CN114646672A - Nano composite electrode material for improving glucose sensing performance and preparation method thereof - Google Patents

Nano composite electrode material for improving glucose sensing performance and preparation method thereof Download PDF

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CN114646672A
CN114646672A CN202011507374.4A CN202011507374A CN114646672A CN 114646672 A CN114646672 A CN 114646672A CN 202011507374 A CN202011507374 A CN 202011507374A CN 114646672 A CN114646672 A CN 114646672A
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electrode material
nanotube
ticuo
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amorphous
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秦凤香
林宗领
陈�峰
池昱晨
王杭宁
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Nanjing University of Science and Technology
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    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y15/00—Nanotechnology for interacting, sensing or actuating, e.g. quantum dots as markers in protein assays or molecular motors
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y40/00—Manufacture or treatment of nanostructures
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    • C25D11/00—Electrolytic coating by surface reaction, i.e. forming conversion layers
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    • C—CHEMISTRY; METALLURGY
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    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
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    • C25D3/56—Electroplating: Baths therefor from solutions of alloys
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    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
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    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
    • G01N27/26—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating electrochemical variables; by using electrolysis or electrophoresis
    • G01N27/416—Systems
    • G01N27/48—Systems using polarography, i.e. measuring changes in current under a slowly-varying voltage

Abstract

The invention discloses a nano composite electrode material for improving glucose sensing performance, which has a composite structure formed by a double-layer nano structure, wherein the double-layer nano structure comprises a bottom layer structure and a surface layer structure, the bottom layer structure is a titanium-based amorphous alloy nanotube with an opening at the upper end surface, the surface layer structure is a nano structure formed by two transition metal elements, and the surface layer structure is attached to the upper end surface of the titanium-based amorphous alloy nanotube; wherein the transition metal elements are any two of Mn, Fe, Co, Ni and Cu. The invention also discloses a preparation method of the nano composite electrode material for improving the glucose sensing performance. The nano composite electrode material of the invention co-deposits the bimetallic element on the surface of the titanium-based amorphous alloy nanotube to form a nano composite structure, so that the electrode material has larger specific surface area, more active sites and faster electron transmission rate, and has higher sensitivity and lower detection limit when detecting glucose.

Description

Nano composite electrode material for improving glucose sensing performance and preparation method thereof
Technical Field
The invention relates to the technical field of nano metal functional materials, in particular to a nano composite electrode material for improving glucose sensing performance and a preparation method thereof.
Background
TiO2The nanotube is a novel inorganic functional material, has application in photocatalysis, dye sensitized batteries, sensors and other aspects due to unique porous structure and semiconductor characteristics, and is prepared from a crystalline alloy and a precursor which are basically adopted by the traditional titanium-based nanotube, because for most alloy systems, the amorphous forming capacity of the nanotube is limited, even the amorphous is not formed; secondly, amorphous alloys have strong corrosion resistance and are limited in the process of preparing nanostructured materials. However, the amorphous structure has a long-range disordered and short-range ordered structure, and when the nanotube structure is formed, the nanotubes arranged in order may further increase the specific surface area, increase the reactive sites, promote the catalytic oxidation in the reaction process, and improve the performance of the nanomaterial to a great extent.
The Chinese patent with the application number of 201810698988.1 discloses a Ti-based amorphous nanotube and a preparation method thereof, the nanotube is subjected to arc melting to obtain a Ti-based alloy ingot, an amorphous strip is obtained through single-roller melt-spinning, the amorphous nanotube is obtained through constant potential polarization in ethylene glycol electrolyte, and glucose is detected through catalysis by an electrochemical method, so that the nanotube with high sensitivity and low detection limit is obtained. However, when the nanotube is used for detecting glucose, the sensitivity and the detection limit of the nanotube need to be further improved.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provide a nano composite electrode material for improving the glucose sensing performance, the nano composite electrode material co-deposits bimetallic elements on the surface of a titanium-based amorphous alloy nanotube to form a nano composite structure, so that the electrode material has a larger specific surface area, more active sites and a faster electron transmission rate, and has higher sensitivity and a lower detection limit when detecting glucose.
Another object of the present invention is to provide a method for preparing a nanocomposite electrode material for improving glucose sensing performance.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows:
a nanometer composite electrode material for improving glucose sensing performance is provided with a composite structure formed by a double-layer nanometer structure, wherein the double-layer nanometer structure comprises a bottom layer structure and a surface layer structure, the bottom layer structure is a titanium-based amorphous alloy nanotube with an opening on the upper end surface, the surface layer structure is a nanometer structure formed by two transition metal elements, and the surface layer structure is attached to the upper end surface of the titanium-based amorphous alloy nanotube;
wherein, the transition metal elements are any two of Mn, Fe, Co, Ni and Cu.
Further, the nano structure of the surface layer is any one of a nano net structure, a nano cotton-like structure, a nano fragment structure, a nano cheese structure, a nano ball structure, a nano particle structure, a nano worm-like structure and a nano bud structure.
Further, the titanium-based amorphous alloy nanotube comprises a plurality of TiCuO amorphous alloy nanotubes, and the plurality of TiCuO amorphous alloy nanotubes are arranged in order to form a nanotube array structure.
Further, the specific surface area of the electrode material is 11-25 times that of the TiCuO amorphous alloy nanotube.
A preparation method of a nano composite electrode material for improving glucose sensing performance specifically comprises the following steps:
s1: preparation of titanium-based amorphous alloy nanotube
Preparing a TiCuO amorphous nanotube by an anodic oxidation method by taking a titanium-copper amorphous alloy strip as a substrate;
s2: preparation of nano composite electrode material
Taking the TiCuO amorphous nanotube obtained in the step S1 as a working electrode, a Pt sheet as a counter electrode and a saturated calomel electrode as a reference electrode, placing the working electrode, the counter electrode and the reference electrode in a deposition solution, connecting an electrochemical workstation, and depositing metal on the TiCuO amorphous nanotube by an electrochemical pulse deposition method;
and taking out the TiCuO amorphous nanotube with the deposited metal, washing in deionized water, and naturally drying at room temperature to obtain the required nano composite electrode material.
Further, the deposition solution in step S2 is a solution of chlorine salts of two transition metal elements at 0.01M to 0.3M, and the molar ratio of the two metals is 1 (1 to 3).
