CN107907578A - The preparation of amino-acid complex nano silver sensor electrode and its detection to hydrogen peroxide - Google Patents
The preparation of amino-acid complex nano silver sensor electrode and its detection to hydrogen peroxide Download PDFInfo
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- CN107907578A CN107907578A CN201711103936.7A CN201711103936A CN107907578A CN 107907578 A CN107907578 A CN 107907578A CN 201711103936 A CN201711103936 A CN 201711103936A CN 107907578 A CN107907578 A CN 107907578A
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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
- G01N27/28—Electrolytic cell components
- G01N27/30—Electrodes, e.g. test electrodes; Half-cells
- G01N27/327—Biochemical electrodes, e.g. electrical or mechanical details for in vitro measurements
- G01N27/3275—Sensing specific biomolecules, e.g. nucleic acid strands, based on an electrode surface reaction
- G01N27/3278—Sensing specific biomolecules, e.g. nucleic acid strands, based on an electrode surface reaction involving nanosized elements, e.g. nanogaps or nanoparticles
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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
- G01N27/28—Electrolytic cell components
- G01N27/30—Electrodes, e.g. test electrodes; Half-cells
- G01N27/327—Biochemical electrodes, e.g. electrical or mechanical details for in vitro measurements
- G01N27/3275—Sensing specific biomolecules, e.g. nucleic acid strands, based on an electrode surface reaction
- G01N27/3277—Sensing specific biomolecules, e.g. nucleic acid strands, based on an electrode surface reaction being a redox reaction, e.g. detection by cyclic voltammetry
Abstract
The present invention provides a kind of preparation method of amino-acid complex nano silver sensor electrode, and the detection method of the electrode pair concentration of hydrogen peroxide obtained using this method.The invention mainly utilizes anodizing and high temperature ammonia reduction method, and titanium nitride film is prepared in titanium sheet, and the Nano silver deposition of amino-acid complex is made sensor electrode on titanium nitride film matrix, and the electroanalysis for concentration of hydrogen peroxide detects.The method constitutes the nano silver of amino-acid complex using the reduction and protective effect of amino acid; the catalytic activity of nano silver can effectively be kept; concerted catalysis in combination with titanium nitride film itself acts on; improve the electro catalytic activity and stability of sensor electrode; and electrode, when being used for electroanalysis and detecting, the response time is short, test limit is low, high sensitivity, the range of linearity is wide, cost is low.
Description
Technical field
The present invention relates to electrochemical analysis technical field of measurement and test, and amino acid auxiliary synthesis is utilized more particularly, to one kind
Nano silver, the electricity of hydrogen peroxide sensor is formed more particularly to a kind of amino-acid complex nano silver of potentiodynamic method deposition
Pole, and use it for concentration of hydrogen peroxide detection.
Technical background
It is a kind of common raw material of industry that hydrogen peroxide, which is also known as hydrogen peroxide, and a kind of important chemicals in organism
Matter, hydrogen peroxide detection have great importance in fields such as environment, food, chemical industries.At present, hydrogen peroxide surveys method bag
Include titration, spectroscopic methodology, fluorescence method, chemoluminescence method, chromatography and electrochemical process etc..Wherein in electrochemical process, based on no enzyme
The hydrogen peroxide detection of electrochemical sensor, which causes, is extensively studied interest.For most of no enzyme electrochemical sensors
Speech, their excellent electron transporting properties and efficient selectivity depend on selecting suitable elctro-catalyst and basis material
In numerous elctro-catalyst candidate materials, the electric conductivity of silver-colored (Ag) is best, and price is also relatively cheap.Silver
The synthetic method of nanostructured has very much, needs mostly using organic solvent, reducing agent and additive etc..As Green Chemistry is general
Thought is rooted in the hearts of the people, and silver nanostructured green synthesis techniques are increasingly valued by the people.Amino acid is considered to health
It is safe, friendly, sustainable with environment.Amino acid molecular, such as tyrosine, tryptophan, by amino acid molecular
- NH2Interact with-COOH group and elargol matter, amino acid molecular can wrap up nano silver and form decorative layer, form one
Stable network frame, makes it possess stable catalytic performance.Amino acid possesses certain reproducibility and protective effect at the same time, when
After amino-acid complex silver nano-grain, silver can be protected not oxidized in atmosphere, presence is stabilized it and keep high electricity to urge
Change activity.Therefore the sensor constructed by amino-acid complex nano silver has more high sensitivity, selectivity to hydrogen peroxide detection
With low test limit.
