CN105675686B - A kind of preparation method and application of four electrode systems hydrogen peroxide electrochemical sensor - Google Patents
A kind of preparation method and application of four electrode systems 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 134
- 238000002360 preparation method Methods 0.000 title claims abstract description 44
- 239000002086 nanomaterial Substances 0.000 claims abstract description 20
- 229960002163 hydrogen peroxide Drugs 0.000 claims description 64
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 31
- 230000005518 electrochemistry Effects 0.000 claims description 23
- 230000003287 optical effect Effects 0.000 claims description 19
- 238000004020 luminiscence type Methods 0.000 claims description 18
- 239000010931 gold Substances 0.000 claims description 16
- 238000000034 method Methods 0.000 claims description 16
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 15
- 239000004408 titanium dioxide Substances 0.000 claims description 12
- 239000011521 glass Substances 0.000 claims description 11
- 239000000243 solution Substances 0.000 claims description 11
- 239000007864 aqueous solution Substances 0.000 claims description 10
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 10
- 229910052946 acanthite Inorganic materials 0.000 claims description 9
- 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
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 7
- 229910052737 gold Inorganic materials 0.000 claims description 7
- 238000004073 vulcanization Methods 0.000 claims description 7
- 239000002105 nanoparticle Substances 0.000 claims description 6
- 229910052697 platinum Inorganic materials 0.000 claims description 5
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 5
- 239000000463 material Substances 0.000 claims description 4
- 239000002073 nanorod Substances 0.000 claims description 4
- 229910052709 silver Inorganic materials 0.000 claims description 4
- 239000004332 silver Substances 0.000 claims description 4
- 108010001336 Horseradish Peroxidase Proteins 0.000 claims description 3
- 229910021607 Silver chloride Inorganic materials 0.000 claims description 3
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 claims description 3
- FSJWWSXPIWGYKC-UHFFFAOYSA-M silver;silver;sulfanide Chemical compound [SH-].[Ag].[Ag+] FSJWWSXPIWGYKC-UHFFFAOYSA-M 0.000 claims description 3
- 238000005868 electrolysis reaction Methods 0.000 claims description 2
- 238000001514 detection method Methods 0.000 abstract description 25
- 238000004519 manufacturing process Methods 0.000 abstract description 4
- 238000011896 sensitive detection Methods 0.000 abstract 1
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 12
- 238000001548 drop coating Methods 0.000 description 12
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 10
- HWYHZTIRURJOHG-UHFFFAOYSA-N luminol Chemical compound O=C1NNC(=O)C2=C1C(N)=CC=C2 HWYHZTIRURJOHG-UHFFFAOYSA-N 0.000 description 10
- 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
- 239000001257 hydrogen Substances 0.000 description 8
- 229910052739 hydrogen Inorganic materials 0.000 description 8
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 6
- 229910019142 PO4 Inorganic materials 0.000 description 6
- 150000003863 ammonium salts Chemical class 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
- 210000002966 serum Anatomy 0.000 description 5
- 239000012086 standard solution Substances 0.000 description 5
- 229910021642 ultra pure water Inorganic materials 0.000 description 5
- 239000012498 ultrapure water 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
- 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
- 239000012491 analyte Substances 0.000 description 4
- 238000000137 annealing Methods 0.000 description 4
- 230000008859 change Effects 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
- 238000005516 engineering process Methods 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 235000019837 monoammonium phosphate Nutrition 0.000 description 4
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical class Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 102000004190 Enzymes Human genes 0.000 description 3
- 108090000790 Enzymes Proteins 0.000 description 3
- 238000002848 electrochemical method Methods 0.000 description 3
- 230000005284 excitation Effects 0.000 description 3
- 230000005622 photoelectricity Effects 0.000 description 3
- 238000011084 recovery Methods 0.000 description 3
- 230000035945 sensitivity Effects 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 229910021586 Nickel(II) chloride Inorganic materials 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
- 238000004458 analytical method Methods 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
- 230000003749 cleanliness Effects 0.000 description 2
- 238000000151 deposition Methods 0.000 description 2
