CN113772619B - Microporous channel membrane and preparation method thereof - Google Patents
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Abstract
The invention discloses a preparation method of a microporous channel membrane, which comprises the steps of preparing an MXene precursor aqueous solution, taking 0.25-5 mL of chitosan aqueous solution with the mass concentration of 3-5 mg/mL, and fully mixing the chitosan aqueous solution with 5-83 mL of the MXene aqueous solution to prepare a precursor solution; filtering 0.8-1.5mL of precursor solution on a porous substrate by a vacuum filtering method, and then drying for 8-24 hours at room temperature; the membrane which is filtered on the ceramic substrate is placed in a protective atmosphere, the heat treatment temperature is 800-1000 ℃, and the calcination is carried out for 2-4 hours. And a microporous channel membrane prepared by the method is also provided. By controlling the parameters in the process of preparing the membrane, the micro-channel membranes with different performances can be obtained, and the most excellent micro-channel membrane of the row can be selected.
Description
Technical Field
The invention relates to the technical field of membranes, in particular to a microporous channel membrane and a preparation method thereof.
Background
The microporous channel membrane, namely the two-dimensional materials are mutually stacked to form a layered structure, and the microporous membrane is formed by stacking the two-dimensional materials by controlling the size of the interlayer between two adjacent layers, and the membrane is provided with a nano capillary network which is used as a mass transfer channel. By size sieving, microporous channel membranes can achieve efficient molecular or ion sieving. The confinement effect of these two-dimensional nano-capillary channels drives water molecules through the membrane in rapid order while at the same time effectively separating or removing hydrated ions or molecules in the water that have a size greater than the two-dimensional channel. Therefore, the nanoscale two-dimensional channel membrane is attractive and is expected to become a new generation of high-performance membrane. However, due to the limitation of the prior art, the interlayer spacing of the two-dimensional material is difficult to be controlled to be in the size of one tenth of nanometers, and the prior two-dimensional materials such as graphene oxide and MXene (Ti 3 C 2 Tx, T=OH, F, H) nanosheets swell in water or a part of organic solvents, resulting in serious degradation of separation performance, thus the two-dimensional microporous channel membranes face great challenges in ion screening and sea water desalination, and the existing two-dimensional material preparation technology limits the large-scale development and application of the membranes.
Journal of Science (Science, 335 (2012) 442-444) reports the preparation of submicron (0.1-10 μm) graphene oxide films by spray or spin coating methods. The graphene oxide film has unique transmission properties, and any gas or liquid cannot permeate the graphene oxide film, but water vapor can be transmitted at a high speed without obstruction. However, the interlayer spacing will increase to 1.3±0.1nm after the graphene oxide film is immersed in water, so that such film is difficult to be used for removing ions and molecules having a small hydration diameter in water.
The Nature journal (Nature, 550 (2017) 380-383) reports that the precise regulation and control of the interlayer spacing of the graphene film reaching one tenth of nanometers can be realized by introducing hydrated cations with different sizes into the graphene oxide laminated layers. In addition, after the interlayer of the membrane is regulated by a cation, the membrane can effectively intercept ions including the cation and all ions larger than the hydration diameter of the cation in the salt solution, and meanwhile, can also keep the rapid permeation of water molecules, so that the salt ions and the pure water are enriched at the feeding side and the permeation side of the graphene membrane respectively. However, this method still has difficulty in effectively suppressing the swelling decay of the graphene oxide film in water.
Disclosure of Invention
Therefore, the technical problem to be solved by the invention is to provide a microporous channel membrane formed by two-dimensional materials and a preparation method thereof, so as to overcome the defects in the prior art and explore a way for preparing the microporous membrane with high performance.
