CN114137029A - TA-MS/AAO heterojunction nanochannel and preparation method thereof - Google Patents
TA-MS/AAO heterojunction nanochannel and preparation method thereof Download PDFInfo
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- G—PHYSICS
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- 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
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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
- G01N27/416—Systems
Abstract
The invention provides a preparation method of a TA-MS/AAO heterojunction nanochannel, which comprises the following steps: step 1, taking anodic aluminum oxide as a substrate, constructing a mesoporous silicon oxide layer with adjustable thickness on the surface of the anodic aluminum oxide as an ion selective layer by spin coating a precursor solution and a subsequent interface super-assembly and evaporation-induced self-assembly method, and preparing to obtain an MS/AAO heterogeneous nano channel; step 2, soaking the MS/AAO heterojunction nano-channel into a 3-aminopropyl triethoxysilane ethanol solution; step 3, cleaning the MS/AAO heterojunction nano-channel soaked in the step 2, and then heating to obtain NH2-MS/AAO nanochannels; step 4, adding NH2-the MS/AAO nanochannels are immersed in a tannic acid solution, soaking at room temperature; step 5, soaking the NH in the step 42And cleaning the MS/AAO nano channel to obtain the TA-MS/AAO heterojunction nano channel. The invention also providesA TA-MS/AAO heterojunction nanochannel is prepared by adopting a preparation method of the TA-MS/AAO heterojunction nanochannel.
Description
Technical Field
The invention belongs to the field of nano ion channels, and particularly relates to a TA-MS/AAO heterojunction nano channel and a preparation method thereof.
Background
In recent years, artificial ion nanochannels with controllable size and surface functionality have been widely used to mimic the ion transport process in biological ion channels. The bionic solid nano ion channel has excellent and adjustable ion transport performance, and is widely applied to the fields of sensing, ultrafiltration, desalination, energy conversion and the like. The surface charge, wettability and geometry of the nanochannels can be adjusted in response to external stimuli (e.g., pH, temperature and specific molecules) to affect ion transport, resulting in a change in the electrical signal. In addition, the nanometer constraint effect of the artificial nanometer channel can further amplify the change of the electric signal, so that the artificial nanometer channel has good sensing sensitivity. Thus, artificial nanochannels have great potential in the construction of nanofluidic sensing devices.
However, current research is always faced with some problems, such as the limited modification methods and techniques of the current nanochannels, and how to realize intelligent molecule recognition and detection by modifying the nanochannels is still a challenge. In the face of the existing bottleneck, the development of a preparation method and a technology of a functionalized nanoparticle channel material for sensing analysis is urgently needed.
Disclosure of Invention
The present invention is made to solve the above problems, and an object of the present invention is to provide a TA-MS/AAO heterojunction nanochannel and a method for preparing the same.
The invention provides a preparation method of a TA-MS/AAO heterojunction nanochannel, which is characterized by comprising the following steps:
step 1, taking anodic aluminum oxide as a substrate, constructing a mesoporous silicon oxide layer with adjustable thickness on the surface of the anodic aluminum oxide as an ion selective layer by spin coating a precursor solution and subsequent interface super-assembly and evaporation-induced self-assembly methods according to the hydrogen bond action between the anodic aluminum oxide and silicon hydroxyl, and preparing to obtain an MS/AAO heterogeneous nano channel;
step 2, soaking the MS/AAO heterojunction nano-channel into a 3-aminopropyl triethoxysilane ethanol solution;
step 3, carrying out MS/AAO heterojunction treatment on the soaked MS/AAO heterojunction in the step 2Cleaning the rice channel, and then heating to obtain NH2-MS/AAO nanochannels;
step 4, adding NH2-the MS/AAO nanochannels are immersed in a tannic acid solution, soaking at room temperature;
step 5, soaking the NH in the step 42And cleaning the MS/AAO nano channel to obtain the TA-MS/AAO heterojunction nano channel.
In the preparation method of the TA-MS/AAO heterojunction nanochannel provided by the invention, the preparation method also has the following characteristics: wherein NH2The MS/AAO nano channel is an amino acid modified mesoporous silica/anodized alumina heterojunction nano channel, and the TA-MS/AAO heterojunction nano channel is a tannic acid modified mesoporous silica/anodized alumina heterojunction nano channel.
