CN105784687B - A kind of preparation method and application based on spontaneous light activated hydrogen peroxide optical electro-chemistry sensor - Google Patents

A kind of preparation method and application based on spontaneous light activated hydrogen peroxide optical electro-chemistry sensor Download PDF

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CN105784687B
CN105784687B CN201610148512.1A CN201610148512A CN105784687B CN 105784687 B CN105784687 B CN 105784687B CN 201610148512 A CN201610148512 A CN 201610148512A CN 105784687 B CN105784687 B CN 105784687B
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hydrogen peroxide
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phosphate
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CN105784687A (en
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张勇
杜斌
任祥
闫涛
吴丹
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University of Jinan
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    • G01N21/75Systems in which material is subjected to a chemical reaction, the progress or the result of the reaction being investigated
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Abstract

The invention discloses a kind of preparation method for possessing spontaneous light activated difunctional hydrogen peroxide sensor based on function nano material structure, prepared sensor operations are simple, easy to carry, detection is fast, cost is low, quick, the Sensitive Detection to hydrogen peroxide available for fields such as daily production and lifes.

Description

A kind of preparation method based on spontaneous light activated hydrogen peroxide optical electro-chemistry sensor And application
Technical field
The present invention relates to a kind of preparation method for being used to detect the sensor of hydrogen peroxide, belong to Nano-function thin films With electrochemical biosensor analysis technical field.
Background technology
Hydrogen peroxide is a kind of oxidant, can generally be decomposed into water and oxygen, but slow, is catalyzed when adding Agent(Or biology enzyme)When, reaction speed is accelerated, it is possible thereby to be made instantly available the amount or catalyst of hydrogen peroxide(Or biology enzyme)'s Amount, while hydrogen peroxide also often exists in the form of reaction intermediate in vivo, therefore, hydrogen peroxide is examined in medical science 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 obtain the attention of people.It is presently used for detecting the electrochemical biosensor analytical technology of hydrogen peroxide according to detection Means have three kinds of electrochemical sensor, Electrochemiluminescsensor sensor and optical electro-chemistry sensor to divide mainly.Wherein, electroluminescentization Luminescence sensor and optical electro-chemistry sensor are learned relative to electrochemical sensor, there is few background signal noise, high sensitivity, inspection The features such as cost is low is surveyed, it is of interest by increasing researcher in recent years.
Electrogenerated chemiluminescence is also referred to as electrochemical luminescence, and it is special to refer to produce some in electrode surface by electrochemical method Material, form excitation state between these materials or by electron transmission between other components in system, returned by excitation state Luminescence phenomenon is produced to ground state.Electrochemiluminescsensor sensor is the decorative material by changing electrode surface, with analyzing produce Raw electrochemical luminescence, in optimal conditions, realized according to the associated change of analyte concentration and electrochemical luminescence intensity to analysis The qualitative and quantitative analysis of thing.
Optical electro-chemistry sensor is to cause electron-hole pair to be separated 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 change of analyte concentration can directly affect the size of photoelectric current, can be according to the change of photoelectric current Change the qualitative and quantitative analysis realized to analyte.
But because Electrochemiluminescsensor sensor needs external optical signal to catch equipment such as photodiode etc., and light Electrochemical sensor needs peripheral hardware light source to excite Electrophotosensitivmaterial material, and this have impact on the convenient of the two operation to a certain extent Property, limit them and be more widely applied in actual production, life.Therefore, design, prepare more simple, fast inspection The electrochemical biosensor analytical technology for surveying hydrogen peroxide has highly important practical value.
