CN114965639B - Preparation method of mesoporous nano-channel with super-assembled multilayer sandwich structure - Google Patents
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Classifications
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
- G01N27/26—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating electrochemical variables; by using electrolysis or electrophoresis
- G01N27/28—Electrolytic cell components
- G01N27/30—Electrodes, e.g. test electrodes; Half-cells
- G01N27/327—Biochemical electrodes, e.g. electrical or mechanical details for in vitro measurements
- G01N27/3275—Sensing specific biomolecules, e.g. nucleic acid strands, based on an electrode surface reaction
- G01N27/3277—Sensing specific biomolecules, e.g. nucleic acid strands, based on an electrode surface reaction being a redox reaction, e.g. detection by cyclic voltammetry
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
- G01N27/26—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating electrochemical variables; by using electrolysis or electrophoresis
- G01N27/28—Electrolytic cell components
- G01N27/30—Electrodes, e.g. test electrodes; Half-cells
- G01N27/327—Biochemical electrodes, e.g. electrical or mechanical details for in vitro measurements
- G01N27/3275—Sensing specific biomolecules, e.g. nucleic acid strands, based on an electrode surface reaction
- G01N27/3278—Sensing specific biomolecules, e.g. nucleic acid strands, based on an electrode surface reaction involving nanosized elements, e.g. nanogaps or nanoparticles
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/13—Energy storage using capacitors
Abstract
The invention provides a preparation method of a mesoporous carbon/anodic aluminum oxide/mesoporous silicon nano channel with a super-assembled multilayer sandwich structure. The mesoporous carbon/anodic aluminum oxide/mesoporous silicon nano-channel device with the super-assembled multilayer sandwich structure prepared by the preparation method has a rich and regular two-dimensional hexagonal channel structure, and the pore sizes are respectively 7.5nm (mesoporous silicon) and 6.1nm (mesoporous carbon). The nanochannel device exhibits an asymmetric chemical composition, a surface charge distribution, and a hydrophilic-hydrophobic nature, and further has a rich oxygen-containing functional group. The preparation method provided by the invention has universality, the composition of the nano channel of the super-assembled multi-layer sandwich structure can be regulated by adjusting the types of mesoporous precursor solutions, and the thickness of the channel can be reasonably controlled by changing the spin coating times.
Description
Technical Field
The invention belongs to the technical field of mesoporous nano-channel film design, and particularly relates to a preparation method of a mesoporous carbon/anodic aluminum oxide/mesoporous silicon nano-channel with a super-assembled multilayer sandwich structure.
Background
Ion channels play a very important role in the human body, can selectively control one-way transmission of ions, and play a very important role in the aspects of cell state maintenance, signal transduction, body temperature regulation and the like. However, ion channels in organisms are generally embedded in cell membranes in the form of proteins, and have the disadvantages of being sensitive to environment and fragile in application, so that the ion channels are difficult to apply to actual life. In view of this, various artificial solid nanochannels have been developed for studying ion selectivity, ion gating, and ion rectification characteristics of ion channels. Common artificial solid nano-channels comprise polymer films prepared by a track etching method, two-dimensional nano-channel films prepared by a vacuum filtration method and the like. However, these membranes still have problems such as low porosity and irregular pore channels, which prevent ion transport. In addition, the uniqueness of the components also limits the functionality of the nanochannels, so that it is necessary to develop a multicomponent and rich and regular nanochannel device for the investigation of ion transport mechanisms.
With the development of thermodynamics, the evaporation-induced self-assembly strategy is widely applied, and the generation of mesoporous films provides a novel material for the field of nanochannels. The mesoporous film has the pore diameter of 2-50nm, and has the advantages of high porosity and regular and ordered pore canal, so that the mesoporous film can be used for constructing nano channel devices. However, the vulnerability of the mesoporous film results in a complex preparation method, and in this respect, the applicant of the present invention previously proposes a super-assembly method for preparing a mesoporous film/alumina composite, but the single component limits the functionality and application range thereof.
Disclosure of Invention
In order to solve the problems in the prior art, the invention provides a preparation method of a mesoporous carbon/anodic aluminum oxide/mesoporous silicon nano channel with a super-assembled multilayer sandwich structure.
The specific technical scheme of the invention is as follows:
the invention provides a preparation method of a mesoporous carbon/anodic aluminum oxide/mesoporous silicon nano channel with a super-assembled multilayer sandwich structure, which is characterized by comprising the following steps: step S1, preparing mesoporous carbon precursor solution; step S2, preparing mesoporous silicon precursor solution; s3, double-sided hole blocking is carried out on the anodic aluminum oxide, and double-sided hole blocking anodic aluminum oxide is obtained; s4, scraping the surfaces of the two sides of the double-sided hole plugging anodized aluminum, and cleaning by a cleaning agent to obtain the double-sided hole plugging anodized aluminum with a clean surface; step S5, respectively spinning Tu Jiekong carbon precursor solution and mesoporous silicon precursor solution on the clean two sides of the double-sided hole plugging anodized aluminum to obtain a multi-layer sandwich structure film; and S6, calcining the multi-layer sandwich structure membrane to obtain the mesoporous carbon/anodic aluminum oxide/mesoporous silicon nano channel of the super-assembled multi-layer sandwich structure.
The preparation method of the mesoporous carbon/anodic aluminum oxide/mesoporous silicon nano channel with the super-assembled multi-layer sandwich structure provided by the invention can also have the technical characteristics that the preparation process of the mesoporous carbon precursor solution in the step S1 is as follows: and (3) dissolving F127 in absolute ethyl alcohol, adding an ethanol solution of a resin carbon source after ultrasonic treatment to clarify, and stirring for 1-2 h at 30-50 ℃ to obtain a mesoporous carbon precursor solution.
