CN111229061A - Porous graphene separation membrane and preparation method thereof - Google Patents
Porous graphene separation membrane and preparation method thereof Download PDFInfo
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- CN111229061A CN111229061A CN202010055265.7A CN202010055265A CN111229061A CN 111229061 A CN111229061 A CN 111229061A CN 202010055265 A CN202010055265 A CN 202010055265A CN 111229061 A CN111229061 A CN 111229061A
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01D—SEPARATION
- B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
- B01D69/02—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor characterised by their properties
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Abstract
The invention discloses a porous graphene separation membrane and a preparation method thereof, wherein the separation membrane comprises a porous substrate and a graphene film attached to the porous substrate, the graphene film is provided with through holes, and the aperture of each through hole is sub-nanometer; the graphene film has a thickness of not more than ten atomic layers, the porous substrate is an insulator, and the surface of the graphene film is charged by chemical functionalization treatment or physical electrification of the separation film, wherein the charge density is 1-6e/nm2(ii) a Selectively charging positive/negative electricity to the surface of the graphene, so that the adsorption capacity of gas molecules on the surface of the graphene and the permeability of the gas molecules in the nano-pores are selectively changed, separation selectivity of the large nano-pores is realized, and finally the performance of the porous graphene separation membrane is improved; the selectivity of the graphene film can be improved without precisely controlling or changing the size of the nano-pores; graphene film surfaceThe electrification is easy to realize, and the operation method is simple; the regulation and control of the selectivity of the graphene film can be realized only by controlling the charge density of the porous graphene separation film.
Description
Technical Field
The invention belongs to the technical field of membrane separation, and particularly relates to a porous graphene separation membrane and a preparation method thereof.
Background
The membrane separation technology has wide application prospect in the field of gas separation, and the existing porous graphene (graphene with nano pores) has ultrahigh permeability as a novel gas separation membrane, and shows outstanding advantages.The basic principle of the separation membrane is based on the screening effect of molecular size, the selectivity of the separation membrane completely depends on the size of a nanopore on a graphene film, and the change of the size of the nanopore on the atomic scale can greatly influence the selectivity of the separation membrane. If the diameter of the nanopore is increased by a few angstroms (10)-10m), the separation selectivity of the porous graphene separation membrane is reduced by many times. For porous graphene gas separation membranes, the biggest challenge at present is to precisely control the size of the nanopores on the graphene thin film so as to produce high-selectivity gas separation. At present, methods for generating the nanopore mainly include electron beam impact, ion impact, chemical corrosion, direct generation in a graphene synthesis process and the like, and the methods are difficult to accurately control the size of the nanopore on an atomic scale. In order to improve the selectivity of the porous graphene separation membrane, people want to accurately control the size of the porous graphene separation membrane in the process of generating the nano-pores. If the technical bias can be overcome, the separation selectivity of the larger nano-pores can be realized, the high-selectivity gas separation of the porous graphene separation membrane can be realized without accurately controlling the size of the nano-pores in the process of generating the nano-pores, so that the problem of accurately controlling the size of the nano-pores is directly solved, and the method has great significance for the development of the porous graphene separation membrane technology.
Disclosure of Invention
In order to solve the problems in the prior art, the invention provides a porous graphene separation membrane and a preparation method thereof, which regulate non-selective large-size nanopores into selective nanopores and directly avoid the harsh requirement on accurate control of the sizes of the nanopores, thereby solving the problem of size control of the nanopores.
In order to achieve the purpose, the invention adopts the technical scheme that the porous graphene separation membrane comprises a porous substrate and a graphene film attached to the porous substrate, the surface of the porous graphene separation membrane is charged, the graphene film is of a porous structure, and the aperture in the porous structure is less than 1 nm; the thickness of the graphene film is not more than ten atomic layers, and the porous substrate is an insulator.
The surface charge density is 1-6e/nm2。
According to the preparation method of the porous graphene separation membrane, the surface of the separation membrane is charged through chemical functionalization treatment or physical electrification.
Carrying out chemical functionalization treatment on the surface of the graphene film, carrying out chemical functionalization treatment on the surface of the graphene film by using polar molecules with charged groups, and then directly transferring the graphene film to a porous substrate to obtain the separation film with charged surface and selectivity.
And (3) directly carrying out chemical functionalization treatment on the surface of the porous substrate by using polar molecules with charged groups, and then transferring the graphene film to the porous substrate after chemical modification treatment to obtain the separation membrane with charged surface and selectivity.
