CN112657345A - Macroscopic film with molecular separation performance - Google Patents
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- CN112657345A CN112657345A CN202011448675.4A CN202011448675A CN112657345A CN 112657345 A CN112657345 A CN 112657345A CN 202011448675 A CN202011448675 A CN 202011448675A CN 112657345 A CN112657345 A CN 112657345A
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- 239000006185 dispersion Substances 0.000 claims abstract description 60
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 38
- 239000000725 suspension Substances 0.000 claims abstract description 27
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- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 claims abstract description 6
- 150000001768 cations Chemical class 0.000 claims abstract description 5
- 238000012986 modification Methods 0.000 claims abstract description 5
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- 239000001110 calcium chloride Substances 0.000 claims abstract description 4
- 229910001628 calcium chloride Inorganic materials 0.000 claims abstract description 4
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 claims abstract description 3
- 229910009523 YCl3 Inorganic materials 0.000 claims abstract description 3
- 229910017053 inorganic salt Inorganic materials 0.000 claims abstract description 3
- 229910001629 magnesium chloride Inorganic materials 0.000 claims abstract description 3
- 239000001103 potassium chloride Substances 0.000 claims abstract description 3
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical group [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 16
- 238000000034 method Methods 0.000 claims description 8
- 239000011780 sodium chloride Substances 0.000 claims description 8
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 claims description 4
- ZCCIPPOKBCJFDN-UHFFFAOYSA-N calcium nitrate Chemical compound [Ca+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ZCCIPPOKBCJFDN-UHFFFAOYSA-N 0.000 claims description 4
- 238000011085 pressure filtration Methods 0.000 claims description 4
- 229910021380 Manganese Chloride Inorganic materials 0.000 claims description 2
- GLFNIEUTAYBVOC-UHFFFAOYSA-L Manganese chloride Chemical compound Cl[Mn]Cl GLFNIEUTAYBVOC-UHFFFAOYSA-L 0.000 claims description 2
- 239000011565 manganese chloride Substances 0.000 claims description 2
- 238000001914 filtration Methods 0.000 abstract description 17
- 239000012046 mixed solvent Substances 0.000 abstract description 12
- IDGUHHHQCWSQLU-UHFFFAOYSA-N ethanol;hydrate Chemical compound O.CCO IDGUHHHQCWSQLU-UHFFFAOYSA-N 0.000 abstract description 5
- NJSUFZNXBBXAAC-UHFFFAOYSA-N ethanol;toluene Chemical compound CCO.CC1=CC=CC=C1 NJSUFZNXBBXAAC-UHFFFAOYSA-N 0.000 abstract description 5
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- 238000005303 weighing Methods 0.000 description 22
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- 238000009210 therapy by ultrasound Methods 0.000 description 15
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- 229910021641 deionized water Inorganic materials 0.000 description 11
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- 230000004907 flux Effects 0.000 description 8
- 239000012466 permeate Substances 0.000 description 7
- 239000002904 solvent Substances 0.000 description 7
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 239000000126 substance Substances 0.000 description 5
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 4
- QARVLSVVCXYDNA-UHFFFAOYSA-N bromobenzene Chemical compound BrC1=CC=CC=C1 QARVLSVVCXYDNA-UHFFFAOYSA-N 0.000 description 4
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 4
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Chemical compound C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 description 4
- 238000005265 energy consumption Methods 0.000 description 4
- 239000011550 stock solution Substances 0.000 description 4
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000011148 porous material Substances 0.000 description 3
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
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- 238000005516 engineering process Methods 0.000 description 2
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- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 2
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- 238000005481 NMR spectroscopy Methods 0.000 description 1
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- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
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- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
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- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 238000004611 spectroscopical analysis Methods 0.000 description 1
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Abstract
The invention discloses a macroscopic film with molecular separation performance, which is prepared by dispersing graphene oxide in water to form graphene oxide dispersion liquid, and then adding KCl and CaCl2、MgCl2、YCl3And (3) carrying out cation modification on the modified suspension by using inorganic salt as a modifier, and filtering the modified suspension under reduced pressure to obtain the macroscopic film. The preparation method of the macroscopic film is simple, the thickness, the size and the shape of the macroscopic film can be adjusted by changing the dosage of raw materials, the shape and the size of the reduced pressure filtering device and the like, and the adjusting mode is simple. The film has obvious separation effect in separating miscible mixed solvents such as ethanol-water, ethanol-toluene and the like, and has good application prospect in the related fields of environmental wastewater treatment and the like.
