CN115138223A - Super-assembled nanowire-porous alumina heterostructure film device and preparation method thereof - Google Patents
Super-assembled nanowire-porous alumina heterostructure film device and preparation method thereof Download PDFInfo
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- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 title claims abstract description 23
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- 239000002070 nanowire Substances 0.000 claims abstract description 106
- CWLKGDAVCFYWJK-UHFFFAOYSA-N 3-aminophenol Chemical compound NC1=CC=CC(O)=C1 CWLKGDAVCFYWJK-UHFFFAOYSA-N 0.000 claims abstract description 48
- VKYKSIONXSXAKP-UHFFFAOYSA-N hexamethylenetetramine Chemical compound C1N(C2)CN3CN1CN2C3 VKYKSIONXSXAKP-UHFFFAOYSA-N 0.000 claims abstract description 46
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims abstract description 36
- 239000012528 membrane Substances 0.000 claims abstract description 29
- 238000000034 method Methods 0.000 claims abstract description 25
- 229940018563 3-aminophenol Drugs 0.000 claims abstract description 24
- 239000004312 hexamethylene tetramine Substances 0.000 claims abstract description 23
- 235000010299 hexamethylene tetramine Nutrition 0.000 claims abstract description 23
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 17
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000000758 substrate Substances 0.000 claims abstract description 8
- 239000002090 nanochannel Substances 0.000 claims abstract description 6
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 4
- 239000002243 precursor Substances 0.000 claims abstract description 3
- 239000002994 raw material Substances 0.000 claims abstract description 3
- 239000000243 solution Substances 0.000 claims description 30
- 239000007864 aqueous solution Substances 0.000 claims description 13
- 238000010790 dilution Methods 0.000 claims description 10
- 239000012895 dilution Substances 0.000 claims description 10
- 238000000967 suction filtration Methods 0.000 claims description 9
- 230000035484 reaction time Effects 0.000 claims description 8
- 239000011148 porous material Substances 0.000 claims description 6
- 238000009210 therapy by ultrasound Methods 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 4
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- 150000002500 ions Chemical class 0.000 abstract description 18
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- 239000003795 chemical substances by application Substances 0.000 abstract description 2
- 238000010248 power generation Methods 0.000 abstract description 2
- 238000003828 vacuum filtration Methods 0.000 abstract description 2
- 230000015784 hyperosmotic salinity response Effects 0.000 abstract 1
- 239000010409 thin film Substances 0.000 description 30
- 229960004011 methenamine Drugs 0.000 description 20
- 238000001878 scanning electron micrograph Methods 0.000 description 18
- 238000006243 chemical reaction Methods 0.000 description 16
- 239000010408 film Substances 0.000 description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 14
- 239000002086 nanomaterial Substances 0.000 description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 8
- 239000008367 deionised water Substances 0.000 description 8
- 229910021641 deionized water Inorganic materials 0.000 description 8
- 150000001768 cations Chemical class 0.000 description 7
- 230000003204 osmotic effect Effects 0.000 description 7
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 6
- 230000035699 permeability Effects 0.000 description 6
- 239000002131 composite material Substances 0.000 description 5
- 238000001914 filtration Methods 0.000 description 5
- 239000000693 micelle Substances 0.000 description 5
- 239000013535 sea water Substances 0.000 description 5
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 238000005406 washing Methods 0.000 description 4
- 239000002134 carbon nanofiber Substances 0.000 description 3
- 229910021393 carbon nanotube Inorganic materials 0.000 description 3
- 239000002041 carbon nanotube Substances 0.000 description 3
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical class C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
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- -1 phenolic aldehyde Chemical class 0.000 description 2
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- 239000011780 sodium chloride Substances 0.000 description 2
- 229910021607 Silver chloride Inorganic materials 0.000 description 1
- 238000003917 TEM image Methods 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 239000012018 catalyst precursor Substances 0.000 description 1
- GTKRFUAGOKINCA-UHFFFAOYSA-M chlorosilver;silver Chemical compound [Ag].[Ag]Cl GTKRFUAGOKINCA-UHFFFAOYSA-M 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 239000003431 cross linking reagent Substances 0.000 description 1
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- 125000000524 functional group Chemical group 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 230000037427 ion transport Effects 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- CWQXQMHSOZUFJS-UHFFFAOYSA-N molybdenum disulfide Chemical compound S=[Mo]=S CWQXQMHSOZUFJS-UHFFFAOYSA-N 0.000 description 1
