Preparation method of vertical channel mesoporous carbon titanium / anodic aluminum oxide heterogeneous nanochannels by a superassembly strategy

Abstract

The present invention provides a preparation method for preparing vertically channeled mesoporous carbon titanium / anodic aluminum oxide heteronanopores (MCT / AAO) by a superassembly strategy. The vertically channeled mesoporous carbon titanium / anodic aluminum oxide heteronanopores prepared by this preparation method have a rich and regular pore structure, and the pore size is 4.87 nm. The nanoholes exhibit an asymmetric chemical composition, surface charge distribution, and channel structure. In the mesoporous carbon titanium layer, the mesoporous carbon framework contains rich oxygen-containing functional groups, which mainly provide negative charge sites for regulating ion transport. The titanium oxide nanocrystals embedded in the mesoporous carbon framework endow the nanoholes with photo-controlled ion transport properties due to their optoelectronic properties. The channels of the mesoporous carbon titanium layer are vertically connected to the anodic aluminum oxide channels, reducing the mass transfer resistance. This preparation method has universality, and nanoholes with different carbon titanium contents and different thicknesses of mesoporous layers can be obtained by adjusting the carbon titanium content and the number of spin coating times in the mesoporous carbon titanium precursor solution.

Description

Technical Field

[0001] The present invention belongs to the technical field of mesoporous material-based nanofluidic design, and particularly relates to a preparation method for preparing vertical-channel mesoporous carbon titanium / anodic aluminum oxide heterogeneous nanochannels (MCT / AAO) by a superassembly strategy. Background Art

[0002] Nanoporous thin films have broad application prospects in the fields of ion transport and energy conversion due to their nano-sized channels and charged channel inner walls. In an electrolyte solution, the charged nano-sized channels will cause the overlap of the electric double layers. Due to the electrostatic repulsion interaction, the concentration of counterions inside the channels will be higher than that of co-ions, making the entire ion channel interior non-neutral, and showing the characteristics of ion rectification, ion selectivity, and ion gating. Currently, the preparation methods of nanoporous channels include ion track etching methods, vacuum-assisted filtration methods for stacking two-dimensional nanosheets, and physical etching methods such as electron beam bombardment. The nanoporous channels constructed based on the above methods have certain defects. For example, the channels are irregular and unevenly distributed on the film surface, which limits the ion transport flux; the high ion transport internal resistance caused by the curved ion transport path; the complex preparation method, high cost, and difficulty in implementation. In view of the above defects, it is necessary to design a preparation method to prepare nanoporous channels with high porosity, regular and vertically connected pores for the research in the field of nanofluidics. Summary of the Invention

[0003] Currently, the construction of nanoporous channels based on mesoporous materials has attracted the attention of many researchers because of their high-density pores, regular pore structures, and highly ordered pore distributions. Considering that it is difficult to achieve large-area self-support of the mesoporous layer, it can be combined with other thin film substrates to form an asymmetric heterogeneous conjunctiva. Anodic aluminum oxide has been widely used in the construction of nanofluidic devices due to its highly regular pore structure, controllable pore size, and positively charged channels. Therefore, the development of nanofluidic devices based on mesoporous material thin films and anodic aluminum oxide has broad application prospects. The superassembly strategy mainly introduces guests into the host based on hydrogen bonds, electrostatic interactions, and other intermolecular forces, and is widely used in the construction of functional nanomaterials and nanodevices.

[0004] To solve the problems of the prior art, the present invention provides a preparation method for preparing vertical-channel mesoporous carbon titanium / anodic aluminum oxide heterogeneous nanochannels by a superassembly strategy.

[0005] The specific technical solution of the present invention is as follows:

[0006] The preparation method of vertical-channel mesoporous carbon titanium / anodic aluminum oxide heteronanopores by the superassembly strategy provided by the present invention is characterized by comprising the following steps: Step S1, preparing a mesoporous titanium dioxide precursor solution and a mesoporous carbon titanium precursor solution; Step S2, plugging one side of anodic aluminum oxide to obtain an anodic aluminum oxide with one side plugged; Step S3, scraping the surface of the anodic aluminum oxide with one side plugged clean and cleaning it with a cleaning agent to obtain an anodic aluminum oxide with one side plugged and a clean surface; Step S4, spin-coating the mesoporous carbon titanium precursor solution on the clean plugged surface of the anodic aluminum oxide with one side plugged to obtain a mesoporous carbon titanium / anodic aluminum oxide film; Step S5, calcining the mesoporous carbon titanium / anodic aluminum oxide film to obtain the vertical-channel mesoporous carbon titanium / anodic aluminum oxide heteronanopores.

[0007] The preparation method of vertical-channel mesoporous carbon titanium / anodic aluminum oxide heteronanopores by the superassembly strategy provided by the present invention may also have the following technical feature: in Step S1, the process of preparing the mesoporous titanium dioxide precursor solution is as follows: dissolving ethanol in deionized water to obtain an ethanol aqueous solution, stirring the ethanol aqueous solution evenly at 0 °C, slowly dropping titanium tetrachloride into the ethanol aqueous solution, and continuing to stir at 0 °C until it is even, thus obtaining the mesoporous titanium dioxide precursor solution.

[0008] The preparation method of vertical-channel mesoporous carbon titanium / anodic aluminum oxide heteronanopores by the superassembly strategy provided by the present invention may also have the following technical feature: in Step S1, the process of preparing the mesoporous carbon titanium precursor solution is as follows: dissolving F127 in absolute ethanol, adding deionized water, and dispersing it until it is clear to obtain a mesoporous carbon titanium precursor template agent F127 solution; adding acetic acid to the mesoporous carbon titanium precursor template agent F127 solution to obtain a first mixed solution; adding the mesoporous titanium dioxide precursor solution to the first mixed solution and stirring until it is clear to obtain a second mixed solution; adding a carbon source resol to the second mixed solution and stirring at room temperature until it is clear, thus obtaining the mesoporous carbon titanium precursor solution.

[0009] The preparation method of vertical-channel mesoporous carbon titanium / anodic aluminum oxide heteronanopores by the superassembly strategy provided by the present invention may also have the following technical feature: the process of preparing the carbon source resol is as follows: heating phenol at 45-48 °C until it melts completely, adding an aqueous sodium hydroxide solution, stirring evenly, adding formaldehyde, stirring evenly at 70-75 °C, adjusting the pH to neutral with hydrochloric acid, and removing the moisture by rotary evaporation, thus obtaining the carbon source resol.

[0010] The preparation method of the vertical-channel mesoporous carbon titanium / anodic aluminum oxide heteronanopores prepared by the superassembly strategy provided by the present invention may further have the following technical feature: in step S2, the specific steps of single-sided hole plugging are as follows: step S2-1, prepare a polymethyl methacrylate solution with a concentration of 8-10 wt%; step S2-2, spin-coat the polymethyl methacrylate solution onto one side of the anodic aluminum oxide and dry it at room temperature for 2-4 h to obtain the anodic aluminum oxide spin-coated with the polymethyl methacrylate solution; step S2-3, put the anodic aluminum oxide spin-coated with the polymethyl methacrylate solution into an oven at 190-210 °C for 6-8 h to obtain the single-sided hole-plugged anodic aluminum oxide.

[0011] The preparation method of the vertical-channel mesoporous carbon titanium / anodic aluminum oxide heteronanopores prepared by the superassembly strategy provided by the present invention may further have the following technical feature: in step S3, the cleaning agent is deionized water and ethanol.

