CN106198693B - The method for detecting solution Nitrite ion concentration - Google Patents
The method for detecting solution Nitrite ion concentration Download PDFInfo
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- CN106198693B CN106198693B CN201610456856.9A CN201610456856A CN106198693B CN 106198693 B CN106198693 B CN 106198693B CN 201610456856 A CN201610456856 A CN 201610456856A CN 106198693 B CN106198693 B CN 106198693B
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- IOVCWXUNBOPUCH-UHFFFAOYSA-M Nitrite anion Chemical compound [O-]N=O IOVCWXUNBOPUCH-UHFFFAOYSA-M 0.000 title claims abstract description 71
- 229940005654 nitrite ion Drugs 0.000 title claims abstract description 66
- 238000000034 method Methods 0.000 title claims abstract description 32
- 229920000128 polypyrrole Polymers 0.000 claims abstract description 43
- 229910021389 graphene Inorganic materials 0.000 claims abstract description 40
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 36
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 30
- 238000001514 detection method Methods 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
- 238000001035 drying Methods 0.000 claims abstract description 8
- 238000002604 ultrasonography Methods 0.000 claims abstract description 6
- 239000000243 solution Substances 0.000 claims description 68
- 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 14
- 229910021642 ultra pure water Inorganic materials 0.000 claims description 13
- 239000012498 ultrapure water Substances 0.000 claims description 13
- -1 carboxyl Graphite alkene Chemical class 0.000 claims description 12
- 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
- 239000000843 powder Substances 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
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 8
- 229910002804 graphite Inorganic materials 0.000 claims description 7
- 239000010439 graphite Substances 0.000 claims description 7
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 6
- 230000008569 process Effects 0.000 claims description 6
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 5
- 239000004744 fabric Substances 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
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 4
- 238000005352 clarification Methods 0.000 claims description 4
- 239000013049 sediment Substances 0.000 claims description 4
- 238000001291 vacuum drying Methods 0.000 claims description 4
- 238000001994 activation 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
- 230000008676 import Effects 0.000 claims description 3
- 230000005855 radiation Effects 0.000 claims description 3
- 244000163122 Curcuma domestica Species 0.000 claims 1
- 235000003392 Curcuma domestica Nutrition 0.000 claims 1
- 235000003373 curcuma longa Nutrition 0.000 claims 1
- 235000013976 turmeric Nutrition 0.000 claims 1
- 230000008901 benefit Effects 0.000 abstract description 8
- 230000035945 sensitivity Effects 0.000 abstract description 7
- 238000002156 mixing Methods 0.000 abstract description 2
- 239000012488 sample solution Substances 0.000 abstract description 2
- 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
- 238000002360 preparation method Methods 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
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 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
- 239000002041 carbon nanotube Substances 0.000 description 2
- 229910021393 carbon nanotube Inorganic materials 0.000 description 2
- 230000005611 electricity Effects 0.000 description 2
- 238000002848 electrochemical method Methods 0.000 description 2
- 239000007788 liquid Substances 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
- 238000011160 research Methods 0.000 description 2
- 239000000523 sample Substances 0.000 description 2
- OXHNLMTVIGZXSG-UHFFFAOYSA-N 1-Methylpyrrole Chemical class CN1C=CC=C1 OXHNLMTVIGZXSG-UHFFFAOYSA-N 0.000 description 1
- OHVDFOBYPMINQJ-UHFFFAOYSA-N 2-methylthiophene;3-methylthiophene Chemical compound CC=1C=CSC=1.CC1=CC=CS1 OHVDFOBYPMINQJ-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
- 108010054147 Hemoglobins Proteins 0.000 description 1
- 102000001554 Hemoglobins Human genes 0.000 description 1
- 108010061951 Methemoglobin 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
- 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
- 230000003197 catalytic effect Effects 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
- 238000004140 cleaning 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
- 230000000694 effects Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 235000021393 food security Nutrition 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 238000007306 functionalization reaction Methods 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold 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
- 238000005259 measurement Methods 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 239000002105 nanoparticle 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
- 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
- HNJBEVLQSNELDL-UHFFFAOYSA-N pyrrolidin-2-one Chemical compound O=C1CCCN1 HNJBEVLQSNELDL-UHFFFAOYSA-N 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
- 238000002798 spectrophotometry method 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
Abstract
The invention discloses a kind of methods of detection solution Nitrite ion concentration, include the following steps：Step 1: carboxylated graphene is polymerize with pyrroles, form carboxylated graphene polypyrrole, it is in 0.5wt% chitosan solutions to be dissolved in mass fraction, ultrasound obtains carboxylated graphene polypyrrole chitosan mixed liquor, it is titrated on glass-carbon electrode, drying obtains carboxylated graphene/polypyrrole/chitosan-modified electrode；Step 2: using carboxylated graphene/polypyrrole/chitosan-modified electrode prepared by step 1 for working electrode, according to the differential pulse voltammetry volt-ampere curve of nitrite ion, the concentration of the nitrite ion in solution to be measured is detected by Differential Pulse Voltammetry using three-electrode system.The present invention has the advantages that easy to operate, detection quickly and high sensitivity, can carry out the highly sensitive identification of mixing sample solution Nitrite ion.
