CN117702216A - Porous alumina template with through and ultra-long nano pore canal and preparation method and application thereof - Google Patents
Porous alumina template with through and ultra-long nano pore canal and preparation method and application thereof Download PDFInfo
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- CN117702216A CN117702216A CN202311717391.4A CN202311717391A CN117702216A CN 117702216 A CN117702216 A CN 117702216A CN 202311717391 A CN202311717391 A CN 202311717391A CN 117702216 A CN117702216 A CN 117702216A
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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 76
- 239000011148 porous material Substances 0.000 title claims abstract description 44
- 238000002360 preparation method Methods 0.000 title claims abstract description 22
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 53
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 50
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims abstract description 31
- MUBZPKHOEPUJKR-UHFFFAOYSA-N oxalic acid group Chemical group C(C(=O)O)(=O)O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims abstract description 30
- 239000000243 solution Substances 0.000 claims abstract description 26
- 239000007864 aqueous solution Substances 0.000 claims abstract description 24
- 239000003792 electrolyte Substances 0.000 claims abstract description 16
- 238000000034 method Methods 0.000 claims abstract description 16
- 239000002070 nanowire Substances 0.000 claims abstract description 16
- 238000007747 plating Methods 0.000 claims abstract description 15
- 235000006408 oxalic acid Nutrition 0.000 claims abstract description 10
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 10
- 230000003647 oxidation Effects 0.000 claims abstract description 8
- 238000004070 electrodeposition Methods 0.000 claims abstract description 4
- 239000002071 nanotube Substances 0.000 claims abstract description 4
- 238000002791 soaking Methods 0.000 claims abstract description 3
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 80
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 52
- 239000010949 copper Substances 0.000 claims description 50
- 229910052802 copper Inorganic materials 0.000 claims description 47
- 229910052759 nickel Inorganic materials 0.000 claims description 33
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 30
- 229910052725 zinc Inorganic materials 0.000 claims description 30
- 239000011701 zinc Substances 0.000 claims description 30
- 238000006056 electrooxidation reaction Methods 0.000 claims description 27
- 229920002379 silicone rubber Polymers 0.000 claims description 19
- 238000006243 chemical reaction Methods 0.000 claims description 16
- 229910001220 stainless steel Inorganic materials 0.000 claims description 16
- 239000010935 stainless steel Substances 0.000 claims description 16
- 239000000853 adhesive Substances 0.000 claims description 14
- 230000001070 adhesive effect Effects 0.000 claims description 14
- 239000007788 liquid Substances 0.000 claims description 14
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 12
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 12
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 9
- YXIWHUQXZSMYRE-UHFFFAOYSA-N 1,3-benzothiazole-2-thiol Chemical compound C1=CC=C2SC(S)=NC2=C1 YXIWHUQXZSMYRE-UHFFFAOYSA-N 0.000 claims description 8
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 8
- 238000007598 dipping method Methods 0.000 claims description 8
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 claims description 8
- 238000001035 drying Methods 0.000 claims description 7
- 229910052799 carbon Inorganic materials 0.000 claims description 6
- 238000004140 cleaning Methods 0.000 claims description 6
- 238000000151 deposition Methods 0.000 claims description 6
- 238000005530 etching Methods 0.000 claims description 6
- 229910021591 Copper(I) chloride Inorganic materials 0.000 claims description 5
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical compound [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 claims description 5
- 239000012528 membrane Substances 0.000 claims description 5
- PEVJCYPAFCUXEZ-UHFFFAOYSA-J dicopper;phosphonato phosphate Chemical compound [Cu+2].[Cu+2].[O-]P([O-])(=O)OP([O-])([O-])=O PEVJCYPAFCUXEZ-UHFFFAOYSA-J 0.000 claims description 4
- 238000007654 immersion Methods 0.000 claims description 4
- LJCNRYVRMXRIQR-OLXYHTOASA-L potassium sodium L-tartrate Chemical compound [Na+].[K+].[O-]C(=O)[C@H](O)[C@@H](O)C([O-])=O LJCNRYVRMXRIQR-OLXYHTOASA-L 0.000 claims description 4
- 239000011734 sodium Substances 0.000 claims description 4
- 239000004317 sodium nitrate Substances 0.000 claims description 4
- 235000010344 sodium nitrate Nutrition 0.000 claims description 4
- 235000011006 sodium potassium tartrate Nutrition 0.000 claims description 4
- RYCLIXPGLDDLTM-UHFFFAOYSA-J tetrapotassium;phosphonato phosphate Chemical compound [K+].[K+].[K+].[K+].[O-]P([O-])(=O)OP([O-])([O-])=O RYCLIXPGLDDLTM-UHFFFAOYSA-J 0.000 claims description 4