The content of the invention
It is an object of the invention to provide a kind of hydrogen peroxide sensing simple to operate, easy to carry, detection is fast, cost is low The preparation method of device, prepared sensor, available for fields such as daily production and lifes 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 is using nickel phosphate ammonium micro-nano material NH4NiPO4Repaiied with the luminol of electropolymerization Decorations, as electrogenerated chemiluminescence working electrode W1, also serve as self-emissive light source, working electrode 2 uses titanium dioxide nano-particle Colloidal sol TiO2NPs and horseradish peroxidase Solution H RP are modified, as optical electro-chemistry working electrode W2.Detected When, after adding hydrogen peroxide in electrolytic cell, apply step voltage on W1, due to NH4NiPO4Stabilized illumination effect, Shandong Minot and hydroperoxidation, electrogenerated chemiluminescence is produced, this is just equivalent to " turning on light ", when step voltage is 0, electroluminescent chemistry Luminous to disappear, this just equivalent to " turning off the light ", at the same time applies constant voltage, due to TiO always on W22NPs can be because electricity Cause to light to excite caused by chemiluminescence to cause electron-hole pair to be separated, HRP catalyzing hydrogen peroxides produce oxygen, make Hydrogen oxide turns into hole " donor ", so as to obtain photoelectric current on W2, when electrogenerated chemiluminescence disappearance, i.e., when " turning off the light ", photoelectricity Stream disappears immediately, size and the concentration of hydrogen peroxide positive correlation of caused photoelectric current, therefore by recording the size of photoelectric current i.e. The detection to hydrogen peroxide can be achieved.
It is as follows based on above inventive principle, the technical solution adopted by the present invention:
A kind of 1. preparation method based on spontaneous light activated hydrogen peroxide optical electro-chemistry sensor, it is characterised in that system It is for step:
(1)Electrogenerated chemiluminescence working electrode W1 preparation:
1)Using ITO electro-conductive glass as working electrode, in electrode surface drop coating nickel phosphate ammonium micro-nano material NH4NiPO4Solution, Area coverage is the cm of 1 cm × 1, is dried at room temperature;
2)By 1)Obtained working electrode, immerse in electrolyte, immersion area is NH4NiPO4The area covered, utilize Three-electrode system carries out electrochemical deposition to working electrode, takes out working electrode after deposition, is cleaned using ultra-pure water, kept away at 4 DEG C Light is dried, and electrogenerated chemiluminescence working electrode W1 is made;
Described NH4NiPO4Solution is the 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, 10 ~ 14h is stirred at 30 ~ 45 DEG C, centrifuged, product is placed at 50 DEG C and dried, that is, is obtained NH4NiPO4
Described ammonium salt is selected from one of following:Ammonium chloride, ammonium bromide, ammonium phosphate, ammonium dihydrogen phosphate, diammonium hydrogen phosphate;
Described phosphate is selected from one of following:Ammonium phosphate, ammonium dihydrogen phosphate, diammonium hydrogen phosphate;
Described electrolyte is the sulfuric acid solution containing luminol, in described electrolyte the concentration of luminol for 1 ~ 10mmol/L, sulfuric acid concentration are 0.1 ~ 1.0 mol/L;
Described three-electrode system, including working electrode, reference electrode and to electrode, described reference electrode is that saturation is sweet Mercury electrode, described is platinum electrode to electrode;
Described electrochemical deposition process, for the electrochemical method used for cyclic voltammetry, starting voltage is -0.2 V, eventually Only voltage is 1.5 V, and it is 100 mv/s to sweep speed, the circle of circulation 20 ~ 30;
(2)Optical electro-chemistry working electrode W2 preparation:
1)Using ITO electro-conductive glass as working electrode, in the μ L titanium dioxide nano-particle colloidal sols of electrode surface drop coating 8 ~ 12 TiO2NPs, dry at room temperature;
2)By 1)In obtained working electrode be put into Muffle furnace, made annealing treatment at 450 DEG C, cooled down after processing To room temperature;
3)By 2)In obtained working electrode surface drop coating 8 ~ 12 μ L horseradish peroxidase Solution Hs RP, do at 4 DEG C It is dry, cleaned with ultra-pure water after drying, dried at 4 DEG C, optical electro-chemistry working electrode W2 is made;
Described TiO2NPs is the 1 mg/mL titanium dioxide nano-particle aqueous solution;
Described HRP is the 5 mU/mL horseradish peroxidase aqueous solution;
(3)Preparation method based on spontaneous light activated hydrogen peroxide optical electro-chemistry sensor:
1)W1 and W2 are inserted in electrolytic cell face to face, W1 and W2 spacing are the cm of 0.5 cm ~ 1.5;
2)It is to electrode CE by reference electrode RE, platinum electrode of Ag/AgCl, inserts in electrolytic cell, 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 systems and electrolytic cell are placed in magazine, that is, are made based on spontaneous light activated Hydrogen peroxide optical electro-chemistry sensor.
