CN105784686B - A kind of preparation method and application of the hydrogen peroxide optical electro-chemistry sensor based on electrochemical luminescence excitation - Google Patents

A kind of preparation method and application of the hydrogen peroxide optical electro-chemistry sensor based on electrochemical luminescence excitation Download PDF

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CN105784686B
CN105784686B CN201610148506.6A CN201610148506A CN105784686B CN 105784686 B CN105784686 B CN 105784686B CN 201610148506 A CN201610148506 A CN 201610148506A CN 105784686 B CN105784686 B CN 105784686B
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hydrogen peroxide
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electrochemical luminescence
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张勇
马洪敏
柳懿芯
李小建
魏琴
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University of Jinan
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Abstract

The invention discloses a kind of preparation methods of the difunctional hydrogen peroxide sensor for having electrochemical luminescence excitation based on function nano material structure, prepared sensor operations are simple, easy to carry, detection is fast, at low cost, can be used for quick, the Sensitive Detection to hydrogen peroxide in the fields such as daily production and life.

Description

A kind of preparation of the hydrogen peroxide optical electro-chemistry sensor based on electrochemical luminescence excitation Method and application
Technical field
The present invention relates to a kind of preparation method for detecting the sensor of hydrogen peroxide, sensor integration electrochemistry It shines and optical electro-chemistry dual function.Belong to Nano-function thin films and electrochemical biosensor analysis technical field.
Background technology
Hydrogen peroxide is a kind of oxidant, can be decomposed into water and oxygen under normal circumstances, but slow, is catalyzed when being added Agent(Or biological enzyme)When, reaction speed is accelerated, it is possible thereby to be made instantly available the amount or catalyst of hydrogen peroxide(Or biological enzyme)'s Amount, while hydrogen peroxide also often exists in the form of reaction intermediate in vivo, therefore, hydrogen peroxide is examined in medicine The fields such as disconnected, clinical treatment, environment measuring and food production play important role, research and development hydrogen peroxide detection side Method also just has highly important application value.Electrochemical biosensor analytical technology is fast etc. due to easy to operate, detection speed Advantage increasingly obtains the attention of people.The electrochemical biosensor analytical technology of detection hydrogen peroxide is presently used for according to detection Means have three kinds of electrochemical sensor, electrochemical luminescence sensor and optical electro-chemistry sensor to divide mainly.Wherein, electrochemistry is sent out Optical sensor and optical electro-chemistry sensor relative to electrochemical sensor, have few background signal noise, high sensitivity, detection at The features such as this is low, it is of interest by more and more researchers in recent years.
Electrochemical luminescence is also referred to as electrogenerated chemiluminescence, refers to that generate some in electrode surface by electrochemical method special Substance, form excitation state between these substances or by electron transmission between other components in system, returned by excitation state It returns to ground state and generates luminescence phenomenon.Electrochemical luminescence sensor is the decorative material by changing electrode surface, with analysis produce Raw electrochemical luminescence is realized according to the associated change of analyte concentration and electrochemical luminescence intensity to analysis in optimal conditions The qualitative and quantitative analysis of object.
Optical electro-chemistry sensor is to cause electron-hole pair to be detached based on additional light source activation Electrophotosensitivmaterial material, Under suitable potential condition partially, quick transmission of the electronics on electrode, semiconductor and trim and analyte is realized, and formed Photoelectric current.In optimal conditions, the variation of analyte concentration will have a direct impact on the size of photoelectric current, can be according to the change of photoelectric current Change the qualitative and quantitative analysis realized to analyte.
But since electrochemical luminescence sensor needs external optical signal to capture equipment such as photodiode etc., and photoelectricity Chemical sensor needs peripheral hardware light source to excite Electrophotosensitivmaterial material, this affects the convenient of the two operation to a certain extent Property, it limits them and is more widely applied in actual production, life.Therefore, it designs, prepare more simple, fast inspection The electrochemical biosensor analytical technology for surveying hydrogen peroxide has highly important practical value.
