CN104777203A - Preparation method of Pt-Ni alloy nano tube array electrode and application for enzyme-free glucose sensor - Google Patents
Preparation method of Pt-Ni alloy nano tube array electrode and application for enzyme-free glucose sensor Download PDFInfo
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- CN104777203A CN104777203A CN201510154106.1A CN201510154106A CN104777203A CN 104777203 A CN104777203 A CN 104777203A CN 201510154106 A CN201510154106 A CN 201510154106A CN 104777203 A CN104777203 A CN 104777203A
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Abstract
The invention relates to a preparation method of a Pt-Ni alloy nano tube array electrode and an application for an enzyme-free glucose sensor. A Ni nano wire array acts as a template, and the Pt-Ni alloy nano tube array electrode is prepared by adopting a current displacement method. The preparation method comprises the following steps: carrying out metal spraying treatment on one surface of a porous template comprising an AAO template and a PC template, fixing conductive silver glue on the surface of the electrode, and sealing the circumference of the template with insulation rubber; carrying out electric deposition in the porous template so as to prepare a Ni nano wire, and then removing the template so as to obtain the Ni nano wire array electrode; and preparing the Pt-Ni alloy nano tube array electrode by adopting a current displacement method, wherein a precursor solution is chloroplatinic acid or potassium chloroplatinate. The Pt-Ni alloy nano tube array electrode can be applied to an enzyme-free glucose sensor. The linear response range of the enzyme-free glucose sensor to glucose is 1-9Mm, and the detection sensitivity is 57.87micron AmM-1.
Description
Technical field
The invention belongs to electrode material technology, particularly relate to a kind of preparation method of Pt-Ni alloy nanotube array electrode and the application at enzyme-free glucose sensor.
Background technology
Diabetes are a kind of common diseases, diabetes can cause various diseases, comprise heart disease, kidney failure and blind etc., these complication can control to monitor by strict blood sugar concentration, therefore the control of monitor and managment to the state of an illness of blood sugar concentration is most important, makes blood sugar test become one of the most common analysis.Therefore the glucose sensor of simple and fast has the very large market demand, in numerous glucose sensor, electrochemical source of current type glucose sensor due to have simple, fast, sensitivity advantages of higher is widely studied.
In the past few decades, the research of glucolase sensor achieves huge achievement, but because the biosome intrinsic propesties that enzyme is intrinsic makes enzyme be easy to be subject to the impact of environment, the such as change of temperature, humidity, potential of hydrogen etc., capital affects the activity of enzyme, in addition complicated enzyme immobilizatio process, limits development and the application of glucolase sensor to a certain extent.Enzyme-free glucose sensor is that glucose detection provides a new approach.
Platinum (Pt) is one of electrode material the most often used in enzyme-free glucose sensor, Pt electrode catalyst avtive spot is less, not very high to the catalytic oxidation activity of glucose, have and can improve above-mentioned deficiency compared with the Pt nano material of bigger serface, have better effect to the catalytic oxidation of glucose.
Three-dimensional manometer array not only has larger specific surface area, add the number of active site in unit area, and three-dimensional manometer array sizes is neatly evenly distributed, be conducive to the resistance reducing electron transmission and reaction substrate diffusion, thus be conducive to the sensitivity and the response intensity that improve electrochemical catalysis, therefore the material of three-dimensional manometer array structure has good application prospect in enzyme-free glucose sensor.
Cubical array nano material has a variety of as the preparation method of electrode.The method that Hong Wang etc. utilizes AAO template electric-sedimentation and magnetron sputtering technique to combine, namely AAO Template preparation Pd nano-array is first utilized, then with Pd nano-wire array for substrate magnetron sputtering Pt layer shell, finally obtain the Pd-Pt nano-wire array of nucleocapsid structure.The people such as Mamun Jamal utilize the three-dimensional Au nano-wire array of template synthesis, then with three-dimensional Au nano wire for substrate continuous current electrodeposition Pt, obtain more orderly cubical array Pt nano line electrode.Liang Xin Ding etc. for template with the ZnO array of preparation, then form Pt-Ni-P shell by electrochemical co-deposition, in acid solution, then remove ZnO core, finally obtain Pt-Ni-P nano-tube array.But above method have high to equipment requirement, experiment material cost is high, the shortcoming of complicated operation.But the method utilizing electric current substitution method to prepare cubical array yet there are no all reports.The method of electric current displacement can save starting material, reduces the use amount of noble metal, reduces costs, and the method for electric current displacement does not need complicated instrument, and method of operating is simple, produces less waste products in course of reaction.