The polar molecules with negative charge groups adopt fatty acid radical, sulfonic acid radical, sulfate radical, amino acid radical, enol radical or keto-sulfonamide polar molecules; the polar molecules with positive charge groups adopt fatty amine radical, aromatic amine radical, quaternary amine radical or pyridine radical polar molecules.
Soaking the graphene film in a polar molecular solution with the pH value of 7-12 at 10-80 ℃ for 1-48h, taking out the soaked graphene film, washing the graphene film with deionized water, and covering the charged graphene film on a porous substrate to obtain the porous graphene separation membrane with the charged surface and selectivity, wherein the solvent of the polar molecular solution is an alcohol solvent.
Soaking the porous substrate in a polar molecular solution with the pH value of 7-12 at the temperature of 10-80 ℃ for 1-48h, taking out the soaked porous substrate, washing the porous substrate with deionized water, and coating a graphene film on the porous substrate to obtain the porous graphene separation film with charged surface and selectivity, wherein the solvent of the polar molecular solution is an alcohol solvent.
The graphene film is directly connected with the charged electrode to obtain the porous graphene separation membrane with charged surface and selectivity.
The electrode is a needle electrode.
Compared with the prior art, the invention has at least the following beneficial effects: the surface of the porous substrate and the graphene film attached to the porous substrate are charged, the graphene film is of a porous structure, and the aperture of the porous structure is smaller than 1 nm; only molecules smaller than the pore diameter can pass through the separation membrane, the thickness of the graphene film is not more than ten atomic layers, the porous substrate is an insulator, the surface of the porous substrate is provided with charges, and the adsorption capacity of gas molecules on the surface of the graphene and the permeability of nanopores are selectively changed by selectively charging positive/negative charges on the surface of the graphene, so that the separation selectivity of the larger nanopores occurs, and the performance of the porous graphene separation membrane is finally improved.
The method can improve the selectivity of the graphene film without accurately controlling or changing the size of the nano-pores; the surface electrification of the graphene film is easy to realize, and the operation method is simple; the selective regulation and control of the graphene film can be realized only by controlling the charge density of surface electrification, the process control variables are few, and the method is easy to realize.
Drawings
Fig. 1 is a schematic view of chemical functionalization of graphene surface;
FIG. 2 is a schematic view of a chemical functionalization process on the surface of a porous substrate;
FIG. 3 is a schematic view of a graphene thin film connection electrode;
FIG. 4 is a graph showing the effect of surface charge density of a separation membrane on the performance of the separation membrane;
Detailed Description
The present invention will be described in further detail with reference to the accompanying drawings.
A porous graphene separation membrane comprises a porous substrate and a graphene film 2 attached to the porous substrate 1, the surface of the porous graphene separation membrane is charged, the graphene film 2 is of a porous structure, and the aperture of the porous structure is smaller than 1 nm; the thickness of the graphene film 2 is not more than ten atomic layers, and the porous substrate 1 is an insulator; the surface charge density is 1-6e/nm2。
The preparation method of the porous graphene separation membrane with the charged surface comprises the steps of carrying out chemical functionalization treatment or physical electrification on the separation membrane to charge the surface of the separation membrane, wherein the charge density is 1-6e/nm2。
Referring to fig. 1, a surface of a graphene film 2 is chemically functionalized, and a polar molecule 3 having a charged group is used to chemically functionalize the surface of the graphene film 2, and then the graphene film is directly transferred to a porous substrate 1, so as to obtain a separation membrane with a charged surface and selectivity.
Referring to fig. 2, a polar molecule 3 having a charged group is used to directly perform a chemical functionalization treatment on the surface of the porous substrate 1, and then the graphene thin film 2 is transferred to the porous substrate 1 after the chemical modification treatment, so as to obtain a separation membrane having a charged surface and selectivity.
The polar molecule 3 with the negative charge group adopts a fatty acid radical, a sulfonic acid radical, a sulfate radical, an amino acid radical, an enol radical or a keto-sulfonamide radical polar molecule; the polar molecule 3 with positive charge group adopts aliphatic amine radical, aromatic amine radical, quaternary amine radical or pyridine radical polar molecule.
Soaking the graphene film 2 in a polar molecular solution with the pH value of 7-12 at 10-80 ℃ for 1-48h, then taking out the soaked graphene film 2, washing the graphene film with deionized water, and covering the charged graphene film 2 on the porous substrate 1 to obtain the porous graphene separation film with charged surface and selectivity, wherein the solvent of the polar molecular solution is an alcohol solvent.