- YWYZEGXAUVWDED-UHFFFAOYSA-N triammonium citrate Chemical compound [NH4+].[NH4+].[NH4+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O YWYZEGXAUVWDED-UHFFFAOYSA-N 0.000 claims description 4
- 239000011787 zinc oxide Substances 0.000 claims description 4
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims description 3
- 239000004327 boric acid Substances 0.000 claims description 3
- 230000008021 deposition Effects 0.000 claims description 3
- 239000000725 suspension Substances 0.000 claims description 3
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 2
- 239000011248 coating agent Substances 0.000 claims description 2
- 238000000576 coating method Methods 0.000 claims description 2
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 claims description 2
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 claims description 2
- 239000001476 sodium potassium tartrate Substances 0.000 claims description 2
- 239000000463 material Substances 0.000 abstract description 8
- 239000000758 substrate Substances 0.000 abstract description 8
- 230000004888 barrier function Effects 0.000 abstract description 6
- 239000004020 conductor Substances 0.000 abstract description 4
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 abstract description 2
- 238000005868 electrolysis reaction Methods 0.000 abstract 2
- 238000001878 scanning electron micrograph Methods 0.000 description 12
- 239000008367 deionised water Substances 0.000 description 11
- 229910021641 deionized water Inorganic materials 0.000 description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 11
- 239000002086 nanomaterial Substances 0.000 description 7
- 238000005406 washing Methods 0.000 description 6
- 239000002090 nanochannel Substances 0.000 description 5
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 4
- 238000004458 analytical method Methods 0.000 description 3
- 230000015556 catabolic process Effects 0.000 description 3
- 230000003247 decreasing effect Effects 0.000 description 3
- 239000003292 glue Substances 0.000 description 3
- 229910002804 graphite Inorganic materials 0.000 description 3
- 239000010439 graphite Substances 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 239000002253 acid Substances 0.000 description 2
- 239000001103 potassium chloride Substances 0.000 description 2
- 235000011164 potassium chloride Nutrition 0.000 description 2
- 229940074439 potassium sodium tartrate Drugs 0.000 description 2
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 2
- 239000004411 aluminium Substances 0.000 description 1
- 238000003491 array Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000013500 data storage Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000002848 electrochemical method Methods 0.000 description 1
- 238000003487 electrochemical reaction Methods 0.000 description 1
- 230000005518 electrochemistry Effects 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 238000007710 freezing Methods 0.000 description 1
- 230000008014 freezing Effects 0.000 description 1
- 239000012212 insulator Substances 0.000 description 1
- 238000002386 leaching Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 230000036632 reaction speed Effects 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 239000004945 silicone rubber Substances 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000005199 ultracentrifugation Methods 0.000 description 1
- 238000004506 ultrasonic cleaning Methods 0.000 description 1
- 239000011592 zinc chloride Substances 0.000 description 1
- 235000005074 zinc chloride Nutrition 0.000 description 1
Abstract
The invention discloses a porous alumina template with through and ultra-long nano pore channels, a preparation method and application thereof. The method comprises the steps of plating a layer of conductive material on one surface of a corresponding part of a pure aluminum sheet to be oxidized. In preparation, single-sided oxidation is carried out in a self-made mold. The electrolyte is oxalic acid aqueous solution containing glycol. The electrolysis temperature is lower than 0 ℃. The oxidation is carried out at the initial stage of constant current and then is converted into a constant voltage mode. If the conductive substrate is removed after oxidation reaction, the nano wire and tube with corresponding materials can be produced by direct electrodeposition. The nanometer pore canal of the porous alumina directly generated by the invention is through, and a barrier layer at the bottom of the pore canal is not present. Eliminating H normally employed in barrier removal 3 PO 4 And (5) soaking and corroding the solution. Not only reduces the preparation process, but also improves the regularity of the nanometer pore canal. The collapse phenomenon during aluminum oxidation is avoided at low temperature during electrolysis, and ultra-long nano pore channels are generated, so that the application range of the porous alumina template is greatly expanded.
Description
Technical Field
The invention relates to a porous alumina template with a through and ultra-long nano pore canal, and an electrochemical preparation method and application of the template, and belongs to the field of nano electrochemistry.