- 230000008021 deposition Effects 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 230000009977 dual effect Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000001378 electrochemiluminescence detection Methods 0.000 description 2
- 150000002431 hydrogen Chemical class 0.000 description 2
- 238000007654 immersion Methods 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 150000002978 peroxides Chemical class 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 238000004451 qualitative analysis Methods 0.000 description 2
- 238000004445 quantitative analysis Methods 0.000 description 2
- 239000011257 shell material Substances 0.000 description 2
- 235000011330 Armoracia rusticana Nutrition 0.000 description 1
- 240000003291 Armoracia rusticana Species 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 230000003321 amplification Effects 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000007806 chemical reaction intermediate Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 230000002153 concerted effect Effects 0.000 description 1
- 235000009508 confectionery Nutrition 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- ZOMNIUBKTOKEHS-UHFFFAOYSA-L dimercury dichloride Chemical group Cl[Hg][Hg]Cl ZOMNIUBKTOKEHS-UHFFFAOYSA-L 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 230000006870 function Effects 0.000 description 1
- 230000005283 ground state Effects 0.000 description 1
- 230000003760 hair shine Effects 0.000 description 1
- 150000004680 hydrogen peroxides Chemical class 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 238000001727 in vivo Methods 0.000 description 1
- 238000003780 insertion Methods 0.000 description 1
- 230000037431 insertion Effects 0.000 description 1
- 238000007689 inspection Methods 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 238000003199 nucleic acid amplification method Methods 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
- 239000000047 product Substances 0.000 description 1
- 230000036632 reaction speed Effects 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 238000011895 specific detection 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
-
- 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
Abstract
The invention discloses a kind of preparation methods of the difunctional hydrogen peroxide sensor of four electrode systems based on function nano material structure, prepared sensor operations are simple, easy to carry, fast, at low cost, quick, the Sensitive Detection to hydrogen peroxide available for fields such as daily production and lifes of detection.
Description
Technical field
The present invention relates to a kind of for detecting the preparation method of the sensor of hydrogen peroxide, sensor integration electrochemistry
It shines and optical electro-chemistry dual function.Belong to Nano-function thin films and electrochemical biosensor analysis technical field.
Background technology
Hydrogen peroxide is a kind of oxidant, can be decomposed into water and oxygen under normal circumstances, but slow, is catalyzed when adding in
Agent（Or biological enzyme）When, reaction speed is accelerated, it is possible thereby to be made instantly available the amount or catalyst of hydrogen peroxide（Or biological enzyme）'s
Amount, while hydrogen peroxide also often exists in the form of reaction intermediate in vivo, therefore, hydrogen peroxide is examined in medicine
The fields such as disconnected, clinical treatment, environment measuring and food production play important role, research and development hydrogen peroxide detection side
Method also just has highly important application value.Electrochemical biosensor analytical technology is fast etc. due to easy to operate, detection speed
Advantage increasingly obtains the attention of people.The electrochemical biosensor analytical technology of detection hydrogen peroxide is presently used for according to detection
Means have three kinds of electrochemical sensor, electrochemical luminescence sensor and optical electro-chemistry sensor to divide mainly.Wherein, electrochemistry is sent out
Optical sensor and optical electro-chemistry sensor compared with electrochemical sensor, have few background signal noise, high sensitivity, detection into
The features such as this is low, it is of interest by more and more researchers in recent years.
Electrochemical luminescence is also referred to as electrogenerated chemiluminescence, and it is special to refer to generate some in electrode surface by electrochemical method
Substance, form excitation state between these substances or by electron transmission between other components in system, returned by excitation state
It returns to ground state and generates luminescence phenomenon.Electrochemical luminescence sensor is the decorative material by changing electrode surface, with analyzing produce
Raw electrochemical luminescence in optimal conditions, is realized according to the associated change of analyte concentration and electrochemical luminescence intensity to analysis
The qualitative and quantitative analysis of object.
