organic matter, Then inorganic matter and microorganism are put in 50 DEG C of baking ovens and dry；
(2) in deionized water by the dispersion of a certain amount of GO powder, in the way of ultrasound centrifugation, configuration concentration ratio is The GO dispersion liquid of 0.003g/L and in four nitric hydrate zinc, concentration 0.01mol/L is wherein added；
(3) by the GO base dispersion liquid of (2) configuration aluminium oxide basement membrane that is assembled into that treated by way of filtering deposition, Suction filtration pressure is 0.1MPa, and the suction filtration time is 3min；
(4) the hygrometric state GO composite membrane prepared in (3) is directly introduced in freeze drying box, temperature is -50 DEG C, ice crystal Time is 3h；Then carry out lyophilization 10h；Final take out is put into 50 DEG C of baking ovens dry 12h；
(5) f-GO composite membrane obtained above is impregnated in 6h in the imidazoles -2- formalin of 1mol/L, takes out and dries It is dry.When operating pressure is 0.1MPa, rejection and flux to methyl blue are respectively 99.6% and 21.8L/m2h bar。
Embodiment 7
Use commercialization perforated membrane for zirconia material, form is tubular ultra-filtration membrane, and membrane aperture is 0.1 μm, and membrane area is 10cm2, selected GO dispersing agent is deionized water, and GO dispersion liquid concentration is 0.003g/L.
The preparation method of Cu-BTC@f-GO hybridized film
(1) pellumina of a length of 5cm or so is rinsed pretreatment with deionized water, remove its surface organic matter, Then inorganic matter and microorganism are put in 50 DEG C of baking ovens and dry；
(2) in deionized water by the dispersion of a certain amount of GO powder, in the way of ultrasound centrifugation, configuration concentration ratio is The GO dispersion liquid of 0.003g/L and in copper nitrate, concentration 0.01mol/L is wherein added；
(3) by the GO base dispersion liquid of (2) configuration aluminium oxide basement membrane that is assembled into that treated by way of filtering deposition, Suction filtration pressure is 0.1MPa, and the suction filtration time is 3min；
(4) the hygrometric state GO composite membrane prepared in (3) is directly introduced in freeze drying box, temperature is -50 DEG C, ice crystal Time is 3h；Then carry out lyophilization 10h；Final take out is put into 50 DEG C of baking ovens dry 12h；
(5) f-GO composite membrane obtained above is impregnated in 6h in the benzenetricarboxylic acid of 0.06mol/L, takes out and dries.Work as behaviour Make pressure be 0.1MPa when, rejection and flux to eriochrome black T are respectively 96.9% and 31.6L/m2h bar。
Embodiment 8
Use commercialization perforated membrane for alumina material, form is tubular ultra-filtration membrane, and membrane aperture is 0.1 μm, and membrane area is 10cm2, selected GO dispersing agent is deionized water, and GO dispersion liquid concentration is 0.003g/L.
The preparation method of ZIF-8@f-GO hydridization nanofiltration membrane
(1) pellumina of a length of 5cm or so is rinsed pretreatment with deionized water, remove its surface organic matter, Then inorganic matter and microorganism are put in 50 DEG C of baking ovens and dry；
(2) in deionized water by the dispersion of a certain amount of GO powder, in the way of ultrasound centrifugation, configuration concentration ratio is The GO dispersion liquid of 0.003g/L and in 2-methylimidazole, concentration 10mol/L is wherein added；
(3) by the GO base dispersion liquid of (2) configuration aluminium oxide basement membrane that is assembled into that treated by way of filtering deposition, Suction filtration pressure is 0.1MPa, and the suction filtration time is 3min；
(4) the hygrometric state GO composite membrane prepared in (3) is directly introduced in freeze drying box, temperature is -50 DEG C, ice crystal Time is 3h；Then carry out lyophilization 10h；Final take out is put into 50 DEG C of baking ovens dry 12h；
(5) f-GO composite membrane obtained above is impregnated in 6h in the zinc nitrate hexahydrate solution of 1mol/L, takes out and dries It is dry.When operating pressure is 0.1MPa, rejection and flux to methyl blue are respectively 99.8% and 18.1L/m2h bar。
Embodiment 9
Use commercialization perforated membrane for alumina material, form is tubular ultra-filtration membrane, and membrane aperture is 0.1 μm, and membrane area is 10cm2, selected GO dispersing agent is deionized water, and GO dispersion liquid concentration is 0.003g/L.
The preparation method of ZIF-8@f-GO hydridization nanofiltration membrane
(1) pellumina of a length of 5cm or so is rinsed pretreatment with deionized water, remove its surface organic matter, Then inorganic matter and microorganism are put in 50 DEG C of baking ovens and dry；
(2) in deionized water by the dispersion of a certain amount of GO powder, in the way of ultrasound centrifugation, configuration concentration ratio is The GO dispersion liquid of 0.003g/L and in 2-methylimidazole, concentration 1mol/L is wherein added；
(3) by the GO base dispersion liquid of (2) configuration aluminium oxide basement membrane that is assembled into that treated by way of filtering deposition, Suction filtration pressure is 0.1MPa, and the suction filtration time is 3min；
(4) the hygrometric state GO composite membrane prepared in (3) is directly introduced in freeze drying box, temperature is -50 DEG C, ice crystal Time is 3h；Then carry out lyophilization 10h；Final take out is put into 50 DEG C of baking ovens dry 12h；
(5) f-GO composite membrane obtained above is impregnated in 6h in the zinc nitrate hexahydrate solution of 10mol/L, takes out and dries It is dry.When operating pressure is 0.1MPa, rejection and flux to methyl blue are respectively 98.9% and 16.2L/m2h bar。

