CN109468668A - A kind of preparation method and applications of platinum nano-cone array structure - Google Patents
A kind of preparation method and applications of platinum nano-cone array structure Download PDFInfo
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- CN109468668A CN109468668A CN201811504013.7A CN201811504013A CN109468668A CN 109468668 A CN109468668 A CN 109468668A CN 201811504013 A CN201811504013 A CN 201811504013A CN 109468668 A CN109468668 A CN 109468668A
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- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 title claims abstract description 226
- 229910052697 platinum Inorganic materials 0.000 title claims abstract description 112
- 239000002110 nanocone Substances 0.000 title claims abstract description 83
- 238000002360 preparation method Methods 0.000 title claims abstract description 33
- 238000004070 electrodeposition Methods 0.000 claims abstract description 34
- 239000000243 solution Substances 0.000 claims abstract description 29
- 238000000151 deposition Methods 0.000 claims abstract description 27
- 239000013078 crystal Substances 0.000 claims abstract description 21
- 150000003057 platinum Chemical class 0.000 claims abstract description 20
- 230000001737 promoting effect Effects 0.000 claims abstract description 19
- 238000000034 method Methods 0.000 claims abstract description 18
- 239000003153 chemical reaction reagent Substances 0.000 claims abstract description 17
- 230000003197 catalytic effect Effects 0.000 claims abstract description 12
- 239000012266 salt solution Substances 0.000 claims abstract description 12
- 150000001412 amines Chemical class 0.000 claims abstract description 11
- 150000003863 ammonium salts Chemical class 0.000 claims abstract description 8
- 230000001537 neural effect Effects 0.000 claims abstract description 7
- 229910052751 metal Inorganic materials 0.000 claims description 17
- 239000002184 metal Substances 0.000 claims description 17
- 230000008021 deposition Effects 0.000 claims description 8
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims description 6
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 6
- 239000011159 matrix material Substances 0.000 claims description 6
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 4
- CLSUSRZJUQMOHH-UHFFFAOYSA-L platinum dichloride Chemical compound Cl[Pt]Cl CLSUSRZJUQMOHH-UHFFFAOYSA-L 0.000 claims description 4
- 229910052700 potassium Inorganic materials 0.000 claims description 4
- 239000011591 potassium Substances 0.000 claims description 4
- PAWQVTBBRAZDMG-UHFFFAOYSA-N 2-(3-bromo-2-fluorophenyl)acetic acid Chemical compound OC(=O)CC1=CC=CC(Br)=C1F PAWQVTBBRAZDMG-UHFFFAOYSA-N 0.000 claims description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 3
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 3
- 239000002253 acid Substances 0.000 claims description 3
- 235000019270 ammonium chloride Nutrition 0.000 claims description 3
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 claims description 3
- 229910052921 ammonium sulfate Inorganic materials 0.000 claims description 3
- 235000011130 ammonium sulphate Nutrition 0.000 claims description 3
- KBKZYWOOZPIUJT-UHFFFAOYSA-N azane;hypochlorous acid Chemical compound N.ClO KBKZYWOOZPIUJT-UHFFFAOYSA-N 0.000 claims description 3
- NWAHZABTSDUXMJ-UHFFFAOYSA-N platinum(2+);dinitrate Chemical compound [Pt+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O NWAHZABTSDUXMJ-UHFFFAOYSA-N 0.000 claims description 3
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 2
- 125000002723 alicyclic group Chemical group 0.000 claims description 2
- 239000004033 plastic Substances 0.000 claims description 2
- 229920003023 plastic Polymers 0.000 claims description 2
- 229910052708 sodium Inorganic materials 0.000 claims description 2
- 239000011734 sodium Substances 0.000 claims description 2
- 239000000126 substance Substances 0.000 abstract description 10
- 230000008569 process Effects 0.000 abstract description 8
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 10
- 229910021607 Silver chloride Inorganic materials 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 7
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 7
- 238000002484 cyclic voltammetry Methods 0.000 description 6
- 230000005611 electricity Effects 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 5
- 230000000694 effects Effects 0.000 description 4
- 239000002086 nanomaterial Substances 0.000 description 4
- 231100000614 poison Toxicity 0.000 description 4
- 230000007096 poisonous effect Effects 0.000 description 4
- 238000003860 storage Methods 0.000 description 4
- 238000010586 diagram Methods 0.000 description 3
- 241000209094 Oryza Species 0.000 description 2
- 235000007164 Oryza sativa Nutrition 0.000 description 2
