CN106198693A - The method of detection solution Nitrite ion concentration - Google Patents
The method of detection solution Nitrite ion concentration Download PDFInfo
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- CN106198693A CN106198693A CN201610456856.9A CN201610456856A CN106198693A CN 106198693 A CN106198693 A CN 106198693A CN 201610456856 A CN201610456856 A CN 201610456856A CN 106198693 A CN106198693 A CN 106198693A
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- nitrite ion
- polypyrrole
- carboxylated graphene
- chitosan
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- IOVCWXUNBOPUCH-UHFFFAOYSA-M Nitrite anion Chemical compound [O-]N=O IOVCWXUNBOPUCH-UHFFFAOYSA-M 0.000 title claims abstract description 75
- 229940005654 nitrite ion Drugs 0.000 title claims abstract description 70
- 238000000034 method Methods 0.000 title claims abstract description 33
- 238000001514 detection method Methods 0.000 title description 21
- 229920000128 polypyrrole Polymers 0.000 claims abstract description 48
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 46
- 229910021389 graphene Inorganic materials 0.000 claims abstract description 44
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 30
- 229920001661 Chitosan Polymers 0.000 claims abstract description 28
- 238000001903 differential pulse voltammetry Methods 0.000 claims abstract description 26
- 150000003233 pyrroles Chemical class 0.000 claims abstract description 11
- 239000000243 solution Substances 0.000 claims description 69
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 22
- 239000007853 buffer solution Substances 0.000 claims description 21
- 238000005498 polishing Methods 0.000 claims description 13
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 12
- 229910021642 ultra pure water Inorganic materials 0.000 claims description 12
- 239000012498 ultrapure water Substances 0.000 claims description 12
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 10
- 239000000843 powder Substances 0.000 claims description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 9
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 8
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims description 8
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 8
- 238000003756 stirring Methods 0.000 claims description 8
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 6
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 5
- 238000005352 clarification Methods 0.000 claims description 5
- 239000004744 fabric Substances 0.000 claims description 5
- 230000008569 process Effects 0.000 claims description 5
- 239000006228 supernatant Substances 0.000 claims description 5
- 240000004808 Saccharomyces cerevisiae Species 0.000 claims description 4
- 239000001569 carbon dioxide Substances 0.000 claims description 4
- 229910002092 carbon dioxide Inorganic materials 0.000 claims description 4
- 230000005611 electricity Effects 0.000 claims description 4
- 230000008676 import Effects 0.000 claims description 4
- 239000013049 sediment Substances 0.000 claims description 4
- 238000001291 vacuum drying Methods 0.000 claims description 4
- 230000004913 activation Effects 0.000 claims description 3
- 238000004140 cleaning Methods 0.000 claims description 3
- 239000008367 deionised water Substances 0.000 claims description 3
- 229910021641 deionized water Inorganic materials 0.000 claims description 3
- 239000007788 liquid Substances 0.000 claims description 3
- 238000012545 processing Methods 0.000 claims description 3
- 230000005855 radiation Effects 0.000 claims description 3
- 230000015572 biosynthetic process Effects 0.000 claims description 2
- 230000007935 neutral effect Effects 0.000 claims description 2
- 239000011521 glass Substances 0.000 claims 2
- 230000008901 benefit Effects 0.000 abstract description 8
- 239000012488 sample solution Substances 0.000 abstract description 2
- 238000002360 preparation method Methods 0.000 description 8
- VFLDPWHFBUODDF-FCXRPNKRSA-N curcumin Chemical compound C1=C(O)C(OC)=CC(\C=C\C(=O)CC(=O)\C=C\C=2C=C(OC)C(O)=CC=2)=C1 VFLDPWHFBUODDF-FCXRPNKRSA-N 0.000 description 6
- 239000012086 standard solution Substances 0.000 description 5
- 150000002500 ions Chemical class 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- -1 nitrite anions Chemical class 0.000 description 4
- 239000002253 acid Substances 0.000 description 3
- 239000002131 composite material Substances 0.000 description 3
- 229940109262 curcumin Drugs 0.000 description 3
- 235000012754 curcumin Nutrition 0.000 description 3
- 239000004148 curcumin Substances 0.000 description 3
- VFLDPWHFBUODDF-UHFFFAOYSA-N diferuloylmethane Natural products C1=C(O)C(OC)=CC(C=CC(=O)CC(=O)C=CC=2C=C(OC)C(O)=CC=2)=C1 VFLDPWHFBUODDF-UHFFFAOYSA-N 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- QENGPZGAWFQWCZ-UHFFFAOYSA-N 3-Methylthiophene Chemical compound CC=1C=CSC=1 QENGPZGAWFQWCZ-UHFFFAOYSA-N 0.000 description 2