The content of the invention
In order to prepare, a kind of response time is short, test limit is low, high sensitivity, the range of linearity are wide, favorable reproducibility, stability
The hydrogen peroxide good, cost is low is without enzyme electrochemical sensor, and the present invention proposes a kind of reduction using amino acid and protection is made
With, auxiliary synthesizing nano-silver modified electrode, and use it for detecting hydrogen peroxide without enzyme electrochemical analysis.
The technical scheme is that：
1st, a kind of amino-acid complex nano silver modified electrode, it is characterised in that the electrode is prepared as follows：With light
As base electrode, platinum electrode is auxiliary electrode for bright titanium sheet, titanium dioxide film or titanium nitride film, and Ag/AgCl is reference electrode,
Contain 10~500mM of nitric acid potassium concn, 0.1~5mM of silver nitrate concentration, 1~10mM of amino acid concentration (preferably 0.5~2.0mM)
Deposition liquid in, stirring it is lower using potentiodynamic method in controlling potential -0.8V~1.6V, 20~50 DEG C of temperature, sweep speed
10~200mVs-1, dynamic potential scanning 1~20 week, obtains amino-acid complex nano silver modified electrode.
The material that can be used as base electrode in the present invention can be carbon material in addition to titanium nitride film, as glass carbon, carbon paper,
Carbon felt etc.；It can also be electro-conductive glass either metallic copper etc.；It can also be the titanium sheet through certain process, titanium-based titanium dioxide
Titanium film, titanium-based titanium nitride film etc..Currently preferred is a kind of titanium nitride film of the growth in situ in titanium sheet.
The preferable titanium nitride film can be used as base electrode, be to be made by two step method, this two step method includes：
Carry out that titanium dioxide film is made in anodic oxidation and high-temperature ammonolysis subsequently in ammonia atmosphere is reduced in titanium plate surface.It is specifically walked
It is rapid as follows：
(1) surface treatment of titanium sheet：The requirement for the high-purity titanium sheet chosen：Purity is more than 99.5%；Thickness selection 0.1mm~
3.0mm；After clipped, 10MPa cold pressings, working face is surface-treated (chemical polishing processing).At the chemical polishing
Reason：Using acetone as degreasing fluid, titanium sheet is subjected to 5~15min of ultrasonic cleaning, is cleaned after taking-up with flowing water, at 20~30 DEG C into
0.5~1min of row chemical polishing, the polishing fluid are urea: ammonium fluoride: hydrogen peroxide (mass concentration 30%): (quality is dense for concentrated nitric acid
The mixed liquor of 68%)=1: 15: 40: 40 (mass ratio) is spent, uses absolute ethyl alcohol after polishing respectively, acetone and deionized water ultrasound are clear
15min is washed, obtains bright, clean titanium sheet.
(2) titanium-based titanium dioxide film is made using anodizing, the anode oxidation method includes：Choose first high
Pure titanium sheet is surface-treated titanium sheet, then using the titanium sheet after surface treatment as anode, large area Pt pieces are made as matrix
For cathode, in the dilution heat of sulfuric acid of 0.5~2M, controlled at 20~40 DEG C, initial current density is arranged to 100~
500A·m-1, 10~50V of DC voltage range, when the electrolytic oxidation time is 0.5~3h small, obtains titanium-based titanium dioxide film.
