CN108483389A - A kind of silver nanoparticle electrode and preparation method thereof - Google Patents
A kind of silver nanoparticle electrode and preparation method thereof Download PDFInfo
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Abstract
The present invention provides a kind of silver nanoparticle electrodes and preparation method thereof, compared with prior art, the present invention by the selection of glass tube and wire, the design of drawing parameters, electrode encapsulating material selection and electrode polishing parameter selection, overcome can not by laser drawing method prepare silver nanoparticle electrode the problem of.The present invention utilizes laser drawing, obtains the silver nanoparticle electrode that radius is less than 50nm, manufacturing process is simply and the electrode size of preparation is small, and advantage of lower cost, compared to other silver electrodes, electrode stability prepared by the present invention is also fine.And the silver nanoparticle electrode size prepared is small, and mass transfer rate is fast, and it is small, light, cheap to detect sensitive and instrument.By the state of OLYMPUS biology microscope sem observation filamentary silver pulling process, the methods of scanning electron microscope (SEM) and X ray energy line spectrum analytic approach (EDX) carry out characterization to electrode and to silver nanoparticle electrode, the performance of itself is studied with cyclic voltammetry.
Description
Technical field
The invention belongs to noble metal electrode preparation fields, and in particular to a kind of silver nanoparticle electrode and preparation method thereof.
Background technology
The nano-electrode of various patterns has obtained development at full speed, especially noble metal nano electrode between recent two decades
It prepares, such as platinum nanometer disc electrode, Pt nanowires electrode, gold nano disc electrode, nanowires of gold electrode and nanometer pore electrod and its
The electrode of his pattern has numerous reports.And in its application aspect, the electrode of these small sizes is due to material itself and geometry
The property of shape is applied in the Electrochemical Detection of varying environment, including single particle analyzer, scan-type electrochemical
Microscope (SECM), atomic force microscope (AFM), the electro-catalysis of fuel, biological living analysis, individual cells dynamic monitoring and electricity
The structure etc. of chemical dna sensor.
People are concentrated mainly on the research of platinum, gold nano electrode at present, but because of expensive and low earth storage capacity etc.
Feature limits it and is widely used, so a kind of new nano material electrode of research and development is of great significance to.
Silver in precious metal material is synthesized Nano silver grain by chemical method, is then modified in Different electrodes
In, have very good application in electro-catalysis and Surface enhanced Raman spectroscopy (TERS), it can also be used as prepare it is various
The substrate of solid ionic selectivity micro-electrode and nano electrode, so that silver becomes the advantageous material of manufacture nano-electrode.But
It is synthesized Nano silver grain by chemical method, building-up process is more complicated, and takes consumptive material；Again by the Nano silver grain of preparation
In electron surface, its stability also needs to be investigated for modification.
Different from platinum and gold, silver is swollen due to the heat of its low fusing point and coefficient of thermal expansion and borosilicate or soda-lime glass
Significant mismatch between swollen coefficient so that preparing silver nanoparticle electrode by laser drawing method has certain difficulty.
Invention content
The purpose of the present invention is to provide a kind of preparation methods of silver nanoparticle electrode, pass through the choosing of glass tube and wire
It selects, the parameter selection of the selection of the encapsulating material of the design of drawing parameters, electrode and electrode polishing, laser can not be passed through by overcoming
Drawing method prepares the problem of silver nanoparticle electrode.And prepare silver nanoparticle electrode size it is small, mass transfer rate is fast, detection it is sensitive and
Instrument is small, light, cheap.
The present invention also provides a kind of silver nanoparticle electrodes.