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical compound C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 238000002848 electrochemical method Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- GQPLMRYTRLFLPF-UHFFFAOYSA-N nitrous oxide Inorganic materials [O-][N+]#N GQPLMRYTRLFLPF-UHFFFAOYSA-N 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 239000000523 sample Substances 0.000 description 2
- 230000035945 sensitivity Effects 0.000 description 2
- MERJTCXDDLWWSK-UHFFFAOYSA-N 1-methylpyrrole pyrrolidin-2-one Chemical compound CN1C=CC=C1.N1C(CCC1)=O MERJTCXDDLWWSK-UHFFFAOYSA-N 0.000 description 1
- 229920002101 Chitin Polymers 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 206010011224 Cough Diseases 0.000 description 1
- 102000001554 Hemoglobins Human genes 0.000 description 1
- 108010054147 Hemoglobins Proteins 0.000 description 1
- IOVCWXUNBOPUCH-UHFFFAOYSA-N Nitrous acid Chemical compound ON=O IOVCWXUNBOPUCH-UHFFFAOYSA-N 0.000 description 1
- QHMLGYJOGFXZOP-UHFFFAOYSA-N [Ni]N Chemical compound [Ni]N QHMLGYJOGFXZOP-UHFFFAOYSA-N 0.000 description 1
- 125000002777 acetyl group Chemical group [H]C([H])([H])C(*)=O 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 210000001367 artery Anatomy 0.000 description 1
- 238000003556 assay Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 239000008280 blood Substances 0.000 description 1
- 210000004369 blood Anatomy 0.000 description 1
- 230000000711 cancerogenic effect Effects 0.000 description 1
- 238000005251 capillar electrophoresis Methods 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 231100000315 carcinogenic Toxicity 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000002322 conducting polymer Substances 0.000 description 1
- 229920001940 conductive polymer Polymers 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 238000007306 functionalization reaction Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 238000004128 high performance liquid chromatography Methods 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- 230000002427 irreversible effect Effects 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- XKLJHFLUAHKGGU-UHFFFAOYSA-N nitrous amide Chemical compound ON=N XKLJHFLUAHKGGU-UHFFFAOYSA-N 0.000 description 1
- 230000008520 organization Effects 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 230000005588 protonation Effects 0.000 description 1
- 230000005180 public health Effects 0.000 description 1
- 238000000083 pulse voltammetry Methods 0.000 description 1
- 230000005616 pyroelectricity Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 239000007974 sodium acetate buffer Substances 0.000 description 1
- 238000000527 sonication Methods 0.000 description 1
- 210000002784 stomach Anatomy 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 210000003462 vein Anatomy 0.000 description 1
- 239000002023 wood 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
- G01N27/416—Systems
- G01N27/48—Systems using polarography, i.e. measuring changes in current under a slowly-varying voltage
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- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Health & Medical Sciences (AREA)
- Physics & Mathematics (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Molecular Biology (AREA)
- Analytical Chemistry (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- General Physics & Mathematics (AREA)
- Immunology (AREA)
- Pathology (AREA)
- Carbon And Carbon Compounds (AREA)
Abstract
The invention discloses a kind of method detecting solution Nitrite ion concentration, comprise the following steps: step one, carboxylated Graphene is polymerized with pyrroles, form carboxylated Graphene polypyrrole, being dissolved in mass fraction is in 0.5wt% chitosan solution, ultrasonic obtain carboxylated Graphene polypyrrole chitosan mixed liquor, it is titrated on glass-carbon electrode, dries and obtain carboxylated Graphene/polypyrrole/chitosan-modified electrode；Step 2, the carboxylated Graphene/polypyrrole/chitosan-modified electrode using step one to prepare are working electrode, differential pulse voltammetry volt-ampere curve according to nitrite ion, uses three-electrode system to be detected the concentration of the nitrite ion in solution to be measured by Differential Pulse Voltammetry.The present invention have simple to operate, detect quick and highly sensitive advantage, the highly sensitive identification of biased sample solution Nitrite ion can be carried out.
Description
Technical field
The present invention relates to nitrite ion detection technique field.It is more particularly related to one is based on carboxyl
Functionalized graphene/polypyrrole/chitosan-modified glass-carbon electrode electrochemical sensing utilizes Differential Pulse Voltammetry to detect the solution Central Asia
The method of nitrate ion concentration.