Description
Technical field
The present invention relates to nitrite ion detection technique fields.It is more particularly related to which a kind of being based on carboxyl
Graphite alkene/polypyrrole/chitosan-modified glass-carbon electrode electrochemical sensing utilizes the Differential Pulse Voltammetry detection 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
Object, and be widely used in food fresh keeping.However, relevant studies have shown that taking in excessive nitrite to human and animal
All it is harmful.For example, nitrite is converted into carcinogenic nitrosamine in stomach, it generates one with hemoglobin irreversible reaction
Kind compound (ferrihemoglobin) can reduce the ability of blood transportation oxygen.The World Health Organization (WHO) clear stipulaties, it is former
The content of nitrite in water is no more than 3mg/L.Therefore, it probes into and how simply effectively to measure nitrite anions to ring
Border, public health and food security etc. have a very important significance.Up to the present, many methods are had been developed that measure Asia
Nitrate anion.For example, spectrophotometry, the chromatography of ions, gas-chromatography-spectroscopic methodology, high performance liquid chromatography, chemoluminescence method,
Capillary Electrophoresis and electrochemical method, wherein electrochemical method are due to having many advantages, such as that quick, easy, sensitive is current relatively more normal
A kind of method.Although nitrite anions directly has electrochemical response on glass-carbon electrode, its redox overpotential compared with
Greatly, the intermediate product possible contaminated electrode surface that the oxidation of nitrous acid generates, other ions are easy to interfere its measurement, reduce electricity
The sensitivity of pole and the accuracy used.In order to overcome these difficulties, some are novel, surface areas are big and catalytic activity is excellent
Good nano material, such as poly- tetra amino nickel phthalocyanine, gold nanoparticle/poly- methylthiophene (3-methylthiophene) composite wood
The electrodes such as material, poly- vanillic aldehyde-carbon nanotube, Nanometer Copper, polypyrrole-potassium ferrocyanide-carbon nanotube can be greatly improved to Asia
The selectivity of the detection of nitrate anion and sensitivity.Therefore novel modified electrode is explored, is established simple, quick and high sensitivity
Nitrite ion detection method is increasingly becoming research emphasis.
Carboxylated graphene (CG) is that graphene surface connects the product after base functionalization, not only the excellent spy with graphene
Property, and a large amount of carboxyl makes CG be easily dispersed in water with carbonyl on CG edge carbons, and these oxygen-containing functional groups are simultaneously
Make CG that can generate strong interaction with polymer or small polar molecule and forms the graphene-based composite material of carboxylated.
Polypyrrole (PPy) is typical conducting polymer, with the electrochemical redox of completely reversibility and higher
Room-temperature conductivity, storage charge capability is stronger, does not need strong acid and strong base environment, and electropolymerization current potential is low, and air stability is good, machinery
The advantages that tolerance is good, and biocompatibility is high, and cost is relatively low, electric conductivity, photo electric, pyroelectricity is preferable, is a kind of bulking property
It can ideal conduction high polymer.
Chitosan (CS) is that chitin sloughs the product after the acetyl group of part, is a kind of important natural macromolecular material.
It is easy to the characteristic of protonation using amino in chitosan molecule, prepares composite film material.