- 229910052982 molybdenum disulfide Inorganic materials 0.000 description 1
- 239000002055 nanoplate Substances 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000001338 self-assembly Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 230000001131 transforming effect Effects 0.000 description 1
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
- B01D69/14—Dynamic membranes
- B01D69/141—Heterogeneous membranes, e.g. containing dispersed material; Mixed matrix membranes
- B01D69/142—Heterogeneous membranes, e.g. containing dispersed material; Mixed matrix membranes with "carriers"
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D61/00—Processes of separation using semi-permeable membranes, e.g. dialysis, osmosis or ultrafiltration; Apparatus, accessories or auxiliary operations specially adapted therefor
- B01D61/002—Forward osmosis or direct osmosis
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
- B01D67/0039—Inorganic membrane manufacture
- B01D67/0069—Inorganic membrane manufacture by deposition from the liquid phase, e.g. electrochemical deposition
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
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- H—ELECTRICITY
- H02—GENERATION; CONVERSION OR DISTRIBUTION OF ELECTRIC POWER
- H02N—ELECTRIC MACHINES NOT OTHERWISE PROVIDED FOR
- H02N3/00—Generators in which thermal or kinetic energy is converted into electrical energy by ionisation of a fluid and removal of the charge therefrom
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- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
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Abstract
The invention relates to a super-assembled nanowire-porous alumina heterostructure membrane device and a preparation method thereof. The method comprises the steps of taking m-aminophenol as a carbon source, taking hexamethylenetetramine as a raw material precursor and taking cetyltrimethylammonium bromide (CTAB) as a template agent, obtaining nanowires by a hydrothermal method, and then taking AAO as a substrate, and preparing a layer of densely assembled nanowire film on the AAO substrate by an interface super-assembly strategy initiated by vacuum filtration. Compared with the prior art, the nanowire/AAO heterojunction membrane device comprises a mesoporous channel with negative charges between nanowires and a nanochannel with positive charges of anodic alumina, and provides rich transmission channels for ions, and the asymmetric structure can provide selective ion transmission performance, so that the nanowire/AAO heterojunction membrane device has excellent salt tolerance power generation capacity. The invention provides a method and a novel idea for constructing a nanofluidic device with ion selectivity and salt difference energy trapping for a functional membrane material.
Description
Technical Field
The invention relates to the technical field of preparation of heterogeneous thin film devices, in particular to a super-assembled nanowire-porous alumina heterostructure film device and a preparation method thereof.
Background
Obtaining clean and sustainable salinity gradient energy is receiving more and more attention under the background of global energy crisis and environmental pollution. To capture the osmotic energy between seawater and river water, various nanofluidic devices have been developed that can control the transport of ions by electrical double layer overlapping in charged nanoscale channels. Among these, low dimensional materials, in particular two dimensional (2D) nanoplatelets, such as graphene, graphene Oxide (GO) and molybdenum disulfide, are commonly used as building blocks for hybrid membranes, since these nanoplatelets stack with ideal ion selectivity in a confined channel space. However, at the same time, the narrow closed space between these ultra-thin nanoplates results in a higher ion permeation energy barrier, resulting in a reduced ion flux and slow ion transport, resulting in a lower power density. The selectivity and permeability of ions are competing, which greatly limits the development of two-dimensional nanofluidic membrane-membrane devices.
Disclosure of Invention
The invention aims to provide a super-assembled nanowire-porous alumina heterostructure film device and a preparation method thereof, and a one-dimensional nanomaterial assembled heterostructure film material is constructed.
The purpose of the invention can be realized by the following technical scheme: a method for preparing a super-assembled nanowire-porous alumina heterostructure film device is characterized in that an AAO is used as a substrate, a nanowire is used as an element, and the nanowire is assembled on the AAO to obtain the nanowire/alumina heterostructure film device.
Preferably, the heteroconjunctival device comprises mesoporous channels with negative charges between nanowires and nano channels with positive charges of anodic alumina, and has asymmetric pore channels, charges and chemical compositions.
The heterojunction film has asymmetric pore channels, charges and chemical compositions, and has good cation selectivity and energy conversion capability.
