CN108828037A - A kind of gold nano electrode and preparation method thereof - Google Patents
A kind of gold nano electrode and preparation method thereof Download PDFInfo
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Abstract
The present invention provides a kind of gold nano electrode and preparation method thereof, belongs to high molecular material and electrochemical field.This method is first to prepare naked gold nano electrode；Then utilize heating device that polyurethane particles melting and solidification on naked gold nano electrode, is obtained gold nano electrode.The present invention also provides the gold nano electrodes that above-mentioned preparation method obtains.Method room temperature of the invention can cool down, and shaping speed is fast, good reproducibility and stability.It is tested by electrochemical cyclic voltammetry, " S " type curve of available approximation nano-electrode, the size of current order of magnitude also can control 10‑8A is even lower, and minimum can achieve 10‑10A or so, what gold nano electrode of the invention can be stable is present in 18.2M Ω * cm ultrapure water, in ethanol solution and in 1*PBS buffer solution, has extraordinary stability.
Description
Technical field
The invention belongs to high molecular materials and electrochemical field, and in particular to a kind of gold nano electrode and preparation method thereof.
Background technique
Microelectrode is applied in the research of cell exocytosis release by Wightman in 1988 for the first time, and is proposed using micro machine
Electrochemical method is come to carry out on-line real time monitoring cell exocytosis situation be a kind of extraordinary method.Later, at 1999 or so,
The microns electrode such as gold, platinum is constantly manufactured, and when by 2005 or so, can monitor dopamine using carbon fiber electrode
Presence.Noble metal electrode is such as after 2007：Gold, platinum etc. just gradually develop.Increasingly developed with the epoch, people are to electrode
Preparation require it is also higher and higher, it is also higher and higher to the performance requirement of electrode, the substance of monitoring also by macroscopic view amount, develop to
Monitor trace materials.
These years, the packaging method of the main Electrode of people, so that range of the tip of gold nano electrode in nanogold
It is interior, in terms of to the exposed area for reducing nano-electrode, there are many method, but in the stability of electrode and repeatability upper one
Directly it is difficult to improve.Polyurethane (TPU) material has preferable glutinous viscosity, in 4 DEG C of refrigerators, room temperature be even higher than room temperature
Under can be stabilized without falling off from electrode, and in aqueous solution, can be stabilized in ethanol solution, electricity
Chemical property will not be interfered.Compared to current using the gimmick sealed with wax, using polyurethane particles melting plastic packaging can once at
Type.
Summary of the invention
The purpose of the invention is to provide a kind of gold nano electrode and preparation method thereof, it is intended to reduce gold nano electrode
Effective electrode area, improves the detection sensitivity of gold nano electrode, and keeps preferable stability, meanwhile, the preparation method work
Skill is simple, at low cost.
Present invention firstly provides a kind of preparation method of gold nano electrode, including it is as follows：
Step 1: preparing naked gold nano electrode；
Step 2: using heating device by polyurethane particles melting and solidification on naked gold nano electrode, obtain gold nano electricity
Pole.
Preferably, the naked gold nano electrode of the step one is to use dehydrated alcohol-HCl solution and spun gold for original
Material, is prepared by the method for electrochemical corrosion.
Preferably, the step one is specially：
1) dehydrated alcohol and hydrochloric acid solution are mixed, obtains corrosive liquid；
2) spun gold is taken, is fixed on corrosion rack, AC power source and oscillograph are corroded in connection, ammeter registration
Control is in 10~15.0 μ A, and etching time is 40s~50s, corrosion potentials 25V~27V, corrodes frequency 4.2kHz, and cleaning obtains
Naked gold nano electrode.
Preferably, the volume ratio of the dehydrated alcohol and hydrochloric acid solution is 1：1.
Preferably, the spun gold length is 1cm.
Preferably, the cleaning step is：It is clean with 18.2M Ω * cm ultrapure water, it is put into plasma cleaner
Middle clean the surface sundries cleans 5~10min.
Preferably, the step two is specially：Heating device is built, polyurethane particles are put on warm table and are added
Naked gold nano electrode is fixed on liftable bracket by heat after melting it, and electrode passes through the urethane solid melted
Particle, eletrode tip cover a strata urethane, stop rising bracket after tip is stretched out, take out, be cooled to room temperature, obtain Jenner
Rice electrode.