In the preparation method of the TA-MS/AAO heterojunction nanochannel provided by the invention, the preparation method also has the following characteristics: wherein, step 1 comprises the following substeps:
step 1-1, coating 0.2ml-0.5ml of 8 wt% -10 wt% polymethyl methacrylate solution on anodic alumina, and heating in an oven at 180 ℃ -200 ℃ for 5h-6 h;
step 1-2, preparing a template solution of a mesoporous silica precursor, weighing 0.4g-1.2g of F127, and dissolving in 8g-12g of ethanol;
step 1-3, weighing 0.3g-0.8g of dilute hydrochloric acid with the concentration of 0.1M, adding 0.5g-0.8g of deionized water and 10.0g-15.0g of ethanol, then adding 2.06g-2.10g of tetraethyl orthosilicate, and placing the mixed solution at the temperature of 20 ℃ to 30 ℃ and stirring for 30min-40 min;
step 1-4, transferring the solution obtained in the step 1-3 to 55-65 ℃ and stirring for 1-1.5 h;
step 1-5, mixing the solution obtained in the step 1-2 and the solution obtained in the step 1-4, and stirring for 1-2 hours to obtain a precursor solution;
step 1-6, spin-coating the precursor solution obtained in the step 1-5 on the anodized aluminum substrate obtained in the step 1-1 at the rotation speed of 1000r-2000r for 60s-90 s;
step 1-7, placing the film obtained in the step 1-6 at 35-45 ℃ for evaporation induction self-assembly for 24h, and then heating to 100 ℃ for 24 h;
and 1-8, calcining the membrane obtained in the step 1-7 for 6 hours at 500 ℃ in the air to obtain the MS/AAO heterogeneous nanochannel.
In the preparation method of the TA-MS/AAO heterojunction nanochannel provided by the invention, the preparation method also has the following characteristics: in the step 2, the MS/AAO heterojunction nano-channel is soaked in 5-10% 3-aminopropyl triethoxysilane ethanol solution for 12-14 h at the temperature of 40-50 ℃.
In the preparation method of the TA-MS/AAO heterojunction nanochannel provided by the invention, the preparation method also has the following characteristics: in the step 3, the soaked MS/AAO heterojunction nano-channel is washed for three times by using ethanol and deionized water respectively, and redundant unreacted 3-aminopropyltriethoxysilane is removed.
In the preparation method of the TA-MS/AAO heterojunction nanochannel provided by the invention, the preparation method also has the following characteristics: wherein, in the step 3, the MS/AAO heterojunction nano-channel is heated for 1h-2h under the temperature condition of 100 ℃ to 120 ℃.
In the preparation method of the TA-MS/AAO heterojunction nanochannel provided by the invention, the preparation method also has the following characteristics: wherein, in the step 4, the concentration of the tannic acid solution is 15mg/ml-25mg/ml, and NH2The soaking time of the MS/AAO nano-channel is 12-14 h.
In the preparation method of the TA-MS/AAO heterojunction nanochannel provided by the invention, the preparation method also has the following characteristics: wherein, in step 5, the NH is removed by washing with deionized water2Excess tannic acid solution on the surface of the MS/AAO nanochannels.
The invention also provides a TA-MS/AAO heterojunction nanochannel, which is characterized in that: the material is prepared by adopting a preparation method of a TA-MS/AAO heterojunction nano-channel.
Action and Effect of the invention
According to the TA-MS/AAO heterojunction nanochannel and the preparation method thereof, a layer of ion selective layer nanochannel is constructed on an anodic alumina substrate by a super-assembly method, and then the ion selective layer is modified in two steps to obtain the TA-MS/AAO heterojunction nanochannel with ordered ion transfer channel, high channel density and rich functional groups.
Drawings
FIG. 1 is a flow chart of the preparation of a method for preparing a TA-MS/AAO heterojunction nanochannel according to an embodiment of the present invention;
FIG. 2 is a TEM image of a TA-modified mesoporous silica film prepared in an example of the present invention;
FIG. 3 is a scanning electron microscope image of the cross section (a) and the surface (b) of a TA-MS/AAO heterojunction nanochannel prepared in an example of the present invention;
fig. 4 shows a nitrogen adsorption/desorption curve (a) and a pore size distribution curve (b) of the TA-modified mesoporous silica film prepared in the example of the present invention;
FIG. 5 is a Fourier infrared absorption spectrum of each modified mesoporous silica film prepared in an example of the present invention;
FIG. 6 is an X-ray photoelectron spectrum of each step of modified heterojunction nanochannel prepared in an example of the present invention;
fig. 7 is a contact angle test chart of each step of modified heterojunction nanochannel prepared in the example of the present invention.