Background
After pure aluminum is subjected to electrochemical oxidation in a certain acid medium for a certain period of time, an aluminum oxide film with a unique nano structure is generated on the surface of the aluminum. In the membrane, mutually parallel nanopores perpendicular to the membrane surface are densely distributed. Under normal conditions, these nanopores are substantially in a regular hexagonal distribution. Alumina having such a structure is often referred to as porous alumina, abbreviated as AAO (anodic aluminum oxide), PAA (porous anodic alumina) or NAA (nanoporous anodic alumina), and the like. The pore diameter, pore spacing and pore canal length reflecting the structural characteristics of the porous alumina are closely related to preparation conditions, such as the type and concentration of electrolyte, voltage (current) during electrochemical oxidation, temperature, oxidation time and the like. Thus, the structural indexes such as pore diameter, pore spacing, and pore channel length of the produced porous alumina can be controlled within a certain range by adjusting the preparation conditions.
Due to the nanostructure uniqueness of porous aluminaThe economy and convenience of the preparation process and some good properties of the alumina material itself, such as high thermal stability, good biocompatibility and mechanical strength, certain chemical inertness and physical properties of transparency, high dielectric constant, etc., have been studied extensively and intensively by many disciplines of researchers over two and thirty years. The method is widely applied to the fields of preparation of nano-structured templates of various materials, optical sensors, biological sensors, drug transportation, release, photoelectrons, energy storage, magnetic data storage and the like. However, there are problems that can be associated with certain applications of porous alumina. Firstly, when preparing porous alumina by electrochemical anodic oxidation, a layer of thin and compacted alumina is always present at the bottom of the pore canal, which blocks the space between the nanometer pore canal and the un-oxidized metal aluminum below. It is referred to as a barrier layer for porous alumina. The thickness of the nano-structure material is only a few to tens of nanometers (depending on the preparation conditions), and the nano-structure material also has certain semiconductor properties, but is an insulator for electron transmission, so that the nano-structure material such as nano-wires and tube arrays cannot be directly prepared by direct current deposition. Currently, it is common practice to remove the barrier layer by stripping the porous alumina from the underlying metallic aluminum, followed by a concentration of H 3 PO 4 The solution is soaked for corrosion removal. However, not only is the process for preparing the porous alumina template increased, but also the structural regularity of the porous alumina channels is greatly affected. In addition, porous alumina suffers from a second problem. When prepared by a common electrochemical method, the length of the nanochannels of the obtained porous alumina is greatly limited. This is because as the length of the nanochannels increases, so does the internal resistance of the channels. In order to maintain a certain reaction rate, the voltage must be increased. The oxidation reaction of aluminum is an exothermic reaction, and if the reaction heat cannot be removed in time, the reaction is accelerated, more heat is further released, and finally the reaction is out of control, so-called breakdown (burning) occurs, and a regular nano structure cannot be obtained. It is therefore highly desirable to provide a method for solving these problems by preparing a porous alumina template with through, very long nanochannels.
Disclosure of Invention
The invention aims to: the first object of the invention is to provide a porous alumina template with through and ultra-long nano pore channels; the second object of the invention is to provide a method for preparing the porous alumina template with through and ultra-long nano pore canals; the third object of the invention is to provide the application of the porous alumina template with through and ultra-long nano pore canal in preparing copper nano wires or nickel nano wires.
The technical scheme is as follows: the invention relates to a preparation method of a porous alumina template with through and ultra-long nano pore channels, which comprises the following steps:
(1) One side of one end of an aluminum sheet is coated with a layer of conductive adhesive or one end of the aluminum sheet is placed in a die 1 provided with an opening, the die 1 is immersed in zinc dipping liquid for zinc dipping treatment, the aluminum sheet with the zinc dipping treatment of the die 1 is used as an electrode cathode, a pure copper sheet, a nickel sheet or a zinc sheet is used as an electrode anode, and electrodeposition is carried out in copper plating liquid, nickel plating liquid or zinc plating liquid to obtain a pretreated aluminum sheet;
(2) Placing the pretreated aluminum sheet in the step (1) in a die 2 provided with an opening, enabling one side containing conductive adhesive or one side for depositing copper, nickel or zinc to face downwards, placing the other side at the opening, and performing electrochemical oxidation reaction in oxalic acid aqueous solution containing ethylene glycol to realize single-sided complete oxidation of the aluminum sheet and generate a porous alumina film with a through nano pore canal;
(3) Taking out the oxidized aluminum sheet from the die 2, removing the aluminum which is not oxidized at the periphery of the aluminum oxide and the copper layer, the nickel layer or the zinc layer on the back of the aluminum oxide or the coated conductive adhesive, cleaning and drying to obtain the perforated and ultra-long pore porous aluminum oxide template.