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 125000004122 cyclic group Chemical group 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- -1 iron ion Chemical class 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 235000009566 rice Nutrition 0.000 description 2
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 210000003477 cochlea Anatomy 0.000 description 1
- 238000001246 colloidal dispersion Methods 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 229910001431 copper ion Inorganic materials 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 230000005518 electrochemistry Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000002057 nanoflower Substances 0.000 description 1
- 239000002061 nanopillar Substances 0.000 description 1
- 239000002070 nanowire Substances 0.000 description 1
- 238000005424 photoluminescence Methods 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 239000001103 potassium chloride Substances 0.000 description 1
- 235000011164 potassium chloride Nutrition 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 230000000638 stimulation Effects 0.000 description 1
- 125000005270 trialkylamine group Chemical group 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D3/00—Electroplating: Baths therefor
- C25D3/02—Electroplating: Baths therefor from solutions
- C25D3/50—Electroplating: Baths therefor from solutions of platinum group metals
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
- B01J23/42—Platinum
-
- B01J35/23—
-
- B01J35/393—
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/34—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation
- B01J37/348—Electrochemical processes, e.g. electrochemical deposition or anodisation
-
- 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
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
- G01N27/26—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating electrochemical variables; by using electrolysis or electrophoresis
- G01N27/28—Electrolytic cell components
- G01N27/30—Electrodes, e.g. test electrodes; Half-cells
Abstract
The present invention provides a kind of preparation methods of platinum nano-cone array structure, include: that platinum salt solution is provided, crystal type promoting reagent is added in Xiang Suoshu platinum salt solution, forms electric depositing solution after mixing, wherein, the crystal type promoting reagent includes at least one of inorganic ammonium salt and organic amine；Conducting base is provided, the conducting base is placed in the electric depositing solution, platinum nano-cone array structure is made on the conducting base surface using the method for electro-deposition.By the way that suitable crystal type promoting reagent is added, the platinum nano-array pattern formed in electrodeposition process is controlled, the uniform platinum nano-cone array structure of pattern is made, improves its chemical property and catalytic performance, while ensure that bio-compatibility；The preparation method is simple, prepares platinum nano-cone array structure suitable for the device surface in various specifications, improves application of the device in sensor field, catalytic field and neural interface field.
Description
Technical field
The present invention relates to technical field of nano material, in particular to the preparation method of a kind of platinum nano-cone array structure and its
Using.
Background technique
Platinum is widely used in catalyst field because of its excellent electrocatalysis characteristic.It finds in application process, platinum
Appearance structure can further influence its catalytic performance, and platinum nanostructure is shown preferably due to its unique structure feature
Catalytic performance.Currently, its catalytic performance is improved by the appearance structure for adjusting the adjustable platinum of thermodynamics and kinetics condition,
Such as: the platinum structure with tetrahedron and cube is prepared in colloidal dispersion with acrylic acid and polyacrylate, but is prepared
Microscopic appearance uniformity it is less unified (PetroskiJ.M.J.Phys.Chem.2001,105,5542-5547)；In system
The iron ion of a small amount of divalent/trivalent is added to adjust rate of reduction (the Lee E.P.Adv.Mater.2006,18,3271- of platinum
3274)；Copper ion is added, cube and spherical platinum structure (Qu are prepared using potential replacement method
L.T.J.Am.Chem.Soc.2006,128,5523).Although the pattern knot of the above method adjustable platinum to a certain extent
Structure, but preparation time is long, appearance structure homogeneity obtained is poor, and poisonous and harmful substance can be added in preparation process, is made
Platinum nanostructure can not be applied to bio-compatible require neural interface direction.
Therefore, a kind of morphology controllable, uniformity are needed and can be applied to sensor field, catalytic field and mind
Through platinum nanostructure in interface field.
