CN112090715A - Graphite/alumina asymmetric membrane and preparation method thereof - Google Patents
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Abstract
The invention relates to a graphite/alumina asymmetric membrane, a preparation method thereof and an ion rectifying device. The invention utilizes a sol-gel method to prepare a graphite/alumina asymmetric membrane, wherein graphite is coated on one side surface of the graphite/alumina asymmetric membrane, and the surface of the graphite/alumina asymmetric membrane is provided with hydroxyl functional groups. The graphite/alumina asymmetric membrane is used for an ion rectifying device, the ion rectifying device is simple in preparation process, low in cost and high in ion rectifying ratio, and can be further applied to the fields of ion directional transportation, salt difference power generation and the like.
Description
Technical Field
The invention relates to the field of biological ion channel bionics.
Background
A wide variety of biological nanochannels exist in organisms, and play a crucial role in the operation of the organisms and the coordination of the internal environment. Biological ion channels are important components of biological nano-channels, control ion entrance and exit, exchange of materials and energy between cells and environment and transfer of information, and have gating, ion selectivity and ion rectification characteristics.
In recent years, under the influence of biological ion channels, biomimetic nano-channels have attracted great research interest. The bionic nano channel is a nano channel which is prepared by imitating a biological ion channel, has the aperture of 1-100 nanometers and the length of a pore channel far larger than the diameter of the pore channel, and can have the performance similar to that of the biological ion channel by a proper construction method. At present, the methodScientific researchers have developed various methods for preparing biomimetic nanochannels, such as a series of methods including track etching, electrochemical oxidation, self-assembly, etc., and the Apel topic group (Nuci. Instr. and meth. in Phys. Rex B,1997,131,55-63) used heavy metal ions238U etches polymer films (PET, PP, PSU) of different materials. The gouwei problem group (chem. Commun.,2014,50,14149-14152) adopts a track etching method to prepare a novel bionic artificial nano-channel, and an ion-track etched mica sheet generates an ultrathin nano-pore membrane in a mechanical peeling mode. After the massive mica sheet is irradiated by a fast heavy ion beam, chemical etching is carried out by hydrofluoric acid, and nanopores are generated on the massive film; and (3) pasting a layer of adhesive tape on the surface of the nano-pore block mica film, then repeatedly stripping the adhesive tape by using other fresh adhesive tapes, and transferring the stripped mica flakes onto a solid silicon window to form the suspended nano-pore film. Siwy group of subjects (j.am. chem. soc.,2020,142,2925-2934) drilled nanopores in a 15nm thick silicon nitride film using a focused ion beam and an electron beam under a transmission electron microscope, then negatively charged by silanization, and achieved a similar gating response to calcium ions as the organism by adjusting the pore size of the drilled pores. The kyania topic group (Angew. chem. int. Ed.,2019,58,17418-17424) transfers gold nano-layer nano-arrays to the surface of Anodic Aluminum Oxide (AAO) to form heterostructure films after gold nano-particles (Au NPs) are self-assembled into ordered nano-layer arrays, thereby generating nano-scale selective asymmetric ion transmission. The single-layer gold nano array is taken as a structural unit, and the ion selectivity can be enhanced by increasing the number of layers of the gold nano array.
However, the preparation methods all involve multistep preparation processes, the process is complex and high in cost, and the components in the preparation processes are single and unadjustable, so that the search for the bionic nano-channel which is simple in preparation method, low in cost and adjustable in components and the preparation method thereof has important significance.
Disclosure of Invention
The inventors of the present invention have made extensive studies to solve the problems of the prior art, and have found that the graphite/alumina asymmetric membrane of the present invention has ion rectification characteristics, and the preparation method is simple in operation and low in cost, thereby completing the present invention. The present invention includes the following configurations.
One aspect of the present invention provides a graphite/alumina asymmetric membrane having a graphite layer and a porous alumina membrane layer, the graphite layer being located on one side surface of the porous alumina membrane; the surface and interlayer of the porous alumina film, and the surface and interlayer of the graphite have hydroxyl functional groups.
The graphite/alumina asymmetric membrane of the present invention has an ion rectification characteristic, wherein the "ion rectification characteristic" means a characteristic that current values obtained under the same positive voltage and negative voltage are different in magnitude, and a larger difference in current values indicates a stronger rectification characteristic.