Further, the die 1 and the die 2 both comprise two stainless steel sheets and two silicon rubber sheets with the same specification, the two silicon rubber sheets are arranged inside the two stainless steel sheets, an opening is formed in the middle of the stainless steel sheet and the silicon rubber sheet on the same side, the stainless steel sheet and the silicon rubber sheet on the same side on the other side are complete and nonporous, screw holes are formed in four corners of the two stainless steel sheets and the two silicon rubber sheets, an aluminum sheet is clamped between the two silicon rubber sheets, and the die is fastened through screws and nuts, and the diameter of the opening in the die 2 is smaller than that in the die 1.
Further, in the step (1), the conductive adhesive is conductive carbon adhesive or conductive silver adhesive. Further, in the step (1), the zinc leaching solution is an aqueous solution containing 6.00mol/Kg of sodium hydroxide, 0.25mol/Kg of zinc oxide, 0.18mol/Kg of potassium sodium tartrate and 0.01mol/Kg of sodium nitrate at the temperature of 40-50 ℃.
Further, in the step (1), the copper plating solution is an aqueous solution containing 0.23mol/Kg copper pyrophosphate, 0.91mol/Kg potassium pyrophosphate, 0.10mol/Kg ammonium citrate and 1.5mg/Kg 2-mercaptobenzothiazole at a temperature of 40-50 ℃.
Further, in the step (1), the nickel plating solution is an aqueous solution containing 0.5mol/Kg nickel sulfate and 0.4mol/Kg boric acid at a temperature of 40-50 ℃.
Further, in the step (1), the zinc plating solution is an aqueous solution containing 0.6mol/Kg zinc chloride, 2.5mol/Kg potassium chloride and 0.4mol/Kg boric acid at a temperature of 40-50 ℃.
Further, in the step (1), a constant current mode is adopted when copper, nickel or zinc is deposited.
Further, in the step (2), the oxalic acid aqueous solution containing ethylene glycol is 0.3mol/Kg oxalic acid aqueous solution containing 10-30 wt% of ethylene glycol.
Further, in the step (2), the temperature of the electrochemical oxidation reaction is lower than 0 ℃, preferably from-3 ℃ to-9 ℃.
In the step (2), a constant current mode is adopted at the initial stage of the electrochemical oxidation reaction, and a constant voltage mode is adopted after the preset voltage is reached.
Further, in the step (3), when the aluminum sheet is treated by coating conductive adhesive, the aluminum sheet is dried and burned in the air at 700-900 ℃ for more than 1 hour to remove the coated conductive adhesive.
Further, in the step (3), when the copper, nickel or zinc pre-treated aluminum sheet is deposited, the deposited copper, nickel or zinc is removed by the etching copper liquid after the cleaning.
Further, the copper etching liquid contains 3.00mol/Kg HCl, 2.70mol/KgKCl and 1.65mol/Kg CuCl 2 Is a solution of (a) and (b).
The porous alumina template with the through and ultra-long nano pore canal obtained by the preparation method is applied to the preparation of copper nanowires or nickel nanowires.
The invention also comprises the application of the porous alumina template with the through and ultra-long nano pore canal obtained by the preparation method in the preparation of copper nanotubes or nickel nanotubes.
The back surface of the porous alumina template of the through and ultra-long nano pore canal is provided with a copper, nickel or zinc or carbon adhesive conducting layer.
Further, the application comprises the steps of: placing the porous alumina mould with through and ultra-long nano pore canal obtained by the preparation method in a mould 3 provided with an opening, wherein one side of the alumina mould corresponds to the opening of the mould 3, taking the porous alumina mould as an electrode cathode, taking a copper sheet or a nickel sheet as an electrode anode, electrodepositing copper or nickel in a copper electrolyte or a nickel electrolyte under constant current, and using Na 2 CO 3 Soaking the alumina film deposited with copper or nickel in the aqueous solution, ultrasonically cleaning for multiple times, and centrifugally separating to obtain a suspension of Cu nanowires or Ni nanowires;
further, the mold 3 is similar to the mold 1 and the mold 2, except that the opening of the mold 3 is smaller than the opening of the mold 2,
further, the Na 2 CO 3 The concentration of the aqueous solution is 5-15 wt%.
Further, the constant current electrodeposited copper, nickel or zinc has a current of 2-6 mA and a deposition time of 12-4 h.