Invention content
The purpose of the present invention is to provide a kind of hydrogen peroxide sensings easy to operate, easy to carry, detection is fast, at low cost The preparation method of device, prepared sensor, can be used for the fields such as daily production and life to the quick, sensitive of hydrogen peroxide Detection.Based on this purpose, the present invention is in same electrolytic cell, and using four electrode systems, i.e. two working electrodes, one to electrode With a reference electrode, wherein working electrode 1 uses ITO electro-conductive glass, is first modifying nickel phosphate ammonium micro-nano material above NH4NiPO4With gold nanorods Sol A u NRs as substrate, then electropolymerization luminol, the electrode are sent out as electrochemistry on it Light working electrode W1, working electrode 2 is using titanium dioxide nanoplate colloidal sol TiO2NSs and horseradish peroxidase Solution H RP is total With being modified, as optical electro-chemistry working electrode W2.When being detected, after hydrogen peroxide is added in electrolytic cell, on W1 Apply step voltage, due to NH4NiPO4Stabilized illumination and effect and the NH for increasing Au NRs loads4NiPO4With Au NRs' Concerted catalysis acts on, and luminol and hydroperoxidation generate electrochemical luminescence, this is just equivalent to " turning on light ", works as step voltage When being 0, electrochemical luminescence disappears, this is just equivalent to " turning off the light ", at the same time applies constant voltage always on W2, due to TiO2 NSs can be because the luminous excitation that electrochemical luminescence generates causes electron-hole pair to be detached, and HRP catalyzing hydrogen peroxides generate Oxygen makes hydrogen peroxide become hole " donor ", to obtain photoelectric current on W2, when electrochemical luminescence disappearance, i.e., " turns off the light " When, photoelectric current disappears immediately, size and the concentration of hydrogen peroxide positive correlation of the photoelectric current of generation, therefore by recording photoelectric current The detection to hydrogen peroxide can be realized in size.
Based on the above inventive principle, the specific technical solution that the present invention uses is as follows:
1. a kind of preparation method of the hydrogen peroxide optical electro-chemistry sensor based on electrochemical luminescence excitation, feature exist In preparation process is:
(1)The preparation method of electrochemical luminescence working electrode W1, the W1 are by NH4NiPO4It is repaiied jointly with Au NRs It is prepared after electropolymerization luminol on the ITO electro-conductive glass of decorations, its main feature is that, specific preparation process is:
1)Using ITO electro-conductive glass as working electrode, in electrode surface drop coating NH4NiPO4Solution, area coverage be 1 cm × 1 cm, dries at room temperature;
2)By 1)Obtained working electrode, in NH4NiPO4Surface drop coating Au NRs, area coverage are the cm of 1 cm × 1, It dries at room temperature;
3)By 2)Obtained working electrode immerses in electrolyte, and immersion area is NH4NiPO4It is covered jointly with Au NRs Area, electrochemical deposition is carried out to working electrode using three-electrode system, takes out working electrode after deposition, it is clear using ultra-pure water It washes, drying is protected from light at 4 DEG C, electrochemical luminescence working electrode W1 is made;
The NH4NiPO4Solution is nickel phosphate ammonium micro-nano material aqueous solution, and the nickel phosphate ammonium micro-nano material is porous Sheet micro-nano material, the NH4NiPO4Preparation process be:2.0 ~ 4.0 g ammonium salts and 0.15 ~ 0.25 g are added in 40mL water Phosphate after being completely dissolved, is added 0.15 ~ 0.25 g Nickel Chlorides, 10 ~ 14h is stirred at 30 ~ 45 DEG C, centrifuges, will produce Product are placed at 50 DEG C and dry to get to NH4NiPO4
The ammonium salt is selected from one of following:Ammonium chloride, ammonium bromide, ammonium phosphate, ammonium dihydrogen phosphate, diammonium hydrogen phosphate;
The phosphate is selected from one of following:Ammonium phosphate, ammonium dihydrogen phosphate, diammonium hydrogen phosphate;
The Au NRs are the aqueous solution of gold nanorods, and the gold nanorods are bar-like gold nanoparticle, length is 20 ~ 40 nm;
The electrolyte is the sulfuric acid solution containing luminol, a concentration of the 1 ~ 10 of luminol in the electrolyte Mmol/L, sulfuric acid concentration are 0.1 ~ 1.0 mol/L;