(3) titanium nitride film is made using high-temperature ammonolysis reduction, the high-temperature ammonolysis includes：First, by obtained by step (2)
Titanium dioxide film is placed in tube furnace, in pure N2Under protection, the temperature of tube furnace is risen to 400~500 DEG C by room temperature, heating
Speed is 2~20 DEG C/min, when fire box temperature reaches 400~500 DEG C, when constant temperature protection 0.5~2 is small.Then, by tube furnace
In gas be switched to high-purity ammonia, purity more than 99.99%, rises to 800~1100 DEG C, heating rate by the temperature of tube furnace
For 1~10 DEG C/min, constant temperature nitrogenizes 1~5h, cools to room temperature with the furnace, takes out, you can obtain titanium nitride film matrix.
Further, the feature of amino acid of the present invention is non-fat race's amino acid, suitably aromatic amino acid,
Heterocyclic amino acid and heterocyclic imino acid, and the side chain feature in amino acid shows as hydrophobicity, amino dissociation constant is more than
9.21, carboxyl dissociation constant is more than 2.20, and preferable amino acid is phenylalanine, tryptophan, tyrosine and proline.
Further, the nano silver of potentiodynamic method deposited amino acids complexing, purity nitrogen gas bell is used before testing
15min, to remove the dissolved oxygen deposited in liquid, and electrode modification process need to carry out under purity nitrogen gas shielded.
2nd, the present invention also provides the amino-acid complex nano silver modified electrode as no enzyme electrochemical sensor electrodes
For the application in the detection of concentration of hydrogen peroxide.The amino-acid complex nano silver modified electrode of the preparation can be directly as biography
Sensor electrode is used for the detection of concentration of hydrogen peroxide.Detection method is as follows：
(1) certain density phosphate buffer solution (PBS) is prepared as detection bottom liquid, the concentration of PBS is 0.01~0.2M,
Use KH2PO4It is 2.0~8.0 to adjust pH value with KOH solution.
(2) working electrode using the amino-acid complex nano silver modified electrode as no enzyme hydrogen peroxide sensor, platinum electricity
Extremely auxiliary electrode, Ag/AgCl are reference electrode, form three-electrode system, and stir PBS solution, stirring speed with constant rate of speed
Rate is 500~2000 revs/min.
(3) apply constant cathode potential -0.1~-0.6V in amino-acid complex nanometer silver working electrode, record
Current versus time curve, it is molten with microsyringe plus the normal concentration hydrogen peroxide of fresh configuration after background current, which reaches, to be stablized
Liquid sample, and record current responds；The current-responsive of modified electrode is measured under various criterion concentration of hydrogen peroxide solution concentration
Value, and 1.0 × 10-7M~1.0 × 10-2In the concentration range of M, the linear relationship curve of electric current and hydrogen peroxide is obtained：
I=a × CH2O2+b (1)
In formula (1), I is current-responsive value, μ A；CH2O2For the concentration of hydrogen peroxide, mM；A is slope of a curve, is represented
The sensitivity of sensor electrode during unit area, μ A (mMcm2)-1；B is the intercept of curve, represents the sensor electrode
Background current in blank solution, μ A.Using the line style relation curve, rung by the electric current for measuring hydrogenperoxide steam generator sample
It should be worth, the concentration value of hydrogenperoxide steam generator sample is calculated.The beneficial effects are mainly as follows：
1st, the present invention proposes one kind using amino acid auxiliary synthesizing nano-silver modified electrode, it is characterised in that ammonia used
Base acid has reduction to silver ion, with reference to dynamic potential scanning method, can on base electrode Direct precipitation nano silver
Grain, while under the complexing of amino acid, nano silver can be protected not oxidized, still maintain the characteristic of nano silver simple substance.Cause
This, one side amino acid is a kind of safe and reliable green reagent, on the other hand can be obtained and be protected by easy steps
The elemental silver nanoparticles of shield, are a kind of easy, quick, environmental-friendly nano silver sensor electrode preparation side in this way
Method.