A kind of 2. system based on spontaneous light activated hydrogen peroxide optical electro-chemistry sensor according to claim 1 Preparation Method, it is characterised in that described sensor application is in the detection of hydrogen peroxide, its detecting step:
(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 on W2 use when m- current methods to W2 Apply constant voltage, voltage is 0 ~ 0.6 v;
(2)The Hydrogen peroxide standard solution of various concentrations 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 relation between gained electric current increment value and concentration of hydrogen peroxide, drawing curve;
(3)Hydrogenperoxide steam generator to be measured is replaced to the standard liquid of hydrogen peroxide, according to(1)With(2)Described peroxidating The method for drafting of hydrogen working curve is detected.
The useful achievement of the present invention
(1)Hydrogen peroxide sensor of the present invention is prepared simply, easy to operate, without external accessory, is utilized The miniaturization of detection device, portability, and realize to the quick, sensitive of hydrogen peroxide, high selectivity detection, have wide Market development prospect;
(2)The present invention realizes electroluminescent chemistry first in same electrolytic cell using four electrode systems detection hydrogen peroxide Luminous signal amplification strategy difunctional with optical electro-chemistry.With the increase of concentration of hydrogen peroxide in electrolytic cell, on the one hand, so that Electrogenerated chemiluminescence intensity is linearly increasing, the photoelectricity streamlined increase excited;On the other hand, hydrogen peroxide is given as electronics Body so that photoelectricity streamlined increases in optical electro-chemistry reaction.Therefore, two methods of electrogenerated chemiluminescence and optical electro-chemistry are same React, interact jointly in electrolytic cell, under same electrochemical workstation, realize to the dual of hydrogen peroxide detection electric signal Amplification, drastically increases detection sensitivity and detection limit, has important scientific meaning.Simultaneously as excited without separately matching somebody with somebody Light source so that detection device more they tend to miniaturization, it is integrated, there is wide market application value.
Embodiment
Embodiment 1 is a kind of to be based on spontaneous light activated hydrogen peroxide optical electro-chemistry sensor
A kind of preparation method based on spontaneous light activated hydrogen peroxide optical electro-chemistry sensor, specific preparation process For:
(1)Electrogenerated chemiluminescence working electrode W1 preparation:
1)Using ITO electro-conductive glass as working electrode, in electrode surface drop coating NH4NiPO4, area coverage is 1 cm × 1 Cm, dry at room temperature;
2)By 1)Obtained working electrode, immerse in electrolyte, immersion area is NH4NiPO4The area covered, utilize Three-electrode system carries out electrochemical deposition to working electrode, takes out working electrode after deposition, is cleaned using ultra-pure water, kept away at 4 DEG C Light is dried, and electrogenerated chemiluminescence working electrode W1 is made;
Described NH4NiPO4Solution is the 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, 10 ~ 14h is stirred at 30 ~ 45 DEG C, centrifuged, product is placed at 50 DEG C and dried, that is, is obtained NH4NiPO4
Described ammonium salt is selected from one of following:Ammonium chloride, ammonium bromide, ammonium phosphate, ammonium dihydrogen phosphate, diammonium hydrogen phosphate;
Described phosphate is selected from one of following:Ammonium phosphate, ammonium dihydrogen phosphate, diammonium hydrogen phosphate;
Described electrolyte is the sulfuric acid solution containing luminol, and the concentration of luminol is 1 in described electrolyte Mmol/L, sulfuric acid concentration are 0.1 mol/L;
Described three-electrode system, including working electrode, reference electrode and to electrode, described reference electrode is that saturation is sweet Mercury electrode, described is platinum electrode to electrode;
Described electrochemical deposition process, for the electrochemical method used for cyclic voltammetry, starting voltage is -0.2V, eventually Only voltage is 1.5V, and it is 100mv/s to sweep speed, the circle of circulation 20.
