CN108828037B - Gold nano electrode and preparation method thereof - Google Patents
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Abstract
The invention provides a gold nano electrode and a preparation method thereof, belonging to the fields of high polymer materials and electrochemistry. The method comprises the steps of firstly preparing a bare gold nano electrode; then useAnd melting and solidifying the polyurethane particles on the bare gold nano-electrode by using a heating device to obtain the gold nano-electrode. The invention also provides the gold nano-electrode prepared by the preparation method. The method can be cooled at room temperature, and has the advantages of high forming speed, good reproducibility and stability. The electrochemical cyclic voltammetry test can obtain an S-shaped curve similar to a nano electrode, and the magnitude order of the current can be controlled to be 10‑8A is even lower and can reach 10 at the minimum‑10And A is about right, the gold nano-electrode can stably exist in 18.2M omega cm ultrapure water, absolute ethyl alcohol solution and 1 PBS buffer solution, and has very good stability.
Description
Technical Field
The invention belongs to the fields of high polymer materials and electrochemistry, and particularly relates to a gold nano electrode and a preparation method thereof.
Background
Wightman first applied microelectrodes to the research on exocytosis release of cells in 1988, and proposed that online real-time monitoring of the exocytosis of cells by using a micromotor electrochemical method is a very good method. Later, around 1999, micron electrodes such as gold and platinum were manufactured, and as of around 2005, the presence of dopamine was monitored using carbon fiber electrodes. Noble metal electrodes such as: gold, platinum, etc. have been developed. With the increasing development of times, people have higher and higher requirements on the preparation of electrodes and the performance of the electrodes, and monitored substances are developed to be monitored from macroscopic quantities to trace substances.
In these years, the encapsulation method of the electrode has been mainly studied so that the tip of the gold nano-electrode is in the range of nano-gold, and there are various methods for reducing the exposed area of the nano-electrode, but it has been difficult to improve and enhance the stability and the reproducibility of the electrode. The Polyurethane (TPU) material has good viscosity, can stably exist in a refrigerator at 4 ℃ and at room temperature or even above room temperature without falling off from an electrode, can stably exist in an aqueous solution and an absolute ethyl alcohol solution, and has no interference on electrochemical performance. Compared with the existing wax sealing method, the method can be used for one-step molding by using polyurethane particle melting plastic sealing.
Disclosure of Invention
The invention aims to provide a gold nano electrode and a preparation method thereof, and aims to reduce the effective electrode area of the gold nano electrode, improve the detection sensitivity of the gold nano electrode, keep better stability, and meanwhile, the preparation method has simple process and low cost.
The invention firstly provides a preparation method of a gold nano electrode, which comprises the following steps:
step one, preparing a bare gold nano electrode;
and step two, melting and solidifying polyurethane particles on the bare gold nano-electrode by using a heating device to obtain the gold nano-electrode.
Preferably, the bare gold nano-electrode in the first step is prepared by adopting an absolute ethyl alcohol-HCl solution and a gold wire as raw materials through an electrochemical corrosion method.
Preferably, the first step is specifically:
1) mixing absolute ethyl alcohol and a hydrochloric acid solution to obtain a corrosive liquid;
2) and (3) taking a gold wire, fixing the gold wire on a corrosion frame, connecting an alternating current power supply and an oscilloscope for corrosion, controlling the current representation number to be 10-15.0 mu A, the corrosion time to be 40-50 s, the corrosion voltage to be 25-27V and the corrosion frequency to be 4.2kHz, and cleaning to obtain the bare gold nano electrode.
Preferably, the volume ratio of the absolute ethyl alcohol to the hydrochloric acid solution is 1: 1.
preferably, the length of the gold wire is 1 cm.
Preferably, the cleaning step is: and (3) washing the substrate by using 18.2M omega cm of ultrapure water, putting the substrate into a plasma cleaning machine to clean impurities on the surface for 5-10 min.