[0012] The preparation method of the vertical-channel mesoporous carbon titanium / anodic aluminum oxide heteronanopores prepared by the superassembly strategy provided by the present invention may further have the following technical feature: in step S4, the specific steps of spin-coating the mesoporous carbon titanium precursor solution onto the clean hole-plugged surface of the single-sided hole-plugged anodic aluminum oxide are as follows: step S4-1, paste the non-hole-plugged surface of the single-sided hole-plugged anodic aluminum oxide onto a glass slide; step S4-2, spin-coat the mesoporous carbon titanium precursor solution onto the clean hole-plugged surface of the single-sided hole-plugged anodic aluminum oxide to obtain the anodic aluminum oxide spin-coated with mesoporous carbon titanium; step S4-3, place the anodic aluminum oxide spin-coated with mesoporous carbon titanium in an oven at 35 °C for evaporation-induced self-assembly for 24-28 h, and then raise the temperature to 100-110 °C for heat treatment for 24-28 h to obtain the mesoporous carbon titanium / anodic aluminum oxide film.

[0013] The preparation method of the vertical-channel mesoporous carbon titanium / anodic aluminum oxide heteronanopores prepared by the superassembly strategy provided by the present invention may further have the following technical feature: in step S5, the calcination temperature for calcination is 400-450 °C, and the calcination time is 5-6 h.

[0014] The present invention also provides a vertical-channel mesoporous carbon titanium / anodic aluminum oxide heteronanopore, which is characterized in that it is prepared by using the preparation method of the vertical-channel mesoporous carbon titanium / anodic aluminum oxide heteronanopores prepared by the above superassembly strategy.

[0015] Functions and effects of the invention

[0016] Since the present invention is based on a superassembly strategy, a vertical-channel mesoporous carbon titanium / anodic aluminum oxide heterogeneous nanochannel is prepared by using a mature superassembly method and an evaporation-induced self-assembly (EISA) method. This nanochannel has a rich and regular pore structure, which can provide abundant ion transport pathways for ions, exhibits an asymmetric chemical composition, surface charge distribution, and channel structure, and has potential application value in the field of nanofluidics. In the mesoporous carbon titanium layer of this nanochannel, the mesoporous carbon framework contains abundant oxygen-containing functional groups, which mainly provide negative charge sites for regulating ion transport. The titanium oxide nanocrystals embedded in the mesoporous carbon framework endow the nanochannel with opto-controlled ion transport performance, and the presence of the two components can endow this nanochannel with multifunctionality. The channels of the mesoporous carbon titanium layer and the anodic aluminum oxide channel are vertically connected, reducing the mass transfer resistance.

[0017] The preparation method of the vertical-channel mesoporous carbon titanium / anodic aluminum oxide heterogeneous nanochannel provided by the present invention has universality. By adjusting the amount of the mesoporous titanium dioxide precursor solution and the amount of the carbon source during the preparation of the mesoporous carbon titanium precursor solution, vertical-channel mesoporous carbon titanium / anodic aluminum oxide heterogeneous nanochannels with mesoporous layers of different carbon titanium contents can be obtained. In addition, by adjusting the number of spin coating times, vertical-channel mesoporous carbon titanium / anodic aluminum oxide heterogeneous nanochannels with mesoporous layers of different thicknesses can be obtained. Description of the Drawings

[0018] Figure 1 is the flow chart of preparing MCT / AAO in Example 1 of the present invention.

[0019] Figure 2 is the TEM image of the MCT layer of MCT / AAO prepared in Examples 1 to 5 of the present invention. Among them, Figure 2 (a) is the TEM image of the MCT layer of MCT / AAO prepared in Example 1; Figure 2 (b) is the TEM image of the MCT layer of MCT / AAO prepared in Example 2; Figure 2 (c) is the TEM image of the MCT layer of MCT / AAO prepared in Example 3; Figure 2 (d) is the TEM image of the MCT layer of MCT / AAO prepared in Example 4;

[0020] Figure 2 (e) is the TEM image of the MCT layer of MCT / AAO prepared in Example 5.

[0021] Figure 3 are the optical photograph and SEM image of MCT / AAO prepared in Example 3 of the present invention. Figure 3 (a) is the optical photograph of MCT / AAO; Figure 3 (b) is the surface SEM image of the MCT layer of MCT / AAO;Figure 3 (c) is the surface SEM magnification of the MCT layer of MCT / AAO; Figure 3 (d) is the cross-sectional SEM image of MCT / AAO.

[0022] Figure 4 is the XPS graph of the MCT layer of MCT / AAO prepared in Example 3 of the present invention.

[0023] Figure 5 is the XRD graph of the mesoporous layer of the nanochannel prepared in the example of the present invention. Figure 5 (a) is the XRD comparison graph of the mesoporous layers of MCT / AAO, MC / AAO, and MT / AAO prepared in Example 3; Figure 5 (b) is the XRD comparison graph of the MCT layers of MCT / AAO prepared in Examples 1-5.

[0024] Figure 6 is the nitrogen adsorption-desorption test graph of the MCT layer of MCT / AAO prepared in Example 3 of the present invention. Figure 6 (a) is the nitrogen desorption-adsorption curve of the MCT layer; Figure 6 (b) is the pore size distribution graph of the MCT layer.

[0025] Figure 7 is the FTIR graph of the mesoporous layer of the nanochannel prepared in the example of the present invention. Figure 7 (a) is the FTIR comparison graph of the mesoporous layers of MCT / AAO, MC / AAO, and MT / AAO prepared in Example 3; Figure 7 (b) is the FTIR comparison graph of the MCT layers of MCT / AAO prepared in Examples 1-5. Detailed Embodiments

[0026] The terms used in the present invention, unless otherwise specified, generally have the meanings commonly understood by those of ordinary skill in the art.

[0027] In the following examples, various processes and methods not described in detail are conventional methods well known in the art.

[0028] The reagents used in the following examples were purchased through ordinary commercial channels, and the experimental operations and conditions not specified refer to the conventional operations and conditions in the art.

[0029] The anodic aluminum oxide (AAO) used in the following examples is a commercial AAO film with a thickness of 60 μm, a pore size of 80 nm, and a shape of a circular substrate with a diameter of 15 mm.

[0030] The following describes the specific embodiments of the present invention with reference to the accompanying drawings.

[0031] <Example 1>

[0032] This embodiment provides a preparation method of vertically channeled mesoporous carbon titanium / anodic aluminum oxide heteronanopores (MCT / AAO) with a titanium-carbon ratio of 3 g / 1.5 g by a superassembly strategy, including the following steps:

[0033] Step S1: Prepare a mesoporous titanium dioxide precursor solution and a mesoporous carbon titanium precursor solution.

[0034] The specific process of preparing the mesoporous titanium dioxide precursor solution is as follows:

[0035] Dissolve 42 g of ethanol in 7 g of deionized water to obtain an ethanol aqueous solution. Stir the ethanol aqueous solution in an ice bath at 0 °C for 10 min until homogeneous. Slowly add 12 g of titanium tetrachloride to the ethanol aqueous solution and continue to stir in the ice bath at 0 °C for 60 min until homogeneous, thus obtaining a yellow-green mesoporous titanium dioxide precursor solution.

[0036] The specific process of preparing the mesoporous carbon titanium precursor solution is as follows:

[0037] Dissolve 0.8 g of F127 in 10 g of absolute ethanol, add 0.43 g of deionized water, ultrasonically disperse until clear, and magnetically stir at 500 r for 30 min to obtain a mesoporous carbon titanium precursor template agent F127 solution. Add 50 μL of acetic acid to the mesoporous carbon titanium precursor template agent F127 solution to obtain a first mixed solution. Add 3 g of the mesoporous titanium dioxide precursor solution to the first mixed solution and stir for 1 h until clear to obtain a second mixed solution. Add 1.5 g of the carbon source resol to the second mixed solution and magnetically stir at 500 r at room temperature for 30 min until clear, thus obtaining the mesoporous carbon titanium precursor solution.

