CN108760863B - Au @ Pt core-shell type ultramicroelectrode and preparation method thereof - Google Patents

Au @ Pt core-shell type ultramicroelectrode and preparation method thereof Download PDF

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CN108760863B
CN108760863B CN201810325329.3A CN201810325329A CN108760863B CN 108760863 B CN108760863 B CN 108760863B CN 201810325329 A CN201810325329 A CN 201810325329A CN 108760863 B CN108760863 B CN 108760863B
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CN108760863A (en
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郭志慧
唐丽芳
郑行望
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Shaanxi Normal University
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Abstract

The invention relates to a preparation method and application of an Au @ Pt core-shell type ultramicroelectrode, which comprises the following steps: s1, winding a gold wire on the platinum wire to obtain a gold-platinum wire; and S2, adhering the gold platinum wire to the tungsten wire: s3, heating and melting: placing the product obtained in the step S2 on a high-temperature outer flame, and wrapping a gold ball on a platinum wire after the gold wire is melted to obtain an Au @ Pt core shell; and S4, electroplating an insulating layer on the core shell. The invention solves the technical problems that the existing preparation method of binary alloy nanoparticles is high in cost and long in time consumption and needs to assist various instruments, and the Au @ Pt core-shell ultramicroelectrode catalytic material is prepared by melting and dispersing gold on the surface of a platinum micron wire by a physical fusion method based on the characteristic that the melting point difference of gold and platinum is large.

Description

Au @ Pt core-shell type ultramicroelectrode and preparation method thereof
Technical Field
The invention belongs to the field of ultramicroelectrodes, and particularly relates to a preparation method and application of an Au @ Pt core-shell type ultramicroelectrode.
Background
The ultramicroelectrode has unique properties of small electrode size, high mass transfer speed, small time constant, easy steady state achievement and the like compared with a conventional large electrode, and is widely applied to various fields such as single cell detection, detection of rapid heterogeneous electron transfer rate, detection of trace substances and the like at present. However, the electrocatalytic activity of a single ultramicroelectrode catalyst is often low and is easily poisoned by a reaction intermediate product, so that the activity is further reduced. For example, pure Pt catalyst is readily reacted with intermediates (e.g., CO) generated during the reaction in catalyzing the oxidation of formic acid or methanolad、CHOad、CH2Oad、CH3OadEtc.) to poison, resulting in a reduction in its electrocatalytic activity. In order to improve the electrocatalytic activity of the catalyst, a second metal element is usually added into the unitary catalyst, for example, a metal element such as Ru, Mo, Au, Sn, etc. is added into a Pt substrate to form a binary alloy catalyst, so that the catalytic activity of the binary alloy catalyst is higher than that of a pure platinum catalyst. At present, the methods for manufacturing binary alloy materials mainly comprise a chemical synthesis method and an electrochemical deposition method. However, these preparation methods usually require multiple equipment and equipment, and generally require chemical changes to be carried out, resulting in high cost, complicated operation and long time consumption. For example, the chemical synthesis method can only obtain binary alloy nanoparticles, and the binary alloy nanoparticles can be used only by being assembled on the surface of another substrate; the electrochemical deposition process requires a chemical change to deposit the second metal on a substrate electrode。
Disclosure of Invention
The invention provides a preparation method and application of an Au @ Pt core-shell type ultramicroelectrode, aiming at solving the technical problems that the existing preparation method of binary alloy nanoparticles is high in cost and long in time consumption and needs to assist various instruments. The preparation method of the Au @ Pt core-shell ultramicro electrode catalytic material does not need to involve complex chemical synthesis and chemical change, has the advantages of simple preparation, short time consumption, low cost and the like, and is expected to be used as an electrode material of a clean fuel cell.