Principle due to electric current displacement reaction is the metal replacement standard electrode potential that the utilizes standard electrode potential low metal higher than it.Ni is as a kind of base metal, and its standard electrode potential is-0.23V (vs SHE.Ni
2++ 2e=Ni), the standard electrode potential of Pt is 1.20V (vs SHE.PtCl6
2-+ 4e=Pt+6Cl
-), both have larger potential difference (PD), and therefore Pt can cement out in the short time by Ni in theory.
Summary of the invention
The object of this invention is to provide a kind of preparation method of Pt-Ni alloy nanotube array electrode and the application at enzyme-free glucose sensor, the present invention for template, adopts the method for electric current displacement to prepare Pt-Ni alloy nanotube array with Ni nano-wire array.
There is researcher with ZnO array for template electric-sedimentation Pt-Ni alloy, then remove ZnO and obtain Pt-Ni alloy nanotube array electrode, have that specific surface area is large, surface reaction activity is high, to reaction substrate, there is good electro catalytic activity.But the preparation of ZnO array and removal complicated operation, extend experimental period, reduce conventional efficient.And the present invention directly with Ni nano-wire array for template, the method of electric current displacement is adopted to prepare Pt-Ni alloy nanotube array, larger potential difference (PD) can complete displacement reaction in the short time, decrease the generation of intermediate product, there is simple efficient feature, providing a kind of new method for preparing Pt-Ni alloy nanotube array.
The present invention modifies Au electrode with Pt-Ni alloy nanotube array, studies catalytic capability and performance study that it is used for building enzyme-free glucose sensor.
And general glucose enzyme electrode sensor stability is poor, limit its development and application to a certain extent, enzyme-free glucose sensor be examination of glucose concentration provide new by way of.The research that this research is enzyme-free glucose sensor provides new trial, the Pt-Ni alloy nanotube array electrode of gained has can directly catalysis glucose, specific surface area is large, active site is many feature, electro-chemical test is carried out to Pt-Ni alloy nanotube array electrode, have studied it and build enzyme-free glucose sensor to the catalytic oxidation ability of glucose and electronic conduction ability.
The preparation method of a kind of Pt-Ni alloy nanotube array electrode of the present invention and as follows in the application technology scheme of enzyme-free glucose sensor:
A preparation method for Pt-Ni alloy nanotube array electrode, with Ni nano-wire array for template, adopts electric current substitution method to prepare Pt-Ni alloy nanotube array electrode.
(1) template fixing at electrode surface
By a wherein metal spraying process of foraminous die plate, foraminous die plate comprises AAO template and PC template is fixed on electrode surface by conductive silver glue, uses electro-insulating rubber to seal around template;
(2) preparation of Pt-Ni alloy nanotube array
In foraminous die plate, Ni nano wire is prepared in electro-deposition, then remove template and obtain Ni nano line array electrode, electric current substitution method is adopted to prepare Pt-Ni alloy nanotube array electrode, precursor solution is chloroplatinic acid or potassium chloroplatinate, concentration range is 5 ~ 10mM, temperature range 30 ~ 60 DEG C, constant temperature electric current displacement 0.5 ~ 1h.
Be described as follows:
A kind of Pt-Ni alloy is received the preparation method of pipe array electrode and is:
1) process of electrode
Au electrode use before on chamois leather sanding and polishing, ultrasonic in ultrasonic cleaning machine, use deionized water rinsing, repeatedly ultrasonic irrigation 3 ~ 5 times, be placed in pH be 6.86 phosphate buffer cyclic voltammetry scan activation 10 ~ 15 circle;
2) AAO template fixing at Au electrode surface
AAO template incites somebody to action a wherein metal spraying before use, as electro-deposition conductive layer, painting conductive silver glue is dripped at Au electrode surface, by conductive silver glue, the metal spraying of AAO template one side is fixed on Au electrode surface, then use electrically insulating silicone rubber to seal AAO template edge, place and within one to two days, treat that it is dry.
