CN101105469A - A kind of preparation method of nano ring-disk electrode - Google Patents

Abstract

Translated fromChinese

一种纳米环－盘电极的制备方法，涉及一种电极，尤其是涉及一种纳米环－盘电极的制备方法。提供一种制作尺寸在纳米尺度，具有良好电化学响应，能实现高环收集效率的纳米环－盘电极的制备方法。在腐蚀溶液中腐蚀得到针尖，在电泳漆中对针尖电泳，烘烤得纳米电极；以单根纳米电极为盘电极，经真空溅射形成Au层，Au层将纳米电极前部覆盖，作为环电极模板；将模板前部包封，冷却，露出环电极模板尖端；在模板后部裸露区和盘电极引出导线，将二次包封后的环电极模板置于刻蚀液中，盘电极接正极，施加脉冲电压，每加一个脉冲后检测盘电极和溅射的Au层间的电阻，当超过10⁹欧姆时停止刻蚀，形成以纳电极为盘、溅射Au层为环的纳米环－盘电极。

The invention relates to a preparation method of a nano ring-disk electrode, relating to an electrode, in particular to a preparation method of a nano ring-disk electrode. Provided is a method for preparing a nano-ring-disk electrode whose size is in the nanometer scale, has good electrochemical response, and can realize high ring collection efficiency. The needle tip is corroded in a corrosive solution, electrophoresed in electrophoretic paint, and baked to obtain a nano-electrode; a single nano-electrode is used as a disk electrode, and an Au layer is formed by vacuum sputtering, and the Au layer covers the front of the nano-electrode as a ring. Electrode template; encapsulate the front of the template, cool it, and expose the tip of the ring electrode template; lead out the wires from the exposed area at the back of the template and the disk electrode, place the ring electrode template after the second encapsulation in the etching solution, and connect the disk electrode Positive electrode, apply a pulse voltage, detect the resistance between the disc electrode and the sputtered Au layer after each pulse, stop etching when it exceeds 10⁹ ohms, and form a nano-ring with the nano-electrode as the disc and the sputtered Au layer as the ring - Disk electrodes.

Description

A kind of preparation method of nanometer ring-disc electrode

Technical field

The present invention relates to a kind of electrode, especially relate to a kind of preparation method of nanometer ring-disc electrode.

Background technology

Concentric ring promptly constitutes ring-disc electrode around a circle ring electrode around disc electrode.The diffusion of electroactive material will take place between electrochemical reaction process mid-game-ring electrode, if make ring electrode work in collection status, then can detect the reaction intermediate on the disc electrode effectively, to study the mechanism of complicated electrochemical reaction.Yet, conventional ring-disc electrode is owing to the thickness of diffusion layer of the distance between the ring-dish greater than reaction species, therefore need accelerate mass transport process by forced convertion (as high speed rotating ring dish), not only experimental provision be had specific (special) requirements, and the collection efficiency lower (30%) of ring.

Advantage such as ultramicroelectrode has the mass transfer rate height, charging current is little and the solution ohmmic drop is little has one's own knack to quick electrode reaction dynamics research.Simultaneously, its little physical dimension makes it have a wide range of applications in various fields such as biological detection, sensor and scanning microprobe technology.Little ring-disc electrode is a member unique in the microelectrode family, its little dish and ring and ring-disc electrode spacing to nanoscale, give little ring-disc electrode many original functions: will coil and encircle respectively as working electrode with to electrode, can reduce the ohmmic drop of solution, realize supper-fast cyclic voltammetry measurement; The diffusion of material is accelerated between electrode, need not forced convertion and just can effectively be diffused into the corresponding electrode surface fast; Along with the development and the needs of microprobe technology and nano-electron etc., the ring-disc electrode of smaller szie will be given more applications.