Preferably, the second step is specifically: and (2) building a heating device, putting polyurethane particles on a heating table for heating, after the polyurethane particles are melted, fixing the bare gold nano-electrode on a liftable support, enabling the electrode to penetrate through the melted polyurethane solid particles, covering a layer of polyurethane on the tip of the electrode, stopping lifting the support after the tip extends out, taking out, and cooling to room temperature to obtain the gold nano-electrode.
Preferably, the heating device comprises a power supply, an intelligent temperature controller, a lifting support, an iron stand, a thermocouple and a heating table, wherein the iron stand is L-shaped, the lifting support is fixed on a cross bar of the iron stand, the thermocouple is fixed on a vertical bar of the iron stand, one end of the thermocouple is connected with the heating table, the intelligent temperature controller is respectively and electrically connected with the thermocouple and the heating table, and the power supply is electrically connected with the intelligent temperature controller; the lifting support is used for placing bare gold nano-electrodes, the bottom of the heating table is provided with through holes used for placing polyurethane fixing particles, and the bare gold nano-electrodes penetrate through the melted polyurethane fixing particles through the through holes.
Preferably, the heating temperature is 170-190 ℃.
The invention also provides the gold nano-electrode prepared by the preparation method.
The invention has the advantages of
The invention provides a gold nano electrode and a preparation method thereof, wherein polyurethane solid particles are used for wrapping after being melted, and the polyurethane particles can be in a molten state at 170-190 ℃, so that the gold nano electrode is beneficial to smooth passing of the tips of the gold nano electrode, and the polyurethane can be rapidly shrunk, cooled and formed at room temperature, so that the preparation time of a single electrode can be greatly shortened, and the working efficiency is improved. The method can be cooled at room temperature, and has the advantages of high forming speed, good reproducibility and stability. The electrochemical cyclic voltammetry test can obtain an S-shaped curve similar to a nano electrode, and the magnitude order of the current can be controlled to be 10-8A is even lower and can reach 10 at the minimum-10And A, roughly calculating the effective electrode area size of the gold nano electrode tip through an electrochemical curve result obtained by cyclic voltammetry. The single living cell is generally only 300nm, and the electrode is about to enterThe cell can detect the substance therein, the electrode tip of the cell is small enough, only when the electrode tip area is small, the cell can be applied to the bioelectricity detection of cells and the like, the tiny current change can be detected in the research of the biological activity of a single cell, and meanwhile, the electrode can be further processed, so that the aim of other specific detection is achieved. And the polyurethane has good viscosity to the gold nano-electrode, can be well attached to the surface of the gold nano-electrode, can stably exist in 18.2M omega cm ultrapure water, absolute ethyl alcohol solution and 1 PBS buffer solution, and has good stability.
Drawings
FIG. 1 is an optical image of a bare gold nanoelectrode prepared in example 1 of the present invention;
FIG. 2 is a Scanning Electron Microscope (SEM) image of a bare gold nano-electrode prepared in example 1 of the present invention;
FIG. 3 is a polyurethane TGA graph;
FIG. 4 is a normal distribution diagram of the effective area of the electrode tip of the gold nanoelectrode prepared in example 1 of the present invention;
FIG. 5 is a cyclic voltammetry characteristic curve measured by continuous immersion of gold nano-electrodes prepared in example 1 of the present invention in distilled water;
FIG. 6 is a graph of electrochemical cyclic voltammetry characteristics of gold nano-electrodes prepared in example 1 of the present invention measured by continuous immersion in an absolute ethanol solution;
fig. 7 is a cyclic voltammetry characteristic curve measured by continuously soaking the gold nano-electrode prepared in example 1 of the present invention in 1 × PBS buffer solution;
FIG. 8 is a graph of electrochemical cyclic voltammetry characteristics of gold nano-electrodes prepared in example 1 of the present invention measured continuously for 4 days;
fig. 9 is a schematic structural view of the heating device of the present invention.
In the figure, 1, a power supply, 2, an intelligent temperature control instrument, 3, an iron support, 4, a lifting support, 5, a thermocouple, 6, a heating table, 7 and a bare gold nano electrode.