3) preparation of Ni nano wire
Adopt three-electrode system, to modify the Au electrode of AAO template for working electrode, use electrochemical workstation prepare Ni nano-wire array by the method for galvanostatic deposition, electric depositing solution consist of NiSO
4, H
3bO
3, PEG-4000, Constant Electric Current mode of deposition is 0.35mA/cm
2, electro-deposition 1-2h; Then in the NaOH solution of 1M, soak 2h and fully remove template, deionized water is used to rinse removing NaOH solution gently, obtain the Ni nano-wire array after removing template, compared with the report of existing deposit N i nano wire, this Ni nano-wire array smooth surface standby by less galvanostatic deposition legal system is flawless, length regulates and controls by sedimentation time.
4) preparation of Pt-Ni alloy nanotube array
To remove the Ni nano-wire array of template for sacrificing template, be placed in the chloroplatinic acid of 5-10mM, displacement temperature 30-60 DEG C, time swap 0.5-1h, obtain Pt-Ni alloy nanotube array electrode.
Pt-Ni alloy nanotube array electrode of the present invention may be used for glucose without enzyme sensor, three-electrode system is adopted to carry out electro-chemical test, at room temperature, add or do not add in the phosphate buffer of pH=6.86 of glucose, carry out cyclic voltammetry scan, result display Pt-Ni alloy nanotube array electrode has obvious direct electrochemistry oxidation susceptibility to glucose, has showed the feasibility as glucose enzyme-free glucose sensor; Containing [Fe (CN)
6]
3-/4-kCl solution in carry out electronic conduction resistance measurement, Pt-Ni alloy nanotube array electrode shows good electronic conduction ability, is conducive to improving the sensitivity of testing result.Adopt the current-responsive of chronoamperometry test Pt-Ni alloy nanotube electrode pair different glucose, and linear fit is carried out to response current and concentration, calculate its range of linearity as enzyme-free glucose sensor, response sensitivity and detectability, the method that the present invention adopts electric current to replace with Ni nano-wire array for template prepares Pt-Ni alloy nanotube array electrode at Au electrode surface, obvious catalytic effect is had to glucose, the good range of linearity, the development for enzyme-free glucose sensor provides a kind of new research method.
Accompanying drawing explanation
AAO template fixing at Au electrode surface in Fig. 1 embodiment 1.
The scanning electron microscope vertical view of a) the Ni nano-wire array that galvanostatic deposition legal system is standby in Fig. 2 embodiment 1; B) the scanning electron microscope outboard profile of the Ni nano-wire array that galvanostatic deposition legal system is standby.
The scanning electron microscope (SEM) photograph of the Pt-Ni alloy nanotube array obtained after electric current displacement in Fig. 3 embodiment 1.
The EDS of the Pt-Ni alloy nanotube array obtained after electric current displacement in Fig. 4 embodiment 1 can spectrogram.
The cyclic voltammetry curve figure of Pt-Ni alloy nanotube array electrode in Fig. 5 embodiment 2, a) adds the CV curve map in the 0.1M PBS solution of the pH=6.86 of 10mM glucose; B) the CV curve map in the 0.1M PBS solution of the pH=6.86 of glucose is not added.
Ni nano line array electrode in Fig. 6 embodiment 2 before and after electric current displacement and the impedance diagram of Pt-Ni alloy nanotube array electrode.
The response current of Pt-Ni alloy nanotube array electrode and concentration of glucose graph of a relation in Fig. 7 embodiment 4.
The response current of Pt-Ni alloy nanotube array electrode and the linear fit curve of concentration in Fig. 8 embodiment 4.
Embodiment
1) configuration of glucose solution:
Configure the glucose solution 50mL of 10mM and 1M respectively, be placed in the refrigerator of 4 DEG C and preserve.
Three electrode test systems are adopted to carry out electro-chemical test to sample: wherein working electrode is the Au electrode (diameter 4mm) being modified with Pt-Ni alloy nanotube array, auxiliary electrode is Pt silk electrode (diameter 1mm), contrast electrode is potassium chloride saturated calomel electrode (SCE), set scanning voltage scope as in-0.3 ~ 0.8V, in the phosphate buffer (PBS) of the pH=6.86 of 0.1M, carry out cyclic voltammetry scan.
Carry out electrochemical impedance (EIS) analysis to Pt-Ni alloy nanotube array electrode, used test solution is the K containing 5mM
3[Fe (CN)
6] and the K of 5mM
4[Fe (CN)
6] 0.1M KCl solution.