2nd, base electrode of the invention selects titanium-based titanium nitride film, and the chemical stability of titanium nitride itself is good, good conductivity,
There is certain catalytic action to hydrogen peroxide at the same time, with reference to nano silver simple substance, obtain concerted catalysis effect, further increase
The catalytic activity of the modified electrode, amino-acid complex nano silver/titanium nitride of preparation are directly used without enzyme hydrogen peroxide sensor
Measured in the fast electrochemical of hydrogen peroxide, detection efficiency is high, accuracy is high, the response time is short, test limit is low, high sensitivity,
The range of linearity is wide, stability is good, cost is low.
3rd, detection method of the invention, good in anti-interference performance, under the same test conditions, common chaff interferent such as Vitamin C
Acid, uric acid, glucose, lactose, glycine etc. do not produce obvious current-responsive.This is good without enzyme sensor electrode stability, and 4
After preserving two weeks at DEG C, current-responsive is positively retained at more than 90%.
Embodiment
With reference to specific embodiment, the present invention is described further, but protection scope of the present invention is not limited in
This：
Embodiment 1：
With glass-carbon electrode (GC) for base electrode, the nanometer modified by silver of l-tyrosine complexing is prepared by potentiodynamic method
Electrode (Tyr-AgNPs/GC), and for the electric analysis determining of hydrogen peroxide.
The surface treatment method of glass-carbon electrode：Successively with 1.0,0.3 and 0.05 μm of Al2O3Powder polishing is polished, every time
Flowing water is spent after polishing to clean, then the ultrasound 15min in acetone, absolute ethyl alcohol and deionized water respectively, finally use deionization
After water is rinsed well, dry.
Using the glass-carbon electrode after surface treated as working electrode, platinum electrode is auxiliary electrode, and Ag/AgCl is reference electricity
Pole, is containing 50mM KNO3, 1.0mM AgNO3In the mixed solution of 2mM l-tyrosine, temperature control is at 25 DEG C, using dynamic
Potential sweep method, in -0.8V~1.6V potential ranges, with 150mVs-1Rate scanning 10 weeks, l-tyrosine complexing is made
Nano silver modified electrode (Tyr-AgNPs/GC) modified electrode.Through XPS analysis, the modified electrode is in the air of normal temperature and pressure
After preserving 10 days, the nano silver on surface still maintains stable；And in the presence of no l-tyrosine, the modified electrode surface of preparation
Principal phase is silver oxide (AgO).The modified electrode is used for the detection of hydrogen peroxide, detects the PBS buffer solutions that bottom liquid is 0.1M,
PH value is 7.0；Detection current potential is -0.3V, in concentration 1.0 × 10-5M~3.257 × 10-3In the range of M, reach steady-state current
Time be less than 2 seconds, as concentration of hydrogen peroxide increases, current-responsive gradually increases, and current-responsive value and hydrogen peroxide are dense
Degree is in good linear relationship.It can be calculated in the present embodimentTyr-The sensitivity of AgNPs/GC modified electrodes up to a be 71.8 μ A
(mM·cm2)-1, b is 0.5265 μ A, and detectable limit is 1.75 μM.
Embodiment 2
Base electrode GC surface treatment methods and Nano silver deposition method are the same as embodiment 1, in this embodiment, Nano silver deposition
Liquid composition is 50mM KNO3With 1.0mM AgNO3Mixed liquor, i.e., when no l-tyrosine, obtain AgNPs/GC.This is modified
Electrode is used for the detection of hydrogen peroxide, and the PBS buffer solutions that detection bottom liquid is 0.1M, pH value 7.0, detection current potential is -0.3V,
In concentration 2.0 × 10-5M~2.365 × 10-3In the range of M, the AgNPs/GC modified electrodes spirit in the present embodiment can be calculated
Sensitivity a is 10.03 μ A (mMcm2)-1, b is 0.4155 μ A, and detectable limit is 2.35 μM.