The three-electrode system, including working electrode, reference electrode and to electrode, the reference electrode be saturated it is sweet Mercury electrode, described is platinum electrode to electrode;
The electrochemical deposition process, the electrochemical method used is cyclic voltammetry, and starting voltage is -0.2 V, eventually Only voltage is 1.5 V, and it is 100 mv/s, 20 ~ 30 circle of cycle to sweep speed;
(2)The preparation method of optical electro-chemistry working electrode W2, the W2 are by TiO2What NSs and HRP was modified jointly ITO electro-conductive glass, its main feature is that, specific preparation process is:
1)Using ITO electro-conductive glass as working electrode, in 8 ~ 12 μ L TiO of electrode surface drop coating2NSs dries at room temperature;
2)By 1)In obtained working electrode be put into Muffle furnace, made annealing treatment at 450 DEG C, handle postcooling To room temperature;
3)By 2)In obtained working electrode surface drop coating 8 ~ 12 μ L HRP, it is dry at 4 DEG C, it is clear with ultra-pure water after dry It washes, it is dry at 4 DEG C, optical electro-chemistry working electrode W2 is made;
The TiO2NSs is the aqueous solution of the titanium dioxide nanoplate of 1 mg/mL, and the titanium dioxide nanoplate is The titanium dioxide nano-particle of rectangular sheet, the length of side are 60 ~ 80 nm;
The HRP is the horseradish peroxidase aqueous solution of 5 mU/mL;
(3)The preparation method of hydrogen peroxide optical electro-chemistry sensor based on electrochemical luminescence excitation:
1)By in the opposite insertion electrolytic cell of the one side of W1 and W2 conductions, W1 is the cm of 0.5 cm ~ 1.5 with W2 spacing;
2)It is to be inserted into electrolytic cell to electrode CE by reference electrode RE, platinum electrode of Ag/AgCl, it is common with W1 and W2 Form four electrode systems;
3)The NaOH solution that 10 mL pH value are 11 ~ 13 is added in electrolytic cell;
4)By 1)~3)Obtained four electrode system and electrolytic cell are placed in magazine, are obtained and are swashed based on electrochemical luminescence The hydrogen peroxide optical electro-chemistry sensor of hair.
2. the detection applied to hydrogen peroxide of hydrogen peroxide optical electro-chemistry sensor of the present invention, its main feature is that Specifically detection method is:
(1)Using electrochemical workstation, step voltage, initial voltage are applied to W1 using the method for step voltage on W1 For 0 v, step voltage is 0.7 ~ 0.9 v, and snap time is 10 ~ 30 s;Meanwhile when being used on W2 m- current methods to W2 Apply constant voltage, voltage is 0 ~ 0.6 v;
(2)The Hydrogen peroxide standard solution of various concentration is added in electrolytic cell, the electric current on W2 can be with hydrogen peroxide The increase of concentration and accordingly increase, according to the relationship between gained electric current increment value and concentration of hydrogen peroxide, drawing curve;
(3)The standard solution that hydrogenperoxide steam generator to be measured is replaced to hydrogen peroxide, according to(1)With(2)The peroxidating Hydrogen detection method is detected, and show that hydrogen peroxide to be measured is molten with the working curve drawn according to obtained electric current increment value The concentration of liquid.
The useful achievement of the present invention
(1)Hydrogen peroxide optical electro-chemistry sensor of the present invention is prepared simply, easy to operate, is set without external auxiliary It is standby, using the micromation of detection device, portability, and quick, sensitive, the highly selective detection to hydrogen peroxide is realized, had There is wide market development foreground;
(2)The present invention detects hydrogen peroxide in same electrolytic cell using four electrode systems for the first time, and realizes electrochemistry It shines and the difunctional signal amplification strategy of optical electro-chemistry.With the increase of concentration of hydrogen peroxide in electrolytic cell, on the one hand, so that Electrochemical luminescence intensity is linearly increasing, and the photoelectricity cleanliness excited increases;On the other hand, hydrogen peroxide is as electron donor, So that photoelectricity cleanliness increases in optical electro-chemistry reaction.Therefore, two methods of electrochemical luminescence and optical electro-chemistry are in same electrolysis It reacts, interact jointly under Chi Zhong, same electrochemical workstation, realize the dual amplification for detecting signal to hydrogen peroxide, Detection sensitivity and detection limit are greatly improved, there is important scientific meaning and application value.