[0038] Among them, the preparation process of the carbon source resol is as follows:

[0039] Add 2.44 g of phenol to a 100 ml two-necked flask, heat and melt it at 45 °C until completely melted, add 0.52 g of 20 wt% sodium hydroxide aqueous solution, stir for 10 min until homogeneous, add 4.2 g of formaldehyde, raise the temperature of the oil bath to 70 °C, stir for 1 h until homogeneous, adjust the pH to neutral with hydrochloric acid, and rotary evaporate to remove the water, thus obtaining the carbon source resol.

[0040] Step S2: Plug one side of the anodic aluminum oxide (AAO) to obtain an anodic aluminum oxide with one side plugged. The specific steps are as follows:

[0041] Step S2-1: Prepare a 10 wt% polymethyl methacrylate (PMMA) solution.

[0042] Step S2-2: Spin-coat the polymethyl methacrylate solution onto one side of the anodic aluminum oxide at a spin-coating speed of 3500 rad / min for 30 s, and dry it at room temperature for 2 h to obtain anodic aluminum oxide spin-coated with the polymethyl methacrylate solution.

[0043] Step S2-3: Place the anodic aluminum oxide spin-coated with the polymethyl methacrylate solution in an oven at 200 °C for 6 h to obtain anodic aluminum oxide with one side plugged.

[0044] Step S3: Scrape off the PMMA on the surface of the anodic aluminum oxide with one side plugged using 1000-mesh sandpaper, and then wash it three times with deionized water and ethanol respectively to obtain anodic aluminum oxide with one side plugged and a clean surface.

[0045] Step S4: Spin-coat the mesoporous carbon-titanium precursor solution onto the clean plugged hole surface of the anodic aluminum oxide with one side plugged to obtain a mesoporous carbon-titanium / anodic aluminum oxide film. The specific steps are as follows:

[0046] Step S4-1: Paste the non-plugged hole surface of the anodic aluminum oxide with one side plugged onto a glass slide.

[0047] Step S4-2: Spin-coat 200 μL of the mesoporous carbon-titanium precursor solution onto the clean plugged hole surface of the anodic aluminum oxide with one side plugged at a spin-coating speed of 3500 rad / min for 60 s to obtain anodic aluminum oxide spin-coated with mesoporous carbon-titanium.

[0048] Step S4-3: Place the anodic aluminum oxide spin-coated with mesoporous carbon-titanium in an oven at 35 °C for evaporation-induced self-assembly for 24 h, and then raise the temperature to 100 °C and perform heat treatment for 24 h to obtain a mesoporous carbon-titanium / anodic aluminum oxide film.

[0049] Step S5: Calcinate the mesoporous carbon-titanium / anodic aluminum oxide film. First, raise the temperature to 400 °C at a rate of 1 °C / min, and then keep it at this temperature for constant-temperature calcination for 5 h to remove the template F127 and excess PMMA, thereby obtaining a vertical-channel mesoporous carbon-titanium / anodic aluminum oxide heteronanopore with a titanium-carbon ratio of 3 g / 1.5 g.

[0050] Figure 1 It is a flowchart for preparing MCT / AAO in Example 1 of the present invention.

[0051] <Example 2>

[0052] This example provides a preparation method for preparing a vertical-channel mesoporous carbon-titanium / anodic aluminum oxide heteronanopore (MCT / AAO) with a titanium-carbon ratio of 5 g / 1.5 g by a superassembly strategy, including the following steps:

[0053] Step S1: Prepare a mesoporous titanium dioxide precursor solution and a mesoporous carbon-titanium precursor solution.

[0054] The specific process of preparing the mesoporous titanium dioxide precursor solution is as follows:

[0055] Dissolve 42 g of ethanol in 7 g of deionized water to obtain an ethanol aqueous solution. Stir the ethanol aqueous solution in an ice bath at 0 °C for 10 min until homogeneous. Slowly add 12 g of titanium tetrachloride to the ethanol aqueous solution and continue to stir in the ice bath at 0 °C for 60 min until homogeneous, thus obtaining a yellow-green mesoporous titanium dioxide precursor solution;

[0056] The specific process of preparing the mesoporous carbon-titanium precursor solution is as follows:

[0057] Dissolve 1.0 g of F127 in 10 g of absolute ethanol, add 0.71 g of deionized water, and ultrasonically disperse until clear. Stir magnetically at 500 r for 30 min to obtain a mesoporous carbon-titanium precursor templating agent F127 solution. Add 100 μL of acetic acid to the mesoporous carbon-titanium precursor templating agent F127 solution to obtain a first mixed solution. Add 5 g of the mesoporous titanium dioxide precursor solution to the first mixed solution and stir for 1 h until clear to obtain a second mixed solution. Add 1.5 g of the carbon source resol to the second mixed solution and stir magnetically at room temperature at 500 r for 30 min until clear, thus obtaining the mesoporous carbon-titanium precursor solution.

[0058] Among them, the preparation process of the carbon source resol is as follows:

[0059] Add 2.44 g of phenol to a 100 ml two-necked flask, heat and melt it at 45 °C until completely melted. Add 0.52 g of 20 wt% sodium hydroxide aqueous solution, stir for 10 min until homogeneous, add 4.2 g of formaldehyde, raise the temperature of the oil bath to 70 °C, stir for 1 h until homogeneous, adjust the pH to neutral with hydrochloric acid, and remove the water by rotary evaporation to obtain the carbon source resol;

[0060] Step S2: Perform single-sided hole plugging on anodic aluminum oxide (AAO) to obtain single-sided hole-plugged anodic aluminum oxide. The specific steps are as follows:

[0061] Step S2-1: Prepare a 10 wt% polymethyl methacrylate (PMMA) solution.

[0062] Step S2-2: Spin-coat the polymethyl methacrylate solution onto one side of the anodic aluminum oxide at a spin-coating speed of 3500 rad / min for 30 s, and dry it at room temperature for 2 h to obtain anodic aluminum oxide spin-coated with the polymethyl methacrylate solution.

[0063] Step S2-3: Place the anodic aluminum oxide spin-coated with the polymethyl methacrylate solution in an oven at 200 °C for 6 h to obtain single-sided hole-plugged anodic aluminum oxide;

[0064] Step S3, scrape off the PMMA on the surface of the single-sided hole-blocked anodic aluminum oxide with 1000-mesh sandpaper, and then wash it 3 times with deionized water and ethanol respectively to obtain the single-sided hole-blocked anodic aluminum oxide with a clean surface;

[0065] Step S4, spin-coat the mesoporous carbon-titanium precursor solution on the clean hole-blocked surface of the single-sided hole-blocked anodic aluminum oxide to obtain a mesoporous carbon-titanium / anodic aluminum oxide film. The specific steps are as follows:

[0066] Step S4-1, paste the unblocked surface of the single-sided hole-blocked anodic aluminum oxide onto a glass slide,

[0067] Step S4-2, spin-coat 200 μL of the mesoporous carbon-titanium precursor solution onto the clean hole-blocked surface of the single-sided hole-blocked anodic aluminum oxide at a spin-coating speed of 3500 rad / min for 60 s to obtain the mesoporous carbon-titanium spin-coated anodic aluminum oxide,

[0068] Step S4-3, place the mesoporous carbon-titanium spin-coated anodic aluminum oxide in an oven at 35 °C for evaporation-induced self-assembly for 24 h, and then raise the temperature to 100 °C for heat treatment for 24 h to obtain the mesoporous carbon-titanium / anodic aluminum oxide film;

[0069] Step S5, calcine the mesoporous carbon-titanium / anodic aluminum oxide film. First, heat it to 400 °C at a rate of 1 °C / min, and then keep it at this temperature for constant-temperature calcination for 5 h to remove the template agent F127 and the excess PMMA, thus obtaining the vertical-channel mesoporous carbon-titanium / anodic aluminum oxide heterogeneous nanochannel with a titanium-carbon ratio of 5 g / 1.5 g.