The invention constructs the one-dimensional nano material assembled heterogeneous membrane material with larger channel size by one-dimensional nano material assembly, can realize the balance between selectivity and permeability, and overcomes the limitation of high permeability energy conversion. The one-dimensional nano material has the advantages of large length-diameter ratio and high functional group density, so that the one-dimensional nano material has unique high anisotropy and excellent thermal, mechanical and electrical properties, and is an ideal choice for the ion exchange nano channel membrane.
Preferably, the nanowire is obtained by a hydrothermal method by using m-aminophenol as a carbon source, using hexamethylenetetramine as a cross-linking agent and a catalyst precursor and using Cetyl Trimethyl Ammonium Bromide (CTAB) as a template.
Preferably, m-aminophenol, cetyltrimethylammonium bromide (CTAB) and hexamethylenetetramine are added into the aqueous solution for hydrothermal reaction, the pre-stabilized solution is diluted after the reaction is carried out for a period of time, and the hydrothermal reaction is further carried out to obtain the superfine soft nanowire.
More preferably, m-aminophenol, cetyltrimethylammonium bromide (CTAB) and hexamethylenetetramine are added into an aqueous solution for hydrothermal reaction, the pre-stabilized solution is diluted after the reaction is carried out for a period of time, and m-aminophenol and hexamethylenetetramine are added for further hydrothermal reaction to obtain the superfine soft nanowire.
More preferably, the temperature of the hydrothermal reaction is 60-200 ℃, the reaction time before dilution is 0.5-3 h, and the reaction time after dilution is 1-72 h.
Further preferably, the temperature of the hydrothermal reaction is 80-120 ℃, the reaction time before dilution is 1-3 h, and the reaction time after dilution is 12-48 h.
More preferably, the temperature of the hydrothermal reaction is 90-110 ℃, the reaction time before dilution is 1.5-2.5 h, and the reaction time after dilution is 18-36 h.
Preferably, the mass concentration of the m-aminophenol in the aqueous solution before the hydrothermal reaction is 0.1 to 100mg/mL.
Further preferably, the mass concentration of the m-aminophenol in the aqueous solution is 2 to 20mg/mL.
More preferably, the mass concentration of the m-aminophenol in the aqueous solution is 4 to 10mg/mL.
Preferably, the charge ratio of the m-aminophenol to the aqueous solution is 1.0 g.
Preferably, the mass concentration of the hexamethylene tetramine in the aqueous solution before the hydrothermal reaction is 0.2-200 mg/mL.
More preferably, the mass concentration of the hexamethylene tetramine in the aqueous solution is 4-50 mg/mL.
More preferably, the mass concentration of the hexamethylene tetramine in the aqueous solution is 10-30 mg/mL.
Preferably, the mass concentration of the cetyl trimethyl ammonium bromide CTAB in the aqueous solution before the hydrothermal reaction is 0.1-100 mg/mL.
Further preferably, the mass concentration of the cetyl trimethyl ammonium bromide CTAB in the aqueous solution is 2-20 mg/mL.
Still more preferably, the mass concentration of the cetyltrimethylammonium bromide CTAB in the water solution is 4-10 mg/mL.
Preferably, the mass ratio of the m-aminophenol, the cetyl trimethyl ammonium bromide CTAB and the hexamethylenetetramine is 0.2-100.
Preferably, the mass ratio of the m-aminophenol, the cetyl trimethyl ammonium bromide CTAB and the hexamethylenetetramine is 2-20.
Preferably, the pre-stabilized solution is diluted 10-1000 fold at the time of dilution.
Further preferably, the pre-stabilized solution is diluted 50-500 times at the time of dilution.
Preferably, the nanowires are assembled on the AAO by suction filtration.
Further preferably, the nanowires are prepared into a nanowire solution, and the nanowire solution is assembled on the AAO surface through a suction filtration method after ultrasonic treatment.
Still more preferably, the concentration of the nanowire solution is 0.01-10mg/mL.
Preferably, the concentration of the nanowire solution is 0.05-2mg/mL.
Preferably, the size of the nano-wire is 20-160 nm.