Summary of the invention
In view of this, the present invention provides a kind of preparation method of platinum nano-cone array structure, it is suitable brilliant by being added
Type promotor controls the platinum nano-array pattern formed in electrodeposition process, and the uniform platinum nano-cone array of pattern is made
Structure improves its chemical property and catalytic performance；Without the addition of poisonous and harmful substance in preparation process, bio-compatible ensure that
Property；The preparation method is simple, prepares platinum nano-cone array structure suitable for the device surface in various specifications, improves it and sensing
Application in device field, catalytic field and neural interface field.
In a first aspect, the present invention provides a kind of preparation methods of platinum nano-cone array structure, comprising:
Platinum salt solution is provided, crystal type promoting reagent is added in Xiang Suoshu platinum salt solution, forms electric depositing solution after mixing,
Wherein, the crystal type promoting reagent includes at least one of inorganic ammonium salt and organic amine；
Conducting base is provided, the conducting base is placed in the electric depositing solution, using the method for electro-deposition in institute
It states conducting base surface and platinum nano-cone array structure is made.
In the present invention, selection has special selection to platinum microscopic appearance from numerous inorganic and organic crystal type promoting reagent
Promotor, so that crystal type promoting reagent, which can guide, to be generated platinum nanocone and avoid other nano junctions during electrodeposition process
Structure generates, such as nano wire, nano-pillar, and platinum nano-cone array structure and morphology uniformity obtained.
Optionally, the inorganic ammonium salt include ammonium sulfate, ammonium chloride, ammonium nitrate, hypochlorous acid ammonium, in ammonium nilrite at least
It is a kind of.
Optionally, the organic amine includes at least one of fatty amines, alcamines and alicyclic ring amine.
Further, the crystal type promoting reagent is inorganic ammonium salt.In the present invention, inorganic ammonium salt and organic amine can be with
The formation for promoting platinum nano-cone array structure, achievees the effect that of the invention, and inorganic ammonium salt is more conducive to platinum than organic amine
The formation of nano-cone array structure.
Optionally, the solute of the platinum salt solution is platinum chloride, ammonium chloroplatinate, potassium platinic chloride, sodium chloroplatinate, chlorine
One of platinic acid, platinum nitrate, platinic sulfate, Platinous Potassium Chloride, Tetrachloroplatinate ammonium are a variety of.
Optionally, the concentration of the platinum salt is 1mmol/L-20mmol/L.Further, the concentration of the platinum salt is
3mmol/L-18mmol/L.Specifically, the concentration of the platinum salt can be, but not limited to as 7mmol/L, 10mmol/L or 15mmol/
L。
Optionally, in the electric depositing solution, the molar ratio of platinum salt and the crystal type promoting reagent in the platinum salt solution
1:(0.1-10).Further, in the platinum salt solution platinum salt and the crystal type promoting reagent molar ratio 1:(0.2-8).Specifically
, platinum salt and the molar ratio of the crystal type promoting reagent can be, but not limited to as 1:0.5,1:1,1:5 or 1 in the platinum salt solution:
7。
Optionally, the pH of the electric depositing solution is not less than 7.
Optionally, the height of the platinum nanocone in the platinum nano-cone array structure is 1nm-10 μm, and tip diameter is less than
10nm, base diameter 100nm-300nm, density are 10/μm-2- 300/μm-2.Further, the platinum nanocone battle array
The height of platinum nanocone in array structure is 2nm-8 μm, and tip diameter is less than 8nm, base diameter 120nm-200nm, density
For 50/μm-2- 280/μm-2。
In the present invention, the surface area of nanocone is big in platinum nano-cone array structure obtained, can effectively improve entirety
The chemical property of structure.
Optionally, the method for the electro-deposition is potentiostatic electrodeposition, galvanostatic deposition or pulse electrodeposition.
Optionally, the voltage in the potentiostatic electrodeposition is -0.5V~-0.75V, the electric current in the galvanostatic deposition
For -0.1 μ μ of A~-0.7 A, the voltage in the pulse electrodeposition is -0.5V~-0.75V, and make-to-break ratio is (2ms-100ms):
(200ms-1000ms)。
Optionally, the time of the electro-deposition is 5min-60min.Further, the time of the electro-deposition is 10min-
50min。
Optionally, it is to electrode that the method for the electro-deposition, which includes with platinized platinum, and Ag/AgCl is reference electrode, the conduction
Matrix is working electrode, forms three-electrode system with the electric depositing solution, and connect with electrochemical workstation and carry out electro-deposition.