Specific technical solution of the present invention is as follows：
A kind of preparation method of silver nanoparticle electrode provided by the invention, includes the following steps：
1) filamentary silver is formed directly into aluminosilicate capillary and filamentary silver is located at the centre position of capillary, using asphalt mixtures modified by epoxy resin
Fat glue seals one end；
2) it uses P-2000 laser to draw instrument to draw, temperature is 440-445 DEG C in heating process in drawing, pulling force is
120N, rate 5m/s, heat four cycles, and process is：Heat 40s, cooling 20s；Heating 4 times, cooling 3 times, the 4th time plus
Heat draws the filamentary silver at position later and capillary is merged and then directly draws, and lasts 3 points altogether 40 seconds, entirely drew
Journey carries out in vacuum environment；Then filamentary silver and capillary are drawn into two ultra-fine tip probes, drawing parameters are：Temperature
450-455 DEG C, pulling force 118N, rate 3m/s；
3) tungsten filament is inserted into from the capillary tail portion of electrode after step 2) processing, is connected tungsten filament and filamentary silver with silver conductive adhesive
It connects；
4) by step 3), treated that electrode is placed in borosilicate glass tube, is sealed both ends with epoxide-resin glue；
5) electrode prepared is subjected to polishing grinding on abrasive paper for metallograph, until the tip of drawing and the quartz ampoule of outer layer
Stop polishing when port flushes；
6) the silver nanoparticle electrode obtained after step 5) polishing treatment is successively placed in deionized water and ethyl alcohol ultrasound respectively
Cleaning 2-3 times, place into ultra-pure water be placed in 4 DEG C of refrigerators store it is spare.
It is specially in step 1)：It is aluminium silicon in 8cm aluminosilicate capillaries that length is penetrated length in the filamentary silver of 2-3cm
Hydrochlorate capillary is specially：O.d.=1.0mm；I.d.=0.64mm seals one end using epoxide-resin glue.The distance of encapsulation is only
Keep it air tight in pulling process, it is ensured that keep vacuum environment in pulling process；
In step 2) pulling process, in order to ensure filamentary silver is uniformly to attenuate and cone that formation rule is ultra-fine in the both ends of drawing
Whether shape tip, the filamentary silver for putting it into OLYMPUS Photobiology microscopically observations tip thawing part are successive.
Tungsten filament diameter 0.5mm length is 5cm in step 3)；Further, it is molten when tungsten filament is connect with the filamentary silver in capillary
Filamentary silver at end is not broken.
Borosilicate glass tube o.d.=2.0mm in step 4)；I.d.=1.16mm.
To ensure that draw tip is complete and tungsten filament and filamentary silver in step 3) will not be made to be detached from step 4) when encapsulation.
The entire processing procedure of polishing is moved under the biomicroscope and cyclic voltammetric electrochemical method of 40x10 in step 5)
State monitors, to ensure that the glass of the metallic perimeter in the case where tip metal exposes is also complete.
Be successively placed on 200,400,600,800 and 1000 mesh according to the degree of roughness difference of sand paper in step 5), metallographic
Polishing grinding is carried out on sand paper, because of the borosilicate quartz ampoule at the tip and outer envelope of drawing electrode when encapsulation
There is distance in port, we are first roughly ground by microscope using the small sand paper of mesh number, and micro- sem observation is used while polishing,
The big sand paper of mesh number is changed successively at a distance from outer layer quartz pipe end according to the tip for drawing filamentary silver, until the tip of drawing and outside
Stop polishing when the quartzy pipe port of layer flushes.
A kind of silver nanoparticle electrode provided by the invention, is prepared using the above method.
The present invention by the selection of glass tube and wire, the design of drawing parameters, electrode encapsulating material selection and
Electrode polishing parameter selection, overcome can not by laser drawing method prepare silver nanoparticle electrode the problem of.The present invention utilizes
Laser drawing obtains the silver nanoparticle electrode that radius is less than 50nm, and manufacturing process is simply and the electrode size of preparation is small, cost phase
To relatively low, compared to other silver electrodes, electrode stability prepared by the present invention is also fine.And the silver nanoparticle electrode size prepared
Small, mass transfer rate is fast, and it is small, light, cheap to detect sensitive and instrument.It was drawn by OLYMPUS biology microscope sem observation filamentary silvers
The state of journey, the methods of scanning electron microscope (SEM) and X-ray energy line spectrum analysis method (EDX) characterize simultaneously electrode
With cyclic voltammetry, to silver nanoparticle electrode, the performance of itself is studied.