Claims (10)

1. a kind of method that MOFs@f-GO hybridized film is prepared in situ in Freeze Drying Technique, which comprises the following steps:
(1) porous basement membrane is pre-processed, removes its surface organic matter, inorganic matter and microorganism；
(2) in deionized water by the dispersion of GO powder, in the way of ultrasound centrifugation, GO dispersion liquid is configured；
(3) a certain amount of metal complex ion or organic ligand are added in GO dispersion liquid；
(4) in the way of suction filtration deposition, GO base dispersion liquid is assembled to porous membrane surface, prepares hygrometric state GO group compound film；
(5) the GO base for the resulting hygrometric state GO group compound film of step (4) being prepared open structure using Freeze Drying Technique is compound Film；
(6) corresponding immerse in organic ligand solution or metal complex ion solution of composite membrane obtained in (5) is subjected to MOFs original Position hydridization growth, prepares metal organic framework@graphene oxide (MOFs@f-GO) hydridization nanofiltration membrane.
2. according to the method for claim 1, which is characterized in that basement membrane is the inorganic porous membrane of tubular membrane or plate membrane, film Material is aluminium oxide, silica, zirconium oxide, and the porous membrane aperture is 0.1~1.0 μm.
3. according to the method for claim 1, which is characterized in that the GO dispersion liquid quality percentage in step (2) for assembling Specific concentration is 0.001~0.5%.
4. according to the method for claim 1, which is characterized in that metal complex ion or organic in step (3) GO dispersion liquid The concentration of ligand is 0.01~1mol/L.
5. according to the method for claim 1, which is characterized in that in step (4), filter deposition pressure limit be 0.01~ 0.1MPa, deposition time ranges are 0.1~10min.
6. according to the method for claim 1, which is characterized in that the Freeze Drying Technique in step (5) is first to freeze ice crystal Change Decompression Sublimation again, cryogenic temperature is -10~-50 DEG C, and ice crystallization time is 0.5~3h, and Decompression Sublimation pressure is 1~10Pa, The lyophilization time is 1~10h.
7. according to the method for claim 1, which is characterized in that reaction temperature in step (6) is 20~60 DEG C, when reaction Between be 1~36h.
8. according to the method for claim 1, which is characterized in that the corresponding organic ligand solution of step (6) or coordinating metal The molar concentration of solion is 0.01-10mol/L.
9. the MOFs@f-GO hybridized film being prepared according to the described in any item methods of claim 1-8.
10. being used for water according to the application for the MOFs@f-GO hybridized film that the described in any item methods of claim 1-8 are prepared The separation of middle dyestuff, high price salt and organic phase small molecular.
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CN115945080A (en) * 2023-01-04 2023-04-11 大连理工大学 Method for preparing metal organic framework membrane by using freezing back diffusion technology

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CN110551318B (en) * 2019-08-12 2021-12-03 上海利物盛纳米科技有限公司 Preparation method of graphene-based heat and moisture exchange composite membrane
CN115945080A (en) * 2023-01-04 2023-04-11 大连理工大学 Method for preparing metal organic framework membrane by using freezing back diffusion technology

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