The preparation method of the mesoporous carbon/anodic aluminum oxide/mesoporous silicon nano channel with the super-assembled multi-layer sandwich structure provided by the invention can also have the technical characteristics that the configuration process of a resin carbon source is as follows: heating and melting phenol at 45-48 ℃ until the phenol is completely melted, adding sodium hydroxide aqueous solution, uniformly stirring, adding formaldehyde, uniformly stirring at 70-75 ℃, adjusting pH to be neutral by hydrochloric acid, and removing water by rotary evaporation to obtain the resin carbon source.
The preparation method of the mesoporous carbon/anodic aluminum oxide/mesoporous silicon nano channel with the super-assembled multilayer sandwich structure provided by the invention can also have the technical characteristics that the preparation method of the mesoporous silicon precursor solution in the step S2 comprises the following specific steps: s2-1, dissolving F127 in absolute ethyl alcohol to obtain a mesoporous silicon precursor template agent F127 solution; s2-2, mixing dilute hydrochloric acid, deionized water and absolute ethyl alcohol to obtain a mixed solution; step S2-3, slowly dripping tetraethyl orthosilicate into the mixed solution, and stirring for 0.5-1 h at room temperature; step S2-4, stirring the mixed solution at 55-65 ℃ for 1-2 hours to obtain silica gel; and S2-5, cooling the silica gel to room temperature, slowly dropwise adding the cooled silica gel into the mesoporous silicon precursor template agent F127 solution, and stirring for 1-2 hours at room temperature to obtain the mesoporous silicon precursor solution.
The preparation method of the mesoporous carbon/anodic aluminum oxide/mesoporous silicon nano channel with the super-assembled multi-layer sandwich structure provided by the invention can also have the technical characteristics that the specific steps of blocking holes on two sides in the step S3 are as follows: s3-1, preparing 8-10wt% polymethyl methacrylate solution; s3-2, spin-coating a polymethyl methacrylate solution on one surface of the anodic aluminum oxide, drying the surface at room temperature for 1-2 hours, spin-coating the polymethyl methacrylate solution on the other surface of the anodic aluminum oxide, and drying the surface at room temperature for 1-2 hours to obtain the spin-coated anodic aluminum oxide of the polymethyl methacrylate solution; and S3-3, placing the polymethyl methacrylate solution spin-coated anodized aluminum into a baking oven at 190-210 ℃ for 3-4 hours, performing turn-over treatment on the polymethyl methacrylate solution spin-coated anodized aluminum, and then continuously placing the aluminum in the baking oven at 190-210 ℃ for 3-4 hours to obtain the double-sided plugged anodized aluminum.
The preparation method of the mesoporous carbon/anodic aluminum oxide/mesoporous silicon nano channel with the super-assembled multi-layer sandwich structure provided by the invention can also have the technical characteristics that the cleaning agent in the step S4 is deionized water and ethanol.
The preparation method of the mesoporous carbon/anodic aluminum oxide/mesoporous silicon nano channel with the super-assembled multilayer sandwich structure provided by the invention can also have the technical characteristics that the clean double-sided rotation Tu Jiekong carbon precursor solution and mesoporous silicon precursor solution of the double-sided hole plugging anodic aluminum oxide in the step S5 comprises the following specific steps: step S5-1, spin-coating a mesoporous silicon precursor solution on one surface of the double-sided hole plugging anodized aluminum to obtain a mesoporous silicon/anodized aluminum film; s5-2, placing the mesoporous silicon/anodic aluminum oxide film in an oven at 38-45 ℃ for evaporation induction self-assembly for 8-10 h; step S5-3, spin-coating a mesoporous carbon precursor solution on the other surface of the double-sided hole plugging anodized aluminum to obtain a mesoporous carbon/anodized aluminum/mesoporous silicon film; and S5-4, placing the mesoporous carbon/anodic aluminum oxide/mesoporous silicon film in an oven at 38-45 ℃ for evaporation induction self-assembly for 12-15 h, and then raising the temperature to 100-110 ℃ for holding for 24-28 h to obtain the multilayer sandwich structure film.
The preparation method of the mesoporous carbon/anodic aluminum oxide/mesoporous silicon nano channel with the super-assembled multi-layer sandwich structure provided by the invention can also have the technical characteristics that the calcining temperature in the step S6 is 400-450 ℃ and the calcining time is 5-6 h.
The invention also provides a mesoporous carbon/anodic aluminum oxide/mesoporous silicon nano channel with the super-assembled multi-layer sandwich structure, which is characterized by being prepared by adopting the preparation method of the mesoporous carbon/anodic aluminum oxide/mesoporous silicon nano channel with the super-assembled multi-layer sandwich structure.
The mesoporous carbon/anodic aluminum oxide/mesoporous silicon nano channel of the super-assembled multi-layer sandwich structure provided by the invention can also have the technical characteristics of rich and ordered two-dimensional hexagonal channel structure, and has asymmetric chemical composition, surface charge distribution and hydrophilicity and hydrophobicity.
Effects and effects of the invention
The mesoporous carbon/anodic aluminum oxide/mesoporous silicon nano channel with the super-assembled multi-layer sandwich structure is prepared by adopting a mature super-assembly method and an evaporation induced self-assembly (EISA) method. The nano channel device has rich and regular pore canal structure, can provide rich ion transmission paths for ions, and has potential application value in the field of nano flow control; the nano-channel device presents asymmetric chemical composition, surface charge distribution and hydrophilicity and hydrophobicity, and can be used for logic gate control, energy conversion and other applications; the nanochannel device also has rich oxygen-containing functional groups that can be further modified with functional molecules for molecular recognition and detection.