In the present invention, electrodeposition technology can control the specific pattern of platinum nanocone, and it is heavy to adjust electricity according to actual needs
Product process conditions change the pattern of platinum nanocone, and the platinum nanocone with uniform morphology is made with crystal type promoting reagent collective effect
Array structure.
Optionally, the conducting base includes microelectrode array, wire, sheet metal, becket, conductive plastics and conduction
At least one of rubber.Specifically, can be, but not limited to as platinum line, artificial cochlea, platinized platinum, platinum loop.
Preparation method provided by the invention is suitable for the device of various specifications, from microelectrode array to filiform, sheet or ring
Shape etc., is not influenced by device specification, the uniform platinum nano-cone array structure of pattern can be made on its surface.
In the present invention, the conducting base may be non-conductive matrix surface deposition layer of conductive material, such as in silicon
Piece surface, which deposits one layer of metal material, can be used as conducting base use.
Optionally, before the conducting base is placed in the electric depositing solution, further includes:
The conducting base is placed in acetone or alcohol solution and is cleaned by ultrasonic, and passes through cyclic voltammetry scan, it is ensured that institute
Conducting base is stated to clean up.
First aspect present invention provides a kind of preparation method of platinum nano-cone array structure, by the way that suitable crystal form is added
Promotor controls the crystal growth of platinum in electrodeposition process, and the uniform platinum nano-cone array structure of pattern is made.The preparation
Method is simple and easy, production cost is low, strong operability, reproducible, mild condition, the addition without poisonous and harmful substance, system
The platinum nano-cone array structure obtained has the excellent chemical properties such as Low ESR, high charge storage capacity and charge injectability
And biocompatibility.
Second aspect, the present invention provides a kind of microelectrodes, including microelectrode matrix and setting are in the microelectrode base
Platinum nano-cone array structure on body, platinum nano-cone array structure platinum nano-cone array structure as described in first aspect
Preparation method is prepared.
Optionally, the height of the platinum nanocone in the platinum nano-cone array structure is 1nm-10 μm, and tip diameter is less than
10nm, base diameter 100nm-300nm, density are 10/μm-2- 300/μm-2.Further, the platinum nanocone battle array
The height of platinum nanocone in array structure is 2nm-8 μm, and tip diameter is less than 8nm, base diameter 120nm-200nm, density
For 50/μm-2- 280/μm-2。
In the present invention, the surface area of nanocone is big in platinum nano-cone array structure, can effectively improve integrally-built
Chemical property.
The third aspect, the microelectrode that the present invention provides a kind of as described in second aspect is in sensor field, catalytic field
And the application in neural interface field.
Beneficial effects of the present invention:
The present invention provides a kind of preparation methods of platinum nano-cone array structure, by the way that suitable crystal type promoting reagent is added,
The crystal growth of platinum in electrodeposition process is controlled, the uniform platinum nano-cone array structure of pattern is made.Preparation method letter
List is easy, production cost is low, strong operability, reproducible, mild condition, the addition without poisonous and harmful substance, platinum obtained
Nano-cone array structure has the excellent chemical properties and biology such as Low ESR, high charge storage capacity and charge injectability
Compatibility.Preparation method of the invention can realize on the conducting base of various specifications and binding force is strong, not easily to fall off, is passing
It is with a wide range of applications in sensor field, catalytic field and neural interface field.
Detailed description of the invention
In order to more clearly explain the embodiment of the invention or the technical proposal in the existing technology, to embodiment or will show below
There is attached drawing needed in technical description to be briefly described.Specific embodiment described herein is only used to explain this
Invention, is not intended to limit the present invention.