[0070] <Example 3>

[0071] This example provides a preparation method of a vertical-channel mesoporous carbon-titanium / anodic aluminum oxide heterogeneous nanochannel (MCT / AAO) with a titanium-carbon ratio of 7 g / 1.5 g by a super-assembly strategy, a mesoporous carbon / anodic aluminum oxide nanochannel (MC / AAO), and a mesoporous titanium / anodic aluminum oxide nanochannel (MT / AAO).

[0072] The preparation of the vertical-channel mesoporous carbon-titanium / anodic aluminum oxide heterogeneous nanochannel (MCT / AAO) with a titanium-carbon ratio of 7 g / 1.5 g includes the following steps:

[0073] Step S1, prepare a mesoporous titanium dioxide precursor solution and a mesoporous carbon-titanium precursor solution,

[0074] The specific process of preparing the mesoporous titanium dioxide precursor solution is as follows:

[0075] Dissolve 42 g of ethanol in 7 g of deionized water to obtain an ethanol aqueous solution. Stir the ethanol aqueous solution in an ice bath at 0 °C for 10 min until homogeneous. Slowly add 12 g of titanium tetrachloride dropwise to the ethanol aqueous solution and continue to stir in the ice bath at 0 °C for 60 min until homogeneous, thus obtaining a yellowish-green mesoporous titanium dioxide precursor solution;

[0076] The specific process for preparing the mesoporous carbon-titanium precursor solution is as follows:

[0077] Dissolve 1.2 g of F127 in 10 g of absolute ethanol, add 1.0 g of deionized water, and ultrasonically disperse until clear. Stir magnetically at 500 r for 30 min to obtain a mesoporous carbon-titanium precursor templating agent F127 solution. Add 150 μL of acetic acid to the mesoporous carbon-titanium precursor templating agent F127 solution to obtain a mixed solution I. Add 7 g of the mesoporous titanium dioxide precursor solution to the mixed solution I and stir for 1 h until clear to obtain a mixed solution II. Add 1.5 g of the carbon source resol to the mixed solution II and stir magnetically at room temperature at 500 r for 30 min until clear, thus obtaining the mesoporous carbon-titanium precursor solution,

[0078] Among them, the preparation process of the carbon source resol is as follows:

[0079] Add 2.44 g of phenol to a 100 ml two-necked flask, heat and melt it at 45 °C until completely melted, add 0.52 g of 20 wt% sodium hydroxide aqueous solution, stir for 10 min until homogeneous, add 4.2 g of formaldehyde, raise the temperature of the oil bath to 70 °C, stir for 1 h until homogeneous, adjust the pH to neutral with hydrochloric acid, and rotary evaporate to remove the water, thus obtaining the carbon source resol;

[0080] Step S2, perform single-sided hole plugging on anodic aluminum oxide (AAO) to obtain single-sided hole-plugged anodic aluminum oxide. The specific steps are as follows:

[0081] Step S2-1, prepare a 10 wt% polymethyl methacrylate (PMMA) solution,

[0082] Step S2-2, spin-coat the polymethyl methacrylate solution onto one side of the anodic aluminum oxide at a spin-coating speed of 3500 rad / min for 30 s, and dry it at room temperature for 2 h to obtain anodic aluminum oxide spin-coated with the polymethyl methacrylate solution,

[0083] Step S2-3, place the anodic aluminum oxide spin-coated with the polymethyl methacrylate solution in an oven at 200 °C for 6 h to obtain single-sided hole-plugged anodic aluminum oxide;

[0084] Step S3, scrape off the PMMA on the surface of the single-sided hole-plugged anodic aluminum oxide with 1000-mesh sandpaper, and then wash it 3 times with deionized water and ethanol respectively to obtain single-sided hole-plugged anodic aluminum oxide with a clean surface;

[0085] Step S4, spin-coat the mesoporous carbon-titanium precursor solution on the clean plugged-hole surface of the single-sided plugged-hole anodic aluminum oxide to obtain a mesoporous carbon-titanium / anodic aluminum oxide film. The specific steps are as follows:

[0086] Step S4-1, paste the non-plugged-hole surface of the single-sided plugged-hole anodic aluminum oxide onto a glass slide.

[0087] Step S4-2, spin-coat 200 μL of the mesoporous carbon-titanium precursor solution onto the clean plugged-hole surface of the single-sided plugged-hole anodic aluminum oxide at a spin-coating speed of 3500 rad / min for 60 s to obtain spin-coated mesoporous carbon-titanium anodic aluminum oxide.

[0088] Step S4-3, place the spin-coated mesoporous carbon-titanium anodic aluminum oxide in an oven at 35 °C for evaporation-induced self-assembly for 24 h, and then raise the temperature to 100 °C for heat treatment for 24 h to obtain the mesoporous carbon-titanium / anodic aluminum oxide film.

[0089] Step S5, calcine the mesoporous carbon-titanium / anodic aluminum oxide film. First, heat it to 400 °C at a rate of 1 °C / min, and then keep it at this temperature for constant-temperature calcination for 5 h to remove the template agent F127 and excess PMMA, thereby obtaining a vertical-channel mesoporous carbon-titanium / anodic aluminum oxide heterogeneous nanochannel with a titanium-carbon ratio of 7 g / 1.5 g.

[0090] The preparation of the mesoporous carbon / anodic aluminum oxide nanochannel (MC / AAO) includes the following steps:

[0091] Step S1, prepare the mesoporous carbon precursor solution. The specific process is as follows:

[0092] Dissolve 1.2 g of F127 in 10 g of absolute ethanol, add 1.0 g of deionized water, ultrasonically disperse it until it is clear, stir magnetically at 500 r for 30 min to obtain the mesoporous carbon precursor template agent F127 solution. Add 1.5 g of the carbon source resol to the mesoporous carbon precursor template agent F127 solution, and stir magnetically at 500 r at room temperature for 30 min until it is clear to obtain the mesoporous carbon precursor solution.

[0093] Among them, the preparation process of the carbon source resol is as follows:

[0094] Add 2.44 g of phenol to a 100 ml two-necked flask, heat it to melt completely at 45 °C, add 0.52 g of 20 wt% sodium hydroxide aqueous solution, stir for 10 min until it is uniform, add 4.2 g of formaldehyde, raise the temperature of the oil bath to 70 °C, stir for 1 h until it is uniform, adjust the pH to neutral with hydrochloric acid, and rotary evaporate to remove the water to obtain the carbon source resol.

[0095] Step S2, perform single-sided plugging on the anodic aluminum oxide (AAO) to obtain single-sided plugged-hole anodic aluminum oxide. The specific steps are as follows:

[0096] Step S2-1: Prepare a 10 wt% polymethyl methacrylate (PMMA) solution.

[0097] Step S2-2: Spin-coat the PMMA solution onto one side of the anodized aluminum oxide at a spin speed of 3500 rad / min for 30 s, and then dry it at room temperature for 2 h to obtain anodized aluminum oxide spin-coated with the PMMA solution.

[0098] Step S2-3: Place the anodized aluminum oxide spin-coated with the PMMA solution in an oven at 200 °C for 6 h to obtain single-sided hole-blocked anodized aluminum oxide.

