CN105717175A - Preparation method and application of hydrogen peroxide sensor based on combination of two electrochemical methods - Google Patents
Preparation method and application of hydrogen peroxide sensor based on combination of two electrochemical methods Download PDFInfo
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- G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
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- G—PHYSICS
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- G01N21/76—Chemiluminescence; Bioluminescence
Abstract
The invention discloses a preparation method of a dual-functional hydrogen peroxide sensor based on combination of two electrochemical methods constructed by functional nanometer materials. The prepared sensor is easy to operate, convenient to carry, rapid in detection, low in cost and capable of being used for rapid and sensitive detection of hydrogen peroxide in the fields of daily production, living and the like.
Description
Technical field
The preparation method that the present invention relates to a kind of sensor for detecting hydrogen peroxide, belongs to Nano-function thin films and electrochemical biosensor analysis technical field.
Background technology
Hydrogen peroxide is a kind of oxidant, generally can be decomposed into water and oxygen, but it is slow, when adding catalyst (or enzyme), response speed is accelerated, thus can be made instantly available the amount of hydrogen peroxide or the amount of catalyst (or enzyme), hydrogen peroxide also often exists with the form of reaction intermediate in vivo simultaneously, therefore, hydrogen peroxide all plays important role in fields such as medical diagnosis, clinical treatment, environment measuring and food productions, and research and development hydrogen peroxide detection method also just has highly important using value.Electrochemical biosensor analytical technology, due to easy and simple to handle, the detection advantages such as speed is fast, obtains the attention of people day by day.The electrochemical biosensor analytical technology being presently used for detection hydrogen peroxide is divided according to detection means and is mainly had electrochemical sensor, Electrochemiluminescsensor sensor and Optical Electro-Chemistry sensor three kinds.Wherein, Electrochemiluminescsensor sensor and Optical Electro-Chemistry sensor, relative to electrochemical sensor, have the features such as background signal noise is few, highly sensitive, testing cost is low, were paid close attention to by increasing researcher in recent years.
Electrogenerated chemiluminescence is also referred to as electrochemiluminescence, refer to and produce some special materials by electrochemical method at electrode surface, between these materials or and system in form excited state by electron transmission between other components, excited state return to ground state and produce luminescence phenomenon.Namely Electrochemiluminescsensor sensor by changing the decorative material of electrode surface, produces electrochemiluminescence with analyte, in optimal conditions, realizes the qualitative and quantitative analysis to analyte according to the associated change of analyte concentration with electrochemiluminescence intensity.
Optical Electro-Chemistry sensor is based on additional light source activation Electrophotosensitivmaterial material and causes that electron-hole pair is easily separated, under suitable inclined potential condition, it is achieved the electronics quick transmission on electrode, quasiconductor and trim and analyte, and forms photoelectric current.In optimal conditions, the change of analyte concentration can directly affect the size of photoelectric current, it is possible to realizes the qualitative and quantitative analysis to analyte according to the change of photoelectric current.
But, owing to Electrochemiluminescsensor sensor needs external optical signal to catch equipment such as photodiode etc., and Optical Electro-Chemistry sensor needs peripheral hardware light source to excite Electrophotosensitivmaterial material, this have impact on the convenience of the two operation to a certain extent, limits them and is more widely applied in actual production, life.Therefore, the electrochemical biosensor analytical technology designing, preparing more simple, fast detection hydrogen peroxide has highly important practical value.