(2)Optical electro-chemistry working electrode W2 preparation:
1)Using ITO electro-conductive glass as working electrode, in the μ L titanium dioxide nano-particle colloidal sols TiO of electrode surface drop coating 82 NPs, dry at room temperature;
2)By 1)In obtained working electrode be put into Muffle furnace, made annealing treatment at 450 DEG C, cooled down after processing To room temperature;
3)By 2)In obtained working electrode surface drop coating 8 μ L horseradish peroxidase Solution Hs RP, dry at 4 DEG C, do Cleaned with ultra-pure water after dry, dried at 4 DEG C, optical electro-chemistry working electrode W2 is made;
Described TiO2NPs is the 1 mg/mL titanium dioxide nano-particle aqueous solution;
Described HRP is the 5 mU/mL horseradish peroxidase aqueous solution.
(3)Preparation method based on spontaneous light activated hydrogen peroxide optical electro-chemistry sensor:
1)Will(1)The W1 of middle preparation and(2)The W2 of middle preparation is inserted in electrolytic cell face to face, and W1 is 0.5 with W2 spacing cm;
2)It is to electrode CE by reference electrode RE, platinum electrode of Ag/AgCl, inserts in electrolytic cell, 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 systems and electrolytic cell are placed in magazine, that is, are made based on spontaneous light activated Hydrogen peroxide optical electro-chemistry sensor.
Embodiment 2 is a kind of to be based on spontaneous light activated hydrogen peroxide optical electro-chemistry sensor
A kind of preparation method based on spontaneous light activated hydrogen peroxide optical electro-chemistry sensor, specific preparation process For:
(1)Electrogenerated chemiluminescence working electrode W1 preparation:
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 is 0.3 g, and phosphate addition is 0.20 g, and Nickel Chloride addition is 0.20 g, whipping temp and when Between be respectively 38 DEG C and 12 h;The concentration of luminol is 5 mmol/L in electrolyte, and sulfuric acid concentration is 0.5 mol/L;Circulation volt When peace method carries out electrochemical deposition, the circle of circulation 25.
(2)Optical electro-chemistry working electrode W2 preparation:
1)Using ITO electro-conductive glass as working electrode, in the μ L titanium dioxide nano-particle colloidal sols of electrode surface drop coating 10 TiO2NPs, dry at room temperature;
2)By 1)In obtained working electrode be put into Muffle furnace, made annealing treatment at 450 DEG C, cooled down after processing To room temperature;
3)By 2)In obtained working electrode surface drop coating 10 μ L horseradish peroxidase Solution Hs RP, dry at 4 DEG C, Cleaned with ultra-pure water after drying, dried at 4 DEG C, optical electro-chemistry working electrode W2 is made;
Remaining preparation process with W2 in embodiment 1.
(3)Preparation method based on spontaneous light activated hydrogen peroxide optical electro-chemistry sensor:
Preparation process is with embodiment 1, and difference is W1 and W2 spacing is 1.0 cm, and the NaOH added in electrolytic cell is molten The pH value of liquid is 12.
Embodiment 3 is a kind of to be based on spontaneous light activated hydrogen peroxide optical electro-chemistry sensor
A kind of preparation method based on spontaneous light activated hydrogen peroxide optical electro-chemistry sensor, specific preparation process For:
(1)Electrogenerated chemiluminescence working electrode W1 preparation:
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 is 0.4 g, and phosphate addition is 0.25 g, and Nickel Chloride addition is 0.25 g, whipping temp and when Between be respectively 45 DEG C and 14 h;The concentration of luminol is 10 mmol/L in electrolyte, and sulfuric acid concentration is 1.0 mol/L;Circulation When voltammetry carries out electrochemical deposition, the circle of circulation 30.