[0099] Step S3: Scrape off the PMMA on the surface of the single-sided hole-blocked anodized aluminum oxide with 1000-mesh sandpaper, and then wash it three times with deionized water and ethanol respectively to obtain single-sided hole-blocked anodized aluminum oxide with a clean surface.

[0100] Step S4: Spin-coat the mesoporous carbon precursor solution on the clean hole-blocked surface of the single-sided hole-blocked anodized aluminum oxide to obtain a mesoporous carbon / anodized aluminum oxide film. The specific steps are as follows:

[0101] Step S4-1: Paste the unblocked surface of the single-sided hole-blocked anodized aluminum oxide onto a glass slide.

[0102] Step S4-2: Spin-coat 200 μL of the mesoporous carbon precursor solution onto the clean hole-blocked surface of the single-sided hole-blocked anodized aluminum oxide at a spin speed of 3500 rad / min for 60 s to obtain anodized aluminum oxide spin-coated with mesoporous carbon.

[0103] Step S4-3: Place the anodized aluminum oxide spin-coated with mesoporous carbon in an oven at 35 °C for evaporation-induced self-assembly for 24 h, and then raise the temperature to 100 °C and perform heat treatment for 24 h to obtain a mesoporous carbon / anodized aluminum oxide film.

[0104] Step S5: Calcinate the mesoporous carbon / anodized aluminum oxide film. First, heat it to 400 °C at a rate of 1 °C / min, and then keep it at this temperature for constant-temperature calcination for 5 h to remove the template F127 and excess PMMA, thus obtaining mesoporous carbon / anodized aluminum oxide nanochannels.

[0105] The preparation of mesoporous titanium / anodized aluminum oxide nanochannels (MT / AAO) includes the following steps:

[0106] Step S1: Prepare a mesoporous titanium precursor solution. The specific process is as follows:

[0107] Dissolve 1.2 g of F127 in 10 g of absolute ethanol, add 1.0 g of deionized water, and ultrasonically disperse until clear. Stir magnetically at 500 r for 30 min to obtain the mesoporous titanium precursor template agent F127 solution. Add 7 g of mesoporous titanium dioxide solution to the mesoporous titanium precursor template agent F127 solution and stir for 1 h until clear to obtain the mesoporous titanium precursor solution.

[0108] Among them, the preparation process of the mesoporous titanium dioxide solution is as follows:

[0109] Dissolve 42 g of ethanol in 7 g of deionized water to obtain an ethanol aqueous solution. Stir the ethanol aqueous solution in an ice bath at 0 °C for 10 min until uniform. Slowly drop 12 g of titanium tetrachloride into the ethanol aqueous solution and continue to stir in an ice bath at 0 °C for 60 min until uniform to obtain the mesoporous titanium dioxide solution.

[0110] Step S2, perform single-sided hole plugging on anodic aluminum oxide (AAO) to obtain single-sided hole-plugged anodic aluminum oxide. The specific steps are as follows:

[0111] Step S2-1, prepare a 10 wt% polymethyl methacrylate (PMMA) solution.

[0112] Step S2-2, spin-coat the polymethyl methacrylate solution onto one side of the anodic aluminum oxide at a spin-coating speed of 3500 rad / min for 30 s, and dry at room temperature for 2 h to obtain anodic aluminum oxide spin-coated with the polymethyl methacrylate solution.

[0113] Step S2-3, place the anodic aluminum oxide spin-coated with the polymethyl methacrylate solution in an oven at 200 °C for 6 h to obtain single-sided hole-plugged anodic aluminum oxide.

[0114] Step S3, scrape the PMMA on the surface of the single-sided hole-plugged anodic aluminum oxide clean with 1000-mesh sandpaper, and then wash it 3 times with deionized water and ethanol respectively to obtain single-sided hole-plugged anodic aluminum oxide with a clean surface.

[0115] Step S4, spin-coat the mesoporous titanium precursor solution on the clean hole-plugged surface of the single-sided hole-plugged anodic aluminum oxide to obtain a mesoporous titanium / anodic aluminum oxide film. The specific steps are as follows:

[0116] Step S4-1, paste the non-hole-plugged surface of the single-sided hole-plugged anodic aluminum oxide onto a glass slide.

[0117] Step S4-2, spin-coat 200 μL of the mesoporous titanium precursor solution onto the clean hole-plugged surface of the single-sided hole-plugged anodic aluminum oxide at a spin-coating speed of 3500 rad / min for 60 s to obtain anodic aluminum oxide spin-coated with mesoporous titanium.

[0118] Step S4-3: Spin-coat the mesoporous titanium on the anodic aluminum oxide and place it in an oven at 35°C for evaporation-induced self-assembly for 24 h, then raise the temperature to 100°C and perform heat treatment for 24 h to obtain the mesoporous titanium / anodic aluminum oxide film;

[0119] Step S5: Calcinate the mesoporous titanium / anodic aluminum oxide film. First, raise the temperature to 400°C at a rate of 1°C / min, and then keep it at this temperature for constant-temperature calcination for 5 h to remove the template F127 and the excess PMMA, thus obtaining the mesoporous titanium / anodic aluminum oxide nanochannels.

[0120] <Example 4>

[0121] This example provides a preparation method for vertically channeled mesoporous carbon titanium / anodic aluminum oxide heteronanostructures (MCT / AAO) with a titanium-carbon ratio of 10 g / 1.5 g by a superassembly strategy, including the following steps:

[0122] Step S1: Prepare a mesoporous titanium dioxide precursor solution and a mesoporous carbon titanium precursor solution.

[0123] The specific process for preparing the mesoporous titanium dioxide precursor solution is as follows:

[0124] Dissolve 42 g of ethanol in 7 g of deionized water to obtain an ethanol aqueous solution. Stir the ethanol aqueous solution in an ice-water bath at 0°C for 10 min until it is homogeneous. Slowly add 12 g of titanium tetrachloride to the ethanol aqueous solution and continue to stir in the ice-water bath at 0°C for 60 min until it is homogeneous, thus obtaining a yellow-green mesoporous titanium dioxide precursor solution;

[0125] The specific process for preparing the mesoporous carbon titanium precursor solution is as follows:

[0126] Dissolve 1.5 g of F127 in 10 g of absolute ethanol, add 1.43 g of deionized water, ultrasonically disperse until it is clear, and magnetically stir at 500 r for 30 min to obtain a mesoporous carbon titanium precursor template agent F127 solution. Add 200 μL of acetic acid to the mesoporous carbon titanium precursor template agent F127 solution to obtain a mixed solution 1. Add 10 g of the mesoporous titanium dioxide precursor solution to the mixed solution 1 and stir for 1 h until it is clear to obtain a mixed solution 2. Add 1.5 g of the carbon source resol to the mixed solution 2 and magnetically stir at 500 r at room temperature for 30 min until it is clear, thus obtaining the mesoporous carbon titanium precursor solution.

[0127] Among them, the preparation process of the carbon source resol is as follows:

[0128] Add 2.44 g of phenol into a 100 ml two-necked flask, heat and melt it at 45 °C until completely melted, add 0.52 g of 20 wt% sodium hydroxide aqueous solution, stir for 10 min until homogeneous, add 4.2 g of formaldehyde, raise the temperature of the oil bath to 70 °C, stir for 1 h until homogeneous, adjust the pH to neutral with hydrochloric acid, and remove the moisture by rotary evaporation to obtain the carbon source resol;

[0129] Step S2, perform single-sided hole plugging on anodic aluminum oxide (AAO) to obtain single-sided hole-plugged anodic aluminum oxide. The specific steps are as follows:

[0130] Step S2-1, prepare a 10 wt% polymethyl methacrylate (PMMA) solution.