The technical solution of the invention is as follows:
a preparation method of an Au @ Pt core-shell type ultramicroelectrode is characterized by comprising the following steps:
s1, preparing a gold platinum wire:
winding a gold wire on the platinum wire to obtain a gold-platinum wire;
and S2, adhering the gold platinum wire to the tungsten wire:
cutting a small section of the gold platinum wire prepared in the step S1, sticking the cut small section of gold platinum wire to one end of the tungsten wire by using a conductive colloid, putting the stuck gold platinum wire and the tungsten wire into a constant-temperature drying box, and taking out the gold platinum wire and the tungsten wire after the conductive colloid is dried; coating a layer of high-temperature-resistant insulating colloid on the conductive colloid between the gold-platinum wire and the tungsten wire;
s3, heating and melting: placing the product obtained in the step S2 on a high-temperature outer flame, and wrapping a gold ball on a platinum wire after the gold wire is melted to obtain an Au @ Pt core shell;
s4, electroplating an insulating layer: the Au @ Pt core shell prepared in the step S3 is used as a working electrode, the platinum electrode is used as a counter electrode, the Au @ Pt core shell working electrode and the platinum electrode are placed in 2-propenyl phenol electroplating solution for electroplating under the condition of a stabilized voltage power supply, and an insulating layer is formed on the Au @ Pt core shell; and cutting the Au @ Pt core shell to obtain the Au @ Pt core shell type ultramicroelectrode.
Further, in step S1, the diameter of the gold wire is 10 to 100 μm, and the diameter of the platinum wire is 10 to 100 μm.
Further, the diameter of the gold wire is 25 μm and the diameter of the platinum wire is 25 μm in step S1.
Further, the conductive paste used in step S2 is a conductive silver paste, and the insulating and high temperature resistant paste is epoxy resin.
Further, the step S3 is to implement electroplating of the insulating layer as follows:
and (2) taking the Au @ Pt core shell prepared in the step (S3) as a working electrode and the platinum electrode as a counter electrode, placing the working electrode and the counter electrode in electroplating solution containing 2-propenyl phenol and having a pH value of 9.0-10.0 under the condition that a stabilized voltage power supply is 4V for electroplating, placing the electroplating solution in a constant-temperature drying box with a temperature of 130-150 ℃ after 10-15 min of electroplating, and drying the electroplating solution at the constant temperature for 30-60 min to obtain the Au @ Pt core-shell type ultramicroelectrode
The utility model provides a super microelectrode of Au @ Pt nuclear shell formula, includes tungsten filament wire, conductive colloid layer and Au @ Pt nuclear shell, the one end of tungsten filament wire is passed through the conductive colloid layer and is glued fixedly with the one end of Au @ Pt nuclear shell, coating has insulating colloid on the conductive colloid layer, the insulating layer has been plated on the Au @ Pt nuclear shell.
Furthermore, the material of the conductive colloid layer is conductive silver paste, and the material of the insulating colloid is epoxy resin.
An application of Au @ Pt core-shell type alloy ultramicroelectrode as a clean fuel cell electrode.
The invention has the advantages and effects that:
1. the preparation method of the Au @ Pt core-shell type alloy ultramicroelectrode provided by the invention does not need to relate to complicated chemical synthesis and chemical change, and has the advantages of less related instruments, low cost, simple operation, short time consumption and the like.
2. The preparation method of the Au @ Pt core-shell type alloy ultramicroelectrode provided by the invention is based on the characteristic that the melting point difference of gold and platinum is large, and utilizes a physical fusion method to melt and disperse gold on the surface of a platinum micrometer wire, so that the Au @ Pt core-shell type ultramicroelectrode catalytic material is prepared.
3. The Au @ Pt core-shell alloy ultramicroelectrode prepared by the method shows good electrocatalytic oxidation activity to formic acid and methanol.
4. The Au @ Pt core-shell alloy ultramicroelectrode prepared by the method can be directly used as an electrocatalytic material and an electrode material of a clean fuel cell.
Drawings
FIG. 1 is a schematic diagram of the principle of the fabrication process of the Au @ Pt core-shell type ultramicroelectrode of the invention;
FIG. 2 is a schematic structural diagram of an Au @ Pt core-shell type ultramicroelectrode of the invention;
FIG. 3 is a micrograph of Au @ Pt core-shell type ultramicroelectrodes of different gold/platinum ratios;
FIG. 4 is a cyclic voltammogram of Au @ Pt core-shell type ultramicroelectrodes at different gold/platinum ratios in a methanol solution containing 1mmol/L ferrocene, sweep rate: 10 mV/s;
FIG. 5 shows Au @ Pt core-shell type ultramicroelectrodes with different Au/Pt ratios at 0.5mol/L H2SO4Cyclic voltammogram in solution, sweep rate: 30 mV/s;
FIG. 6 is a plot of cyclic voltammograms of formic acid on pure Pt nanoelectrodes and Au @ Pt core-shell nanoelectrodes at different gold/platinum ratios, sweep rates: 30 mV/s;
FIG. 7 is a plot of cyclic voltammograms of methanol on pure Pt nanoelectrodes and Au @ Pt core-shell type nanoelectrodes at different gold/platinum ratios, sweep rates: 30 mV/s.