Compared with the prior art, the preparation method of the mesoporous carbon/anodic aluminum oxide/mesoporous silicon nano channel with the super-assembled multi-layer sandwich structure has the following advantages:
1. different mesoporous materials can be respectively grown on two sides of the anodic aluminum oxide by adopting a double hole blocking method;
2. the nano channel with the multi-layer multi-component sandwich structure can be prepared by adopting the super assembly method, the multi-component device has more functions, and the nano channel device can be further used in the fields of molecular recognition, separation detection and the like by carrying out functional modification;
3. the preparation method has universality, and the nano-channel device with various multi-layer sandwich structures can be prepared by adjusting the types of mesoporous precursor solutions, the spin coating rotating speed and the spin coating times.
Drawings
FIG. 1 is a flow chart showing the preparation of MC/AAO/MS prepared in example 1 of the present invention.
FIG. 2 is an SEM image of MC/AAO/MS produced in example 1 of the present invention. Among them, fig. 2 (a), fig. (b) and fig. 2 (c) are surface SEM images of the MC side; fig. 2 (d), fig. (e) and fig. 2 (f) are surface SEM images of the MS side; FIG. 2 (g) is an SEM of a section of MC/AAO/MS; FIG. 2 (h) is an enlarged SEM of a section of the MC side; fig. 2 (i) is an enlarged SEM image of a cross section of the MS side.
FIG. 3 is a TEM image of MC and MS of MC/AAO/MS prepared in example 1 of the present invention. FIG. 3 (a) is a TEM image of the MS (110) face; FIG. 3 (b) is a TEM image of the MS (001) side; FIG. 3 (c) is a TEM image of the MC (110) plane; fig. 3 (d) is a TEM image of the MC (001) plane.
FIG. 4 is a SAXS diagram of MC and MS of MC/AAO/MS prepared in example 1 of the present invention. FIG. 4 (a) is a SAXS diagram of MC; fig. 4 (b) is a SAXS diagram of the MS.
FIG. 5 is a graph showing the nitrogen adsorption and desorption curves and pore size distribution of MC and MS of MC/AAO/MS prepared in example 1 of the present invention. FIG. 5 (a) is a nitrogen adsorption and desorption curve of MS; FIG. 5 (b) is a pore size distribution diagram of MS;
FIG. 5 (c) is a nitrogen adsorption and desorption curve of MC; fig. 5 (d) is a pore size distribution diagram of MC.
FIG. 6 is a FTIR chart of MC and MS of MC/AAO/MS prepared in example 1 of the present invention. FIG. 6 (a) is an FTIR diagram of MC; fig. 6 (b) is an FTIR diagram of the MS.
Detailed Description
The terms used in the present invention generally have meanings commonly understood by those of ordinary skill in the art unless otherwise indicated.
In the following examples, various processes and methods, which are not described in detail, are conventional methods well known in the art.
The reagents used in the examples below are commercially available in general, and the experimental procedures and conditions not noted are referred to in the art as conventional procedures and conditions.
The Anodic Aluminum Oxide (AAO) used in each of the examples described below was a commercial AAO film having a thickness of 60 μm, a pore size of 80nm, and a circular substrate having a diameter of 15 mm.
Specific embodiments of the present invention are described below with reference to the accompanying drawings.
Example 1 ]
The embodiment provides a preparation method of a mesoporous carbon/anodic aluminum oxide/mesoporous silicon nano channel (MC/AAO/MS) with a super-assembled multilayer sandwich structure, which comprises the following steps:
step S1, preparing mesoporous carbon precursor solution, wherein the specific process is as follows:
dissolving 0.5g of F127 in 5g of absolute ethyl alcohol, adding 6g of 20wt% of ethanol solution of a resin carbon source after ultrasonic treatment to clarification, transferring into an oil bath pot at 40 ℃ and magnetically stirring for 1h to obtain mesoporous carbon precursor solution,
wherein, the configuration process of the resin carbon source is as follows:
adding 2.44g of phenol into a 100ml two-neck flask, heating and melting at 45 ℃ until the phenol is completely melted, adding 0.52g of 20wt% sodium hydroxide aqueous solution, stirring for 10min until the phenol is uniform, adding 4.2g of formaldehyde, heating an oil bath to 70 ℃, stirring for 1h until the phenol is uniform, regulating the pH to be neutral by hydrochloric acid, and removing water by rotary evaporation to obtain a resol carbon source;
step S2, preparing mesoporous silicon precursor solution, wherein the specific process is as follows:
step S2-1, dissolving 0.4g of F127 in 10g of absolute ethyl alcohol to obtain mesoporous silicon precursor template F127 solution,
step S2-2, mixing 0.4g of 0.1M dilute hydrochloric acid, 0.5g of deionized water and 10.0g of absolute ethyl alcohol to obtain a mixed solution,
step S2-3, slowly dripping 2.08g of tetraethyl orthosilicate (TEOS) into the mixed solution stirred on a magnetic stirrer, stirring for 0.5h at room temperature,
s2-4, transferring the solution into an oil bath pot at 60 ℃ and stirring for 1h to obtain silica gel,