Optical electro-chemistry sensor is based on additional light source activation Electrophotosensitivmaterial material electron-hole pair to be caused to be separated,
Under suitable potential condition partially, realize quick transmission of the electronics on electrode, semiconductor and trim and analyte, and formed
Photoelectric current.In optimal conditions, the variation 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 since electrochemical luminescence sensor needs external optical signal to capture equipment such as photodiode etc., and photoelectricity
Chemical sensor needs peripheral hardware light source to excite Electrophotosensitivmaterial material, this affects the convenient of the two operation to a certain extent
Property, it limits them and is more widely applied in actual production, life.Therefore, 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 sensings easy to operate, easy to carry, detection is fast, at low cost
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 uses ITO electro-conductive glass, is first modifying nickel phosphate ammonium micro-nano material above
NH4NiPO4With gold vulcanization Silver nanorod Sol A u Ag2S NRs are as substrate, then electropolymerization luminol on it, the electrode
As electrochemical luminescence working electrode W1, working electrode 2 is using titanium dioxide nanoplate colloidal sol TiO2NSs and horseradish peroxidating
Object enzyme solutions HRP is modified jointly, as optical electro-chemistry working electrode W2.When being detected, peroxide is added in electrolytic cell
After changing hydrogen, apply step voltage on W1, due to NH4NiPO4Stabilized illumination and increase Au@Ag2The effect of S NRs loads,
NH4NiPO4With Au@Ag2The concerted catalysis effect of S NRs and Au@Ag2Strong suction-operateds of the S NRs to electropolymerization luminol,
Luminol and hydroperoxidation generate electrochemical luminescence, this is just equivalent to " turning on light ", when step voltage is 0, electrochemistry hair
Light disappears, this is just equivalent to " turning off the light ", at the same time applies constant voltage always on W2, due to TiO2NSs can be because electrification
Learning the luminous excitation for shining and generating causes electron-hole pair to be separated, and HRP catalyzing hydrogen peroxides generate oxygen, make peroxidating
Hydrogen becomes hole " donor ", and so as to obtain photoelectric current on W2, when electrochemical luminescence disappears, i.e., when " turning off the light ", photoelectric current is immediately
It disappears, size and the concentration of hydrogen peroxide positive correlation of the photoelectric current of generation, therefore the size by recording photoelectric current can be realized
Detection to hydrogen peroxide.
More than inventive principle is based on, the specific technical solution that the present invention uses is as follows：
1. a kind of preparation method of four electrode systems hydrogen peroxide electrochemical sensor, feature are, preparation process
For：
（1）The preparation method of electrochemical luminescence working electrode W1, the W1 are by NH4NiPO4With Au@Ag2S NRs
It is prepared on the ITO electro-conductive glass modified jointly after electropolymerization luminol, its main feature is that, specific preparation process is：
1）Using ITO electro-conductive glass as working electrode, in electrode surface drop coating NH4NiPO4Solution, area coverage for 1 cm ×
1 cm, dries at room temperature；
2）By 1）Obtained working electrode, in NH4NiPO4Surface drop coating Au@Ag2S NRs, area coverage are 1 cm × 1
Cm dries at room temperature；
3）By 2）Obtained working electrode is immersed in electrolyte, and immersion area is NH4NiPO4With Au@Ag2S NRs are common
The area covered carries out electrochemical deposition to working electrode using electrochemistry three-electrode system, working electrode is taken out after deposition,
It is cleaned using ultra-pure water, drying is protected from light at 4 DEG C, electrochemical luminescence working electrode W1 is made；