The reason why the graphite/alumina asymmetric membrane of the present invention has ion rectification characteristics may be that: in the asymmetric graphite/alumina membrane, the graphite layer has tiny pores, the porous alumina membrane has pores larger than the pores in the graphite layer, and the pore channel surfaces of the pores of the graphite and the alumina membrane are both negatively charged and have selective permeability to cations. When positive voltage is applied to one side coated with the graphite layer, cations are easy to pass through the pore channel due to electrostatic action to form an ion enrichment area, and the ion current is large; on the contrary, when negative voltage is applied to the side coated with the graphite layer, cations are not easy to pass through the pore channel to form an ion dissipation area, and the ion current is small. Thus, the graphite/alumina asymmetric membrane of the present invention has the aforementioned ion rectification characteristics.
The graphite/alumina asymmetric membrane has a rectification characteristic ratio in the range of 2 to 6.
In another aspect of the present invention, there is provided a method for preparing a graphite/alumina asymmetric membrane, comprising the steps of:
a graphite gel preparation procedure: hydrolyzing methyltrimethoxysilane and concentrated hydrochloric acid in anhydrous methanol, adding graphite powder while hydrolyzing, and stirring to obtain gel containing graphite;
a graphite coating procedure: and coating the obtained gel containing the graphite on one side surface of alumina, and drying to obtain the graphite/alumina asymmetric membrane.
In the preparation method of the graphite/alumina asymmetric membrane, the gel containing graphite is prepared by hydrolyzing methyltrimethoxysilane and concentrated hydrochloric acid in anhydrous methanol and adding graphite powder while stirring. By adopting the preparation process of the graphite gel, the hydrolysis of methyltrimethoxysilane is utilized, so that the graphite layer coated on the surface of the porous alumina membrane has hydroxyl functional groups on the surface and between layers of the graphite layer.
In yet another aspect of the invention, there is provided an ion rectifying device comprising the asymmetric graphite/alumina membrane of the invention, a dual-chamber electrolytic cell, an electrolyte, and two electrodes, the asymmetric graphite/alumina membrane being disposed in the dual-chamber electrolytic cell, the two electrodes being connected.
The graphite/alumina asymmetric membrane has the advantages of ion rectification characteristic, simple preparation method process and low cost. The ion rectifying device has the advantages of simple structure, high ion rectifying ratio and the like. The graphite/alumina asymmetric membrane and the ion rectifying device can be further applied to the fields of ion directional transport, salt difference power generation and the like.
Drawings
FIG. 1 is a scanning electron micrograph of the surface of a graphite/alumina asymmetric membrane prepared according to one embodiment of the present invention.
FIG. 2 is a scanning electron micrograph of a cross-section of an asymmetric graphite/alumina film made according to one embodiment of the present invention.
Fig. 3 is an apparatus diagram of an ion rectifying device according to an embodiment of the present invention.
FIG. 4 is a graph of current-voltage curves of an ion rectifying device prepared according to an embodiment of the present invention tested in 1mmol/L electrolyte.
Detailed Description
Reference will now be made in detail to various exemplary embodiments of the invention, the detailed description should not be construed as limiting the invention but as a more detailed description of certain aspects, features and embodiments of the invention.
It is to be understood that the terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. Further, for numerical ranges in this disclosure, it is understood that the upper and lower limits of the range, and each intervening value therebetween, is specifically disclosed. Every smaller range between any stated value or intervening value in a stated range and any other stated or intervening value in a stated range is encompassed within the invention. The upper and lower limits of these smaller ranges may independently be included or excluded in the range.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. Although only preferred methods and materials are described herein, any methods and materials similar or equivalent to those described herein can be used in the practice or testing of the present invention. All documents mentioned in this specification are incorporated by reference herein for the purpose of disclosing and describing the methods and/or materials associated with the documents. In case of conflict with any incorporated document, the present specification will control. Unless otherwise indicated, "%" is percent by weight.
[ graphite/alumina asymmetric film ]
In the graphite/alumina asymmetric membrane, the graphite layer is positioned on one side surface of the porous alumina membrane.