Detailed Description
In order to make the technical means and functions of the present invention easy to understand, the present invention is specifically described below with reference to the embodiments and the accompanying drawings.
< example >
FIG. 1 is a flow chart of the preparation of a method for preparing a TA-MS/AAO heterojunction nanochannel according to an embodiment of the present invention.
As shown in fig. 1, the method for preparing a TA-MS/AAO heterojunction nanochannel according to this embodiment includes the following steps:
step 1, taking anodic aluminum oxide as a substrate, constructing a mesoporous silicon oxide layer with adjustable thickness on the surface of the anodic aluminum oxide as an ion selective layer by spin coating a precursor solution and subsequent interface super-assembly and evaporation-induced self-assembly methods according to the hydrogen bond action between the anodic aluminum oxide and silicon hydroxyl, and preparing the MS/AAO heterogeneous nanochannel.
Step 1 comprises the following substeps:
step 1-1, coating 0.2ml-0.5ml of 8 wt% -10 wt% polymethyl methacrylate solution on anodic alumina, and heating in an oven at 180 ℃ -200 ℃ for 5h-6 h;
step 1-2, preparing a template solution of a mesoporous silica precursor, weighing 0.4g-1.2g of F127, and dissolving in 8g-12g of ethanol;
step 1-3, weighing 0.3g-0.8g of dilute hydrochloric acid with the concentration of 0.1M, adding 0.5g-0.8g of deionized water and 10.0g-15.0g of ethanol, then adding 2.06g-2.10g of tetraethyl orthosilicate, and placing the mixed solution at the temperature of 20 ℃ to 30 ℃ and stirring for 30min-40 min;
step 1-4, transferring the solution obtained in the step 1-3 to 55-65 ℃ and stirring for 1-1.5 h;
step 1-5, mixing the solution obtained in the step 1-2 and the solution obtained in the step 1-4, and stirring for 1-2 hours to obtain a precursor solution;
step 1-6, spin-coating the precursor solution obtained in the step 1-5 on the anodized aluminum substrate obtained in the step 1-1 at the rotating speed of 1000r-2000r for 60s-90 s;
step 1-7, placing the film obtained in the step 1-6 at 35-45 ℃ for evaporation induction self-assembly for 24h, and then heating to 100 ℃ for 24 h;
and (3) calcining the membrane obtained in the step (1) to (7) for 6 hours at 500 ℃ in the air to obtain the MS/AAO heterogeneous nanochannel.
And 2, soaking the MS/AAO heterojunction nano-channel into 3-aminopropyl triethoxysilane (APTES) ethanol solution.
In the step 2, the MS/AAO heterojunction nano-channel is immersed in 5-10% 3-aminopropyl triethoxysilane ethanol solution for 12-14 h at the temperature of 40-50 ℃.
In this example, the concentration, time, and temperature of the modified 3-Aminopropyltriethoxysilane (APTES) have a certain influence on the subsequent further modification.
Step 3, cleaning the MS/AAO heterojunction nanochannel soaked in the step 2, and then heating to enable the surface silane and the MS/AAO heterojunction nanochannel to have more stable effect to obtain NH2-MS/AAO nanochannels.
And in the step 3, the soaked MS/AAO heterojunction nano-channel is washed for three times by using ethanol and deionized water respectively, and redundant unreacted 3-aminopropyltriethoxysilane is removed.
In step 3, the MS/AAO heterojunction nano-channel is heated for 1h-2h at the temperature of 100-120 ℃.
NH2the-MS/AAO nano-channel is an amino acid modified mesoporous silica/anodic alumina heterojunction nano-channel.
Step 4, adding NH2-MS/AAO nanochannels were immersed in tannic acid solution and soaked at room temperature.
In step 4, the concentration of the tannic acid solution is 15mg/ml-25mg/ml, NH2The soaking time of the MS/AAO nano-channel is 12-14 h.
In this embodiment, the TA modification time has a certain influence on the modification degree, and heterojunction nanochannels with different TA modification degrees can be obtained by controlling the concentration of the tannic acid solution.
Step 5, soaking the NH in the step 42And cleaning the MS/AAO nano channel to obtain the TA-MS/AAO heterojunction nano channel.
In step 5, NH is removed by washing with deionized water2Excess tannic acid solution on the surface of the MS/AAO nanochannels.
The TA-MS/AAO heterojunction nano-channel is a tannin modified mesoporous silica/anodic alumina heterojunction nano-channel.