The NH4NiPO4Solution is nickel phosphate ammonium micro-nano material aqueous solution, and the nickel phosphate ammonium micro-nano material is porous
Sheet micro-nano material, the NH4NiPO4Preparation process be：2.0 ~ 4.0 g ammonium salts and 0.15 ~ 0.25 g are added in 40mL water
Phosphate after being completely dissolved, adds in 0.15 ~ 0.25 g Nickel Chlorides, 10 ~ 14h is stirred at 30 ~ 45 DEG C, centrifuges, will produce
Product are placed at 50 DEG C and dry to get to NH4NiPO4；
The ammonium salt is selected from one of following：Ammonium chloride, ammonium bromide, ammonium phosphate, ammonium dihydrogen phosphate, diammonium hydrogen phosphate；
The phosphate is selected from one of following：Ammonium phosphate, ammonium dihydrogen phosphate, diammonium hydrogen phosphate；
The gold vulcanization Silver nanorod Sol A u Ag2S NRs are the aqueous solution of the rod-like nano material of nucleocapsid,
The rod-like nano material of the nucleocapsid is using gold nanorods as core, and vulcanization Nano silver grain is the rod-like nano material of shell
Material, the gold nanorods are bar-like gold nanoparticle, and length is 20 ~ 40 nm；
The electrolyte is the sulfuric acid solution containing luminol, and the concentration of luminol is 1 ~ 10 in the electrolyte
Mmol/L, sulfuric acid concentration are 0.1 ~ 1.0 mol/L；
The electrochemistry three-electrode system, including working electrode, reference electrode and to electrode, the reference electrode is
Saturated calomel electrode, described is platinum electrode to electrode；
The electrochemical deposition process, the electrochemical method used is cyclic voltammetry, and starting voltage is -0.2 V, eventually
Only voltage is 1.5 V, sweeps speed as 100 mv/s, 20 ~ 30 circle of Xun Huan；
（2）The preparation method of optical electro-chemistry working electrode W2, the W2 are by TiO2What NSs and HRP was modified jointly
ITO electro-conductive glass, its main feature is that, specific preparation process is：
1）Using ITO electro-conductive glass as working electrode, in 8 ~ 12 μ L TiO of electrode surface drop coating2NSs dries at room temperature；
2）By 1）In obtained working electrode be put into Muffle furnace, made annealing treatment at 450 DEG C, handle postcooling
To room temperature；
3）By 2）In obtained working electrode surface drop coating 8 ~ 12 μ L HRP, it is dry at 4 DEG C, it is clear with ultra-pure water after dry
It washes, it is dry at 4 DEG C, optical electro-chemistry working electrode W2 is made；
The TiO2NSs is the aqueous solution of the titanium dioxide nanoplate of 1 mg/mL, and the titanium dioxide nanoplate is
The titanium dioxide nano-particle of square sheet, the length of side are 60 ~ 80 nm；
The HRP is the horseradish peroxidase aqueous solution of 5 mU/mL；
（3）The preparation method of four electrode system hydrogen peroxide electrochemical sensors：
1）By in the opposite insertion electrolytic cell of the one side of W1 and W2 conductions, 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, is inserted into 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 system and electrolytic cell are placed in magazine, that is, four electrode system peroxidating are made
Hydrogen electrochemical sensor.
2. four electrode systems hydrogen peroxide electrochemical sensor of the present invention is applied to the detection of hydrogen peroxide,
Feature is that specific detection method is：
（1）Using electrochemical workstation, step voltage, initial voltage are applied to W1 using the method for step voltage on W1
For 0 v, step voltage is 0.7 ~ 0.9 v, and snap time is 10 ~ 30 s；Meanwhile 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 concentration is added in electrolytic cell, the electric current on W2 can be with hydrogen peroxide
The increase of concentration and accordingly increase, according to the 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 solution of hydrogen peroxide, according to（1）With（2）The peroxidating
Hydrogen detection method is detected, and show that hydrogen peroxide to be measured is molten with the working curve drawn according to obtained electric current increment value
The concentration of liquid.
