CN115138223B - 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 14
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- 239000002070 nanowire Substances 0.000 claims abstract description 102
- CWLKGDAVCFYWJK-UHFFFAOYSA-N 3-aminophenol Chemical compound NC1=CC=CC(O)=C1 CWLKGDAVCFYWJK-UHFFFAOYSA-N 0.000 claims abstract description 51
- VKYKSIONXSXAKP-UHFFFAOYSA-N hexamethylenetetramine Chemical compound C1N(C2)CN3CN1CN2C3 VKYKSIONXSXAKP-UHFFFAOYSA-N 0.000 claims abstract description 50
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims abstract description 39
- 229940018563 3-aminophenol Drugs 0.000 claims abstract description 25
- 239000004312 hexamethylene tetramine Substances 0.000 claims abstract description 25
- 235000010299 hexamethylene tetramine Nutrition 0.000 claims abstract description 25
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 20
- 238000000034 method Methods 0.000 claims abstract description 13
- 239000000758 substrate Substances 0.000 claims abstract description 8
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000002090 nanochannel Substances 0.000 claims abstract description 6
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims abstract description 5
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 4
- 239000003795 chemical substances by application Substances 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 32
- 238000006243 chemical reaction Methods 0.000 claims description 17
- 239000007864 aqueous solution Substances 0.000 claims description 16
- 238000010790 dilution Methods 0.000 claims description 11
- 239000012895 dilution Substances 0.000 claims description 11
- 238000000967 suction filtration Methods 0.000 claims description 10
- 230000035484 reaction time Effects 0.000 claims description 8
- 239000000203 mixture Substances 0.000 claims description 7
- 239000011148 porous material Substances 0.000 claims description 6
- 238000009210 therapy by ultrasound Methods 0.000 claims description 6
- 238000007865 diluting Methods 0.000 claims description 4
- 239000000126 substance Substances 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims 1
- 239000012528 membrane Substances 0.000 abstract description 17
- 150000002500 ions Chemical class 0.000 abstract description 14
- 239000000463 material Substances 0.000 abstract description 10
- 230000005540 biological transmission Effects 0.000 abstract description 7
- 230000015784 hyperosmotic salinity response Effects 0.000 abstract description 2
- 238000003828 vacuum filtration Methods 0.000 abstract description 2
- 239000010409 thin film Substances 0.000 description 30
- 229960004011 methenamine Drugs 0.000 description 20
- 238000001878 scanning electron micrograph Methods 0.000 description 15
- 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
- 230000003204 osmotic effect Effects 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
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 6
- 239000002131 composite material Substances 0.000 description 5
- 239000000693 micelle 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
- 238000001914 filtration Methods 0.000 description 4
- 230000001105 regulatory effect Effects 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 238000005406 washing Methods 0.000 description 4
- 102100028292 Aladin Human genes 0.000 description 3
- 101710065039 Aladin Proteins 0.000 description 3
- 230000035699 permeability Effects 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- 238000006482 condensation reaction Methods 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 230000005684 electric field Effects 0.000 description 2
- 239000013505 freshwater Substances 0.000 description 2
- 229910021389 graphene Inorganic materials 0.000 description 2
- 230000037427 ion transport Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000002064 nanoplatelet Substances 0.000 description 2
- -1 phenolic aldehyde Chemical class 0.000 description 2
- 239000013535 sea water Substances 0.000 description 2
- 239000011780 sodium chloride Substances 0.000 description 2
- 229920001046 Nanocellulose Polymers 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 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
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000002134 carbon nanofiber Substances 0.000 description 1
- 229910021393 carbon nanotube Inorganic materials 0.000 description 1
- 239000002041 carbon nanotube Substances 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
- 210000000795 conjunctiva Anatomy 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 239000003431 cross linking reagent Substances 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 230000004907 flux Effects 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 125000005842 heteroatom Chemical group 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical class C VNWKTOKETHGBQD-UHFFFAOYSA-N 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
- 239000002060 nanoflake Substances 0.000 description 1
- 239000002055 nanoplate Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 238000010248 power generation Methods 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
- 230000032258 transport Effects 0.000 description 1