Specific implementation mode
A kind of hydrogen peroxide optical electro-chemistry sensor based on electrochemical luminescence excitation of embodiment 1, it is specific to prepare step Suddenly it is:
(1)The preparation of electrochemical luminescence working electrode W1:
1)Using ITO electro-conductive glass as working electrode, in electrode surface drop coating NH4NiPO4Solution, area coverage be 1 cm × 1 cm, dries at room temperature;
2)By 1)Obtained working electrode, in NH4NiPO4Surface drop coating Au NRs, area coverage are the cm of 1 cm × 1, It dries at room temperature;
3)By 2)Obtained working electrode immerses in electrolyte, and immersion area is NH4NiPO4It is covered jointly with Au NRs Area, electrochemical deposition is carried out to working electrode using three-electrode system, takes out working electrode after deposition, it is clear using ultra-pure water It washes, drying is protected from light at 4 DEG C, electrochemical luminescence working electrode W1 is made;
The NH4NiPO4Solution is nickel phosphate ammonium micro-nano material aqueous solution, the preparation of the nickel phosphate ammonium micro-nano material Step is:2.0 ~ 4.0 g ammonium salts and 0.15 ~ 0.25 g phosphate are added in 40mL water, after being completely dissolved, addition 0.15 ~ 0.25 g Nickel Chlorides, at 30 ~ 45 DEG C stir 10 ~ 14h, centrifuge, by product be placed at 50 DEG C dry to get to NH4NiPO4
The ammonium salt is selected from one of following:Ammonium chloride, ammonium bromide, ammonium phosphate, ammonium dihydrogen phosphate, diammonium hydrogen phosphate;
The phosphate is selected from one of following:Ammonium phosphate, ammonium dihydrogen phosphate, diammonium hydrogen phosphate;
The Au NRs are the aqueous solution of gold nanorods, and the gold nanorods are bar-like gold nanoparticle, length 20 nm;
The electrolyte is the sulfuric acid solution containing luminol, a concentration of the 1 of luminol in the electrolyte Mmol/L, sulfuric acid concentration are 0.1 mol/L;
The three-electrode system, including working electrode, reference electrode and to electrode, the reference electrode be saturated it is sweet Mercury electrode, described is platinum electrode to electrode;
The electrochemical deposition process, the electrochemical method used is cyclic voltammetry, and starting voltage is -0.2 V, eventually Only voltage is 1.5 V, and it is 100 mv/s, 20 ~ 30 circle of cycle to sweep speed.
(2)The preparation of optical electro-chemistry working electrode W2:
1)Using ITO electro-conductive glass as working electrode, in 8 μ L TiO of electrode surface drop coating2NSs dries at room temperature;
2)By 1)In obtained working electrode be put into Muffle furnace, made annealing treatment at 450 DEG C, handle postcooling To room temperature;
3)By 2)In obtained working electrode surface drop coating 8 μ L HRP, it is dry at 4 DEG C, cleaned with ultra-pure water after dry, It is dry at 4 DEG C, optical electro-chemistry working electrode W2 is made;
The TiO2NSs is the aqueous solution of the titanium dioxide nanoplate of 1 mg/mL, and the titanium dioxide nanoplate is The titanium dioxide nano-particle of rectangular sheet, the length of side are 60 ~ 80 nm;
The HRP is the horseradish peroxidase aqueous solution of 5 mU/mL.
(3)The preparation method of hydrogen peroxide optical electro-chemistry sensor based on electrochemical luminescence excitation:
1)It will(1)The W1 of middle preparation and(2)The W2 of middle preparation is inserted into electrolytic cell face to face, and W1 is 0.5 with W2 spacing cm;
2)It is to be inserted into electrolytic cell to electrode CE by reference electrode RE, platinum electrode of Ag/AgCl, it is common with W1 and W2 Form four electrode systems;
3)The NaOH solution that 10 mL pH value are 11 is added in electrolytic cell;
4)By 1)~3)Obtained four electrode system and electrolytic cell are placed in magazine, are obtained and are swashed based on electrochemical luminescence The hydrogen peroxide optical electro-chemistry sensor of hair.
A kind of hydrogen peroxide optical electro-chemistry sensor based on electrochemical luminescence excitation of embodiment 2, it is specific to prepare step Suddenly it is:
(1)The preparation of electrochemical luminescence working electrode W1:
With the preparation process of W1 in embodiment 1, difference is preparation process:The preparation process of nickel phosphate ammonium micro-nano material Middle ammonium salt addition be 0.3 g, phosphate addition be 0.20 g, Nickel Chloride addition be 0.20 g, whipping temp and when Between be respectively 38 DEG C and 12 h;The length of gold nanorods is 30 nm;A concentration of 5 mmol/L of luminol, sulfuric acid in electrolyte A concentration of 0.5 mol/L;When cyclic voltammetry carries out electrochemical deposition, 25 circle of cycle.