The technical scheme of the invention is that the preparation method of the microporous channel membrane comprises the following steps:
a. precursor solution preparation: dissolving lithium fluoride in 6-9 mol/L hydrochloric acid solution, introducing inert gas, stirring for 1-2 hr, and adding Ti 3 AlC 2 Lithium fluoride, hydrochloric acid solution and Ti 3 AlC 2 The ratio of (2) is: 0.5 to 1.5:15-25:0.5 to 1.5, the unit is g/mL/g, the reaction temperature is kept at 20 to 35 ℃ and stirring is continued for 12 to 24 hours under the condition of introducing inert gas; ultrasonically treating the reacted solution for 5-15 min, using deionized water and centrifugal auxiliary cleaning for 3-5 times, wherein the centrifugal speed is 3000-5000 r/min, the centrifugal time is 4-10 min, retaining bottom sediment in the previous 3-5 cleaning processes, adding deionized water, shaking to uniformly disperse sediment, retaining the centrifugal speed of 3000-5000 r/min for 0.5-1.5 h, taking supernatant, and diluting to 60-100 mg/mL to obtain an MXene precursor aqueous solution;
b. taking 0.25-5 mL of acetic acid solution with the mass concentration of 3-5 mg/mL of chitosan, and fully mixing with 5-83 mL of MXene aqueous solution obtained in the step a to obtain a precursor solution;
c. and (3) deposition: filtering 0.8-1.5mL of precursor solution on a porous substrate by a vacuum filtering method, and then drying for 8-24 hours at room temperature;
d. and (3) heat treatment: the membrane which is filtered on the ceramic substrate is placed in a protective atmosphere, the heat treatment temperature is 800-1000 ℃, and the calcination is carried out for 2-4 hours.
In step a, in order to wash out the acid in the solution, the solution is adjusted from the acid to be close to neutral, and in order that the MXene nano-sheets can be fully peeled and dispersed, centrifugal washing is carried out before 3-5 times, and the supernatant after each washing is discarded. After 3-5 times, the precipitate was dispersed and centrifuged again for a longer period of time, and then the supernatant was taken to dilute into an aqueous precursor solution. The previous operation was a wash followed by the addition of water to the precipitate to disperse the precipitate.
The acetic acid solution in step b is preferably used in a concentration of 0.02 to 0.1mol/L.
The heat treatment process is a process of reducing MXene and carbonizing and crystallizing chitosan. MXene is Ti 3 C 2 T x Where t=can be OH, F, H. Several components are present simultaneously.
According to one method of preparing a microporous passageway membrane of the present invention, it is preferable that the mixing in step b is performed by magnetic stirring. Magnetic stirring allows for thorough mixing of the chitosan and MXene solutions.
According to one method of preparing a microporous passageway membrane of the present invention, preferably, 8-12mL deionized water is added to the solution before mixing in step b.
According to the preparation method of the microporous channel membrane of the present invention, it is preferable that the inert gas in the step a is nitrogen or argon.
According to the preparation method of the microporous channel membrane of the present invention, preferably, the porous substrate in the step c is a porous alumina ceramic substrate.
According to the preparation method of the microporous channel membrane of the present invention, preferably, the protective atmosphere in the step d is nitrogen or argon.
The invention also provides a microporous channel membrane formed by the two-dimensional material prepared by the preparation method, and the microporous channel membrane comprises a porous basal layer and a Ti3C 2/graphene composite layer on the porous basal layer; the Ti3C 2/graphene composite layer consists of an upper graphene layer, a lower graphene layer and Ti sandwiched between the two graphene layers 3 C 2 The graphene layer is of a broken piece discontinuous structure and is obtained by layer compounding, and the Ti is 3 C 2 The layer is also a broken piece discontinuous structure;
Ti 3 C 2 from Ti 3 AlC 2 Stripping and removing functional groups introduced by stripping to form a sheet structure; the saidThe graphene layer is formed by chitosan on Ti 3 C 2 And carbonizing and crystallizing on the sheet.
Preferably, the concentration ratio of the two precursors MXene and chitosan is 0.08:27.2-0.83:27.2.
MXene is Ti 3 C 2 T x Wherein t=oh, F, H.
Ti 3 AlC 2 Is the initial raw material, and after etching, al is removed, thereby Ti 3 AlC 2 The block is peeled into a sheet. For acid etching reasons, ti after etching 3 C 2 The layer is introduced with new functional groups: -F, -OH and-O-, thereby forming Ti 3 C 2 T x . After heat treatment, these functional groups are removed to form Ti 3 C 2 。
Carbonization and crystallization correspond to the previous heat treatment process.
Ti 3 C 2 Must be separated from each other, and the graphenes are alternately positioned on Ti 3 C 2 An upper layer and a lower layer. Each bar represents a nanoplatelet.
The finished film is deposited on a porous substrate with a chemical force therebetween. Because the finished film is thin, the porous substrate is required to serve as a support to enhance the mechanical strength, and is not easy to break during use.