Cetyl trimethyl ammonium bromide CTAB will self-assemble into columnar micelles in solution. As the reaction proceeds, the temperature begins to rise and hexamethylenetetramine will gradually decompose into formaldehyde and ammonia. M-aminophenol and limited formaldehyde generate oligomer stable micelles through phenolic aldehyde condensation reaction, the self-assembly of the micelles and the slow phenolic aldehyde condensation reaction are carried out synchronously, and a pre-stable micelle solution is obtained after the reaction is carried out for a certain time. And then diluting the solution, and continuing to react to obtain the nanowire. The size of the nano-wire can be adjusted and controlled through the content of m-aminophenol and hexamethylenetetramine, and can be adjusted between 20 nanometers and 160 nanometers. And then, obtaining the nanowire/alumina heterostructure film device by using the AAO as a substrate and the nanowire as an element through a suction filtration method.
Carbon nanotubes, carbon nanofibers, nanocellulose fibers and the like are used for preparing membrane devices, and the sizes and the like of the carbon nanotubes, the carbon nanofibers, the nanocellulose fibers and the like are difficult to effectively regulate and control, so that research and application of the carbon nanotubes, the carbon nanofibers and the like are limited. The invention develops the one-dimensional nano material with adjustable size and uses the one-dimensional nano material as a basic element to assemble a novel heterostructure film device, thereby having important scientific significance and wide application value.
A super-assembled nanowire-porous alumina heterostructure film device is prepared by the preparation method. The heterostructure membrane device (nanowire/AAO heterogeneous thin film device) has asymmetric components, surface charges and a pore channel structure.
Compared with the prior art, the invention has the following advantages:
1. the invention constructs the one-dimensional nanomaterial assembled heterogeneous membrane material with larger channel size by the assembly of the one-dimensional nanomaterial, can realize the balance between selectivity and permeability, and overcomes the limitation of high permeability energy conversion;
2. the invention firstly adopts a super-assembly strategy to prepare the nano wire with adjustable size, and then the nano wire is used as an element to be assembled on an AAO substrate, thereby obtaining the nano wire/AAO composite membrane with excellent cation selectivity, realizing the application in the field of osmotic energy conversion and being used for capturing osmotic energy;
3. the nanowire/AAO heterogeneous thin film device has surface charges with an asymmetric structure and a nano channel structure, and can provide rich channels for ion transmission, so that excellent performance can be realized in the field of osmotic energy conversion;
4. the size and the content of the nano wire can be accurately regulated and controlled, and the method has important scientific significance and wide application value;
5. the nanowire/AAO heterogeneous thin film device is formed by assembling and filtering based on micelles, and the method is simple and easy to operate, environment-friendly, strong in sustainability, capable of realizing large-scale production and high in application value.
Drawings
FIG. 1 is a schematic diagram of the construction of a nanowire/AAO heterogeneous thin film device of the present invention;
FIG. 2 is a side Scanning Electron Micrograph (SEM) of the nanowire/AAO heterogeneous thin film device prepared according to example 1 of the present invention;
FIG. 3 is a side high magnification SEM image of a nanowire/AAO heterogeneous thin film device prepared in example 1 of the present invention;
FIG. 4 is a side higher magnification SEM image of a nanowire/AAO heterogeneous thin film device prepared according to example 1 of the present invention;
FIG. 5 is an upper SEM image of a nanowire/AAO heterogeneous thin-film device prepared in example 1 of the present invention;
FIG. 6 is a top high magnification SEM image of a nanowire/AAO heterogeneous thin film device prepared in example 1 of the present invention;
FIG. 7 is a top higher magnification SEM image of a nanowire/AAO heterogeneous thin film device made in example 1 of the present invention;
FIG. 8 is an upper SEM image of a nanowire/AAO heterogeneous thin-film device prepared in example 2 of the invention;
FIG. 9 is a top high magnification SEM image of a nanowire/AAO heterogeneous thin film device prepared in example 2 of the present invention;
FIG. 10 is an upper SEM image of a nanowire/AAO heterogeneous thin film device prepared according to example 3 of the present invention;
FIG. 11 is a top high magnification SEM image of a nanowire/AAO heterogeneous thin film device prepared according to example 3 of the present invention;
FIG. 12 is an upper SEM image of a nanowire/AAO heterogeneous thin film device prepared in example 4 of the present invention;
FIG. 13 is a top high magnification SEM image of a nanowire/AAO heterogeneous thin film device prepared in example 4 of the present invention;
FIG. 14 is an ion performance test chart of the nanowire/AAO heterogeneous thin film device in example 5 of the present invention;
FIG. 15 is a graph of the performance of transforming osmotic energy into electric energy of the nanowire/AAO heterogeneous thin film device in accordance with example 6 of the present invention, which is a graph of the variation of current density and power density with external resistance.