Detailed Description
For a further understanding of the invention, preferred embodiments of the invention are described below in conjunction with the examples, but it should be understood that these descriptions are included merely to further illustrate the features and advantages of the invention and are not intended to limit the invention to the claims.
The invention firstly provides a preparation method of a gold nano electrode, which comprises the following steps:
step one, preparing a bare gold nano electrode;
and step two, melting and solidifying polyurethane particles on the bare gold nano-electrode by using a heating table to obtain the gold nano-electrode.
According to the invention, the bare gold nano electrode in the first step is prepared by adopting an absolute ethyl alcohol-HCl solution and gold wires as raw materials through an electrochemical corrosion method, and specifically comprises the following steps:
1) mixing absolute ethyl alcohol and a hydrochloric acid solution to obtain a corrosive liquid; the volume ratio of the absolute ethyl alcohol to the hydrochloric acid solution is preferably 1: 1.
2) taking a gold wire, fixing the gold wire on a corrosion frame, connecting an alternating current power supply and an oscilloscope for corrosion, controlling the number of ammeter indications to be 10-15.0 muA, controlling the corrosion time to be 40-50 s, the corrosion voltage to be 25V-27V and the corrosion frequency to be 4.2kHz, and cleaning to obtain the bare gold nano electrode, wherein the length of the gold wire is preferably 1cm, the diameter of the gold wire is 0.25mm, the gold wire is commercially available and is selected from the group of national medicines.
According to the invention, the corrosion rack can be lifted up and down, so that gold wires can enter and exit a corrosion solution conveniently, the operation is simple and easy to control, the corrosion shape is preliminarily judged by using a current value displayed by an ammeter, the initial current is generally controlled to be about 10-15.0 muA, the corrosion time is timed by a stopwatch, the required time is about 40-50 s, the corrosion shape can be preliminarily proved to be better when the ammeter displays back and forth fluctuation, the corrosion termination is indicated when the number displayed by the ammeter is reduced to 0A, the prepared gold electrode is ensured to be usable, the gold electrode needs to be cleaned immediately after general preparation, and is preferably cleaned by using 18.2M omega cm ultra-pure water, and is put into a plasma cleaner to clean surface impurities, and is cleaned into a pencil shape for 5-10 min, and the next packaging experiment is facilitated.
According to the invention, the second step is specifically as follows: building a heating device, wherein the heating device is shown in fig. 9, the heating device comprises a power supply 1, an intelligent temperature controller 2, a liftable support 4, an iron stand 3, a thermocouple 5 and a heating table 6, the iron stand 3 is L-shaped, the liftable support 4 is fixed on a cross rod of the iron stand 3, the thermocouple 5 is fixed on a vertical rod of the iron stand 3, one end of the thermocouple 5 is connected with the heating table 6, the intelligent temperature controller 2 is respectively and electrically connected with the thermocouple 5 and the heating table 6, and the power supply 1 is electrically connected with the intelligent temperature controller 2; liftable support 4 be used for placing bare gold nano-electrode 7, heating stage 6 bottom sets up the through-hole for place the fixed granule of polyurethane, the fixed granule's of polyurethane diameter be greater than the diameter of through-hole, bare gold nano-electrode 7 pass through the fixed granule of fused polyurethane through the through-hole. The intelligent temperature controller 2 is commercially available and is not particularly limited, and has the function of controlling the heating temperature of the thermocouple 5 through a feedback system in the intelligent temperature controller 2, so that polyurethane fixed particles are molten, and the phenomenon that the temperature is too high and the packaging material is damaged is prevented.