Detailed Description
For better understanding of the present invention, the following further explains the contents of the present invention with reference to the present embodiment and the accompanying drawings, but the contents of the present invention are not limited to the implementations explained below.
Example 1
A preparation method of an Au @ Pt core-shell type ultramicroelectrode is shown in a schematic diagram of a manufacturing process of the Au @ Pt core-shell type ultramicroelectrode in figure 1, and comprises the following steps:
step 1) taking a section of gold wire with the diameter of 25 mu m, and winding the section of gold wire on a platinum wire with the diameter of 25 mu m compactly to obtain a gold-platinum wire;
step 2) cutting a small section of the gold platinum wire wound with the gold wire in the step 1, wherein the length of the gold platinum wire is about 1-2 cm, adhering the gold platinum wire to the end of the tungsten wire by using conductive silver paste, putting the tungsten wire into a constant-temperature drying oven (35-60 ℃, 15-30 min), and after the conductive silver paste is dried, coating a layer of insulating and high-temperature-resistant epoxy resin adhesive on the surface coated with the conductive silver paste to enable the gold platinum wire to be adhered to the tungsten wire more firmly;
step 3) placing the gold and platinum wire adhered to the tungsten wire in the step 2 on an outer flame of an alcohol lamp, wherein the melting point of the platinum wire is higher than that of the gold wire, so that the gold wire is heated and melted in the heating process, the platinum wire is wrapped, and some gold balls are formed on some parts of the platinum wire to wrap the platinum wire, so that an Au @ Pt core shell is formed;
and 4) taking the Au @ Pt core shell prepared in the step 3 as a working electrode and a platinum electrode as a counter electrode, placing the Au @ Pt core-shell alloy ultramicroelectrode and the counter electrode (Pt electrode) in an electroplating solution (PH is 9.0-10.0) containing 2-propenyl phenol for electroplating under the condition that a stabilized voltage supply is 4V, placing the Au @ Pt core-shell alloy ultramicroelectrode in a constant-temperature drying box at the temperature of 130-150 ℃ after electroplating for 10-15 min, drying at the constant temperature for 30-60 min to form a non-conductive polymer insulating layer on the surface of the Au @ Pt core-shell alloy ultramicroelectrode, and cutting different parts of the Au @ Pt core-shell alloy ultramicroelectrode by using a small knife under a binocular magnifier to obtain the Au @ Pt core-shell ultramicroelectrode with different platinum-gold content ratios.
Example 2
As shown in figure 2, the Au @ Pt core-shell type ultramicroelectrode comprises a tungsten wire 1, a conductive colloid layer 2 and an Au @ Pt core shell body 3, wherein one end of the tungsten wire is fixedly bonded with one end of the Au @ Pt core shell body 3 through the conductive colloid layer 2, an insulating colloid is coated on the conductive colloid layer, and an insulating layer is plated on the Au @ Pt core shell body.
FIGS. 3 and 4 are micrographs of Au @ Pt core-shell ultramicroelectrodes with different gold/platinum ratios prepared according to the invention and cyclic voltammograms thereof in a 1mmol/L ferrocene methanol solution, respectively. As can be seen from FIGS. 3 and 4, the Au @ Pt core-shell ultramicro disk electrode with different gold/platinum ratios can be obtained by cutting different parts of the Au @ P core shell. The radiuses of Au @ Pt core-shell ultramicroelectrodes a-d obtained in the experiment are 14.0 mu m, 15.6 mu m, 17.7 mu m and 37.5 mu m respectively.