s2-5, cooling the silica gel to room temperature, slowly dropwise adding the cooled silica gel into a mesoporous silicon precursor template agent F127 solution, and stirring for 1h at room temperature to obtain a mesoporous silicon precursor solution;
step S3, double-sided hole plugging is carried out on the anodized aluminum, and the double-sided hole plugging anodized aluminum is obtained, which comprises the following specific steps:
step S3-1, preparing 8wt% polymethyl methacrylate (PMMA) solution,
step S3-2, spin-coating PMMA solution on one surface of Anodic Aluminum Oxide (AAO) at a spin-coating rotating speed of 3000rad/S for 30S, drying at room temperature for 1h, spin-coating PMMA solution on the other surface of AAO by the same method, drying at room temperature for 1h to obtain polymethyl methacrylate solution spin-coated anodic aluminum oxide,
s3-3, placing the polymethyl methacrylate solution spin-coated anodized aluminum into a 200 ℃ oven for 3 hours, then performing turn-over treatment on the polymethyl methacrylate solution spin-coated anodized aluminum, and then continuously placing the mixture in the 200 ℃ oven for 3 hours to obtain double-sided hole plugging anodized aluminum;
step S4, scraping PMMA on the surfaces of the two sides of the double-sided hole-blocking anodized aluminum by adopting 1000-mesh sand paper, and then cleaning the PMMA with deionized water and ethanol for 3 times respectively to obtain the double-sided hole-blocking anodized aluminum with a clean surface;
step S5, respectively spinning Tu Jiekong carbon precursor solution and mesoporous silicon precursor solution on the clean two sides of the double-sided hole plugging anodized aluminum to obtain a multi-layer sandwich structure film, wherein the specific steps are as follows:
step S5-1, spin-coating a mesoporous silicon precursor solution on one surface of the double-sided hole plugging anodized aluminum, wherein the spin-coating speed is 3500rad/S, the spin-coating time is 40S, and a mesoporous silicon/anodized aluminum film is obtained,
step S5-2, the mesoporous silicon/anodic aluminum oxide film is put in a baking oven at 40 ℃ for evaporation induction self-assembly for 8 hours,
step S5-3, spin-coating mesoporous carbon precursor solution on the other surface of the double-sided hole-plugging anodized aluminum, spin-coating rotating speed is 3000rad/S, spin-coating time is 60S, obtaining a mesoporous carbon/anodized aluminum/mesoporous silicon film,
s5-4, placing the mesoporous carbon/anodic aluminum oxide/mesoporous silicon film in a baking oven at 40 ℃ for evaporation induction self-assembly for 12 hours, then raising the temperature to 100 ℃, and keeping for 24 hours to obtain a multi-layer sandwich structure film;
and S6, placing the multilayer sandwich structure membrane in a tube furnace for calcination, firstly heating to 400 ℃ at a speed of 1 ℃/min, then calcining for 5 hours at a constant temperature, and removing the template agent F127 and redundant PMMA to obtain the mesoporous carbon/anodic aluminum oxide/mesoporous silicon nano channel of the super-assembled multilayer sandwich structure.
FIG. 1 is a flow chart showing the preparation of MC/AAO/MS prepared in example 1 of the present invention. In fig. 1, 1 is Mesoporous Silicon (MS), 2 is Anodic Aluminum Oxide (AAO), 3 is Mesoporous Carbon (MC), and 4 is polymethyl methacrylate (PMMA).
Scanning Electron Microscope (SEM) characterization is carried out on mesoporous carbon/anodic aluminum oxide/mesoporous silicon nano channels (MC/AAO/MS) of the super-assembled multilayer sandwich structure prepared in the embodiment, and Transmission Electron Microscope (TEM), X-ray small angle scattering (SAXS), nitrogen adsorption and desorption curves and Fourier Transform Infrared (FTIR) characterization are carried out on Mesoporous Silicon (MS) and Mesoporous Carbon (MC) in the MC/AAO/MS.
FIG. 2 is an SEM image of MC/AAO/MS produced in example 1 of the present invention. Among them, fig. 2 (a), fig. (b) and fig. 2 (c) are surface SEM images of the MC side; fig. 2 (d), fig. (e) and fig. 2 (f) are surface SEM images of the MS side; FIG. 2 (g) is an SEM of a section of MC/AAO/MS; FIG. 2 (h) is an enlarged SEM of a section of the MC side; fig. 2 (i) is an enlarged SEM image of a cross section of the MS side.
FIG. 3 is a TEM image of MC and MS of MC/AAO/MS prepared in example 1 of the present invention. FIG. 3 (a) is a TEM image of the MS (110) face; FIG. 3 (b) is a TEM image of the MS (001) side; FIG. 3 (c) is a TEM image of the MC (110) plane; fig. 3 (d) is a TEM image of the MC (001) plane. As shown in fig. 3, the mesoporous carbon/anodized aluminum/mesoporous silicon nanochannel (MC/AAO/MS) of the super-assembled multi-layer sandwich structure prepared in this embodiment has a rich and regular pore structure.
FIG. 4 is a SAXS diagram of MC and MS of MC/AAO/MS prepared in example 1 of the present invention. FIG. 4 (a) is a SAXS diagram of MC; fig. 4 (b) is a SAXS diagram of the MS. As can be seen from fig. 4, the mesoporous carbon/anodized aluminum/mesoporous silicon nano-channel (MC/AAO/MS) of the super-assembled multi-layer sandwich structure prepared in this embodiment has a two-dimensional hexagonal channel structure.
