CN105929002A - Gold nanowell array electrode and production method thereof - Google Patents
Gold nanowell array electrode and production method thereof Download PDFInfo
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- CN105929002A CN105929002A CN201610263223.6A CN201610263223A CN105929002A CN 105929002 A CN105929002 A CN 105929002A CN 201610263223 A CN201610263223 A CN 201610263223A CN 105929002 A CN105929002 A CN 105929002A
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- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
- 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
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- G01N27/327—Biochemical electrodes, e.g. electrical or mechanical details for in vitro measurements
Abstract
The invention relates to a gold nanowell array electrode and a production method thereof. The gold nanowell array electrode comprises gold nanotube array main bodies, gold nanopillar array substrates and a current collector, the gold nanotube array main bodies are made through chemically depositing gold on a polycarbonate filter film with the film aperture diameter of 400-800nm and the wall thickness of gold nanotubes is 50-200nm; the gold nanopillar array substrates are made through chemically depositing gold on a polycarbonate filter film with the film aperture diameter of 80-200nm; and the gold nanopillar array substrates are fixed to the current collector through conductive adhesive bonding, the gold nanotube array main bodies are spread and cover the gold nanopillar array substrates, and circumferences are fixed to the current collector in a sealing manner through insulating adhesive tapes in order to obtain the gold nanowell array electrode. The gold nanowell array electrode has the advantages of simple and reasonable composition structure, reliable and stable connection, three dimensional structure, large surface area, realization of micromation and integration of a detection system, and effective avoiding of electrochemical response signal interferences induced by different materials.
Description
Technical field
The present invention relates to a kind of nano-array electrode and preparation method thereof, specifically a kind of gold nano well array electrode
And preparation method thereof.
Background technology
Nano-array electrode is the aggregation of multiple nano-electrode.It not only has single electrode height mass transfer rate, low double
Electric layer charging current, little time constant, little IR fall and high s/n ratio etc. are excellent, and due to thousands of single nano-electrodes
Concentrate on a matrix, overcome that single nano-electrode response signal is too small, be easily disturbed and be difficult to the shortcomings such as operation, can pole
The earth improves the sensitivity and reliability measured, and reduces operation easier and measures cost.
Gold electrode has the features such as good conductivity, stable chemical nature height and biomacromolecule compatibility are good, thus is raw
One of electrode most-often used in thing electrochemistry.People prepare the gold-nano array electrode of various ways at present.Such as one-dimensional grain
Shape gold-nano array electrode, two dimension banding gold are inserted and are referred to electrode, two dimension plate-like gold-nano array electrode, three-dimensional columnar nanometer array electricity
Pole and gold nanotubes array electrode.Wherein nanometer pipe array electrode has bigger active area compared with other array electrodes,
More excellent electrocatalysis characteristic, in recent years, causes the particular concern of researcher.
The report of gold nanotubes array electrode preparation method mainly has following two classes at present: a class is at polycarbonate leaching film
Deposited Au pipe in alumina formwork (polycarbonate leaching film template) hole of chemical deposition gold pipe or metal spraying overleaf in nib,
It is fixed on base electrode with adhesive again, then dissolves template, make nano-tube array (modification) electrode.Another kind of it is
Use nanometer gold that CNT is modified, then it is fixed on base electrode with adhesive.
But, there is deficiency in varying degrees in the electrode that above method is prepared.(1) electrode prepared by electrodeposition process,
Preparation process is complicated, it is difficult to ensure effective control of nanotube length, pipe thickness and uniformity；(2) owing to being nano-scale,
Exposed nanotube out easily snaps off；(3) the gold nanotubes array electrode no matter prepared by electrodeposition process or chemical deposition,
The bottom of its nanotube is uncovered, is base electrode surface with base electrode connecting portion, or adhesive, its material with
Gold nano tube wall be different (even if base electrode surfacing is gold, owing to preparation technology is different with golden tube wall, the table of the two
Surface state is also different).Thus electrode is put in solution, solution not only can contact with gold nano tube wall also can be with base electrode
Surface or adhesive contact, owing to solid liquid interface is inconsistent, can cause electrochemical response signal necessarily to be disturbed.