Summary of the invention
The preparation method that it is an object of the invention to provide a kind of simple to operate, easy to carry, detection is fast, cost is low hydrogen peroxide sensor, prepared sensor, can be used for quick, the Sensitive Detection to hydrogen peroxide in the fields such as daily production, life.Based on this purpose, the present invention, in same electrolyzer, adopts four electrode systems, namely two working electrodes, one to electrode and a reference electrode, wherein working electrode 1 adopts the molybdenum bisuphide two-dimension nano materials Cd-MoS that cadmium adulterates2Modifying with the luminol of electropolymerization, as electrogenerated chemiluminescence working electrode W1, also serve as self-emissive light source, working electrode 2 adopts titanium dioxide nano-particle colloidal sol TiO2NPs and horseradish peroxidase Solution H RP modifies, as Optical Electro-Chemistry working electrode W2.When detecting, after adding hydrogen peroxide in electrolyzer, W1 applies step voltage, due to Cd-MoS2Catalysis, enhancing and stabilized illumination effect, luminol and hydroperoxidation, produce electrogenerated chemiluminescence, this is just equivalent to " turning on light ", and when step voltage is 0, electrogenerated chemiluminescence disappears, this is just equivalent to " turning off the light ", meanwhile applies constant voltage on W2, due to TiO always2NPs can because the luminescence that electrogenerated chemiluminescence produces excites causes that electron-hole pair is easily separated, HRP catalyzing hydrogen peroxide produces oxygen, hydrogen peroxide is made to become hole " donor ", thus obtaining photoelectric current on W2, when electrogenerated chemiluminescence disappears, when namely " turning off the light ", photoelectric current disappears immediately, the size of the photoelectric current produced and concentration of hydrogen peroxide positive correlation, therefore can realize the detection to hydrogen peroxide by the size of recording light electric current.
Based on above inventive principle, the technical solution used in the present invention is as follows:
1. the preparation method based on the hydrogen peroxide sensor of two kinds of electrochemical method couplings, it is characterised in that preparation process is:
(1) preparation of electrogenerated chemiluminescence working electrode W1:
1) with ITO electro-conductive glass for working electrode, at the molybdenum bisuphide two-dimension nano materials Cd-MoS of electrode surface drop coating cadmium doping2Solution, area coverage is 1cm × 1cm, dries under room temperature；
2) by 1) working electrode that obtains, immerse in electrolyte, immersion area is Cd-MoS2The area covered, utilizes three-electrode system that working electrode is carried out electrochemical deposition, takes out working electrode after deposition, uses ultra-pure water to clean, and at 4 DEG C, lucifuge dries, and prepares electrogenerated chemiluminescence working electrode W1；
The molybdenum bisuphide two-dimension nano materials Cd-MoS of described cadmium doping2Solution is Cd-MoS2Aqueous solution, described Cd-MoS2For the molybdenum bisuphide two-dimension nano materials doped with cadmium ion, described two-dimension nano materials is scraps of paper shape, and thickness is about 10 ~ 20nm, described Cd-MoS2Preparation method be: by 0.005 ~ 0.01g Caddy (Cleary) CdCl2, the 0.1mol/L ascorbic acid solution of 2 ~ 6mL, 0.5 ~ 1.5mL sodium molybdate Na2MoO4Solution and 0.01 ~ 0.03g sodium sulfide Na2S, after being mixed and stirred for 15 minutes, puts in reactor, at 150 ~ 220 DEG C, reacts 12 ~ 16 hours；After being cooled to room temperature, use deionized water centrifuge washing, at 40 DEG C, carry out vacuum drying, namely prepare the molybdenum bisuphide two-dimension nano materials Cd-MoS of cadmium doping2, it is dissolved in deionized water and prepares Cd-MoS2Solution；
Described electrolyte is the sulfuric acid solution containing luminol, and in described electrolyte, the concentration of luminol is 1 ~ 10mmol/L, and sulfuric acid concentration is 0.1 ~ 1.0mol/L；
Described three-electrode system, including working electrode, reference electrode and to electrode, described reference electrode is saturated calomel electrode, and described is platinum electrode to electrode；