According to the invention, polyurethane particles are placed on a heating table for heating, the heating temperature is preferably 170-190 ℃, after the polyurethane particles are melted, the bare gold nano-electrode is fixed on a liftable fixed support, the electrode slowly penetrates through the melted polyurethane solid particles, the process is more than 5s, at the moment, the tip of the electrode is covered with a layer of polyurethane, after the electrode is cooled, the tip can shrink due to the cooling resilience of the polyurethane, the tip is exposed, after the tip extends out, the fixed support stops rising, the electrode is taken out and cooled to room temperature, and therefore the electrode is packaged, and the gold nano-electrode is obtained. The process takes less than 1min, the preparation is very quick, and the electrode is formed in one step and is put into a closed box after the preparation in order to prevent the tip of the electrode from falling into dust.
The invention uses polyurethane to wrap the gold electrode, thereby reducing the effective area of the electrode tip, and the polyurethane raw material is from Germany Bayer 3970D.
The invention also provides the gold nano-electrode prepared by the preparation method.
The obtained wrapped gold nano-electrode is subjected to primary characterization by an electrochemical means, and whether the preparation of the gold nano-electrode is successful or not is verified, wherein the specific characterization steps comprise:
and C1, washing the prepared gold nano electrode with absolute ethyl alcohol for 2 times, then washing the gold nano electrode with 18.2M omega cm ultra-pure water, then blowing the gold nano electrode with argon, and then putting the gold nano electrode into the prepared electrolyte for electrochemical test.
C2, firstly, placing the gold nano-electrode into 1mL of water for soaking, carrying out electrochemical test every 1h, and recording the experimental result;
c3, secondly, soaking in 1mL of absolute ethyl alcohol solution, carrying out electrochemical test every 1h, and recording the experimental result;
c4, finally soaking in 1 × PBS solution, performing electrochemical test every 1h, and recording the experimental results.
C2-C4, all measured 6 times continuously.
C5, performing electrochemical test on the packaged electrode once a day, continuously measuring for 4 days, and recording the experimental result.
Another electrochemical measurement was performed after 15 days from C6, and the results were compared with the previous results.
The water of the soaking solution is 18.2M omega cm of ultrapure water, absolute ethyl alcohol is analytically pure, 1 PBS buffer solution has pH of 7.30 (at 25 ℃), and 1mL is used for the required amount of soaking. The cell solution used for the electrochemical test was argon deoxygenated potassium ferrocyanide and potassium chloride solution, with 100mM potassium ferrocyanide and 1M potassium chloride solution. The corrosive liquid is prepared by absolute ethyl alcohol-HCl according to the volume ratio of 1: 1.
The above characterization method mainly explores the electrochemical behavior after the gold electrode is coated with polyurethane, and the change of the electrochemical current after the gold electrode is soaked in 18.2M omega cm ultrapure water, absolute ethyl alcohol and 1 PBS buffer solution for a long time, and researches show that after the gold electrode is coated with the polyurethane one-step packaging method and soaked in the three solutions for a period of time, the change of the electrochemical current is not very obvious, and the current value has no large deviation, so that the gold electrode and the polyurethane at the tip thereof can be basically considered to be stably present in the 18.2M omega cm ultrapure water, the absolute ethyl alcohol and the 1 PBS buffer solution. The effective electrode area of the tip of the nano electrode can not change due to soaking in the three solutions, and the polyurethane can be stably attached to the gold electrode without expansion, separation and falling. The stability of the electrode can be well ensured. The method has the characteristics of improving the reproducibility and stability of the gold nano-electrode preparation and improving the success rate of the preparation, and has the advantages of simple operation and preparation and low cost.
The present invention will be described in detail below with reference to specific examples.
Example 1
a. Preparation of bare gold nano-electrode
(1) And preparing the corrosive liquid: according to V(HCl)：V(C2H5OH)20mL of the glass surface dish is prepared in a ratio of 1: 1;
(2) fixing a 1cm long gold wire on a corrosion rack, connecting an alternating current power supply and an oscilloscope for corrosion, controlling the ammeter representation number to be 15.0 muA, controlling the corrosion time to be 45s, controlling the corrosion voltage to be 26V, and controlling the corrosion frequency to be 4.2 kHz;
(3) washing with 18.2M omega cm of ultrapure water, putting into a plasma cleaning machine to clean surface impurities, and cleaning for 8min to obtain a bare gold nano electrode with a clean surface;
b. wrapping preparation of gold nano-electrode
(1) Preparation work: putting the polyurethane particles into 18.2M omega cm ultra-pure water for ultrasonic cleaning for 5min, and then putting the polyurethane particles into an oven for drying, wherein the temperature of the oven is set to be 90 ℃.