In the graphite/alumina asymmetric membrane of the present invention, the porous alumina membrane has a pore channel, and the size is not particularly limited, and may be, for example, 40 to 150nm, preferably 40 to 110nm, and more preferably 40 to 70 nm. The surface of the pore channel of the porous alumina film is provided with a hydroxyl functional group.
In the graphite/alumina asymmetric membrane of the present invention, the graphite layer has irregular pores. Preferably, the graphite layer has pores with an average pore diameter smaller than the pore diameter in the porous alumina film. The pore size of the graphite layer is, for example, 1 to 100nm, preferably 1 to 50 nm.
In the asymmetric graphite/alumina film of the present invention, the thickness of the porous alumina film is about 1 to 500 μm, preferably 50 to 200 μm, and more preferably 50 to 100 μm.
In the graphite/alumina asymmetric membrane of the present invention, the thickness of the graphite layer is 1 to 100 μm, preferably 5 to 50 μm, and more preferably 5 to 15 μm.
The graphite layer in the asymmetric graphite/alumina membrane of the present invention can be obtained by, for example, coating a graphite gel as described later.
The asymmetric graphite/alumina film of the present invention exhibits rectifying properties, which may be analyzed for reasons: in the asymmetric graphite/alumina membrane, the graphite layer has tiny pores, the porous alumina membrane has pores larger than the pores in the graphite layer, and the pore channel surfaces of the pores of the graphite and the alumina membrane are both negatively charged and have selective permeability to cations. When positive voltage is applied to one side coated with the graphite layer, cations are easy to pass through the pore channel due to electrostatic action to form an ion enrichment area, and the ion current is large; on the contrary, when negative voltage is applied to the side coated with the graphite layer, cations are not easy to pass through the pore channel to form an ion dissipation area, and the ion current is small.
The rectification ratio of the graphite/alumina asymmetric membrane is in the range of 2-6.
The "rectification characteristic ratio" refers to a characteristic that the magnitude of current values obtained at positive and negative voltages having the same value is different, and the larger the difference between the current values is, the stronger the rectification characteristic is. The aforementioned "rectification characteristic ratio" is obtained by a method of calculating a ratio of a current at a positive voltage to a current at a negative voltage of the same absolute value.
[ method for producing graphite/alumina asymmetric Membrane ]
The preparation method of the graphite/alumina asymmetric membrane comprises the following steps:
a graphite gel preparation procedure: adding methyltrimethoxysilane and concentrated hydrochloric acid into anhydrous methanol as a solvent for hydrolysis, adding graphite powder while hydrolyzing, and stirring to obtain gel containing graphite.
In the graphite gel preparation step, anhydrous methanol is used as a solvent. The purity of the solvent, i.e., absolute methanol, may be 99.5% or more.
The methyltrimethoxysilane and the concentrated hydrochloric acid are hydrolyzed in anhydrous methanol, and the reaction formula of the hydrolysis is as follows:
n CH3Si(OCH3)3+2n H2O→(-CH3Si(OH)3-)n+3n CH3OH
the concentration of concentrated hydrochloric acid is 12mol/L, and the mass ratio of methyltrimethoxysilane to concentrated hydrochloric acid is not particularly limited, but is, for example, 10 to 100, preferably, 10 to 20.
The temperature of the hydrolysis reaction may be room temperature or may be heated. The hydrolysis reaction is carried out for a period of, for example, 1 to 3 hours at a temperature of, for example, 25 to 40 ℃.
The preparation method of the graphite/alumina asymmetric membrane further comprises a graphite/alumina asymmetric membrane preparation process of coating the obtained gel containing graphite on one side of the surface of the porous alumina membrane and drying to obtain the graphite/alumina asymmetric membrane.
The coating method is not particularly limited. For example, it may be sprayed, drawn, spin-coated, or the like. Preferably by knife coating. The amount of the graphite-containing gel to be coated may be such that the thickness of the graphite layer after drying is 1 to 100 μm.
Then, the porous alumina film coated with the graphite gel is dried to obtain the graphite/alumina asymmetric film. The drying method is not particularly limited. The porous alumina film coated with the graphite gel can be placed to be naturally dried, or can be dried by heating. When the drying is performed by heating, the heating temperature is, for example, 30 to 60 ℃.