Embodiment 3
Base electrode GC surface treatment methods and Nano silver deposition method are the same as embodiment 1, in this embodiment, Nano silver deposition
Liquid composition is 50mM KNO3、5.0mM AgNO3With 0.5mM l-tyrosine mixed liquors, obtainTyr-AgNPs/GC.By modification electricity
Pole is used for the detection of hydrogen peroxide, and the PBS buffer solutions that detection bottom liquid is 0.02M, pH value 7.0, detection current potential is -0.3V,
In concentration 5 × 10-6M~4.356 × 10-3In the range of M, it can be calculated in the present embodimentTyr-The spirit of AgNPs/GC modified electrodes
Sensitivity a is 116.88 μ A (mMcm2)-1, b is 1.9698 μ A, and detectable limit is 2.17 μM.
Embodiment 4
Base electrode GC surface treatment methods and Nano silver deposition method with embodiment 1 (the scanning number of turns is set to 20 weeks),
In this implementation, Nano silver deposition liquid composition is 50mM KNO3、0.5mM AgNO3With 2mM l-tyrosine mixed liquors, obtainTyr-
AgNPs/GC.The modified electrode is used for the detection of hydrogen peroxide, the PBS buffer solutions that detection bottom liquid is 0.02M, pH value to be
7.0, detection current potential is -0.3V, in concentration 2.0 × 10-5M~4.193 × 10-3In the range of M, it can be calculated in the present embodiment
'sTyr-AgNPs/GC modified electrode sensitivity a is 7.18 μ A (mMcm2)-1, b is 0.2102 μ A, and detectable limit is 6.32 μ
M。
Embodiment 5
Using high-purity titanium sheet as base electrode, the nano silver modified electrode of l-tyrosine complexing is prepared by potentiodynamic method
(Tyr-AgNPs/Ti), and for the electric analysis determining of hydrogen peroxide.
The surface treatment method of matrix titanium sheet：The purity of titanium sheet is 99.6%, and thickness chooses 0.2mm, clipped, 10MPa
After cold pressing, chemical polishing processing is carried out to working face.The process of surface treatment：Using acetone as degreasing fluid, titanium sheet is carried out
It is cleaned by ultrasonic 10min, is cleaned after taking-up with flowing water, chemical polishing 1min is carried out at 20 DEG C, the polishing fluid is urea: ammonium fluoride
: hydrogen peroxide (mass concentration 30%): the mixed liquor of concentrated nitric acid (mass concentration 68%)=1: 15: 40: 40 (mass ratio), after polishing
Absolute ethyl alcohol is used respectively, and acetone and deionized water are cleaned by ultrasonic 15min, obtain bright, clean titanium sheet.
Using the titanium sheet of polishing as working electrode, platinum electrode is auxiliary electrode, and Ag/AgCl is reference electrode, is containing 50mM
KNO3, 1.0mM AgNO3In the mixed solution of 2mM l-tyrosine, temperature control is at 25 DEG C, using potentiodynamic method ,-
In 0.8V~1.6V potential ranges, with 150mVs-1Rate scanning 10 weeks, the nanometer modified by silver electricity of l-tyrosine complexing is made
Pole (Tyr-AgNPs/Ti) modified electrode.The modified electrode is used for the detection of hydrogen peroxide, the PBS that detection bottom liquid is 0.02M to delay
Rush solution, pH value 7.0；Detection current potential is -0.3V, in concentration 5.0 × 10-6M~0.578 × 10-3In the range of M, reach steady
The time of state electric current is less than 2 seconds, and as concentration of hydrogen peroxide increases, current-responsive gradually increases, and current-responsive value and peroxide
It is in good linear relationship to change hydrogen concentration.It can be calculated in the present embodimentTyr-AgNPs/Ti modified electrode sensitivity a is 20.1
μA·(mM·cm2)-1, b is 0.0072 μ A, and detectable limit is 2.97 μM.
Embodiment 6
Using titanium dioxide film as base electrode, the nanometer modified by silver electricity of l-tyrosine complexing is prepared by potentiodynamic method
Pole (Tyr-AgNPs/TiO2), and for the electric analysis determining of hydrogen peroxide.