(2) And putting the cleaned polyurethane solid particles on a heating table, starting a heating device, waiting for a moment when the temperature rises to 170 ℃, melting the polyurethane, slowly lifting the support fixed with the bare gold nano electrode until the tip of the support is exposed, slowly taking the support out of the heating table, and cooling to room temperature to obtain the gold nano electrode.
The gold nano electrode prepared by the method is characterized by comprising the following specific steps:
(1) preparing an electrochemical electrolyte, wherein the electrolyte contains 100mM potassium ferrocyanide and 1M KCl, respectively weighing 422mg potassium ferrocyanide and 74.5mg KCl by using an electronic balance, dissolving in 10mL of 18.2M omega cm ultrapure water, uniformly mixing after completely dissolving, and then conducting argon introduction for deoxidization for 5 min;
(2) washing the prepared gold nano electrode with absolute ethyl alcohol for 2-3 times, then washing the gold nano electrode with 18.2M omega cm ultrapure water for one time, removing impurities such as residual ethyl alcohol in the previous step, and then drying the gold nano electrode with nitrogen
(3) And putting the cleaned and wrapped gold nano electrode into the prepared electrochemical base solution for cyclic voltammetry testing. The test potential range is 0 to +0.6V, and the sweep rate is 10 mV/s. Repeating the operation for 4 days continuously, and testing the stability of the gold nano-electrode.
The operation was repeated for four consecutive days to see if the electrode performance was stable.
(4) The washed electrode is respectively put into 1mL of water, 1mL of absolute ethyl alcohol and 1mL of 1 × PBS solution, the test is carried out for 1 time every time the electrode is soaked for 1 hour, and the continuous measurement is carried out for 6 times to see whether the electrode can stably exist in the water, the absolute ethyl alcohol and the 1 × PBS solution or not, the growth environment and the experimental environment of the cell are generally in the water environment, and the absolute ethyl alcohol is used for carrying out disinfection treatment before the cell is cultured and tested in the 1 × PBS environment, so the performance of the electrode prepared by the three solutions needs to be tested.
Fig. 1 is an optical image of a bare gold nano-electrode prepared in example 1 of the present invention, fig. a is an image under an optical microscope, and fig. b is an image under a dark-field optical microscope, and it can be seen from fig. 1 that the bare gold nano-electrode of the present invention has a smooth and flat etched surface and a sharp tip.
Fig. 2 is a Scanning Electron Microscope (SEM) image of the bare gold nano-electrode prepared in example 1 of the present invention. As can be seen from FIG. 2, the corroded surface of the gold electrode is smooth and flat, and the size of the corroded surface reaches below 300 nm.
Fig. 3 is a TGA graph of polyurethane, and it can be seen from fig. 3 that the sample is relatively stable at 200 ℃ or lower, and no weight loss occurs, and when the temperature reaches 220 ℃, the sample undergoes weight loss and partial weight loss, indicating that the sample is decomposed and has instability. In order to facilitate experimental operation and ensure the stability of a sample, the temperature is selected within the range of 170-190 ℃, so that the melting of the sample can be ensured, and the structure of the sample is not damaged.
FIG. 4 is a normal distribution diagram of the effective area of the electrode tip of the gold nanoelectrode prepared in example 1 of the present invention, and it can be seen from FIG. 4 that the effective area of the electrode tip is approximately distributed in the range of 0-1 μm2The specific value is calculated to be about 0.05-0.8 μm2And the size of the effective area of the electrode can be effectively reduced as long as the packaging link is well controlled.