Yet, although along with little, the development of nanometer technology, the size of ultramicroelectrode can be as small as several nanometers, but the preparation method of the ultra micro ring-disc electrode of report mostly adopts polishing or patterning method preparation (Peter Liljeroth at present, Christoffer Johans, Christopher J Slevin et al.Micro ring-disk electrode probes for scanning electrochemicalmicroscopy.Electrochemistry Communications 2002 4:67-71), the ring dish microelectrode size for preparing is all bigger, the dish diameter is at 10-20 μ m, distance between ring electrode and the disc electrode is greatly to more than the 100 μ m, and therefore the contact by the material diffusion is not very tight between ring-dish.(Alois Lugstein such as Alois Lugstein, Emmerich Bertagnolli, Christine Kranz, and Boris Mizaikoff.Surf Interface Anal 2002 33:146-150) reported the becket electrode of using method combined nano size on the AFM probe of focused-ion-beam lithography, for the ring-disc electrode for preparing smaller szie provides feasible method.But the instrument and equipment that this technology is used is expensive, and cost of manufacture is very high, and is not suitable for the common lab utilization.

Summary of the invention

The object of the present invention is to provide a kind of manufactured size on nanoscale, have good electrochemical response, can realize the preparation method of the nanometer ring-disc electrode of high ring collection efficiency.

Technical scheme of the present invention is based on the nano metal electrode, seals and controlled steps such as ultrashort pulse electrochemical etching by metal sputtering, secondary, obtains the ring-disc electrode of nanoscale.

With the Pt-Ir nano electrode is that dish, sputter Au layer are that its concrete steps of preparation method of the nanometer ring-disc electrode of ring are:

1) preparation of Pt-Ir nano-electrode: by volume is saturated CaCl₂Solution: H₂O: acetone=1: (2～5): in the etchant solution of (1～2), obtain the Pt-Ir needle point with alternating voltage corrosion Pt-Ir silk, in the polyester Soluble Electrophoretic Paint, the Pt-Ir needle point is carried out electrophoresis, again through baking, electrophoretic paint molecule generation polymerization and form insulation course, insulation course shrinks at the most advanced and sophisticated place of needle point, thereby expose needle point than tip portion, obtain the Pt-Ir nano-electrode;

2) vacuum sputtering gold layer: with single Pt-Ir nano-electrode is disc electrode, forms the Au layer by vacuum sputtering, and this Au layer covers the forward part of Pt-Ir nano-electrode, as the ring electrode template;

3) secondary is sealed: the forward part of ring electrode template is sealed with the encapsulating material of heating and melting, treat its cooling after, the tip of exposing the ring electrode template;

4) ultrashort pulse electrochemical etching eseparation ring-dish: draw lead respectively at ring electrode template rear section exposed region and disc electrode, ring electrode template after secondary sealed places the HCl etching liquid, disc electrode connects positive pole, with respect to electrode is applied pulse voltage, whenever apply the resistance between the Au layer that detects disc electrode and sputter after the etching pulse, when resistance surpasses 109 ohm, stop etching, forming with the Pt-Ir nano electrode is that dish, sputter Au layer are the nanometer ring-disc electrode of ring.

In step 1), alternating voltage is preferably 5～20V.The tip size of Pt-Ir needle point is 10～1000nm.In the polyester Soluble Electrophoretic Paint, the voltage that the Pt-Ir needle point is carried out electrophoresis is 2～100V DC voltage, and the time of electrophoresis is preferably 3～10min.The temperature of baking is preferably 160～180 ℃ of bakings.By adjusting the length of electrophoresis time, can obtain the nano-electrode of different scale.Through electrochemical Characterization, the effective radius of this type of nano-electrode is 10～1000nm.

In step 2) in, the thickness of Au layer is 100～150nm.

In step 3), encapsulating material can be selected polymethylstyrene, nail wet goods for use.

In step 4), the concentration of HCl etching liquid is preferably 0.01～0.1mol/L.The pulse width of pulse voltage is 100～200ns, and pulse height is 1～1.2V.

With the Au nano electrode is that dish, sputter Au layer are that its concrete steps of preparation method of the nanometer ring-disc electrode of ring are:

1) preparation of Au nano-electrode: be fuming hydrochloric acid by volume: in the etchant solution of absolute ethyl alcohol=1: 1, obtain the Au needle point, in the polyester Soluble Electrophoretic Paint, the Au needle point is carried out electrophoresis with DC voltage corrosion Au silk; Again through baking, electrophoretic paint molecule generation polymerization and form insulation course, insulation course shrinks at the most advanced and sophisticated place of needle point, thereby exposes needle point than tip portion, obtains the Au nano-electrode.