Background technology
Nitrite is a kind of approved inorganic pollution being widely present in environment, food, industry and physiological system
Thing, and be widely used in food fresh keeping.But, relevant research shows, takes in too much nitrite to human and animal
It is all harmful.Such as, nitrite is converted into carcinogenic nitrosamine in stomach, and it produces one with hemoglobin irreversible reaction
Plant compound (metahemoglobin) and the ability of blood transportation oxygen can be reduced.World Health Organization (WHO) (WHO) clear stipulaties, former
The content of the nitrite in water not can exceed that 3mg/L.Therefore, probe into and the most simply and effectively measure nitrite anions to ring
Border, the tool such as public health and food safety is of great significance.Up to the present, have been developed that many methods are to measure Asia
Nitrate anion.Such as, spectrophotography, the chromatography of ions, gas chromatogram-spectrographic method, high performance liquid chromatography, chemoluminescence method,
Capillary electrophoresis and electrochemical method, wherein electrochemical method is the most often owing to having the advantage such as quick, easy, sensitive
A kind of method.Although nitrite anions directly has electrochemical response on glass-carbon electrode, but its oxidoreduction overpotential is relatively
Greatly, the possible contaminated electrode surface of intermediate product that the oxidation of nitrous acid generates, other ions are easy to disturb it to measure, and reduce electricity
The sensitivity of pole and the accuracy of use.In order to overcome these difficulties, some novelties, surface area is big and catalysis activity is excellent
Good nano material, such as poly-tetra amino nickel phthalocyanine, golden nanometer particle/poly-methylthiophene (3-methylthiophene) composite wood
The electrode such as material, poly-vanillin-CNT, Nanometer Copper, polypyrrole-potassium ferrocyanide-CNT can be greatly improved Asia
The selectivity of the detection of nitrate anion and sensitivity.Therefore explore novel modified electrode, set up simple, quick and highly sensitive
Nitrite ion detection method is increasingly becoming research emphasis.
Carboxylated Graphene (CG) is the product after graphenic surface connects base functionalization, not only has the excellent spy of Graphene
Property, and on CG edge carbons, substantial amounts of carboxyl and carbonyl make CG be easily dispersed in water, and these oxygen-containing functional groups are simultaneously
Make CG can produce strong interaction with polymer or little polar molecule and form carboxylated graphene-based composite.
Polypyrrole (PPy) is typical conducting polymer, has the electrochemical redox of completely reversibility and higher
Room-temperature conductivity, stores charge capability stronger, it is not necessary to strong acid and strong base environment, and electropolymerization current potential is low, and air stability is good, machinery
The advantages such as toleration is good, and biocompatibility is high, and cost is relatively low, electric conductivity, photo electric, and pyroelectricity is preferable, are a kind of bulking properties
Can preferable conduction high polymer.
Chitosan (CS) is the product after chitin sloughs part acetyl group, is a kind of important natural macromolecular material.
Utilize amino in chitosan molecule to be prone to the characteristic of protonation, prepare composite film material.
Summary of the invention
It is an object of the invention to solve at least the above, and the advantage that at least will be described later is provided.
It is a still further object of the present invention to provide a kind of method detecting solution Nitrite ion concentration, there is operation
Simply, detect quick and highly sensitive advantage, the highly sensitive identification of biased sample solution Nitrite ion can be carried out.
In order to realize according to object of the present invention and further advantage, it is provided that a kind of detection solution Nitrite from
The method of sub-concentration, comprises the following steps:
Step one, by mass/volume than be 0.8～1.2mg:4mL carboxylated Graphene be polymerized with pyrroles, formation carboxyl
Functionalized graphene-polypyrrole, the mass/volume with 3～5mg:1mL than carboxylated graphene-polypyrrole is dissolved in mass fraction is
In 0.5wt% chitosan solution, ultrasonic obtain carboxylated graphene-polypyrrole-chitosan mixed liquor, be titrated to glass-carbon electrode
On, dry and obtain carboxylated Graphene/polypyrrole/chitosan-modified electrode；
Step 2, the carboxylated Graphene/polypyrrole/chitosan-modified electrode using step one to prepare are working electrode,
Differential pulse voltammetry volt-ampere curve according to nitrite ion, uses three-electrode system by Differential Pulse Voltammetry to solution to be measured
In the concentration of nitrite ion detect.