Preferably, the heating device include power supply, intelligent temperature control instrument, liftable support, iron stand, thermocouple and
Warm table, the iron stand are L-type, and liftable support is fixed on the cross bar of iron stand, and thermocouple is fixed on iron stand
On vertical bar, thermocouple one end connects warm table, and intelligent temperature control instrument is electrically connected with thermocouple and warm table respectively, power supply and intelligence control
Warm instrument electrical connection；For the liftable support for placing naked gold nano electrode, through-hole is arranged in warm table bottom, poly- for placing
Urethane fixes particle, and the naked gold nano electrode passes through the fixed particle of the polyurethane melted by through-hole.
Preferably, the heating temperature is 170~190 DEG C.
The present invention also provides the gold nano electrodes that above-mentioned preparation method obtains.
Beneficial effects of the present invention
The present invention provides a kind of gold nano electrode and preparation method thereof, this method is to utilize urethane solid particle fusion
After wrapped up, can be in a molten state when polyurethane particles are at 170~190 DEG C, thus be conducive to gold electrode tip it is smooth
Pass through, and polyurethane can be both cooled and shaped at room temperature with rapid desufflation, can be substantially reduced the preparation time of single electrode,
Improve working efficiency.Method room temperature of the invention can cool down, and shaping speed is fast, good reproducibility and stability.By electrochemistry
Cyclic voltammetry test, " S " type curve of available approximation nano-electrode, the size of current order of magnitude also can control 10-8A
Even lower, minimum can achieve 10-10A or so, the electrochemical profiles obtained by cyclic voltammetric are as a result, can substantially calculate
The effective electrode area size of gold nano eletrode tip out.Single active somatic cell generally only has 300nm, and electrode is to entering cell
Substance therein is detected, eletrode tip must be sufficiently small, only when eletrode tip area very little, just can apply to cell etc.
In bioelectric detection, for can just detect its small curent change in the research of the bioactivity of individual cells, together
When electrode can also be further processed, have reached the purpose of other specific detections.And polyurethane has gold nano electrode
Glutinous viscosity well, can be very good to be attached to gold nano electrode surface, and can be stable to be present in 18.2M Ω * cm ultrapure
In water, in ethanol solution and in 1*PBS buffer solution, there is extraordinary stability.
Detailed description of the invention
Fig. 1 is the optical imagery of naked gold nano electrode prepared by the embodiment of the present invention 1；
Fig. 2 is scanning electron microscope (SEM) figure of naked gold nano electrode prepared by the embodiment of the present invention 1；
Fig. 3 is polyurethane TGA curve graph；
Fig. 4 is the eletrode tip effective area normal distribution for the gold nano electrode that the embodiment of the present invention 1 is prepared；
Fig. 5 is the gold nano electrode circulation that continuous dipping measures in the distilled water volt that the embodiment of the present invention 1 is prepared
Pacify characteristic curve；
Fig. 6 is gold nano electrode continuous dipping measurement in ethanol solution that the embodiment of the present invention 1 is prepared
Electrochemistry Cyclic voltamogram curve；
Fig. 7 is gold nano electrode continuous dipping measurement in 1*PBS buffer solution that the embodiment of the present invention 1 is prepared
Cyclic voltamogram curve；
Fig. 8 is that the gold nano electrode that the embodiment of the present invention 1 is prepared continuously measures 4 atmospheric electricity chemical cycle C-V characteristics songs
Line；
Fig. 9 is the structural schematic diagram of heating device of the present invention.
In figure, 1, power supply, 2, intelligent temperature control instrument, 3, iron stand, 4, liftable support, 5, thermocouple, 6, warm table, 7, naked
Gold nano electrode.
Specific embodiment
In order to further appreciate that the present invention, the preferred embodiments of the invention are described below with reference to embodiment, but
It is it should be appreciated that these descriptions only require the invention patent to further illustrate the features and advantages of the present invention
Limitation.
Present invention firstly provides a kind of preparation method of gold nano electrode, including it is as follows：
Step 1: preparing naked gold nano electrode；
Step 2: using warm table by polyurethane particles melting and solidification on naked gold nano electrode, obtain gold nano electrode.