Further, in step S2, the parameters of the electrochemical pulse deposition method are: pulsed positive current density: + 40- +80mA/cm2The duration is 2-5 ms; pulsed positive current density: -30 to-80 mA/cm2The duration is 8-12 ms; circulating ring: 500 to 1000; pulse interval time: 50-100 ms.
Further, the temperature of the deposition solution was 35-40 ℃ and stirring was performed using magnetons at a stirring speed of 140-160 rpm.
Further, in step S2, the time for washing the metal-deposited tico amorphous nanotubes in deionized water is 30 to 60 seconds.
Further, the preparation method in step S1 is as follows: mixing Ti60Cu40Smelting metal simple substance to obtain mother alloy, and then carrying out quenching and strip throwing on the mother alloy through a copper roller rotating at high speed to obtain Ti60Cu40Amorphous alloy strip of Ti60Cu40And after the amorphous alloy strip is subjected to constant potential polarization treatment in ethylene glycol electrolyte, washing the amorphous alloy strip by using deionized water and absolute ethyl alcohol to obtain the TiCuO amorphous nanotube.
Compared with the prior art, the invention has the beneficial effects that:
1. the nano composite electrode material has a double-layer nano structure, the bottom layer is a TiCuO amorphous nano tube with an opening on the upper end surface, the surface layer is a nano structure formed by codeposition of two transition metal elements, the nano structure of the surface layer is formed by codeposition of the two transition metal elements on the upper end surface of the TiCuO amorphous nano tube through an electrochemical pulse deposition method, and the two transition metal elements jointly form a nano structure in the deposition process through specific conditions, the transition metal elements have strong oxidation-reduction performance due to the fact that the transition metal elements have a plurality of electron tracks and are easy to lose or obtain electrons, and simultaneously the two metal components also have synergistic effect, geometric effect or coupling effect, so that the nano composite electrode material has more excellent catalytic activity compared with a single metal component, the adhesion of the jointly formed nano structure and the nano tube is stronger, and the structural stability of the electrode material in the working process is enhanced, thereby ensuring the sensing performance thereof.
2. The electrode material has high specific surface area, and the part of the nano structure formed by codeposition penetrates into the nanotube without causing blockage, so that the specific surface area of the electrode material is further improved, the specific surface area of the electrode material is 11-25 times of that of the TiCuO amorphous alloy nanotube, the electrode material has more active sites, more attachment points are provided for glucose, more redox reaction sites are provided, and the reaction speed is accelerated; on the other hand, the electrode material has both excellent longitudinal electron transmission rate of the nanotube and excellent catalytic performance and conductivity of the transition metal element, and when detecting glucose, the sensitivity is as high as 3340 muA.mM < -1 >. cm < -2 >, and the detection limit is as low as 0.041 muM.
3. The electrode material has a self-supporting structure, avoids the pretreatment of catalytic electrode materials, is uniformly dispersed, cannot agglomerate in the working process, has high efficiency, is simple to operate and is easy to repeat; meanwhile, the electrode material disclosed by the invention is simple in preparation process, low in cost, short in time consumption, easy to industrially and widely apply, better in practicability, free of strong acid solution in the whole process, environment-friendly and beneficial to environmental protection.
Drawings
Fig. 1 and 2 are SEM images of the inventive tico amorphous nanotube.
FIG. 3 is an SEM photograph of the (Ni-Co)/TiCuO nanocomposite electrode material obtained in example 1.
FIG. 4 is a TEM surface scan of the (Ni-Co)/TiCuO nanocomposite electrode material obtained in example 1.
FIGS. 5a, 5b, and 5c are EDS maps of Ti, Ni, and Co, respectively, for FIG. 4.
FIGS. 6-14 are SEM images of the nanocomposite electrode materials obtained in examples 2-10, respectively.
Fig. 15 is a fitted straight line graph of the electrochemical active areas of four samples of the electrode material of example 1, the tico amorphous nanotube, the electrode material of comparative example 1, and the electrode material of comparative example 2.
Fig. 16 is a fitted straight line graph of the electrochemical active areas of four samples of the electrode material of example 1, the tico amorphous nanotube, the electrode material of comparative example 1, and the electrode material of comparative example 2.
Detailed Description
In order to better understand the technical content of the present invention, specific embodiments are described below with reference to the accompanying drawings.
The raw materials in the following examples were all purchased commercially unless otherwise specified.
Example 1
S1: preparation of titanium-based amorphous alloy nanotube
Mixing Ti and Cu with purity of 99.99% according to Ti60Cu40Weighing the required mass, putting the weighed mass into an electric arc melting furnace, repeatedly melting the alloy for 5 times in the atmosphere of high-purity argon, and simultaneously turning on magnetic stirring to ensure that the alloy elements are uniformly mixed; taking out an alloy ingot, polishing to remove an oxide layer on the surface, putting the alloy ingot into a quartz tube for 5g, and spinning under the atmosphere of high-purity argon to prepare a strip with the width of about 1mm and the thickness of about 20 microns; cutting a small part, welding with nickel wire, coating with common nail polish, and maintaining the exposed surface area of the strip at 0.3cm2(ii) a The prepared sample was placed as an anode and a platinum sheet as a counter electrode in about 50ml of ethylene glycol electrolyte as 0.2 wt% NH4F+2.0vol％H2And applying constant voltage 15V for polarization for 4h by using an electrochemical workstation, taking out, placing in deionized water, ultrasonically cleaning for 5s, and then cleaning with absolute ethyl alcohol to obtain the TiCuO amorphous nanotube.
S2: preparation of (Ni-Co)/TiCuO nano composite electrode material
Taking the TiCuO amorphous nanotube obtained in the step S1 as a working electrode, a Pt sheet as a counter electrode and a saturated calomel electrode as a reference electrode, and placing the working electrode, the counter electrode and the reference electrode in 0.02M NiCl2+0.02M CoCl2In the solution, the temperature of the solution is 40 ℃, magnetons are used for stirring at the speed of 150rpm and are connected with an electrochemical workstation, and Ni-Co is deposited on the TiCuO amorphous nano tube by an electrochemical pulse deposition method; the pulse deposition conditions were: negative current-50 mA/cm2(8ms), positive current 40mA/cm2(2ms), pulse interval 100ms, cycle number 1000 cycles.