The microporous channel membrane formed of the two-dimensional material according to the present invention is preferably a porous alumina ceramic substrate.
The pore diameter of the porous substrate is 0.9-1.1 μm. In order to prevent the Ti3C 2/graphene composite layer from being locally detached from the porous substrate, the thickness generally cannot be greater than 500 nanometers, such as 30-500nm. The film thickness can be controlled by controlling the volume of the precursor solution used for the suction filtration film formation. However, as a membrane, a membrane having a high flux Gao Jie rate is generally required, so in our study, the properties of a membrane of 30 to 100nm are mainly studied. This is the thinnest range of film thickness that can be achieved under our manufacturing conditions. In the subsequent runs (3, 4,5, 6), the flux and the salt cut-off rates of the films of different thicknesses obtained under different experimental conditions were also compared.
Micro-scale formed of two-dimensional material according to the present inventionPore channel film, preferably, the graphene layer is bonded to titanium carbide (i.e., ti 3 C 2 ) Intermolecular forces exist between them, stacked together. But the upper and lower layers are not directly connected.
Currently, graphene oxide films are widely focused on, and are mainly formed by stacking graphene oxide nano-sheets or MXene nano-sheets. The presence of a large number of oxygen-containing functional groups on these nanoplatelets makes the nanoplatelets extremely easy to disperse uniformly in water for the subsequent preparation of the membrane, whereas the presence of these functional groups makes the membrane immersed in water or readily swelled in a humid environment, impairing the stability of the membrane and the interlayer spacing of the membrane difficult to control to sub-nanometer scale. The invention removes the functional group on the MXene nano-sheet by using the heat treatment result, and simultaneously forms graphene linkage on Ti through carbonization and crystallization of chitosan 3 C 2 The surface of the nano layer can effectively control the two-dimensional channel to the sub-nano level, and has no obstruction of functional groups on the water transmission in the channel, so that the water flux is greatly improved. The removal of the functional groups on the surface of the nano-sheet overcomes the problem of swelling of the membrane in water and the stability thereof. The invention can control the film thickness below 100nm, effectively reduce the thickness of the selective layer and effectively improve the water flux of the film. The microporous channel membrane prepared by the invention has excellent performance in water flux and desalination rate.
The beneficial effects of the invention are as follows:
the chitosan and the porous ceramic substrate adopted by the invention are common and cheap industrial raw materials and industrial products. The vacuum filtration employed is a common method of preparing membranes, which facilitates the expanded production of the present invention. In addition, by controlling each parameter in the process of preparing the membrane, the micro-channel membrane with different performances can be obtained, and the most excellent micro-channel membrane in the row can be selected.
The water flux and salt interception rate of the membrane are 67.0-130.4LLMH under the testing condition of 20 ℃ when 2000mg/L NaCl solution is used as an extracting solution, and the salt interception rate is as high as 99.9 percent under the testing condition of 20 ℃.
Drawings
FIG. 1 is a schematic view of the microporous passageway membrane structure of the present invention.
FIG. 2 is Ti of FIG. 1 3 C 2 Schematic enlarged partial view of graphene composite layer.
FIG. 3a is Ti 3 C 2 Graphene film is photomicrograph on a ceramic wafer substrate.
Fig. 3b is a scanning electron microscope SEM) picture-cross section of the film.
Detailed Description
Example 1
Precursor solution preparation:
MXene(Ti 3 C 2 tx, t=oh, F, H): 1.0g of lithium fluoride was dissolved in 20ml of a 9mol/L hydrochloric acid solution, and the solution was stirred for 1.5 hours under nitrogen, followed by addition of 1.0g of Ti 3 AlC 2 Stirring for 22 hours under the condition of keeping the reaction temperature at 25 ℃ and continuously introducing nitrogen; and (3) carrying out ultrasonic treatment on the reacted solution for 10 minutes, carrying out auxiliary cleaning for 4 times by using deionized water and centrifugation, wherein the centrifugal speed is 3500 r/min, the centrifugal time is 5 minutes, preserving bottom sediment in the cleaning process for 4 times, shaking up and dispersing sediment after adding deionized water for 5 th time, keeping the centrifugal speed of 3500 r/min for 1 hour, taking supernatant, and diluting to 83mg/L solution to obtain the MXene precursor aqueous solution.