Detailed Description
The invention is described in detail below with reference to the figures and specific embodiments. The following examples are carried out on the premise of the technical scheme of the invention, and detailed embodiments and specific operation procedures are given, but the scope of the invention is not limited to the following examples.
A preparation method of a nanowire/AAO heterojunction membrane device comprises the steps of adding m-aminophenol, cetyl Trimethyl Ammonium Bromide (CTAB) and hexamethylenetetramine into an aqueous solution for hydrothermal reaction, diluting after a period of time, and continuing the reaction to obtain a nanowire. Nanowires of varying sizes and contents were then assembled on the AAO, resulting in the nanowire/AAO heterojunction film device as shown in fig. 1. The heterojunction film has asymmetric pore channels, charges and chemical compositions, and has good cation selectivity and energy conversion capability.
Cetyl trimethyl ammonium bromide CTAB adopted in the embodiment is purchased from Aladdin company, the product number is H108983-100g, and the CTAB is referred to as CTAB in the following; m-aminophenol was purchased from Aladdin, inc. under a brand number of A301746-500g; hexamethylene tetramine is purchased from Aladdin under the trade name H116380-100g.
Example 1
100mL of deionized water was removed and added to a 250mL Erlenmeyer flask, then 1.0g of m-aminophenol (10 mg/mL) and 1.0g of CTAB (10 mg/mL) and 1.5g of hexamethylenetetramine (15 mg/mL) were added to the solution and stirred for 2 hours. The Erlenmeyer flask was then placed in an oven at 100 ℃ and allowed to react for 2 hours. 1mL of the solution was taken out and added to 199mL of deionized water, and stirred for 2 hours, after which the reaction was continued for 36 hours while being placed in an oven at 100 ℃. Cooling to room temperature, filtering, washing with water and ethanol respectively, and drying to obtain the one-dimensional nanowire material. Preparing the obtained nanowire into 0.1mg/mL solution, performing ultrasonic treatment for 2 hours, and assembling the nanowire on the AAO surface by a suction filtration method to obtain the nanowire/AAO heterogeneous thin film device.
The side Scanning Electron Microscope (SEM) of the nanowire/AAO heterogeneous thin film device prepared in this example is shown in FIGS. 2-5, and it can be seen from FIG. 2 that the prepared nanowire/AAO heterogeneous thin film device has a heterostructure, the AAO thickness is 90 μm, and the nanowire thickness is 3 μm; fig. 3 and 4 are further enlarged TEM images with nanowires having an average size of 30 nm. The front SEM images of the nanowire/AAO heterogeneous thin film device prepared in this example are shown in fig. 5-7, which show that the nanowire layer has a flat surface and rich pore structure.
Example 2
100mL of deionized water was removed and added to a 250mL Erlenmeyer flask, and then 0.6g of m-aminophenol (6 mg/mL), 1.0g of CTAB (10 mg/mL) and 0.9g of hexamethylenetetramine (9 mg/mL) were added to the solution and stirred for 2 hours. The Erlenmeyer flask was then placed in an oven at 100 ℃ and allowed to react for 2 hours. 1mL of the solution was taken out and added to 199mL of deionized water, and stirred for 2 hours, after which the reaction was continued in an oven at 100 ℃ for 36 hours. Cooling to room temperature, filtering, washing with water and ethanol respectively, and drying to obtain the one-dimensional nanowire material. Preparing the obtained nanowire into 0.1mg/mL solution, performing ultrasonic treatment for 2 hours, and assembling the nanowire on the AAO surface by a suction filtration method to obtain the nanowire/AAO heterogeneous thin film device.
SEM images of the nanowire/AAO heterogeneous thin film device prepared in this example are shown in fig. 8 and 9, and it can be seen that the prepared nanowire has a diameter of about 20 nm and a flat surface.
