CN105675686A - Preparation method and application of four-electrode system hydrogen peroxide electrochemical sensor - Google Patents
Preparation method and application of four-electrode system hydrogen peroxide electrochemical sensor Download PDFInfo
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- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 title claims abstract description 152
- 238000002360 preparation method Methods 0.000 title claims abstract description 48
- 238000001514 detection method Methods 0.000 claims abstract description 25
- 239000002086 nanomaterial Substances 0.000 claims abstract description 21
- 229960002163 hydrogen peroxide Drugs 0.000 claims description 73
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 29
- 230000005518 electrochemistry Effects 0.000 claims description 20
- 238000000034 method Methods 0.000 claims description 19
- 230000003287 optical effect Effects 0.000 claims description 19
- 239000000243 solution Substances 0.000 claims description 12
- 239000004408 titanium dioxide Substances 0.000 claims description 12
- 239000011521 glass Substances 0.000 claims description 11
- HWYHZTIRURJOHG-UHFFFAOYSA-N luminol Chemical compound O=C1NNC(=O)C2=C1C(N)=CC=C2 HWYHZTIRURJOHG-UHFFFAOYSA-N 0.000 claims description 11
- 239000007864 aqueous solution Substances 0.000 claims description 10
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 10
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 10
- PJDBVVBEOBZFDJ-UHFFFAOYSA-L azanium nickel(2+) phosphate Chemical compound [NH4+].[Ni+2].[O-]P([O-])([O-])=O PJDBVVBEOBZFDJ-UHFFFAOYSA-L 0.000 claims description 9
- 239000002055 nanoplate Substances 0.000 claims description 9
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 claims description 7
- 239000002105 nanoparticle Substances 0.000 claims description 6
- 229910052697 platinum Inorganic materials 0.000 claims description 5
- 108010001336 Horseradish Peroxidase Proteins 0.000 claims description 4
- 229910021607 Silver chloride Inorganic materials 0.000 claims description 3
- 239000002245 particle Substances 0.000 claims description 3
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 claims description 3
- 230000005611 electricity Effects 0.000 claims description 2
- 229910052737 gold Inorganic materials 0.000 claims description 2
- 239000010931 gold Substances 0.000 claims description 2
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 abstract description 4
- 238000011896 sensitive detection Methods 0.000 abstract description 2
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 12
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 12
- 238000001548 drop coating Methods 0.000 description 12
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 description 8
- 239000003792 electrolyte Substances 0.000 description 8
- 229910019142 PO4 Inorganic materials 0.000 description 6
- 150000003863 ammonium salts Chemical class 0.000 description 6
- 239000012491 analyte Substances 0.000 description 6
- 238000004070 electrodeposition Methods 0.000 description 6
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 6
- 239000010452 phosphate Substances 0.000 description 6
- 230000008569 process Effects 0.000 description 6
- 229910021642 ultra pure water Inorganic materials 0.000 description 6
- 239000012498 ultrapure water Substances 0.000 description 6
- 239000000463 material Substances 0.000 description 5
- 210000002966 serum Anatomy 0.000 description 5
- 239000012086 standard solution Substances 0.000 description 5
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 4
- 239000004254 Ammonium phosphate Substances 0.000 description 4
- 239000005696 Diammonium phosphate Substances 0.000 description 4
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 description 4
- LFVGISIMTYGQHF-UHFFFAOYSA-N ammonium dihydrogen phosphate Chemical compound [NH4+].OP(O)([O-])=O LFVGISIMTYGQHF-UHFFFAOYSA-N 0.000 description 4
- 229910000387 ammonium dihydrogen phosphate Inorganic materials 0.000 description 4
- 229910000148 ammonium phosphate Inorganic materials 0.000 description 4
- 235000019289 ammonium phosphates Nutrition 0.000 description 4
- 238000002484 cyclic voltammetry Methods 0.000 description 4