According to the present invention, the naked gold nano electrode of the step one is to use dehydrated alcohol-HCl solution and spun gold for original
Material, is prepared, specially by the method for electrochemical corrosion：
1) dehydrated alcohol and hydrochloric acid solution are mixed, obtains corrosive liquid；The volume of the dehydrated alcohol and hydrochloric acid solution
Than being preferably 1：1.
2) spun gold is taken, is fixed on corrosion rack, AC power source and oscillograph are corroded in connection, ammeter registration
Control is in 10~15.0 μ A, and etching time is 40~50s, corrosion potentials 25V~27V, corrodes frequency 4.2kHz, and cleaning obtains
Naked gold nano electrode, the spun gold length are preferably 1cm, diameter 0.25mm, source be it is commercially available, be selected from Chinese medicines group.
According to the present invention, the corrosion rack can enter convenient for spun gold and exit corrosive liquid, and operate with oscilaltion
Simply, easily controllable, current value that used ammeter is shown tentatively to judge to corrode shape, general initial current control 10~
15.0 μ A or so, etching time carry out echo when ammeter is shown in 40~50s or so by manual time-keeping, about required time
It is preferable that shape can be corroded when dynamic with preliminary proof, indicate that corrosion terminates when the registration of ammeter is reduced to 0A, to ensure to prepare
Gold electrode it is available, be typically prepared and needed to clean immediately, it is preferably clean with 18.2M Ω * cm ultrapure water, be put into plasma
Clean the surface sundries in cleaning machine, preferably at " pencil-shaped ", this is also conducive to the package experiment of lower step to 5~10min of cleaning.
According to the present invention, the step two is specially：Heating device is built, the heating device was as shown in figure 9, should
Device includes power supply 1, intelligent temperature control instrument 2, liftable support 4, iron stand 3, thermocouple 5 and warm table 6, the iron stand 3
For L-type, liftable support 4 is fixed on the cross bar of iron stand 3, and thermocouple 5 is fixed on the vertical bar of iron stand 3, thermocouple 5 one
End connection warm table 6, intelligent temperature control instrument 2 are electrically connected with thermocouple 5 and warm table 6 respectively, and power supply 1 and intelligent temperature control instrument 2 are electrically connected
It connects；The liftable support 4 is for placing naked gold nano electrode 7, and through-hole is arranged in 6 bottom of warm table, for placing polyurethane
The diameter of fixed particle, the fixed particle of the polyurethane is greater than the diameter of through-hole, and the naked gold nano electrode 7 passes through through-hole
Across the fixed particle of polyurethane melted.The source of the intelligent temperature control instrument 2 be it is commercially available, be not particularly limited, act on
It is the heating temperature for regulating and controlling thermocouple 5 by the feedback system in intelligent temperature control instrument 2, makes the fixed particle fusion of polyurethane, prevent
Temperature is excessively high, damages encapsulating material.
According to the present invention, polyurethane particles are put on warm table and are heated, the heating temperature is preferably 170-190
DEG C, after melting it, naked gold nano electrode is fixed on liftable fixed bracket, electrode flow slowly over melted it is poly-
Urethane solid particle, this process are greater than 5s, at this point, eletrode tip will cover a strata urethane, after its cooling, tip can be by
In polyurethane cooling resilience and shrink, expose tip, stop rising fixed bracket after tip is stretched out, take out, it is cooling
To room temperature, so that the encapsulation of complete paired electrode, obtains gold nano electrode.For the process time-consuming within 1min, preparation is very quick,
And one step forming will be put into closed enclosure after having prepared to prevent eletrode tip from falling into dust.
Using polyurethane package gold electrode to make eletrode tip effective area reduce, urethane raw derives from the present invention
Bayer Bitterfeld GmbH 3970D.
The present invention also provides the gold nano electrodes that above-mentioned preparation method obtains.
Gold nano electrode after resulting package is subjected to preliminary characterization using electrochemical means, has verified that gold nano
Whether electrode preparation succeeds, and embodiments step includes：
C1, the gold nano electrode dehydrated alcohol prepared is rinsed 2 times, then dry with 18.2M Ω * cm ultrapure water
Only, it is dried up, is then placed in configured good electrolyte with argon gas later, carry out electro-chemical test.
C2, gold nano electrode is put into 1mL water impregnates first, every 1h carries out primary electrochemical test, record experiment knot
Fruit；
C3, it is secondly put into 1mL ethanol solution and impregnates, every 1h carries out primary electrochemical test, records experimental result；
C4, it is finally putting into 1*PBS solution and impregnates, every 1h carries out primary electrochemical test, records experimental result.
