CN110006983A - The method of content of nitrite in electrode, electrolysis system and test sample - Google Patents

The method of content of nitrite in electrode, electrolysis system and test sample Download PDF

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Publication number
CN110006983A
CN110006983A CN201910287799.XA CN201910287799A CN110006983A CN 110006983 A CN110006983 A CN 110006983A CN 201910287799 A CN201910287799 A CN 201910287799A CN 110006983 A CN110006983 A CN 110006983A
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China
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electrode
nitrite
modified electrode
carbon nano
tube
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许贺
李爱莉
邹晨
张雨琪
黄金烨
史书宽
李致霆
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Donghua University
National Dong Hwa University
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Donghua University
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    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
    • G01N27/26—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating electrochemical variables; by using electrolysis or electrophoresis
    • G01N27/28—Electrolytic cell components
    • G01N27/30—Electrodes, e.g. test electrodes; Half-cells
    • G01N27/308—Electrodes, e.g. test electrodes; Half-cells at least partially made of carbon
    • 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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  • Life Sciences & Earth Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Physics & Mathematics (AREA)
  • Chemical Kinetics & Catalysis (AREA)
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  • General Health & Medical Sciences (AREA)
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  • Carbon And Carbon Compounds (AREA)

Abstract

The invention belongs to electrochemical sensor detection fields, it is related to the rapid sensitive detection method of a kind of pair of nitrite, disclose a kind of modified electrode, the electrode includes: a drop coating in the carbon nano tube suspension of glassy carbon electrode surface, with one with carbon nano tube modified electrode (CNTs/GCE) be working electrode, carbon nano-tube/poly naphthylenediamine/nano Pd particle modified electrode is made using cyclic voltammetry scan method.The invention also discloses the preparation methods of the electrode.The invention also discloses the electrolysis system that the electrode is working electrode and the methods for detecting nitrite with the electrolysis system.Electrode of the invention has many advantages, such as that response is rapid, high sensitivity, stability are good, and online for exploitation nitrite ion, real-time detection technique provides new method and refers to.