Embodiment 1
Au electrode (diameter 4mm) use successively before using the alumina powder of 1.0 μm, 0.3 μm and 0.05 μm on chamois leather in 8-shaped polishing electrode surface, then the ultrasonic cleaning 5 times repeatedly of deionized water and ethanol is used, until electrode surface is mirror-smooth, then in the 0.1M phosphate buffer of pH=6.86, scanning voltage window is-0.3 ~ 0.8V, cyclic voltammetry scan 10 encloses, until scanning curve is stablized.Aperture is that the AAO template of 200nm incites somebody to action a wherein metal spraying before use, as electro-deposition conductive layer, painting conductive silver glue is dripped at Au electrode surface, spreadablely rapidly the metal spraying of AAO template one side is fixed on Au electrode surface afterwards by even for conductive silver glue, electrically insulating silicone rubber is used to fix AAO template edge, reserve the AAO template of Au electrode area size, place and within one day, treat that it is dry, AAO template is shown in accompanying drawing 1 at the fixing rough schematic of electrode surface.
Electrochemical workstation is used to prepare Ni nano-wire array by the method for galvanostatic deposition, adopt three-electrode system, with the Au electrode of fixing AAO template for working electrode, Pt silk electrode (diameter 1mm) is auxiliary electrode, saturated calomel electrode (SCE) is contrast electrode, configuration 40mL nickel salt electrolytic solution presoma, wherein 0.15M NiSO
4, 20g/L H
3bO
3, 10g/L PEG-4000, first soaks 15min by electrode before electro-deposition in the solution, and ultrasonic 30s, to discharge the air in AAO template duct, makes electric depositing solution fully enter the hole of template under 50W power.Carry out continuous current electro-deposition below, mode of deposition is set to 0.35mA/cm
2, electro-deposition 1h, gained Ni nanometer alignment is shown in accompanying drawing 2, and a Ni nano-wire array marshalling soilless sticking phenomenon, smooth surface are flawless as seen from the figure, and b nano-wire array height is about 2.2 μm.Electro-deposition terminates rear taking-up electrode and uses deionized water rinsing electrode, the electrolytic solution of removing electrode surface, then 2h is soaked under Ni nano line array electrode being put into the NaOH solution room temperature of 1M, make fully to remove template, taking out electrode uses deionized water to rinse out NaOH solution gently, obtains the Ni nano line array electrode after removing template.
Ni nano line array electrode after removal template is placed in the platinum acid chloride solution of the 5mM of 10mL, 30 DEG C of constant temperature electric current displacements, time swap is 1h, obtain the structure shown in accompanying drawing 3, substitution product is nano-tube array as we can see from the figure, wherein the external diameter of nanotube is about 250nm, thickness of pipe about 40 μm, tube wall is made up of alloying pellet, add the active site of unit area, the EDS of Pt-Ni alloy nanotube array can be shown in accompanying drawing 4 by spectrogram, as can be seen from the figure, peak and the Ni element peak of Pt element occur simultaneously, show that the success of Ni nano-wire array displaces Pt from the precursor solution of platinum, displacement reaction formula is as follows, due to the use of conductive silver glue, there is the peak of a small amount of Ag element.
2Ni+PtCl
6 2-＝Pt+2Ni
2++6Cl
-。
Embodiment 2
Polishing flannelet polishing electrode surface before Au electrode (diameter 4mm) uses, then the ultrasonic cleaning 3 times repeatedly of deionized water and ethanol is used, until electrode surface is mirror-smooth, then in the 0.1M phosphate buffer of pH=6.86, cyclic voltammetric 15 encloses, until scanning curve is stablized.AAO template incites somebody to action a wherein metal spraying before use, painting conductive silver glue is dripped at Au electrode surface, spreadablely rapidly the metal spraying of AAO template one side is fixed on Au electrode surface afterwards by even for conductive silver glue, electrically insulating silicone rubber is used to fix AAO template edge, reserve the AAO template of Au electrode area size, place 24h and treat that it is dry.