(2)Optical electro-chemistry working electrode W2 preparation:
1)Using ITO electro-conductive glass as working electrode, in the μ L titanium dioxide nano-particle colloidal sols of electrode surface drop coating 12 TiO2NPs, dry at room temperature;
2)By 1)In obtained working electrode be put into Muffle furnace, made annealing treatment at 450 DEG C, cooled down after processing To room temperature;
3)By 2)In obtained working electrode surface drop coating 12 μ L horseradish peroxidase Solution Hs RP, dry at 4 DEG C, Cleaned with ultra-pure water after drying, dried at 4 DEG C, optical electro-chemistry working electrode W2 is made;
Remaining preparation process with W2 in embodiment 1.
(3)Preparation method based on spontaneous light activated hydrogen peroxide optical electro-chemistry sensor:
Preparation process is with embodiment 1, and difference is W1 and W2 spacing is 1.5 cm, and the NaOH added in electrolytic cell is molten The pH value of liquid is 13.
A kind of application based on spontaneous light activated hydrogen peroxide optical electro-chemistry sensor of embodiment 4
One kind prepared by embodiment 1 is based on spontaneous light activated hydrogen peroxide optical electro-chemistry sensor application in hydrogen peroxide Detection, its 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 concentrations 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 relation between gained electric current increment value and concentration of hydrogen peroxide, drawing curve;
(3)Hydrogenperoxide steam generator to be measured is replaced to the standard liquid of hydrogen peroxide, according to(1)With(2)Described peroxidating The method for drafting of hydrogen working curve is detected.
A kind of application based on spontaneous light activated hydrogen peroxide optical electro-chemistry sensor of embodiment 5
One kind prepared by embodiment 2 is based on spontaneous light activated hydrogen peroxide optical electro-chemistry sensor application in hydrogen peroxide Detection, its 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 based on spontaneous light activated hydrogen peroxide optical electro-chemistry sensor of embodiment 6
One kind prepared by embodiment 3 is based on spontaneous light activated hydrogen peroxide optical electro-chemistry sensor application in hydrogen peroxide Detection, its 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 the embodiment 1-3 of embodiment 7, applied to the detection of hydrogen peroxide, have excellent Good Detection results, detection are limited to 22 μm of ol/L.
The detection of hydrogen peroxide in the human serum of embodiment 8
Human serum sample accurately is pipetted, the Hydrogen peroxide standard solution of certain molar concentration is added, not add peroxidating 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 the human serum of table 1
Knowable to the testing result of table 1, relative standard deviation as a result(RSD)Less than 2.8 %, the rate of recovery is 96 ~ 104%, table Detection of the bright present invention available for hydrogen peroxide in human serum, the high sensitivity of method, high specificity, as a result accurately and reliably.