The useful achievement of the present invention
（1）Hydrogen peroxide sensor of the present invention is prepared simply, easy to operate, without external accessory, is utilized
The micromation of detection device, portability, and quick, sensitive, the highly selective detection to hydrogen peroxide is realized, have wide
Market development prospect；
（2）The present invention detects hydrogen peroxide in same electrolytic cell using four electrode systems for the first time, and realizes electrochemistry
Shine 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
Electrochemical luminescence intensity is linearly increasing, the photoelectricity cleanliness increase excited；On the other hand, hydrogen peroxide is as electron donor,
So that photoelectricity cleanliness increases in optical electro-chemistry reaction.Therefore, two methods of electrochemical luminescence and optical electro-chemistry are in same electrolysis
It reacts, interact jointly under Chi Zhong, same electrochemical workstation, realize and hydrogen peroxide detection the dual of electric signal is put
Greatly, detection sensitivity and detection limit are drastically increased, there is important scientific meaning and application value.
Specific embodiment
A kind of four electrode system hydrogen peroxide electrochemical sensors of embodiment 1, specific preparation process are：
（1）The preparation of electrochemical luminescence working electrode W1：
1）Using ITO electro-conductive glass as working electrode, in electrode surface drop coating NH4NiPO4Solution, area coverage for 1 cm ×
1 cm, dries at room temperature；
2）By 1）Obtained working electrode, in NH4NiPO4Surface drop coating Au@Ag2S NRs, area coverage are 1 cm × 1
Cm dries at room temperature；
3）By 2）Obtained working electrode is immersed in electrolyte, and immersion area is NH4NiPO4With Au@Ag2S NRs are common
The area covered carries out electrochemical deposition to working electrode using three-electrode system, working electrode is taken out after deposition, using super
Pure water cleans, and drying is protected from light at 4 DEG C, and electrochemical luminescence working electrode W1 is made；
The NH4NiPO4Solution be nickel phosphate ammonium micro-nano material aqueous solution, the preparation of the nickel phosphate ammonium micro-nano material
Step is：2.0 ~ 4.0 g ammonium salts and 0.15 ~ 0.25 g phosphate are added in 40mL water, after being completely dissolved, addition 0.15 ~
0.25 g Nickel Chlorides, at 30 ~ 45 DEG C stir 10 ~ 14h, centrifuge, by product be placed at 50 DEG C dry to get to
NH4NiPO4；
The ammonium salt is selected from one of following：Ammonium chloride, ammonium bromide, ammonium phosphate, ammonium dihydrogen phosphate, diammonium hydrogen phosphate；
The phosphate is selected from one of following：Ammonium phosphate, ammonium dihydrogen phosphate, diammonium hydrogen phosphate；
The Au@Ag2S NRs be nucleocapsid rod-like nano material aqueous solution, the nucleocapsid it is rodlike
Nano material is using gold nanorods as core, and vulcanization Nano silver grain is the rod-like nano material of shell, and the gold nanorods are sticks
Shape gold nanoparticle, length are 20 nm；
The electrolyte is the sulfuric acid solution containing luminol, and the concentration of luminol is 1 in the electrolyte
Mmol/L, sulfuric acid concentration are 0.1 mol/L；
The three-electrode system, including working electrode, reference electrode and to electrode, the reference electrode is that saturation is sweet
Mercury electrode, described is platinum electrode to electrode；
The electrochemical deposition process, the electrochemical method used is cyclic voltammetry, and starting voltage is -0.2 V, eventually
Only voltage is 1.5 V, sweeps speed as 100 mv/s, 20 ~ 30 circle of Xun Huan.
（2）The preparation of optical electro-chemistry working electrode W2：
1）Using ITO electro-conductive glass as working electrode, in 8 μ L TiO of electrode surface drop coating2NSs dries at room temperature；
2）By 1）In obtained working electrode be put into Muffle furnace, made annealing treatment at 450 DEG C, handle postcooling
To room temperature；
3）By 2）In obtained working electrode surface drop coating 8 μ L HRP, it is dry at 4 DEG C, cleaned after dry with ultra-pure water,
It is dry at 4 DEG C, optical electro-chemistry working electrode W2 is made；
The TiO2NSs is the aqueous solution of the titanium dioxide nanoplate of 1 mg/mL, and the titanium dioxide nanoplate is
The titanium dioxide nano-particle of square sheet, the length of side are 60 ~ 80 nm；
The HRP is the horseradish peroxidase aqueous solution of 5 mU/mL.