Electrochemical workstation is used to prepare Ni nano-wire array by the method for galvanostatic deposition, adopt three-electrode system, the Au electrode of fixing AAO template is working electrode, Pt silk electrode (diameter 1mm) is auxiliary electrode, saturated calomel electrode (SCE) is contrast electrode, the wherein 1.577g NiSO of configuration 40mL electrolytic solution
4, 0.8g H
3bO
3, 0.1g PEG-4000, first by electrode static soak 30min in the solution before electro-deposition, fully discharges the air in AAO template duct, makes electrolytic solution fully enter the hole of AAO template.Adopt Princeton 2263 type electrochemical workstation to carry out galvanostatic deposition, setting model is current density 0.35mA/cm
2, electrodeposition time 2h, obtains the Ni nano-wire array of height about 5 μm.Use deionized water rinsing template, the electrolytic solution of removing template surface, then Ni nano line array electrode is soaked in the NaOH solution of 1M 2h and remove template, after taking out array electrode, use a large amount of deionized water carefully to rinse out NaOH solution, obtain the Ni nano-wire array after removing template.
Ni nano line array electrode after removal template is placed in the platinum acid chloride solution of the 5mM of 10mL, electric current displacement 0.5h at 60 DEG C, after displacement reaction completes, a large amount of deionized water of use carefully rinses out solution and the impurity of electrode surface, obtains Pt-Ni alloy nanotube array electrode.Three electrode test systems are adopted to carry out electrochemical property test to electrode: wherein working electrode is Pt-Ni alloy nanotube array electrode, auxiliary electrode is Pt silk electrode (diameter 1mm), contrast electrode is potassium chloride saturated calomel electrode (SCE), set scanning voltage scope as in-0.3 ~ 0.8V, cyclic voltammetry scan is carried out in the phosphate buffer (PBS) of the pH=6.86 of 0.1M, sweep velocity is 10mV/s, as shown in Figure 5, wherein a line is the CV figure containing 10mM glucose, and b line is the CV figure not adding glucose.Both there is redox peak, relative to do not add glucose CV curve, adding the CV curve of glucose has more significantly oxidation peak, and oxidation peak current improves greatly, can find out that Pt-Ni alloy nanotube array has obvious catalytic action to glucose.
Embodiment 3
The alumina powder of 1.0 μm, 0.3 μm and 0.05 μm is used to polish on chamois leather Au electrode surface 10min, then the ultrasonic cleaning 5 times repeatedly of deionized water and ethanol is used, until electrode surface is mirror-smooth, then in the 0.1M phosphate buffer of pH=6.86, cyclic voltammetric 15 encloses, until scanning curve reappearance is better.Painting conductive silver glue is dripped at Au electrode surface, spreadablely rapidly the metal spraying of AAO template one side is fixed on Au electrode surface afterwards by even for conductive silver glue, use electrically insulating silicone rubber to fix AAO template edge, reserve the AAO template of Au electrode area size, its natural drying of left at room temperature one angel.
Electrochemical workstation is used to prepare Ni nano-wire array by the method for galvanostatic deposition, adopt three-electrode system, the Au electrode of fixing AAO template is working electrode, Pt silk electrode (diameter 1mm) is auxiliary electrode, saturated calomel electrode (SCE) is contrast electrode, and configuration 40mL's contains 0.15M NiSO
4, 20g/L H
3bO
3, 10g/L PEG-4000 the precursor solution of nickel, first electrode is soaked 20min in the solution before electro-deposition, and ultrasonic 30s, to discharge the air in AAO template duct, makes electric depositing solution fully enter the hole of template under 50W power.At 0.35mA/cm
2current density under deposit 1h, obtain Ni nano line array electrode.Use deionized water rinsing template, the electrolytic solution of removing template surface, then NaOH solution Ni nano line array electrode being put into 1M soaks 2h, fully reaction is made to remove AAO template, taking out array electrode uses deionized water to rinse out NaOH solution gently, obtains the Ni nano line array electrode after removing template.