Description
Technical Field
The invention relates to a macroscopic film which is constructed by nano-structure elements and can separate miscible mixed solvents.
Background
A membrane is a functional material that enables selective separation of multi-component substances. In recent years, inorganic thin film materials have attracted more and more attention because, firstly, the process of separating mixed components by using an inorganic thin film belongs to a typical physical separation process, and no chemical additive is required to be added in the separation process, so that not only can the product be prevented from being polluted, but also the stability of the structure and properties of the thin film can be protected. And secondly, the process of membrane separation generally only needs to be carried out at normal temperature, so that the loss of effective components is low, the energy consumption required by the separation process is extremely low, and compared with the traditional freeze concentration method or evaporation concentration method, the energy consumption required by the membrane separation process is only 1/3-1/8 of the former. And thirdly, the process of the membrane separation is simple in process and easy to operate and automatically control.
Based on the many advantages of the membrane separation techniques described above, membrane separation processes have now gained widespread acceptance and interest in countries throughout the world. Especially, under the current situation of deteriorating ecological environment and severe shortage of resources and energy, the membrane separation technology is more important, so that how to design and prepare a separation membrane with high selectivity, high stability and high flux has become one of the hot spots of research in 21 st century, so that scientists have pointed out: who mastered the membrane technology and who mastered the tomorrow of the chemical industry!
In general, the principle of membrane separation process is based on the molecular size of the separated components and the pore size of the membrane, molecules with size smaller than the pore size of the membrane permeate the membrane, while molecules with size larger than the pore size of the membrane cannot permeate the membrane, i.e. molecular sieve effect. However, it is due to this principle that the membrane separation process also has certain limitations, such as inefficient separation of two components of close molecular size. To overcome this drawback and further improve the separation performance of the membrane, a new membrane must be designed based on different principles.
Graphene oxide is an ideal structural element for preparing a thin film material as a natural two-dimensional structure. The various oxygen-containing groups (hydroxyl, carboxyl and epoxy) contained in the sheet layer and at the edge of the sheet layer enable the graphene oxide to have relatively active chemical properties, so that the graphene oxide can be easily chemically modified. In addition, the large pi system formed by the special six-membered ring structure has high electron cloud density and is easy to react with external ions with opposite electric properties. These unique properties all lead to the excellent potential of graphene oxide in the field of thin film separation.
Disclosure of Invention
The invention aims to provide a macroscopic film capable of realizing the separation of molecules of a mutual-soluble mixed solvent under the condition of low energy consumption.
In order to achieve the above object, the present invention provides a macroscopic membrane with molecular separation performance, which is prepared by the following steps: and dispersing graphene oxide in water to form a graphene oxide dispersion liquid, then carrying out cation modification by using an inorganic salt as a modifier, and carrying out reduced pressure filtration on the suspension after cation modification to obtain the macroscopic film.
In the graphene oxide dispersion liquid, the concentration of the graphene oxide is 0.05-5 mg/mL, and the preferred concentration of the graphene oxide is 0.5-1.5 mg/mL.
The modifier is NaCl, KCl, CaCl2、Ca(NO3)2、MgCl2、MnCl2、YCl3In any of the above methods, the concentration of the modifier in the dispersion is controlled to be 0.01 to 5mol/L, and preferably 0.1 to 1 mol/L.
The pressure of the reduced pressure filtration is 0.01 to 0.099 MPa.
The thickness of the macro film is 1 to 1000 μm.
The invention has the following beneficial effects:
the raw materials used by the macroscopic film are cheap and easy to obtain, the cost is low, the preparation process is simple, the energy consumption is low, the thickness, the size and the shape of the macroscopic film can be adjusted by changing the consumption of the raw materials, the shape and the size of the reduced pressure filtering device and the like, and the adjusting mode is simple. The obtained film has good physical and chemical stability, shows different permeation behaviors to various common solvents, has excellent separation performance in the separation aspect of mutually soluble mixed solvent molecules, has obvious separation effect in the separation of mutually soluble mixed solvents such as ethanol-water, ethanol-toluene and the like, and has good application prospect in the related fields of separation engineering, sewage treatment and the like.
Drawings
FIG. 1 shows Na in example 1+And (3) a photo of the modified graphene oxide macroscopic film and a scanning electron microscope picture of the cross section.
FIG. 2 is a graph comparing flux levels of the macroscopic films prepared in examples 1, 4, 7, and 10 for different solvents.