FIG. 5 is a graph showing the nitrogen adsorption and desorption curves and pore size distribution of MC and MS of MC/AAO/MS prepared in example 1 of the present invention. FIG. 5 (a) is a nitrogen adsorption and desorption curve of MS; FIG. 5 (b) is a pore size distribution diagram of MS; FIG. 5 (c) is a nitrogen adsorption and desorption curve of MC; fig. 5 (d) is a pore size distribution diagram of MC. As shown in fig. 5 (a) and fig. 5 (c), the nitrogen adsorption and desorption curves of MS and MC are typical IV curves, which further proves that the mesoporous carbon/anodized aluminum/mesoporous silicon nanochannel (MC/AAO/MS) of the super-assembled multi-layer sandwich structure prepared in this embodiment has a regular pore structure; as shown in FIGS. 5 (b) and 5 (d), the MS has a pore diameter of about 7.5nm and the MC has a pore diameter of about 6.11 nm.
FIG. 6 is a FTIR chart of MC and MS of MC/AAO/MS prepared in example 1 of the present invention. FIG. 6 (a) is an FTIR diagram of MC; fig. 6 (b) is an FTIR diagram of the MS. As shown in FIG. 6 (a), on the FTIR chart of MC, 3438cm -1 Is the absorption peak of a large amount of phenolic hydroxyl groups, 2939cm -1 Is the absorption peak of benzene ring hydrocarbon, 1735cm -1 Is the absorption peak of carboxyl carbonyl generated after calcination, 1063cm -1 Is the vibration absorption peak of the benzene ring framework. As shown in FIG. 6 (b), on the FTIR chart of MS, 3451cm -1 Is the absorption peak of silicon hydroxyl group, 1063cm -1 Is the absorption peak of the siloxane bond. The mesoporous carbon/anodic aluminum oxide/mesoporous silicon nano channel (MC/AAO/MS) of the super-assembled multi-layer sandwich structure prepared by the embodiment has rich oxygen-containing functional groups, and further has rich negative charges.
Example 2 ]
The embodiment provides a preparation method of mesoporous carbon/anodic aluminum oxide/mesoporous carbon nano channel (MC/AAO/MC) of a super-assembled multilayer sandwich structure, which comprises the following steps:
step S1, preparing mesoporous carbon precursor solution, wherein the specific process is as follows:
dissolving 0.5g of F127 in 5g of absolute ethyl alcohol, adding 6g of 20wt% of ethanol solution of a resin carbon source after ultrasonic treatment to clarification, transferring into an oil bath pot at 40 ℃ and magnetically stirring for 1h to obtain mesoporous carbon precursor solution,
wherein, the configuration process of the resin carbon source is as follows:
adding 2.44g of phenol into a 100ml two-neck flask, heating and melting at 45 ℃ until the phenol is completely melted, adding 0.52g of 20wt% sodium hydroxide aqueous solution, stirring for 10min until the phenol is uniform, adding 4.2g of formaldehyde, heating an oil bath to 70 ℃, stirring for 1h until the phenol is uniform, regulating the pH to be neutral by hydrochloric acid, and removing water by rotary evaporation to obtain a resol carbon source;
step S2, double-sided hole plugging is carried out on the anodized aluminum, and the double-sided hole plugging anodized aluminum is obtained, which comprises the following specific steps:
step S2-1, preparing 9wt% polymethyl methacrylate (PMMA) solution,
step S2-2, spin-coating PMMA solution on one surface of Anodic Aluminum Oxide (AAO) at a spin-coating rotating speed of 3000rad/S for 30S, drying at room temperature for 1h, spin-coating PMMA solution on the other surface of AAO by adopting the same method, drying at room temperature for 1h to obtain polymethyl methacrylate solution spin-coated anodic aluminum oxide,
s2-3, placing the polymethyl methacrylate solution spin-coated anodized aluminum into a 200 ℃ oven for 3 hours, then performing turn-over treatment on the polymethyl methacrylate solution spin-coated anodized aluminum, and then continuously placing the mixture in the 200 ℃ oven for 3 hours to obtain double-sided hole plugging anodized aluminum;
step S3, scraping PMMA on the surfaces of the two sides of the double-sided hole-blocking anodized aluminum by adopting 1000-mesh sand paper, and then cleaning the PMMA with deionized water and ethanol for 3 times respectively to obtain the double-sided hole-blocking anodized aluminum with a clean surface;
step S4, respectively spinning Tu Jiekong carbon precursor solutions on the clean two sides of the double-sided hole plugging anodized aluminum to obtain a multi-layer sandwich structure film, wherein the specific steps are as follows:
step S4-1, spin-coating mesoporous carbon precursor solution on one surface of double-sided hole plugging anodized aluminum, spin-coating rotating speed is 3000rad/S, spin-coating time is 60S, obtaining mesoporous carbon/anodized aluminum film,
step S4-2, the mesoporous carbon/anodic aluminum oxide film is placed in a baking oven at 40 ℃ to be evaporated and induced to self-assemble for 8 hours,
step S4-3, spin-coating mesoporous carbon precursor solution on the other surface of the double-sided hole-plugging anodized aluminum, spin-coating rotating speed is 3000rad/S, spin-coating time is 60S, obtaining mesoporous carbon/anodized aluminum/mesoporous carbon film,
step S4-4, placing the mesoporous carbon/anodic aluminum oxide/mesoporous carbon film in a baking oven at 40 ℃ for evaporation induction self-assembly for 12 hours, then raising the temperature to 100 ℃, and keeping for 24 hours to obtain a multi-layer sandwich structure film;
and S5, placing the multilayer sandwich structure membrane in a tube furnace for calcination, firstly heating to 400 ℃ at a speed of 1 ℃/min, then calcining for 5 hours at a constant temperature, and removing the template agent F127 and redundant PMMA to obtain the mesoporous carbon/anodic aluminum oxide/mesoporous carbon nano channel of the super-assembled multilayer sandwich structure.