Soaking the porous substrate 1 in a polar molecular solution with the pH value of 7-12 at 10-80 ℃ for 1-48h, taking out the soaked porous substrate 1, washing with deionized water, and covering the porous substrate 1 with the graphene film 2 to obtain the porous graphene separation membrane with charged surface and selectivity, wherein the solvent of the polar molecular solution is an alcohol solvent.
Referring to fig. 3, the graphene film 2 is directly connected to the charged electrode 4, so as to obtain a porous graphene separation membrane with a charged surface and selectivity.
The basic principle of the method is that the adsorption capacity of gas molecules on the surface of graphene is improved by charging the surface of the graphene, so that the permeability of the molecules in graphene nanopores is improved; by selectively charging positive electricity or negative electricity to the surface of the graphene, the adsorption capacity of gas molecules on the surface of the graphene and the permeability of the gas molecules in the nano holes can be selectively changed, so that the selectivity of the nano holes of the graphene is improved, and finally the performance of the porous graphene separation membrane is improved. Since the permeation rate of a gas molecule in a graphene nanopore is directly related to the adsorption strength of the gas molecule on the surface, the stronger the adsorption capacity of the gas molecule is, the faster the gas molecule diffuses through the nanopore through the surface, and the higher the permeation rate of the porous graphene separation membrane. In order to realize the electrification of the surface of the graphene, the invention provides two methods for a composite separation membrane consisting of a substrate and porous graphene, wherein the method comprises the steps of performing surface chemical functionalization treatment, connecting electrodes through the separation membrane and performing electrification treatment; the chemical functionalization treatment has two ways, namely, the chemical functionalization treatment is carried out on the surface of the porous substrate supporting the graphene film 2, and the chemical functionalization treatment is directly carried out on the surface of the graphene film 2.
Fig. 1 is a schematic diagram of a graphene film 2 directly subjected to chemical functionalization treatment, the graphene film 2 directly contacts with a porous substrate, and the porous substrate 1 is used for supporting the graphene film 2; the surface of the graphene film 2 is chemically modified by the polar molecules 3 with charged groups, so that the surface of the separation membrane is charged, and the aim of improving the selectivity of the porous graphene separation membrane is finally achieved. There are many choices of polar molecules having charged groups, for example, polar molecules having negatively charged groups including polar molecules such as fatty acid groups, sulfonic acid groups, sulfuric acid ester groups, amino acid groups, enol groups, and keto-sulfonamides, the present invention is carried out according to the above scheme, with specific parameters as shown in table 1,
table 1 process parameters for chemical functionalization of graphene thin film 2
| Examples | Temperature of | pH value | Time of day | |
| 1 | 10 | 10 | 48 | |
| 2 | 20 | 9 | 25 | Ketosulfonamides |
| 3 | 25 | 7 | 30 | |
| 4 | 30 | 12 | 20 | Fatty amine radical |
| 5 | 45 | 8 | 20 | Sulfonic acid radical |
| 6 | 55 | 11 | 15 | Sulfonic acid radical |
| 7 | 60 | 9 | 10 | Ketosulfonamides |
| 8 | 75 | 12 | 5 | Fatty acid radicals |
| 9 | 80 | 10 | 2 | Aromatic amine radical |
| 10 | 80 | 12 | 1 | Pyridine radical |
Charging of the porous graphene separation membrane is achieved by performing chemical functionalization treatment on the surface of the porous substrate 1, and fig. 2 is a schematic diagram of performing chemical functionalization treatment on the surface of the porous substrate; firstly, carrying out chemical modification treatment on the surface of a porous substrate 1 by using polar molecules 3 with charged groups, and then transferring a graphene film 2 to the porous substrate 1 after the chemical modification treatment to realize charging of the porous graphene separation film. The process parameters for the chemical functionalization of the surface of the porous substrate 1 were as described in table 1.
FIG. 3 is a schematic diagram of a graphene film 2 connecting electrode, which is directly connected to the graphene film 2 and a power supply electrode 4, and positive/negative charges are dispersed after electrificationIn the graphene film 2, charging of the porous graphene separation film is finally achieved. In order to ensure that the charges are uniformly dispersed in the graphene film 2, the porous substrate 1 is made of an insulating material. According to the invention, the polarity and charge density of the charged graphene film 2 are controlled by adopting the needle electrode and adjusting the connection mode of the anode and the cathode of the diode in the circuit and the pressurizing time of the electrode. When the performance of the porous graphene separation membrane is optimized, the charge density of the graphene film 2 is low, and the charge density reaches e/nm2In order of magnitude, the example of the graphene film with negative charge is shown in fig. 3.