- 229910000388 diammonium phosphate Inorganic materials 0.000 description 4
- 235000019838 diammonium phosphate Nutrition 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 235000019837 monoammonium phosphate Nutrition 0.000 description 4
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 description 4
- 238000012545 processing Methods 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 230000008859 change Effects 0.000 description 3
- 238000002848 electrochemical method Methods 0.000 description 3
- 230000004044 response Effects 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- 102000004190 Enzymes Human genes 0.000 description 2
- 108090000790 Enzymes Proteins 0.000 description 2
- SWLVFNYSXGMGBS-UHFFFAOYSA-N ammonium bromide Chemical compound [NH4+].[Br-] SWLVFNYSXGMGBS-UHFFFAOYSA-N 0.000 description 2
- 235000019270 ammonium chloride Nutrition 0.000 description 2
- 230000003321 amplification Effects 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 238000005119 centrifugation Methods 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000000151 deposition Methods 0.000 description 2
- 230000008021 deposition Effects 0.000 description 2
- ZOMNIUBKTOKEHS-UHFFFAOYSA-L dimercury dichloride Chemical group Cl[Hg][Hg]Cl ZOMNIUBKTOKEHS-UHFFFAOYSA-L 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000005281 excited state Effects 0.000 description 2
- 238000007654 immersion Methods 0.000 description 2
- 238000004020 luminiscence type Methods 0.000 description 2
- 238000003199 nucleic acid amplification method Methods 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 238000004451 qualitative analysis Methods 0.000 description 2
- 238000004445 quantitative analysis Methods 0.000 description 2
- 230000004913 activation Effects 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000007806 chemical reaction intermediate Substances 0.000 description 1
- 230000002153 concerted effect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000003745 diagnosis Methods 0.000 description 1
- 230000009977 dual effect Effects 0.000 description 1
- 238000001378 electrochemiluminescence detection Methods 0.000 description 1
- 230000005283 ground state Effects 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 238000001727 in vivo Methods 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 230000002093 peripheral effect Effects 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
Classifications
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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
- G01N27/3271—Amperometric enzyme electrodes for analytes in body fluids, e.g. glucose in blood
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- Health & Medical Sciences (AREA)
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- Life Sciences & Earth Sciences (AREA)
- Analytical Chemistry (AREA)
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- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
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- General Health & Medical Sciences (AREA)
- General Physics & Mathematics (AREA)
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- Investigating Or Analysing Materials By The Use Of Chemical Reactions (AREA)
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Abstract
The invention discloses a preparation method of a four-electrode system hydrogen peroxide electrochemical sensor which is constructed based on a functional nano material. The prepared sensor is simple in operation, convenient to carry, high in detection speed, low in cost and capable of being applied to rapid and sensitive detection of hydrogen peroxide in the fields of daily production, life and the like.
Description
Technical field
The preparation method that the present invention relates to a kind of sensor for detecting hydrogen peroxide, this sensor integration electrochemiluminescence and Optical Electro-Chemistry dual-use function. Belong 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, electrochemical luminous sensor and Optical Electro-Chemistry sensor three kinds. Wherein, electrochemical luminous 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.