Example 3 ]
The embodiment provides a preparation method of a mesoporous silicon/anodic aluminum oxide/mesoporous silicon nano channel (MS/AAO/MS) with a super-assembled multilayer sandwich structure, which comprises the following steps:
step S1, preparing mesoporous silicon precursor solution, wherein the specific process is as follows:
step S1-1, 1.2g of F127 is dissolved in 10g of absolute ethyl alcohol to obtain mesoporous silicon precursor template agent F127 solution,
step S1-2, mixing 0.6g of 0.1M dilute hydrochloric acid, 0.8g of deionized water and 10.0g of absolute ethyl alcohol to obtain a mixed solution,
step S1-3, slowly dripping 2.08g of tetraethyl orthosilicate (TEOS) into the mixed solution stirred on a magnetic stirrer, stirring for 0.5h at room temperature,
step S1-4, transferring the solution into an oil bath pot at 60 ℃ and stirring for 1h to obtain silica gel,
s1-5, cooling the silica gel to room temperature, slowly dripping the cooled silica gel into a mesoporous silicon precursor template agent F127 solution, and stirring the solution for 1h at room temperature to obtain a mesoporous silicon precursor solution;
step S2, double-sided hole plugging is carried out on the anodized aluminum, and the double-sided hole plugging anodized aluminum is obtained, which comprises the following specific steps:
step S2-1, preparing 10wt% polymethyl methacrylate (PMMA) solution,
step S2-2, spin-coating PMMA solution on one surface of Anodic Aluminum Oxide (AAO) at a spin-coating rotating speed of 3000rad/S for 30S, drying at room temperature for 1h, spin-coating PMMA solution on the other surface of AAO by adopting the same method, drying at room temperature for 1h to obtain polymethyl methacrylate solution spin-coated anodic aluminum oxide,
s2-3, placing the polymethyl methacrylate solution spin-coated anodized aluminum into a 200 ℃ oven for 3 hours, then performing turn-over treatment on the polymethyl methacrylate solution spin-coated anodized aluminum, and then continuously placing the mixture in the 200 ℃ oven for 3 hours to obtain double-sided hole plugging anodized aluminum;
step S3, scraping PMMA on the surfaces of the two sides of the double-sided hole-blocking anodized aluminum by adopting 1000-mesh sand paper, and then cleaning the PMMA with deionized water and ethanol for 3 times respectively to obtain the double-sided hole-blocking anodized aluminum with a clean surface;
step S4, respectively spinning Tu Jiekong silicon precursor solution on the clean two sides of the double-sided hole plugging anodized aluminum to obtain a multi-layer sandwich structure film, wherein the specific steps are as follows:
step S4-1, spin-coating a mesoporous silicon precursor solution on one surface of the double-sided hole plugging anodized aluminum, wherein the spin-coating speed is 3500rad/S, the spin-coating time is 40S, and a mesoporous silicon/anodized aluminum film is obtained,
step S4-2, placing the mesoporous silicon/anodic aluminum oxide film in a baking oven at 40 ℃ for evaporation induction self-assembly for 8 hours,
step S4-3, spin-coating mesoporous silicon precursor solution on the other surface of the double-sided hole plugging anodized aluminum, spin-coating rotating speed is 3500rad/S, spin-coating time is 40S, obtaining mesoporous silicon/anodized aluminum/mesoporous silicon film,
step S4-4, placing the mesoporous silicon/anodic aluminum oxide/mesoporous silicon film in a baking oven at 40 ℃ for evaporation induction self-assembly for 12 hours, then raising the temperature to 100 ℃, and keeping for 24 hours to obtain a multi-layer sandwich structure film;
and S5, placing the multilayer sandwich structure membrane in a tube furnace for calcination, firstly heating to 400 ℃ at a speed of 1 ℃/min, then calcining for 5 hours at a constant temperature, and removing the template agent F127 and redundant PMMA to obtain the mesoporous silicon/anodic aluminum oxide/mesoporous silicon nano channel of the super-assembled multilayer sandwich structure.