The invention firstly electroplates a layer of copper, nickel or zinc on one surface of the pure aluminum sheet before electrochemical oxidation is carried out, or coats a layer of conductive adhesive. The layer of conductive material acts as an anode for the electrochemical oxidation process and is not in contact with the electrolyte, so that the layer of conductive material itself is not oxidized before the metallic aluminum is fully oxidized to alumina. Then, the metal aluminum can be oxidized to form porous aluminum oxide without a barrier layer and through pore channels.
The key point of the aluminum is to have a high reaction speed and not to cause breakdown in the electrochemical oxidation process is to remove the reaction heat in time. Therefore, it is necessary to lower the reaction temperature. Of course, proper control of the voltage (current) is also necessary. The method adopted by the invention is to add a certain amount of glycol into the electrolyte, and reduce the freezing point of the electrolyte so that the electrochemical reaction can be carried out at a lower temperature below 0 ℃. In addition, a constant current mode is adopted in the early stage of the electrochemical process, the length of the nano pore canal is gradually increased along with the progress of the reaction, the internal resistance of the pore canal is also increased along with the gradual increase of the reaction, and the voltage is inevitably increased along with the gradual increase of the reaction. In order to avoid the occurrence of "breakdown" of the nanostructure, the power supply is turned into a constant voltage mode after the electrolytic voltage reaches a certain maximum set value. Later, with further growth of the nanochannel, the current gradually decreases, and after reaching a minimum, it indicates that the metallic aluminum has been completely oxidized. At this time, the porous alumina template with through pore channels is obtained after the substrate conductive material is removed. If the initial metal aluminum sheet is thicker, the nano template with the ultra-long pore canal can be obtained. If electrodeposition is directly carried out before the conductive substrate is removed, nanowires and tubes of corresponding materials can be produced.
The beneficial effects are that: compared with the prior art, the invention has the following remarkable advantages: the method can prevent the generation of a barrier layer at the bottom of the nano pore canal when pure aluminum is electrochemically oxidized in the acid electrolyte to generate the porous alumina template, and the obtained nano pore canal of the porous alumina is communicated. The method ensures that the pure aluminum is prevented from collapsing in the electrochemical oxidation process, and the prepared porous alumina template can have ultra-long nano pore channels.
Drawings
FIG. 1 is a schematic view of the structure of a mold 1 in example 1;
FIG. 2 is a SEM image of the back and side of a blank porous alumina film obtained in example 2;
FIG. 3 is a SEM image of the back and side of a blank porous alumina film obtained in example 3;
fig. 4 is an SEM image of the front and side surfaces of the porous alumina film deposited with Ni nanowires obtained in example 4.
Detailed Description
The technical scheme of the invention is further described below with reference to the accompanying drawings.
Example 1
As shown in FIG. 1, the self-made mold used in the invention comprises two stainless steel sheets and two silicon rubber sheets with the same specification, wherein the two silicon rubber sheets are arranged inside the two stainless steel sheets, two or more openings with the same diameter are arranged between the stainless steel sheets and the silicon rubber sheets on the same side, the stainless steel sheets and the silicon rubber sheets on the same side on the other side are complete and nonporous, screw holes are arranged at four corners of the two stainless steel sheets and the two silicon rubber sheets, an aluminum sheet is clamped between the two silicon rubber sheets, and the mold is fastened through screws and nuts. The present invention has no strict requirement on the size and number of the holes in the mold. The structures and the sizes of the die 1, the die 2 and the die 3 are similar, and the difference is that the sizes of the open holes are different, and the sizes of the open holes of the dies 1,2 and 3 must be reduced in sequence. In this example, the stainless steel sheet and the silicone rubber sheet of the self-made mold were 70mm in length, 40mm in width and 3mm in height. Wherein the diameters of 2 circular openings with the same size in the dies 1,2 and 3 are 16mm,14mm and 12mm respectively.
Example 2
A blank porous alumina template with through and ultra-long channels was prepared using the mold 1 and the mold 2 of example 1.