Summary of the invention
The technical problem to be solved is to overcome above-mentioned the deficiencies in the prior art, it is provided that a kind of composition structure letter
Single, rationally, connect reliable, stable, there is three dimensional structure, surface area is big, it is possible to realize the miniaturization of detection system and integrated,
Gold nano well array electrode of interference being prevented effectively from the electrochemical response signal that unlike material causes and preparation method thereof.
The present invention solves above-mentioned technical problem and the technical scheme is that a kind of gold nano well array electrode, and it includes
Gold nanotubes array body, gold nanorod array egative film, collector body, it is characterised in that: described gold nanotubes array body be
Die throat diameter is that on the polycarbonate leaching film of 400-800nm, chemical deposition gold is made, and wherein in nib, deposition has gold nanotubes,
The wall thickness of gold nanotubes is 50-200nm；Described gold nanorod array egative film is to be the Merlon of 80-200nm at die throat diameter
On filter membrane, chemical deposition gold is made, and wherein in nib, deposition has solid gold nanorod, filter membrane upper and lower surface is gold-plated film；Institute
Stating gold nanorod array egative film and be adhesively fixed on the current collector by conducting resinl, the tiling of gold nanotubes array body covers Jenner
On rice post array egative film, periphery seals with insulating tape and fixes on the current collector, obtains gold nano well array electrode.
The preparation method of the present invention above-mentioned gold nano well array electrode, it initially with chemical deposition at die throat diameter is
Deposition gold in the polycarbonate leaching film template of 400-800nm, in nib, deposition has gold nanotubes, by controlling sedimentation time, makes
The wall thickness depositing gold nanotubes in nib is 50-200nm, then removes the Gold plated Layer of this polycarbonate leaching film upper surface, obtains
Gold nanotubes array body；Then, use chemical deposition in the polycarbonate leaching film template that die throat diameter is 80-200nm
Deposition gold, by controlling sedimentation time, makes to be full of in nib solid gold nanorod, obtains gold nanorod array egative film；Then
Being adhesively fixed on the current collector by the gold nanorod array egative film lower surface obtained by conducting resinl, gold nanotubes array body is put down
Being coated with and cover on gold nanorod array egative film, periphery seals with insulating tape and fixes on the current collector, makes gold nano well array
Electrode.
Gold nanotubes array body of the present invention is fastened on collector body, at gold by gold nanorod array egative film
Nano-tube array bottom part body forms the shaft bottom of same material.Against existing technologies, advantages of the present invention and effect are: (1) makes
Simply, stability is high, low cost.The pipe thickness of gold nanotubes array and the big I of internal diameter were controlled by the chemical deposition time,
Being additionally, since tube wall to be embedded in polycarbonate leaching film, intensity is good, is effectively guaranteed the stability of product.(2) gold nano
The shaft bottom that post array egative film is formed is same material with the borehole wall of gold nanotubes array, and contact surface is all gold, therebetween can nothing
Seam superposition, contact is good, can be prevented effectively from the interference of the electrochemical response signal that unlike material is caused.(3) there is three-dimensional knot
Structure, surface area is bigger, and wherein gold nanotubes inner surface not only has the skin effect of nano material, bulk effect, quantum size
The speciality of the nano materials such as effect, it is also possible to carry out functionalized design by the method for modifying such as self assembly and chemistry, builds nanometer
Assemble electrode system, it is achieved the miniaturization of detection system and integrated.This electrode has spy in electrochemica biological sensor field
Different advantage.
Accompanying drawing explanation
The present invention will be further described below in conjunction with the accompanying drawings.
Fig. 1 is theory of constitution schematic diagram of the present invention.
In figure, label is: 1. gold nanotubes array body, 2. gold nanorod array egative film, 3. collector body, 4. insulating tape.
Detailed description of the invention
From figure 1 it appears that a kind of gold nano well array electrode, it includes gold nanotubes array body 1, gold nano
Post array egative film 2, collector body 3 etc..Described gold nanotubes array body 1 is to be the Merlon of 400-800nm at die throat diameter
On filter membrane, chemical deposition gold is made, and wherein in nib, deposition has gold nanotubes, and the wall thickness of gold nanotubes is 50-200nm.Described
Gold nanotubes array body thickness be 4-6 μm.
Described gold nanorod array egative film 2 is chemical deposition gold on the polycarbonate leaching film that die throat diameter is 80-200nm
Making, wherein in nib, deposition has solid gold nanorod, filter membrane upper and lower surface is gold-plated film.