Electrochemiluminescence 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 electrochemical luminous 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 electrochemical luminous 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 ITO electro-conductive glass, first modifies nickel phosphate ammonium micro-nano material NH herein above4NiPO4With gold Argentous sulfide. nanometer rods Sol A uAg2SNRs is as substrate, and then electropolymerization luminol thereon, this electrode is as electrochemiluminescence working electrode W1, and working electrode 2 adopts titanium dioxide nanoplate colloidal sol TiO2NSs and horseradish peroxidase Solution H RP modifies jointly, as Optical Electro-Chemistry working electrode W2. When detecting, after adding hydrogen peroxide in electrolyzer, W1 applies step voltage, due to NH4NiPO4Stabilized illumination and increase AuAg2The effect of SNRs load, NH4NiPO4And AuAg2The concerted catalysis effect of SNRs and AuAg2The SNRs strong adsorption to electropolymerization luminol, luminol and hydroperoxidation, produce electrochemiluminescence, this is just equivalent to " turning on light ", and when step voltage is 0, electrochemiluminescence disappears, this is just equivalent to " turning off the light ", meanwhile applies constant voltage on W2, due to TiO always2NSs can because the luminescence that electrochemiluminescence 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 electrochemiluminescence 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 concrete technical scheme that the present invention adopts is as follows:
1. a preparation method for four electrode system hydrogen peroxide electrochemical sensor, it is characterized in that, preparation process is:
(1) preparation method of electrochemiluminescence working electrode W1, described W1 is by NH4NiPO4And AuAg2Preparing after electropolymerization luminol on the ITO electro-conductive glass that SNRs modifies jointly, be characterized in, concrete preparation process is:
1) with ITO electro-conductive glass for working electrode, at electrode surface drop coating NH4NiPO4Solution, area coverage is 1cm × 1cm, dries under room temperature;
2) by 1) working electrode that obtains, at NH4NiPO4Surface drop coating AuAg2SNRs, area coverage is 1cm × 1cm, dries under room temperature;
3) by 2) working electrode that obtains, immerse in electrolyte, immersion area is NH4NiPO4And AuAg2The area that SNRs is common covered, utilizes electrochemistry 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 electrochemiluminescence working electrode W1;
Described NH4NiPO4Solution is nickel phosphate ammonium micro-nano material aqueous solution, and described nickel phosphate ammonium micro-nano material is porous flake micro-nano material, described NH4NiPO4Preparation process be: in 40mL water, add 2.0 ~ 4.0g ammonium salt and 0.15 ~ 0.25g phosphate, after being completely dissolved, add 0.15 ~ 0.25g Nickel Chloride, at 30 ~ 45 DEG C, stir 10 ~ 14h, centrifugation, product is placed at 50 DEG C dry, namely obtains NH4NiPO4;
Described ammonium salt is selected from one of following: ammonium chloride, ammonium bromide, ammonium phosphate, ammonium dihydrogen phosphate, diammonium phosphate;
Described phosphate is selected from one of following: ammonium phosphate, ammonium dihydrogen phosphate, diammonium phosphate;
Described golden Argentous sulfide. nanometer rods Sol A uAg2SNRs is the aqueous solution of the rod-like nano material of nucleocapsid structure, and the rod-like nano material of described nucleocapsid structure is with gold nanorods for core, and Argentous sulfide. nanoparticle is the rod-like nano material of shell, and described gold nanorods is bar-like golden nanometer particle, and length is 20 ~ 40nm;
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 electrochemistry 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 method of Optical Electro-Chemistry working electrode W2, described W2 is by TiO2The ITO electro-conductive glass that NSs and HRP modifies jointly, is characterized in, concrete preparation process is:
1) with ITO electro-conductive glass for working electrode, at electrode surface drop coating 8 ~ 12 μ LTiO2NSs, 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 LHRP 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 TiO2NSs is the aqueous solution of the titanium dioxide nanoplate of 1mg/mL, and described titanium dioxide nanoplate is the titanium dioxide nano-particle of square lamellar, and the length of side is 60 ~ 80nm;
Described HRP is the horseradish peroxidase aqueous solution of 5mU/mL;
The preparation method of (3) four electrode system hydrogen peroxide electrochemical sensor:
1) one side that W1 and W2 conducts electricity relatively being inserted in electrolyzer, 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 four electrode system hydrogen peroxide electrochemical sensor.
2. four electrode system hydrogen peroxide electrochemical sensor of the present invention are applied to the detection of hydrogen peroxide, and the detection method being characterized in concrete 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 is replaced the standard solution of hydrogen peroxide, hydrogen peroxide detection method described in (1) and (2) detects, and draws the concentration of hydrogenperoxide steam generator to be measured according to obtained electric current increase value and the working curve drawn.
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, and achieves electrochemiluminescence signal amplification strategy difunctional with Optical Electro-Chemistry.Along with the increase of concentration of hydrogen peroxide in electrolyzer, on the one hand, make electrochemiluminescence 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, electrochemiluminescence 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 and using value.