FIG. 5 shows pure Pt electrode and example 1 preparationThe Au @ Pt core-shell ultramicroelectrode contains 0.5mol/L H2SO4The sweep rate of the cyclic voltammogram measured in the solution of (1) is 30mV/s, and it can be seen from the graph that compared with a pure Pt ultramicroelectrode, a cyclic voltammogram curve of an Au @ Pt core-shell ultramicroelectrode in a sulfuric acid solution has a peak at a potential of about 0.9V, namely the reduction peak of the Au oxide, and a peak consistent with a pure Pt electrode also appears at the potential of about 0.3V, namely the reduction peak of the Pt oxide, which indicates that the surface of the Au @ Pt core-shell ultramicroelectrode prepared by the invention contains Pt and Au elements at the same time, and in addition, the peak height and the peak type of the reduction peak of the Pt oxide of the Au @ Pt core-shell ultramicroelectrode at the potential of 0.3V are basically consistent with those of a pure Pt electrode, which indicates that the Pt content and the radius of the Pt content on the surface of the Au @ Pt core-shell ultramicro disk electrode are consistent with those of the surface of the pure Pt ultramicro electrode, so that the gold/platinum ratio on the surface of the Au @ Pt core-shell ultramicro disk electrode can be quickly estimated through the steady-state volt-ampere current measured in figure 4. The Au/Pt ratio (rho) of the Au @ Pt core-shell ultramicroelectrodes a-d obtained in the experiment(Au/Pt)) Respectively 0.25, 0.56, 1.01, 25.0.
Compared with the traditional Au @ Pt alloy material manufacturing method (such as a chemical synthesis method, an electrodeposition method and the like), the Au @ Pt core-shell ultramicro disc electrode manufacturing method is simpler in operation, shorter in time consumption, lower in cost and easier to realize. Compared with the Au @ Pt catalytic material prepared by a synthesis method, the Au @ Pt core-shell ultramicro disc electrode does not need complicated chemical modification or dripping on other substrates to realize the electrocatalysis effect, so the Au @ Pt core-shell ultramicro disc electrode is expected to be directly used as the electrocatalysis material of fuel cells.
The diameter of the platinum wire in the embodiment 1 affects the size of the Au @ Pt core-shell ultramicroelectrode, and if the diameter is large, the Au @ Pt core-shell ultramicroelectrode is large; and the diameter is small, so that the Au @ Pt core-shell ultramicroelectrode is small.
The electroplating mode is also various, different electroplating solutions can be selected, and the purpose is to plate an insulating layer on the Au @ Pt core shell.
The Au @ Pt core-shell alloy ultramicroelectrode prepared by the method shows good electrocatalytic oxidation activity to formic acid and methanol;
(1) determination of catalytic formic acid: using two electrodesThe system takes an Au @ Pt core-shell type alloy super-micro electrode as a working electrode and Ag/AgCl (saturated potassium chloride) as a reference electrode, and 0.5mol/L formic acid and 0.5mol/L H are contained in the reference electrode2SO4The solution is measured by cyclic voltammetry scanning, the scanning speed is 20mV/s, and the potential range is-0.2V-0.6V.
FIG. 6 is a cyclic voltammogram of formic acid on pure Pt ultramicroelectrodes and Au @ Pt core-shell alloy ultramicroelectrodes of different sizes, and it can be observed from FIG. 6A that a very distinct oxidation peak, namely the oxidation peak of formic acid, appears on the voltammogram at a potential of about 0.38V after formic acid is added into a solution. In addition, it can be observed from FIG. 6 that Au @ Pt core-shell alloy ultramicroelectrodes with different gold/platinum ratios have different catalytic oxidation effects on formic acid. And as can be seen from fig. 6B-C, the oxidation peak potentials of formic acid on Au @ Pt core-shell alloy ultramicroelectrodes with different gold/platinum ratios are obviously shifted negatively relative to the oxidation peak potentials of formic acid on pure Pt ultramicroelectrodes, and the experimental results show that the alloy ultramicroelectrodes have certain electrocatalytic effect on the oxidation of formic acid, so that the formic acid is easier to be oxidized at a low potential. This is mainly due to a bifunctional mechanism, i.e. when gold is added to the Pt surface, the OH adsorbed on the Au surface is allowed toadIntermediate (e.g. CO) to be adsorbed on Pt surfacead) The reaction is carried out and the intermediate product thereof is oxidized, thereby enhancing the poison resistance of the Pt electrode and enabling the alloy electrode to have catalytic action.