Invention content
It is an object of the invention to solve at least the above, and provide the advantages of at least will be described later.
It is a still further object of the present invention to provide a kind of methods of detection solution Nitrite ion concentration, have operation
Simply, the advantages of detecting quick and high sensitivity, can carry out the highly sensitive identification of mixing sample solution Nitrite ion.
In order to realize these purposes and other advantages according to the present invention, provide a kind of detection solution Nitrite from
The method of sub- concentration, includes the following steps：
Step 1: being 0.8~1.2mg by mass/volume ratio:The carboxylated graphene of 4mL polymerize with pyrroles, forms carboxyl
Graphite alkene-polypyrrole, with 3~5mg:Carboxylated graphene-polypyrrole is dissolved in mass fraction and is by the mass/volume ratio of 1mL
In 0.5wt% chitosan solutions, ultrasound obtains carboxylated graphene-polypyrrole-chitosan mixed liquor, is titrated to glass-carbon electrode
On, drying obtains carboxylated graphene/polypyrrole/chitosan-modified electrode；
Step 2: use carboxylated graphene/polypyrrole/chitosan-modified electrode prepared by step 1 for working electrode,
According to the differential pulse voltammetry volt-ampere curve of nitrite ion, using three-electrode system by Differential Pulse Voltammetry to solution to be measured
In the concentration of nitrite ion be detected.
Preferably, the method for the detection solution Nitrite ion concentration, step 1 are specially：
S1：It is soaked in ethanol solution after 0.8~1.2mg carboxylated graphenes are mixed with 4mL pyrroles, is then added
The ferric chloride solution of 0.08~0.12mol/L makes polypyrrole be aggregated in the surface of carboxylated graphene, at room temperature stir 50~
Deionized water is added in 70min, and height is centrifuged and is repeated as many times, until supernatant liquor clarification and the aobvious neutrality of pH, isolated lower layer
Precipitation obtains carboxylated graphene-polypyrrole in 55~65 DEG C of vacuum drying；
S2：It is that 0.5wt% chitosans are molten that 3~5mg carboxylated graphene-polypyrroles, which are dissolved in 0.8~1.2mL mass fractions,
In liquid, 50~70min of ultrasound obtains carboxylated graphene-polypyrrole-chitosan mixed liquor；
S3：3~5 μ L carboxylated graphene-polypyrroles-chitosan mixed liquor is taken to be titrated on glass-carbon electrode, drying obtains
Carboxylated graphene/polypyrrole/chitosan-modified electrode.
Preferably, the method for the detection solution Nitrite ion concentration, step 2 Nitrite ion
The acquisition of differential pulse voltammetry volt-ampere curve pass through following steps：
Step I：Three-electrode system is built using the working electrode, using Differential Pulse Voltammetry, measures and remembers respectively
The differential pulse voltammetry volt-ampere curve of the NaAc_HAc buffer solution of the more parts of nitrite ions containing various concentration is recorded, herein
The current strength peak value of the NaAc_HAc buffer solution of every part of nitrite ion is recorded in the process；
Step II：With the current strength of every part of obtained NaAc_HAc buffer solution containing nitrite ion of step I
The difference of peak value and the current strength peak value of the NaAc_HAc buffer solution without nitrite ion as ordinate, with
A concentration of abscissa of every part of nitrite ion draws standard curve and calculates linear equation.
Preferably, the method for the detection solution Nitrite ion concentration, using three-electrode system by showing
The concrete mode that poor pulse voltammetry is detected the concentration of the nitrite ion in solution to be measured is：It is surveyed according to step II
The differential pulse voltammetry volt-ampere curve of solution to be detected is measured and records, and by the current strength peak value of the differential pulse voltammetry volt-ampere curve and not
The difference of the current strength peak value of NaAc_HAc buffer solution containing nitrite ion is updated in the linear equation,
It can be obtained the concentration of solution Nitrite ion to be detected.
Preferably, the method for the described detection solution Nitrite ion concentration, more parts prepared in step I contain
The pH of the NaAc_HAc buffer solution of the nitrite ion of various concentration, NaAc_HAc buffer solution is 4.0,
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 the detection solution Nitrite ion concentration, the glass-carbon electrode is by pre- place
Reason：The polishing powder that granularity is 1.0 μm, 0.3 μm and 0.05 μm is used to polish successively on polishing cloth glass-carbon electrode, then with ultrapure
Water cleans.