2) vacuum sputtering gold layer: with single Au nano-electrode is disc electrode, forms the Au layer by vacuum sputtering, and this Au layer covers the forward part of Au nano-electrode, as the ring electrode template.

3) secondary is sealed: the forward part of ring electrode template is sealed with the encapsulating material of heating and melting, treat its cooling after, the tip of exposing the ring electrode template.

4) ultrashort pulse electrochemical etching eseparation ring-dish: draw lead respectively at ring electrode template rear section exposed region and disc electrode, ring electrode template after secondary sealed places the HCl etching liquid, disc electrode connects positive pole, with respect to electrode is applied pulse voltage, whenever apply the resistance between the Au layer that detects disc electrode and sputter after the etching pulse, when resistance surpasses 10⁹During ohm, stop etching, forming with the Au nano electrode is that dish, sputter Au layer are the nanometer ring-disc electrode of ring.

In step 1), DC voltage is preferably 2～3V.The tip size of Au needle point is 10～100nm.In the polyester Soluble Electrophoretic Paint, the voltage that the Au needle point is carried out electrophoresis is 2～100V DC voltage, and the time of electrophoresis is preferably 3～10min.The temperature of baking is preferably 160～180 ℃ of bakings.By adjusting the length of electrophoresis time, can obtain the nano-electrode of different scale.Through electrochemical Characterization, the effective radius of this type of nano-electrode is 10～500nm.

In step 2) in, the thickness of Au layer is 100～150nm.

In step 3), encapsulating material can be selected polymethylstyrene, nail wet goods for use.

In step 4), the concentration of HCl etching liquid is preferably 0.01～0.1mol/L.The pulse width of pulse voltage is 100～200ns, and pulse height is 1～1.2V.

Preparation method's cost of the present invention is low, and by vacuum sputtering and ultrashort pulse electrochemical etching, successfully associative ring electrode on single nano-electrode forms nanometer ring-disc electrode.Experimental results show that between ring electrode and the disc electrode and can set up good retroactive effect, the electrochemical Characterization collection efficiency reaches as high as 100%, apparently higher than the collection efficiency (30%) of conventional ring-disc electrode.

Description of drawings

Fig. 1 is the schematic flow sheet of the embodiment of the invention.

Fig. 2 is the structural representation of the employed ultrashort pulse electro chemical etching apparatus of the embodiment of the invention.

Fig. 3 is that 15nm, Au ring electrode effective radius are that the ring-disc electrode of 300nm is at 20mmol/L Ru (NH for Pt-Ir disc electrode effective radius₃)₆Cl₃Collect curve with 1mol/L KCl solution mid-game generation-ring.In Fig. 3, dotted line: dish produces reaction Ru (NH₃)₆³⁺+ e → Ru (NH₃)₆²⁺, current potential is scanned up to-350mV from 0V, and sweep velocity is 20mV/s; Solid line: ring is collected reaction Ru (NH₃)₆²⁺→ Ru (NH₃)₆³⁺+ e, control of Electric potentials is 0V, collection efficiency is 38%.

Fig. 4 is that 40nm, Au ring effective radius is that the ring-disc electrode of 800nm is at 20mmol/L Ru (NH for another Au disc electrode effective radius₃)₆Cl₃Collect curve with 1mol/LKCl solution mid-game generation-ring.In Fig. 4, dotted line: dish produces reaction Ru (NH₃)₆³⁺+ e → Ru (NH₃)₆²⁺, current potential is scanned up to-350mV from 0V, and sweep velocity is 20mV/s; Solid line: ring is collected reaction Ru (NH₃)₆²⁺→ Ru (NH₃)₆³⁺+ e, control of Electric potentials is 0V, collection efficiency is 75%.

In Fig. 3 and 4, horizontal ordinate is current potential Potential/V, and ordinate is electric current Current/A.