Detailed description of the invention
1 one kind of four electrode system hydrogen peroxide electrochemical sensor of embodiment, concrete preparation process is:
(1) preparation of electrochemiluminescence working electrode W1:
1) with ITO electro-conductive glass for working electrode, at electrode surface drop coating NH4NiPO4Solution, area coverage is 1cm × 1cm, dries under room temperature;
2) by 1) working electrode that obtains, at NH4NiPO4Surface drop coating AuAg2SNRs, area coverage is 1cm × 1cm, dries under room temperature;
3) by 2) working electrode that obtains, immerse in electrolyte, immersion area is NH4NiPO4And AuAg2The area that SNRs is common 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 electrochemiluminescence working electrode W1;
Described NH4NiPO4Solution is nickel phosphate ammonium micro-nano material aqueous solution, the preparation process of described nickel phosphate ammonium micro-nano material is: add 2.0 ~ 4.0g ammonium salt and 0.15 ~ 0.25g phosphate in 40mL water, after being completely dissolved, add 0.15 ~ 0.25g Nickel Chloride, 10 ~ 14h is stirred at 30 ~ 45 DEG C, centrifugation, is placed in product at 50 DEG C dry, namely obtains NH4NiPO4;
Described ammonium salt is selected from one of following: ammonium chloride, ammonium bromide, ammonium phosphate, ammonium dihydrogen phosphate, diammonium phosphate;
Described phosphate is selected from one of following: ammonium phosphate, ammonium dihydrogen phosphate, diammonium phosphate;
Described AuAg2SNRs is the aqueous solution of the rod-like nano material of nucleocapsid structure, and the rod-like nano material of described nucleocapsid structure is with gold nanorods for core, and Argentous sulfide. nanoparticle is the rod-like nano material of shell, and described gold nanorods is bar-like golden nanometer particle, and length is 20nm;
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 ~ 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 μ LTiO2NSs, 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 LHRP 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 TiO2NSs is the aqueous solution of the titanium dioxide nanoplate of 1mg/mL, and described titanium dioxide nanoplate is the titanium dioxide nano-particle of square lamellar, and the length of side is 60 ~ 80nm;
Described HRP is the horseradish peroxidase aqueous solution of 5mU/mL.
(3) based on the preparation method of four electrode system hydrogen peroxide electrochemical sensor:
1) being inserted face to face in electrolyzer by the W1 of preparation in (1) and the W2 of (2) 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 four electrode system hydrogen peroxide electrochemical sensor.
2 one kind of four electrode system hydrogen peroxide electrochemical sensor of embodiment, concrete preparation process is:
(1) preparation of electrochemiluminescence working electrode W1:
Preparation process is with the preparation process of W1 in embodiment 1, difference is: in the preparation process of nickel phosphate ammonium micro-nano material, ammonium salt addition is 0.3g, phosphate addition is 0.20g, and Nickel Chloride addition is 0.20g, whipping temp and time respectively 38 DEG C and 12h; The length of gold nanorods is 30nm; 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.
(2) preparation of Optical Electro-Chemistry working electrode W2:
1) with ITO electro-conductive glass for working electrode, at electrode surface drop coating 10 μ LTiO2NSs, 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 LHRP 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.
The preparation method of (3) four electrode system hydrogen peroxide electrochemical sensor:
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 kind of four electrode system hydrogen peroxide electrochemical sensor of embodiment, concrete preparation process is:
(1) preparation of electrogenerated chemiluminescence working electrode W1:
Preparation process is with the preparation process of W1 in embodiment 1, difference is: in the preparation process of nickel phosphate ammonium micro-nano material, ammonium salt addition is 0.4g, phosphate addition is 0.25g, and Nickel Chloride addition is 0.25g, whipping temp and time respectively 45 DEG C and 14h; The length of gold nanorods is 40nm; 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.