C2~C4 step, it is measurement 6 times continuous.
C5, primary electrochemical test is carried out daily to packaged electrode later, continuous measurement 4 days records experimental result.
C6, it is measured again into primary electrochemical after 15 days, with Comparative result before.
The soaking solution water is the ultrapure water of 18.2M Ω * cm, and dehydrated alcohol is that analysis is pure, and 1*PBS buffer solution is
PH=7.30 (at 25 DEG C), impregnates required amount and is all made of 1mL.The electrolytic solution cell that electro-chemical test uses is logical argon deoxygenation
Potassium ferrocyanide and Klorvess Liquid, wherein potassium ferrocyanide is 100mM, Klorvess Liquid 1M.Corrosive liquid uses anhydrous second
Alcohol-HCl by volume 1:1 configuration.
Above-mentioned characterizing method mainly probe into using polyurethane wrap up gold electrode after electrochemical behavior and its
The situation of change of electrochemical source of current after being impregnated for a long time in 18.2M Ω * cm ultrapure water, dehydrated alcohol and 1*PBS buffer solution,
It finds, after one step package method of polyurethane package, is immersed in three of the above solution after a period of time, electrification after study
It is not fairly obvious to learn curent change, does not have big deviation in current values, it is basic it is considered that gold electrode and its tip it is poly-
Urethane can be stable in the presence of in 18.2M Ω * cm ultrapure water, dehydrated alcohol and 1*PBS buffer solution.Nano-electrode tip has
Effect electrode area will not change because of being immersed in three of the above solution, and what polyurethane can be stable is attached to gold electrode
On, the case where without expanding, separating and fall off.It can guarantee the stability of electrode well.Method of the invention
It is simple with the characteristics of reproducibility and stability for improving the preparation of gold nano electrode, raising is prepared into power and operation preparation,
Low-cost advantage.
Below by specific embodiment, the present invention is described in detail.
Embodiment 1
A, the preparation of naked gold nano electrode
(1), the configuration of corrosive liquid：According to V(HCl)：V(C2H5OH)=1:1 proportional arrangement 20mL is as in glass surface ware；
(2), 1cm long spun gold is taken, is fixed on corrosion rack, AC power source and oscillograph are corroded in connection, electricity
The control of flow table registration corrodes frequency 4.2kHz in 15.0 μ A, etching time 45s, corrosion potentials 26V；
(3), clean with 18.2M Ω * cm ultrapure water, it is put into clean the surface sundries in plasma cleaner, is cleaned
8min obtains the naked gold nano electrode of clean surface；
B, the package preparation of gold nano electrode
(1) preparation：Polyurethane particles are put into 18.2M Ω * cm ultrapure water and carry out ultrasonic cleaning 5min, are then put
Enter in baking oven and dry, baking oven set temperature is 90 DEG C.
(2), it is put into the urethane solid particle being cleaned in thermal station, starts heating device, rises to 170 to temperature
DEG C when hang on, polyurethane can melt, and later slowly rise the bracket for fixing naked gold nano electrode fast to tip
Stop rising bracket when exposing, is slowly taken out from thermal station, be cooled to room temperature and obtain gold nano electrode.
The above-mentioned gold nano electrode being prepared is characterized, specially：
(1), electrochemical electrolysis liquid is configured, electrolyte contains 100mM potassium ferrocyanide and 1M KCl, distinguished with electronic balance
422mg potassium ferrocyanide is weighed, 74.5mg KCl is dissolved in 10mL 18.2M Ω * cm ultrapure water, and mixing is equal until completely dissolved
It is even, then carry out logical argon gas deoxygenation 5min；
(2), the gold nano electrode prepared is first used washes of absolute alcohol 2~3 times, then clear with 18.2M Ω * cm ultrapure water
It washes one time, removes the impurity such as remaining ethyl alcohol of previous step, then with being dried with nitrogen
(3), the gold nano electrode wrapped cleaned up is put into the liquid of configured electrochemistry bottom and carries out circulation volt
Peace test.Test potential range selects 0~+0.6V, and sweeping speed is 10mV/s.It is carried out continuously repetitive operation in 4 days, test gold nano electricity
The stability of pole.