Description

The method of content of nitrite in electrode, electrolysis system and test sample
Technical field
The present invention relates to a kind of carbon nanotubes, the preparation method of polydiaminonaphthalene and nano Pd particle modified electrode, the electrode, and Electrolysis system is detected using the nitrite of the electrode, and utilizes nitrous acid in electrode rapid sensitive detection sample to be tested The method of salt content.
Background technique
Nitrite is generally deposited in people's daily life as a kind of important food additives and antibiotic antiseptic ?.However nitrite can cause damages to health the intracorporal content of people is exceeded.Nitrite is strong oxygen in acid condition Agent, into blood after in conjunction with hemoglobin, so that oxyhemoglobin is become ferrihemoglobin, so that hemoglobin loses The function of transporting oxygen, oxyhemoglobin release oxygen, occurs livid purple and is poisoned, and have dilating effect to peripheral vessels.In addition, nitrous Hydrochlorate is the important as precursors of violent carcinogenic substance N- nitrosamine, it can by nitrite nature and gastrointestinal tract acyclic acidic It is converted in border, generates carcinogenesis.World health organization is 3mg/L to the highest limit standard of nitrite.Therefore, to nitrous The Sensitive Detection of hydrochlorate has important practical significance.
The main method of detection nitrite has spectrophotometry, electrophoresis, high performance liquid chromatography and chemistry hair at present Light method etc..For these methods although sensitivity with higher and lower detection limit, they need expensive experiment instrument mostly Device, the operative skill of cumbersome pre-treatment and profession, it is difficult to realize the on-line real-time measuremen of nitrite.Electrochemical sensing utensil Have the advantages that instrument is simple, analysis speed is fast, the good, high sensitivity of selectivity, has very to the quick detection of nitrite at present Good application.But bare electrode for nitrite detection there are higher overpotential, easily cause electrode " poisoning " to influence inspection Survey result.
Summary of the invention
The object of the present invention is to provide the electrochemical detection methods of a kind of pair of nitrite, reduce overpotential, improve sensitive Degree and stability realize the sensitive and Accurate Determining to nitrite anions.
In order to achieve the above object, there is provided a kind of modified electrodes, including base for a technical solution of the invention Hearth electrode and working electrode, which is characterized in that the working electrode uses the carbon nano-tube/poly naphthalene of cyclic voltammetry scan method preparation Diamines/nano Pd particle modified electrode.
Preferably, in the carbon nano-tube/poly naphthylenediamine/nano Pd particle modified electrode carbon nanotube be multi-walled carbon nanotube or Single-walled carbon nanotube.Preferably, in the carbon nano-tube/poly naphthylenediamine/nano Pd particle modified electrode Pd nano particle by size compared with For uniform spherical nanostructure composition, average-size about 30~100nm.
Preferably, the scanning current potential of the cyclic voltammetry scan method is in -0.2~1.2V.
Preferably, the sweep speed of the cyclic voltammetry scan method is in 50~200mV/s.
There is provided a kind of application of above-mentioned modified electrode, features to exist for another technical solution of the invention In for detecting the content of nitrite in sample to be tested.
There is provided a kind of preparation method of above-mentioned modified electrode, features for another technical solution of the invention It is, comprising the following steps:
(a) by uniform carbon nano tube suspension drop coating to the surface of basal electrode, carbon nano tube modified electrode is formed CNTs/GCE；
In this step, can with behind the surface of carbon nano tube suspension drop coating to basal electrode under infrared lamp it is dry, to Carbon nano tube modified electrode CNTs/GCE is made after solvent volatilization；
(b) it is working electrode by carbon nano tube modified electrode CNTs/GCE, prepares and contain HNO3, polydiaminonaphthalene and PbCl2It is molten Above-mentioned electrode is made using cyclic voltammetry scan method for liquid.
Preferably, it before step (a), further comprises the steps of: and basal electrode is pre-processed.It is selected in the pretreatment It is cleaned from (but being not limited to): electrode surface polishing, electrode surface polishing and/or electrode surface.
It is furthermore preferred that the electrode surface polishing includes: the careful sanding and polishing Cheng Jing of alumina powder with 0.05 μm Electrode is placed in cyclic voltammetry scan (cyclic in the 5mM potassium ferricyanide/potassium ferrocyanide+0.1M KCl solution by face Voltammetry), voltage range 0.2V-0.8V.Oxidation peak/reduction peak potential difference is available less than 100mV.
It is furthermore preferred that the electrode surface cleaning includes: successively in 1:1 nitric acid solution, dehydrated alcohol and distilled water Each 5min of ultrasound, finally dries electrode at room temperature.
There is provided a kind of nitrite to detect electrolysis system for another technical solution of the invention, which is characterized in that institute Contain above-mentioned electrode in the electrolysis system stated.
Preferably, also contain in the electrolysis system:
One reference electrode；With
A pair of electrodes.
One feasible to be achieved in that: using carbon nano tube modified electrode CNTs/GCE as working electrode, being made with Ag/Agcl For reference electrode, using Pt as to electrode, and HNO containing 0.6mol/L is prepared3With 0.25mM polydiaminonaphthalene and 0.5mmol/L PbCl2Solution, after using cyclic voltammetry scan method to enclose between -0.2~1.2V with the rate loop voltammetric scan 20 of 50mv/s Carbon nano-tube/poly naphthylenediamine/nano Pd particle electrode is made.
Preferably, in Ag/Agcl reference electrode, containing KCl, it is used for conducting medium.It is highly preferred that the KCl's is dense Degree is 2~3mol/L；Preferable about 3mol/L.