[ ion rectifying device ]
The ion rectifying device of the present invention includes, in addition to the graphite/alumina asymmetric membrane of the present invention, other components such as an electrolytic cell, an electrolytic solution, and two electrodes. The choice of the electrolytic cell, the electrolyte and the electrodes is not subject to any restrictions and can be selected by the person skilled in the art as desired.
The two electrodes are preferably Ag/AgCl electrodes.
The electrolyte can beFor example, KCl solution, K2SO4The electrolyte solution is not particularly limited, but is preferably a KCl electrolyte solution having a concentration of 1 to 100mM, and more preferably a KCl electrolyte solution having a concentration of 5 to 50 mM.
As one embodiment of the ion rectifying device of the present invention, as shown in fig. 3, it comprises a graphite/alumina asymmetric membrane 3, a two-chamber electrolytic cell 4, an electrolyte solution 1, and two Ag/AgCl electrodes 2.
The ion rectifying device of the present invention may be constructed in the manner described below: the graphite/alumina asymmetric membrane is placed in the middle of a double-chamber electrolytic cell, and electrolyte and two electrodes are added and electrically connected to construct an ion rectifier.
Examples
(1) Graphite/alumina asymmetric membrane characterization:
the microscopic morphology of the sample was observed using a scanning electron microscope environment Quanta FEG 250, FEI USA.
(2) Testing the rectification characteristic:
the current-voltage properties of the samples were tested using a Keithley company 6487 pean meter, usa. The graphite/alumina asymmetric membrane obtained in the example was placed in the middle of a double-chamber electrochemical cell, which was filled with a 1mmol/L potassium chloride solution, and 1 pair of silver/silver chloride electrodes were used to apply transmembrane voltage, with one side of the graphite fixed as the positive electrode, to assemble an ion rectifier device. The ion current of the ion rectifying device at different voltages is recorded by using a picoammeter, and the device is shown as a figure 3.
Example 1
Taking 18mL of anhydrous methanol as a solvent, adding 2mL of methyltrimethoxysilane, then adding 0.1mL of 12mol/L concentrated hydrochloric acid for hydrolysis, adding 4g of graphite powder while hydrolyzing, and stirring for 2h to obtain the gel containing graphite. And (3) coating the obtained graphite gel on one side of the surface of porous alumina with the aperture of 40-70 nm and the thickness of about 100 mu m, which is prepared by Puyuan nanotechnology company, and heating and drying at 55 ℃ for 24 hours to obtain the graphite/alumina asymmetric membrane 1.
Fig. 2 is a scanning electron microscope image of the surface environment of the asymmetric graphite/alumina film obtained in example 1, and fig. 1 and 2 are a scanning electron microscope image of the surface of the graphite layer and a scanning electron microscope image of the cross section of the asymmetric graphite/alumina film obtained in example 1, respectively. As can be seen from fig. 1, the graphite coated on the surface side of the alumina is in a porous layered form, and as can be seen from fig. 2, the upper layer is a graphite layer stacked in a layered structure, and the lower layer is a porous alumina film. Wherein the aperture of the graphite layer is about 20-40 nm, and the aperture of the porous alumina film is about 40-70 nm.
The graphite/alumina asymmetric membrane obtained in example 1 was placed in a double-chamber electrolytic cell, and potassium chloride electrolyte at a concentration of 1mmol/L and two silver/silver chloride electrodes were added and electrically connected to construct an ion rectifying device. The obtained ion rectifying device is subjected to rectification characteristic test to obtain a current-voltage curve as shown in FIG. 4, and the ion rectifying ratio I+2V/I-2VIs 2.8.