Described gold nanorod array egative film 3 is bonded and fixed on collector body 3 by conducting resinl, gold nanotubes array body 1
Tiling covers on gold nanorod array egative film 2, and periphery insulating tape 4 seals and is fixed on collector body 3, makes and obtains Jenner
Rice well array electrode.So can ensure that when putting the electrodes in solution, the most unencapsulated part gold nanotubes array produces
Raw electrochemical response signal.
The preparation method of the present invention above-mentioned gold nano well array electrode, it initially with chemical deposition at die throat diameter is
Deposition gold in the polycarbonate leaching film template of 400-800nm, in nib, deposition has gold nanotubes, by controlling sedimentation time, makes
The wall thickness depositing gold nanotubes in nib is 50-200nm；Then remove the Gold plated Layer of this polycarbonate leaching film upper surface, obtain
Gold nanotubes array body.
Then, use chemical deposition to deposit gold in the polycarbonate leaching film template that die throat diameter is 80-200nm, logical
Cross control sedimentation time, make nib is full of solid gold nanorod, obtain gold nanorod array egative film.
Then the gold nanorod array egative film lower surface obtained is adhesively fixed on the current collector by conducting resinl, gold nano
The tiling of pipe array body covers on gold nanorod array egative film, and periphery seals with insulating tape and fixes on the current collector, makes
Gold nano well array electrode.Described conducting resinl is conductive aluminum two-sided tape.During assembling, first by viscous for gold nanorod array egative film one side
On conductive aluminum two-sided tape, the another side of conductive aluminum two-sided tape is bonded on the metal copper sheet making collector body, reserves certain
After area, remainder insulating tape seals, and makes gold nano well array electrode.
The concrete steps of the preparation method of the present invention above-mentioned gold nano well array electrode include:
(1) preparation of nano-tube array main body:
First the polycarbonate leaching film that die throat diameter is 400-800nm is fixed on non-metal plate or nonmetal clamping plate, puts
Enter soaking and washing 5 minutes in methanol, be aided with ultrasonic Treatment；
B. the polycarbonate leaching film after methanol soaking and washing is put into containing SnCl2、CF3The methanol of COOH and water mixed liquid enter
Row sensitization pre-treatment, described sensitization mixed liquor is SnCl2 0.026M, CF3COOH 0.05M, the methanol of volume ratio 1:1 (v/v)
And water mixed liquid, temperature is room temperature, and the time is 40-60 min；
C. by sensitization and clean after polycarbonate leaching film put into silver the silver ammino solution that content is 0.04 M in carry out pre-silver-plated；
D. pre-silver-plated and after cleaning polycarbonate leaching film is put into and carried out chemical plating in gold plating solution, the master of described gold plating solution
Form and with craft of gilding be: Na3Au(SO3)20.006M ；Na2SO30.08M；Formaldehyde 0.04M；PH value 9.50 ~ 10.50；
Temperature: 2-5 DEG C；Time: 16-26 h；
E. by the polycarbonate leaching film after chemical plating at 20-25% HNO3Aqueous solution soaks 12 hours, then cleans with water；
F. remove the gold-plated film of the one side of the polycarbonate leaching film after above-mentioned process, expose gold nanotubes port, at the baking oven of 150 DEG C
Middle heating 20 minutes, eliminates the space between gold nanotubes and polycarbonate leaching film in filter opening nib, deposits gold nano in nib
The wall thickness of pipe is 50-200nm, obtains gold nanotubes array.
(2) preparation of gold nanorod array egative film:
A. the polycarbonate leaching film that die throat diameter is 80-200nm is fixed on non-metal plate or nonmetal clamping plate, puts into methanol
Middle soaking and washing 5 minutes, is aided with ultrasonic Treatment；
B. the polycarbonate leaching film after methanol soaking and washing is put into containing SnCl2、CF3The methanol of COOH and water mixed liquid enter
Row sensitization pre-treatment, described sensitization mixed liquor is SnCl2 0.026M, CF3COOH 0.05M, the first of volume ratio 1:1 (v/v)
Alcohol and water mixed liquor, temperature is room temperature, and the time is 40-60 min；
C. by sensitization and clean after polycarbonate leaching film put into silver the silver ammino solution that content is 0.04 M in carry out pre-silver-plated；
D. pre-silver-plated and after cleaning polycarbonate leaching film is put into and carried out chemical plating in gold plating solution, the master of described gold plating solution
Form and with craft of gilding be: Na3Au(SO3)2 0.005-0.05M；Na2SO30.01-0.1M；Formaldehyde 0.3-0.8M；PH value
9.50~10.50；Temperature: 2-8 DEG C；Time: 12-24 h；
E. by the polycarbonate leaching film after chemical plating at 20-25% HNO3Aqueous solution soaks 12 hours, then cleans with water；
F. heat 20 minutes in the baking oven of 150 DEG C, eliminate the space between nanowires of gold and polycarbonate leaching film in filter opening,
Obtain gold nanorod array.