[0131] Step S2-2, spin-coat the polymethyl methacrylate solution onto one side of the anodic aluminum oxide at a spin-coating speed of 3500 rad / min for 30 s, and dry it at room temperature for 2 h to obtain anodic aluminum oxide spin-coated with the polymethyl methacrylate solution.

[0132] Step S2-3, place the anodic aluminum oxide spin-coated with the polymethyl methacrylate solution in an oven at 200 °C for 6 h to obtain single-sided hole-plugged anodic aluminum oxide.

[0133] Step S3, scrape off the PMMA on the surface of the single-sided hole-plugged anodic aluminum oxide with 1000-mesh sandpaper, and then wash it 3 times with deionized water and ethanol respectively to obtain single-sided hole-plugged anodic aluminum oxide with a clean surface.

[0134] Step S4, spin-coat the mesoporous carbon titanium precursor solution on the clean hole-plugged surface of the single-sided hole-plugged anodic aluminum oxide to obtain a mesoporous carbon titanium / anodic aluminum oxide film. The specific steps are as follows:

[0135] Step S4-1, paste the non-hole-plugged surface of the single-sided hole-plugged anodic aluminum oxide onto a glass slide.

[0136] Step S4-2, spin-coat 200 μL of the mesoporous carbon titanium precursor solution onto the clean hole-plugged surface of the single-sided hole-plugged anodic aluminum oxide at a spin-coating speed of 3500 rad / min for 60 s to obtain anodic aluminum oxide spin-coated with mesoporous carbon titanium.

[0137] Step S4-3, place the anodic aluminum oxide spin-coated with mesoporous carbon titanium in an oven at 35 °C for evaporation-induced self-assembly for 24 h, and then raise the temperature to 100 °C for heat treatment for 24 h to obtain a mesoporous carbon titanium / anodic aluminum oxide film.

[0138] Step S5: Calcinate the mesoporous carbon titanium / anodic aluminum oxide film. First, heat it to 400°C at a rate of 1°C / min, and then keep it calcined at this temperature for 5 h to remove the template agent F127 and the excess PMMA, thus obtaining the vertical-channel mesoporous carbon titanium / anodic aluminum oxide heteronanopores with a titanium-carbon ratio of 10 g / 1.5 g.

[0139] <Example 5>

[0140] This example provides a preparation method for vertical-channel mesoporous carbon titanium / anodic aluminum oxide heteronanopores (MCT / AAO) with a titanium-carbon ratio of 12 g / 1.5 g by a superassembly strategy, including the following steps:

[0141] Step S1: Prepare a mesoporous titanium dioxide precursor solution and a mesoporous carbon titanium precursor solution.

[0142] The specific process of preparing the mesoporous titanium dioxide precursor solution is as follows:

[0143] Dissolve 42 g of ethanol in 7 g of deionized water to obtain an ethanol aqueous solution. Stir the ethanol aqueous solution in an ice bath at 0°C for 10 min until it is homogeneous. Slowly add 12 g of titanium tetrachloride to the ethanol aqueous solution and continue to stir in the ice bath at 0°C for 60 min until it is homogeneous, thus obtaining a yellow-green mesoporous titanium dioxide precursor solution.

[0144] The specific process of preparing the mesoporous carbon titanium precursor solution is as follows:

[0145] Dissolve 1.5 g of F127 in 10 g of absolute ethanol, add 1.71 g of deionized water, and ultrasonically disperse it until it is clear. Stir magnetically at 500 r for 30 min to obtain a mesoporous carbon titanium precursor template agent F127 solution. Add 250 μL of acetic acid to the mesoporous carbon titanium precursor template agent F127 solution to obtain a mixed solution I. Add 12 g of the mesoporous titanium dioxide precursor solution to the mixed solution I and stir for 1 h until it is clear to obtain a mixed solution II. Add 1.5 g of the carbon source resol to the mixed solution II and stir magnetically at room temperature at 500 r for 30 min until it is clear, thus obtaining the mesoporous carbon titanium precursor solution.

[0146] Among them, the preparation process of the carbon source resol is as follows:

[0147] Add 2.44 g of phenol to a 100-ml two-necked flask, heat it to melt completely at 45°C, add 0.52 g of 20 wt% sodium hydroxide aqueous solution, stir for 10 min until it is homogeneous, add 4.2 g of formaldehyde, raise the temperature of the oil bath to 70°C, stir for 1 h until it is homogeneous, adjust the pH to neutral with hydrochloric acid, and remove the water by rotary evaporation, thus obtaining the carbon source resol.

[0148] Step S2, perform single-sided hole plugging on anodic aluminum oxide (AAO) to obtain single-sided hole-plugged anodic aluminum oxide. The specific steps are as follows:

[0149] Step S2-1, prepare a 10 wt% polymethyl methacrylate (PMMA) solution.

[0150] Step S2-2, spin-coat the PMMA solution onto one side of the anodic aluminum oxide at a spin-coating speed of 3500 rad / min for 30 s, and dry it at room temperature for 2 h to obtain anodic aluminum oxide spin-coated with the PMMA solution.

[0151] Step S2-3, place the anodic aluminum oxide spin-coated with the PMMA solution in an oven at 200 °C for 6 h to obtain single-sided hole-plugged anodic aluminum oxide.

[0152] Step S3, scrape off the PMMA on the surface of the single-sided hole-plugged anodic aluminum oxide with 1000-mesh sandpaper, and then wash it 3 times with deionized water and ethanol respectively to obtain single-sided hole-plugged anodic aluminum oxide with a clean surface.

[0153] Step S4, spin-coat a mesoporous carbon-titanium precursor solution on the clean hole-plugged surface of the single-sided hole-plugged anodic aluminum oxide to obtain a mesoporous carbon-titanium / anodic aluminum oxide film. The specific steps are as follows:

[0154] Step S4-1, paste the non-hole-plugged surface of the single-sided hole-plugged anodic aluminum oxide onto a glass slide.

[0155] Step S4-2, spin-coat 200 μL of the mesoporous carbon-titanium precursor solution onto the clean hole-plugged surface of the single-sided hole-plugged anodic aluminum oxide at a spin-coating speed of 3500 rad / min for 60 s to obtain anodic aluminum oxide spin-coated with mesoporous carbon-titanium.

[0156] Step S4-3, place the anodic aluminum oxide spin-coated with mesoporous carbon-titanium in an oven at 35 °C for evaporation-induced self-assembly for 24 h, and then raise the temperature to 100 °C for heat treatment for 24 h to obtain a mesoporous carbon-titanium / anodic aluminum oxide film.

[0157] Step S5, calcine the mesoporous carbon-titanium / anodic aluminum oxide film. First, heat it to 400 °C at a rate of 1 °C / min, and then keep it at this temperature for constant-temperature calcination for 5 h to remove the template F127 and excess PMMA, thereby obtaining a vertical-channel mesoporous carbon-titanium / anodic aluminum oxide heterogeneous nanochannel with a titanium-carbon ratio of 12 g / 1.5 g.

[0158] <Example 6>

[0159] This example provides a preparation method for vertical-channel mesoporous carbon-titanium / anodic aluminum oxide heterogeneous nanochannels (MCT / AAO) with a titanium-carbon ratio of 7 g / 1.5 g and different MCT layer thicknesses by a super-assembly strategy, including the following steps:

[0160] Step S1, configure a mesoporous titanium dioxide precursor solution and prepare a mesoporous carbon-titanium precursor solution.

[0161] The specific process of configuring the mesoporous titanium dioxide precursor solution is as follows:

[0162] Dissolve 42 g of ethanol in 7 g of deionized water to obtain an ethanol aqueous solution. Stir the ethanol aqueous solution in an ice bath at 0 °C for 10 min until homogeneous. Slowly add 12 g of titanium tetrachloride to the ethanol aqueous solution and continue to stir in the ice bath at 0 °C for 60 min until homogeneous, thus obtaining a yellow-green mesoporous titanium dioxide precursor solution.