FIG. 3 shows Na in example 1+And comparing the modified graphene oxide macroscopic film with different permeation fluxes of the solvent.
FIG. 4 shows Ca in example 42+And comparing the modified graphene oxide macroscopic film with different permeation fluxes of the solvent.
FIG. 5 is Mg in example 72+And comparing the modified graphene oxide macroscopic film with different permeation fluxes of the solvent.
FIG. 6 shows Y in example 103+And comparing the modified graphene oxide macroscopic film with different permeation fluxes of the solvent.
FIG. 7 shows Na in example 1+And (3) analyzing the content of ethanol in the stock solution and the filtrate before and after the modified graphene oxide macroscopic film is used for separating the ethanol-water mixed solvent.
FIG. 8 shows Na in example 1+And (3) analyzing the content of ethanol in the stock solution and the filtrate before and after the modified graphene oxide macroscopic film is used for separating the ethanol-toluene mixed solvent.
Detailed Description
The invention will be further described in detail with reference to the following figures and examples, but the scope of the invention is not limited to these examples.
Example 1
Weighing 0.25g of solid graphene oxide, adding the solid graphene oxide into a beaker filled with 500mL of deionized water, stirring to primarily disperse the added solid graphene oxide in the water, and performing ultrasonic treatment on the solid graphene oxide for 0.5 hour by using a KH5200E ultrasonic cleaning instrument after the stirring is finished to further enable the graphene oxide to be further subjected to ultrasonic treatmentUniformly dispersing in water to obtain a graphene oxide dispersion liquid with the concentration of 0.5 mg/mL. Weighing 80mL of the graphene oxide dispersion liquid, adding NaCl into the graphene oxide dispersion liquid under continuous stirring to enable the concentration of the NaCl in the dispersion liquid to be 0.250mol/L, and then carrying out ultrasonic treatment on the graphene oxide dispersion liquid for 0.5 hour by using a KH5200E type ultrasonic cleaning instrument to obtain a uniformly dispersed suspension liquid. Filtering the obtained suspension under reduced pressure of 0.09MPa to obtain Na+Modified graphene oxide macroscopic film (noted as Na)+-GO thin films).
Example 2
Weighing 0.5g of solid graphene oxide, adding the solid graphene oxide into a beaker filled with 500mL of deionized water, stirring to primarily disperse the added solid graphene oxide in water, and performing ultrasonic treatment on the solid graphene oxide for 0.5 hour by using a KH5200E type ultrasonic cleaning instrument after the stirring is finished to further uniformly disperse the solid graphene oxide in the water to obtain a graphene oxide dispersion liquid with the concentration of 1.0 mg/mL. Weighing 80mL of the graphene oxide dispersion liquid, adding NaCl into the graphene oxide dispersion liquid under continuous stirring to enable the concentration of the NaCl in the dispersion liquid to be 0.250mol/L, and then carrying out ultrasonic treatment on the graphene oxide dispersion liquid for 0.5 hour by using a KH5200E type ultrasonic cleaning instrument to obtain a uniformly dispersed suspension liquid. Filtering the obtained suspension under reduced pressure of 0.09MPa to obtain Na+Modified graphene oxide macroscopic film (noted as Na)+-GO thin films).
Example 3
Weighing 1.0g of solid graphene oxide, adding the solid graphene oxide into a beaker filled with 500mL of deionized water, stirring to primarily disperse the added solid graphene oxide in water, and performing ultrasonic treatment on the solid graphene oxide for 0.5 hour by using a KH5200E type ultrasonic cleaning instrument after the stirring is finished to further uniformly disperse the solid graphene oxide in the water to obtain a graphene oxide dispersion liquid with the concentration of 2.0 mg/mL. Weighing 80mL of the graphene oxide dispersion liquid, adding NaCl into the graphene oxide dispersion liquid under continuous stirring to enable the concentration of the NaCl in the dispersion liquid to be 0.50mol/L, and then carrying out ultrasonic treatment on the graphene oxide dispersion liquid for 0.5 hour by using a KH5200E type ultrasonic cleaning instrument to obtain a uniformly dispersed suspension liquid. Filtering the obtained suspension under reduced pressure of 0.09MPa to obtain Na+Modified graphene oxide macroscopic film (noted as Na)+-GO thin films).