It is carried out continuously repetitive operation in four days, sees whether electrode performance is stable.
(4) electrode that will be cleaned is respectively put into 1mL water, in 1mL dehydrated alcohol and in 1mL 1*PBS solution, every leaching
It steeps 1h to test 1 time, continuous measurement 6 times, sees whether electrode can be stabilized in water, in dehydrated alcohol and in 1*PBS solution,
The growing environment and experimental situation of cell are generally all under water environment, and under 1*PBS environment, dehydrated alcohol is to cell culture and survey
Carry out disinfection processing before examination, it is therefore desirable to the electrode performance of test preparation is carried out in three of the above solution.
Fig. 1 is the optical imagery of naked gold nano electrode prepared by the embodiment of the present invention 1, and figure a is the figure under optical microscopy
Picture, figure b is image under dark field optical microscope, it will be seen from figure 1 that naked gold nano electrode corrosion surface relatively light of the invention
Cunning is smooth, and tip is very sharp keen.
Fig. 2 is scanning electron microscope (SEM) figure of naked gold nano electrode prepared by the embodiment of the present invention 1.Figure it is seen that
Gold electrode corrosion surface is relatively smooth, and size reaches 300nm or less.
From the figure 3, it may be seen that sample is more stable at 200 DEG C or less weightlessness does not occur for Fig. 3 for polyurethane TGA curve graph,
When temperature reaches 220 DEG C, weightless loss occurs for sample, has moiety by weight loss, shows that sample is decomposed, there are unstable
Property.For the benefit of experimental implementation guarantees that sample is stablized, we select within the scope of 170~190 DEG C, can both guarantee sample in this way
Melting does not damage sample itself structure also.
Fig. 4 is the eletrode tip effective area normal distribution for the gold nano electrode that the embodiment of the present invention 1 is prepared, from
As can be seen that the effective area of eletrode tip is about distributed in 0~1 μm in Fig. 42Between, specific value about exists by calculating
0.05~0.8 μm2Left and right, as long as controlling encapsulation link, that is, can effectively reduce the effective area size of electrode.
Fig. 5 is the gold nano electrode circulation that continuous dipping measures in the distilled water volt that the embodiment of the present invention 1 is prepared
Pacifying characteristic curve, a represents first time test result in curve, and b represents second of test result, and c represents third time test result,
D represents the 4th test result, and e represents the 5th test result, and f represents the 6th test result, and g represents the 7th test knot
Fruit, every immersion 1h test is primary, and continuous dipping 6h, co-continuous test 6 times, sweep speed 10mV/s, scanning potential range is 0
~+0.6V.It is found by 6 tests, peak current size has small variation, about differs several nA, in error range, do not have
There is the deviation of the order of magnitude, why curve is not completely coincident other than the error of instrument itself, and there are also the loss of electrode, solution
The reasons such as it is oxidized.But it can be seen that its peak current size can be stablized 10 from the general trend of curve-8On the order of magnitude, table
It is bright that there is good insulating properties, stability and repetition using the gold nano electrode of polyurethane package in 18.2M Ω * cm ultrapure water
Property, retention property it can stablize in 18.2M Ω * cm distilled water.
Fig. 6 is gold nano electrode continuous dipping measurement in ethanol solution that the embodiment of the present invention 1 is prepared
Electrochemistry Cyclic voltamogram curve, a represents first time test result in curve, and b represents second of test result, and c represents
Test result three times, d represent the 4th test result, and e represents the 5th test result, and f represents the 6th test result, g generation
The 7th test result of table, every immersion 1h are tested 1 time, continuous dipping 6h, sweep speed 10mV/s, and potential range is 0~+
0.6V, co-continuous test 6 times find that electric current has small variation, about differs several nA, in error model by 6 tests
In enclosing, why the deviation of the order of magnitude, curve are not completely coincident other than the error of instrument itself, and there are also the damages of electrode
Consumption, electrolyte such as are oxidized at the reasons.But it can be seen that its peak current size can be stablized 10 from the general trend of curve-8Number
In magnitude, show in ethanol solution using polyurethane package gold nano electrode have good insulating properties, stability and
Repeatability retention property can be stablized in ethanol solution.