Preferably, the method for described detection solution Nitrite ion concentration, step one particularly as follows:
S1: be soaked in ethanol solution after 0.8～1.2mg carboxylated Graphene is mixed with 4mL pyrroles, be subsequently adding
The ferric chloride solution of 0.08～0.12mol/L, makes polypyrrole be aggregated in the surface of carboxylated Graphene, under room temperature stir 50～
70min, adds deionized water, highly centrifugal and repeatedly, until supernatant clarification and pH are aobvious neutral, and isolated lower floor
Precipitation, in 55～65 DEG C of vacuum drying, obtains carboxylated graphene-polypyrrole；
S2: 3～5mg carboxylated graphene-polypyrroles are dissolved in 0.8～1.2mL mass fraction is that 0.5wt% chitosan is molten
In liquid, ultrasonic 50～70min, obtain carboxylated graphene-polypyrrole-chitosan mixed liquor；
S3: taking the 3～5 carboxylated graphene-polypyrroles of μ L-chitosan mixed liquor and be titrated on glass-carbon electrode, drying obtains
Carboxylated Graphene/polypyrrole/chitosan-modified electrode.
Preferably, the method for described detection solution Nitrite ion concentration, step 2 Nitrite ion
The acquisition of differential pulse voltammetry volt-ampere curve pass through following steps:
Step I: use described working electrode to build three-electrode system, utilize Differential Pulse Voltammetry, measure respectively and remember
Record the differential pulse voltammetry volt-ampere curve of the NaAc_HAc buffer solution of the many parts of nitrite ions containing variable concentrations, at this
During record the current intensity peak value of NaAc_HAc buffer solution of every part of nitrite ion；
Step II: with the current intensity of every part of NaAc_HAc buffer solution containing nitrite ion that step I obtains
The difference of peak value and the current intensity peak value of NaAc_HAc buffer solution without nitrite ion as vertical coordinate, with
The concentration of every part of nitrite ion is abscissa, draws standard curve and calculates linear equation.
Preferably, the method for described detection solution Nitrite ion concentration, use three-electrode system by showing
The concrete mode that the concentration of the nitrite ion in solution to be measured is detected by difference pulse voltammetry is: survey according to step II
Measure and record the differential pulse voltammetry volt-ampere curve of solution to be detected, and by the current intensity peak value of this differential pulse voltammetry volt-ampere curve with not
The difference of the current intensity peak value of the NaAc_HAc buffer solution containing nitrite ion is updated in described linear equation,
I.e. can get the concentration of solution Nitrite ion to be detected.
Preferably, the method for described detection solution Nitrite ion concentration, in step I, many parts of preparation contain
The NaAc_HAc buffer solution of the nitrite ion of variable concentrations, the pH of NaAc_HAc buffer solution is 4.0, its
Concentration is 0.1mol/L, and nitrite ion concentration is followed successively by 2.0 × 10-5mol/L、5×10-5mol/L、1×10-4mol/
L、2×10-4mol/L、5×10-4mol/L、1×10-3mol/L。
Preferably, the method for described detection solution Nitrite ion concentration, described glass-carbon electrode is through pre-place
Reason: glass-carbon electrode is polished, then with ultrapure with the polishing powder that granularity is 1.0 μm, 0.3 μm and 0.05 μm on polishing cloth successively
Water cleans.
Preferably, the method for described detection solution Nitrite ion concentration, described glass-carbon electrode is with ultrapure
Water has also carried out activation processing after cleaning: be first soaked in the citric acid solution of 0～4 DEG C by described glass-carbon electrode, at microwave
Reason 3～5min, cleans with ultra-pure water, is then soaked in the solution of yeast powder by described glass-carbon electrode, and imports in solution
Carbon dioxide, import volume is 1L/min, and infrared radiation keeps temperature to be 20～25 DEG C, and holding 3～5h is then clear with ultra-pure water
Wash.
Preferably, the method for described detection solution Nitrite ion concentration, S2 obtains carboxylated Graphene-poly-
After pyrroles-chitosan mixed liquor, before carrying out S3, add N-Methyl pyrrolidone and stir 20～30min, then surpassing
Sonication 40～50min, the addition of N-Methyl pyrrolidone is the 2%～4% of carboxylated Graphene quality.
Preferably, the method for described detection solution Nitrite ion concentration, carboxylated Graphene and pyrrole in S1
Cough up and be soaked in ethanol solution, before adding ferric chloride solution, in ethanol solution, add the curcumin of 0.1mg.