Preferably, the method for the described detection solution Nitrite ion concentration, the glass-carbon electrode is with ultrapure
Activation process has also been carried out after water cleaning：The glass-carbon electrode is first soaked in 0~4 DEG C of citric acid solution, at microwave
3~5min is managed, is cleaned, then the glass-carbon electrode is soaked in the solution of yeast powder, and imported into solution with ultra-pure water
Carbon dioxide, import volume 1L/min, it is 20~25 DEG C that infrared radiation, which keeps temperature, keeps 3~5h, then clear with ultra-pure water
It washes.
Preferably, the method for the detection solution Nitrite ion concentration, it is poly- that S2 obtains carboxylated graphene-
After pyrroles-chitosan mixed liquor, before carrying out S3, N-Methyl pyrrolidone is added and stirs 20~30min, then is surpassed
40~50min of sonication, the addition of N-Methyl pyrrolidone are the 2%~4% of carboxylated graphene quality.
Preferably, the method for the described detection solution Nitrite ion concentration, carboxylated graphene and pyrrole in S1
It coughs up and is soaked in ethanol solution, be added before ferric chloride solution, the curcumin of 0.1mg is added into ethanol solution.
The present invention includes at least following advantageous effect：
The first, carboxylated graphene/polypyrrole/chitosan-modified electrode prepared by the present invention has electron transport rate
Soon, stability is good, prepares the advantages of being simple and convenient to operate, and the carboxylated graphene/polypyrrole/shell prepared using the present invention is poly-
Sugar-modified electrode carries out the detection of nitrite ion, and detection process is simple and convenient, high sensitivity, detection limit are low, it can be achieved that real
The quick detection of border sample Nitrite ion；
The second, it can be seen that the corresponding current strength of solution to be detected is with nitrite ion from differential pulse voltammetry volt-ampere curve
Concentration increase and enhance, and current strength and nitrite ion concentration have good linear relationship, therefore, carboxyl fossil
Black alkene/polypyrrole/chitosan-modified electrode quickly and can quantify in detection solution as the electrode of detection nitrite ion
The content of nitrite ion can reach 2.9 × 10- to the detection limit of nitrite ion7mol/L；
Third, carboxylated graphene and pyrroles's polymerization process add curcumin, and method of modifying is simple, and obtained polymerization
Object prepare electrode stability more preferably, reproducibility it is high；Carboxylated graphene-polypyrrole-chitosan mixed liquor passes through minimal amount of
Modification of the N-Methyl pyrrolidone to electrode substantially increases the electrochemical signals intensity of electrode, and overpotential is small, electron-transport is fast
Degree is fast, high sensitivity；Glass-carbon electrode is soaked in successively in citric acid solution, yeast powder solution, and introducing carbon dioxide, promotes electricity
Son transfer increases current-responsive, the electrochemical stability still having had after 1000 times recycle.
Part is illustrated to embody by further advantage, target and the feature of the present invention by following, and part will also be by this
The research and practice of invention and be understood by the person skilled in the art.
Description of the drawings
Fig. 1 is that the differential pulse voltammetry volt-ampere of the NaAc_HAc buffer solution of the nitrite ion containing various concentration is bent
Line chart；
Fig. 2 is the canonical plotting of 4 Nitrite ion of the embodiment of the present invention.
Specific implementation mode
With reference to embodiment, the present invention is described in further detail, to enable those skilled in the art with reference to specification
Word can be implemented according to this.
It should be appreciated that such as " having ", "comprising" and " comprising " term used herein do not allot one or more
The presence or addition of a other elements or combinations thereof.
It should be noted that experimental method described in following embodiments is unless otherwise specified conventional method, institute
Reagent and material are stated, unless otherwise specified, is commercially obtained.