- 235000012431 wafers Nutrition 0.000 description 1
Classifications
-
- 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
-
- 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
-
- 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
-
- 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
-
- 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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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Nanotechnology (AREA)
- Crystallography & Structural Chemistry (AREA)
- Manufacturing & Machinery (AREA)
- Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Water Supply & Treatment (AREA)
- Dispersion Chemistry (AREA)
- Composite Materials (AREA)
- Materials Engineering (AREA)
- Inorganic Chemistry (AREA)
- Electrochemistry (AREA)
- Carbon And Carbon Compounds (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
Abstract
The invention relates to a super-assembled nanowire-porous alumina heterostructure film device and a preparation method thereof. Taking m-aminophenol as a carbon source, hexamethylenetetramine as a raw material precursor, cetyl trimethyl ammonium bromide CTAB as a template agent, obtaining nanowires through a hydrothermal method, and then preparing a layer of densely assembled nanowire film on an AAO substrate by taking the AAO as a substrate and adopting an interface super-assembly strategy induced by vacuum filtration. Compared with the prior art, the nanowire/AAO heterojunction film device comprises a mesoporous channel with negative charges and a nano channel with positive charges of anodic aluminum oxide between nanowires, and provides rich transmission channels for ions. The invention provides a method and a novel idea for constructing a nanofluidic device with ion selectivity and salt tolerance energy capture 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
In the context of global energy crisis and environmental pollution, the acquisition of clean, sustainable salinity gradient energy is becoming increasingly interesting. In order to capture the osmotic energy between sea and river water, various nanofluidic membrane devices have been developed that can control the transport of ions through the overlapping of electrical bilayers in charged nanoscale channels. Among other things, low dimensional materials, particularly two dimensional (2D) nanoplatelets, such as graphene, graphene Oxide (GO), and molybdenum disulfide, are often used as primitives for constructing hybrid membranes because these nanoplatelet stacks have ideal ion selectivity in confined channel spaces. At the same time, however, the narrow confined space between these ultrathin nanoplates results in a higher ion permeation energy barrier, resulting in reduced ion flux, slow ion transport, and thus lower power density. Ion selectivity and permeability are competing, which greatly limits the development of nanofluidic membrane-membrane devices based on two-dimensional nanoflakes.
Disclosure of Invention
The invention aims to provide a super-assembled nanowire-porous alumina heterostructure membrane device and a preparation method thereof, and a one-dimensional nanomaterial assembled heterogeneous membrane material is constructed.
The aim of the invention can be achieved by the following technical scheme: a preparation method of a super-assembled nanowire-porous alumina heterostructure film device uses AAO as a substrate and nanowires as primitives, and the nanowires are assembled on the AAO to obtain the nanowire/alumina heterostructure film device.
Preferably, the hetero-conjunctival device comprises negatively charged mesoporous channels between nanowires and positively charged anodic aluminum oxide nanochannels with asymmetric pore channels, charges and chemical compositions.
The hetero-conjunctiva has asymmetric pore canal, charge and chemical composition, and has good cation selectivity and energy conversion capability.
The one-dimensional nanomaterial assembled heterogeneous membrane material with larger channel size is assembled and constructed by the one-dimensional nanomaterial, so that the balance between selectivity and permeability can be realized, and the limit of high-permeability energy conversion is overcome. 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 of the ion exchange nano channel membrane.
Preferably, the nanowire is prepared by taking m-aminophenol as a carbon source, hexamethylenetetramine as a cross-linking agent and a catalyst precursor, and cetyl trimethyl ammonium bromide CTAB as a template agent through a hydrothermal method.
Further preferably, m-aminophenol, cetyl trimethyl ammonium bromide CTAB and hexamethylenetetramine are added into an aqueous solution for hydrothermal reaction, after a period of reaction, the pre-stabilized solution is diluted for further hydrothermal reaction, and the ultra-fine soft nanowires are obtained.
Still more preferably, m-aminophenol, cetyl trimethyl ammonium bromide CTAB and hexamethylenetetramine are added into an aqueous solution for hydrothermal reaction, after a period of reaction, the pre-stabilized solution is diluted, and m-aminophenol and hexamethylenetetramine are added for further hydrothermal reaction, so that the ultra-fine soft nanowire is obtained.