(3) assembling of electrode:
The above-mentioned gold nanorod array egative film lower surface prepared is bonded on conductive aluminum two-sided tape, conductive aluminum two-sided tape
Another side be bonded on the metal copper sheet making collector body, gold nanotubes array body tiling cover at gold nanorod array egative film
On, can be according to measuring needs, after the upper surface of gold nanotubes array body reserves certain area, remainder insulating tape
Seal and fix on the current collector, making gold nano well array electrode.So can ensure that when putting the electrodes in solution, only
Unencapsulated part gold nanotubes array produces electrochemical response signal.
Gold nanotubes array body of the present invention is fastened on collector body, at gold by gold nanorod array egative film
Nano-tube array bottom part body forms the shaft bottom of same material.Advantages of the present invention and effect be:
(1) making simply, stability is high, low cost.The pipe thickness of gold nanotubes array and the big I of internal diameter are heavy by chemistry
The long-pending time controls, and is additionally, since tube wall and is embedded in polycarbonate leaching film, and Stability Analysis of Structures, intensity is good, is effectively guaranteed product
Stability.
(2) borehole wall of gold nanotubes array and the shaft bottom of gold nanorod array egative film formation are same material, gold nanotubes battle array
Row main body and gold nanorod array egative film therebetween can be with seamless matching, and contact surface is all gold, and contact is good.Can be prevented effectively from
The interference of the electrochemical response signal that unlike material is caused.
(3) having three dimensional structure, surface area is bigger, and wherein gold nanotubes inner surface not only has the surface effect of nano material
Should, the speciality of the nano material such as bulk effect, quantum size effect, it is also possible to carried out by the method for modifying such as self assembly and chemistry
Functionalized design, builds nanometer and assembles electrode system, it is achieved the miniaturization of detection system and integrated.This electrode is electrification student
Thing sensor field has special advantage.
Claims (2)
1. a gold nano well array electrode, it includes gold nanotubes array body, gold nanorod array egative film, collector body,
It is characterized in that: described gold nanotubes array body is that chemistry is heavy on the polycarbonate leaching film that die throat diameter is 400-800nm
Long-pending gold is made, and wherein in nib, deposition has gold nanotubes, and the wall thickness of gold nanotubes is 50-200nm；Described gold nanorod array
Egative film is that chemical deposition gold is made on the polycarbonate leaching film that die throat diameter is 80-200nm, and wherein in nib, deposition has reality
The gold nanorod of the heart, filter membrane upper and lower surface is gold-plated film；Described gold nanorod array egative film is bonded and fixed at collection by conducting resinl
On electricity body, the tiling of gold nanotubes array body covers on gold nanorod array egative film, and periphery insulating tape seals and is fixed on
On collector body, obtain gold nano well array electrode.
2. the preparation method stating gold nano well array electrode described in a claim 1, it is characterised in that: initially with chemistry
Sedimentation deposits gold in the polycarbonate leaching film template that die throat diameter is 400-800nm, and in nib, deposition has gold nanotubes, logical
Crossing control sedimentation time, making the wall thickness depositing gold nanotubes in nib is 50-200nm；Then remove on this polycarbonate leaching film
The Gold plated Layer on surface, obtains gold nanotubes array body；Then, using chemical deposition is the poly-of 80-200nm at die throat diameter
Deposition gold in carbonic ester filter membrane template, by controlling sedimentation time, makes to be full of in nib solid gold nanorod, obtains gold nano
Post array egative film；Then the gold nanorod array egative film lower surface obtained is adhesively fixed on the current collector by conducting resinl, gold
The tiling of nano-tube array main body covers on gold nanorod array egative film, and periphery seals with insulating tape and fixes on the current collector,
Make gold nano well array electrode.
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