The TA-MS/AAO heterojunction nanochannel of the embodiment is prepared by adopting a preparation method of the TA-MS/AAO heterojunction nanochannel.
The TA-MS/AAO heterojunction nanochannel comprises a one-dimensional anodic aluminum oxide nanochannel with the thickness of 60 mu m and the average pore size of 20nm, and a tannin-modified mesoporous silicon oxide layer with the thickness of about 135nm and the average pore size of about 5nm-6 nm.
Fig. 2 is a TEM image of a TA modified mesoporous silica film prepared in an example of the present invention.
As shown in fig. 2, the prepared mesoporous silica has a regular pore structure and a high pore density.
FIG. 3 is a scanning electron microscope image of the cross section (a) and the surface (b) of the TA-MS/AAO heterojunction nanochannel prepared in the example of the present invention.
As shown in fig. 3, fig. 3(a) is a cross-sectional view of the TA-MS/AAO heterojunction nanochannel, and it can be seen that the modified mesoporous silica is closely located on the upper layer of the AAO, and the thickness is about 135nm, and fig. 3(b) is a surface of the TA-MS/AAO heterojunction nanochannel, and a regular pore structure can be seen.
Fig. 4 shows a nitrogen adsorption/desorption curve (a) and a pore size distribution curve (b) of the TA-modified mesoporous silica film prepared in the example of the present invention.
As shown in fig. 4, it can be seen from the nitrogen adsorption/desorption curve of fig. 4(a) that the TA-modified mesoporous silica film has a high specific surface area, and the pore size is about 5.58nm as can be seen from the pore size distribution curve of fig. 4 (b).
Fig. 5 is a fourier infrared absorption spectrum of each modified mesoporous silica film prepared in the example of the present invention.
As shown in FIG. 5, 1590 and 687cm were observed after modification of 3-Aminopropyltriethoxysilane (APTES) into the MS layer-1Peaks at (D), corresponding to the bands of N-H tensile and flexural vibrations, respectively, indicate-NH2The group is successfully grafted on an MS layer, and TA-MS/AAO is 1582cm after amidation reaction of APTES and TA-1And 1709cm-1Additional peaks appear at (a) and C ═ C stretching vibrations corresponding to the aromatic ring and ester groups, respectively, of TA, indicating successful TA modification on the MS layer.
Fig. 6 is an X-ray photoelectron spectrum of each step of modified heterojunction nanochannel prepared in the example of the present invention.
As shown in FIG. 6, MS/AAO exhibited a typical peak of N1s after APTES modification, which was not observed prior to amino functionalization. After TA modification, the nanochannel surface C1s content increased from 70.3% to 58.1%, because of TA modification, which introduced more carbon content.
Fig. 7 is a contact angle test chart of each step of modified heterojunction nanochannel prepared in the example of the present invention.
As shown in fig. 7, the wettability of the heterogeneous channel changes after each modification. For MS/AAO, the water contact angle is only 4.6 + -1.0 deg. due to the rich silicon hydroxyl groups of the MS layer. After modification with APTES, the contact angle increased to 23.9 ± 1.4 °, with more hydrophobic surface due to the introduction of APTES fatty chains. After modification of MS/AAO with TA, the contact angle reached 38.6. + -. 1.7. this is due to the phenyl group in the TA molecule.
In conclusion, the TA-MS/AAO heterojunction nanochannel can be successfully modified to the MS/AAO by the preparation method of the TA-MS/AAO heterojunction nanochannel, and the prepared TA-MS/AAO heterojunction nanochannel has the functionalized modified ion selective layer, so that a new material is provided for the intelligent nanofluidic nanochannel device in the field of sensing analysis.
Effects and effects of the embodiments
According to the TA-MS/AAO heterojunction nanochannel and the preparation method thereof related by the embodiment, a layer of ion selective layer nanochannel is constructed on an anodic alumina substrate by a super-assembly method, and then the ion selective layer is modified in two steps to obtain the TA-MS/AAO heterojunction nanochannel with ordered ion transfer channel, high channel density and rich functional groups.
The above embodiments are preferred examples of the present invention, and are not intended to limit the scope of the present invention.