<Embodiment 1>
A kind of carboxylated graphene/polypyrrole/chitosan-modified electrode, preparation method include the following steps：
S1：It is soaked in ethanol solution after 0.8mg carboxylated graphenes are mixed with 4mL pyrroles, is then added
The ferric chloride solution of 0.08mol/L makes polypyrrole be aggregated in the surface of carboxylated graphene, stirs 50min at room temperature, and addition is gone
Ionized water, height are centrifuged and are repeated as many times, until supernatant liquor clarification and the aobvious neutrality of pH, isolated lower sediment, in 55 DEG C
Vacuum drying, obtains carboxylated graphene-polypyrrole；
S2：It is to surpass in 0.5wt% chitosan solutions that 3mg carboxylated graphene-polypyrroles, which are dissolved in 0.8mL mass fractions,
Sound 50min obtains carboxylated graphene-polypyrrole-chitosan mixed liquor；
S3：3 μ L carboxylated graphene-polypyrroles-chitosan mixed liquor is taken to be titrated on glass-carbon electrode, drying obtains carboxyl
Graphite alkene/polypyrrole/chitosan-modified electrode.
Wherein, the glass-carbon electrode is by pretreatment：By glass-carbon electrode on polishing cloth successively use granularity be 1.0 μm, 0.3
μm and 0.05 μm polishing powder polishing, then cleaned with ultra-pure water.
<Embodiment 2>
A kind of carboxylated graphene/polypyrrole/chitosan-modified electrode, preparation method include the following steps：
S1：It is soaked in ethanol solution after 1.2mg carboxylated graphenes are mixed with 4mL pyrroles, is then added
The ferric chloride solution of 0.12mol/L makes polypyrrole be aggregated in the surface of carboxylated graphene, stirs 70min at room temperature, and addition is gone
Ionized water, height are centrifuged and are repeated as many times, until supernatant liquor clarification and the aobvious neutrality of pH, isolated lower sediment, in 65 DEG C
Vacuum drying, obtains carboxylated graphene-polypyrrole；
S2：It is to surpass in 0.5wt% chitosan solutions that 5mg carboxylated graphene-polypyrroles, which are dissolved in 1.2mL mass fractions,
Sound 70min obtains carboxylated graphene-polypyrrole-chitosan mixed liquor；
S3：5 μ L carboxylated graphene-polypyrroles-chitosan mixed liquor is taken to be titrated on glass-carbon electrode, drying obtains carboxyl
Graphite alkene/polypyrrole/chitosan-modified electrode.
Wherein, the glass-carbon electrode is by pretreatment：By glass-carbon electrode on polishing cloth successively use granularity be 1.0 μm, 0.3
μm and 0.05 μm polishing powder polishing, then cleaned with ultra-pure water.
<Embodiment 3>
A kind of carboxylated graphene/polypyrrole/chitosan-modified electrode, preparation method include the following steps：
S1：It is soaked in ethanol solution after 1.0mg carboxylated graphenes are mixed with 4mL pyrroles, 0.1mol/ is then added
The ferric chloride solution of L makes polypyrrole be aggregated in the surface of carboxylated graphene, stirs 60min at room temperature, and deionized water is added,
Height is centrifuged and is repeated as many times, until supernatant liquor is clarified and the aobvious neutrality of pH, isolated lower sediment are dry in 60 DEG C of vacuum
It is dry, obtain carboxylated graphene-polypyrrole；
S2：It is ultrasound in 0.5wt% chitosan solutions that 4mg carboxylated graphene-polypyrroles, which are dissolved in 1mL mass fractions,
60min obtains carboxylated graphene-polypyrrole-chitosan mixed liquor；
S3：4 μ L carboxylated graphene-polypyrroles-chitosan mixed liquor is taken to be titrated on glass-carbon electrode, drying obtains carboxyl
Graphite alkene/polypyrrole/chitosan-modified electrode.
Wherein, the glass-carbon electrode is by pretreatment：By glass-carbon electrode on polishing cloth successively use granularity be 1.0 μm, 0.3
μm and 0.05 μm polishing powder polishing, then cleaned with ultra-pure water.
<Embodiment 4>
A kind of carboxylated graphene/polypyrrole/chitosan-modified electrode, raw material and preparation method is the same as embodiment 3, wherein
Carboxylated graphene is soaked in pyrroles in ethanol solution in S1, is added before 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, N- methyl pyrroles are added
Pyrrolidone simultaneously stirs 25min, then carries 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 process after being cleaned with ultra-pure water：The glass-carbon electrode is first impregnated
In 2 DEG C of citric acid solution, microwave treatment 4min is cleaned with ultra-pure water, and the glass-carbon electrode is then soaked in yeast powder
Solution in, and the introducing carbon dioxide into solution, import volume 1L/min, it is 25 DEG C that infrared radiation, which keeps temperature, keeps 4h,
Then it is cleaned with ultra-pure water.