The technique that titanium-based titanium dioxide film is made using anodizing：First, high-purity titanium sheet is chosen as matrix, surface
Treatment process is the same as embodiment 5.Then, using the titanium sheet of polishing as anode, large area Pt pieces are as cathode, in the dilute sulfuric acid of 1.0M
In solution, controlled at 20 DEG C, initial current density is arranged to 100Am-1, DC voltage range 30V, the electrolytic oxidation time
For 2h, titanium-based titanium dioxide film is obtained.
Using titanium-based titanium dioxide film as working electrode, platinum electrode is auxiliary electrode, and Ag/AgCl is reference electrode, containing
50mM KNO3, 1.0mM AgNO3In the mixed solution of 2mM l-tyrosine, temperature control is at 25 DEG C, using dynamic potential scanning
Method, in -0.8V~1.6V potential ranges, with 150mVs-1Rate scanning 10 weeks, the nano silver of l-tyrosine complexing is made
Modified electrode (Tyr-AgNPs/TiO2) modified electrode.The modified electrode is used for the detection of hydrogen peroxide, detection bottom liquid to be 0.02M
PBS buffer solutions, pH value 7.0；Detection current potential is -0.4V, in concentration 2.0 × 10-6M~0.218 × 10-3The scope of M
Interior, the time for reaching steady-state current is less than 2 seconds, and as concentration of hydrogen peroxide increases, current-responsive gradually increases, and current-responsive
Value and concentration of hydrogen peroxide are in good linear relationship.It can be calculated in the present embodimentTyr-AgNPs/TiO2Modified electrode is sensitive
Degree a is 35.9 μ A (mMcm2)-1, b is 0.1116 μ A, and detectable limit is 1.36 μM.
Embodiment 7
Using titanium nitride film as base electrode, the nano silver modified electrode of l-tyrosine complexing is prepared by potentiodynamic method
(Tyr-AgNPs/TiN), and for the electric analysis determining of hydrogen peroxide.
Reduced using high-temperature ammonolysis and make titanium nitride film, the high-temperature ammonolysis includes：First, by the titanium dioxide film
(production method is with embodiment 6) is placed in tube furnace, in pure N2Under protection, the temperature of tube furnace is risen to 450 DEG C by room temperature,
Heating rate is 5 DEG C/min, when fire box temperature reaches 450 DEG C, constant temperature protection 1h.Then, the gas in tube furnace is switched
For high-purity ammonia, purity 99.99%, rises to 900 DEG C, heating rate is 2 DEG C/min, and constant temperature is nitrogenized by the temperature of tube furnace
2h, cools to room temperature with the furnace, takes out, you can obtain titanium nitride film matrix.
Using titanium-based titanium nitride film as working electrode, platinum electrode is auxiliary electrode, and Ag/AgCl is reference electrode, containing
50.0mM KNO3, 1.0mM AgNO3In the mixed solution of 2.0mM l-tyrosine, temperature control is at 25 DEG C, using electrokinetic potential
Scanning method, in -0.8V~1.6V potential ranges, with 150mVs-1Rate scanning 10 weeks, receiving for l-tyrosine complexing is made
Rice modified by silver electrode (Tyr-AgNPs/TiN) modified electrode.The modified electrode is used for the detection of hydrogen peroxide, detection bottom liquid to be
The PBS buffer solutions of 0.02M, pH value 7.0；Detection current potential is -0.4V, in concentration 2.5 × 10-7M~4.11 × 10-4The model of M
In enclosing, the time for reaching steady-state current is less than 2 seconds, and as concentration of hydrogen peroxide increases, current-responsive gradually increases, and electric current is rung
It is in good linear relationship that should be worth with concentration of hydrogen peroxide.It can be calculated in the present embodimentTyr-The spirit of AgNPs/TiN modified electrodes
Sensitivity a is 86.75 μ A (mMcm2)-1, b is 0.6741 μ A, and detectable limit is 0.15 μM.