For example, when ρ(Au/Pt)At 0.25 f (fig. 6B), the oxidation peak of formic acid on the alloy microelectrode appeared at approximately 0.16V, the peak potential shifted negatively by about 0.22V relative to the pure Pt ultramicroelectrode, and the peak current value decreased slightly, probably because OH adsorbed on the gold surface when the gold content on the electrode surface was lowadAdsorbing intermediate product CO on Pt surfaceadPartial reaction is carried out, so that formic acid can be oxidized on the alloy electrode at a more negative potential, but partial Pt atoms on the surface of the electrode are still subjected to an intermediate product COadThe poisoning effect of the Pt causes that the part of Pt atoms do not generate new formic acid active sites under the condition of more negative potential, so that the peak current value of the Pt atoms is slightly reduced compared with the peak current value of a pure Pt ultramicroelectrode; when rho(Au/Pt)At 1.01 (fig. 6C), the oxidation peak of formic acid on the alloy microelectrode occurred at approximately 0.18V, the peak potential was shifted negatively by approximately 0.20V and the peak current value increased approximately 2-fold relative to the pure Pt ultramicroelectrode, probably because of the intermediate CO adsorbed on each Pt atom at this timeadExactly with OH provided on each Au atomadAnd (3) reacting to remove toxic species on the Pt surface and regenerate active sites for absorbing formic acid on Pt atoms, so that the formic acid has a more negative peak potential than a pure Pt ultramicroelectrode on the alloy electrode, and the peak current value is relatively increased. However, when ρ(Au/Pt)When the ratio of gold on the surface of the alloy electrode is higher than 8.00 (fig. 6D), the oxidation peak potential (0.46V) of formic acid on the alloy ultramicroelectrode is shifted positively relative to the oxidation peak potential (0.38V) of formic acid on the pure Pt ultramicroelectrode, which is probably because gold itself has no electrocatalytic activity on formic acid, and thus the catalytic effect of the alloy electrode is gradually reduced as the ratio of gold on the surface of the alloy electrode is increased. In conclusion, the Au @ Pt core-shell alloy ultramicroelectrode can show electrocatalytic oxidation effect on formic acid only when the ratio of gold on the surface of the Au @ Pt core-shell alloy ultramicroelectrode is smaller, and the formed Au @ Pt core-shell alloy ultramicroelectrode has the best catalytic effect on formic acid when the ratio of gold to platinum is close to 1.
(2) Determination of catalytic methanol: a two-electrode system is adopted, an Au @ Pt core-shell alloy ultramicroelectrode is taken as a working electrode, Ag/AgCl (saturated potassium chloride) is taken as a reference electrode, and the measurement is carried out by carrying out cyclic voltammetry scanning in a solution containing 3 mol/L methanol and 0.5mol/L NaOH, wherein the scanning speed is 20mV/s, and the potential range is-0.6V-0.2V.
FIG. 7A shows the cyclic voltammogram of methanol on pure Au (black line) and pure Pt (red line) microelectrodes, both 12.5 μm in radius, from which it can be seen that the pure Au ultramicroelectrodes have no electrocatalytic oxidation on methanol. However, pure Pt ultramicroelectrodes have certain electrocatalytic oxidation capacity to methanol, and the peak current value is 0.24 muA. As shown in FIGS. 7B-D, the addition of gold to increase the ratio of gold/platinum on the surface of the electrode to a certain ratio improves the catalytic activity of platinum on methanol, mainly due to the decrease of the initial oxidation potential of methanol and the increase of the oxidation peak current of methanol. This is also mainly due to the bifunctional mechanism, i.e. when gold is added to the Pt surface, the OH adsorbed on the Au surface is allowedadIntermediate (e.g. CO) to be adsorbed on Pt surfacead) The reaction is carried out and the intermediate product thereof is oxidized, thereby enhancing the poison resistance of the Pt electrode and enabling the alloy electrode to have catalytic action.