The present invention at least includes following beneficial effect:
The first, carboxylated Graphene/polypyrrole/chitosan-modified electrode prepared by the present invention has electron transport rate
Hurry up, advantage that good stability, preparation are simple and convenient to operate, the carboxylated Graphene/polypyrrole/shell using the present invention to prepare gathers
Sugar-modified electrode carries out the detection of nitrite ion, and detection process is simple and convenient, highly sensitive, detection limit is low, can realize reality
The quick detection of border sample Nitrite ion；
The second, can learn that from differential pulse voltammetry volt-ampere curve current intensity that solution to be detected is corresponding is with nitrite ion
The increase of concentration and strengthen, and current intensity has good linear relationship with nitrite ion concentration, therefore, carboxyl fossil
Ink alkene/polypyrrole/chitosan-modified electrode can be as the electrode of detection nitrite ion, the most also in detection by quantitative solution
The content of nitrite ion, can reach 2.9 × 10-to the detection limit of nitrite ion7mol/L；
3rd, carboxylated Graphene and pyrroles's polymerization process add curcumin, and method of modifying is simple, and the polymerization obtained
Thing prepare electrode stability more preferably, reproducibility high；Carboxylated graphene-polypyrrole-chitosan mixed liquor is by minimal amount of
The N-Methyl pyrrolidone modification to electrode, substantially increases the electrochemical signals intensity of electrode, and overpotential is little, electric transmission is fast
Degree is fast, highly sensitive；Glass-carbon electrode is soaked in citric acid solution, yeast powder solution successively, and introducing carbon dioxide, promotes electricity
Son transfer, increase current-responsive, the electrochemical stability still having had after 1000 times recycle.
Part is embodied by the further advantage of the present invention, target and feature by description below, and part also will be by this
Invention research and practice and be understood by the person skilled in the art.
Accompanying drawing explanation
Fig. 1 is that the differential pulse voltammetry volt-ampere of the NaAc_HAc buffer solution of the nitrite ion containing variable concentrations is bent
Line chart；
Fig. 2 is the canonical plotting of embodiments of the invention 4 Nitrite ion.
Detailed description of the invention
Below in conjunction with embodiment, the present invention is described in further detail, to make those skilled in the art with reference to description
Word can be implemented according to this.
Should be appreciated that used herein such as " have ", " comprising " and " including " term do not allot one or many
Other element individual or the existence of a combination thereof or interpolation.
It should be noted that experimental technique described in following embodiment, if no special instructions, it is conventional method, institute
State reagent and material, if no special instructions, the most commercially obtain.
<embodiment 1>
A kind of carboxylated Graphene/polypyrrole/chitosan-modified electrode, preparation method comprises the following steps:
S1: be soaked in ethanol solution after carboxylated for 0.8mg Graphene is mixed with 4mL pyrroles, be subsequently adding
The ferric chloride solution of 0.08mol/L, makes polypyrrole be aggregated in the surface of carboxylated Graphene, stirs 50min under room temperature, and addition is gone
Ionized water, is highly centrifuged and repeatedly, until supernatant clarification and the aobvious neutrality of pH, isolated lower sediment, in 55 DEG C
Vacuum drying, obtains carboxylated graphene-polypyrrole；
S2: carboxylated for 3mg graphene-polypyrrole is dissolved in 0.8mL mass fraction is in 0.5wt% chitosan solution is super
Sound 50min, obtains carboxylated graphene-polypyrrole-chitosan mixed liquor；
S3: take the 3 carboxylated graphene-polypyrroles of μ L-chitosan mixed liquor and be titrated on glass-carbon electrode, dries and obtains carboxyl
Functionalized graphene/polypyrrole/chitosan-modified electrode.
Wherein, described glass-carbon electrode is through pretreatment: by glass-carbon electrode on polishing cloth successively with granularity be 1.0 μm, 0.3
The polishing powder polishing of μm and 0.05 μm, then cleans with ultra-pure water.
<embodiment 2>
A kind of carboxylated Graphene/polypyrrole/chitosan-modified electrode, preparation method comprises the following steps:
S1: be soaked in ethanol solution after carboxylated for 1.2mg Graphene is mixed with 4mL pyrroles, be subsequently adding
The ferric chloride solution of 0.12mol/L, makes polypyrrole be aggregated in the surface of carboxylated Graphene, stirs 70min under room temperature, and addition is gone
Ionized water, is highly centrifuged and repeatedly, until supernatant clarification and the aobvious neutrality of pH, isolated lower sediment, in 65 DEG C
Vacuum drying, obtains carboxylated graphene-polypyrrole；
S2: carboxylated for 5mg graphene-polypyrrole is dissolved in 1.2mL mass fraction is in 0.5wt% chitosan solution is super
Sound 70min, obtains carboxylated graphene-polypyrrole-chitosan mixed liquor；
S3: take the 5 carboxylated graphene-polypyrroles of μ L-chitosan mixed liquor and be titrated on glass-carbon electrode, dries and obtains carboxyl
Functionalized graphene/polypyrrole/chitosan-modified electrode.
Wherein, described glass-carbon electrode is through pretreatment: by glass-carbon electrode on polishing cloth successively with granularity be 1.0 μm, 0.3
The polishing powder polishing of μm and 0.05 μm, then cleans with ultra-pure water.