The preparation process of the chitosan precursor solution comprises the following steps: 50mg of chitosan is dissolved in 10mL of acetic acid solution with the concentration of 0.05mol/L, and the solution is fully stirred for 4 hours by a magnetic stirrer, and the chitosan is fully dissolved in the acetic acid solution to obtain the chitosan precursor solution with the concentration of 5 mg/mL.
Example 2
Precursor solution preparation:
MXene(Ti 3 C 2 tx, t=oh, F, H): 1.5g of lithium fluoride was dissolved in 20ml of 8mol/L hydrochloric acid solution, nitrogen was introduced and stirred for 2 hours, and 1.2g of Ti was further added 3 AlC 2 Stirring for 18 hours under the condition of keeping the reaction temperature at 28 ℃ and continuously introducing nitrogen; ultrasonic-treating the reacted solution for 12 min, washing with deionized water and centrifugal auxiliary for 4 times at 3800 rpm for 6 min, maintaining the bottom precipitate during the 4 times of washing, adding deionized water for 5 times, shaking and dispersingAfter the precipitate was kept at a centrifugation speed of 4000 rpm for 1.2 hours, the supernatant was taken and diluted to 90mg/L to obtain an aqueous solution of the MXene precursor.
The preparation process of the chitosan precursor solution comprises the following steps: 35mg chitosan is dissolved in 10mL acetic acid solution with the concentration of 0.05mol/L, and the solution is fully stirred for 4 hours by a magnetic stirrer, so as to obtain chitosan precursor solution with the concentration of 3.5 mg/mL.
Example 3
5mL of the MXene solution in example 1 was dispersed in 10mL of deionized water, and 0.25mL of the 5mg/mL chitosan solution in example 1 was added, and the solution was stirred by a magnetic stirrer for 6 hours to allow the solution to be sufficiently mixed, thereby obtaining a precursor solution. 1mL of the precursor was filtered on a porous ceramic substrate by vacuum filtration, then dried at room temperature for 16 hours, then placed in an argon-protected atmosphere and calcined at 900℃for 3 hours. And finally obtaining the microporous channel membrane.
FIG. 2 is a photograph and cross-section of a Scanning Electron Microscope (SEM) of the resulting microporous channel membrane from which we can see that the membrane is formed from a stack of two-dimensional nanoplatelets. The thickness of the selected layer of the film can be controlled by adjusting the volume of the precursor solution, and the film thickness can be controlled between 30 and 100nm, and the film with the thickness in the range is used for performance test research. This thickness does not include the porous substrate thickness, we have studied mainly the water flux and salt rejection performance of membranes with a thickness in the range of 30-100nm, since the thinner the membrane the higher the water flux but generally the lower the rejection. In optimizing membrane performance parameters, it is often desirable to balance flux and rejection. The precursor solution volume was between 0.8 and 1.5mL when the membrane was prepared by suction filtration.
The test results of water flux and salt interception rate of the membrane show that when 2000mg/L NaCl solution is used as an extracting solution, the water flux of the membrane is up to 82.8LMH and the salt interception rate is up to 99.9% under the test condition of 20 ℃. Experimental data indicate that the membrane has good water treatment performance.
Example 4
Using a method for preparing a membrane similar to that of example 3, 1mL of a 5mg/mL chitosan solution and 5mL of 83mg/mL MXene of example 1 were sufficiently dispersed in 10mL of water, followed by obtaining a membrane having a similar structure.
The test results of water flux and salt interception rate of the membrane show that when 2000mg/L NaCl solution is used as an extracting solution, the water flux of the membrane is up to 99.0LMH and the salt interception rate is up to 99.9% under the test condition of 20 ℃.
Example 5
A membrane was prepared in a similar manner to example 3, except that 2mL of a 5mg/mL chitosan solution and 5mL of 83mg/mL MXene were thoroughly dispersed in 10mL of water, followed by obtaining a membrane of similar structure.
The test results of water flux and salt interception rate of the membrane show that when 2000mg/L NaCl solution is used as an extracting solution, the water flux of the membrane is up to 68.9LMH and the salt interception rate is up to 99.9% under the test condition of 20 ℃.
Example 6
A membrane was prepared in a similar manner to example 3, except that 3mL of a 5mg/mL chitosan solution and 5mL of 83mg/mL MXene were thoroughly dispersed in 10mL of water, followed by obtaining a membrane of similar structure.