Example 4
Weighing 0.25g of solid graphene oxide, adding the solid graphene oxide into a beaker filled with 500mL of deionized water, stirring to primarily disperse the added solid graphene oxide in water, and performing ultrasonic treatment on the solid graphene oxide for 0.5 hour by using a KH5200E type ultrasonic cleaning instrument after the stirring is finished to further uniformly disperse the solid graphene oxide in the water to obtain a graphene oxide dispersion liquid with the concentration of 0.5 mg/mL. Weighing 80mL of the graphene oxide dispersion liquid, and adding CaCl into the graphene oxide dispersion liquid under continuous stirring2Allowing CaCl to be present in the dispersion2Was adjusted to a concentration of 0.250mol/L, and then sonicated for 0.5 hour using an ultrasonic cleaning apparatus of KH5200E type to give a uniformly dispersed suspension. Filtering the obtained suspension under reduced pressure of 0.09MPa to obtain Ca2+Modified graphene oxide macroscopic film (noted as Ca)2 +-GO)。
Example 5
Weighing 0.5g of solid graphene oxide, adding the solid graphene oxide into a beaker filled with 500mL of deionized water, stirring to primarily disperse the added solid graphene oxide in water, and performing ultrasonic treatment on the solid graphene oxide for 0.5 hour by using a KH5200E type ultrasonic cleaning instrument after the stirring is finished to further uniformly disperse the solid graphene oxide in the water to obtain a graphene oxide dispersion liquid with the concentration of 1.0 mg/mL. Weighing 80mL of the graphene oxide dispersion liquid, and adding CaCl into the graphene oxide dispersion liquid under continuous stirring2Allowing CaCl to be present in the dispersion2Was adjusted to a concentration of 0.250mol/L, and then sonicated for 0.5 hour using an ultrasonic cleaning apparatus of KH5200E type to give a uniformly dispersed suspension. Filtering the obtained suspension under reduced pressure of 0.09MPa to obtain Ca2+Modified graphene oxide macroscopic film (noted as Ca)2 +-GO)。
Example 6
Weighing 1.0g of solid graphene oxide, adding the solid graphene oxide into a beaker filled with 500mL of deionized water, stirring to primarily disperse the added solid graphene oxide in water, and performing ultrasonic treatment on the solid graphene oxide for 0.5 hour by using a KH5200E type ultrasonic cleaning instrument after the stirring is finished to further uniformly disperse the solid graphene oxide in the water to obtain a graphene oxide dispersion liquid with the concentration of 2.0 mg/mL. Weighing 80mL of the graphene oxide dispersion liquid, and adding CaCl into the graphene oxide dispersion liquid under continuous stirring2Dispersing the dispersion liquidMiddle CaCl2Was adjusted to a concentration of 0.50mol/L, and then sonicated for 0.5 hour using an ultrasonic cleaning apparatus of KH5200E type to give a uniformly dispersed suspension. Filtering the obtained suspension under reduced pressure of 0.09MPa to obtain Ca2+Modified graphene oxide macroscopic film (noted as Ca)2 +-GO)。
Example 7
Weighing 0.25g of solid graphene oxide, adding the solid graphene oxide into a beaker filled with 500mL of deionized water, stirring to primarily disperse the added solid graphene oxide in water, and performing ultrasonic treatment on the solid graphene oxide for 0.5 hour by using a KH5200E type ultrasonic cleaning instrument after the stirring is finished to further uniformly disperse the solid graphene oxide in the water to obtain a graphene oxide dispersion liquid with the concentration of 0.5 mg/mL. Measuring 80mL of the graphene oxide dispersion liquid, and adding MgCl into the graphene oxide dispersion liquid under continuous stirring2Allowing MgCl to stand in the dispersion2Was adjusted to a concentration of 0.250mol/L, and then sonicated for 0.5 hour using an ultrasonic cleaning apparatus of KH5200E type to give a uniformly dispersed suspension. Filtering the obtained suspension under reduced pressure of 0.09MPa to obtain Mg2+Modified graphene oxide macroscopic film (noted as Mg)2 +-GO)。
Example 8
Weighing 0.5g of solid graphene oxide, adding the solid graphene oxide into a beaker filled with 500mL of deionized water, stirring to primarily disperse the added solid graphene oxide in water, and performing ultrasonic treatment on the solid graphene oxide for 0.5 hour by using a KH5200E type ultrasonic cleaning instrument after the stirring is finished to further uniformly disperse the solid graphene oxide in the water to obtain a graphene oxide dispersion liquid with the concentration of 1.0 mg/mL. Measuring 80mL of the graphene oxide dispersion liquid, and adding MgCl into the graphene oxide dispersion liquid under continuous stirring2Allowing MgCl to stand in the dispersion2Was adjusted to a concentration of 0.250mol/L, and then sonicated for 0.5 hour using an ultrasonic cleaning apparatus of KH5200E type to give a uniformly dispersed suspension. Filtering the obtained suspension under reduced pressure of 0.09MPa to obtain Mg2+Modified graphene oxide macroscopic film (noted as Mg)2 +-GO)。
Example 9