Claims (9)
1. A preparation method of a TA-MS/AAO heterojunction nanochannel is characterized by comprising the following steps:
step 1, taking anodic aluminum oxide as a substrate, constructing a mesoporous silicon oxide layer with adjustable thickness on the surface of the anodic aluminum oxide as an ion selective layer by spin coating a precursor solution and subsequent interface super-assembly and evaporation-induced self-assembly methods according to the hydrogen bond action between the anodic aluminum oxide and silicon hydroxyl, and preparing to obtain an MS/AAO heterogeneous nanochannel;
step 2, soaking the MS/AAO heterojunction nano-channel into a 3-aminopropyltriethoxysilane ethanol solution;
step 3, cleaning the MS/AAO heterojunction nano-channel soaked in the step 2, and then heating to obtain NH2-MS/AAO nanochannels;
step 4, adding the NH2-the MS/AAO nanochannels are immersed in a tannic acid solution, soaking at room temperature;
step 5, soaking the NH soaked in the step 42And cleaning the MS/AAO nano channel to obtain the TA-MS/AAO heterojunction nano channel.
2. The method of claim 1, wherein the TA-MS/AAO heterojunction nanochannel is formed by:
wherein, the NH2the-MS/AAO nano-channel is an amino acid modified mesoporous silica/anodic alumina heterojunction nano-channel,
the TA-MS/AAO heterojunction nano-channel is a tannin-modified mesoporous silica/anodic alumina heterojunction nano-channel.
3. The method of claim 1, wherein the TA-MS/AAO heterojunction nanochannel is formed by:
wherein, step 1 comprises the following substeps:
step 1-1, coating 0.2ml-0.5ml of 8 wt% -10 wt% polymethyl methacrylate solution on the anodic alumina, and heating in an oven at 180 ℃ -200 ℃ for 5h-6 h;
step 1-2, preparing a template solution of a mesoporous silica precursor, weighing 0.4g-1.2g of F127, and dissolving in 8g-12g of ethanol;
step 1-3, weighing 0.3g-0.8g of dilute hydrochloric acid with the concentration of 0.1M, adding 0.5g-0.8g of deionized water and 10.0g-15.0g of ethanol, then adding 2.06g-2.10g of tetraethyl orthosilicate, and placing the mixed solution at the temperature of 20 ℃ to 30 ℃ and stirring for 30min-40 min;
step 1-4, transferring the solution obtained in the step 1-3 to 55-65 ℃ and stirring for 1-1.5 h;
step 1-5, mixing the solution obtained in the step 1-2 and the solution obtained in the step 1-4, and stirring for 1-2 hours to obtain a precursor solution;
step 1-6, spin-coating the precursor solution obtained in the step 1-5 on the anodized aluminum substrate obtained in the step 1-1 at a spin-coating speed of 1000r-2000r for 60s-90 s;
step 1-7, placing the film obtained in the step 1-6 at 35-45 ℃ for evaporation induction self-assembly for 24h, and then heating to 100 ℃ for 24 h;
and 1-8, calcining the membrane obtained in the step 1-7 for 6 hours at 500 ℃ in the air to obtain the MS/AAO heterogeneous nano channel.
4. The method of claim 1, wherein the TA-MS/AAO heterojunction nanochannel is formed by:
in the step 2, the MS/AAO heterojunction nano-channel is immersed in 5% -10% of the 3-aminopropyltriethoxysilane ethanol solution for 12-14 h at the temperature of 40-50 ℃.
5. The method of claim 1, wherein the TA-MS/AAO heterojunction nanochannel is formed by:
and in the step 3, the soaked MS/AAO heterojunction nano-channel is washed for three times by using ethanol and deionized water respectively, and redundant unreacted 3-aminopropyltriethoxysilane is removed.
6. The method of claim 1, wherein the TA-MS/AAO heterojunction nanochannel is formed by:
wherein, in the step 3, the MS/AAO heterojunction nano-channel is heated for 1h-2h under the temperature condition of 100 ℃ to 120 ℃.
7. The method of claim 1, wherein the TA-MS/AAO heterojunction nanochannel is formed by:
wherein, in the step 4, the concentration of the tannic acid solution is 15mg/ml-25mg/ml, and the NH is2The soaking time of the MS/AAO nano-channel is 12-14 h.
8. The method of claim 1, wherein the TA-MS/AAO heterojunction nanochannel is formed by:
wherein, in step 5, the NH is removed by washing with deionized water2-excess of said tannic acid solution on the surface of the MS/AAO nanochannels.
9. A TA-MS/AAO heterojunction nanochannel is characterized in that: the TA-MS/AAO heterojunction nanochannel as claimed in any one of claims 1 to 8.
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