Ni nano line array electrode after removal template is placed in the platinum acid chloride solution of the 10mM of 10mL, at 30 DEG C, carries out electric current displacement 0.5h.Use Princeton 2263 type electrochemical workstation, three electrode test systems are adopted to carry out electro-chemical test to sample: wherein working electrode is the Au electrode being modified with Pt-Ni alloy nanotube array, auxiliary electrode is Pt silk electrode (diameter 1mm), contrast electrode is potassium chloride saturated calomel electrode (SCE), is [the Fe (CN) of 5mM at solution
6]
3-/4-1M KCl solution in, impedance analysis is carried out to sample electrode.The frequency range of test is 10
5hz ~ 10
-2hz.Its comparing result is shown in accompanying drawing 6, can obviously find out from figure, and the electronic conduction impedance of Pt-Ni alloy nanotube array electrode is far smaller than the electronic conduction impedance of Ni nano line array electrode, close to the impedance of naked Au electrode.This may be due to after carrying out electric current displacement, defines the nano-tube array be made up of granule, and due to the synergy between Pt and Ni, electronic conduction ability is strengthened.Illustrate that Pt-Ni alloy nanotube array electrode is more conducive to the conduction of electronics.
Embodiment 4
Use polishing flannelet polishing Au electrode surface 10min, then use the ultrasonic cleaning 4 times repeatedly of deionized water and ethanol, until electrode surface be mirror-smooth, then in the PBS solution of pH=6.86, cyclic voltammetric 10 encloses, until scanning curve is stable.Painting conductive silver glue is dripped at Au electrode surface, spreadablely rapidly the metal spraying of AAO template one side is fixed on Au electrode surface afterwards by even for conductive silver glue, use electrically insulating silicone rubber to fix AAO template edge, reserve the AAO template of Au electrode area size, left at room temperature is dry.
Electrochemical workstation is used to prepare Ni nano-wire array by the method for galvanostatic deposition, adopt three-electrode system, the Au electrode of fixing AAO template is working electrode, Pt silk electrode (diameter 1mm) is auxiliary electrode, saturated calomel electrode (SCE) is contrast electrode, and configuration 40mL's contains 0.15M NiSO
4, 20g/L H
3bO
3, 10g/L PEG-4000 the precursor solution of nickel, first electrode is soaked 30min in the solution before electro-deposition, makes electric depositing solution fully enter the hole of template.At 0.35mA/cm
2current density under deposit 1h, obtain Ni nano line array electrode.Use deionized water rinsing template, the electrolytic solution of removing template surface, the NaOH solution then Ni nano line array electrode being put into 1M is soaked 2h and is removed AAO template and obtain the Ni nano line array electrode after removing template.
Ni nano line array electrode after removal template is placed in the potassium chloroplatinate solution of the 5mM of 10mL, at 30 DEG C, carries out electric current displacement 1h.Three-electrode system is adopted to carry out electro-chemical test: with Pt-Ni alloy nanotube array electrode for working electrode, saturated calomel electrode is contrast electrode, Pt silk electrode (diameter 1mm) is to electrode, get in the PBS solution of the pH=6.86 of the 0.1M of 40mL, under the condition stirred gently, at interval of certain hour, drip 40 μ L 1mol/L glucose solutions wherein successively, service time current method test response electric current.Utilize concentration of glucose and the mapping of response current magnitude relationship, see accompanying drawing 7, linear fit is carried out to response current size and concentration of glucose, sees accompanying drawing 8, result shows that the range of linearity of Pt-Ni alloy nanotube array enzyme-free glucose sensor is 1-9mM, and response sensitivity is 57.87 μ AmM
-1, related coefficient is 0.9991, and detectability can by formula 3 σ
b/ m tries to achieve, and m refers to the slope of fitting a straight line in accompanying drawing 8, σ
brefer to the standard deviation of blank signal under certain signal to noise ratio (S/N ratio), detection can be obtained and be limited to 174 μMs.
All methods and applications that the present invention discloses and proposes, those skilled in the art are by using for reference present disclosure, the links such as suitable feed change and process route realize, although methods and applications of the present invention are described by preferred embodiment, person skilled obviously can change methods and applications as herein described or reconfigure not departing from content of the present invention, spirit and scope, realizes final technology of preparing.Special needs to be pointed out is, all similar replacements and change apparent to those skilled in the art, they are deemed to be included in spirit of the present invention, scope and content.
Claims (4)
1. a preparation method for Pt ?Ni alloy nanotube array electrode, is characterized in that with Ni nano-wire array for template, adopts electric current substitution method to prepare Pt-Ni alloy nanotube array electrode.
2. the method for claim 1, is characterized in that the preparation method of described Pt-Ni alloy nanotube array is:
(1) template fixing at electrode surface
By a wherein metal spraying process of foraminous die plate, be fixed on electrode surface by conductive silver glue, use electro-insulating rubber to seal around template.