Example 4 ]
The embodiment provides a preparation method of a mesoporous carbon/anodic aluminum oxide/mesoporous silicon nano channel (MC/AAO/MS) with different spin-coating thicknesses and a super-assembled multi-layer sandwich structure, which comprises the following steps:
step S1, preparing mesoporous carbon precursor solution, wherein the specific process is as follows:
dissolving 0.5g of F127 in 5g of absolute ethyl alcohol, adding 6g of 20wt% of ethanol solution of a resin carbon source after ultrasonic treatment to clarification, transferring into an oil bath pot at 40 ℃ and magnetically stirring for 1h to obtain mesoporous carbon precursor solution,
wherein, the configuration process of the resin carbon source is as follows:
adding 2.44g of phenol into a 100ml two-neck flask, heating and melting at 45 ℃ until the phenol is completely melted, adding 0.52g of 20wt% sodium hydroxide aqueous solution, stirring for 10min until the phenol is uniform, adding 4.2g of formaldehyde, heating an oil bath to 70 ℃, stirring for 1h until the phenol is uniform, regulating the pH to be neutral by hydrochloric acid, and removing water by rotary evaporation to obtain a resol carbon source;
step S2, preparing mesoporous silicon precursor solution, wherein the specific process is as follows:
step S2-1, 1.2g of F127 is dissolved in 10g of absolute ethyl alcohol to obtain mesoporous silicon precursor template F127 solution,
step S2-2, mixing 0.6g of 0.1M dilute hydrochloric acid, 0.8g of deionized water and 10.0g of absolute ethyl alcohol to obtain a mixed solution,
step S2-3, slowly dripping 2.08g of tetraethyl orthosilicate (TEOS) into the mixed solution stirred on a magnetic stirrer, stirring for 0.5h at room temperature,
s2-4, transferring the solution into an oil bath pot at 60 ℃ and stirring for 1h to obtain silica gel,
s2-5, cooling the silica gel to room temperature, slowly dropwise adding the cooled silica gel into a mesoporous silicon precursor template agent F127 solution, and stirring for 1h at room temperature to obtain a mesoporous silicon precursor solution;
step S3, double-sided hole plugging is carried out on the anodized aluminum, and the double-sided hole plugging anodized aluminum is obtained, which comprises the following specific steps:
step S3-1, preparing 10wt% polymethyl methacrylate (PMMA) solution,
step S3-2, spin-coating PMMA solution on one surface of Anodic Aluminum Oxide (AAO) at a spin-coating rotating speed of 3000rad/S for 30S, drying at room temperature for 1h, spin-coating PMMA solution on the other surface of AAO by the same method, drying at room temperature for 1h to obtain polymethyl methacrylate solution spin-coated anodic aluminum oxide,
s3-3, placing the polymethyl methacrylate solution spin-coated anodized aluminum into a 200 ℃ oven for 3 hours, then performing turn-over treatment on the polymethyl methacrylate solution spin-coated anodized aluminum, and then continuously placing the mixture in the 200 ℃ oven for 3 hours to obtain double-sided hole plugging anodized aluminum;
step S4, scraping PMMA on the surfaces of the two sides of the double-sided hole-blocking anodized aluminum by adopting 1000-mesh sand paper, and then cleaning the PMMA with deionized water and ethanol for 3 times respectively to obtain the double-sided hole-blocking anodized aluminum with a clean surface;
step S5, respectively spinning Tu Jiekong carbon precursor solution and mesoporous silicon precursor solution on the clean two sides of the double-sided hole plugging anodized aluminum to obtain a multi-layer sandwich structure film, wherein the specific steps are as follows:
step S5-1, spin-coating mesoporous silicon precursor solution on one surface of the double-sided hole plugging anodized aluminum for 2 times, wherein the spin-coating rotating speed is 3500rad/S each time, the spin-coating time is 40S each time, the spin-coating time interval is 2h each time, so as to ensure that the evaporation induction self-assembly of the silicon precursor solution is completed each time, the mesoporous silicon/anodized aluminum film is obtained after 2 times of spin-coating,
step S5-2, the mesoporous silicon/anodic aluminum oxide film is put in a baking oven at 40 ℃ for evaporation induction self-assembly for 8 hours,
step S5-3, spin-coating the mesoporous carbon precursor solution on the other surface of the double-sided hole plugging anodized aluminum for 2 times, wherein the spin-coating rotating speed is 3000rad/S each time, the spin-coating time is 60S each time, the spin-coating time interval is 2h each time, so as to ensure that the evaporation induction self-assembly of the Tu Jiekong carbon precursor solution is completed each time, the mesoporous carbon/anodized aluminum/mesoporous silicon film is obtained after 2 times of spin-coating,
s5-4, placing the mesoporous carbon/anodic aluminum oxide/mesoporous silicon film in a baking oven at 40 ℃ for evaporation induction self-assembly for 12 hours, then raising the temperature to 100 ℃, and keeping for 24 hours to obtain a multi-layer sandwich structure film;
and S6, placing the multilayer sandwich structure film in a tube furnace for calcination, firstly heating to 400 ℃ at a speed of 1 ℃/min, then calcining for 5 hours at a constant temperature, and removing the template agent F127 and redundant PMMA to obtain the mesoporous carbon/anodic aluminum oxide/mesoporous silicon nano-channels of the super-assembled multilayer sandwich structure with different spin-coating thicknesses.
The foregoing is a detailed description of the embodiments, convenient those skilled in the art are able to make and use the present invention. Those skilled in the art, based on the present invention, should not be subjected to innovative work, but rather should be able to obtain improvements or modifications by means of analysis, analogies or limited enumeration, etc. within the scope of protection defined by the following claims.
Claims (10)
1. The preparation method of the mesoporous carbon/anodic aluminum oxide/mesoporous silicon nano channel of the super-assembled multilayer sandwich structure is characterized by comprising the following steps of:
step S1, preparing mesoporous carbon precursor solution;
step S2, preparing mesoporous silicon precursor solution;
s3, double-sided hole blocking is carried out on the anodic aluminum oxide, and double-sided hole blocking anodic aluminum oxide is obtained;
s4, scraping the surfaces of the two sides of the double-sided hole plugging anodized aluminum, and cleaning by a cleaning agent to obtain the double-sided hole plugging anodized aluminum with a clean surface;
step S5, respectively spin-coating the mesoporous carbon precursor solution and the mesoporous silicon precursor solution on clean two sides of the double-sided hole plugging anodic aluminum oxide to obtain a multilayer sandwich structure film;
and S6, calcining the multilayer sandwich structure membrane to obtain the mesoporous carbon/anodic aluminum oxide/mesoporous silicon nano channel of the super-assembled multilayer sandwich structure.