<embodiment 3>
A kind of carboxylated Graphene/polypyrrole/chitosan-modified electrode, preparation method comprises the following steps:
S1: be soaked in ethanol solution after carboxylated for 1.0mg Graphene is mixed with 4mL pyrroles, be subsequently adding 0.1mol/
The ferric chloride solution of L, makes polypyrrole be aggregated in the surface of carboxylated Graphene, stirs 60min, add deionized water under room temperature,
Highly it is centrifuged and repeatedly, until supernatant clarification and the aobvious neutrality of pH, isolated lower sediment, does in 60 DEG C of vacuum
Dry, obtain carboxylated graphene-polypyrrole；
S2: carboxylated for 4mg graphene-polypyrrole is dissolved in 1mL mass fraction is in 0.5wt% chitosan solution, ultrasonic
60min, obtains carboxylated graphene-polypyrrole-chitosan mixed liquor；
S3: take the 4 carboxylated graphene-polypyrroles of μ L-chitosan mixed liquor and be titrated on glass-carbon electrode, dries and obtains carboxyl
Functionalized graphene/polypyrrole/chitosan-modified electrode.
Wherein, described glass-carbon electrode is through pretreatment: by glass-carbon electrode on polishing cloth successively with granularity be 1.0 μm, 0.3
The polishing powder polishing of μm and 0.05 μm, then cleans with ultra-pure water.
<embodiment 4>
A kind of carboxylated Graphene/polypyrrole/chitosan-modified electrode, raw material and preparation method are with embodiment 3, wherein,
In S1, carboxylated Graphene and pyrroles are soaked in ethanol solution, before adding ferric chloride solution, to ethanol solution
In add the curcumin of 0.1mg.
After S2 obtains carboxylated graphene-polypyrrole-chitosan mixed liquor, before carrying out S3, add N-methyl pyrrole
Pyrrolidone also stirs 25min, then carry out supersound process 45min, and the addition of N-Methyl pyrrolidone is carboxylated Graphene matter
The 3% of amount.
Glass-carbon electrode described in S3 has also carried out activation processing after cleaning with ultra-pure water: first soaked by described glass-carbon electrode
In the citric acid solution of 2 DEG C, microwave treatment 4min, clean with ultra-pure water, then described glass-carbon electrode is soaked in yeast powder
Solution in, and introducing carbon dioxide in solution, import volume is 1L/min, and infrared radiation keeps temperature to be 25 DEG C, keeps 4h,
Then clean with ultra-pure water.
Assay method:
Step I: the NaAc_HAc buffer solution of many parts of the preparation nitrite ion containing variable concentrations, acetic acid-
The pH of sodium acetate buffer is 4.0, and its concentration is 0.1mol/L, and nitrite ion concentration is followed successively by 2.0 × 10- 5mol/L、5×10-5mol/L、1×10-4mol/L、2×10-4mol/L、5×10-4mol/L、1×10-3Mol/L, uses and implements
Carboxylated Graphene/polypyrrole/chitosan-modified the electrode of example 4 preparation is that working electrode builds three-electrode system, by embodiment 4
The working electrode, reference electrode and the auxiliary electrode that obtain are separately fixed in above-mentioned standard solution, set initial potential as 0.5V,
Termination current potential is 0.8V, then arranges following pulse parameter: current potential increment is 0.004V, and square wave frequency is 50Hz, square wave amplitude
For 0.05V, the waiting time is 10s.Utilize Differential Pulse Voltammetry, measure and record the many parts of nitrous containing variable concentrations respectively
The differential pulse voltammetry volt-ampere curve of the NaAc_HAc buffer solution of acid ion, record in the process every part of nitrite anions from
The current intensity peak value of the NaAc_HAc buffer solution of son；
Step II: with the current intensity of every part of NaAc_HAc buffer solution containing nitrite ion that step I obtains
The difference of peak value and the current intensity peak value of NaAc_HAc buffer solution without nitrite ion as vertical coordinate, with
The concentration of every part of nitrite ion is abscissa, draws standard curve and calculates linear equation.
If Fig. 1 is differential pulse voltammetry volt-ampere curve, wherein curve a, b, c, d, e, f is respectively the titer of nitrite ion
Concentration is 2.0 × 10-5mol/L、5.0×10-5mol/L、1.0×10-4mol/L、2.0×10-4mol/L、5.0×10-4mol/L
With 1.0 × 10-3The differential pulse voltammetry volt-ampere curve of the standard solution of mol/L.With 2.0 × 10-5mol/L、5.0×10-5mol/L、
1.0×10-4mol/L、2.0×10-4mol/L、5.0×10-4Mol/L and 1.0 × 10-3The current intensity of the standard solution of mol/L
Peak value is individually subtracted the peak point current of 0mol/L standard solution, obtains four current intensity peak difference values.Can learn to be measured from Fig. 1
The current intensity that solution is corresponding strengthens with the increase of the concentration of nitrite ion.