Analyzing the influence of surface charge on the performance of the porous graphene separation membrane, the invention adopts molecular dynamics simulation to obtain the permeability and selectivity of the porous graphene membrane under different surface charge densities, as shown in figure 4, the porous graphene is used for separating CO2/N2The selectivity of the mixed molecule increases with the increase of the negative charge density of the porous graphene film, CO2The permeability of the molecule increases gradually and N2The permeability of the molecules gradually decreases. Notably, for CO2/N2Separation of mixed molecules to increase CO2The permeability of the molecule further increases the selectivity, so that the porous graphene membrane 2 is negatively charged; for separating other mixed molecules of different types, the positive and negative properties of the surface charge are selected according to actual conditions. Therefore, the selectivity of the graphene nanopore can be improved through the electrification of the porous graphene membrane, and the performance of the porous graphene separation membrane is finally improved. In conclusion, the present invention achieves the intended object to improve the selectivity of a porous graphene separation membrane through surface charging.
Claims (10)
1. The porous graphene separation membrane is characterized by comprising a porous substrate (1) and a graphene film (2) attached to the porous substrate (1), wherein the surface of the porous graphene separation membrane is charged, the graphene film (2) is of a porous structure, and the aperture of the porous structure is smaller than 1 nm; the thickness of the graphene film (2) is not more than ten atomic layers, and the porous substrate (1) is an insulator.
2. The porous graphite of claim 1An olefin separation membrane characterized in that it has a surface charge density of 1 to 6e/nm2。
3. A method for preparing the porous graphene separation membrane according to claim 1 or 2, wherein the surface of the separation membrane is electrically charged by chemical functionalization treatment or physical electrification.
4. The preparation method of the porous graphene separation membrane according to claim 3, wherein the surface of the graphene thin film (2) is chemically functionalized, the surface of the graphene thin film (2) is chemically functionalized by the polar molecule (3) having the charged group, and then the graphene thin film is directly transferred to the porous substrate (1) to obtain the separation membrane with charged surface and selectivity.
5. The preparation method of the porous graphene separation membrane according to claim 3, wherein the surface of the porous substrate (1) is directly subjected to chemical functionalization treatment by using the polar molecule (3) with a charged group, and then the graphene thin film (2) is transferred to the porous substrate (1) after the chemical modification treatment, so as to obtain the separation membrane with charged surface and selectivity.
6. The method for preparing the porous graphene separation membrane according to claim 4 or 5, wherein the polar molecules (3) with negative charge groups are fatty acid radical, sulfonate, sulfate radical, amino acid radical, enol radical or keto-sulfonamide radical polar molecules; the polar molecule (3) with positive charge group adopts aliphatic amine radical, aromatic amine radical, quaternary amine radical or pyridine radical.
7. The preparation method of the porous graphene separation membrane according to claim 6, wherein the graphene film (2) is soaked in a polar molecular solution with the pH value of 7-12 at 10-80 ℃ for 1-48h, then the soaked graphene film (2) is taken out, washed with deionized water, and the charged graphene film (2) is coated on the porous substrate (1), so that the porous graphene separation membrane with the charged surface and the selectivity is obtained, wherein a solvent of the polar molecular solution is an alcohol solvent.
8. The preparation method of the porous graphene separation membrane according to claim 6, wherein the porous substrate (1) is soaked in a polar molecular solution with a pH value of 7-12 at 10-80 ℃ for 1-48h, then the soaked porous substrate (1) is taken out, washed with deionized water, and then the graphene thin film (2) is coated on the porous substrate (1) to obtain the porous graphene separation membrane with a charged surface and selectivity, wherein a solvent of the polar molecular solution is an alcohol solvent.
9. The preparation method of the porous graphene separation membrane according to claim 3, wherein the graphene film (2) is directly connected with the charged electrode (4) to obtain the porous graphene separation membrane with charged surface and selectivity.
10. The method for preparing a porous graphene separation membrane according to claim 9, wherein the electrode (4) is a needle electrode.
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| CN112897643A (en) * | 2021-01-29 | 2021-06-04 | 西安交通大学 | Reverse osmosis seawater desalination device based on graphene oxide separation membrane and desalination method thereof |
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