Claims (2)

1. a kind of preparation method based on spontaneous light activated hydrogen peroxide optical electro-chemistry sensor, it is characterised in that prepare step Suddenly it is:
(1)Electrogenerated chemiluminescence working electrode W1 preparation:
1)Using ITO electro-conductive glass as working electrode, in electrode surface drop coating nickel phosphate ammonium micro-nano material NH4NiPO4Solution, covering Area is the cm of 1 cm × 1, is dried at room temperature;
2)By 1)Obtained working electrode, immerse in electrolyte, immersion area is NH4NiPO4The area covered, utilize three electricity Electrode systems carry out electrochemical deposition to working electrode, take out working electrode after deposition, are cleaned using ultra-pure water, lucifuge is done at 4 DEG C It is dry, electrogenerated chemiluminescence working electrode W1 is made;
Described NH4NiPO4Solution is the nickel phosphate ammonium micro-nano material aqueous solution, the preparation process of the nickel phosphate ammonium micro-nano material For:2.0 ~ 4.0 g ammonium salts and 0.15 ~ 0.25 g phosphate are added in 40mL water, after being completely dissolved, adds 0.15 ~ 0.25 g Nickel Chloride, 10 ~ 14h is stirred at 30 ~ 45 DEG C, centrifuged, product is placed at 50 DEG C and dried, that is, obtains NH4NiPO4
Described ammonium salt is selected from one of following:Ammonium chloride, ammonium bromide, ammonium phosphate, ammonium dihydrogen phosphate, diammonium hydrogen phosphate;
Described phosphate is selected from one of following:Ammonium phosphate, ammonium dihydrogen phosphate, diammonium hydrogen phosphate;
Described electrolyte is the sulfuric acid solution containing luminol, and the concentration of luminol is 1 ~ 10mmol/ in described electrolyte L, sulfuric acid concentration are 0.1 ~ 1.0 mol/L;
Described three-electrode system, including working electrode, reference electrode and to electrode, described reference electrode is saturation calomel electricity Pole, described is platinum electrode to electrode;
Described electrochemical deposition process, for the electrochemical method used for cyclic voltammetry, starting voltage is -0.2 V, terminates electricity Press as 1.5 V, it is 100 mv/s to sweep speed, the circle of circulation 20 ~ 30;
(2)Optical electro-chemistry working electrode W2 preparation:
1)Using ITO electro-conductive glass as working electrode, in the μ L titanium dioxide nano-particle colloidal sols TiO of electrode surface drop coating 8 ~ 122 NPs, dry at room temperature;
2)By 1)In obtained working electrode be put into Muffle furnace, made annealing treatment at 450 DEG C, room be cooled to after processing Temperature;
3)By 2)In obtained working electrode surface drop coating 8 ~ 12 μ L horseradish peroxidase Solution Hs RP, dry at 4 DEG C, do Cleaned with ultra-pure water after dry, dried at 4 DEG C, optical electro-chemistry working electrode W2 is made;
Described TiO2NPs is the 1 mg/mL titanium dioxide nano-particle aqueous solution;
Described HRP is the 5 mU/mL horseradish peroxidase aqueous solution;
(3)Preparation method based on spontaneous light activated hydrogen peroxide optical electro-chemistry sensor:
1)W1 and W2 are inserted in electrolytic cell face to face, W1 and W2 spacing are the cm of 0.5 cm ~ 1.5;
2)It is to electrode CE by reference electrode RE, platinum electrode of Ag/AgCl, inserts in electrolytic cell, collectively constituted with W1 and W2 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 systems and electrolytic cell are placed in magazine, that is, are made and are based on spontaneous light activated peroxide Change hydrogen optical electro-chemistry sensor.
2. the application of optical electro-chemistry hydrogen peroxide sensor prepared by preparation method according to claim 1, its feature exist In, including following applying step:
(1)Using electrochemical workstation, step voltage, initial voltage 0 are applied to W1 using the method for step voltage on W1 V, step voltage are 0.7 ~ 0.9 v, and snap time is 10 ~ 30 s;Meanwhile m- current methods apply to W2 when being used on W2 Constant voltage, voltage are 0 ~ 0.6 v;
(2)The Hydrogen peroxide standard solution of various concentrations is added in electrolytic cell, the electric current on W2 can be with concentration of hydrogen peroxide Increase and accordingly increase, according to the relation between gained electric current increment value and concentration of hydrogen peroxide, drawing curve;
(3)Hydrogenperoxide steam generator to be measured is replaced to the standard liquid of hydrogen peroxide, according to(1)With(2)Described hydrogen peroxide work The method for drafting for making curve is detected.
CN201610148512.1A 2016-03-16 2016-03-16 A kind of preparation method and application based on spontaneous light activated hydrogen peroxide optical electro-chemistry sensor Expired - Fee Related CN105784687B (en)

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