Fig. 2 is the canonical plotting of nitrite ion, and in figure, Y is current intensity peak difference values, and unit is μ A, and X is sub-
The concentration of standard solution of nitrate ion, unit is μM, and current intensity and nitrite ion concentration have good linear relationship, R2
=0.9966.
Step III: measure and record the differential pulse voltammetry volt-ampere curve of solution to be detected according to step II, and by this differential arteries and veins
Rush the current intensity peak value of the current intensity peak value of volt-ampere curve and the NaAc_HAc buffer solution without nitrite ion
Difference be updated in described linear equation, deduct 0mol/L standard from differential pulse voltammetry volt-ampere curve read current intensity peak molten
The current intensity peak value of liquid, i.e. obtains Y value, Y brings into linear equation and can solve X, i.e. can get nitrous in solution to be detected
The concentration of acid ion.
Number of devices described herein and treatment scale are used to the explanation of the simplification present invention.To the application of the present invention,
Modifications and variations will be readily apparent to persons skilled in the art.
Although embodiment of the present invention are disclosed as above, but it is not restricted in description and embodiment listed
Using, it can be applied to various applicable the field of the invention completely, for those skilled in the art, and can be easily
Realizing other amendment, therefore under the general concept limited without departing substantially from claim and equivalency range, the present invention does not limit
In specific details with shown here as the embodiment with description.
Claims (9)
1. the method detecting solution Nitrite ion concentration, it is characterised in that comprise the following steps:
Step one, by mass/volume than be 0.8～1.2mg:4mL carboxylated Graphene be polymerized with pyrroles, formation carboxyl fossil
Ink alkene-polypyrrole, the mass/volume with 3～5mg:1mL than carboxylated graphene-polypyrrole is dissolved in mass fraction is
In 0.5wt% chitosan solution, ultrasonic obtain carboxylated graphene-polypyrrole-chitosan mixed liquor, be titrated to glass-carbon electrode
On, dry and obtain carboxylated Graphene/polypyrrole/chitosan-modified electrode；
Step 2, the carboxylated Graphene/polypyrrole/chitosan-modified electrode using step one to prepare are working electrode, according to
The differential pulse voltammetry volt-ampere curve of nitrite ion, uses three-electrode system by Differential Pulse Voltammetry in solution to be measured
The concentration of nitrite ion detects.
2. the method detecting solution Nitrite ion concentration as claimed in claim 1, it is characterised in that step one is concrete
For:
S1: be soaked in ethanol solution after 0.8～1.2mg carboxylated Graphene is mixed with 4mL pyrroles, be subsequently adding 0.08～
The ferric chloride solution of 0.12mol/L, makes polypyrrole be aggregated in the surface of carboxylated Graphene, stirs 50～70min, add under room temperature
Enter deionized water, highly centrifugal and repeatedly, until supernatant clarification and pH are aobvious neutral, isolated lower sediment, in
55～65 DEG C of vacuum drying, obtain carboxylated graphene-polypyrrole；
S2: 3～5mg carboxylated graphene-polypyrroles are dissolved in 0.8～1.2mL mass fraction is 0.5wt% chitosan solution
In, ultrasonic 50～70min, obtain carboxylated graphene-polypyrrole-chitosan mixed liquor；
S3: take the 3～5 carboxylated graphene-polypyrroles of μ L-chitosan mixed liquor and be titrated on glass-carbon electrode, dries and obtains carboxyl
Functionalized graphene/polypyrrole/chitosan-modified electrode.
3. the method detecting solution Nitrite ion concentration as claimed in claim 1, it is characterised in that the step 2 Central Asia
Following steps are passed through in the acquisition of the differential pulse voltammetry volt-ampere curve of nitrate ion:
Step I: use described working electrode to build three-electrode system, utilize Differential Pulse Voltammetry, measure and record many respectively
The differential pulse voltammetry volt-ampere curve of the NaAc_HAc buffer solution of the part nitrite ion containing variable concentrations, in this process
The current intensity peak value of the middle NaAc_HAc buffer solution recording every part of nitrite ion；
Step II: with the current intensity peak value of every part of NaAc_HAc buffer solution containing nitrite ion that step I obtains
With the difference of the current intensity peak value of the NaAc_HAc buffer solution without nitrite ion as vertical coordinate, with every part
The concentration of nitrite ion is abscissa, draws standard curve and calculates linear equation.