Weighing 1.0g of solid graphene oxide, and adding the solid graphene oxide into a beaker filled with 500mL of deionized waterAnd stirring to primarily disperse the added solid graphene oxide in water, and performing ultrasonic treatment on the solid graphene oxide for 0.5 hour by using a KH5200E ultrasonic cleaning instrument after the stirring is finished to further uniformly disperse the graphene oxide in the water to obtain a graphene oxide dispersion liquid with the concentration of 2.0 mg/mL. Measuring 80mL of the graphene oxide dispersion liquid, and adding MgCl into the graphene oxide dispersion liquid under continuous stirring2Allowing MgCl to stand in the dispersion2Was adjusted to a concentration of 0.50mol/L, and then sonicated for 0.5 hour using an ultrasonic cleaning apparatus of KH5200E type to give a uniformly dispersed suspension. Filtering the obtained suspension under reduced pressure of 0.09MPa to obtain Mg2+Modified graphene oxide macroscopic film (noted as Mg)2 +-GO)。
Example 10
Weighing 0.25g of solid graphene oxide, adding the solid graphene oxide into a beaker filled with 500mL of deionized water, stirring to primarily disperse the added solid graphene oxide in water, and performing ultrasonic treatment on the solid graphene oxide for 0.5 hour by using a KH5200E type ultrasonic cleaning instrument after the stirring is finished to further uniformly disperse the solid graphene oxide in the water to obtain a graphene oxide dispersion liquid with the concentration of 0.5 mg/mL. Weighing 80mL of the graphene oxide dispersion liquid, and adding YCl into the graphene oxide dispersion liquid under continuous stirring3Making YCl in the dispersion liquid3Was adjusted to a concentration of 0.250mol/L, and then sonicated for 0.5 hour using an ultrasonic cleaning apparatus of KH5200E type to give a uniformly dispersed suspension. Filtering the obtained suspension under reduced pressure of 0.09MPa to obtain Y3+Modified graphene oxide macroscopic film (denoted as Y)3+-GO)。
Example 11
Weighing 0.5g of solid graphene oxide, adding the solid graphene oxide into a beaker filled with 500mL of deionized water, stirring to primarily disperse the added solid graphene oxide in water, and performing ultrasonic treatment on the solid graphene oxide for 0.5 hour by using a KH5200E type ultrasonic cleaning instrument after the stirring is finished to further uniformly disperse the solid graphene oxide in the water to obtain a graphene oxide dispersion liquid with the concentration of 1.0 mg/mL. Weighing 80mL of the graphene oxide dispersion liquid, and adding YCl into the graphene oxide dispersion liquid under continuous stirring3Making YCl in the dispersion liquid3Is 0.250mol/L, and then is subjected to ultrasonic cleaning for 0.5 hour by using a KH5200E ultrasonic cleaner to obtain a dispersionAnd (4) uniformly suspending the solution. Filtering the obtained suspension under reduced pressure of 0.09MPa to obtain Y3+Modified graphene oxide macroscopic film (denoted as Y)3+-GO)。
Example 12
Weighing 1.0g of solid graphene oxide, adding the solid graphene oxide into a beaker filled with 500mL of deionized water, stirring to primarily disperse the added solid graphene oxide in water, and performing ultrasonic treatment on the solid graphene oxide for 0.5 hour by using a KH5200E type ultrasonic cleaning instrument after the stirring is finished to further uniformly disperse the solid graphene oxide in the water to obtain a graphene oxide dispersion liquid with the concentration of 2.0 mg/mL. Weighing 80mL of the graphene oxide dispersion liquid, and adding YCl into the graphene oxide dispersion liquid under continuous stirring3Making YCl in the dispersion liquid3Was adjusted to a concentration of 0.50mol/L, and then sonicated for 0.5 hour using an ultrasonic cleaning apparatus of KH5200E type to give a uniformly dispersed suspension. Filtering the obtained suspension under reduced pressure of 0.09MPa to obtain Y3+Modified graphene oxide macroscopic film (denoted as Y)3+-GO)。
In order to prove the beneficial effects of the invention, the inventor carries out various characterization and performance tests on the macroscopic film prepared by the embodiment, and specific results are shown in fig. 1-6. As can be seen from fig. 1, the obtained macroscopic thin film is a layered structure constructed by GO nanosheets. The results in fig. 2 show that methanol, ethanol, propanol and butanol hardly permeate the macroscopic membrane, aromatic solvents can permeate the macroscopic membrane (benzene, toluene, xylene, diphenyl ether, chlorobenzene, bromobenzene) at a certain flux, and solvents with lone electron pairs such as acetone, acetonitrile, dichloromethane and ethyl acetate can permeate the macroscopic membrane unimpeded. The results of fig. 3 to 6 also demonstrate the rule in fig. 2 that alcohol solvents (methanol, ethanol, propanol, butanol) hardly permeate the macroscopic thin film, while aromatic solvents can permeate the macroscopic thin film (benzene, toluene, xylene, diphenyl ether, chlorobenzene, bromobenzene) with a large flux.