Embodiment

Embodiment 1

Fig. 1 provides the schematic flow sheet of the embodiment of the invention.In Fig. 1, divide 4 steps: a) preparation of metal nano electrode; B) vacuum sputtering Au thin layer; C) polymethylstyrene is sealed; D) ultrashort pulse electrochemical etching.Wherein code name 1 is a Pt-Ir metal needle point, and 2 is the electrophoretic paint encapsulated layer, and 3 are sputter Au layer, and 4 is the polymethylstyrene encapsulated layer.

Fig. 2 provides the structural representation of the employed ultrashort pulse electro chemical etching apparatus of the embodiment of the invention.In Fig. 2, Pt ringauxiliary electrode 5 connects the negative pole ofdirect supply 7, positive pole is then received disc electrode 6 by lead-in wire, controls the open and close state thatanalog switches 9 are controlled whole loop bycomputing machine 8, applies controlled ultrashort pulse voltage at disc electrode and between to electrode.

The Pt-Ir silk that is 0.25mm with the about 15mm diameter of a segment length carries out galvanic corrosion, etchant solution consist of saturated lime chloride 15ml, water 65ml, the mixed solution of acetone 20ml.Under the alternating voltage of 15V, 50Hz, corrode, obtain the Pt-Ir needle point.Electrophoretic paint (Glassophor GY850030) electrophoresis 9min under the 80V DC voltage with German BASF AG produces toasts 30min down at 180 ℃ then, forms nano-electrode.With Ru (NH₃)₆²⁺/ Ru (NH₃)₆³⁺Oxidation-reduction reaction is a probe reaction, estimates that by dome-type electrode limiting current formula I=2 π nFDC its effective radius is 15nm.The Au layer that the about 100nm of vacuum sputtering is thick is sealed through polymethylstyrene and to be placed in the 0.1mol/L HCl solution, is auxiliary electrode with Pt, apply 2 ultrashort pulse (100ns, 1.2V), front-end A u layer can be separated with disc electrode, obtain the ring electrode that effective radius is about 300nm.The effective radius that obtains the Pt-Ir disc electrode at last is that the effective radius of 15nm, Au ring electrode is the Au ring-Pt-Ir disc electrode of 300nm.With Ru (NH₃)₆²⁺/ Ru (NH₃)₆³⁺Oxidation-reduction reaction is that the electrochemical Characterization of probe reaction shows that the collection efficiency of ring was 38% (as shown in Figure 3).

Embodiment 2

In volume ratio is fuming hydrochloric acid: in the etchant solution of absolute ethyl alcohol=1: 1, be that the Au silk of 0.25mm obtains the Au needle point with 2.2V DC voltage corrosion diameter.Electrophoretic paint (Glassophor GY850030) electrophoresis 6min under the 100V DC voltage with German BASF AG produces toasts 30min down at 180 ℃ then, forms the Au nano-electrode.With Ru (NH₃)₆²⁺/ Ru (NH₃)₆³⁺Oxidation-reduction reaction is a probe reaction, estimates that by dome-type electrode limiting current formula I=2 π nFDC its effective radius is 40nm.The Au layer that the about 150nm of vacuum sputtering is thick is sealed through polymethylstyrene and to be placed on 0.05mol dm^-3In the HCl solution, be auxiliary electrode with Pt, (100ns 1.2V), can separate front-end A u layer with disc electrode, obtain the ring electrode that effective radius is about 800nm to apply 2 ultrashort pulses.The effective radius that obtains the Au disc electrode at last is that the effective radius of 40nm, Au ring electrode is the Au ring-Au disc electrode of 800nm.With Ru (NH₃)₆²⁺/ Ru (NH₃)₆³⁺Oxidation-reduction reaction is that the electrochemical Characterization of probe reaction shows that the collection efficiency of ring was 75% (as shown in Figure 4).