Described electrochemical deposition process, the electrochemical method of employing is cyclic voltammetry, and starting voltage is-0.2V, and final voltage is 1.5V, sweeps speed for 100mv/s, circulation 20 ~ 30 circle；
(2) preparation of Optical Electro-Chemistry working electrode W2:
1) with ITO electro-conductive glass for working electrode, at electrode surface drop coating 8 ~ 12 μ L titanium dioxide nano-particle colloidal sol TiO2NPs, dries under room temperature；
2) by 1) in the working electrode that obtains put in Muffle furnace, be annealed processing at 450 DEG C, after process, be cooled to room temperature；
3) by 2) in working electrode surface drop coating 8 ~ 12 μ L horseradish peroxidase Solution H RP that obtains, dry at 4 DEG C, clean with ultra-pure water after drying, dry at 4 DEG C, prepare Optical Electro-Chemistry working electrode W2；
Described TiO2NPs is the titanium dioxide nano-particle aqueous solution of 1mg/mL；
Described HRP is the horseradish peroxidase aqueous solution of 5mU/mL；
(3) based on the preparation method of the hydrogen peroxide sensor of two kinds of electrochemical method couplings:
1) being inserted face to face in electrolyzer by W1 and W2, W1 and W2 spacing is 0.5cm ~ 1.5cm；
2) with Ag/AgCl be reference electrode RE, platinum electrode be to electrode CE, insert in electrolyzer, collectively constitute four electrode systems with W1 and W2；
3) adding 10mLpH value in electrolyzer is the NaOH solution of 11 ~ 13；
4) by 1) ~ 3) obtained by four electrode systems and electrolyzer be placed in magazine, namely prepare the hydrogen peroxide sensor based on two kinds of electrochemical method couplings.
2. the preparation method of a kind of hydrogen peroxide sensor based on two kinds of electrochemical method couplings according to claim 1, it is characterised in that described sensor is applied to the detection of hydrogen peroxide, and its detecting step is:
(1) utilizing electrochemical workstation, adopt the method for step voltage that W1 applies step voltage on W1, initial voltage is 0v, and step voltage is 0.7 ~ 0.9v, and snap time is 10 ~ 30s；Meanwhile, when adopting on W2, W2 is applied constant voltage by m-current methods, and voltage is 0 ~ 0.6v；
(2) adding the Hydrogen peroxide standard solution of variable concentrations in electrolyzer, the electric current on W2 can increase accordingly along with the increase of concentration of hydrogen peroxide, according to the relation between gained electric current increase value and concentration of hydrogen peroxide, drawing curve；
(3) hydrogenperoxide steam generator to be measured replaces the standard solution of hydrogen peroxide, and the method for drafting of the hydrogen peroxide working curve described in (1) and (2) detects.
The useful achievement of the present invention
(1) hydrogen peroxide sensor of the present invention preparation is simple, easy to operate, it is not necessary to external accessory, utilize the microminiaturization of detection equipment, portability, and achieve the selective enumeration method quick, sensitive, high to hydrogen peroxide, there is wide market development prospect；
(2) present invention adopts four electrode system detection hydrogen peroxide first in same electrolyzer, it is achieved that electrogenerated chemiluminescence amplifies strategy with the difunctional signal of Optical Electro-Chemistry.Along with the increase of concentration of hydrogen peroxide in electrolyzer, on the one hand, make electrogenerated chemiluminescence intensity linearly increasing, the linear increase of photoelectric current excited；On the other hand, hydrogen peroxide is as electron donor so that the linear increase of photoelectric current in Optical Electro-Chemistry reaction.Therefore, electrogenerated chemiluminescence and two kinds of methods of Optical Electro-Chemistry are reaction jointly, interaction in same electrolyzer, under same electrochemical workstation, achieve the dual amplification that hydrogen peroxide is detected the signal of telecommunication, drastically increase detection sensitivity and detection limit, there is important scientific meaning.Simultaneously as without separately joining excitation source so that detection equipment more they tends to microminiaturization, integrated, there is wide market using value.