[0163] The specific process of preparing the mesoporous carbon-titanium precursor solution is as follows:

[0164] Dissolve 1.2 g of F127 in 10 g of absolute ethanol, add 1.0 g of deionized water, and ultrasonically disperse until clear. Stir magnetically at 500 r for 30 min to obtain a mesoporous carbon-titanium precursor templating agent F127 solution. Add 150 μL of acetic acid to the mesoporous carbon-titanium precursor templating agent F127 solution to obtain a first mixed solution. Add 7 g of the mesoporous titanium dioxide precursor solution to the first mixed solution and stir for 1 h until clear to obtain a second mixed solution. Add 1.5 g of the carbon source resol to the second mixed solution and stir magnetically at 500 r at room temperature for 30 min until clear, thus obtaining the mesoporous carbon-titanium precursor solution.

[0165] Among them, the configuration process of the carbon source resol is as follows:

[0166] Add 2.44 g of phenol to a 100 ml two-necked flask, heat and melt it at 45 °C until completely melted. Add 0.52 g of 20 wt% sodium hydroxide aqueous solution, stir for 10 min until homogeneous, add 4.2 g of formaldehyde, raise the temperature of the oil bath to 70 °C, stir for 1 h until homogeneous, adjust the pH to neutral with hydrochloric acid, and rotary evaporate to remove the water, thus obtaining the carbon source resol.

[0167] Step S2, perform single-sided hole plugging on anodic aluminum oxide (AAO) to obtain single-sided hole-plugged anodic aluminum oxide. The specific steps are as follows:

[0168] Step S2-1, prepare a 10 wt% polymethyl methacrylate (PMMA) solution.

[0169] Step S2-2, spin-coat the polymethyl methacrylate solution onto one side of the anodic aluminum oxide at a spin-coating speed of 3500 rad / min for 30 s, and dry it at room temperature for 2 h to obtain anodic aluminum oxide spin-coated with the polymethyl methacrylate solution.

[0170] Step S2-3: Spin-coat the polymethyl methacrylate solution on the anodic aluminum oxide and place it in an oven at 200 °C for 6 h to obtain the single-sided hole-blocked anodic aluminum oxide.

[0171] Step S3: Scrape the PMMA on the surface of the single-sided hole-blocked anodic aluminum oxide clean with 1000-mesh sandpaper, and then wash it 3 times with deionized water and ethanol respectively to obtain the single-sided hole-blocked anodic aluminum oxide with a clean surface.

[0172] Step S4: Spin-coat the mesoporous carbon-titanium precursor solution on the clean hole-blocked surface of the single-sided hole-blocked anodic aluminum oxide to obtain the mesoporous carbon-titanium / anodic aluminum oxide film. The specific steps are as follows:

[0173] Step S4-1: Paste the unblocked surface of the single-sided hole-blocked anodic aluminum oxide onto a glass slide.

[0174] Step S4-2: Spin-coat 200 μL of the mesoporous carbon-titanium precursor solution on the clean hole-blocked surface of the single-sided hole-blocked anodic aluminum oxide at a spin-coating speed of 3500 rad / min for 60 s to obtain the mesoporous carbon-titanium first-spin-coated anodic aluminum oxide.

[0175] Step S4-3: Place the mesoporous carbon-titanium first-spin-coated anodic aluminum oxide in an oven at 35 °C for evaporation-induced self-assembly for 24 h.

[0176] Step S4-4: Spin-coat the second and third layers using the same spin-coating method. After each spin-coating, place it in an oven at 35 °C for evaporation-induced self-assembly for 24 h to obtain the mesoporous carbon-titanium three-spin-coated anodic aluminum oxide.

[0177] Step S4-5: Place the mesoporous carbon-titanium three-spin-coated anodic aluminum oxide in an oven at 100 °C and heat-treat it for 24 h to obtain the mesoporous carbon-titanium / anodic aluminum oxide film.

[0178] Step S5: Calcinate the mesoporous carbon-titanium / anodic aluminum oxide film. First, heat it to 400 °C at a rate of 1 °C / min, and then keep it at this temperature for constant-temperature calcination for 5 h to remove the template F127 and excess PMMA, thus obtaining the vertical-channel mesoporous carbon-titanium / anodic aluminum oxide heterogeneous nanochannels with a titanium-carbon ratio of 7 g / 1.5 g and different MCT layer thicknesses.

[0179] <Test Example>

[0180] Characterize the vertical-channel mesoporous carbon-titanium / anodic aluminum oxide heterogeneous nanochannels (MCT / AAO) prepared in the examples of the present invention by transmission electron microscopy (TEM), scanning electron microscopy (SEM), X-ray photoelectron spectroscopy (XPS), X-ray diffraction (XRD), nitrogen adsorption-desorption, and Fourier transform infrared absorption spectroscopy.

[0181] Figure 2These are TEM images of the MCT layer of MCT / AAO prepared in Examples 1-5 of the present invention. Among them, Figure 2 (a) is the TEM image of the MCT layer of MCT / AAO prepared in Example 1; Figure 2 (b) is the TEM image of the MCT layer of MCT / AAO prepared in Example 2; Figure 2 (c) is the TEM image of the MCT layer of MCT / AAO prepared in Example 3; Figure 2 (d) is the TEM image of the MCT layer of MCT / AAO prepared in Example 4; Figure 2 (e) is the TEM image of the MCT layer of MCT / AAO prepared in Example 5. As Figure 2 shown, the vertically channeled mesoporous carbon titanium / anodic aluminum oxide heteronanopores (MCT / AAO) prepared in Examples 1-5 have a rich and regular pore structure.

[0182] Figure 3 These are the optical photograph and SEM images of MCT / AAO prepared in Example 3 of the present invention. Figure 3 (a) is the optical photograph of MCT / AAO; Figure 3 (b) is the surface SEM image of the MCT layer of MCT / AAO; Figure 3 (c) is the magnified surface SEM image of the MCT layer of MCT / AAO; Figure 3 (d) is the cross-sectional SEM image of MCT / AAO. As Figure 3 shown in (b), the surface of the MCT layer of MCT / AAO is smooth and continuous without any cracks; as Figure 3 shown in (c), the surface of the MCT layer of MCT / AAO has rich mesopores perpendicular to the substrate; as Figure 3 shown in (d), MCT / AAO has an obvious two-layer heterostructure.

[0183] Figure 4 These are the XPS spectra of the MCT layer of MCT / AAO prepared in Example 3 of the present invention. As Figure 4 can be seen, C, Ti, and O coexist in the MCT layer of MCT / AAO, and carbon and titanium dioxide nanocrystals coexist in the MCT layer, verifying the co-assembly process during the evaporation-induced self-assembly process.

[0184] Figure 5 These are the XRD patterns of the mesoporous layers of the nanoscale channels prepared in the examples of the present invention. Figure 5 (a) is the XRD comparison chart of the mesoporous layers of MCT / AAO, MC / AAO, and MT / AAO prepared in Example 3; Figure 5 (b) is the XRD comparison chart of the MCT layers of MCT / AAO prepared in Examples 1-5. As Figure 5As shown in (a), the X-ray diffraction peaks of titanium dioxide nanocrystals in the MCT layer of MCT / AAO prepared in Example 3 prove the existence of titanium dioxide nanocrystals in the MCT layer; from Figure 5 As shown in (b), for MCT / AAO, as the titanium content in the MCT layer increases, the intensity of the X-ray diffraction peaks of titanium dioxide nanocrystals gradually increases.