Embodiment 8
Base electrode titanium nitride production method and Nano silver deposition method are the same as embodiment 7, in this embodiment, Nano silver deposition
Liquid composition is 50mM KNO3With 1.0mM AgNO3Mitigation liquid, i.e., when no l-tyrosine, obtain AgNPs/TiN.This is modified
Electrode be used for hydrogen peroxide detection, detection bottom liquid be 0.02M PBS buffer solutions, pH value 7.0, detection current potential for-
0.4V, in concentration 1.0 × 10-6M~4.56 × 10-4In the range of M, the AgNPs/TiN modification electricity in the present embodiment can be calculated
Sensitivity a in pole is 13.7 μ A (mMcm2)-1, b is 0.0855 μ A, and detectable limit is 0.83 μM.
Embodiment 9
Base electrode titanium nitride production method and Nano silver deposition method are the same as embodiment 7, in this embodiment, Nano silver deposition
Liquid composition is 50mM KNO3, 1.0mM AgNO3With the mitigation liquid of L-PROLINE, i.e., when replacing amino acid, obtainPro-AgNPs/
TiN.The modified electrode is used for the detection of hydrogen peroxide, the PBS buffer solutions that detection bottom liquid is 0.02M, pH value 7.0, inspection
Survey current potential is -0.4V, in concentration 2.0 × 10-6M~6.403 × 10-3In the range of M, it can be calculated in the present embodiment
AgNPs/TiN modified electrode sensitivity a is 12.79 μ A (mMcm2)-1, b is 0.0.3524 μ A, and detectable limit is 1.31 μM.
Content described in this specification embodiment is only enumerating to the way of realization of inventive concept, protection model of the invention
Enclose and be not construed as being only limitted to the concrete form that embodiment is stated, protection scope of the present invention also includes people in the art
Member according to the present invention design it is conceivable that equivalent technologies mean.
Claims (10)
1. a kind of amino-acid complex nano silver modified electrode, it is characterised in that the electrode is prepared as follows：With bright titanium
As base electrode, platinum electrode is auxiliary electrode for piece, titanium dioxide film or titanium nitride film, and Ag/AgCl is reference electrode, containing
10~500mM of nitric acid potassium concn, 0.5~5mM of silver nitrate concentration, 0.5~2.0mM of amino acid concentration deposition liquid in, under stirring
Using potentiodynamic method in controlling potential -0.8V~1.6V, 20~50 DEG C of temperature, 10~200mVs of sweep speed-1, move electricity
Bit scan 1~20 week, obtains amino-acid complex nano silver modified electrode.
2. electrode as claimed in claim 1, it is characterised in that：The amino acid is non-fat race's amino acid, and described
Side chain feature in amino acid shows as hydrophobicity, and amino dissociation constant is more than 9.21, and carboxyl dissociation constant is more than 2.20；It is described
Non-fat race's amino acid be aromatic amino acid, heterocyclic amino acid or heterocyclic imino acid.
3. the electrode as described in one of claim 1~2, it is characterised in that：The amino acid is phenylalanine, tryptophan, junket
Propylhomoserin or proline.
4. electrode as claimed in claim 1, it is characterised in that the titanium dioxide film is enterprising by surface treated titanium sheet
Row anodic oxidation is made, and specific method is as follows：(1) surface treatment of titanium sheet：Choose titanium sheet purity and be more than 99.5%, thickness
0.1mm~3.0mm, using acetone as degreasing fluid, carries out 5~15min of ultrasonic cleaning by titanium sheet, is eluted with water after taking-up, then soaks
Enter urea: ammonium fluoride: 30wt% hydrogen peroxide: 68wt% concentrated nitric acids mass ratio is in 1: 15: 40: 40 polishing fluid, in 20~30 DEG C
Lower progress 0.5~1min of chemical polishing, is cleaned by ultrasonic 15min, with absolute ethyl alcohol, acetone and deionized water respectively after taking-up to obtain the final product
To surface treated titanium sheet；
(2) using surface treated titanium sheet as anode, Pt pieces are as cathode, in the dilution heat of sulfuric acid of 0.5~2M, control temperature
Spend for 20~40 DEG C, initial current density is 100~500Am-1, 10~50V of DC voltage range, 0.5~3h of electrolytic oxidation
Hour, obtain titanium-based titanium dioxide film.