Description of the drawings
Fig. 1 is the flow diagram that the application laser drawing prepares silver nanoparticle electrode；
Fig. 2A is the situation that 50um filamentary silvers are located at tip and molten end after drawing；
Fig. 2 B are that embodiment 1 draws successful tapered capillaries tip and uniformly extends the filamentary silver to attenuate in capillary；
Fig. 2 C are the filamentary silver of the most advanced part prepared under enlargement ratio 252X enlargement ratios；
Fig. 3 A are state diagram (low power number amplification) of the silver nanoparticle electrode of radius 40nm in SEM；
Fig. 3 B are state diagram (high magnification numbe amplification) of the silver nanoparticle electrode of radius 40nm in SEM；
Fig. 3 C are the X-ray energy spectrogram of silver nanoparticle electrode；
Fig. 4 A are various sizes of silver nanoparticle electrode in the solution of six ammino ruthenium of the potassium nitrate containing 0.2M and 5mM trichlorines
Cyclic voltammetric response, sweep speed be 10mv s-1；
Fig. 4 B be radius be 23.2nm silver nanoparticle electrode in the molten of six ammino ruthenium of the potassium nitrate containing 0.2M and 5mM trichlorines
The different cyclic voltammetric responses for sweeping speed in liquid；
Fig. 4 C be radius be 179.4nm silver nanoparticle electrode in six ammino ruthenium of the potassium nitrate containing 0.2M and 5mM trichlorines
The different cyclic voltammetric responses for sweeping speed in solution；
Fig. 5 A are various sizes of silver nanoparticle electrode in the solution of six ammino ruthenium of the potassium nitrate containing 0.2M and 5mM trichlorines
Cyclic voltammetric response；
Fig. 5 B are the normalization process of various sizes of silver nanoparticle electrode cycle volt-ampere；Sweep speed is 10mv s-1；
Fig. 6 is that cyclic voltammetric of the various sizes of silver nanoparticle electrode in the 0.1M phosphate buffer solutions of nitrogen atmosphere is rung
(a) 77nm is answered, (b) 104nm, (c) 225nm；Sweep speed is 10mv s-1。
Fig. 7 A radiuses are cycle of the silver nanoparticle electrode of 261nm in 0.1M phosphate buffer solutions and 0.2M Klorvess Liquids
Volt-ampere response；A lines are 0.1M phosphate buffer solutions, and b lines are in 0.2M Klorvess Liquids；Sweep speed is 10mv s-1, at room temperature into
Row；
Fig. 7 B are that the silver nanoparticle electrode prepared is lied prostrate in the cycle of the 0.1M phosphate buffer solutions of the potassium chloride containing various concentration
Peace response, sweep speed are 10mv s-1；It carries out at room temperature.
Specific implementation mode
Embodiment 1
A kind of preparation method of silver nanoparticle electrode, includes the following steps：
1) it is 8cm aluminosilicate capillaries (o.d.=1.0mm length to be penetrated length in the filamentary silver of 2-3cm or so；i.d.