Assay method：
Step I：The NaAc_HAc buffer solution for the more parts of nitrite ions containing various concentration prepared, acetic acid-
The pH of sodium acetate buffer is 4.0, and 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, using implementation
Carboxylated graphene/polypyrrole/chitosan-modified electrode prepared by example 4 is that working electrode builds three-electrode system, by embodiment 4
Obtained working electrode, reference electrode and auxiliary electrode is separately fixed in above-mentioned standard solution, sets initial potential as 0.5V,
Termination current potential is 0.8V, and following pulse parameter is then arranged：Current potential increment is 0.004V, square wave frequency 50Hz, square wave amplitude
For 0.05V, stand-by period 10s.Using Differential Pulse Voltammetry, measures respectively and record the more parts of nitrous containing various concentration
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 strength peak value of the NaAc_HAc buffer solution of son；
Step II：With the current strength of every part of obtained NaAc_HAc buffer solution containing nitrite ion of step I
The difference of peak value and the current strength peak value of the NaAc_HAc buffer solution without nitrite ion as ordinate, with
A concentration of abscissa of every part of nitrite ion 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
A concentration of 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 strength of the standard solution of mol/L
The peak point current of 0mol/L standard solution is individually subtracted in peak value, obtains four current strength peak difference values.It is from Fig. 1 it can be seen that be measured
The corresponding current strength of solution enhances with the increase of the concentration of nitrite ion.
Fig. 2 is the canonical plotting of nitrite ion, and Y is current strength peak difference values in figure, and unit is μ A, and X is Asia
The concentration of standard solution of nitrate ion, unit are μM that current strength and nitrite ion concentration have good linear relationship, R2
=0.9966.
Step III：The differential pulse voltammetry volt-ampere curve of solution to be detected is measured and recorded according to step II, and this is shown into poor arteries and veins
Rush the current strength peak value of the current strength peak value and the NaAc_HAc buffer solution without nitrite ion of volt-ampere curve
Difference be updated in the linear equation, it is molten to subtract 0mol/L standards from differential pulse voltammetry volt-ampere curve read current intensity peak
For the current strength peak value of liquid to get to Y value, X can be solved by bringing Y into linear equations, you can obtain nitrous in solution to be detected
The concentration of acid ion.
Number of devices and treatment scale described herein are the explanations for simplifying the present invention.To the present invention application,
Modifications and variations will be readily apparent to persons skilled in the art.
Although the embodiments of the present invention have been disclosed as above, but its is not only in the description and the implementation listed
With it can be fully applied to various fields suitable for the present invention, for those skilled in the art, can be easily
Realize other modification, therefore without departing from the general concept defined in the claims and the equivalent scope, the present invention is simultaneously unlimited
In specific details and embodiment shown and described herein.
Claims (7)
1. a kind of method of detection solution Nitrite ion concentration, which is characterized in that include the following steps：
Step 1: being 0.8~1.2mg by mass/volume ratio:The carboxylated graphene of 4mL polymerize with pyrroles, forms carboxyl fossil
Black alkene-polypyrrole, with 3~5mg:Carboxylated graphene-polypyrrole is dissolved in mass fraction and is by the mass/volume ratio of 1mL
In 0.5wt% chitosan solutions, ultrasound obtains carboxylated graphene-polypyrrole-chitosan mixed liquor, is titrated to glass-carbon electrode
On, drying obtains carboxylated graphene/polypyrrole/chitosan-modified electrode；
Step 2: use carboxylated graphene/polypyrrole/chitosan-modified electrode prepared by step 1 for working electrode, according to
The differential pulse voltammetry volt-ampere curve of nitrite ion, using three-electrode system by Differential Pulse Voltammetry in solution to be measured
The concentration of nitrite ion is detected；
Wherein, the glass-carbon electrode is by pretreatment：By glass-carbon electrode on polishing cloth successively use granularity be 1.0 μm, 0.3 μm and
0.05 μm of polishing powder polishing, is then cleaned with ultra-pure water；
The glass-carbon electrode has also carried out activation process after being cleaned with ultra-pure water：The glass-carbon electrode is first soaked in 0~4
DEG C citric acid solution in, 3~5min of microwave treatment is cleaned with ultra-pure water, and the glass-carbon electrode is then soaked in yeast powder
Solution in, and the introducing carbon dioxide into solution, import volume 1L/min, it is 20~25 DEG C that infrared radiation, which keeps temperature, is protected
3~5h is held, is then cleaned with ultra-pure water.