5. electrode as claimed in claim 1, it is characterised in that the titanium nitride film base electrode is prepared by two step method,
Anodic oxidation is carried out first in surface treated titanium sheet titanium dioxide film is made, then nitrogenized in ammonia atmosphere high temperature
Titanium nitride film is made in reduction.
6. electrode as claimed in claim 5, it is characterised in that the preparation method of the titanium nitride film base electrode is as follows：(1)
The surface treatment of titanium sheet：Choose titanium sheet purity and be more than 99.5%, thickness 0.1mm~3.0mm, using acetone as degreasing fluid, by titanium sheet
5~15min of ultrasonic cleaning is carried out, is eluted with water after taking-up, is then immersed in urea: ammonium fluoride: 30wt% hydrogen peroxide: the dense nitre of 68wt%
Sour mass ratio is in 1: 15: 40: 40 polishing fluid, and 0.5~1min of chemical polishing is carried out at 20~30 DEG C, is used respectively after taking-up
Absolute ethyl alcohol, acetone and deionized water are cleaned by ultrasonic 15min, that is, obtain surface treated titanium sheet；
(2) using surface treated titanium sheet as anode, Pt pieces are as cathode, in the dilution heat of sulfuric acid of 0.5~2M, control temperature
Spend for 20~40 DEG C, initial current density is 100~500Am-1, 10~50V of DC voltage range, 0.5~3h of electrolytic oxidation
Hour, obtain titanium-based titanium dioxide film；
(3) titanium dioxide film obtained by step (2) is placed in tube furnace, in pure N2Under protection, by the temperature of tube furnace by room temperature
400~500 DEG C are risen to, heating rate is 2~20 DEG C/min, when fire box temperature reaches 400~500 DEG C, constant temperature protection 0.5~
2h, then, is switched to high-purity ammonia, purity more than 99.99%, 800 are risen to by the temperature of tube furnace by the gas in tube furnace
~1100 DEG C, heating rate is 1~10 DEG C/min, and constant temperature nitrogenizes 1~5h, cools to room temperature with the furnace, you can obtain titanium nitride film.
7. a kind of amino-acid complex nano silver modified electrode as described in claim 1~6 is as no enzyme electrochemical sensor electricity
Application of the pole in concentration of hydrogen peroxide is detected.
8. application as claimed in claim 7, the application include：With the amino-acid complex nanometer modified by silver of claim 1~6
For electrode as working electrode, platinum electrode is auxiliary electrode, and Ag/AgCl is reference electrode, three-electrode system is formed, with constant rate of speed
The phosphate buffer solution of stirring applies constant cathode potential -0.1~-0.6V on the working electrode (s as bottom liquid is detected,
Current versus time curve is recorded, after background current, which reaches, to be stablized, with microsyringe plus the normal concentration peroxide of fresh configuration
Change hydrogen solution sample, and record current response；Working electrode is measured under various criterion concentration of hydrogen peroxide solution concentration
Current-responsive value, and 1.0 × 10-7M~1.0 × 10-2In the concentration range of M, the linear relationship of electric current and hydrogen peroxide is obtained
Curve：
I=a × CH2O2+b (1)
In formula (1), I is current-responsive value, μ A；CH2O2For the concentration of hydrogen peroxide, mM；A is slope of a curve, represents unit
The sensitivity of sensor electrode during area, μ A (mMcm2)-1；B is the intercept of curve, represents the sensor electrode in sky
Background current in white solution, μ A, using the linear relationship curve, by the current-responsive for measuring hydrogenperoxide steam generator sample
Value, is calculated the concentration value of hydrogenperoxide steam generator sample.
9. application as claimed in claim 8, it is characterised in that：0.01~0.2M of the phosphate buffer solution concentration, uses
KH2PO4It is 2.0~8.0 to adjust pH value with KOH solution.
10. method as claimed in claim 8, it is characterised in that：Turn when the phosphate buffer solution is stirred with constant rate of speed
Speed is 500~2000 revs/min.
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