The inventors further performed a filtration separation experiment using the macro-film prepared in examples 1, 4, 7, and 10 on a mixed solvent of ethanol-water and a mixed solvent of ethanol-toluene (ethanol volume content is 50%), and performed a filtration separation experiment on the stock solution before and after the separation and the filtrationThe content of ethanol in the solution was analyzed. Wherein, for the ethanol-water mixed solvent, in the separation process, a certain volume of filtrate is taken for weighing, the density of the filtrate is calculated, and a standard curve is checked to obtain the corresponding ethanol content; subjecting the stock solution before separation and the collected filtrate to nuclear magnetic resonance hydrogen spectroscopy (for ethanol-toluene mixed solvent) ((1H-NMR), the results are shown in fig. 7 and fig. 8. As can be seen from fig. 7, the ethanol content before separation was 50%, the density of the filtrate after separation using the macro membrane of example 1 was 0.9888, and the corresponding ethanol content in the filtrate was reduced to 4.5% by looking up the standard curve; the results in FIG. 8 show that the residual ethanol content in the filtrate after separation using the macro-membrane of example 1 decreased from 50% before separation to 3.5% in the filtrate. The separation performance of the macro films prepared in examples 4, 7, 10 is similar to that of the macro film of example 1. The macroscopic film of the invention can play a more obvious separation role on the mixed solvent.
Claims (8)
1. A macroscopic film having molecular separation properties, characterized in that said macroscopic film is prepared by a method comprising: and dispersing graphene oxide in water to form a graphene oxide dispersion liquid, then carrying out cation modification by using an inorganic salt as a modifier, and carrying out reduced pressure filtration on the suspension after cation modification to obtain the macroscopic film.
2. The macroscopic film having molecular separation properties of claim 1, wherein: in the graphene oxide dispersion liquid, the concentration of graphene oxide is 0.05-5 mg/mL.
3. The macroscopic film having molecular separation properties of claim 2, wherein: in the graphene oxide dispersion liquid, the concentration of graphene oxide is 0.5-1.5 mg/mL.
4. The macroscopic film having a molecular separation property of any one of claims 1 to 3, wherein: the modifier is NaCl, KCl, CaCl2、Ca(NO3)2、MgCl2、MnCl2、YCl3Any one of them.
5. The macroscopic film having molecular separation properties of claim 4, wherein: the concentration of the modifier in the dispersion liquid is controlled to be 0.01-5 mol/L.
6. The macroscopic film having molecular separation properties of claim 5, wherein: the concentration of the modifier in the dispersion liquid is controlled to be 0.1-1 mol/L.
7. The macroscopic film having molecular separation properties of claim 1, wherein: the pressure of the reduced pressure filtration is 0.01-0.099 MPa.
8. The macroscopic film having molecular separation properties of claim 1, wherein: the thickness of the macroscopic film is 1-1000 mu m.
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| CN109890488A (en) * | 2016-05-20 | 2019-06-14 | 日东电工株式会社 | Permselective graphene oxide membrane |
| CN110573240A (en) * | 2017-03-01 | 2019-12-13 | 日东电工株式会社 | selectively permeable graphene oxide membranes |
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| CN105727758A (en) * | 2016-04-13 | 2016-07-06 | 天津大学 | Preparation method and application of graphene oxide composite membrane |
| CN109890488A (en) * | 2016-05-20 | 2019-06-14 | 日东电工株式会社 | Permselective graphene oxide membrane |
| CN110573240A (en) * | 2017-03-01 | 2019-12-13 | 日东电工株式会社 | selectively permeable graphene oxide membranes |
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