Taking out the TiCuO amorphous nanotube deposited with Ni-Co, washing in deionized water for 60s, and naturally drying at room temperature to obtain the required (Ni-Co)/TiCuO nano composite electrode material.
Example 2
S1: preparation of titanium-based amorphous alloy nanotube
Mixing Ti and Cu with purity of 99.99% according to Ti60Cu40Weighing the required mass, putting the weighed mass into an electric arc melting furnace, repeatedly melting the alloy for 5 times in the atmosphere of high-purity argon, and simultaneously turning on magnetic stirring to ensure that the alloy elements are uniformly mixed; taking out an alloy ingot, polishing to remove an oxide layer on the surface, putting the alloy ingot into a quartz tube for 5g, and spinning under the atmosphere of high-purity argon to prepare a strip with the width of about 1mm and the thickness of about 20 microns; cutting a small part, welding with nickel wire, coating with common nail polish, and maintaining the exposed surface area of the strip at 0.3cm2(ii) a The prepared sample was placed as an anode and a platinum sheet as a counter electrode in about 50ml of ethylene glycol electrolyte as 0.2 wt% NH4F+2.0vol％H2And applying constant voltage 15V for polarization for 4h by using an electrochemical workstation, taking out, placing in deionized water, ultrasonically cleaning for 5s, and then cleaning with absolute ethyl alcohol to obtain the TiCuO amorphous nanotube.
S2: preparation of (Ni-Fe)/TiCuO nano composite electrode material
Taking the TiCuO amorphous nanotube obtained in the step S1 as a working electrode, a Pt sheet as a counter electrode and a saturated calomel electrode as a reference electrode, and carrying out counter electrode treatment on the working electrode and the counter electrodeThe electrode and reference electrode are placed in a 0.01M NiCl2+0.02M FeCl2In the solution, the temperature of the solution is 35 ℃, magnetons are used for stirring at the speed of 140rpm and are connected with an electrochemical workstation, and Ni-Co is deposited on the TiCuO amorphous nano tube by an electrochemical pulse deposition method; the pulse deposition conditions were: negative current-40 mA/cm2(8ms) positive current 60mA/cm2(2ms), pulse interval 50ms, cycle number 1000 cycles.
Taking out the TiCuO amorphous nanotube deposited with Ni-Fe, washing in deionized water for 40s, and naturally drying at room temperature to obtain the required (Ni-Fe)/TiCuO nano composite electrode material.
Example 3
S1: preparation of titanium-based amorphous alloy nanotube
Mixing Ti and Cu with purity of 99.99% according to Ti60Cu40Weighing the required mass, putting the weighed mass into an electric arc melting furnace, repeatedly melting the alloy for 5 times in the atmosphere of high-purity argon, and simultaneously turning on magnetic stirring to ensure that the alloy elements are uniformly mixed; taking out an alloy ingot, polishing to remove an oxide layer on the surface, putting the alloy ingot into a quartz tube for 5g, and spinning under the atmosphere of high-purity argon to prepare a strip with the width of about 1mm and the thickness of about 20 microns; cutting a small part, welding with nickel wire, coating with common nail polish, and maintaining the exposed surface area of the strip at 0.3cm2(ii) a The prepared sample was placed as an anode and a platinum sheet as a counter electrode in about 50ml of ethylene glycol electrolyte as 0.2 wt% NH4F+2.0vol％H2And applying constant voltage 15V for polarization for 4h by using an electrochemical workstation, taking out, placing in deionized water, ultrasonically cleaning for 5s, and then cleaning with absolute ethyl alcohol to obtain the TiCuO amorphous nanotube.
S2: preparation of (Ni-Mn)/TiCuO nano composite electrode material
Taking the TiCuO amorphous nanotube obtained in the step S1 as a working electrode, a Pt sheet as a counter electrode and a saturated calomel electrode as a reference electrode, and placing the working electrode, the counter electrode and the reference electrode in 0.1M NiCl2+0.3M MnCl2In the solution, the temperature of the solution is 35 ℃, magnetons are used for stirring at the speed of 160rpm and are connected with an electrochemical workstation, and Ni-Mn is deposited to TiCuO amorphous nano-particles by an electrochemical pulse deposition methodOn the tube; the pulse deposition conditions were: negative current-80 mA/cm2(8ms) positive current 60mA/cm2(2ms), pulse interval 70ms, cycle number 500 cycles.
And taking out the TiCuO amorphous nanotube deposited with Ni-Mn, washing in deionized water for 40s, and naturally drying at room temperature to obtain the required (Ni-Mn)/TiCuO nano composite electrode material.
Example 4
S1: preparation of titanium-based amorphous alloy nanotube
Mixing Ti and Cu with purity of 99.99% according to Ti60Cu40Weighing the required mass, putting the weighed mass into an electric arc melting furnace, repeatedly melting the alloy for 5 times in the atmosphere of high-purity argon, and simultaneously turning on magnetic stirring to ensure that the alloy elements are uniformly mixed; taking out an alloy ingot, polishing to remove an oxide layer on the surface, putting the alloy ingot into a quartz tube for 5g, and spinning under the atmosphere of high-purity argon to prepare a strip with the width of about 1mm and the thickness of about 20 microns; cutting a small part, welding with nickel wire, coating with common nail polish, and maintaining the exposed surface area of the strip at 0.3cm2(ii) a The prepared sample was placed as an anode and a platinum sheet as a counter electrode in about 50ml of ethylene glycol electrolyte as 0.2 wt% NH4F+2.0vol％H2And applying constant voltage 15V for polarization for 4h by using an electrochemical workstation, taking out, placing in deionized water, ultrasonically cleaning for 5s, and then cleaning with absolute ethyl alcohol to obtain the TiCuO amorphous nanotube.
S2: preparation of (Co-Cu)/TiCuO nano composite electrode material
Taking the TiCuO amorphous nanotube obtained in the step S1 as a working electrode, a Pt sheet as a counter electrode and a saturated calomel electrode as a reference electrode, and placing the working electrode, the counter electrode and the reference electrode in 0.07M CuCl2+0.07M CoCl2In the solution, the temperature of the solution is 35 ℃, magnetons are used for stirring at the speed of 160rpm and are connected with an electrochemical workstation, and Co-Cu is deposited on the TiCuO amorphous nano tube by an electrochemical pulse deposition method; the pulse deposition conditions were: negative current-50 mA/cm2(8ms), positive current 80mA/cm2(2ms), pulse interval 60ms, cycle number 1000 cycles.