（3）Preparation method based on four electrode system hydrogen peroxide electrochemical sensors：
1）It will（1）The W1 of middle preparation and（2）The W2 of middle preparation is inserted into electrolytic cell face to face, and W1 is 0.5 with W2 spacing
cm；
2）It is to electrode CE by reference electrode RE, platinum electrode of Ag/AgCl, is inserted into 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 system and electrolytic cell are placed in magazine, that is, four electrode system peroxidating are made
Hydrogen electrochemical sensor.
A kind of four electrode system hydrogen peroxide electrochemical sensors of embodiment 2, specific preparation process are：
（1）The preparation of electrochemical luminescence working electrode W1：
With the preparation process of W1 in embodiment 1, difference is preparation process：The preparation process of nickel phosphate ammonium micro-nano material
Middle ammonium salt addition be 0.3 g, phosphate addition be 0.20 g, Nickel Chloride addition be 0.20 g, whipping temp and when
Between be respectively 38 DEG C and 12 h；The length of gold nanorods is 30 nm；In electrolyte the concentration of luminol be 5 mmol/L, sulfuric acid
Concentration is 0.5 mol/L；When cyclic voltammetry carries out electrochemical deposition, 25 circle of Xun Huan.
（2）The preparation of optical electro-chemistry working electrode W2：
1）Using ITO electro-conductive glass as working electrode, in 10 μ L TiO of electrode surface drop coating2NSs dries at room temperature；
2）By 1）In obtained working electrode be put into Muffle furnace, made annealing treatment at 450 DEG C, handle postcooling
To room temperature；
3）By 2）In obtained working electrode surface drop coating 10 μ L HRP, it is dry at 4 DEG C, it is clear with ultra-pure water after dry
It washes, it is dry at 4 DEG C, optical electro-chemistry working electrode W2 is made；
Remaining is the same as the preparation process of W2 in embodiment 1.
（3）The preparation method of four electrode system hydrogen peroxide electrochemical sensors：
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.
A kind of four electrode system hydrogen peroxide electrochemical sensors of embodiment 3, specific preparation process are：
（1）The preparation of electrogenerated chemiluminescence working electrode W1：
With the preparation process of W1 in embodiment 1, difference is preparation process：The preparation process of nickel phosphate ammonium micro-nano material
Middle ammonium salt addition be 0.4 g, phosphate addition be 0.25 g, Nickel Chloride addition be 0.25 g, whipping temp and when
Between be respectively 45 DEG C and 14 h；The length of gold nanorods is 40 nm；In electrolyte the concentration of luminol be 10 mmol/L, sulphur
Acid concentration is 1.0 mol/L；When cyclic voltammetry carries out electrochemical deposition, 30 circle of Xun Huan.
（2）The preparation of optical electro-chemistry working electrode W2：
1）Using ITO electro-conductive glass as working electrode, in 12 μ L TiO of electrode surface drop coating2NSs dries at room temperature；
2）By 1）In obtained working electrode be put into Muffle furnace, made annealing treatment at 450 DEG C, handle postcooling
To room temperature；
3）By 2）In obtained working electrode surface drop coating 12 μ L HRP, it is dry at 4 DEG C, it is clear with ultra-pure water after dry
It washes, it is dry at 4 DEG C, optical electro-chemistry working electrode W2 is made；
Remaining is the same as the preparation process of W2 in embodiment 1.
（3）The preparation method of four electrode system hydrogen peroxide electrochemical sensors：
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 of 4 four electrode systems hydrogen peroxide electrochemical sensor of embodiment
A kind of four electrode systems hydrogen peroxide electrochemical sensor prepared by embodiment 1 is applied to the detection of hydrogen peroxide,
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 concentration is added in electrolytic cell, the electric current on W2 can be with hydrogen peroxide
The increase of concentration and accordingly increase, according to the 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 solution of hydrogen peroxide, according to（1）With（2）The peroxidating
Hydrogen detection method is detected, and show that hydrogen peroxide to be measured is molten with the working curve drawn according to obtained electric current increment value
The concentration of liquid.