One end of a flat, clean, 99.99% purity aluminum sheet having a thickness of 175 μm was taken and placed in a mold 1 together with the mold 1 immersed in a zinc immersion liquid at 45℃containing 6.00mol/Kg sodium hydroxide, 0.25mol/Kg zinc oxide, 0.18mol/Kg potassium sodium tartrate (C 4 H 4 KNaO 6 ·4H 2 O), 0.01mol/Kg of sodium nitrate) for 20 seconds. The surface is washed with deionized water to remove loose surface products. Immersing in the zinc dipping solution again for 5 seconds, and forming a compact film with grey surface. After washing with deionized water, the solution was rapidly placed in a copper plating solution (copper plating solution is an aqueous solution containing 0.23mol/Kg of copper pyrophosphate, 0.91mol/Kg of potassium pyrophosphate, 0.10mol/Kg of ammonium citrate, 1.5mg/Kg of 2-mercaptobenzothiazole, pH 8.3-8.8) at 45℃and Cu was deposited in a two-electrode electrolytic cell in a 30mA constant current mode for 1.5 hours. The anode of the counter electrode is a pure copper sheet. The copper-deposited aluminum sheet is then removed from the mold 1. Washing with deionized water, and drying. Facing the copper deposit faceNext, the other side of the bare aluminum is placed up in the mold 2, ensuring that the copper layer deposited as a substrate is directly under the openings. Electrochemical oxidation is carried out in a two-electrode electrolytic cell with stirring function. The cathode is a graphite rod. The electrolyte was a 0.3mol/Kg aqueous oxalic acid solution containing 20wt% ethylene glycol. During electrochemical oxidation, the solution temperature is kept at-5 to-7 ℃. The electrochemical oxidation is in constant current mode in the initial stage. After reaching a predetermined voltage, such as 200V, the electrochemical oxidation is converted to a constant voltage mode. When the current reaches a minimum value that is no longer decreasing within one hour, it indicates that the aluminum in this region has completely oxidized to aluminum oxide. The constant current value at the initial stage of electrochemical oxidation was 50mA, and the highest voltage was set to 200V. After the power supply was turned off, the electrochemically oxidized sample was taken out of the mold 2 and washed with deionized water. Then the sample is placed in 2.0mol/Kg CuCl 2 The aqueous solution removes the unoxidized aluminum surrounding the porous alumina. Then the copper etching solution (the copper etching solution contains 3.00mol/Kg HCl, 2.70mol/Kg KCl and 1.65mol/Kg CuCl) 2 Is used) to remove the pre-deposited copper substrate layer. And washing with deionized water, and drying to obtain the blank porous alumina template with through and ultra-long nanometer pore canal.
Scanning electron microscope analysis is carried out on the blank porous alumina template with the through and ultra-long nano pore canal obtained in the embodiment, and the result is shown in figure 2. FIG. 2 is a SEM image of the back and side of a blank porous alumina film obtained in example 2. Wherein A is an SEM image of the back surface of the porous alumina film, B, C is an SEM image of the side surface of the porous alumina film, and the magnification of B, C is 10000 times and 250 times respectively. As can be seen from fig. 2, the porous alumina membrane is perforated and has a thickness, i.e. a nanopore length of 272.0 μm.
Example 3
A blank porous alumina template with through and ultra-long channels was prepared using die 2 of example 1.
One end of an aluminum sheet with the thickness of 175 mu m, the surface of which is flat and clean, and the purity of 99.99 percent is coated with a layer of conductive carbon glue with the thickness of about 0.1mm, one surface coated with the conductive carbon glue faces downwards after drying, and the other surface of the aluminum sheet is exposed upwards and is placed in a die 2, so that the substrate layer coated with the conductive carbon glue is ensured to be right below the open pores.The cathode is a graphite rod. Electrochemical oxidation is carried out in a two-electrode electrolytic cell with stirring function. The electrolyte was an aqueous solution of 0.3m oxalic acid containing 20wt% ethylene glycol. During electrochemical oxidation, the solution temperature is kept at-5 to-7 ℃. The electrochemical oxidation is in constant current mode in the initial stage. After reaching a predetermined voltage, such as 200V, the electrochemical oxidation is converted to a constant voltage mode. When the current reaches a minimum value that is no longer decreasing within one hour, it indicates that the aluminum in this region has completely oxidized to aluminum oxide. The constant current value at the initial stage of electrochemical oxidation was 50mA, and the highest voltage was set to 200V. After the power supply was turned off, the electrochemically oxidized sample was taken out of the mold 2 and washed with deionized water. Then the sample is placed in 2.0mol/Kg CuCl 2 The aqueous solution removes the unoxidized aluminum surrounding the porous alumina. Washing with deionized water, drying, and burning at 800 deg.C in air for 2 hr. And cooling to obtain the blank porous alumina template with the through and ultra-long nano pore channels.
Scanning electron microscope analysis is carried out on the blank porous alumina template with the through and ultra-long nano pore canal obtained in the embodiment, and the result is shown in figure 3. FIG. 3 is an SEM image of the back and side of a blank porous alumina film obtained in example 3. A is an SEM image of the back side of the porous alumina film, B, C is an SEM image of the side of the porous alumina film, and B, C is magnified 25000 and 250 times, respectively. As can be seen from fig. 3, the porous alumina membrane is perforated, and the diameter of the nano-pore canal is 105.8nm. The thickness, i.e. the length of the nanochannels, was 258.6 μm.