Embodiment 3

The Pt-Ir silk that is 0.25mm with the about 15mm diameter of a segment length carries out galvanic corrosion, etchant solution consist of saturated lime chloride 20ml, water 60ml, the mixed solution of acetone 20ml.Under the alternating voltage of 10V, 50Hz, corrode, obtain the Pt-Ir needle point.Electrophoretic paint (Glassophor GY850030) electrophoresis 3min under the 80V DC voltage with German BASF AG produces toasts 30min down at 170 ℃ then, forms the Pt-Ir nano-electrode.With Ru (NH₃)₆²⁺/ Ru (NH₃)₆³⁺Oxidation-reduction reaction is a probe reaction, estimates that by dome-type electrode limiting current formula I=2 π nFDC its effective radius is 200nm.The Au layer that the about 100nm of vacuum sputtering is thick is sealed through nail polish and to be placed in the 0.01mol/L HCl solution, is auxiliary electrode with Pt, apply 5 ultrashort pulse (100ns, 1.2V), front-end A u layer can be separated with disc electrode, obtain the Au ring electrode that effective radius is about 600nm.The effective radius that obtains the Pt-Ir disc electrode at last is that the effective radius of 200nm, Au ring electrode is the Au ring-Pt-Ir disc electrode of 600nm.

Embodiment 4

In volume ratio is fuming hydrochloric acid: in the etchant solution of absolute ethyl alcohol=1: 1, be that the Au silk of 0.25mm obtains the Au needle point with 2.1V DC voltage corrosion diameter.Electrophoretic paint (Glassophor GY850030) electrophoresis 3min under the 100V DC voltage with German BASF AG produces toasts 30min down at 170 ℃ then, forms the Au nano-electrode.With Ru (NH₃)₆²⁺/ Ru (NH₃)₆³⁺Oxidation-reduction reaction is a probe reaction, estimates that by dome-type electrode limiting current formula I=2 π nFDC its effective radius is 150nm.The Au layer that the about 150nm of vacuum sputtering is thick is sealed through nail polish and to be placed in the 0.02mol/L HCl solution, is auxiliary electrode with Pt, apply 8 ultrashort pulse (100ns, 1.2V), front-end A u layer can be separated with disc electrode, obtain the ring electrode that effective radius is about 900nm.The effective radius that obtains the Au disc electrode at last is that the effective radius of 150nm, Au ring electrode is the Au ring-Au disc electrode of 900nm.

Claims (10)