=0.64mm) in, sealing one end using epoxide-resin glue ensures to keep vacuum environment in pulling process；
2) using P-2000 laser to draw instrument drawing makes capillary be merged well with filamentary silver, is drawn in silver nanoparticle electrode
Parameter, by the drawing parameters for probing into determining silver nanoparticle electrode：When drawing, temperature is 440-445 DEG C in heating process, pulling force is
120N, rate 5m/s heat four cyclic processes：Heat 40s, cooling 20s；Heating 4 times, it is 3 times cooling, 3 are lasted altogether
Divide 40 seconds, entire pulling process carries out all in vacuum environment；The 4th heated rear filamentary silver and capillary for drawing position
Then pipe, which is merged, directly to be drawn, filamentary silver and capillary are drawn into two ultra-fine tip probes, drawing parameters are：Temperature
450-455 DEG C, pulling force 118N, rate 3m/s.In order to ensure filamentary silver is uniformly to attenuate and formation rule is super in the both ends of drawing
Whether thin cone point, the filamentary silver for putting it into OLYMPUS Photobiology microscopically observations tip thawing part are continuous not
It is disconnected；
3) tungsten filament of a diameter of 0.5mm length about 5cm is connected with filamentary silver with silver conductive adhesive, it should be noted that tungsten filament and glass tube
In filamentary silver connection when molten end at filamentary silver be not broken；4) borosilicate glass tube (o.d.=2.0mm is taken；I.d.=
1.16mm) to ensure that draw tip is complete when packaged, and tungsten filament and filamentary silver in step 3) will not be made to be detached from, then use epoxy resin
Glue seals both ends；
5) electrode prepared is placed on the abrasive paper for metallograph of different meshes (200,400,600,800,1000 mesh) successively
It is polished polishing, entire processing procedure is the dynamic monitoring under the biomicroscope and cyclic voltammetric electrochemical method of 40*10,
To ensure that the glass of the metallic perimeter in the case where tip metal exposes is also complete；
6) the Silver nanodisks electrode of the good acquisition of polishing treatment is successively placed on deionized water ultrasonic cleaning 2-3 times, then again
Be placed in ethyl alcohol and be cleaned by ultrasonic 2-3 times, place into ultra-pure water be placed in 4 DEG C of refrigerators store it is spare.
Whole preparation process is as shown in Figure 1.
OLYMPUS Photobiology microscopes have the function of that maximum can amplify 10000 (100*100) times, can observe
Under to 1um sizes filamentary silver under drawn condition whether continuous uniform, this to the application adjust drawing parameters process provide it is important
Help.What is provided in Fig. 2A is the situation that 50um filamentary silvers are located at tip and molten end after drawing, can be gem-pure in figure
Observe that filamentary silver positioned at capillary centre position and from molten end to tip is uniformly to attenuate.The filamentary silver of wherein molten end part
It is easiest to occur melting and be broken in heating and drawing, it is contemplated that this may be since molten the heated of end is by laser
The limitation of source range, the application improve drawing parameters and drawing cycle process in electrode production process.Since the conduction of silver is led
Hot property and golden incomparable and fusing point want low compared to gold, are 440 DEG C by the temperature design of heating so in preparation process,
The temperature design of drawing is 450 DEG C, and will be controlled heating time in 40s, and control cooling time is in 20s, whole process cycle 4
It is secondary.It can be clearly seen that the successful tapered capillaries tip of a drawing in fig. 2b and uniformly extend in capillary and attenuate
Filamentary silver.Filamentary silver inside the means suitable at glass tip has good ductility and toughness in pulling process and has with glass
Good amalgamation, but the ductility of filamentary silver is not as good as gold, such hardware condition, which limits, obtains smaller size of silver electricity
Pole.Fig. 2 C are the most advanced parts that simply prepared by the observation present invention under larger enlargement ratio by Photobiology microscope
Filamentary silver, this for subsequently using electrode and selection electrode size have important basis for estimation.
The microscopic appearance of nano material often affects the performance of material, the observational study for material morphology be can not or
Scarce step, field emission scanning electron microscope (FE-SEM) are a kind of characterizations for being often used to observation nano material microscopic appearance
Method.Fig. 3 A and Fig. 3 B are the state diagram of different amplification of the same root nano silver electrode in SEM.It can be clear from Fig. 3 A
Chu sees that electrode surface has smooth pattern, and without apparent gap, the two between metallic silver wire and glass
Between merge it is very close；It is clear that the surface size of Silver nanodisks electrode is about 40nm from Fig. 3 B figures,
Fig. 3 C are the phenogram of X-ray energy-ray spectrum analysis method (EDX), the silver nanoparticle for seeing preparation that can be perfectly clear in figure
Silver-colored elemental analysis figure in electrode, this also demonstrates silver nanoparticle electrode from side and has been successfully prepared.