Example 3
100mL of deionized water was removed and added to a 250mL Erlenmeyer flask, and then 1.0g of m-aminophenol (10 mg/mL), 1.0g of CTAB (10 mg/mL) and 1.5g of hexamethylenetetramine (15 mg/mL) were added to the solution and stirred for 2 hours. The Erlenmeyer flask was then placed in an oven at 100 ℃ and allowed to react for 2 hours. 1mL of the solution was taken out and added to 199mL of deionized water, and 0.2g of m-aminophenol and 0.3g of hexamethylenetetramine were added simultaneously, stirred for 2 hours, and then reacted for 36 hours while being placed in an oven at 100 ℃. Cooling to room temperature, filtering, washing with water and ethanol respectively, and drying to obtain the nanowire material. Preparing the obtained nanowire into 0.1mg/mL solution, performing ultrasonic treatment for 2 hours, and assembling the nanowire on the AAO surface by a suction filtration method to obtain the nanowire/AAO heterogeneous thin film device.
SEM images of the nanowire/AAO heterogeneous thin film device prepared in this example are shown in fig. 10 and 11, and it can be seen that the prepared nanowire has a diameter of about 80 nm and a flat surface.
Example 4
100mL of deionized water was removed and added to a 250mL Erlenmeyer flask, and then 1.0g of m-aminophenol (10 mg/mL), 1.0g of CTAB (10 mg/mL) and 1.5g of hexamethylenetetramine (15 mg/mL) were added to the solution and stirred for 2 hours. The Erlenmeyer flask was then placed in an oven at 100 ℃ and allowed to react for 2 hours. 1mL of the solution was taken out and added to 199mL of deionized water, and 0.6g of m-aminophenol and 0.9g of hexamethylenetetramine were added thereto, and stirred for 2 hours, after which the reaction was continued in an oven at 100 ℃ for 36 hours. Cooling to room temperature, filtering, washing with water and ethanol respectively, and drying to obtain the one-dimensional nanowire material. Preparing the obtained nanowire into 0.1mg/mL solution, performing ultrasonic treatment for 2 hours, and assembling the nanowire on the AAO surface by a suction filtration method to obtain the nanowire/AAO heterogeneous thin film device.
SEM images of the nanowire/AAO heterogeneous thin film device prepared in this example are shown in fig. 12 and 13, and it can be seen that the prepared nanowire has a diameter of about 160nm and a flat surface.
Example 5
The ion transmission performance test adopts two commonly used semi-conductive tanks of glass, and the nano wire/AAO heterogeneous filmThe membrane device is sandwiched between two conductivity cells, and the membrane is provided with a membrane containing 3 x 10 ions -8 m 2 A small window of silicon is used to determine the current density. In the test process, two silver-silver chloride electrodes are adopted to connect the whole circuit, one side of the AAO is connected with the negative electrode, and one side of the nanowire is connected with the positive electrode. The current was monitored using a picometer. For the ion selectivity test and the permeability test, the mode that the AAO side faces low concentration and the nanowire faces high concentration is adopted.
Selection 1M and 10 -6 M and KCl solution, the high concentration is placed on the side of the nanowire, the low concentration is placed on the side of AAO, and therefore the ion transmission direction is mainly from the side of the nanowire to the side of AAO. The positions of the anode and the cathode are changed to judge the selectivity of the ions. When the anode is arranged on one side of the nanowire, the concentration direction is consistent with the electric field direction under the positive bias condition, so that the transmission of cations is facilitated, and the high current is generated in consideration of the excellent cation selectivity presented by the composite membrane; when the negative electrode is arranged on one side of the nanowire, the concentration direction is opposite to the electric field direction under the positive bias condition, anion transmission is facilitated, which is contrary to the excellent cation selectivity presented by the composite membrane, and therefore, smaller current is generated. As shown in fig. 14, it can be seen that the current generated at the nanowire side by the positive electrode is higher than that generated at the nanowire side by the negative electrode, and the result indicates that the composite membrane has superior cation selectivity.