Fig. 5 is a cyclic voltammetry characteristic curve measured by continuously soaking the gold nano-electrode prepared in example 1 in distilled water, wherein a represents a first test result, b represents a second test result, c represents a third test result, d represents a fourth test result, e represents a fifth test result, f represents a sixth test result, g represents a seventh test result, and the gold nano-electrode is continuously soaked for 6 hours every 1 hour for 6 times, the scanning rate is 10mV/s, and the scanning potential range is 0 to + 0.6V. After 6 times of tests, the peak current changes slightly, the difference is about several nA, no order of magnitude deviation exists in an error range, and the curves are not completely overlapped, so that the errors of the instrument, the loss of the electrode, the oxidation of the solution and the like exist. However, it can be seen from the general trend of the curve that the peak current can be stabilized at 10-8On the order of magnitude, the gold nano-electrode wrapped by polyurethane in the 18.2M omega cm ultrapure water has good insulation, stability and repeatability, and can keep stable performance in 18.2M omega cm distilled water.
FIG. 6 is a graph of electrochemical cyclic voltammetry characteristics of gold nano-electrodes prepared in example 1 of the present invention measured by continuous immersion in absolute ethanol solution, where a represents the first test result, b represents the second test result, c represents the third test result, d represents the fourth test result, e represents the fifth test result, f represents the sixth test result, g represents the seventh test result, 1 test time per immersion 1h, 6 continuous immersion, scan rate of 10mV/s, potential range of 0 to +0.6V, total 6 continuous tests, and after 6 tests, the current has slight change, about several nA difference, within the error range, there is no deviation of orders of magnitude, and the curve has no deviation of orders of magnitudeThe complete superposition causes the loss of the electrode, the oxidation of the electrolyte and the like besides the error of the instrument. However, it can be seen from the general trend of the curve that the peak current can be stabilized at 10-8In order of magnitude, the gold nano electrode wrapped by polyurethane in the absolute ethyl alcohol solution has good insulativity, stability and repeatability, and can keep stable performance in the absolute ethyl alcohol solution.
FIG. 7 is a cyclic voltammetry characteristic curve measured by continuously soaking the gold nano-electrode prepared in example 1 in 1 × PBS buffer solution, wherein a represents the first test result, b represents the second test result, c represents the third test result, d represents the fourth test result, e represents the fifth test result, f represents the sixth test result, and g represents the seventh test result, the test is performed 1 time per soaking 1 hour, the soaking is performed continuously for 6 hours, the scanning rate is 10mV/s, the potential range is 0 to +0.6V, the test is performed for 6 times in total, and the current is slightly changed after the test of 6 times, and the difference is about several nanoamperes at zero point, within the error range, there is no deviation of orders of magnitude, and the curves are not completely overlapped, so that besides the error of the instrument, there are also the loss of the electrode, the oxidation of the electrolyte and other reasons. However, it can be seen from the general trend of the curve that the peak current can be stabilized at 10-9In order of magnitude, the gold nano-electrode coated by polyurethane in the 1 × PBS buffer solution has good insulation, stability and repeatability, and can keep stable performance in the 1 × PBS buffer solution.
Fig. 8 is an electrochemical cyclic voltammetry characteristic curve of the gold nano-electrode prepared in example 1 of the present invention, measured continuously for 4 days, where a represents a first test result, b represents a second test result, c represents a third test result, and d represents a fourth test result, the same electrochemical electrolyte is prepared every day and measured at the same time every day, argon is introduced to remove oxygen in the same way, the electrolyte is introduced for 5-10 min every time, the electrolyte is taken out after each test is completed, the salt solution remaining on the surface is cleaned with ultrapure water of 18.2M Ω · cm, the salt solution is blown dry with nitrogen, the salt solution is placed in a sealed storage box, and the sealed storage box is placed in a refrigerator at 4 ℃ and kept away from light. Before the second test, the surface of the gold nano electrode is taken out and cleaned again by using 18.2M omega cm distilled water, the electrochemical test is carried out after the gold nano electrode is dried by using nitrogen, the same operation is carried out for 4 days continuously, and the results are arranged and summarized, as shown in figure 8, the electrode has good repeatability, is always in an S shape and can be reused within the time of being stored for several days, the change of the magnitude of the current is slightly changed, but the change of the magnitude of the current is not influenced, the change of the magnitude of the current can be ignored, the effective area of the tip of the electrode is not increased, and the application of the electrode is not influenced. The gold nano electrode is coated by polyurethane melting, so that the gold nano electrode cannot fall off, separate, age and other changes, and the polyurethane coated gold nano electrode has good insulativity, stability and repeatability, and can keep stable performance for a long time.