A kind of application of 5 four electrode systems hydrogen peroxide electrochemical sensor of embodiment
A kind of four electrode systems hydrogen peroxide electrochemical sensor prepared by embodiment 2 is applied to the detection of hydrogen peroxide,
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 of 6 four electrode systems hydrogen peroxide electrochemical sensor of embodiment
A kind of four electrode systems hydrogen peroxide electrochemical sensor prepared by embodiment 3 is applied to the detection of hydrogen peroxide,
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 electrochemical sensor prepared by 7 embodiment 1-3 of embodiment, applied to the detection of hydrogen peroxide,
With excellent detection result, detection is limited to 8 μm of ol/L.
The detection of hydrogen peroxide in 8 human serum of embodiment
Human serum sample accurately is pipetted, the Hydrogen peroxide standard solution of certain molar concentration is added in, not add in 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 1 human serum of table
Knowable to 1 testing result of table, relative standard deviation as a result（RSD）No more than 2.1 %, the rate of recovery is 98 ~ 102%,
Show the present invention can be used for human serum in hydrogen peroxide detection, the high sensitivity of method, high specificity, as a result accurately and reliably.
Claims (6)
1. a kind of preparation method of four electrode systems hydrogen peroxide electrochemical sensor, which is characterized in that micro- using nickel phosphate ammonium
Receive material NH4NiPO4With gold vulcanization Silver nanorod Sol A u Ag2Electropolymerization Shandong on the ITO electro-conductive glass that S NRs are modified jointly
Electrochemical luminescence working electrode W1, titanium dioxide nanoplate colloidal sol TiO are used as after minot2NSs and horseradish peroxidase solution
The ITO electro-conductive glass that HRP is modified jointly is as optical electro-chemistry working electrode W2, Ag/AgCl electrode as reference electrode RE, platinum filament
Electrode is used as to electrode CE, and four electrodes are inserted into jointly in same electrolytic cell and form four electrode systems, by four electrode obtained
System is placed in magazine, that is, four electrode system hydrogen peroxide electrochemical sensors are made.
2. preparation method according to claim 1, which is characterized in that the nickel phosphate ammonium micro-nano material NH4NiPO4To be more
Hole sheet micro-nano material.
3. preparation method according to claim 1, which is characterized in that the gold vulcanization Silver nanorod Sol A u Ag2S
NRs is the aqueous solution of the rod-like nano material of nucleocapsid, the rod-like nano material of the nucleocapsid be using gold nanorods as
Core, vulcanization Nano silver grain are the rod-like nano material of shell, and the gold nanorods are bar-like gold nanoparticle, length for 20 ~
40 nm。
4. preparation method according to claim 1, which is characterized in that the titanium dioxide nanoplate colloidal sol TiO2 NSs
For the aqueous solution of titanium dioxide nanoplate, the titanium dioxide nanoplate is the titanium dioxide nano-particle of square sheet, the length of side
For 60 ~ 80 nm.
5. preparation method according to claim 1, which is characterized in that the one side of W1 and W2 conductions is inserted into electrolysis relatively
Chi Zhong, W1 and W2 spacing are the cm of 0.5 cm ~ 1.5.
6. hydrogen peroxide electrochemical sensor prepared by preparation method according to claim 1, which is characterized in that described
Hydrogen peroxide electrochemical sensor be applied to hydrogen peroxide detect the step of be：Using electrochemical workstation, used on W1
The method of step voltage to W1 apply step voltage, initial voltage be 0 v, step voltage be 0.7 ~ 0.9 v, snap time 10
~30 s；Meanwhile m- current methods apply W2 constant voltage when being used on W2, voltage is 0 ~ 0.6 v；Add in electrolytic cell
Enter hydrogenperoxide steam generator to be measured, the electric current on W2 can accordingly increase with the increase of concentration of hydrogen peroxide, according to gained electric current
Increment value draws 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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