Fig. 1 is the electron microscope of the microelectrode array obtained with platinum nano-cone array structure of the embodiment of the present invention 1；
Fig. 2 is the electron microscope of the wire obtained with platinum nano-cone array structure of the embodiment of the present invention 2；
Fig. 3 is the electron microscope of the becket obtained with platinum nano-cone array structure of the embodiment of the present invention 3；
Fig. 4 is the electron microscope of the sheet metal obtained with platinum nano-cone array structure of the embodiment of the present invention 5, wherein Fig. 4
In (A) be the electron microscope in the case where scale is 50 μm, (B) is the electron microscope in the case where scale is 1 μm in Fig. 4；
Fig. 5 is the electron microscope of the comparative example sheet metal obtained with platinum nano array structure；
Fig. 6 is the electrochemistry resistance of the embodiment of the present invention 5 and the comparative example sheet metal obtained with platinum nano array structure
Anti- and cyclic voltammetric comparison diagram, wherein (A) is electrochemical impedance comparison diagram in Fig. 6, and (B) is cyclic voltammetric comparison diagram in Fig. 6.
Specific embodiment
Following will be combined with the drawings in the embodiments of the present invention, and technical solution in the embodiment of the present invention carries out clear, complete
Site preparation description, it is clear that described embodiments are only a part of the embodiments of the present invention, instead of all the embodiments.It is based on
Embodiment in the present invention, it is obtained by those of ordinary skill in the art without making creative efforts every other
Embodiment shall fall within the protection scope of the present invention.
Embodiment 1
A kind of preparation method of microelectrode
1L water, the potassium platinic chloride of 1mmol/L and the ammonium sulfate of 5mmol/L are added in a reservoir, is formed after mixing
Electric depositing solution.
The microelectrode array of different size is provided, is respectively placed in electric depositing solution, is to electrode, Ag/AgCl with platinized platinum
For reference electrode, microelectrode array is working electrode, and connect with electrochemical workstation, in a manner of potentiostatic electrodeposition ,-
Under the conditions of 0.5V, electro-deposition 5min forms platinum nano-cone array structure on microelectrode array surface, such as by electron-microscope scanning result
Shown in Fig. 1, the uniform platinum nano-cone array structure of one layer of pattern has been made in microelectrode array surface, wherein platinum nanocone
Height be about 1 μm, tip diameter is less than 10nm, and base diameter is about 300nm, and density is 100/μm-2。
Embodiment 2
A kind of preparation method of platinum nano-cone array structure
1L water, the chloroplatinic acid of 5mmol/L and the hypochlorous acid ammonium of 5mmol/L are added in a reservoir, forms electricity after mixing
Deposition solution.
Wire is provided, places it in acetone or alcohol solution and is cleaned by ultrasonic, and pass through cyclic voltammetry scan, it is ensured that is clear
It is placed in electric depositing solution again after wash clean.It is to electrode with platinized platinum, Ag/AgCl is reference electrode, and wire is working electrode,
And connect with electrochemical workstation, in a manner of galvanostatic deposition, under the conditions of -0.3 μ A, electro-deposition 30min, in metal silk table
Face forms platinum nano-cone array structure, by electron-microscope scanning result as shown in Fig. 2, wire surface has been uniformly distributed one layer of platinum receives
Rice cone array structure, wherein the height of platinum nanocone is about 3 μm, and tip diameter is less than 10nm, and base diameter is about 100nm, close
Degree is 160/μm-2。
Embodiment 3
A kind of preparation method of platinum nano-cone array structure
1L water, the platinic sulfate of 20mmol/L and the trialkylamine of 2mmol/L are added in a reservoir, forms electricity after mixing
Deposition solution.
Becket is provided, is placed in electric depositing solution, is to electrode with platinized platinum, Ag/AgCl is reference electrode, becket
For working electrode, and it is connect with electrochemical workstation, in a manner of potentiostatic electrodeposition, under the conditions of -0.1V, electro-deposition 30min,
Platinum nano-cone array structure is formed in metal ring surface, by electron-microscope scanning result as shown in figure 3, wire surface is uniformly distributed
One layer of platinum nano-cone array structure, wherein the height of platinum nanocone is about 50nm, and tip diameter is less than 10nm, base diameter
About 180nm, density are 50/μm-2。
Embodiment 4
A kind of preparation method of platinum nano-cone array structure
1L water, the platinum nitrate of 15mmol/L and the ammonium nitrate of 5mmol/L are added in a reservoir, it is heavy to form electricity after mixing
Product solution.