And taking out the CuO amorphous nanotube deposited with the Co-Cu, washing the CuO amorphous nanotube in deionized water for 30s, and naturally drying the washed CuO amorphous nanotube at room temperature to obtain the required (Co-Cu)/CuO nano composite electrode material.
Example 5
S1: preparation of titanium-based amorphous alloy nanotube
Mixing Ti and Cu with purity of 99.99% according to Ti60Cu40Weighing the required mass, putting the weighed mass into an electric arc melting furnace, repeatedly melting the alloy for 5 times in the atmosphere of high-purity argon, and simultaneously turning on magnetic stirring to ensure that the alloy elements are uniformly mixed; taking out an alloy ingot, polishing to remove an oxide layer on the surface, putting the alloy ingot into a quartz tube for 5g, and spinning under the atmosphere of high-purity argon to prepare a strip with the width of about 1mm and the thickness of about 20 microns; cutting a small part, welding with nickel wire, coating with common nail polish, and maintaining the exposed surface area of the strip at 0.3cm2(ii) a The prepared sample was placed as an anode and a platinum sheet as a counter electrode in about 50ml of ethylene glycol electrolyte as 0.2 wt% NH4F+2.0vol％H2And applying constant voltage 15V for polarization for 4h by using an electrochemical workstation, taking out, placing in deionized water, ultrasonically cleaning for 5s, and then cleaning with absolute ethyl alcohol to obtain the TiCuO amorphous nanotube.
S2: preparation of (Fe-Mn)/TiCuO nano composite electrode material
Taking the TiCuO amorphous nanotube obtained in the step S1 as a working electrode, a Pt sheet as a counter electrode and a saturated calomel electrode as a reference electrode, and placing the working electrode, the counter electrode and the reference electrode in 0.03M FeCl2+0.06M MnCl2In the solution, the temperature of the solution is 35 ℃, magnetons are used for stirring at the speed of 160rpm and are connected with an electrochemical workstation, and Fe-Mn is deposited on the TiCuO amorphous nano-tube by an electrochemical pulse deposition method; the pulse deposition conditions were: negative current-70 mA/cm2(8ms) positive current 60mA/cm2(2ms), pulse interval 80ms, cycle number 800 cycles.
And taking out the TiCuO amorphous nanotube deposited with Fe-Mn, washing in deionized water for 30s, and naturally drying at room temperature to obtain the required (Fe-Mn)/TiCuO nano composite electrode material.
Example 6
S1: preparation of titanium-based amorphous alloy nanotube
Mixing Ti and Cu with purity of 99.99% according to Ti60Cu40Weighing the required mass, putting the weighed mass into an electric arc melting furnace, repeatedly melting the alloy for 5 times in the atmosphere of high-purity argon, and simultaneously turning on magnetic stirring to ensure that the alloy elements are uniformly mixed; taking out an alloy ingot, polishing to remove an oxide layer on the surface, putting the alloy ingot into a quartz tube for 5g, and spinning under the atmosphere of high-purity argon to prepare a strip with the width of about 1mm and the thickness of about 20 mu m; cutting a small part, welding with nickel wire, coating with common nail polish, and maintaining the exposed surface area of the strip at 0.3cm2(ii) a The prepared sample was placed as an anode and a platinum sheet as a counter electrode in about 50ml of ethylene glycol electrolyte as 0.2 wt% NH4F+2.0vol％H2And applying constant voltage 15V for polarization for 4h by using an electrochemical workstation, taking out, placing in deionized water, ultrasonically cleaning for 5s, and then cleaning with absolute ethyl alcohol to obtain the TiCuO amorphous nanotube.
S2: preparation of (Fe-Co)/TiCuO nano composite electrode material
Taking the TiCO amorphous nanotube obtained in the step S1 as a working electrode, a Pt sheet as a counter electrode and a saturated calomel electrode as a reference electrode, and placing the working electrode, the counter electrode and the reference electrode in 0.08M FeCl2+0.08M CoCl2In the solution, the temperature of the solution is 35 ℃, magnetons are used for stirring at the speed of 160rpm and are connected with an electrochemical workstation, and Fe-Co is deposited on the TiCuO amorphous nano tube by an electrochemical pulse deposition method; the pulse deposition conditions were: negative current-40 mA/cm2(8ms), positive current 50mA/cm2(2ms), pulse interval 90ms, cycle number 800 cycles.
Taking out the TiCuO amorphous nanotube deposited with Fe-Co, washing in deionized water for 60s, and naturally drying at room temperature to obtain the required (Fe-Co)/TiCuO nano composite electrode material.
Example 7
S1: preparation of titanium-based amorphous alloy nanotube
Mixing Ti and Cu with purity of 99.99% according to Ti60Cu40The required mass is weighed and put into an electric arc melting furnace, the alloy is repeatedly melted for 5 times in the atmosphere of high-purity argon, and magnetic stirring is started at the same time,ensuring that the alloy elements are uniformly mixed; taking out an alloy ingot, polishing to remove an oxide layer on the surface, putting the alloy ingot into a quartz tube for 5g, and spinning under the atmosphere of high-purity argon to prepare a strip with the width of about 1mm and the thickness of about 20 microns; cutting a small part, welding with nickel wire, coating with common nail polish, and maintaining the exposed surface area of the strip at 0.3cm2(ii) a The prepared sample was placed as an anode and a platinum sheet as a counter electrode in about 50ml of ethylene glycol electrolyte as 0.2 wt% NH4F+2.0vol％H2And applying constant voltage 15V polarization for 4h by using an electrochemical workstation, taking out the product, placing the product in deionized water, performing ultrasonic cleaning for 5s, and then cleaning with absolute ethyl alcohol to obtain the TiCuO amorphous nanotube.