Example 2
Taking 18mL of anhydrous methanol as a solvent, adding 2mL of methyltrimethoxysilane, then adding 0.1mL of 12mol/L concentrated hydrochloric acid for hydrolysis, adding 8g of graphite powder while hydrolyzing, and stirring for 2h to obtain the gel containing graphite. And (3) coating the obtained graphite gel on one side of the surface of porous alumina with the aperture of 40-70 nm and the thickness of about 100 mu m, which is prepared by Puyuan nanotechnology company, and heating and drying at 55 ℃ for 24 hours to obtain the graphite/alumina asymmetric membrane 2. Ion rectification ratio I+2V/I-2VIs 6.0
Example 3
Taking 18mL of anhydrous methanol as a solvent, adding 2mL of methyltrimethoxysilane, then adding 0.1mL of 12mol/L concentrated hydrochloric acid for hydrolysis, adding 4g of graphite powder while hydrolyzing, and stirring for 2h to obtain the gel containing graphite. And (3) coating the obtained graphite gel on one side of the surface of porous alumina with the aperture of 80-100 nm and the thickness of about 100 mu m, which is prepared by Puyuan nanotechnology company, and heating and drying at 55 ℃ for 24 hours to obtain the graphite/alumina asymmetric membrane 3. Ion rectification ratio I+2V/I-2VIs 2.3
Example 4
Taking 18mL of anhydrous methanol as a solvent, adding 2mL of methyltrimethoxysilane and then adding 0.1mL12 mol/L concentrated hydrochloric acid is hydrolyzed, 4g of graphite powder is added during hydrolysis, and the mixture is stirred for 2 hours to obtain gel containing graphite. And (3) coating the obtained graphite gel on one side of the surface of porous alumina with the aperture of 110-150 nm and the thickness of about 100 mu m, which is prepared by Puyuan nanotechnology company, and heating and drying at 55 ℃ for 24 hours to obtain the graphite/alumina asymmetric membrane 4. Ion rectification ratio I+2V/I-2VIs 2.0
And performing morphology characterization and rectification characteristic test on the graphite/aluminum oxide asymmetric films 2-4 obtained in the embodiments 2-4. The surface appearance characterization shows that the graphite coated on one side of the surface of the alumina is in a porous layered state, the cross section appearance characterization shows that the upper layer is graphite stacked in a layered structure, and the lower layer is a porous alumina film.
It will be apparent to those skilled in the art that various modifications and variations can be made in the specific embodiments of the present disclosure without departing from the scope or spirit of the disclosure. Other embodiments will be apparent to those skilled in the art from consideration of the specification. The specification and examples are exemplary only.
Claims (9)
1. A graphite/alumina asymmetric membrane having a graphite layer and a porous alumina membrane layer, the graphite layer being located on one side surface of the porous alumina membrane,
the surface and interlayer of the porous alumina film, and the surface and interlayer of the graphite have hydroxyl functional groups.
2. The asymmetric graphite/alumina membrane of claim 1, wherein the pores in the porous alumina membrane layer have a size of 40 to 150 nm.
3. The asymmetric graphite/alumina membrane according to claim 1 or 2, having a rectification ratio of 2 to 6.
4. The asymmetric graphite/alumina membrane according to any one of claims 1 to 3, wherein the graphite layer has a thickness of 1 to 100 μm, and the porous alumina membrane layer has a thickness of 1 to 500 μm.
5. The method for producing the asymmetric graphite/alumina membrane according to any one of claims 1 to 4, which comprises the steps of:
a graphite gel preparation procedure: hydrolyzing methyltrimethoxysilane and concentrated hydrochloric acid in anhydrous methanol, adding graphite powder while hydrolyzing, and stirring to obtain gel containing graphite;
a graphite coating procedure: and coating the obtained gel containing the graphite on one side surface of alumina, and drying to obtain the graphite/alumina asymmetric membrane.
6. The method for preparing the asymmetric graphite/alumina membrane as claimed in claim 5, wherein the mass ratio of graphite powder to methyltrimethoxysilane is 1: 1-10: 1.
7. an ion rectifying device having the asymmetric graphite/alumina membrane of any one of claims 1 to 4, a dual chamber electrolytic cell, an electrolyte and two electrodes, the asymmetric graphite/alumina membrane being placed in the dual chamber electrolytic cell, the two electrodes being electrically connected.
8. The ion rectifying device of claim 7, wherein the two electrodes are Ag/AgCl electrodes.
9. The ion rectifying device according to claim 7 or 8, wherein the electrolyte is a KCl electrolyte having a concentration of 1 to 100 mM.
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Application publication date: 20201218 |