The electrochemical Characterization of the silver nanoparticle electrode of above-mentioned preparation：
For the size and geometry of nano-electrode in an experiment usually by cyclic voltammetry (CV), scan-type electrochemical is micro-
The methods of mirror method (SECM) and atomic force microscopy (AFM) are assessed.The 5mM trichlorines six of the potassium nitrate containing 0.2M are prepared first
Ammino ruthenium solution：It weighs six ammino ruthenium of 0.0387g trichlorines and is configured to 25mL for table with deionized water with 0.5055g potassium nitrate
Sign.Characterization carries out at ambient temperature.Fig. 4 A are various sizes of silver nanoparticle electrodes in 5mM Ru (NH3)6Cl3Following in solution
Ring voltammogram.It gem-pure can observe the stacking chart of " S " type curve of an almost Perfect from figure, electrode ruler in figure
The charging capacitor of very little smaller reverse scan is also small, and such phenomenon and reports numerous before match.In cyclic voltammetric
The silver nanoparticle electrode that radius is less than 20nm is obtained under the characterization of electrochemistry, this also demonstrates the preparation and polishing in nano-electrode
Technical maturation.
id=4nFDCba (1)
It is typically to be assessed by above-mentioned formula (1) diffusion-carrying current formula that the nanometer plate electrode size of silver, which calculates,
's.Wherein idIt is the carrying current value of " S " type, n, which is catholyte redox species, must shift electron number, and F is Faraday constant,
D is the expanding coefficient of redox materials, CbFor the molar concentration of redox materials, a is the radius ruler by calculating electrode
It is very little.Fig. 4 B and Fig. 4 C are set forth that radius is 23.2nm and the electrode of 179.4nm in sweep speed is 5mV s-1With
1000mVs-1Stacking chart.From two it can be seen from the figure thats under two kinds of different sizes, when sweep speed is 5mV s-1When figure
It is typical " S " type, and the figure of forward and reverse scanning is almost overlapped；1000mV s are reached when sweeping speed-1When two kinds of sizes
Although electrode possesses larger charging capacitor but still remains " S " type curve.This is because relatively fast sweep speed or height
It sweeps flooding mechanism under speed to be changed, to generate larger capacitor layers.And also without other oxygen in height sweeps fast figure below
The appearance for changing reduction peak does not have between the generation of the capillary on side to demonstrate metallic silver wire during preparation and polishing
Gap.
The measurement of electron transport rate constant：
For electron transport rate constant k0Measurement mostly by way of electrode surface molecule mass transfer rate, however should
Numerical value commonly greater than or equal to electronics delivery rate.Hemispherical or sufficiently small disc electrode its stable state voltammetry of radius are mainly
The diffusion of substance, expression formula are：
(D/K0a)≥0.1
K0Value generally in 1-100cm/s, can be used for the measurement of 100-1nm nano-electrodes, and the classical value of D is
10-5cm/s.5mM Ru (NH are measured using nano silver electrode in this work3)6 3+Oxidation electron transmission constant.
Fig. 5 A are the silver nanoparticle electrodes of different radii in 5mM Ru (NH3)6Cl3Cyclic voltammetric response diagram, it can be seen that with
The increase diffusion limiting current value i of electrode sizedIt is consequently increased.By obtained volt-ampere response current value than upper maximum pole
Threshold currents idThe normalized curve such as Fig. 5 B can be obtained, can preferably be reflected between volt-ampere response and nano-electrode size
Relationship.The half wave potential of electrode is moved to the left, this knot with the increase of nano-electrode radius as can be observed from Figure
It is consistent by with many reports before.