S2: preparation of (Mn-Co)/TiCuO nano composite electrode material
Taking the TiCO amorphous nanotube obtained in the step S1 as a working electrode, a Pt sheet as a counter electrode and a saturated calomel electrode as a reference electrode, and placing the working electrode, the counter electrode and the reference electrode in 0.05M MnCl2+0.15M CoCl2In the solution, the temperature of the solution is 35 ℃, magnetons are used for stirring at the speed of 160rpm and are connected with an electrochemical workstation, and Mn-Co is deposited on the TiCuO amorphous nano tube by an electrochemical pulse deposition method; the pulse deposition conditions were: negative current-80 mA/cm2(8ms) positive current 60mA/cm2(2ms), pulse interval 90ms, cycle number 500 cycles.
And taking out the TiCuO amorphous nanotube deposited with Mn-Co, washing in deionized water for 60s, and naturally drying at room temperature to obtain the required (Mn-Co)/TiCuO nano composite electrode material.
Example 8
S1: preparation of titanium-based amorphous alloy nanotube
Mixing Ti and Cu with purity of 99.99% according to Ti60Cu40Weighing the required mass, putting the weighed mass into an electric arc melting furnace, repeatedly melting the alloy for 5 times in the atmosphere of high-purity argon, and simultaneously turning on magnetic stirring to ensure that the alloy elements are uniformly mixed; taking out an alloy ingot, polishing to remove an oxide layer on the surface, putting the alloy ingot into a quartz tube for 5g, and spinning under the atmosphere of high-purity argon to prepare a strip with the width of about 1mm and the thickness of about 20 microns; cutting a small part, welding with nickel wire, and using common nailCoating oil on the welding position, and ensuring the exposed surface area of the strip to be 0.3cm2(ii) a The prepared sample was placed as an anode and a platinum sheet as a counter electrode in about 50ml of ethylene glycol electrolyte as 0.2 wt% NH4F+2.0vol％H2And applying constant voltage 15V for polarization for 4h by using an electrochemical workstation, taking out, placing in deionized water, ultrasonically cleaning for 5s, and then cleaning with absolute ethyl alcohol to obtain the TiCuO amorphous nanotube.
S2: preparation of (Ni-Cu)/TiCuO nano composite electrode material
Taking the TiCuO amorphous nanotube obtained in the step S1 as a working electrode, a Pt sheet as a counter electrode and a saturated calomel electrode as a reference electrode, and placing the working electrode, the counter electrode and the reference electrode in 0.07M NiCl2+0.07M CuCl2In the solution, the temperature of the solution is 35 ℃, magnetons are used for stirring at the speed of 160rpm and are connected with an electrochemical workstation, and Ni-Cu is deposited on the TiCuO amorphous nano-tube by an electrochemical pulse deposition method; the pulse deposition conditions were: negative current-65 mA/cm2(8ms), positive current 30mA/cm2(2ms), pulse interval 60ms, cycle number 1000 cycles.
Taking out the TiCuO amorphous nanotube deposited with Ni-Cu, washing in deionized water for 60s, and naturally drying at room temperature to obtain the required (Ni-Cu)/TiCuO nano composite electrode material.
Example 9
S1: preparation of titanium-based amorphous alloy nanotube
Mixing Ti and Cu with purity of 99.99% according to Ti60Cu40Weighing the required mass, putting the weighed mass into an electric arc melting furnace, repeatedly melting the alloy for 5 times in the atmosphere of high-purity argon, and simultaneously turning on magnetic stirring to ensure that the alloy elements are uniformly mixed; taking out an alloy ingot, polishing to remove an oxide layer on the surface, putting the alloy ingot into a quartz tube for 5g, and spinning under the atmosphere of high-purity argon to prepare a strip with the width of about 1mm and the thickness of about 20 microns; cutting a small part, welding with nickel wire, coating with common nail polish, and maintaining the exposed surface area of the strip at 0.3cm2(ii) a The prepared sample was placed as an anode and a platinum sheet as a counter electrode in about 50ml of ethylene glycol electrolyte as 0.2 wt% NH4F+2.0vol％H2Electrochemical engineering for O utilizationAnd (3) applying a constant voltage of 15V for polarization for 4h, taking out, putting in deionized water, ultrasonically cleaning for 5s, and then cleaning with absolute ethyl alcohol to obtain the TiCuO amorphous nanotube.
S2: preparation of (Fe-Cu)/TiCuO nano composite electrode material
Taking the TiCuO amorphous nanotube obtained in the step S1 as a working electrode, a Pt sheet as a counter electrode and a saturated calomel electrode as a reference electrode, and placing the working electrode, the counter electrode and the reference electrode in 0.03M FeCl2+0.03M CuCl2In the solution, the temperature of the solution is 35 ℃, magnetons are used for stirring at the speed of 160rpm and are connected with an electrochemical workstation, and Fe-Cu is deposited on the TiCuO amorphous nano tube by an electrochemical pulse deposition method; the pulse deposition conditions were: negative current-65 mA/cm2(8ms), positive current 30mA/cm2(2ms), pulse interval 60ms, cycle number 1000 cycles.
And taking out the TiCuO amorphous nanotube deposited with the Fe-Cu, washing the TiCuO amorphous nanotube in deionized water for 60s, and naturally drying the TiCuO amorphous nanotube at room temperature to obtain the required (Fe-Cu)/TiCuO nano composite electrode material.
Example 10
S1: preparation of titanium-based amorphous alloy nanotube
Ti and Cu with the purity of 99.99 percent are mixed according to the Ti60Cu40Weighing the required mass of the alloy, putting the alloy into an electric arc melting furnace, repeatedly melting the alloy for 5 times in the atmosphere of high-purity argon, and simultaneously opening magnetic stirring to ensure that the alloy elements are uniformly mixed; taking out an alloy ingot, polishing to remove an oxide layer on the surface, putting the alloy ingot into a quartz tube for 5g, and spinning under the atmosphere of high-purity argon to prepare a strip with the width of about 1mm and the thickness of about 20 microns; cutting a small part, welding with nickel wire, coating with common nail polish, and maintaining the exposed surface area of the strip at 0.3cm2(ii) a The prepared sample was placed as an anode and a platinum sheet as a counter electrode in about 50ml of ethylene glycol electrolyte containing 0.2 wt% NH4F+2.0vol％H2And applying constant voltage 15V for polarization for 4h by using an electrochemical workstation, taking out, placing in deionized water, ultrasonically cleaning for 5s, and then cleaning with absolute ethyl alcohol to obtain the TiCuO amorphous nanotube.