2. the method for detection solution Nitrite ion concentration as described in claim 1, which is characterized in that step 1 is specific
For：
S1：Be soaked in ethanol solution after 0.8~1.2mg carboxylated graphenes are mixed with 4mL pyrroles, then be added 0.08~
The ferric chloride solution of 0.12mol/L makes polypyrrole be aggregated in the surface of carboxylated graphene, stirs 50~70min at room temperature, adds
Entering deionized water, height is centrifuged and is repeated as many times, until supernatant liquor clarification and the aobvious neutrality of pH, isolated lower sediment, in
55~65 DEG C of vacuum drying, obtain carboxylated graphene-polypyrrole；
S2：It is 0.5wt% chitosan solutions that 3~5mg carboxylated graphene-polypyrroles, which are dissolved in 0.8~1.2mL mass fractions,
In, 50~70min of ultrasound obtains carboxylated graphene-polypyrrole-chitosan mixed liquor；
S3：3~5 μ L carboxylated graphene-polypyrroles-chitosan mixed liquor is taken to be titrated on glass-carbon electrode, drying obtains carboxyl
Graphite alkene/polypyrrole/chitosan-modified electrode.
3. the method for detection solution Nitrite ion concentration as described in claim 1, which is characterized in that the step 2 Central Asia
The acquisition of the differential pulse voltammetry volt-ampere curve of nitrate ion passes through following steps：
Step I：Three-electrode system is built using the working electrode, using Differential Pulse Voltammetry, measures and records more respectively
The differential pulse voltammetry volt-ampere curve of the NaAc_HAc buffer solution of nitrite ion of the part containing various concentration, in this process
The current strength peak value of the middle NaAc_HAc buffer solution for recording every part of nitrite ion；
Step II：With the current strength peak value of every part of obtained NaAc_HAc buffer solution containing nitrite ion of step I
Difference with the current strength peak value of the NaAc_HAc buffer solution without nitrite ion is as ordinate, with every part
A concentration of abscissa of nitrite ion draws standard curve and calculates linear equation.
4. the method for detection solution Nitrite ion concentration as claimed in claim 3, which is characterized in that use three electrodes
System is by the concrete mode that Differential Pulse Voltammetry is detected the concentration of the nitrite ion in solution to be measured：It presses
The differential pulse voltammetry volt-ampere curve of solution to be detected is measured and recorded according to step II, and the electric current of the differential pulse voltammetry volt-ampere curve is strong
Degree peak value and the difference of the current strength peak value of the NaAc_HAc buffer solution without nitrite ion are updated to the line
In property equation, you can obtain the concentration of solution Nitrite ion to be detected.
5. the method for detection solution Nitrite ion concentration as claimed in claim 3, which is characterized in that match in step I
The NaAc_HAc buffer solution of the more parts of nitrite ions containing various concentration of system, NaAc_HAc buffer solution
PH is 4.0, and 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 for detection solution Nitrite ion concentration as claimed in claim 2, which is characterized in that S2 obtains carboxyl
After graphite alkene-polypyrrole-chitosan mixed liquor, before carrying out S3, be added N-Methyl pyrrolidone and stir 20~
30min, then carry out 40~50min of supersound process, the addition of N-Methyl pyrrolidone be carboxylated graphene quality 2%~
4%.
7. the method for detection solution Nitrite ion concentration as claimed in claim 2, which is characterized in that carboxylated in S1
Graphene is soaked in pyrroles in ethanol solution, is added before ferric chloride solution, the turmeric of 0.1mg is added into ethanol solution
Element.
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| 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 |
| 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 |
| 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 |
| 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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