Example 2
a. Preparation of bare gold nano-electrode
(1) And preparing the corrosive liquid: according to V(HCl)：V(C2H5OH)20mL of the glass surface dish is prepared in a ratio of 1: 1;
(2) fixing a 1cm long gold wire on a corrosion rack, connecting an alternating current power supply and an oscilloscope for corrosion, controlling the ammeter number to be 10.0 muA, controlling the corrosion time to be 40s, controlling the corrosion voltage to be 25V, and controlling the corrosion frequency to be 4.2 kHz;
(3) washing with 18.2M omega cm of ultrapure water, putting into a plasma cleaning machine to clean surface impurities, and cleaning for 5min to obtain a bare gold nano electrode with a clean surface;
b. wrapping preparation of gold nano-electrode
(1) Preparation work: putting the polyurethane particles into 18.2M omega cm ultra-pure water for ultrasonic cleaning for 5min, and then putting the polyurethane particles into an oven for drying, wherein the temperature of the oven is set to be 80 ℃.
(2) And putting the cleaned polyurethane solid particles on a heating table, starting a heating device, waiting for a moment when the temperature rises to 170 ℃, melting the polyurethane, slowly lifting the support fixed with the bare gold nano electrode until the tip of the support is exposed, slowly taking the support out of the heating table, and cooling to room temperature to obtain the gold nano electrode.
Example 3
a. Preparation of bare gold nano-electrode
(1) And preparing the corrosive liquid: according to V(HCl)：V(C2H5OH)20mL of the glass surface dish is prepared in a ratio of 1: 1;
(2) fixing a 1cm long gold wire on a corrosion rack, connecting an alternating current power supply and an oscilloscope for corrosion, controlling the ammeter number to be 15.0 muA, controlling the corrosion time to be 50s, controlling the corrosion voltage to be 27V, and controlling the corrosion frequency to be 4.2 kHz;
(3) washing with 18.2M omega cm of ultrapure water, putting into a plasma cleaning machine to clean surface impurities, and cleaning for 10min to obtain a bare gold nano electrode with a clean surface;
b. wrapping preparation of gold nano-electrode
(1) Preparation work: putting the polyurethane particles into 18.2M omega cm ultra-pure water for ultrasonic cleaning for 5min, and then putting the polyurethane particles into an oven for drying, wherein the temperature of the oven is 100 ℃.
(2) And putting the cleaned polyurethane solid particles on a heating table, starting a heating device, waiting for a moment when the temperature rises to 170 ℃, melting the polyurethane, slowly lifting the support fixed with the bare gold nano electrode until the tip of the support is exposed, slowly taking the support out of the heating table, and cooling to room temperature to obtain the gold nano electrode.
In conclusion, the preparation method of the gold nano-electrode coated with polyurethane can ensure that the gold nano-electrode coated with polyurethane can stably exist in 18.2M omega cm of ultrapure water, absolute ethanol solution and 1 PBS buffer solution, does not influence the use of the electrode, and can still keep a good state after being placed for 4 days. The gold nano electrode wrapped by polyurethane has certain stability. The gold nano-electrode is prepared firstly, then the gold nano-electrode is wrapped by polyurethane, and finally the gold nano-electrode wrapped by polyurethane is prepared. The polyurethane coating can have good insulating property, and can be closely attached to the gold nano-electrodes in 18.2M omega cm ultrapure water, absolute ethyl alcohol solution and 1 & ltPBS buffer solution without falling off or surface defects, and the polyurethane can reach a molten state in a short time, so that the packaging is convenient and rapid, and the packaging can be completed in one step. Therefore, the time for preparing the electrode can be greatly shortened, the polyurethane can be stored for a long time, the stability is good, the raw materials are wide in source and low in price, the operation is facilitated, and the preparation method is easy to realize.