Detailed description of the invention
1 one kinds of hydrogen peroxide sensors based on two kinds of electrochemical method couplings of embodiment
A kind of preparation method of the hydrogen peroxide sensor based on two kinds of electrochemical method couplings, concrete preparation process is:
(1) the molybdenum bisuphide two-dimension nano materials Cd-MoS of cadmium doping2The preparation of solution:
The molybdenum bisuphide two-dimension nano materials Cd-MoS of described cadmium doping2Solution is Cd-MoS2Aqueous solution, described Cd-MoS2For the molybdenum bisuphide two-dimension nano materials doped with cadmium ion, described two-dimension nano materials is scraps of paper shape, and thickness is about 10 ~ 20nm, described Cd-MoS2Preparation method be: by 0.005g Caddy (Cleary) CdCl2, the 0.1mol/L ascorbic acid solution of 2mL, 0.5mL sodium molybdate Na2MoO4Solution and 0.01g sodium sulfide Na2S, after being mixed and stirred for 15 minutes, puts in reactor, at 150 DEG C, reacts 16 hours；After being cooled to room temperature, use deionized water centrifuge washing, at 40 DEG C, carry out vacuum drying, namely prepare the molybdenum bisuphide two-dimension nano materials Cd-MoS of cadmium doping2, it is dissolved in deionized water and prepares Cd-MoS2Solution.
(2) preparation of electrogenerated chemiluminescence working electrode W1:
1) with ITO electro-conductive glass for working electrode, the Cd-MoS of preparation in electrode surface drop coating (1)2Solution, area coverage is 1cm × 1cm, dries under room temperature；
2) by 1) working electrode that obtains, immerse in electrolyte, immersion area is Cd-MoS2The area covered, utilizes three-electrode system that working electrode is carried out electrochemical deposition, takes out working electrode after deposition, uses ultra-pure water to clean, and at 4 DEG C, lucifuge dries, and prepares electrogenerated chemiluminescence working electrode W1；
Described electrolyte is the sulfuric acid solution containing luminol, and in described electrolyte, the concentration of luminol is 1mmol/L, and sulfuric acid concentration is 0.1mol/L；
Described three-electrode system, including working electrode, reference electrode and to electrode, described reference electrode is saturated calomel electrode, and described is platinum electrode to electrode；
Described electrochemical deposition process, the electrochemical method of employing is cyclic voltammetry, and starting voltage is-0.2V, and final voltage is 1.5V, sweeps speed for 100mv/s, circulation 20 circle.
(3) preparation of Optical Electro-Chemistry working electrode W2:
1) with ITO electro-conductive glass for working electrode, at electrode surface drop coating 8 μ L titanium dioxide nano-particle colloidal sol TiO2NPs, dries under room temperature；
2) by 1) in the working electrode that obtains put in Muffle furnace, be annealed processing at 450 DEG C, after process, be cooled to room temperature；
3) by 2) in the working electrode surface drop coating 8 μ L horseradish peroxidase Solution H RP that obtains, dry at 4 DEG C, clean with ultra-pure water after drying, dry at 4 DEG C, prepare Optical Electro-Chemistry working electrode W2；
Described TiO2NPs is the titanium dioxide nano-particle aqueous solution of 1mg/mL；
Described HRP is the horseradish peroxidase aqueous solution of 5mU/mL.
(4) based on the preparation method of the hydrogen peroxide sensor of two kinds of electrochemical method couplings:
1) being inserted face to face in electrolyzer by the W1 of preparation in (2) and the W2 of (3) middle preparation, W1 and W2 spacing is 0.5cm；
2) with Ag/AgCl be reference electrode RE, platinum electrode be to electrode CE, insert in electrolyzer, collectively constitute four electrode systems with W1 and W2；
3) adding 10mLpH value in electrolyzer is the NaOH solution of 11；
4) by 1) ~ 3) obtained by four electrode systems and electrolyzer be placed in magazine, namely prepare the hydrogen peroxide sensor based on two kinds of electrochemical method couplings.