Still more preferably, the hydrothermal reaction temperature 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.
Still more preferably, the hydrothermal reaction temperature is 90 to 110 ℃, the reaction time before dilution is 1.5 to 2.5 hours, and the reaction time after dilution is 18 to 36 hours.
Preferably, before the hydrothermal reaction, the mass concentration of the m-aminophenol in the aqueous solution is 0.1-100 mg/mL.
Further preferably, the mass concentration of the m-aminophenol in the aqueous solution is 2-20 mg/mL.
Still more preferably, the mass concentration of the m-aminophenol in the aqueous solution is 4 to 10mg/mL.
Preferably, the feeding ratio of the m-aminophenol to the aqueous solution is 1.0 g/100 g.
Preferably, before the hydrothermal reaction, the mass concentration of the hexamethylenetetramine in the aqueous solution is 0.2-200 mg/mL.
Further preferably, the mass concentration of the hexamethylenetetramine in the aqueous solution is 4-50 mg/mL.
Still more preferably, the mass concentration of the hexamethylenetetramine in the aqueous solution is 10-30 mg/mL.
Preferably, before the hydrothermal reaction, the mass concentration of the cetyltrimethylammonium bromide CTAB in the aqueous solution 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 cetyl trimethylammonium bromide CTAB has a mass concentration of 4-10 mg/mL in the aqueous solution.
Preferably, the mass ratio of the m-aminophenol to the cetyl trimethyl ammonium bromide CTAB to the hexamethylenetetramine is 0.2-100:0.2-200:0.1-100.
Preferably, the mass ratio of the m-aminophenol to the cetyl trimethyl ammonium bromide CTAB to the hexamethylenetetramine is 2-20:4-50:2-20.
Preferably, the pre-stabilized solution is diluted 10-1000 times during dilution.
Further preferably, the pre-stabilized solution is diluted 50-500 times during dilution.
Preferably, the nanowires are assembled on the AAO by suction filtration.
Further preferably, the nanowires are prepared into nanowire solution, and assembled on the surface of AAO by suction filtration 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 nanowire size is 20-160 nm.
Cetyl trimethylammonium 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. The meta-aminophenol and limited formaldehyde are subjected to phenolic aldehyde condensation reaction to generate oligomer stable micelle, self-assembly of the micelle and slow phenolic aldehyde condensation reaction are synchronously carried out, and a pre-stable micelle solution is obtained after a certain time of reaction. And then diluting the solution, and continuing the reaction to obtain the nanowire. The size of the nanowire and the like can be regulated and controlled through the content of m-aminophenol and hexamethylenetetramine, and can be regulated between 20 nanometers and 160 nanometers. And then taking AAO as a substrate and the nanowire as a primitive, and obtaining the nanowire/alumina heterostructure film device by a suction filtration method.
Carbon nanotubes, carbon nanofibers, nanocellulose fibers and the like are used for preparing membrane devices, the sizes and the like of the membrane devices are difficult to effectively regulate and control, and scientific research and application of the membrane devices are limited. The invention develops the one-dimensional nano material with adjustable size and uses the nano material as a primitive to assemble a novel heterostructure membrane device, and has important scientific significance and wide application value.
The super-assembled nanowire-porous alumina heterostructure film device is prepared by the preparation method. The heterostructure film device (nanowire/AAO heterostructure film device) has an asymmetric composition, surface charge and pore structure.