Traditional Butler-Volmer electrode kinetics is most classical one of the formula of Electrode surface kinetics, this
In assume initially that the result of study of Fig. 5 A and Fig. 5 B are to meet that BV is dynamic (dynamical), so according to the formula of i-E：
In formula, A is the surface area of electrode, E0' be electrode take-off potential, α is electron transmission coefficient, and T is absolute temperature
Degree, n transmit the number of electronics, and F Faraday constants, R is thermodynamic equilibrium constant.Wherein K0Numerical value with α be according to Mirkin and
The method of Bard development obtains, i.e., by E that in statistical chart 5A various sizes of nano-electrode measurement obtains1/2、E3/4And E1/4
When electrode potential, E1/2、E3/4And E1/4Electrode potential be different dimension limit electric current i respectivelyd1/2,3/4 and 1/4 correspond to
Current potential.It counts to have obtained radius to be to close measured by 5 kinds of various sizes of nano-electrodes of 16nm to 361nm by the above method
In Ru (NH3)6 3+α and K in aqueous solution0Value be listed in table 1.Test obtained mean values k0=3.4 ± 2.5cm/s, α=
0.33±0.2。
1. silver nanoparticle electrode of table joins the dynamics in the solution of six ammino ruthenium water of the potassium nitrate containing 0.2M and 5mM trichlorines
Several measurement
Table 1
Redox of the silver nanoparticle electrode in phosphate buffer solution
It is also detected with being usually chosen in neutral phosphate buffer solution since silver is easily aoxidized itself, it can be excluded in this way
The interference of his substance.Three kinds of various sizes of nano silver electrodes of preparation are placed in 0.1M phosphate buffer solutions and (lead to nitrogen to remove
Oxygen) in obtain the cyclic voltammogram such as Fig. 6, radius is (a) 77nm, (b) 105nm, (c) 825nm respectively, sweep speed be 10mVs-1。
As can be seen from the figure three kinds of various sizes of electrodes have the appearance of the oxidation peak of silver in forward scan near+0.4V, and
And with the increase of electrode size, positive movement occurs for current potential, and this phenomenon and Francis seminars reported not in 2010
With size Nano silver grain in sulfuric acid oxidizing potential movement report it is consistent；However during reverse scan, silver-colored oxygen
With the increase reduction peak of electrode size negative shifting occurs for the reduction peak of compound, and reduction peak is reported with before when radius is 825nm
The reduction spike potential for the micron electrode that road is crossed is similar.
Explore Cl﹣Influence to silver nanoparticle anodizing reduction
Given in Fig. 7 A radius be 261nm silver nanoparticle electrode respectively at 0.1M phosphate buffer solutions (pH=7.0)
With the disproportionation in 0.2M KCl solution, wherein a lines are in phosphate buffer solution, it can be seen that silver-colored when forward scan
The formation current potential of oxide be near+0.4V, and reverse scan restore when current potential near+0.1V；B lines are in 0.2M KCl
Oxidation-reduction process in solution, as can be seen from the figure the position of silver-colored oxidation peak near+0.1V, the position of reduction peak-
0.16V or so, and the shape size of oxidation peak and reduction peak is also different, and this phenomenon and report before are kissings
It closes.It can show that negative shifting has occurred compared to PBS in oxidation-reduction potential of the silver nanoparticle electrode in KCl solution by comparison, I
In view of may be Ag that silver nanoparticle electrode aoxidizes generation in KCl solution+Cl in binding soln-It is generated in electrode surface
AgCl layers, to reduce Ag+In the diffusion rate of electrode surface the position size and shape of reduction peak is changed.For
This imagination of verification, the KCl of various concentration is added to adjust Cl in solution in we in phosphate buffer solution-Concentration.Figure
A represents the addition without KCl in 7B, and b c d e, which are respectively represented, adds 0.01M in solution, tetra- kinds of the good 0.2M KCl of 0.05M, 0.1M
Different amounts.See that the redox variation of a and b is not Cl of this explanation in low concentration very greatly in right illustration-To the oxygen of silver
The influence for changing reduction is not very big.But it is gem-pure from influence from the point of view of entire concentration gradient, is aoxidized with the increase of KCl amounts
It restores spike potential and negative shifting gradually occurs, and peak shape is also changing, peak area is also accordingly increasing.For this experimental phenomena,
We can obtain Cl-Influence to silver-colored disproportionation and other performances be can not ignore in an experiment.