The test results of water flux and salt interception rate of the membrane show that when 2000mg/L NaCl solution is used as an extracting solution, the water flux of the membrane is 67.0LMH and the salt interception rate is 99.9% under the test condition of 20 ℃.
Example 7
A film similar in structure to example 4 was difficult to obtain as the film was not dried at room temperature for 8 hours enough to remove most of the water in the film, so that MXene was converted to particle precipitation at subsequent high temperature treatment.
The results of the salt cut rate test performed on the film showed no salt cut rate.
Example 8
A film similar in structure to example 4 was obtained using a method similar to example 4 except that the drying time was changed to 24 hours.
The test results of water flux and salt interception rate of the membrane show that when 2000mg/L NaCl solution is used as an extracting solution, the water flux of the membrane is up to 99.1LMH and the salt interception rate is up to 99.9% under the test condition of 20 ℃.
The water flux and the salt interception rate of the membrane obtained in the drying time of 16 hours and 24 hours are almost consistent, so that the optimized drying time is 16 hours, and meanwhile, the fact that the membrane is sufficiently dried in 16 hours is indicated, and the follow-up process is not influenced.
Example 9
A film similar in structure to example 4 was obtained using a method similar to example 4 except that the heat treatment temperature was changed to 800 ℃.
The test results of water flux and salt interception rate of the membrane show that when 2000mg/L NaCl solution is used as an extracting solution, the water flux of the membrane is up to 69.1LMH and the salt interception rate is up to 99.9% under the test condition of 20 ℃.
Example 10
A film similar in structure to example 3 was obtained using a method similar to that of example 4 except that the heat treatment temperature was changed to 1000 ℃.
The test results of water flux and salt interception rate of the membrane show that when 2000mg/L NaCl solution is used as an extracting solution, the water flux of the membrane is up to 93.2LMH and the salt interception rate is up to 99.9% under the test condition of 20 ℃. The processing temperature has an impact on the process of the chitosan to graphene boulder process, as it may affect the water flux of the membrane. In general, the heat treatment temperature reaches 900-1000 ℃, and the crystallization of the graphene is optimal, so that the water flux of the film after the heat treatment at 900 ℃ and 1000 ℃ is not greatly different, and the growing part is within the error range. In order to further save energy consumption in the film preparation process, the optimal heat treatment temperature is 900 ℃.
Example 11
A film similar in structure to example 4 was obtained, except that the heat treatment time was changed to 2h.
The test results of water flux and salt interception rate of the membrane show that when 2000mg/L NaCl solution is used as an extracting solution, the water flux of the membrane is up to 89.8LMH and the salt interception rate is up to 99.9% under the test condition of 20 ℃.
Example 12
A film similar in structure to example 4 was obtained, except that the heat treatment time was changed to 4h.
The test results of water flux and salt interception rate of the membrane show that when 2000mg/L NaCl solution is used as an extracting solution, the water flux of the membrane is up to 96.8LMH and the salt interception rate is up to 99.9% under the test condition of 20 ℃.
Example 13
A membrane similar in structure to example 4 was obtained using a method similar to that of example 4 except that the volume of the precursor solution used for the suction filtration membrane was changed to 0.8mL.
The test results of water flux and salt interception rate of the membrane show that when 2000mg/L NaCl solution is used as an extracting solution, the water flux of the membrane is up to 130.4LMH and the salt interception rate is up to 99.9% under the test condition of 20 ℃. However, because the film formed under this condition is too thin, the success rate of producing a film with perfect structure is low.
Example 14
A membrane similar in structure to example 4 was obtained using a method similar to that of example 4 except that the volume of the precursor solution used for the suction filtration membrane was changed to 1.5mL.
The test results of water flux and salt interception rate of the membrane show that when 2000mg/L NaCl solution is used as an extracting solution, the water flux of the membrane is 67.3LMH and the salt interception rate is 99.9% under the test condition of 20 ℃.
Example 15
The same method for preparing a membrane as in example 4 was employed except that the test conditions for membrane performance, i.e., the temperature of the NaCl extract, was adjusted to 70 ℃.
The test results of water flux and salt interception rate of the membrane show that when 2000mg/L NaCl solution is used as an extracting solution, the water flux of the membrane prepared by different MXene/chitosan ratios reaches 230.5-300.8LMH, and the salt interception rate reaches 99.9% under the test condition of 70 ℃.