Fig. 7 is gold nano electrode continuous dipping measurement in 1*PBS buffer solution that the embodiment of the present invention 1 is prepared
Cyclic voltamogram curve, a represents first time test result in curve, and b represents second of test result, and c represents third time and surveys
Test result, d represent the 4th test result, and e represents the 5th test result, and f represents the 6th test result, and g represents the 7th
Secondary test result, every immersion 1h are tested 1 time, continuous dipping 6h, sweep speed 10mV/s, and potential range is 0~+0.6V, altogether
It follow-on test 6 times, is found by 6 tests, electric current has small variation, about difference several Naans of zero point, in error model
In enclosing, why the deviation of the order of magnitude, curve are not completely coincident other than the error of instrument itself, and there are also the damages of electrode
Consumption, electrolyte such as are oxidized at the reasons.But it can be seen that its peak current size can be stablized 10 from the general trend of curve-9Number
In magnitude, show in 1*PBS buffer solution using polyurethane package gold nano electrode have good insulating properties, stability and
Repeatability retention property can be stablized in 1*PBS buffer solution.
Fig. 8 is that the gold nano electrode that the embodiment of the present invention 1 is prepared continuously measures 4 atmospheric electricity chemical cycle C-V characteristics songs
Line, a represents first time test result in curve, and b represents second of test result, and c represents third time test result, and d represents
Four test results measure in the same time daily, prepare identical electrochemical electrolysis liquid daily, equally carry out logical argon gas and remove
Oxygen leads to 5~10min every time, takes out after testing every time, and the salt for cleaning surface remaining with 18.2M Ω * cm ultrapure water is molten
Liquid is put into closed conserving case after being dried with nitrogen, and is then placed in 4 DEG C of refrigerators, is kept in dark place.Before second is tested, take out
Gold nano electrode surface is cleaned again with 18.2M Ω * cm distilled water, with carrying out after being dried with nitrogen, electro-chemical test, continuous 4 days
Identical operation is carried out, and result is aggregated, as shown in figure 8, electrode has repeatability well, is presented always
" S " type can reuse within the time for saving several days, have small variation in the numerical values recited of electric current certainly, but
The variation of the order of magnitude is not interfered with, its variation can be ignored, the tip effective area of electrode not will increase, will not be to electrode
Application have an impact.Illustrate to wrap up gold nano electrode using melt polyurethane, will not fall off, separate, the variation such as aging,
Show that there is good insulating properties, stability and repeatability using polyurethane package gold nano electrode, it can long-time retentivity
It can stablize.
Embodiment 2
A, the preparation of naked gold nano electrode
(1), the configuration of corrosive liquid：According to V(HCl)：V(C2H5OH)=1:1 proportional arrangement 20mL is as in glass surface ware；
(2), 1cm long spun gold is taken, is fixed on corrosion rack, AC power source and oscillograph are corroded in connection, electricity
The control of flow table registration corrodes frequency 4.2kHz in 10.0 μ A, etching time 40s, corrosion potentials 25V；
(3), clean with 18.2M Ω * cm ultrapure water, it is put into clean the surface sundries in plasma cleaner, is cleaned
5min obtains the naked gold nano electrode of clean surface；
B, the package preparation of gold nano electrode
(1) preparation：Polyurethane particles are put into 18.2M Ω * cm ultrapure water and carry out ultrasonic cleaning 5min, are then put
Enter in baking oven and dry, baking oven set temperature be 80 DEG C can be with.
(2), it is put into the urethane solid particle being cleaned in thermal station, starts heating device, rises to 170 to temperature
DEG C when hang on, polyurethane can melt, and later slowly rise the bracket for fixing naked gold nano electrode fast to tip
Stop rising bracket when exposing, is slowly taken out from thermal station, be cooled to room temperature and obtain gold nano electrode.
Embodiment 3
A, the preparation of naked gold nano electrode
(1), the configuration of corrosive liquid：According to V(HCl)：V(C2H5OH)=1:1 proportional arrangement 20mL is as in glass surface ware；
(2), 1cm long spun gold is taken, is fixed on corrosion rack, AC power source and oscillograph are corroded in connection, electricity
The control of flow table registration corrodes frequency 4.2kHz in 15.0 μ A, etching time 50s, corrosion potentials 27V；
(3), clean with 18.2M Ω * cm ultrapure water, it is put into clean the surface sundries in plasma cleaner, is cleaned
10min obtains the naked gold nano electrode of clean surface；
B, the package preparation of gold nano electrode
(1) preparation：Polyurethane particles are put into 18.2M Ω * cm ultrapure water and carry out ultrasonic cleaning 5min, are then put
Enter in baking oven and dry, baking oven set temperature be 100 DEG C can be with.