Claims (9)
1. a kind of preparation method of silver nanoparticle electrode, which is characterized in that the preparation method comprises the following steps：
1) filamentary silver is formed directly into aluminosilicate capillary and filamentary silver is located at the centre position of capillary, using epoxide-resin glue
Seal one end；
2) use P-2000 laser draw instrument draw, in drawing in heating process temperature be 440-445 DEG C, pulling force 120N, speed
Rate is 5m/s, heats four cycles, and process is：Heat 40s, cooling 20s；Heating 4 times, 3 times cooling, the 4th heated post-tensioning
The filamentary silver at position processed is merged with capillary and then directly draws, and lasts 3 points altogether 40 seconds, entire pulling process is in vacuum
It is carried out in environment；Then filamentary silver and capillary are drawn into two ultra-fine tip probes, drawing parameters are：450-455 DEG C of temperature,
Pulling force 118N, rate 3m/s；
3) tungsten filament is inserted into from the capillary tail portion of electrode after step 2) processing, is connect tungsten filament with filamentary silver with silver conductive adhesive；
4) by step 3), treated that electrode is placed in borosilicate glass tube, is sealed both ends with epoxide-resin glue；
5) electrode prepared is subjected to polishing grinding on abrasive paper for metallograph, until the tip of drawing and the quartzy pipe port of outer layer
Stop polishing when flushing；
6) the silver nanoparticle electrode obtained after step 5) polishing treatment is successively placed in deionized water and ethyl alcohol and is cleaned by ultrasonic respectively
2-3 times, place into ultra-pure water be placed in 4 DEG C of refrigerators store it is spare.
2. preparation method according to claim 1, which is characterized in that be specially in step 1)：By length 2-3cm silver
It is in 8cm aluminosilicate capillaries that silk, which penetrates length, and aluminosilicate capillary is specially：O.d.=1.0mm；I.d.=
0.64mm seals one end using epoxide-resin glue.
3. preparation method according to claim 1 or 2, which is characterized in that in step 2) pulling process, in order to ensure drawing
Both ends in filamentary silver be uniformly to attenuate and cone point that formation rule is ultra-fine, put it into OLYMPUS Photobiology microscopes
Whether the filamentary silver that part is melted at lower observation tip is successive.
4. preparation method according to claim 1 or 2, which is characterized in that tungsten filament diameter 0.5mm length is in step 3)
5cm。
5. preparation method according to claim 1 or 2, which is characterized in that tungsten filament and the filamentary silver in capillary in step 3)
The filamentary silver at end is melted when connection to be not broken.
6. preparation method according to claim 1 or 2, which is characterized in that borosilicate glass tube o.d.=in step 4)
2.0mm；I.d.=1.16mm.
7. preparation method according to claim 1 or 2, which is characterized in that ensure draw tip when encapsulation in step 4)
Completely and tungsten filament and filamentary silver in step 3) will not be made to be detached from.
8. preparation method according to claim 1 or 2, which is characterized in that in step 5) the entire processing procedure of polishing be
Dynamic monitoring under the biomicroscope and cyclic voltammetric electrochemical method of 40x10, to ensure in the case where tip metal exposes
The glass of metallic perimeter is also complete.
9. silver nanoparticle electrode prepared by a kind of any one of claim 1-8.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110767913A (en) * | 2019-11-07 | 2020-02-07 | 安徽师范大学 | Single silver-palladium alloy nanowire electrode and preparation method and application thereof |
| CN111661814A (en) * | 2020-05-26 | 2020-09-15 | 上海交通大学 | Multifunctional integrated ultramicro/nano electrode and preparation method thereof |
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| CN111661814B (en) * | 2020-05-26 | 2022-09-23 | 上海交通大学 | Multifunctional integrated ultramicro/nano electrode and preparation method thereof |
| CN113884554A (en) * | 2021-10-27 | 2022-01-04 | 中国科学院过程工程研究所 | Method for preparing size-controllable nano needle type electrode |
| CN115464511A (en) * | 2022-09-19 | 2022-12-13 | 厦门大学 | Device integrating multi-channel aperture detection and nanopore preparation and using method thereof |
| CN115464511B (en) * | 2022-09-19 | 2023-08-01 | 厦门大学 | Device integrating multi-channel aperture detection and nanopore preparation and application method thereof |
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