Claims (10)
1. A method for preparing a microporous passageway membrane, which is characterized in that: the method comprises the following steps:
a. precursor(s)Preparing a bulk solution: dissolving lithium fluoride in 6-9 mol/L hydrochloric acid solution, introducing inert gas, stirring for 1-2 hr, and adding Ti 3 AlC 2 Lithium fluoride, hydrochloric acid solution and Ti 3 AlC 2 The ratio of (2) is: 0.5 to 1.5:15-25:0.5 to 1.5, the unit is g/mL/g, the reaction temperature is kept at 20 to 35 ℃ and stirring is continued for 12 to 24 hours under the condition of introducing inert gas; ultrasonically treating the reacted solution for 5-15 min, using deionized water and centrifugal auxiliary cleaning for 3-5 times, wherein the centrifugal speed is 3000-5000 r/min, the centrifugal time is 4-10 min, retaining bottom sediment in the previous 3-5 cleaning processes, adding deionized water, shaking to uniformly disperse sediment, retaining the centrifugal speed of 3000-5000 r/min for 0.5-1.5 h, taking supernatant, and diluting to 60-100 mg/mL to obtain an MXene precursor aqueous solution;
b. taking 0.25-5 mL of acetic acid solution with the mass concentration of 3-5 mg/mL of chitosan, and fully mixing with 5-83 mL of the MXene aqueous solution obtained in the step a to obtain a precursor solution;
c. and (3) deposition: filtering 0.8-1.5mL of precursor solution on a porous substrate by a vacuum filtering method, and then drying for 8-24 hours at room temperature;
d. and (3) heat treatment: placing the membrane which is filtered on the ceramic substrate in a protective atmosphere, and calcining for 2-4 hours at the temperature of 800-1000 ℃;
the microporous channel membrane comprises a porous substrate layer and Ti on the porous substrate layer 3 C 2 A graphene composite layer; the Ti is 3 C 2 The graphene composite layer consists of an upper graphene layer, a lower graphene layer and Ti sandwiched between the two graphene layers 3 C 2 The graphene layer is of a broken piece discontinuous structure and is obtained by layer compounding, and the Ti is 3 C 2 The layer is also a broken piece discontinuous structure;
Ti 3 C 2 from Ti 3 AlC 2 Stripping and removing functional groups introduced by stripping to form a sheet structure; the graphene layer is prepared from chitosan in Ti 3 C 2 And carbonizing and crystallizing on the sheet.
2. The method for preparing a microporous passageway membrane according to claim 1, wherein: the mixing in step b is carried out by magnetic stirring.
3. The method for preparing a microporous passageway membrane according to claim 1, wherein: and (c) adding 8-12mL of deionized water into the solution before mixing in the step b.
4. The method for preparing a microporous passageway membrane according to claim 1, wherein: the inert gas in the step a is nitrogen or argon.
5. The method for preparing a microporous passageway membrane according to claim 1, wherein: and c, the porous substrate is a porous alumina ceramic substrate.
6. The method for preparing a microporous passageway membrane according to claim 1, wherein: the protective atmosphere in the step d is nitrogen or argon.
7. The microporous passageway membrane formed by the two-dimensional material prepared by the preparation method according to any one of claims 1 to 6, which is characterized in that: the microporous channel membrane comprises a porous substrate layer and Ti on the porous substrate layer 3 C 2 A graphene composite layer; the Ti is 3 C 2 The graphene composite layer consists of an upper graphene layer, a lower graphene layer and Ti sandwiched between the two graphene layers 3 C 2 The graphene layer is of a broken piece discontinuous structure and is obtained by layer compounding, and the Ti is 3 C 2 The layer is also a broken piece discontinuous structure;
Ti 3 C 2 from Ti 3 AlC 2 Stripping and removing functional groups introduced by stripping to form a sheet structure; the graphene layer is prepared from chitosan in Ti 3 C 2 And carbonizing and crystallizing on the sheet.
8. The microporous passageway membrane formed of a two-dimensional material according to claim 7, wherein: the concentration ratio of the two precursors MXene and chitosan is 0.08:27.2-0.83:27.2.
9. The microporous passageway membrane formed of a two-dimensional material according to claim 7, wherein: the porous substrate is a porous alumina ceramic substrate.
10. The microporous passageway membrane formed of a two-dimensional material according to claim 7, wherein: the graphene layer and Ti 3 C 2 Intermolecular forces exist between them, stacked together.
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