(2), it is put into the urethane solid particle being cleaned in thermal station, starts heating device, rises to 170 to temperature
DEG C when hang on, polyurethane can melt, and later slowly rise the bracket for fixing naked gold nano electrode fast to tip
Stop rising bracket when exposing, is slowly taken out from thermal station, be cooled to room temperature and obtain gold nano electrode.
In conclusion preparation method of the present invention using polyurethane package gold nano electrode, polyurethane wrap up gold nano electricity
After extremely, can in 18.2M Ω * cm ultrapure water, in ethanol solution and can be stable in 1*PBS buffer solution deposit
The use of electrode will not had an impact, and place 4 days, still be able to maintain good state.Polyurethane wraps up gold nano
Electrode has certain stability.The method comprises the steps of firstly, preparing gold nano electrodes, then wrap up gold nano electrode using polyurethane, most
The gold nano electrode of polyurethane package is made afterwards.The package of the polyurethane can play good insulation performance, Hai Neng
In 18.2M Ω * cm ultrapure water, in ethanol solution and can be with gold nano electrode seal in 1*PBS buffer solution
It is attached onto, without falling off or generating surface defect, and polyurethane can reach molten in a short time
State, encapsulation is convenient, and fast, a step can be completed.It can be substantially reduced the time for preparing electrode in this way, and polyurethane can be grown
The preservation of time has good stability, and raw material sources are extensive, cheap, is conducive to operation, it is easy to realize.
The above description of the embodiment is only used to help understand the method for the present invention and its core ideas, it is noted that right
For those skilled in the art, without departing from the principle of the present invention, the present invention can also be carried out
Some improvements and modifications, these improvements and modifications also fall within the scope of protection of the claims of the present invention.
Claims (10)
1. a kind of preparation method of gold nano electrode, which is characterized in that including as follows：
Step 1: preparing naked gold nano electrode；
Step 2: using heating device by polyurethane particles melting and solidification on naked gold nano electrode, obtain gold nano electrode.
2. a kind of preparation method of gold nano electrode according to claim 1, which is characterized in that the step one it is naked
Gold nano electrode is to use dehydrated alcohol-HCl solution and spun gold for raw material, is prepared by the method for electrochemical corrosion.
3. a kind of preparation method of gold nano electrode according to claim 1 or 2, which is characterized in that the step one
Specially：
1) dehydrated alcohol and hydrochloric acid solution are mixed, obtains corrosive liquid；
2) spun gold is taken, is fixed on corrosion rack, AC power source and oscillograph are corroded in connection, the control of ammeter registration
In 10~15.0 μ A, etching time is 40s~50s, corrosion potentials 25V~27V, corrodes frequency 4.2kHz, and cleaning obtains naked gold
Nano-electrode.
4. a kind of preparation method of gold nano electrode according to claim 3, which is characterized in that the dehydrated alcohol and
The volume ratio of hydrochloric acid solution is 1：1.
5. a kind of preparation method of gold nano electrode according to claim 3, which is characterized in that the spun gold length is
1cm。
6. a kind of preparation method of gold nano electrode according to claim 3, which is characterized in that the cleaning step
For：It is clean with 18.2M Ω * cm ultrapure water, it is put into clean the surface sundries in plasma cleaner, cleans 5~10min.
7. a kind of preparation method of gold nano electrode according to claim 1, which is characterized in that the step two is specific
For：Heating device is built, polyurethane particles are put on warm table and are heated, after melting it, naked gold nano electrode is fixed on
On liftable bracket, electrode passes through the urethane solid particle melted, and eletrode tip covers a strata urethane, to tip
Stop rising bracket after stretching, takes out, be cooled to room temperature, obtain gold nano electrode.