(2) preparation of Pt-Ni alloy nanotube array
In foraminous die plate, Ni nano wire is prepared in electro-deposition, then remove template and obtain Ni nano line array electrode, electric current substitution method is adopted to prepare Pt-Ni alloy nanotube array electrode, precursor solution is chloroplatinic acid or potassium chloroplatinate, concentration range is 5 ~ 10mM, temperature range 30 ~ 60 DEG C, constant temperature electric current displacement 0.5 ~ 1h.
3. method as claimed in claim 2, is characterized in that gained Ni nano-wire array height is 2 ~ 5 μm.
4.Pt-Ni alloy nanotube array electrode is used for enzyme-free glucose sensor.
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| CN105527319A (en) * | 2015-11-30 | 2016-04-27 | 中国科学院长春应用化学研究所 | Sample clamp for dielectric spectrometer |
| CN105675693A (en) * | 2016-01-13 | 2016-06-15 | 天津大学 | Preparation method of Pt nanometer particle-modified Cu nanowire array electrode and use of Pt nanometer particle-modified Cu nanowire array electrode in enzyme-free glucose sensor |
| CN108982615A (en) * | 2018-07-02 | 2018-12-11 | 浙江大学 | Based on nanochannel arrays surface spraying plating gold/platinum integrative electrochemical electrode system |
| CN108982612A (en) * | 2018-07-02 | 2018-12-11 | 浙江大学 | Integrative electrochemical electrode system based on nanochannel arrays surface spraying plating gold |
| CN108982615B (en) * | 2018-07-02 | 2020-08-11 | 浙江大学 | Integrated electrochemical electrode system based on nanochannel array surface gold/platinum spraying |
| CN110873746A (en) * | 2019-11-13 | 2020-03-10 | 西北工业大学 | Wearable glucose sensor based on platinum-nickel aerogel nanoenzyme sensitive chip |
| CN112993268A (en) * | 2019-12-18 | 2021-06-18 | 大连大学 | Nano nickel/nano platinum composite electrode based on GCE and application thereof |
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| CN111307904B (en) * | 2020-03-27 | 2023-03-24 | 西安工程大学 | Preparation method and application of bamboo-shaped copper-nickel nanowire array glucose sensor electrode |
| CN111505078A (en) * | 2020-05-20 | 2020-08-07 | 郑州轻工业大学 | Ni/Au composite nanowire array enzyme-free glucose sensor electrode and preparation method thereof |
| CN111505078B (en) * | 2020-05-20 | 2021-04-23 | 郑州轻工业大学 | Ni/Au composite nanowire array enzyme-free glucose sensor electrode and preparation method thereof |
| CN113189176B (en) * | 2020-05-20 | 2023-12-29 | 郑州轻工业大学 | Ni/Au composite nanowire array and application thereof in enzyme-free glucose sensor electrode |
| CN113189176A (en) * | 2020-05-20 | 2021-07-30 | 郑州轻工业大学 | Ni/Au composite nanowire array and application thereof in enzyme-free glucose sensor electrode |
| US11733199B2 (en) | 2020-09-24 | 2023-08-22 | Jiangsu University | Fabrication method of enzyme-free glucose sensor and use of enzyme-free glucose sensor fabricated by the same |
| WO2022062409A1 (en) * | 2020-09-24 | 2022-03-31 | 江苏大学 | Enzyme-free glucose sensor, manufacturing method for same, and uses thereof |
| CN112683967A (en) * | 2020-12-08 | 2021-04-20 | 中国科学院长春应用化学研究所 | Micro-nano charged electrode, preparation method thereof and enzyme-free biosensor |
| CN112683967B (en) * | 2020-12-08 | 2022-03-29 | 中国科学院长春应用化学研究所 | Micro-nano charged electrode, preparation method thereof and enzyme-free biosensor |
| CN113176315A (en) * | 2021-03-15 | 2021-07-27 | 杭州电子科技大学 | NiO/Au nanotube array flexible electrode with core-shell structure and application thereof |
| CN113176316A (en) * | 2021-03-15 | 2021-07-27 | 杭州电子科技大学 | Sheet Pt/NiCo alloy nano flexible electrode material and application thereof to enzyme-free glucose sensor |
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