Translated fromChinese

1.一种纳米环-盘电极的制备方法，以Pt-Ir纳电极为盘、溅射Au层为环，其特征在于其步骤为：1. a kind of preparation method of nano ring-disc electrode, take Pt-Ir nano electrode as disc, sputtering Au layer as ring, it is characterized in that its steps are:1)Pt-Ir纳米电极的制备：在按体积比为饱和CaCl₂溶液∶H₂O∶丙酮＝1∶2～5∶1～2的腐蚀溶液中，用交流电压腐蚀Pt-Ir丝得到Pt-Ir针尖，在聚脂类水溶性电泳漆中，对Pt-Ir针尖进行电泳，再经烘烤，电泳漆分子发生聚合而形成绝缘层，绝缘层在针尖尖端处发生收缩，从而露出针尖较尖端部分，得到Pt-Ir纳米电极；1) Preparation of Pt-Ir nano-electrode: In the corrosion solution of saturated CaCl₂ solution: H₂ O: acetone = 1: 2～5: 1～2 by volume ratio, corrode Pt-Ir wire with AC voltage to obtain Pt -Ir needle tip, in polyester water-soluble electrophoretic paint, electrophoresis is performed on Pt-Ir needle tip, and then baked, the electrophoretic paint molecules polymerize to form an insulating layer, and the insulating layer shrinks at the tip of the needle tip, thus exposing the needle tip. Tip part, obtains Pt-Ir nano electrode;2)真空溅射金层：以单根Pt-Ir纳米电极为盘电极，通过真空溅射形成Au层，该Au层将Pt-Ir纳米电极的前部分覆盖，作为环电极模板；2) Vacuum sputtering gold layer: a single Pt-Ir nano-electrode is used as a disc electrode, and an Au layer is formed by vacuum sputtering, and the Au layer covers the front part of the Pt-Ir nano-electrode as a ring electrode template;3)二次包封：将环电极模板的前部分用加热熔融的包封材料包封，待其冷却后，露出环电极模板的尖端；3) Secondary encapsulation: Encapsulate the front part of the ring electrode template with a heated and melted encapsulation material, and after it cools down, expose the tip of the ring electrode template;4)超短脉冲电化学刻蚀分离环-盘：在环电极模板后部分裸露区域和盘电极分别引出导线，将二次包封后的环电极模板置于HCl刻蚀液中，盘电极接正极，相对于对电极施加脉冲电压，每施加一个刻蚀脉冲后检测盘电极和溅射的Au层之间的电阻，当阻值超过10⁹欧姆时，停止刻蚀，形成以Pt-Ir纳电极为盘、溅射Au层为环的纳米环-盘电极。4) Ultrashort pulse electrochemical etching to separate the ring-disk: Lead out the wires from the partially exposed area behind the ring electrode template and the disk electrode, place the ring electrode template after the second encapsulation in HCl etching solution, and connect the disk electrode to Positive electrode, apply pulse voltage to the counter electrode, detect the resistance between the disk electrode and the sputtered Au layer after each etching pulse is applied, and stop etching when the resistance value exceeds 10⁹ ohms, forming a Pt-Ir nanometer The electrode is a disk, and the sputtered Au layer is a nano-ring-disk electrode.2.如权利要求1所述的一种纳米环-盘电极的制备方法，其特征在于在步骤1)中，交流电压为5～20V；Pt-Ir针尖的尖端尺寸为10～1000nm；在聚脂类水溶性电泳漆中，对Pt-Ir针尖进行电泳的电压为2～100V直流电压，电泳的时间为3～10min；烘烤的温度为160～180℃烘烤。2. the preparation method of a kind of nano ring-disk electrode as claimed in claim 1 is characterized in that in step 1) in, alternating voltage is 5～20V; The tip size of Pt-Ir needle point is 10～1000nm; In the lipid water-soluble electrophoretic paint, the electrophoresis voltage on the Pt-Ir needle tip is 2-100V DC voltage, and the electrophoresis time is 3-10min; the baking temperature is 160-180°C.3.如权利要求1所述的一种纳米环-盘电极的制备方法，其特征在于在步骤2)中，Au层的厚度为100～150nm。3. The preparation method of a nano ring-disk electrode as claimed in claim 1, characterized in that in step 2), the thickness of the Au layer is 100-150 nm.4.如权利要求1所述的一种纳米环-盘电极的制备方法，其特征在于在步骤3)中，包封材料为聚甲基苯乙烯或指甲油。4. the preparation method of a kind of nano ring-disk electrode as claimed in claim 1 is characterized in that in step 3), encapsulating material is polymethylstyrene or nail polish.5.如权利要求1所述的一种纳米环-盘电极的制备方法，其特征在于在步骤4)中，HCl刻蚀液的浓度为0.01～0.1mol/L；脉冲电压的脉冲宽度为100～200ns，脉冲幅度为1～1.2V。5. the preparation method of a kind of nano ring-disk electrode as claimed in claim 1 is characterized in that in step 4), the concentration of HCl etching solution is 0.01～0.1mol/L; The pulse width of pulse voltage is 100 ~ 200ns, the pulse amplitude is 1 ~ 1.2V.6.