Example 4
The Ni nanowires were prepared using the molds 1,2 and 3 of example 1.
One end of a flat, clean, 99.99% purity aluminum sheet having a thickness of 175 μm was placed in a mold 1 and immersed in a 45℃zinc immersion solution (the zinc immersion solution being an aqueous solution containing 6.00mol/Kg sodium hydroxide, 0.25mol/Kg zinc oxide, 0.18mol/Kg sodium potassium tartrate, 0.01mol/Kg sodium nitrate) for 20 seconds. The loose surface product is removed by washing with deionized water. Immersing in the zinc dipping solution again for 5 seconds, and forming a compact film with grey surface. After being washed by deionized water, the copper-plated film is used as a cathode of a counter electrode and is rapidly placed at 45 ℃ for copper platingThe solution (copper plating solution is an aqueous solution containing 0.23mol/Kg copper pyrophosphate, 0.91mol/Kg potassium pyrophosphate, 0.10mol/Kg ammonium citrate, 1.5mg/Kg 2-mercaptobenzothiazole, pH 8.3-8.8), and Cu was deposited in a two-electrode electrolytic cell in a 30mA constant current mode for 1.5 hours. The anode of the counter electrode is a pure copper sheet. The copper deposited sample is then removed from the mould 1. Washing with deionized water, and drying. One side of the deposited copper is facing down and the other side of the exposed aluminum is facing up in the mold 2, ensuring that the copper layer deposited as a substrate is directly beneath the openings. The cathode is a graphite rod. Electrochemical oxidation is carried out in a two-electrode electrolytic cell with stirring function. The electrolyte was an aqueous solution of 0.3m oxalic acid containing 20wt% ethylene glycol. During electrochemical oxidation, the solution temperature is kept at-5 to-7 ℃. The electrochemical oxidation is in constant current mode in the initial stage. After reaching a predetermined voltage, such as 200V, the electrochemical oxidation is converted to a constant voltage mode. When the current reaches a minimum value that is no longer decreasing within one hour, it indicates that the aluminum in this region has completely oxidized to aluminum oxide. The constant current value at the initial stage of electrochemical oxidation was 50mA, and the highest voltage was set to 200V. After the power supply was turned off, the electrochemically oxidized sample was taken out of the mold 2 and washed with deionized water. The side of the deposited copper facing downwards and the side of the alumina, which has just been formed by the complete oxidation of aluminium, is placed face up in the mould 3 ensuring that the copper layer deposited as a substrate is directly underneath the openings. This is used as the counter electrode cathode, which is placed in an electrolyte containing the corresponding material, the present example is a nickel electrolyte (the nickel electrolyte contains 1.26mol/KgNiCl 2 、0.61mol/KgH 3 BO 3 The aqueous solution of (2) is used for electrodepositing nickel for 6 hours with constant current of 4mA, and a pure nickel sheet is used as a counter electrode anode, thus obtaining the porous alumina film deposited with the Ni nanowires. The Ni-deposited porous alumina film was treated with 10wt% Na 2 CO 3 After the alumina is dissolved after being soaked in the aqueous solution, the free Ni nano wires can be released. And (5) carrying out ultrasonic cleaning and ultracentrifugation for multiple times to obtain a suspension of the Ni nanowires.
The porous alumina film deposited with Ni nanowires obtained in this example was subjected to scanning electron microscope analysis, and the result is shown in fig. 4. Fig. 4 is an SEM image of the front and side surfaces of the porous alumina film with Ni nanowires deposited obtained in example 4, wherein a is an SEM image of the front surface of the porous alumina film with Ni nanowires deposited, B, C is an SEM image of the side surface of the porous alumina film with Ni nanowires deposited, and the magnification of B, C is 20000 and 250 times, respectively. As can be seen from fig. 4, ni has been deposited on the front surface of the porous alumina film, further confirming that the porous alumina film obtained from example 3 is through-going.