4. the method detecting solution Nitrite ion concentration as claimed in claim 3, it is characterised in that use three electrodes
The concrete mode that the concentration of the nitrite ion in solution to be measured is detected by system by Differential Pulse Voltammetry is: press
Measure and record the differential pulse voltammetry volt-ampere curve of solution to be detected according to step II, and by strong for the electric current of this differential pulse voltammetry volt-ampere curve
Degree peak value is updated to described line with the difference of the current intensity peak value of the NaAc_HAc buffer solution without nitrite ion
In property equation, i.e. can get the concentration of solution Nitrite ion to be detected.
5. the method detecting solution Nitrite ion concentration as claimed in claim 3, it is characterised in that join in step I
The NaAc_HAc buffer solution of many parts of the system nitrite ion containing variable concentrations, NaAc_HAc buffer solution
PH is 4.0, and its concentration is 0.1mol/L, and nitrite ion concentration is followed successively by 2.0 × 10-5mol/L、5×10-5mol/
L、1×10-4mol/L、2×10-4mol/L、5×10-4mol/L、1×10-3mol/L。
6. the method detecting solution Nitrite ion concentration as claimed in claim 1, it is characterised in that described glass carbon electricity
Pole is through pretreatment: polished with the polishing powder that granularity is 1.0 μm, 0.3 μm and 0.05 μm successively on polishing cloth by glass-carbon electrode,
Then clean with ultra-pure water.
7. the method detecting solution Nitrite ion concentration as claimed in claim 6, it is characterised in that described glass carbon electricity
Pole has also carried out activation processing after cleaning with ultra-pure water: described glass-carbon electrode is first soaked in the citric acid solution of 0～4 DEG C
In, microwave treatment 3～5min, clean with ultra-pure water, then described glass-carbon electrode is soaked in the solution of yeast powder, and to molten
Introducing carbon dioxide in liquid, import volume is 1L/min, and infrared radiation keeps temperature to be 20～25 DEG C, keeps 3～5h, then with super
Pure water cleans.
8. the method detecting solution Nitrite ion concentration as claimed in claim 2, it is characterised in that S2 obtains carboxyl
After functionalized graphene-polypyrrole-chitosan mixed liquor, before carrying out S3, add N-Methyl pyrrolidone and stir 20～
30min, then carry out supersound process 40～50min, the addition of N-Methyl pyrrolidone be carboxylated Graphene quality 2%～
4%.
9. the method detecting solution Nitrite ion concentration as claimed in claim 2, it is characterised in that carboxylated in S1
Graphene and pyrroles are soaked in ethanol solution, before adding ferric chloride solution, add the Rhizoma Curcumae Longae of 0.1mg in ethanol solution
Element.
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| CN112394095A (en) * | 2020-11-30 | 2021-02-23 | 江西农业大学 | Electrochemical sensor for selectively detecting nitrite ions and preparation method and application thereof |
| CN112505123A (en) * | 2020-10-30 | 2021-03-16 | 山西农业大学 | Preparation method of carboxylated graphene and nitrate radical doped polypyrrole nano ionic membrane |
| CN114910532A (en) * | 2022-05-10 | 2022-08-16 | 哈尔滨商业大学 | Detection method of nitrite by using methanotrophin in-situ reduction nanogold modified electrode and application of detection method |
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| CN112394095A (en) * | 2020-11-30 | 2021-02-23 | 江西农业大学 | Electrochemical sensor for selectively detecting nitrite ions and preparation method and application thereof |
| CN112394095B (en) * | 2020-11-30 | 2021-10-12 | 江西农业大学 | Electrochemical sensor for selectively detecting nitrite ions and preparation method and application thereof |
| CN114910532A (en) * | 2022-05-10 | 2022-08-16 | 哈尔滨商业大学 | Detection method of nitrite by using methanotrophin in-situ reduction nanogold modified electrode and application of detection method |
| CN114910532B (en) * | 2022-05-10 | 2022-12-16 | 哈尔滨商业大学 | Detection method of nitrite by using methane-oxidizing rhzomorph in-situ reduction nanogold modified electrode and application of detection method |
| CN116908273A (en) * | 2023-09-14 | 2023-10-20 | 宁波检验检疫科学技术研究院(宁波国检贸易便利化服务中心) | Method for rapidly detecting harmful substances in food |
| CN116908273B (en) * | 2023-09-14 | 2023-11-28 | 宁波检验检疫科学技术研究院(宁波国检贸易便利化服务中心) | Method for rapidly detecting harmful substances in food |
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