S2: preparation of (Mn-Cu)/TiCuO nano composite electrode material
Taking the TiCuO amorphous nanotube obtained in the step S1 as a working electrode, a Pt sheet as a counter electrode and a saturated calomel electrode as a reference electrode, and placing the working electrode, the counter electrode and the reference electrode in 0.02M MnCl2+0.02M CuCl2In the solution, the temperature of the solution is 35 ℃, magnetons are used for stirring at the speed of 160rpm and are connected with an electrochemical workstation, and Mn-Cu is deposited on the TiCuO amorphous nanotube by an electrochemical pulse deposition method; the pulse deposition conditions were: negative current-65 mA/cm2(8ms), positive current 55mA/cm2(2ms), pulse interval 100ms, cycle number 600 cycles.
And taking out the TiCuO amorphous nanotube deposited with Mn-Cu, washing in deionized water for 60s, and naturally drying at room temperature to obtain the required (Mn-Cu)/TiCuO nano composite electrode material.
Comparative example 1
S1: preparation of titanium-based amorphous alloy nanotube
Mixing Ti and Cu with purity of 99.99% according to Ti60Cu40Weighing the required mass, putting the weighed mass into an electric arc melting furnace, repeatedly melting the alloy for 5 times in the atmosphere of high-purity argon, and simultaneously turning on magnetic stirring to ensure that the alloy elements are uniformly mixed; taking out an alloy ingot, polishing to remove an oxide layer on the surface, putting the alloy ingot into a quartz tube for 5g, and spinning under the atmosphere of high-purity argon to prepare a strip with the width of about 1mm and the thickness of about 20 microns; cutting a small part, welding with nickel wire, coating common nail polish on the welding part, and ensuring the exposed surface area of the strip to be 0.3cm 2; and (3) placing the prepared sample as an anode and a platinum sheet as a counter electrode into about 50ml of ethylene glycol electrolyte, applying a constant voltage of 0.2 wt% NH4F +2.0 vol% H2O for 4H by using an electrochemical workstation, taking out, placing in deionized water, ultrasonically cleaning for 5s, and then cleaning with absolute ethyl alcohol to obtain the TiCuO amorphous nanotube.
S2: preparation of Ni/TiCuO nano composite electrode material
Taking the TiCuO amorphous nanotube obtained in the step S1 as a working electrode, a Pt sheet as a counter electrode and a saturated calomel electrode as a reference electrode, and placing the working electrode, the counter electrode and the reference electrode in 0.02M NiCl2In the solution, the temperature of the solution is 40 ℃, and the magneton is used for 15 DEG CStirring at the speed of 0rpm, connecting an electrochemical workstation, and depositing Ni on the TiCuO amorphous nanotube by an electrochemical pulse deposition method; the pulse deposition conditions were: negative current-50 mA/cm2(8ms), positive current 40mA/cm2(2ms), pulse interval 100ms, cycle number 1000 cycles.
And taking out the TiCuO amorphous nanotube deposited with the Ni, washing the TiCuO amorphous nanotube in deionized water for 60s, and naturally drying the TiCuO amorphous nanotube at room temperature to obtain the required Ni/TiCuO nano composite electrode material.
Comparative example 2
S1: preparation of titanium-based amorphous alloy nanotube
Mixing Ti and Cu with purity of 99.99% according to Ti60Cu40Weighing the required mass of the alloy, putting the alloy into an electric arc melting furnace, repeatedly melting the alloy for 5 times in the atmosphere of high-purity argon, and simultaneously opening magnetic stirring to ensure that the alloy elements are uniformly mixed; taking out an alloy ingot, polishing to remove an oxide layer on the surface, putting the alloy ingot into a quartz tube for 5g, and spinning under the atmosphere of high-purity argon to prepare a strip with the width of about 1mm and the thickness of about 20 mu m; cutting a small part, welding with nickel wire, coating common nail polish on the welding part, and ensuring the exposed surface area of the strip to be 0.3cm 2; and (3) placing the prepared sample as an anode and a platinum sheet as a counter electrode into about 50ml of ethylene glycol electrolyte, applying a constant voltage of 0.2 wt% NH4F +2.0 vol% H2O for 4H by using an electrochemical workstation, taking out, placing in deionized water, ultrasonically cleaning for 5s, and then cleaning with absolute ethyl alcohol to obtain the TiCuO amorphous nanotube.
S2: preparation of Co/TiCuO nano composite electrode material
Taking the TiCuO amorphous nanotube obtained in the step S1 as a working electrode, a Pt sheet as a counter electrode and a saturated calomel electrode as a reference electrode, and placing the working electrode, the counter electrode and the reference electrode in 0.02M CoCl2In the solution, the temperature of the solution is 40 ℃, magnetons are used for stirring at the speed of 150rpm and are connected with an electrochemical workstation, and Co is deposited on the TiCuO amorphous nanotube by an electrochemical pulse deposition method; the pulse deposition conditions were: negative current-50 mA/cm2(8ms), positive current 40mA/cm2(2ms), pulse interval 100ms, cycle number 1000 cycles.
And taking out the Co-deposited TiCuO amorphous nanotube, washing the Co-deposited TiCuO amorphous nanotube in deionized water for 60s, and naturally drying the Co-deposited TiCuO amorphous nanotube at room temperature to obtain the required Co/TiCuO nano composite electrode material.
[ characterization ] A
1. SEM, TEM and EDS
Fig. 1 and 2 are SEM images of the tico amorphous nanotubes, and it can be seen from the SEM images that the tico amorphous nanotubes are open at the upper end surface, and a plurality of tico amorphous alloy nanotubes are arranged in order to form a nanotube array structure.