Compared with the prior art, the invention has the following advantages:
1. The one-dimensional nanomaterial assembled heterogeneous membrane material with larger channel size is assembled and constructed by the one-dimensional nanomaterial, so that the balance between selectivity and permeability can be realized, and the limit of high-permeability energy conversion is overcome;
2. the invention firstly adopts a super-assembly strategy to prepare the nanowire with adjustable size, and then assembles the nanowire on an AAO substrate as a primitive, thereby obtaining the nanowire/AAO composite membrane with excellent cation selectivity, being capable of realizing the application in the field of osmotic energy conversion and being capable of being used for capturing osmotic energy;
3. The nanowire/AAO heterogeneous thin film device has an asymmetric surface charge and 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 nanowire can be accurately regulated and controlled, and the nanowire has important scientific significance and wide application value;
5. the nanowire/AAO heterogeneous thin film device is formed by micelle assembly and suction filtration, and the method is simple and easy to operate, environment-friendly, high 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 Microscope (SEM) image of a nanowire/AAO heterogeneous thin film device prepared in 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 in example 1 of the present invention;
FIG. 5 is an upper SEM image of a nanowire/AAO heterogeneous thin film device prepared according to example 1 of the present invention;
FIG. 6 is an SEM image of the top high magnification of a nanowire/AAO heterogeneous thin film device prepared according to example 1 of the present invention;
FIG. 7 is a higher magnification SEM image of the top of a nanowire/AAO heterogeneous thin film device prepared according to example 1 of the present invention;
FIG. 8 is an upper SEM image of a nanowire/AAO heterogeneous thin film device fabricated according to example 2 of the present invention;
FIG. 9 is an SEM image of the top high magnification of a nanowire/AAO heterogeneous thin film device prepared according to example 2 of the present invention;
FIG. 10 is an upper SEM image of a nanowire/AAO heterogeneous thin film device fabricated according to example 3 of the present invention;
FIG. 11 is an SEM image of the top high magnification 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 fabricated according to example 4 of the present invention;
FIG. 13 is an SEM image of the top high magnification of a nanowire/AAO heterogeneous thin film device fabricated according to example 4 of the present invention;
FIG. 14 is an ionic property test chart of a nanowire/AAO heterogeneous thin film device of example 5 of the present invention;
Fig. 15 is a graph of the osmotic energy converted to electrical energy performance of the nanowire/AAO heterogeneous thin film device of example 6 of the present invention, showing the current density and power density as a function of external resistance, respectively.
Detailed Description
The invention will now be described in detail with reference to the drawings and specific examples. The following examples are given by way of illustration of detailed embodiments and specific procedures based on the technical scheme of the present invention, but the scope of the present invention is not limited to the following examples.
The preparation process of nanometer wire/AAO hetero conjunctiva device includes adding m-aminophenol, cetyl trimethyl ammonium bromide CTAB and hexamethylenetetramine into water solution for hydrothermal reaction, diluting after some period of time, and continuing reaction to obtain nanometer wire. Nanowires of different sizes and contents were then assembled on AAO to give nanowire/AAO hetero-conjunctiva devices as shown in fig. 1. The hetero-conjunctiva has asymmetric pore channels, charges and chemical compositions, and endows the hetero-conjunctiva with good cation selectivity and energy conversion capability.
The cetyl trimethyl ammonium bromide CTAB used in the examples is purchased from Aladin company under the trade designation H108983-100g, hereinafter referred to as CTAB; m-aminophenol is purchased from Aladin company under the product number A301746-500g; hexamethylene tetramine is purchased from Aladin under the trade designation 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 100deg.C and allowed to react for 2 hours. 1mL of the solution was taken out and added to 199mL of deionized water, stirred for 2 hours, and then reacted in an oven at 100℃for 36 hours. Cooling to room temperature, suction filtering, washing with water and ethanol respectively, and drying to obtain the one-dimensional nanowire material. Preparing the obtained nanowire into a solution with the concentration of 0.1mg/mL, carrying out ultrasonic treatment for 2 hours, and then assembling the solution on the surface of the AAO by a suction filtration method to obtain the nanowire/AAO heterogeneous thin film device.
The lateral Scanning Electron Microscope (SEM) of the nanowire/AAO heterogeneous thin film device prepared in the embodiment is shown in figures 2-5, and the prepared nanowire/AAO heterogeneous thin film device has a heterostructure, wherein the AAO thickness is 90 μm and the nanowire thickness is 3 μm as shown in figure 2; 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 a rich pore structure.