The above description of the embodiments is only for the purpose of assisting understanding of the method of the present invention and the core idea thereof, and it should be noted that those skilled in the art can make several improvements and modifications to the present invention without departing from the principle of the present invention, and these improvements and modifications also fall into the protection scope of the claims of the present invention.
Claims (8)
1. A preparation method of a gold nano electrode is characterized by comprising the following steps:
step one, preparing a bare gold nano electrode: the alloy is prepared by adopting absolute ethyl alcohol-HCl solution and gold wire as raw materials through an electrochemical corrosion method;
step two, melting and solidifying polyurethane particles on the bare gold nano-electrode by using a heating device to obtain the gold nano-electrode, which specifically comprises the following steps:
and (2) building a heating device, putting polyurethane particles on a heating table for heating, after the polyurethane particles are melted, fixing the bare gold nano-electrode on a liftable support, enabling the electrode to penetrate through the melted polyurethane solid particles, covering a layer of polyurethane on the tip of the electrode, stopping lifting the support after the tip extends out, taking out, and cooling to room temperature to obtain the gold nano-electrode.
2. The method for preparing a gold nano-electrode according to claim 1, wherein the first step is specifically as follows:
1) mixing absolute ethyl alcohol and a hydrochloric acid solution to obtain a corrosive liquid;
2) and (3) taking a gold wire, fixing the gold wire on a corrosion frame, connecting an alternating current power supply and an oscilloscope for corrosion, controlling the current representation number to be 10-15.0 mu A, the corrosion time to be 40-50 s, the corrosion voltage to be 25-27V and the corrosion frequency to be 4.2kHz, and cleaning to obtain the bare gold nano electrode.
3. The method for preparing a gold nano-electrode according to claim 2, wherein the volume ratio of the absolute ethanol to the hydrochloric acid solution is 1: 1.
4. the method as claimed in claim 2, wherein the gold wire is 1cm long.
5. The method for preparing a gold nano-electrode according to claim 2, wherein the cleaning step comprises: and (3) washing the substrate by using 18.2M omega cm of ultrapure water, putting the substrate into a plasma cleaning machine to clean impurities on the surface for 5-10 min.
6. The preparation method of the gold nano-electrode according to claim 1, characterized in that the heating device comprises a power supply (1), an intelligent temperature controller (2), a liftable support (4), an iron stand platform (3), a thermocouple (5) and a heating platform (6), wherein the iron stand platform (3) is L-shaped, the liftable support (4) is fixed on a cross rod of the iron stand platform (3), the thermocouple (5) is fixed on a vertical rod of the iron stand platform (3), one end of the thermocouple (5) is connected with the heating platform (6), the intelligent temperature controller (2) is respectively and electrically connected with the thermocouple (5) and the heating platform (6), and the power supply (1) is electrically connected with the intelligent temperature controller (2); liftable support (4) be used for placing bare gold nano-electrode (7), heating table (6) bottom sets up the through-hole for place polyurethane fixed particle, bare gold nano-electrode (7) pass through the fixed particle of fused polyurethane through the through-hole.
7. The method for preparing gold nano-electrodes according to claim 1, wherein the heating temperature is 170-190 ℃.
8. Gold nano-electrodes obtained by the preparation method according to claim 1.
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| CN113189156B (en) * | 2021-03-23 | 2024-08-16 | 中国石油大学(华东) | Manual control device for probe tip sealing and opening and use method thereof |
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| 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 |
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