2 one kinds of hydrogen peroxide sensors based on two kinds of electrochemical method couplings of embodiment
A kind of preparation method of the hydrogen peroxide sensor based on two kinds of electrochemical method couplings, concrete preparation process is:
(1) Cd-MoS2The preparation of solution:
Preparation process is with Cd-MoS in embodiment 12The preparation method of solution, difference is: CdCl2Addition be 0.008g, ascorbic acid solution addition be 4mL, Na2MoO4The addition of solution is 1.0mL and Na2The addition of S is 0.02g, at 220 DEG C, reacts 12 hours.
(2) preparation of electrogenerated chemiluminescence working electrode W1:
Preparation process is with the preparation process of W1 in embodiment 1, and difference is: use the Cd-MoS obtained by (1) in the present embodiment2Modified electrode；In electrolyte, the concentration of luminol is 5mmol/L, and sulfuric acid concentration is 0.5mol/L；When cyclic voltammetry carries out electrochemical deposition, circulation 25 circle.
(3) preparation of Optical Electro-Chemistry working electrode W2:
1) with ITO electro-conductive glass for working electrode, at electrode surface drop coating 10 μ L titanium dioxide nano-particle colloidal sol TiO2NPs, dries under room temperature；
2) by 1) in the working electrode that obtains put in Muffle furnace, be annealed processing at 450 DEG C, after process, be cooled to room temperature；
3) by 2) in the working electrode surface drop coating 10 μ L horseradish peroxidase Solution H RP that obtains, dry at 4 DEG C, clean with ultra-pure water after drying, dry at 4 DEG C, prepare Optical Electro-Chemistry working electrode W2；
All the other are with the preparation process of W2 in embodiment 1.
(4) based on the preparation method of the hydrogen peroxide sensor of two kinds of electrochemical method couplings:
Preparation process is with embodiment 1, and difference is W1 and W2 spacing is 1.0cm, and the pH value of the NaOH solution added in electrolyzer is 12.
3 one kinds of hydrogen peroxide sensors based on two kinds of electrochemical method couplings of embodiment
A kind of preparation method of the hydrogen peroxide sensor based on two kinds of electrochemical method couplings, concrete preparation process is:
(1) Cd-MoS2The preparation of solution:
Preparation process is with Cd-MoS in embodiment 12The preparation method of solution, difference is: CdCl2Addition be 0.01g, ascorbic acid solution addition be 6mL, Na2MoO4The addition of solution is 1.5mL and Na2The addition of S is 0.03g, at 220 DEG C, reacts 12 hours.
(2) preparation of electrogenerated chemiluminescence working electrode W1:
Preparation process is with the preparation process of W1 in embodiment 1, and difference is: use the Cd-MoS obtained by (1) in the present embodiment2Modified electrode；In electrolyte, the concentration of luminol is 10mmol/L, and sulfuric acid concentration is 1.0mol/L；When cyclic voltammetry carries out electrochemical deposition, circulation 30 circle.
(3) preparation of Optical Electro-Chemistry working electrode W2:
1) with ITO electro-conductive glass for working electrode, at electrode surface drop coating 12 μ L titanium dioxide nano-particle colloidal sol TiO2NPs, dries under room temperature；
2) by 1) in the working electrode that obtains put in Muffle furnace, be annealed processing at 450 DEG C, after process, be cooled to room temperature；
3) by 2) in the working electrode surface drop coating 12 μ L horseradish peroxidase Solution H RP that obtains, dry at 4 DEG C, clean with ultra-pure water after drying, dry at 4 DEG C, prepare Optical Electro-Chemistry working electrode W2；
All the other are with the preparation process of W2 in embodiment 1.
(4) based on the preparation method of the hydrogen peroxide sensor of two kinds of electrochemical method couplings:
Preparation process is with embodiment 1, and difference is W1 and W2 spacing is 1.5cm, and the pH value of the NaOH solution added in electrolyzer is 13.