一种纳米环-盘电极的制备方法，以Au纳电极为盘、溅射Au层为环，其特征在于其步骤为：6. A preparation method of a nano-ring-disc electrode, using an Au nano-electrode as a disc, and a sputtering Au layer as a ring, is characterized in that its steps are:1)Au纳米电极的制备：在按体积比为发烟盐酸∶无水乙醇＝1∶1的腐蚀溶液中，用直流电压腐蚀Au丝得到Au针尖，在聚脂类水溶性电泳漆中，对Au针尖进行电泳；再经烘烤，电泳漆分子发生聚合而形成绝缘层，绝缘层在针尖尖端处发生收缩，从而露出针尖较尖端部分，得到Au纳米电极；1) Preparation of Au nano-electrode: in the corrosion solution of fuming hydrochloric acid: absolute ethanol = 1: 1 by volume, corrode Au wire with DC voltage to obtain Au needle tip, in polyester water-soluble electrophoretic paint, for Electrophoresis is performed on the Au needle tip; after baking, the electrophoretic paint molecules polymerize to form an insulating layer, and the insulating layer shrinks at the tip of the needle tip, thereby exposing the tip part of the needle tip to obtain an Au nano-electrode;2)真空溅射金层：以单根Au纳米电极为盘电极，通过真空溅射形成Au层，该Au层将Au纳米电极的前部分覆盖，作为环电极模板；2) Vacuum sputtering gold layer: a single Au nanoelectrode is used as a disk electrode, and an Au layer is formed by vacuum sputtering, and the Au layer covers the front part of the Au nanoelectrode as a ring electrode template;3)二次包封：将环电极模板的前部分用加热熔融的包封材料包封，待其冷却后，露出环电极模板的尖端；3) Secondary encapsulation: Encapsulate the front part of the ring electrode template with a heated and melted encapsulation material, and after it cools down, expose the tip of the ring electrode template;4)超短脉冲电化学刻蚀分离环-盘：在环电极模板后部分裸露区域和盘电极分别引出导线，将二次包封后的环电极模板置于HCl刻蚀液中，盘电极接正极，相对于对电极施加脉冲电压，每施加一个刻蚀脉冲后检测盘电极和溅射的Au层之间的电阻，当阻值超过10⁹欧姆时，停止刻蚀，形成以Au纳电极为盘、溅射Au层为环的纳米环-盘电极。4) Ultrashort pulse electrochemical etching to separate the ring-disk: Lead out the wires from the partially exposed area behind the ring electrode template and the disk electrode, place the ring electrode template after the second encapsulation in HCl etching solution, and connect the disk electrode to Positive electrode, apply pulse voltage with respect to opposite electrode, detect the resistance between disc electrode and sputtered Au layer after applying an etching pulse, when the resistance exceeds 10⁹ ohms, stop etching, form Au nano-electrode as Disk, sputtered Au layer as ring nano-ring-disk electrode.7.如权利要求6所述的一种纳米环-盘电极的制备方法，其特征在于在步骤1)中，直流电压为2～3V；Au针尖的尖端尺寸为10～100nm；在聚脂类水溶性电泳漆中，对Au针尖进行电泳的电压为2～100V直流电压，电泳的时间为3～10min；烘烤的温度为160～180℃烘烤。7. the preparation method of a kind of nano-ring-disk electrode as claimed in claim 6 is characterized in that in step 1), DC voltage is 2～3V; The tip size of Au tip is 10～100nm; In polyester In the water-soluble electrophoretic paint, the voltage for electrophoresis on the Au needle tip is 2-100V DC voltage, and the electrophoresis time is 3-10 minutes; the baking temperature is 160-180°C.8.如权利要求6所述的一种纳米环-盘电极的制备方法，其特征在于在步骤2)中，Au层的厚度为100～150nm。8. The preparation method of a nano-ring-disk electrode as claimed in claim 6, characterized in that in step 2), the thickness of the Au layer is 100-150 nm.9.如权利要求6所述的-种纳米环-盘电极的制备方法，其特征在于在步骤3)中，包封材料为聚甲基苯乙烯可指甲油。9. the preparation method of a kind of nano ring-disk electrode as claimed in claim 6 is characterized in that in step 3), encapsulating material is polymethylstyrene nail polish.10.如权利要求6所述的一种纳米环-盘电极的制备方法，其特征在于在步骤4)中，HCl刻蚀液的浓度为0.01～0.1mol/L；脉冲电压的脉冲宽度为100～200ns，脉冲幅度为1～1.2V。10. the preparation method of a kind of nano-ring-disk electrode as claimed in claim 6 is characterized in that in step 4), the concentration of HCl etching solution is 0.01～0.1mol/L; The pulse width of pulse voltage is 100 ~ 200ns, the pulse amplitude is 1 ~ 1.2V.

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