Claims (10)
1. The preparation method of the porous alumina template with the through and ultra-long nano pore channels is characterized by comprising the following steps:
(1) One side of one end of an aluminum sheet is coated with a layer of conductive adhesive or one end of the aluminum sheet is placed in a die 1 provided with an opening, the die 1 is immersed in zinc dipping liquid for zinc dipping treatment, the aluminum sheet with the zinc dipping treatment of the die 1 is used as an electrode cathode, a pure copper sheet, a nickel sheet or a zinc sheet is used as an electrode anode, and electrodeposition is carried out in copper plating liquid, nickel plating liquid or zinc plating liquid to obtain a pretreated aluminum sheet;
(2) Placing the pretreated aluminum sheet in the step (1) in a die 2 provided with an opening, enabling one side containing conductive adhesive or one side for depositing copper, nickel or zinc to face downwards, placing the other side at the opening, and performing electrochemical oxidation reaction in oxalic acid aqueous solution containing ethylene glycol to realize single-sided complete oxidation of the aluminum sheet and generate a porous alumina film with a through nano pore canal;
(3) Taking out the oxidized aluminum sheet from the die 2, removing the aluminum which is not oxidized at the periphery of the aluminum oxide and the copper layer, the nickel layer or the zinc layer on the back of the aluminum oxide or the coated conductive adhesive, cleaning and drying to obtain the porous aluminum oxide template with through and ultra-long nano pore channels.
2. The preparation method according to claim 1, wherein the mold 1 and the mold 2 each comprise two stainless steel sheets and two silicon rubber sheets of the same specification, the two silicon rubber sheets are arranged inside the two stainless steel sheets, an opening is arranged between the stainless steel sheets and the silicon rubber sheets on the same side, the stainless steel sheets and the silicon rubber sheets on the same side are completely non-porous, screw holes are formed in four corners of the two stainless steel sheets and the two silicon rubber sheets, an aluminum sheet is clamped between the two silicon rubber sheets, and the mold is fastened by screws and nuts, wherein the diameter of the opening in the mold 2 is smaller than that in the mold 1.
3. The method according to claim 1, wherein in the step (1), the conductive paste is a conductive carbon paste or a conductive silver paste.
4. The method according to claim 1, wherein in the step (1), the zinc immersion liquid is an aqueous solution containing 6.00mol/Kg sodium hydroxide, 0.25mol/Kg zinc oxide, 0.18mol/Kg sodium potassium tartrate and 0.01mol/Kg sodium nitrate at 40 to 50 ℃, the copper plating liquid is an aqueous solution containing 0.23mol/Kg copper pyrophosphate, 0.91mol/Kg potassium pyrophosphate, 0.10mol/Kg ammonium citrate and 1.5mg/Kg 2-mercaptobenzothiazole at 40 to 50 ℃, and the nickel plating liquid is an aqueous solution containing 0.5mol/Kg nickel sulfate and 0.4mol/Kg boric acid at 40 to 50 ℃.
5. The method of claim 1, wherein in step (1), the deposition of copper, nickel or zinc is performed in a constant current mode.
6. The method according to claim 1, wherein in the step (2), the aqueous oxalic acid solution containing ethylene glycol is 0.3mol/Kg aqueous oxalic acid solution containing 10 to 30wt% of ethylene glycol, and the electrochemical oxidation reaction temperature is lower than 0 ℃.
7. The method according to claim 1, wherein in the step (2), a constant current mode is used at an initial stage of the electrochemical oxidation reaction, and a constant voltage mode is used after a predetermined voltage is reached.
8. The preparation method according to claim 1, wherein in the step (3), when the aluminum sheet is treated by coating conductive adhesive, the aluminum sheet is burned for more than 1 hour at 700-900 ℃ in air after being dried; when depositing copper, nickel or zinc pre-treated aluminum sheet, the cleaning is followed by removal with a copper etching solutionDeposited copper, nickel or zinc, the copper etching solution contains 3.00mol/Kg HCl, 2.70mol/Kg KCl and 1.65mol/Kg CuCl 2 Is a solution of (a) and (b).
9. Use of a porous alumina template of through, ultralong nanopores obtained by the preparation method of any one of claims 1 to 8 for preparing copper nanowires or nickel nanowires and copper nanotubes or nickel nanotubes.
10. The use according to claim 9, characterized by the steps of: placing the porous alumina template with through and ultra-long nano pore canal obtained by the preparation method of any one of claims 1-8 in a mold 3 provided with an opening, wherein one side of the alumina membrane corresponds to the opening of the mold 3, taking the porous alumina template as an electrode cathode, a copper sheet or a nickel sheet as an electrode anode, electrodepositing copper or nickel in a copper electrolyte or a nickel electrolyte under constant current, and using 5-15wt% of Na 2 CO 3 Soaking the alumina film deposited with copper or nickel in the aqueous solution, ultrasonically cleaning for multiple times, and centrifugally separating to obtain a suspension of Cu nanowires or Ni nanowires; the opening of the die 3 is smaller than the opening of the die 2.
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