4 one kinds of application based on the hydrogen peroxide sensor of two kinds of electrochemical method couplings of embodiment
A kind of hydrogen peroxide sensor based on two kinds of electrochemical method couplings of embodiment 1 preparation is applied to the detection of hydrogen peroxide, and its detecting step is:
(1) utilizing electrochemical workstation, adopt the method for step voltage that W1 applies step voltage on W1, initial voltage is 0v, and step voltage is 0.7v, and snap time is 10s；Meanwhile, when adopting on W2, W2 is applied constant voltage by m-current methods, and voltage is 0v；
(2) adding the Hydrogen peroxide standard solution of variable concentrations in electrolyzer, the electric current on W2 can increase accordingly along with the increase of concentration of hydrogen peroxide, according to the relation between gained electric current increase value and concentration of hydrogen peroxide, drawing curve；
(3) hydrogenperoxide steam generator to be measured replaces the standard solution of hydrogen peroxide, and the method for drafting of the hydrogen peroxide working curve described in (1) and (2) detects.
5 one kinds of application based on the hydrogen peroxide sensor of two kinds of electrochemical method couplings of embodiment
A kind of hydrogen peroxide sensor based on two kinds of electrochemical method couplings of embodiment 2 preparation is applied to the detection of hydrogen peroxide, and its detecting step is:
(1) utilizing electrochemical workstation, adopt the method for step voltage that W1 applies step voltage on W1, initial voltage is 0v, and step voltage is 0.8v, and snap time is 20s；Meanwhile, when adopting on W2, W2 is applied constant voltage by m-current methods, and voltage is 0.3v；
(2) and (3) with embodiment 4.
The application of the hydrogen peroxide sensor of 6 one kinds of two kinds of electrochemical method couplings of embodiment
A kind of hydrogen peroxide sensor based on two kinds of electrochemical method couplings of embodiment 3 preparation is applied to the detection of hydrogen peroxide, and its detecting step is:
(1) utilizing electrochemical workstation, adopt the method for step voltage that W1 applies step voltage on W1, initial voltage is 0v, and step voltage is 0.9v, and snap time is 30s；Meanwhile, when adopting on W2, W2 is applied constant voltage by m-current methods, and voltage is 0.6v；
(2) and (3) with embodiment 4.
Embodiment 7Hydrogen peroxide sensor prepared by embodiment 1-3, is applied to the detection of hydrogen peroxide, has excellent Detection results, and detection is limited to 20 μm of ol/L.
The detection of hydrogen peroxide in embodiment 8 human serum
Accurately pipette human serum sample, add the Hydrogen peroxide standard solution of certain molar concentration, with do not add hydrogen peroxide human serum for blank, carry out recovery testu, detecting according to the step of embodiment 4 ~ 6, measure the response rate of hydrogen peroxide in sample, testing result is in Table 1.
The testing result of hydrogen peroxide in table 1 human serum
Table 1 testing result is it can be seen that the relative standard deviation (RSD) of result is less than 2.3%, and the response rate is 96 ~ 102%, it was shown that the present invention can be used for the detection of hydrogen peroxide in human serum, and highly sensitive, the high specificity of method, result is accurately and reliably.