(2) preparation of Optical Electro-Chemistry working electrode W2:
1) with ITO electro-conductive glass for working electrode, at electrode surface drop coating 12 μ LTiO2NSs, 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 LHRP 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.
The preparation method of (3) four electrode system hydrogen peroxide electrochemical sensor:
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.
The application of 4 one kind of four electrode system hydrogen peroxide electrochemical sensor of embodiment
A kind of four electrode system hydrogen peroxide electrochemical sensor of embodiment 1 preparation are 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 is replaced the standard solution of hydrogen peroxide, hydrogen peroxide detection method described in (1) and (2) detects, and draws the concentration of hydrogenperoxide steam generator to be measured according to obtained electric current increase value and the working curve drawn.
The application of 5 one kind of four electrode system hydrogen peroxide electrochemical sensor of embodiment
A kind of four electrode system hydrogen peroxide electrochemical sensor of embodiment 2 preparation are 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 6 one kind of four electrode system hydrogen peroxide electrochemical sensor of embodiment
A kind of four electrode system hydrogen peroxide electrochemical sensor of embodiment 3 preparation are 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.
Hydrogen peroxide sensor prepared by embodiment 7 embodiment 1-3, is applied to the detection of hydrogen peroxide, has excellent Detection results, and detection is limited to 8 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 not more than 2.1%, and the response rate is 98 ~ 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 (6)
1. the preparation method of an electrode system hydrogen peroxide electrochemical sensor, it is characterised in that adopt nickel phosphate ammonium micro-nano material NH4NiPO4With gold Argentous sulfide. nanometer rods Sol A uAg2As electrochemiluminescence working electrode W1, titanium dioxide nanoplate colloidal sol TiO after electropolymerization luminol on the ITO electro-conductive glass that SNRs modifies jointly2The ITO electro-conductive glass that NSs and horseradish peroxidase Solution H RP modifies jointly is as Optical Electro-Chemistry working electrode W2, Ag/AgCl electrode as reference electrode RE, platinum electrode as to electrode CE, four electrodes are inserted jointly same electrolyzer forms four electrode systems, four prepared electrode systems are placed in magazine, namely prepare four electrode system hydrogen peroxide electrochemical sensor.
2. preparation method according to claim 1, it is characterised in that described nickel phosphate ammonium micro-nano material NH4NiPO4For porous flake micro-nano material.
3. preparation method according to claim 1, it is characterised in that described golden Argentous sulfide. nanometer rods Sol A uAg2SNRs is the aqueous solution of the rod-like nano material of nucleocapsid structure, and the rod-like nano material of described nucleocapsid structure is with gold nanorods for core, and Argentous sulfide. nanoparticle is the rod-like nano material of shell, and described gold nanorods is bar-like golden nanometer particle, and length is 20 ~ 40nm.
4. preparation method according to claim 1, it is characterised in that described titanium dioxide nanoplate colloidal sol TiO2NSs is the aqueous solution of titanium dioxide nanoplate, and described titanium dioxide nanoplate is the titanium dioxide nano-particle of square lamellar, and the length of side is 60 ~ 80nm.
5. preparation method according to claim 1, it is characterised in that the one side that W1 and W2 conducts electricity relatively being inserted in electrolyzer, W1 and W2 spacing is 0.5cm ~ 1.5cm.
6. the hydrogen peroxide electrochemical sensor that prepared by preparation method according to claim 1, it is characterized in that, described hydrogen peroxide electrochemical sensor is applied to the step of hydrogen peroxide detection: utilize electrochemical workstation, W1 is applied step voltage by the method adopting step voltage on W1, initial voltage is 0v, 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; Adding hydrogenperoxide steam generator to be measured in electrolyzer, the electric current on W2 can increase accordingly along with the increase of concentration of hydrogen peroxide, and increasing according to gained electric current is worth hydrogenperoxide steam generator concentration to be measured.
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| CN203824914U (en) * | 2014-04-17 | 2014-09-10 | 苏州大学 | Double-constant -potential excited electrochemical luminescence analysis device |
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