2. The method for preparing the mesoporous carbon/anodized aluminum/mesoporous silicon nanochannel with the super-assembled multi-layer sandwich structure according to claim 1, wherein the method comprises the steps of,
the preparation process of the mesoporous carbon precursor solution in the step S1 is as follows:
and dissolving F127 in absolute ethyl alcohol, carrying out ultrasonic treatment until the solution is clear, adding an ethanol solution of a resin carbon source, and stirring for 1-2 hours at 30-50 ℃ to obtain the mesoporous carbon precursor solution.
3. The method for preparing the mesoporous carbon/anodized aluminum/mesoporous silicon nanochannel with the super-assembled multi-layer sandwich structure according to claim 2, wherein the method comprises the steps of,
wherein, the configuration process of the resin carbon source is as follows:
and heating and melting phenol at 45-48 ℃ until the phenol is completely melted, adding sodium hydroxide aqueous solution, uniformly stirring, adding formaldehyde, uniformly stirring at 70-75 ℃, adjusting the pH to be neutral by hydrochloric acid, and removing water by rotary evaporation to obtain the resol carbon source.
4. The method for preparing the mesoporous carbon/anodized aluminum/mesoporous silicon nanochannel with the super-assembled multi-layer sandwich structure according to claim 1, wherein the method comprises the steps of,
the specific process of preparing the mesoporous silicon precursor solution in the step S2 is as follows:
s2-1, dissolving F127 in absolute ethyl alcohol to obtain a mesoporous silicon precursor template agent F127 solution;
s2-2, mixing dilute hydrochloric acid, deionized water and absolute ethyl alcohol to obtain a mixed solution;
step S2-3, slowly dripping tetraethyl orthosilicate into the mixed solution, and stirring for 0.5-1 h at room temperature;
step S2-4, stirring the mixed solution at 55-65 ℃ for 1-2 hours to obtain silica gel;
and S2-5, cooling the silica gel to room temperature, slowly dropwise adding the cooled silica gel into the mesoporous silicon precursor template agent F127 solution, and stirring for 1-2 hours at room temperature to obtain the mesoporous silicon precursor solution.
5. The method for preparing the mesoporous carbon/anodized aluminum/mesoporous silicon nanochannel with the super-assembled multi-layer sandwich structure according to claim 1, wherein the method comprises the steps of,
the specific steps of the double-sided hole blocking in the step S3 are as follows:
s3-1, preparing 8-10wt% of polymethyl methacrylate solution;
s3-2, spin-coating the polymethyl methacrylate solution on one surface of the anodic aluminum oxide, drying the polymethyl methacrylate solution at room temperature for 1-2 hours, spin-coating the polymethyl methacrylate solution on the other surface of the anodic aluminum oxide, and drying the polymethyl methacrylate solution at room temperature for 1-2 hours to obtain the polymethyl methacrylate solution spin-coated anodic aluminum oxide;
and S3-3, placing the polymethyl methacrylate solution spin-coated anodized aluminum into a baking oven at 190-210 ℃ for 3-4 hours, performing turn-over treatment on the polymethyl methacrylate solution spin-coated anodized aluminum, and then continuously placing the aluminum in the baking oven at 190-210 ℃ for 3-4 hours to obtain the double-sided plugged anodized aluminum.
6. The method for preparing the mesoporous carbon/anodized aluminum/mesoporous silicon nanochannel with the super-assembled multi-layer sandwich structure according to claim 1, wherein the method comprises the steps of,
the cleaning agent in the step S4 is deionized water and ethanol.
7. The method for preparing the mesoporous carbon/anodized aluminum/mesoporous silicon nanochannel with the super-assembled multi-layer sandwich structure according to claim 1, wherein the method comprises the steps of,
the step S5 of spin-coating the mesoporous carbon precursor solution and the mesoporous silicon precursor solution on the clean two sides of the double-sided plugged anodized aluminum comprises the following specific steps:
step S5-1, spin-coating the mesoporous silicon precursor solution on one surface of the double-sided hole plugging anodized aluminum to obtain a mesoporous silicon/anodized aluminum film;
s5-2, placing the mesoporous silicon/anodic aluminum oxide film in an oven at 38-45 ℃ for evaporation induction self-assembly for 8-10 h;
s5-3, spin-coating the mesoporous carbon precursor solution on the other surface of the double-sided hole plugging anodized aluminum to obtain a mesoporous carbon/anodized aluminum/mesoporous silicon film;
and S5-4, placing the mesoporous carbon/anodic aluminum oxide/mesoporous silicon film in an oven at 38-45 ℃ to evaporate and induce self-assembly for 12-15 h, then raising the temperature to 100-110 ℃ and keeping for 24-28 h to obtain the multilayer sandwich structure film.
8. The method for preparing the mesoporous carbon/anodized aluminum/mesoporous silicon nanochannel with the super-assembled multi-layer sandwich structure according to claim 1, wherein the method comprises the steps of,
wherein the calcining temperature of the calcining in the step S6 is 400-450 ℃,
the calcination time is 5-6 h.
9. The mesoporous carbon/anodic aluminum oxide/mesoporous silicon nanochannel of a super-assembled multi-layer sandwich structure, which is characterized in that the mesoporous carbon/anodic aluminum oxide/mesoporous silicon nanochannel of the super-assembled multi-layer sandwich structure is prepared by adopting the preparation method of the mesoporous carbon/anodic aluminum oxide/mesoporous silicon nanochannel of the super-assembled multi-layer sandwich structure as claimed in any one of claims 1 to 8.
10. The mesoporous carbon/anodized aluminum/mesoporous silicon nanochannel of the super assembled multi-layered sandwich structure according to claim 9, wherein it has a two-dimensional hexagonal channel structure exhibiting asymmetric chemical composition, surface charge distribution and hydrophilicity and hydrophobicity.
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