Claims (2)
1. the preparation method based on the hydrogen peroxide sensor of two kinds of electrochemical method couplings, it is characterised in that preparation process is:
(1) preparation of electrogenerated chemiluminescence working electrode W1:
1) with ITO electro-conductive glass for working electrode, at the molybdenum bisuphide two-dimension nano materials Cd-MoS of electrode surface drop coating cadmium doping2Solution, area coverage is 1cm × 1cm, dries under room temperature；
2) by 1) working electrode that obtains, immerse in electrolyte, immersion area is Cd-MoS2The area covered, utilizes three-electrode system that working electrode is carried out electrochemical deposition, takes out working electrode after deposition, uses ultra-pure water to clean, and at 4 DEG C, lucifuge dries, and prepares electrogenerated chemiluminescence working electrode W1；
The molybdenum bisuphide two-dimension nano materials Cd-MoS of described cadmium doping2Solution is Cd-MoS2Aqueous solution, described Cd-MoS2For the molybdenum bisuphide two-dimension nano materials doped with cadmium ion, described two-dimension nano materials is scraps of paper shape, and thickness is about 10 ~ 20nm；
Described electrolyte is the sulfuric acid solution containing luminol, and in described electrolyte, the concentration of luminol is 1 ~ 10mmol/L, and sulfuric acid concentration is 0.1 ~ 1.0mol/L；
Described three-electrode system, including working electrode, reference electrode and to electrode, described reference electrode is saturated calomel electrode, and described is platinum electrode to electrode；
Described electrochemical deposition process, the electrochemical method of employing is cyclic voltammetry, and starting voltage is-0.2V, and final voltage is 1.5V, sweeps speed for 100mv/s, circulation 20 ~ 30 circle；
(2) preparation of Optical Electro-Chemistry working electrode W2:
1) with ITO electro-conductive glass for working electrode, at electrode surface drop coating 8 ~ 12 μ L titanium dioxide nano-particle colloidal sol TiO2NPs, dries under room temperature；
2) by 1) in the working electrode that obtains put in Muffle furnace, be annealed processing at 450 DEG C, after process, be cooled to room temperature；
3) by 2) in working electrode surface drop coating 8 ~ 12 μ L horseradish peroxidase Solution H RP that obtains, dry at 4 DEG C, clean with ultra-pure water after drying, dry at 4 DEG C, prepare Optical Electro-Chemistry working electrode W2；
Described TiO2NPs is the titanium dioxide nano-particle aqueous solution of 1mg/mL；
Described HRP is the horseradish peroxidase aqueous solution of 5mU/mL；
(3) based on the preparation method of the hydrogen peroxide sensor of two kinds of electrochemical method couplings:
1) being inserted face to face in electrolyzer by W1 and W2, W1 and W2 spacing is 0.5cm ~ 1.5cm；
2) with Ag/AgCl be reference electrode RE, platinum electrode be to electrode CE, insert in electrolyzer, collectively constitute four electrode systems with W1 and W2；
3) adding 10mLpH value in electrolyzer is the NaOH solution of 11 ~ 13；
4) by 1) ~ 3) obtained by four electrode systems and electrolyzer be placed in magazine, namely prepare the hydrogen peroxide sensor based on two kinds of electrochemical method couplings.
2. the hydrogen peroxide sensor that prepared by preparation method according to claim 1, it is characterised in that described hydrogen peroxide sensor is applied to the step of hydrogen peroxide detection and is:
(1) utilizing electrochemical workstation, adopt the method for step voltage that W1 applies step voltage on W1, initial voltage is 0v, and step voltage is 0.7 ~ 0.9v, and snap time is 10 ~ 30s；Meanwhile, when adopting on W2, W2 is applied constant voltage by m-current methods, and voltage is 0 ~ 0.6v；
(2) adding the Hydrogen peroxide standard solution of variable concentrations in electrolyzer, the electric current on W2 can increase accordingly along with the increase of concentration of hydrogen peroxide, according to the relation between gained electric current increase value and concentration of hydrogen peroxide, drawing curve；
(3) hydrogenperoxide steam generator to be measured replaces the standard solution of hydrogen peroxide, and the method for drafting of the hydrogen peroxide working curve described in (1) and (2) detects.
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| CN115184425A (en) * | 2022-07-11 | 2022-10-14 | 陕西师范大学 | Molybdenum disulfide coated nitrogen-containing carbon nanotube fixed CPO biosensor and detection H 2 O 2 Application of |
| CN115184425B (en) * | 2022-07-11 | 2024-01-16 | 陕西师范大学 | Molybdenum disulfide coated nitrogen-containing carbon nanotube fixed CPO biosensor and detection H 2 O 2 Applications of (2) |
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