Example 2
100ML of deionized water was removed and added to a 250mL Erlenmeyer flask, then 0.6g of m-aminophenol (6 mg/mL) and 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 100deg.C and allowed to react for 2 hours. 1mL of the solution was taken out and added to 199mL of deionized water, stirred for 2 hours, and then reacted in an oven at 100℃for 36 hours. Cooling to room temperature, suction filtering, washing with water and ethanol respectively, and drying to obtain the one-dimensional nanowire material. Preparing the obtained nanowire into a solution with the concentration of 0.1mg/mL, carrying out ultrasonic treatment for 2 hours, and then assembling the solution on the surface of the AAO by a suction filtration method to obtain the nanowire/AAO heterogeneous thin film device.
SEM images of the nanowire/AAO hetero-thin film device prepared in this example are shown in fig. 8 and 9, and it is known that the diameter of the nanowire prepared is about 20nm, and the nanowire has a flat surface.
Example 3
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 100deg.C and allowed to react for 2 hours. 1mL of the solution was taken out and added to 199mL of deionized water, 0.2g of m-aminophenol and 0.3g of hexamethylenetetramine were simultaneously added thereto, and the mixture was stirred for 2 hours, and then the reaction was continued in an oven at 100℃for 36 hours. Cooling to room temperature, suction filtering, washing with water and ethanol respectively, and drying to obtain the nanowire material. Preparing the obtained nanowire into a solution with the concentration of 0.1mg/mL, carrying out ultrasonic treatment for 2 hours, and then assembling the solution on the surface of the AAO by a suction filtration method to obtain the nanowire/AAO heterogeneous thin film device.
SEM images of the nanowire/AAO hetero-thin film device prepared in this example are shown in fig. 10 and 11, and it is known that the diameter of the nanowire prepared is about 80 nm, and the nanowire has a flat surface.
Example 4
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 100deg.C and allowed to react for 2 hours. 1mL of the solution was taken out and added to 199mL of deionized water, 0.6g of m-aminophenol and 0.9g of hexamethylenetetramine were simultaneously added, and the mixture was stirred for 2 hours, and then the reaction was continued in an oven at 100℃for 36 hours. Cooling to room temperature, suction filtering, washing with water and ethanol respectively, and drying to obtain the one-dimensional nanowire material. Preparing the obtained nanowire into a solution with the concentration of 0.1mg/mL, carrying out ultrasonic treatment for 2 hours, and then assembling the solution on the surface of the AAO by a suction filtration method to obtain the nanowire/AAO heterogeneous thin film device.
SEM images of the nanowire/AAO hetero-thin film device prepared in this example are shown in fig. 12 and 13, and it is known that the diameter of the nanowire prepared is about 160 nm, and the nanowire has a flat surface.
Example 5
The ion transmission performance test adopts a commonly used semi-conductive cell of two glasses, a nanowire/AAO heterogeneous thin film device is clamped between the two conductive cells, and silicon wafers containing 3 x 10 -8m2 small windows are placed on two sides of the film for determining the current density. In the test process, two silver-silver chloride electrodes are used for connecting the whole circuit, one AAO side is connected with a negative electrode, and one nanowire side is connected with a positive electrode. Current was monitored using a picoammeter. For ion selectivity and osmotic energy tests, the AAO side was facing low concentrations and the nanowires were facing high concentrations.
The KCl solution of 1M and 10 -6 M is selected, the high concentration is placed on the nanowire side, and the low concentration is placed on the AAO side, so that the ion transmission direction is mainly from the nanowire side to the AAO side. The position of the anode and the cathode is changed to judge the selectivity of ions. When the positive electrode 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 more facilitated, and the composite membrane has excellent cation selectivity, so that high current is generated; when the negative electrode is arranged on one side of the nanowire and under the positive bias condition, the concentration direction is opposite to the electric field direction, so that the negative electrode is more beneficial to anion transmission, and the negative electrode is contrary to the superior cation selectivity of the composite film, so that smaller current is generated. As shown in fig. 14, it can be seen that the current generated by the positive electrode on the nanowire side is higher than that generated by the negative electrode on the nanowire side, and the result shows that the composite film has superior cation selectivity.