(2)The preparation of optical electro-chemistry working electrode W2:
1)Using ITO electro-conductive glass as working electrode, in 10 μ L TiO of electrode surface drop coating2NSs dries at room temperature;
2)By 1)In obtained working electrode be put into Muffle furnace, made annealing treatment at 450 DEG C, handle postcooling To room temperature;
3)By 2)In obtained working electrode surface drop coating 10 μ L HRP, it is dry at 4 DEG C, it is clear with ultra-pure water after dry It washes, it is dry at 4 DEG C, optical electro-chemistry working electrode W2 is made;
Remaining preparation process with W2 in embodiment 1.
(3)The preparation method of hydrogen peroxide optical electro-chemistry sensor based on electrochemical luminescence excitation:
Preparation process is with embodiment 1, and difference is W1 and W2 spacing is 1.0 cm, and the NaOH being added in electrolytic cell is molten The pH value of liquid is 12.
A kind of hydrogen peroxide optical electro-chemistry sensor based on electrochemical luminescence excitation of embodiment 3, it is specific to prepare step Suddenly it is:
(1)The preparation of electrogenerated chemiluminescence working electrode W1:
With the preparation process of W1 in embodiment 1, difference is preparation process:The preparation process of nickel phosphate ammonium micro-nano material Middle ammonium salt addition be 0.4 g, phosphate addition be 0.25 g, Nickel Chloride addition be 0.25 g, whipping temp and when Between be respectively 45 DEG C and 14 h;The length of gold nanorods is 40 nm;A concentration of 10 mmol/L of luminol, sulphur in electrolyte Acid concentration is 1.0 mol/L;When cyclic voltammetry carries out electrochemical deposition, 30 circle of cycle.
(2)The preparation of optical electro-chemistry working electrode W2:
1)Using ITO electro-conductive glass as working electrode, in 12 μ L TiO of electrode surface drop coating2NSs dries at room temperature;
2)By 1)In obtained working electrode be put into Muffle furnace, made annealing treatment at 450 DEG C, handle postcooling To room temperature;
3)By 2)In obtained working electrode surface drop coating 12 μ L HRP, it is dry at 4 DEG C, it is clear with ultra-pure water after dry It washes, it is dry at 4 DEG C, optical electro-chemistry working electrode W2 is made;
Remaining preparation process with W2 in embodiment 1.
(3)The preparation method of hydrogen peroxide optical electro-chemistry sensor based on electrochemical luminescence excitation:
Preparation process is with embodiment 1, and difference is W1 and W2 spacing is 1.5 cm, and the NaOH being added in electrolytic cell is molten The pH value of liquid is 13.
A kind of application of the hydrogen peroxide optical electro-chemistry sensor based on electrochemical luminescence excitation of embodiment 4
A kind of hydrogen peroxide optical electro-chemistry sensor application based on electrochemical luminescence excitation prepared by embodiment 1 is in peroxide Change the detection of hydrogen, detecting step is:
(1)Using electrochemical workstation, step voltage, initial voltage are applied to W1 using the method for step voltage on W1 For 0 v, step voltage is 0.7 v, and snap time is 10 s;Meanwhile m- current methods are constant to W2 applications when being used on W2 Voltage, voltage are 0 v;
(2)The Hydrogen peroxide standard solution of various concentration is added in electrolytic cell, the electric current on W2 can be with hydrogen peroxide The increase of concentration and accordingly increase, according to the relationship between gained electric current increment value and concentration of hydrogen peroxide, drawing curve;
(3)The standard solution that hydrogenperoxide steam generator to be measured is replaced to hydrogen peroxide, according to(1)With(2)The peroxidating Hydrogen detection method is detected, and show that hydrogen peroxide to be measured is molten with the working curve drawn according to obtained electric current increment value The concentration of liquid.
A kind of application of the hydrogen peroxide optical electro-chemistry sensor based on electrochemical luminescence excitation of embodiment 5
A kind of hydrogen peroxide optical electro-chemistry sensor application based on electrochemical luminescence excitation prepared by embodiment 2 is in peroxide Change the detection of hydrogen, detecting step is:
(1)Using electrochemical workstation, step voltage, initial voltage are applied to W1 using the method for step voltage on W1 For 0 v, step voltage is 0.8 v, and snap time is 20 s;Meanwhile m- current methods are constant to W2 applications when being used on W2 Voltage, voltage are 0.3 v;
(2)With(3)With embodiment 4.