Example 6
The nanowire/AAO heterogeneous thin film device is further applied to the field of osmotic energy conversion. The magnitude of the current was also monitored using a picometer using silver chloride electrodes. The electrolytes used in the test procedure were 0.5M NaCl solution (seawater) and 0.01M NaCl (fresh water), respectively. And (3) putting high-concentration seawater into the conductivity cell on one side of the nanowire, connecting the high-concentration seawater with the anode of a picometer, putting fresh water on one side of the AAO, and connecting the high-concentration seawater with the cathode. And (3) converting the seepage energy into electric energy, supplying external resistance, adjusting the resistance of an external resistance box, and recording the current corresponding to different resistances to obtain a current density and power density diagram. Fig. 15 shows a graph of current density versus energy density for different resistances. It can be seen from the graph that the current density gradually decreases with the increase of the external resistance, and the energyThe density is increased and then reduced, and the maximum value of the energy density can reach 4.5W/m 2 . Experimental results show that the nanowire/AAO composite membrane can realize excellent performance in the field of osmotic energy conversion.
The invention discloses a preparation method and application of a nanowire/Anodic Aluminum Oxide (AAO) heterojunction film device based on an interface super-assembly strategy. The method takes m-aminophenol as a carbon source, hexamethylenetetramine as a raw material precursor and cetyltrimethylammonium bromide (CTAB) as a template agent, and obtains the nanowire by a hydrothermal method, wherein the size of the nanowire can be regulated and controlled between 10 nm and 160nm. And then preparing a layer of densely assembled nanowire film on the AAO substrate by using the AAO as the substrate and adopting an interfacial super-assembly strategy initiated by vacuum filtration. The nanowire/AAO heterojunction membrane device comprises a mesoporous channel with negative charges between nanowires and a nanochannel with positive charges of anodic alumina, and provides abundant transmission channels for ions. The asymmetric structure can provide selective ion transmission performance, and therefore, the salt difference power generation capacity is excellent. The invention provides a method for constructing a nanofluidic device with ion selectivity and salt difference energy capture for a functional membrane material and a novel idea.
The embodiments described above are described to facilitate an understanding and use of the invention by those skilled in the art. It will be readily apparent to those skilled in the art that various modifications to these embodiments may be made, and the generic principles described herein may be applied to other embodiments without the use of the inventive faculty. Therefore, the present invention is not limited to the above embodiments, and those skilled in the art should make improvements and modifications within the scope of the present invention based on the disclosure of the present invention.
Claims (10)
1. A preparation method of a super-assembled nanowire-porous alumina heterostructure film device is characterized in that an AAO is used as a substrate, a nanowire is used as an element, and the nanowire is assembled on the AAO to obtain the heterostructure film device.
2. The method of preparing a super-assembled nanowire-porous alumina heterostructure membrane device according to claim 1, wherein the heteroconjunctival device comprises mesoporous channels with negative charges between nanowires and nano channels with positive charges of anodic alumina, and has asymmetric pore channels, charges and chemical composition.
3. The method for preparing a super-assembled nanowire-porous alumina heterostructure membrane device according to claim 1, wherein the nanowire is prepared by a hydrothermal method by using m-aminophenol as a carbon source, hexamethylenetetramine as a raw material precursor and cetyltrimethylammonium bromide (CTAB) as a template.
4. The method for preparing a super-assembled nanowire-porous alumina heterostructure membrane device according to claim 3, wherein m-aminophenol, cetyltrimethylammonium bromide (CTAB) and hexamethylenetetramine are added into an aqueous solution to perform a hydrothermal reaction, and after a period of time, the solution is diluted and continuously reacted to obtain the nanowire.
5. The method for preparing a super-assembled nanowire-porous alumina heterostructure membrane device according to claim 4, wherein the temperature of the hydrothermal reaction is 60-200 ℃, the reaction time before dilution is 0.5-3 h, and the reaction time after dilution is 1-72 h.
6. The method for preparing a super-assembled nanowire-porous alumina heterostructure membrane device according to claim 1, wherein the nanowire is assembled on the AAO by a suction filtration method.
7. The method for preparing a super-assembled nanowire-porous alumina heterostructure membrane device according to claim 6, wherein the nanowire is prepared into a nanowire solution, and the nanowire solution is assembled on the AAO surface through a suction filtration method after being subjected to ultrasonic treatment.
8. The method for preparing a super-assembled nanowire-porous alumina heterostructure membrane device according to claim 7, wherein the concentration of the nanowire solution is 0.01-10mg/mL.
9. The method for preparing a super-assembled nanowire-porous alumina heterostructure film device according to claim 1, wherein the size of the nanowire is 20-160 nm.
10. A super-assembled nanowire-porous alumina heterostructure film device, characterized by being prepared by the preparation method of any one of claims 1 to 9.
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