8. a kind of preparation method of gold nano electrode according to claim 7, which is characterized in that the heating device packet
Include power supply (1), intelligent temperature control instrument (2), liftable support (4), iron stand (3), thermocouple (5) and warm table (6), the iron
Pallet (3) is L-type, and liftable support (4) is fixed on the cross bar of iron stand (3), and thermocouple (5) is fixed on iron stand (3)
On vertical bar, thermocouple (5) one end connects warm table (6), and intelligent temperature control instrument (2) is electrically connected with thermocouple (5) and warm table (6) respectively
It connects, power supply (1) and intelligent temperature control instrument (2) electrical connection；The liftable support (4) adds for placing naked gold nano electrode (7)
Through-hole is arranged in thermal station (6) bottom, and for placing the fixed particle of polyurethane, the naked gold nano electrode (7) is passed through by through-hole
The fixed particle of the polyurethane melted.
9. a kind of preparation method of gold nano electrode according to claim 7, which is characterized in that the heating temperature is
170~190 DEG C.
10. the gold nano electrode that preparation method described in claim 1 obtains.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110297019A (en) * | 2019-06-26 | 2019-10-01 | 中国石油大学(华东) | A kind of pen holder type can carry probe preparation, sealing, opening, assembling and its design method |
| CN113189156A (en) * | 2021-03-23 | 2021-07-30 | 中国石油大学(华东) | Manual control device for probe tip sealing and opening and using method thereof |
| CN115376756A (en) * | 2022-07-29 | 2022-11-22 | 华南理工大学 | Stable electric control supercooling phase change embedded electrode based on melting solidification method and preparation method thereof |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS63173574A (en) * | 1987-01-13 | 1988-07-18 | Nok Corp | Electrode for cell fusion |
| JP2007021974A (en) * | 2005-07-20 | 2007-02-01 | Toray Ind Inc | Metallized film |
| CN1963485A (en) * | 2006-10-25 | 2007-05-16 | 浙江大学 | Needle biosensor based on carbon nano tube and manufacturing method of the same |
| CN102141451A (en) * | 2011-04-06 | 2011-08-03 | 东北大学 | Method for developing flexible pressure sensitive probe with side electrode |
| CN102392069A (en) * | 2011-10-25 | 2012-03-28 | 常熟理工学院 | Method for rapid detection of total number of bacterial colonies based on functionalized nano-gold electrode |
| CN103446665A (en) * | 2013-08-29 | 2013-12-18 | 河南理工大学 | Implanted flexible biological electrode and manufacturing method thereof |
-
2018
- 2018-06-26 CN CN201810669939.5A patent/CN108828037B/en not_active Expired - Fee Related
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS63173574A (en) * | 1987-01-13 | 1988-07-18 | Nok Corp | Electrode for cell fusion |
| JP2007021974A (en) * | 2005-07-20 | 2007-02-01 | Toray Ind Inc | Metallized film |
| CN1963485A (en) * | 2006-10-25 | 2007-05-16 | 浙江大学 | Needle biosensor based on carbon nano tube and manufacturing method of the same |
| CN102141451A (en) * | 2011-04-06 | 2011-08-03 | 东北大学 | Method for developing flexible pressure sensitive probe with side electrode |
| CN102392069A (en) * | 2011-10-25 | 2012-03-28 | 常熟理工学院 | Method for rapid detection of total number of bacterial colonies based on functionalized nano-gold electrode |
| CN103446665A (en) * | 2013-08-29 | 2013-12-18 | 河南理工大学 | Implanted flexible biological electrode and manufacturing method thereof |
Non-Patent Citations (1)
| Title |
|---|
| 邹文君等: "电化学腐蚀制备纳米级间距的金电极对", 《高等学校化学学报》 * |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110297019A (en) * | 2019-06-26 | 2019-10-01 | 中国石油大学(华东) | A kind of pen holder type can carry probe preparation, sealing, opening, assembling and its design method |
| CN110297019B (en) * | 2019-06-26 | 2021-08-06 | 中国石油大学(华东) | Preparation, sealing, opening and assembling of pen-tube type portable probe and design method thereof |
| CN113189156A (en) * | 2021-03-23 | 2021-07-30 | 中国石油大学(华东) | Manual control device for probe tip sealing and opening and using method thereof |
| CN115376756A (en) * | 2022-07-29 | 2022-11-22 | 华南理工大学 | Stable electric control supercooling phase change embedded electrode based on melting solidification method and preparation method thereof |
| CN115376756B (en) * | 2022-07-29 | 2023-06-20 | 华南理工大学 | Preparation method of stable electric control supercooling phase change mosaic electrode based on melting solidification method |
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