Wire is provided, places it in acetone or alcohol solution and is cleaned by ultrasonic, and pass through cyclic voltammetry scan, it is ensured that is clear
It is placed in electric depositing solution again after wash clean.It is to electrode with platinized platinum, Ag/AgCl is reference electrode, and wire is working electrode,
And connect with electrochemical workstation, in a manner of pulse electrodeposition, in -0.6V, under the conditions of make-to-break ratio is 5ms:200ms, electricity is heavy
Product 20min.It is found through detection, forms one layer of equally distributed platinum nano-cone array structure, and platinum nanocone in wire surface
Pattern uniformity, wherein the height of platinum nanocone is about 5 μm, tip diameter be less than 10nm, base diameter is about 300nm,
Density is 250/μm-2。
Embodiment 5
A kind of preparation method of platinum nano-cone array structure
1L water, the platinum chloride of 10mmol/L and the ammonium chloride of 5mmol/L are added in a reservoir, it is heavy to form electricity after mixing
Product solution.
Sheet metal is provided, places it in acetone or alcohol solution and is cleaned by ultrasonic, and pass through cyclic voltammetry scan, it is ensured that is clear
It is placed in electric depositing solution again after wash clean.It is to electrode with platinized platinum, Ag/AgCl is reference electrode, and sheet metal is working electrode,
And connect with electrochemical workstation, in a manner of potentiostatic electrodeposition, under the conditions of -0.7V, electro-deposition 15min, in sheet metal table
Face forms platinum nano-cone array structure.By electron-microscope scanning, as a result as shown in figure 4, wherein (A) can be seen that in metal in Fig. 4
One layer of platinum nano-cone array structure of surface uniform fold of piece, (B) is it can be seen that nanometer in the platinum nano-cone array structure in Fig. 4
The appearance structure of cone is identical, generates without other impurities, and nanocone is evenly distributed on the surface of sheet metal, the height of platinum nanocone
About 1.5 μm, tip diameter is less than 8nm, and base diameter is about 220nm, and density is 200/μm-2。
Comparative example
The platinum chloride of 1L water and 10mmol/L is added in a reservoir, forms electric depositing solution after mixing.
Sheet metal is provided, places it in acetone or alcohol solution and is cleaned by ultrasonic, and pass through cyclic voltammetry scan, it is ensured that is clear
It is placed in electric depositing solution again after wash clean.It is to electrode with platinized platinum, Ag/AgCl is reference electrode, and sheet metal is working electrode,
And connect with electrochemical workstation, in a manner of potentiostatic electrodeposition, under the conditions of -0.7V, electro-deposition 15min, in sheet metal table
Face forms platinum nano array structure.By electron-microscope scanning, as a result as shown in Figure 5, it can be seen that platinum nano array structure is received by platinum
Popped rice composition, without the generation of platinum nanocone, and platinum nano flower is of different sizes, pattern is inhomogenous.As can be seen that the present invention provides
Suitable crystal type promoting reagent the crystal growth of platinum can be controlled in electrodeposition process, the life for the nanocone for promoting pattern uniform
At.
Effect example
To there is platinum nano array structure sheet metal, and the sheet metal not handled made from embodiment 5 and comparative example
(blank group) carries out electrochemical impedance and cyclic voltammetry experiment, as a result as shown in Figure 6.(A) is as can be seen that phase from Fig. 6
For blank group and comparative example, the impedance value of platinum nano-cone array structure made from embodiment 5 is lower, about 2k Ω (1kHz).Resistance
The reduction of anti-value can largely reduce the energy consumption of later period implantable stimulation.(B) is as can be seen that relative to blank from Fig. 6
The CV area of group and comparative example, platinum nano-cone array structure made from embodiment 5 obviously increases, substantially the 60 of a comparative example times left side
The right side, and it is reproducible, show it with more excellent charge storage.Therefore, it is made using method provided by the invention
Platinum nano-cone array structure have big surface area and excellent charge storage, be conducive to promoted electro photoluminescence and catalysis effect
Rate is with a wide range of applications in sensor field, catalytic field and neural interface field.
The above is a preferred embodiment of the present invention, and but it cannot be understood as to the invention patent range
Limitation.It should be pointed out that for those skilled in the art, without departing from the principle of the present invention, also
Several improvements and modifications can be made, these modifications and embellishments are also considered to be within the scope of the present invention.