[0185] Figure 6 Figure 6 is the nitrogen adsorption-desorption test chart of the MCT layer of MCT / AAO prepared in Example 3 of the present invention. Figure 6 (a) is the nitrogen desorption-adsorption curve of the MCT layer; Figure 6 (b) is the pore size distribution chart of the MCT layer. As shown in Figure 6 (a), the nitrogen adsorption-desorption curve of the MCT layer shows a typical type-IV curve, indicating that the MCT layer has a regular mesoporous structure; as shown in Figure 6 (b), the pore size in the MCT layer is about 4.87 nm.

[0186] Figure 7 Figure 8 is the FTIR chart of the mesoporous layer of the nanochannel prepared in the example of the present invention. Figure 7 (a) is the FTIR comparison chart of the mesoporous layers of MCT / AAO, MC / AAO, and MT / AAO prepared in Example 3; Figure 7 (b) is the FTIR comparison chart of the MCT layers of MCT / AAO prepared in Examples 1-5. As shown in Figure 7 (a), the vibration peak at 2930 cm -1 in the MC layer of MC / AAO is the vibration peak of saturated hydrocarbons, which comes from the resol skeleton of the carbon source. The MC layer can generate carboxyl functional groups after calcination. The vibration peak at 1710 cm -1 is the vibration peak of the carboxyl functional group; the stretching vibration absorption peak of the hydroxyl oxygen-containing functional group at 3415 cm -1 in the MT layer of MT / AAO, and the vibration peak of -OH at 1621 cm -1 The MCT layer of MCT / AAO contains the above four peaks, indicating that the MCT layer contains rich oxygen-containing functional groups. The rich oxygen-containing functional groups can ensure that it has rich negative charges. Among them, the MCT layer has absorption peaks of mesoporous carbon and mesoporous titanium, and no new functional groups are generated, further proving the co-assembly process of carbon and titanium; as shown in Figure 7 (b), for MCT / AAO, as the titanium content in the MCT layer increases, the absorption peak intensity of titanium oxide gradually increases.

[0187] The above is a detailed description of the embodiments, which is convenient for those skilled in the art to correctly understand and use the present invention. Any improvement or modification of the technical solution obtained by those skilled in the art based on the present invention on the basis of the prior art without creative labor, only through methods such as analysis, analogy or limited enumeration, should be within the protection scope determined by the claims.

Claims

1. A preparation method for vertically channeled mesoporous carbon titanium / anodic aluminum oxide heterogeneous nanochannels by a superassembly strategy, characterized in that, It includes the following steps: Step S1, configure a mesoporous titanium dioxide precursor solution and prepare a mesoporous carbon-titanium precursor solution; Step S2, perform single-sided hole plugging on anodic aluminum oxide to obtain single-sided hole-plugged anodic aluminum oxide; Step S3, scrape the surface of the single-sided hole-plugged anodic aluminum oxide clean, and clean it with a cleaning agent to obtain the single-sided hole-plugged anodic aluminum oxide with a clean surface; Step S4, spin-coat the mesoporous carbon-titanium precursor solution on the clean hole-plugged surface of the single-sided hole-plugged anodic aluminum oxide to obtain a mesoporous carbon-titanium / anodic aluminum oxide film; Step S5, calcine the mesoporous carbon-titanium / anodic aluminum oxide film to obtain the vertical-channel mesoporous carbon-titanium / anodic aluminum oxide heterogeneous nanochannels, wherein, the configuration process of the mesoporous titanium dioxide precursor solution in Step S1 is as follows: Dissolve ethanol in deionized water to obtain an ethanol aqueous solution, stir the ethanol aqueous solution evenly in an ice bath at 0 °C, slowly drop titanium tetrachloride into the ethanol aqueous solution, and continue to stir at 0 °C in an ice bath for 60 min until it is uniform, then the yellow-green mesoporous titanium dioxide precursor solution is obtained; The specific steps of spin-coating the mesoporous carbon-titanium precursor solution on the clean hole-plugged surface of the single-sided hole-plugged anodic aluminum oxide in Step S4 are as follows: Step S4-1, paste the non-hole-plugged surface of the single-sided hole-plugged anodic aluminum oxide onto a glass slide; Step S4-2, spin-coat the mesoporous carbon-titanium precursor solution onto the clean hole-plugged surface of the single-sided hole-plugged anodic aluminum oxide to obtain spin-coated mesoporous carbon-titanium anodic aluminum oxide; Step S4-3, place the spin-coated mesoporous carbon-titanium anodic aluminum oxide in an oven at 35 °C for evaporation-induced self-assembly for 24 - 28 h, then raise the temperature to 100 - 110 °C and perform heat treatment for 24 - 28 h to obtain the mesoporous carbon-titanium / anodic aluminum oxide film.

2. The preparation method of the vertical-channel mesoporous carbon-titanium / anodic aluminum oxide heterogeneous nanochannels by the super-assembly strategy according to Claim 1, characterized in that Among them, the configuration process of the mesoporous carbon-titanium precursor solution in Step S1 is as follows: Dissolve F127 in absolute ethanol, add deionized water, and disperse until it is clear to obtain a mesoporous carbon-titanium precursor template agent F127 solution; Add acetic acid to the mesoporous carbon-titanium precursor template agent F127 solution to obtain a mixed solution one; Add the mesoporous titanium dioxide precursor solution to the mixed solution one, and stir until it is clear to obtain a mixed solution two; Add the carbon source resol to the mixed solution two, and stir at room temperature until it is clear to obtain the mesoporous carbon-titanium precursor solution.

3. The preparation method of the vertical-channel mesoporous carbon-titanium / anodic aluminum oxide heterogeneous nanochannels by the super-assembly strategy according to Claim 2, characterized in that Among them, the configuration process of the carbon source resol is as follows: Heat phenol to melt completely at 45 - 48 °C, add an aqueous sodium hydroxide solution, stir evenly, add formaldehyde, stir evenly at 70 - 75 °C, adjust the pH to neutral with hydrochloric acid, and remove the water by rotary evaporation to obtain the carbon source resol.

4. The preparation method of the vertical-channel mesoporous carbon-titanium / anodic aluminum oxide heterogeneous nanochannels by the super-assembly strategy according to Claim 1, characterized in that Among them, The specific steps of the single-sided hole plugging described in step S2 are as follows: Step S2-1: Prepare a polymethyl methacrylate solution with a concentration of 8-10 wt%. Step S2-2: Spin-coat the polymethyl methacrylate solution onto one side of the anodic aluminum oxide, and dry it at room temperature for 2-4 h to obtain an anodic aluminum oxide spin-coated with the polymethyl methacrylate solution. Step S2-3: Place the anodic aluminum oxide spin-coated with the polymethyl methacrylate solution in an oven at 190-210 °C for 6-8 h to obtain the single-sided hole-plugged anodic aluminum oxide.

5. The method for preparing a vertical-channel mesoporous carbon titanium / anodic aluminum oxide heteronanopore by the superassembly strategy according to claim 1, wherein Among them, the cleaning agent described in step S3 is deionized water and ethanol.

6. The method for preparing a vertical-channel mesoporous carbon titanium / anodic aluminum oxide heteronanopore by the superassembly strategy according to claim 1, wherein Among them, in the calcination process described in step S5, the temperature is raised to the calcination temperature at a rate of 1 °C / min, and the calcination temperature is 400-450 °C, and the calcination time is 5-6 h.

7. A vertical-channel mesoporous carbon titanium / anodic aluminum oxide heteronanopore, characterized in that it is prepared by the method for preparing a vertical-channel mesoporous carbon titanium / anodic aluminum oxide heteronanopore by the superassembly strategy according to any one of claims 1-6.

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