Example 6
The nanowire/AAO heterogeneous thin film device is further applied to the field of osmotic energy conversion. Silver chloride electrodes were also used and the magnitude of the current was monitored using a picometer. The electrolytes used in the test were 0.5M NaCl solution (seawater) and 0.01M NaCl (fresh water), respectively. The high-concentration seawater is put into a conductivity cell at one side of the nanowire and is connected with the anode of the Piano meter, and the fresh water is put at one side of the AAO and is connected with the cathode. The osmotic energy is converted into electric energy, external resistors are supplied, the size of the external resistor box resistor is adjusted, and currents corresponding to different resistors are recorded, so that a current density and power density diagram can be obtained. The current density versus energy density curves for the different resistances are shown in fig. 15. From the graph, it can be seen that the current density gradually decreases with the increase of the external resistance, the energy density increases and then decreases, and the highest 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. According to the method, m-aminophenol is used as a carbon source, hexamethylenetetramine is used as a raw material precursor, cetyltrimethylammonium bromide CTAB is used as a template agent, the nanowire is obtained through a hydrothermal method, and the size of the nanowire can be regulated and controlled between 10 nm and 160 nm. And then preparing a layer of densely assembled nanowire film on the AAO substrate by taking the AAO as the substrate and adopting an interface super-assembly strategy induced by vacuum filtration. The nanowire/AAO heterojunction film device comprises a mesoporous channel with negative charges between nanowires and a nano channel with positive charges of anodic aluminum oxide, and provides a rich transmission channel for ions. The asymmetric structure can provide selective ion transport performance, and thus has excellent salt-poor power generation capability. The invention provides a method for constructing a nanofluidic device with ion selectivity and salt tolerance energy capture for a functional membrane material and a novel thought.
The previous description of the embodiments is provided to facilitate a person of ordinary skill in the art in order to make and use the present invention. It will be apparent to those skilled in the art that various modifications can be readily made to these embodiments 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-described embodiments, and those skilled in the art, based on the present disclosure, should make improvements and modifications without departing from the scope of the present invention.
Claims (5)
1. A preparation method of a super-assembled nanowire-porous alumina heterostructure film device is characterized in that AAO is taken as a substrate, nanowires are taken as primitives, and nanowires are assembled on the AAO to obtain the heterostructure film device;
The heterogeneous conjunctival device comprises a mesoporous channel with negative charges between nanowires and a nano channel with positive charges of anodic aluminum oxide, and has asymmetric pore channels, charges and chemical compositions;
The nanowire is prepared by taking m-aminophenol as a carbon source, hexamethylenetetramine as a raw material precursor and cetyl trimethyl ammonium bromide CTAB as a template agent through a hydrothermal method;
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 nanowires;
The temperature of the hydrothermal reaction is 60-200 o ℃, the reaction time before dilution is 0.5-3 h, and the reaction time after dilution is 1-72 h;
Before the hydrothermal reaction, the mass concentration of the m-aminophenol in the aqueous solution is 0.1-100 mg/mL;
Before the hydrothermal reaction, the mass concentration of the hexamethylenetetramine in the aqueous solution is 0.2-200 mg/mL;
before the hydrothermal reaction, the mass concentration of the cetyl trimethyl ammonium bromide CTAB in the aqueous solution is 0.1-100 mg/mL;
The mass ratio of the m-aminophenol to the cetyl trimethyl ammonium bromide CTAB to the hexamethylenetetramine is 0.2-100:0.2-200:0.1-100;
diluting the pre-stabilized solution by 10-1000 times during dilution;
the size of the nanowire is 20-160 nm.
2. The method for preparing a super-assembled nanowire-porous alumina heterostructure film device according to claim 1, wherein the nanowire is assembled on AAO by suction filtration.
3. The method for preparing the super-assembled nanowire-porous alumina heterostructure film device according to claim 2, wherein the nanowire is prepared into nanowire solution, and the nanowire is assembled on the surface of AAO by suction filtration after ultrasonic treatment.
4. The method of fabricating a super-assembled nanowire-porous alumina heterostructure film device of claim 3, wherein the concentration of the nanowire solution is 0.01-10 mg/mL.
5. A super-assembled nanowire-porous alumina heterostructure film device, characterized in that the device is prepared by the preparation method of any one of claims 1-4.
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