Claims (10)
1. a kind of preparation method of platinum nano-cone array structure characterized by comprising
Platinum salt solution is provided, crystal type promoting reagent is added in Xiang Suoshu platinum salt solution, forms electric depositing solution after mixing,
In, the crystal type promoting reagent includes at least one of inorganic ammonium salt and organic amine；
Conducting base is provided, the conducting base is placed in the electric depositing solution, is led using the method for electro-deposition described
Platinum nano-cone array structure is made in electric matrix surface.
2. the preparation method of platinum nano-cone array structure as described in claim 1, which is characterized in that the inorganic ammonium salt includes
At least one of ammonium sulfate, ammonium chloride, ammonium nitrate, hypochlorous acid ammonium, ammonium nilrite, the organic amine include fatty amines,
At least one of alcamines and alicyclic ring amine.
3. the preparation method of platinum nano-cone array structure as described in claim 1, which is characterized in that in the electric depositing solution
In, the molar ratio 1:(0.1-10 of platinum salt and the crystal type promoting reagent in the platinum salt solution).
4. the preparation method of platinum nano-cone array structure as described in claim 1, which is characterized in that in the platinum salt solution
Platinum salt includes platinum chloride, ammonium chloroplatinate, potassium platinic chloride, sodium chloroplatinate, chloroplatinic acid, platinum nitrate, platinic sulfate, Tetrachloroplatinate
One of potassium, Tetrachloroplatinate ammonium are a variety of.
5. the preparation method of platinum nano-cone array structure as described in claim 1, which is characterized in that the platinum nano-cone array
The height of platinum nanocone in structure is 1nm-10 μm, and tip diameter is less than 10nm, base diameter 100nm-300nm, density
For 10/μm-2- 300/μm-2。
6. the preparation method of platinum nano-cone array structure as described in claim 1, which is characterized in that the method for the electro-deposition
For potentiostatic electrodeposition, galvanostatic deposition or pulse electrodeposition.
7. the preparation method of platinum nano-cone array structure as claimed in claim 6, which is characterized in that in the potentiostatic electrodeposition
Voltage be -0.5V~-0.75V, the electric current in the galvanostatic deposition is -0.1 μ μ of A~-0.7 A, in the pulse electrodeposition
Voltage be -0.5V~-0.75V, make-to-break ratio be (2ms-100ms): (200ms-1000ms).
8. the preparation method of platinum nano-cone array structure as described in claim 1, which is characterized in that the conducting base includes
At least one of microelectrode array, wire, sheet metal, becket, conductive plastics and conductive rubber.
9. a kind of microelectrode, which is characterized in that including microelectrode matrix and the platinum nanometer being arranged on the microelectrode matrix
Bore array structure, the platinum nano-cone array structure by the described in any item platinum nano-cone array structures of claim 1-8 system
Preparation Method is prepared.
10. application of the microelectrode as claimed in claim 9 in sensor field, catalytic field and neural interface field.
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| WO2020119607A1 (en) * | 2018-12-10 | 2020-06-18 | 深圳先进技术研究院 | Preparation method for platinum nanocone array structure and application thereof |
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| US20100270650A1 (en) * | 2009-04-27 | 2010-10-28 | Aurotek Corporation | Silicon substrate with periodical structure |
| CN103985836A (en) * | 2014-05-27 | 2014-08-13 | 哈尔滨工业大学 | Method for preparing germanium cathode material on nickel nanoneedle conical array |
| CN106835219A (en) * | 2017-01-19 | 2017-06-13 | 中国科学院深圳先进技术研究院 | A kind of super-hydrophobic stainless steel watch finishing coat and preparation method thereof |
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| CN108360026B (en) * | 2017-12-29 | 2019-11-29 | 郑州轻工业学院 | A kind of method that direct electro-deposition prepares metal nano-tube array |
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| US20100270650A1 (en) * | 2009-04-27 | 2010-10-28 | Aurotek Corporation | Silicon substrate with periodical structure |
| CN103985836A (en) * | 2014-05-27 | 2014-08-13 | 哈尔滨工业大学 | Method for preparing germanium cathode material on nickel nanoneedle conical array |
| CN106835219A (en) * | 2017-01-19 | 2017-06-13 | 中国科学院深圳先进技术研究院 | A kind of super-hydrophobic stainless steel watch finishing coat and preparation method thereof |
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