FIG. 3 is an SEM image of the (Ni-Co)/TiCuO nanocomposite electrode material obtained in example 1, in which it can be seen that a Ni-Co bimetal element forms a nano-network structure on the surface of the TiCuO amorphous nanotube; fig. 4 is a TEM scan corresponding to the (Ni-Co)/tico nanocomposite electrode material, and it can be seen from fig. 4 that the middle 2 region of the two transverse lines is a structure of longitudinally closely arranged nanotubes, the region 3 below the lower transverse line is a TiCu amorphous alloy substrate, and the region 1 above the upper transverse line is a nano-mesh structure formed by Co-deposition of Ni-Co bimetallic, which corresponds to the SEM; FIGS. 5a, 5b and 5c clearly show that the Co-deposited elements on the titanium-based nanotubes are Ni and Co, and some enter the inside of the nanotubes; and the EDS results showed that the Ni element content was 9.10 at.%, the Co element content was 33.83 at%
Fig. 6 to 14 are SEM images of the nanocomposite electrode materials obtained in examples 2 to 10, respectively, and it can be seen from the SEM images that the Ni — Fe bimetallic element forms a nano-cotton-like structure on the surface of the amorphous nanotube in the nanocomposite electrode material obtained in example 2, wherein the content of the Ni element is 29.21 at.%, and the content of the Fe element is 12.03 at.%; in the nanocomposite electrode material obtained in example 3, a Ni — Mn bimetallic element forms a nano-fragment structure on the surface of an amorphous nanotube, wherein the content of the Ni element is 19.32 at.%, and the content of the Mn element is 21.83 at.%; in the nanocomposite electrode material obtained in example 4, a Co-Cu bimetallic element forms a nano cheese structure on the surface of the amorphous nanotube, wherein the Co element content is 20.11 at.%, and the Cu element content is 21.33 at.%; in the nanocomposite electrode material obtained in example 5, a Fe-Mn bimetallic element forms a nanosphere structure on the surface of an amorphous nanotube, wherein the content of the Fe element is 10.34 at.%, and the content of the Mn element is 32.66 at.%; in the nanocomposite electrode material obtained in example 6, Fe — Co bimetallic elements form a nanoparticle structure on the surface of the amorphous nanotube, wherein the Fe element content is 12.44 at.%, and the Co element content is 29.79 at.%; in the nanocomposite electrode material obtained in example 7, Mn — Co bimetallic elements form a nanobud-like structure on the surface of the amorphous nanotube, where the content of Fe is 7.39 at.%, and the content of Co is 35.22 at.%; in the nanocomposite electrode material obtained in example 8, a Ni — Cu bimetallic element forms a nanofabric structure on the surface of an amorphous nanotube, wherein the content of the Ni element is 17.54 at.%, and the content of the Cu element is 25.01 at.%; in the nanocomposite electrode material obtained in example 9, a Fe-Cu bimetallic element forms a nanofbract structure on the surface of an amorphous nanotube, wherein the content of the Fe element is 25.36 at.%, and the content of the Cu element is 17.88 at.%; in the nanocomposite electrode material obtained in example 10, Mn — Cu bimetallic elements form a nanoparticle structure on the surface of an amorphous nanotube, where the content of Mn element is 13.84 at.%, and the content of Cu element is 27.91 at.%; as can be seen from EDS, in the materials obtained in the examples, the nanostructure formed on the surface of the tico amorphous nanotube was composed of the target deposit metal element.
2. Specific surface area
FIG. 15 is a fitting straight line of electrochemical active areas of four samples, i.e., (Ni-Co)/TiCuO nanocomposite electrode material prepared in example 1, TiCuO amorphous nanotube, Ni/TiCuO nanocomposite electrode material obtained in comparative example 1, and Co/TiCuO nanocomposite electrode material obtained in comparative example 2, according to the slope of the straight line, the size of the electrochemical active area (i.e., specific surface area) can be determined, and half of the slope of the straight line is the capacitance value CdlThe obtained capacitance value CdlThe specific surface area of the electrode material can be obtained by dividing the standard capacitance (0.04 mF). The specific surface areas are respectively: the (Ni-Co)/TiCuO nano composite electrode material is 57.25cm-2The Ni/TiCuO nano composite electrode material is 16.25cm-2The Co/TiCuO nano composite electrode material is 3.15cm-2The thickness of the TiCuO amorphous nanotube is 2.28cm-2Namely, the specific surface area of the (Ni-Co)/TiCuO nano composite electrode material is 25 times of that of the TiCuO amorphous nano tube.
The specific surface areas of the (Ni-Fe)/TiCuO nanocomposite electrode material obtained in example 2 were measured by the same method and found to be 33.25cm-214 times of the TiCuO amorphous nanotube; the specific surface areas of the (Ni-Mn)/TiCuO nanocomposite electrode material obtained in example 3 were 41.38cm each-218 times of the TiCuO amorphous nanotube; the specific surface areas of the (Co-Cu)/TiCuO nanocomposite electrode materials obtained in example 4 were 45.11cm each-219 times of the TiCuO amorphous nanotube; the specific surface areas of the (Fe-Mn)/TiCuO nanocomposite electrode materials obtained in example 5 were 26.42cm each-211 times of the TiCuO amorphous nanotube; the specific surface areas of the (Fe-Co)/TiCuO nanocomposite electrode material obtained in example 6 were 35.89cm each-215 times of the TiCuO amorphous nanotube; the specific surface areas of the (Mn-Co)/TiCuO nanocomposite electrode material obtained in example 7 were 45.64cm-220 times of the TiCuO amorphous nanotube; the specific surface areas of the (Ni-Cu)/TiCuO nanocomposite electrode materials obtained in example 8 were each 25.71cm-211 times of the TiCuO amorphous nanotube; the specific surface areas of the (Fe-Cu)/TiCuO nanocomposite electrode material obtained in example 9 were each 30.27cm-213 times of the TiCuO amorphous nanotube; the specific surface areas of the (Mn-Cu)/TiCuO nanocomposite electrode materials obtained in example 10 were 36.47cm each-216 times of the TiCO amorphous nanotube.
From the above results, the specific surface area of the TiCuO amorphous nanotube deposited with the bimetallic element is larger than that of the original TiCuO amorphous nanotube, and is 11-25 times of that of the TiCuO amorphous alloy nanotube.
[ Performance test ]
The (Ni-Co)/tico nanocomposite electrode material prepared in example 1, the tico amorphous nanotube, the Ni/tico nanocomposite electrode material obtained in comparative example 1, and the Co/tico nanocomposite electrode material obtained in comparative example 2 were used as electrodes, the performance of catalytic oxidation of glucose by each electrode material was measured by cyclic voltammetry and chronoamperometry, glucose solutions of different concentrations were respectively dropped to perform current response, the current response curve of each electrode material was fitted to the glucose concentration, the slope of the fitted curve represents the sensitivity of the electrode material to glucose sensing, the larger the slope, the higher the sensitivity, and the results are shown in fig. 15, which shows that the sensitivity of the electrode material to glucose sensing was from high to low: the (Ni-Co)/TiCuO nano composite electrode material is more than the Ni/TiCuO nano composite electrode material is more than the Co/TiCuO nano composite electrode material is more than the TiCuO amorphous nano tube.