A kind of application of the hydrogen peroxide optical electro-chemistry sensor based on electrochemical luminescence excitation of embodiment 6
A kind of hydrogen peroxide optical electro-chemistry sensor application based on electrochemical luminescence excitation prepared by embodiment 3 is in peroxide Change the detection of hydrogen, detecting step is:
(1)Using electrochemical workstation, step voltage, initial voltage are applied to W1 using the method for step voltage on W1 For 0 v, step voltage is 0.9 v, and snap time is 30 s;Meanwhile m- current methods are constant to W2 applications when being used on W2 Voltage, voltage are 0.6 v;
(2)With(3)With embodiment 4.
Hydrogen peroxide sensor prepared by 7 embodiment 1-3 of embodiment is applied to the detection of hydrogen peroxide, has excellent Good detection result, detection are limited to 15 μm of ol/L.
The detection of hydrogen peroxide in 8 human serum of embodiment
Human serum sample accurately is pipetted, the Hydrogen peroxide standard solution of certain molar concentration is added, peroxidating not to be added The human serum of hydrogen is blank, carries out recovery testu, is detected according to the step of embodiment 4 ~ 6, peroxide in determination sample Change the rate of recovery of hydrogen, testing result is shown in Table 1.
The testing result of hydrogen peroxide in 1 human serum of table
1 testing result of table it is found that result relative standard deviation(RSD)No more than 3.0 %, the rate of recovery is 96 ~ 102%, Show that the present invention can be used for the detection of hydrogen peroxide in human serum, the high sensitivity of method, high specificity, as a result accurately and reliably.

Claims (6)

1. a kind of preparation method of the hydrogen peroxide optical electro-chemistry sensor based on electrochemical luminescence excitation, which is characterized in that adopt With nickel phosphate ammonium micro-nano material NH4NiPO4Electropolymerization Shandong on the ITO electro-conductive glass modified jointly with gold nanorods Sol A u NRs Electrochemical luminescence working electrode W1, titanium dioxide nanoplate colloidal sol TiO are used as after minot2NSs and horseradish peroxidase solution The ITO electro-conductive glass that HRP is modified jointly is as optical electro-chemistry working electrode W2, Ag/AgCl electrode as reference electrode RE, platinum filament Electrode is used as to electrode CE, and four electrodes are inserted into jointly in same electrolytic cell and form four electrode systems, by four electrode obtained System is placed in magazine, obtains the hydrogen peroxide optical electro-chemistry sensor excited based on electrochemical luminescence.
2. preparation method according to claim 1, which is characterized in that the nickel phosphate ammonium micro-nano material NH4NiPO4It is more Hole sheet micro-nano material.
3. preparation method according to claim 1, which is characterized in that the gold nanorods Sol A u NRs are gold nano The aqueous solution of stick, the gold nanorods are bar-like gold nanoparticle, and length is 20 ~ 40 nm.
4. preparation method according to claim 1, which is characterized in that the titanium dioxide nanoplate colloidal sol TiO2 NSs For the aqueous solution of titanium dioxide nanoplate, the titanium dioxide nanoplate is the titanium dioxide nano-particle of rectangular sheet, the length of side For 60 ~ 80 nm.
5. preparation method according to claim 1, which is characterized in that the one side of W1 and W2 conductions is inserted into electrolytic cell relatively In, W1 is the cm of 0.5 cm ~ 1.5 with W2 spacing.
6. the application of hydrogen peroxide optical electro-chemistry sensor prepared by preparation method according to claim 1, feature exist In the hydrogen peroxide optical electro-chemistry sensor application is the step of hydrogen peroxide detects:Using electrochemical workstation, Step voltage is applied to W1 using the method for step voltage on W1, initial voltage is 0 v, and step voltage is 0.7 ~ 0.9 v, step Time is 10 ~ 30 s;Meanwhile m- current methods apply constant voltage to W2 when being used on W2, voltage is 0 ~ 0.6 v;In electricity Hydrogenperoxide steam generator to be measured is added in Xie Chizhong, and the electric current on W2 can accordingly increase with the increase of concentration of hydrogen peroxide, according to Gained electric current increment value obtains hydrogenperoxide steam generator concentration to be measured.
CN201610148506.6A 2016-03-16 2016-03-16 A kind of preparation method and application of the hydrogen peroxide optical electro-chemistry sensor based on electrochemical luminescence excitation Expired - Fee Related CN105784686B (en)

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