In addition, the alloy electrodes with different gold contents have different electrocatalytic oxidation effects on methanol, and the difference of the gold contents has great influence on the catalytic effect. As can be seen from FIG. 6, when the ratio of gold/platinum is ρ(Au/Pt)At 0.25 (red line in fig. 7B), the oxidation peak current of methanol (0.58 μ a) increased by about 2.4 times relative to that on its pure Pt ultramicroelectrode (0.24 μ a); when ratio of gold/platinum ρ(Au/Pt)At 1.01 (red line in fig. 7C), the oxidation peak current of methanol (1.03 μ a) increased by about 4.3 times relative to its oxidation peak current on a pure Pt ultramicroelectrode (0.24 μ a); however, when the ratio of gold/platinum is ρ(Au/Pt)At 8.00 (red line in fig. 7D), the oxidation peak current of methanol (0.15 μ a) was reduced by 0.09 μ a relative to its oxidation peak current on a pure Pt ultramicroelectrode (0.24 μ a), probably because gold itself had no electrocatalytic oxidation on methanol, resulting in a decrease in the catalytic effect of the alloy electrode on formic acid as the gold content further increased after the ratio of gold/platinum on the surface of the alloy electrode reached a certain ratio. From this, the ratio of gold/platinum ρ(Au/Pt)The Au @ Pt core-shell alloy ultramicroelectrode formed by the electrode 1.01 has the best effect on the electrocatalytic oxidation of methanol. And the results were consistent with those measured for formic acid catalytic oxidation as described above.

Claims (6)

1. A preparation method of an Au @ Pt core-shell type ultramicroelectrode is characterized by comprising the following steps:
s1, preparing a gold platinum wire:
winding a gold wire on the platinum wire to obtain a gold-platinum wire;
and S2, adhering the gold platinum wire to the tungsten wire:
cutting a small section of the gold platinum wire prepared in the step S1, sticking the cut small section of gold platinum wire to one end of the tungsten wire by using a conductive colloid, putting the stuck gold platinum wire and the tungsten wire into a constant-temperature drying box, and taking out the gold platinum wire and the tungsten wire after the conductive colloid is dried; coating a layer of high-temperature-resistant insulating colloid on the conductive colloid between the gold-platinum wire and the tungsten wire;
s3, heating and melting: placing the product obtained in the step S2 on a high-temperature outer flame, and wrapping a gold ball on a platinum wire after the gold wire is melted to obtain an Au @ Pt core shell;
s4, electroplating an insulating layer: the Au @ Pt core shell prepared in the step S3 is used as a working electrode, the platinum electrode is used as a counter electrode, the Au @ Pt core shell working electrode and the platinum electrode are placed in an electroplating solution containing 2-propenyl phenol to be electroplated under the condition of a stabilized voltage power supply, and an insulating layer is formed on the Au @ Pt core shell; and cutting the Au @ Pt core shell to obtain the Au @ Pt core shell type ultramicroelectrode.
2. The method for preparing the Au @ Pt core-shell type microelectrode of claim 1, wherein the method comprises the following steps: in step S1, the diameter of the gold wire is 10-100 μm, and the diameter of the platinum wire is 10-100 μm.
3. The method for preparing the Au @ Pt core-shell type microelectrode of claim 1, wherein the method comprises the following steps: the diameter of the gold wire in step S1 was 25 μm, and the diameter of the platinum wire was 25 μm.
4. The method for preparing the Au @ Pt core-shell type microelectrode of claim 1, wherein the method comprises the following steps:
the conductive colloid used in step S2 is conductive silver paste, and the high-temperature-resistant insulating colloid is epoxy resin.
5. The method for preparing the Au @ Pt core-shell type microelectrode of claim 1, wherein the method comprises the following steps:
the step S4 of electroplating the insulating layer is specifically realized as follows:
and (2) taking the Au @ Pt core shell prepared in the step (S3) as a working electrode and a platinum electrode as a counter electrode, placing the working electrode and the counter electrode in an electroplating solution containing 2-propenyl phenol and having a pH value of 9.0-10.0 under the condition that a stabilized voltage power supply is 4V for electroplating, after 10-15 min of electroplating, placing the Au @ Pt core shell in a constant-temperature drying box at the temperature of 130-150 ℃, and drying at constant temperature for 30-60 min to obtain the Au @ Pt core-shell type ultramicroelectrode.
6. An Au @ Pt core-shell type ultramicroelectrode is characterized in that: the Au @ Pt core-shell type ultramicroelectrode is prepared by the preparation method of any one of claims 1 to 4.
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