The limit of detection refers to the corresponding amount of 3-fold value of the instrument background signal generated by the matrix blank, or the mean value of the background signal generated by the matrix blank plus the mean standard deviation of 3-fold. According to the formula L, kSb/S (wherein Sb is the standard deviation of blank multiple measurement, S is the sensitivity of the measurement method, namely the slope obtained above, k is a coefficient determined according to a certain confidence level, and is generally 3.29), the detection limit of the obtained (Ni-Co)/TiCuO nano composite electrode material is 0.041 mu M, the detection limit of the Ni/TiCuO nano composite electrode material is 0.052 mu M, the detection limit of the Co/TiCuO nano composite electrode material is 0.183 mu M, the detection limit of the TiCuO amorphous nanotube is 0.290 mu M, and the detection limit of the (Ni-Co)/TiCuO nano composite electrode material is the lowest.
Although the present invention has been described with reference to the preferred embodiments, it is not intended to be limited thereto. Those skilled in the art can make various changes and modifications without departing from the spirit and scope of the invention. Therefore, the protection scope of the present invention should be defined by the appended claims.

Claims (10)

1. A nanocomposite electrode material for improving glucose sensing performance, comprising: the nano composite electrode material has a composite structure formed by double-layer nano structures, wherein each double-layer nano structure comprises a bottom layer structure and a surface layer structure, the bottom layer structure is a titanium-based amorphous alloy nanotube with an opening on the upper end surface, the surface layer structure is a nano structure formed by two transition metal elements, and the surface layer structure is attached to the upper end surface of the titanium-based amorphous alloy nanotube;
wherein the transition metal elements are any two of Mn, Fe, Co, Ni and Cu.
2. The nanocomposite electrode material for improving glucose sensing performance of claim 1, wherein: the surface nanostructure is any one of a nano net structure, a nano cotton-like structure, a nano fragment structure, a nano cheese structure, a nano ball structure, a nano particle structure, a nano worm-like structure and a nano bud structure.
3. The nanocomposite electrode material for improving glucose sensing performance of claim 1, wherein: the titanium-based amorphous alloy nanotube comprises a plurality of TiCuO amorphous alloy nanotubes which are arranged in order to form a nanotube array structure.
4. The nanocomposite electrode material for improving glucose sensing performance according to any one of claims 1 to 3, wherein: the specific surface area of the electrode material is 11-25 times of that of the TiCuO amorphous alloy nanotube.
5. The preparation method of the nanocomposite electrode material for improving glucose sensing performance according to any one of claims 1 to 4, which comprises the following steps:
s1: preparation of titanium-based amorphous alloy nanotube
Preparing a TiCuO amorphous nanotube by an anodic oxidation method by taking a titanium-copper amorphous alloy strip as a substrate;
s2: preparation of nano composite electrode material
Taking the TiCuO amorphous nanotube obtained in the step S1 as a working electrode, a Pt sheet as a counter electrode and a saturated calomel electrode as a reference electrode, placing the working electrode, the counter electrode and the reference electrode in a deposition solution, connecting an electrochemical workstation, and depositing metal on the TiCuO amorphous nanotube by an electrochemical pulse deposition method;
and taking out the TiCuO amorphous nanotube with the deposited metal, washing in deionized water, and naturally drying at room temperature to obtain the required nano composite electrode material.
6. The method of claim 5, wherein the step of preparing the nanocomposite electrode material for improving glucose sensing performance comprises: the deposition solution in step S2 is a 0.01M-0.3M solution of chloride salts of two transition metal elements, and the molar ratio of the two metals is 1 (1-3).
7. The method of claim 5, wherein the step of preparing the nanocomposite electrode material for improving glucose sensing performance comprises: in step S2, the parameters of the electrochemical pulse deposition method are: pulsed positive current density: + 40- +80mA/cm2The duration is 2-5 ms; pulsed positive current density: minus 30 to minus 80mA/cm2The duration is 8-12 ms; circulating and looping: 500 to 1000; pulse interval time: 50-100 ms.
8. The method for preparing a nanocomposite electrode material for improving glucose sensing performance according to claim 5 or 6, wherein: the temperature of the deposition solution was 35-40 ℃ and stirring was carried out using a magneton at a stirring speed of 140-160 rpm.
9. The method of claim 5, wherein the step of preparing the nanocomposite electrode material for improving glucose sensing performance comprises: in step S2, the time for washing the metal-deposited tico amorphous nanotubes in deionized water is 30-60S.
10. The method for preparing a nanocomposite electrode material for improving glucose sensing performance according to claim 5, wherein the preparation method in the step S1 is as follows: mixing Ti60Cu40Smelting metal simple substance to obtain mother alloy, and then carrying out quenching and strip throwing on the mother alloy through a copper roller rotating at high speed to obtain Ti60Cu40Amorphous alloy strip of Ti60Cu40And after the amorphous alloy strip is subjected to constant potential polarization treatment in ethylene glycol electrolyte, washing the amorphous alloy strip by using deionized water and absolute ethyl alcohol to obtain the TiCuO amorphous nanotube.
CN202011507374.4A 2020-12-18 2020-12-18 Nano composite electrode material for improving glucose sensing performance and preparation method thereof Pending CN114646672A (en)

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CN103409657A (en) * 2013-07-08 2013-11-27 北京航空航天大学 (Zr100-tTit)xCuyRz bulk amorphous alloy as well as preparation method and application thereof in non-enzyme glucose sensor electrode
CN110656257A (en) * 2018-06-29 2020-01-07 南京理工大学 Method for preparing nano porous gold based on titanium-based amorphous alloy
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Publication number Priority date Publication date Assignee Title
CN103409657A (en) * 2013-07-08 2013-11-27 北京航空航天大学 (Zr100-tTit)xCuyRz bulk amorphous alloy as well as preparation method and application thereof in non-enzyme glucose sensor electrode
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