Preferably, the electrolysis system is electrolytic cell.
It is furthermore preferred that the electrolyte in electrolytic cell is to be made with potassium dihydrogen phosphate and dipotassium hydrogen phosphate containing K2HPO4- KH2PO4, PBS buffer solution；It is further preferred that the K2HPO4-KH2PO4Solution concentration is 0.1mol/L, the PBS The PH of buffer is 4~5, preferably about PH=4.5.
There is provided a kind of method of content of nitrite in test sample, features for another technical solution of the invention It is, comprising the following steps:
(a) sample to be tested is added in electrolysis system described in any one of claim 10, containing certain density nitrite, Cyclic voltammetry scans potential range -0.2~1.2V, sweeps 50~200mV/s of speed；
(b) Amperometric i-t curve is used, 0.8~1.0V of oxidation voltage is set, and solution is in stirring, to blank PBS Electric current baseline walk steady 20s after, successively with microsyringe by nitrite solution injection enter, carry out ampere detection；
(c) it is acted on by the concerted catalysis of carbon nanotube, polydiaminonaphthalene and nano Pd particle, reduces nitrite electrocatalytic oxidation Overvoltage, catalytic current is provided, the quantitative relationship between catalytic current and nitrite concentration is established.
The present invention provides one kind based on carbon nano-tube/poly naphthylenediamine/nano Pd particle composite material modified electrode to nitrous acid The model electrochemical detection method of salt.Overpotential can be reduced using the method for chemically modified electrode, improve sensitivity and stabilization Property, realize the accurate and sensitive determination to nitrite anions.
Detailed description of the invention
Figure 1A and Figure 1B shows carbon nano-tube/poly naphthylenediamine/nano Pd particle modified electrode SEM figure of the invention, wherein As shown in Figure 1A, the polydiaminonaphthalene film being deposited on carbon nano-tube/poly naphthylenediamine/nano Pd particle electrode is clearly visible for covering The grey deposit of CNTs most surfaces, and accumulate polydiaminonaphthalene film on the surface CNTs thickness and distribution in terms of It is relatively uniform.As can be seen that Pd nanoparticle is mainly by the more uniform ball shaped nano knot of size from image shown in Figure 1B Structure composition, these spherical nanostructures are well dispersed on the surface polydiaminonaphthalene-CNTs；
Carbon nano-tube/poly naphthylenediamine/nano Pd particle modified electrode EDX figure Fig. 2 of the invention, in which: in the composite material Pd content is higher, there is apparent absorption peak；
Fig. 3 shows carbon nano-tube/poly naphthylenediamine/Pd in 3mM NaNO2In cyclic voltammogram, sweep speed: 50mV/s, In: a blank solution；B is 3mM NaNO2Solution；
Fig. 4 shows that carbon nano-tube/poly naphthylenediamine/nano Pd particle modified electrode of the invention detects the ampere of nitrite Figure, in which: linear relationship of the interior illustration between catalytic current and nitrite concentration.
Specific embodiment
Present invention will be further explained below with reference to specific examples.It should be understood that these embodiments are merely to illustrate the present invention Rather than it limits the scope of the invention.In addition, it should also be understood that, after reading the content taught by the present invention, those skilled in the art Member can make various changes or modifications the present invention, and such equivalent forms equally fall within the application the appended claims and limited Range.
One, carbon nano-tube/poly naphthylenediamine/nano Pd particle electrode preparation
Using glass-carbon electrode as basal electrode, electrode is placed in the 5mM potassium ferricyanide/ferrous iron cyanogen at after mirror surface by sanding and polishing Change cyclic voltammetry scan in potassium 0.1M KCl solution, voltage range 0.2V-0.8V sweeps 100~150mV/s of speed.Then it successively sets In 1:1 nitric acid solution, ultrasound 5min, finally places an electrode within and dries at room temperature in dehydrated alcohol and distilled water.It is more to weigh 1mg Wall carbon nano tube is added in 1mL n,N-Dimethylformamide (DMF) solution, and ultrasonic 30min forms uniform black suspension Liquid.The 10 uniform drop coatings of μ L carbon nano tube suspension are drawn in glassy carbon electrode surface with microsyringe, it is dry under infrared lamp, Carbon nano tube modified electrode (CNTs/GCE) is made after the solvent is volatilized.
Using CNTs/GCE as working electrode, HNO containing 0.6mol/L is prepared3With 0.25mM polydiaminonaphthalene and 0.5mmol/L PbCl2Solution, after using cyclic voltammetry scan method to enclose between -0.2~1.2V with the rate loop voltammetric scan 20 of 50mv/s Carbon nano-tube/poly naphthylenediamine/nano Pd particle electrode is made.
Two, cyclic voltammetry detects nitrite
It is made with potassium dihydrogen phosphate and dipotassium hydrogen phosphate containing 0.1mol/LK2HPO4-KH2PO4, pH=4.5 PBS (pH 4.5) buffer.The carbon nano-tube/poly prepared naphthylenediamine/nano Pd particle electrode is immersed in respectively without NO2 -With contain In PBS (pH=4.5) solution of a certain amount of nitrite, use cyclic voltammetry with the sweep speed of 0.04~0.07V/s, The current potential for applying -0.2~1.2V is detected.
Three, amperometric detection nitrite
Carbon nano-tube/poly naphthylenediamine/nano Pd particle electrode is put into 10 milliliters of PBS (PH=4.5) solution, and is stirred, if Set 0.8~1.0V of voltage.Then the NaNO of 1mM is prepared2Solution, after the electric current baseline of blank PBS 4.5 walks steady 20s, according to Secondary 5uL, 10uL, 20uL, 50uL, 100uL microsyringe enter nitrite solution injection.According to the oxygen of nitrite anions Relationship between galvanic current and its concentration establishes the linear equation of nitrite anions oxidation current and concentration, so that quantitative detection is sub- The content of nitrate ion.

Claims (10)

1. a kind of modified electrode, including basal electrode and working electrode, which is characterized in that the working electrode is using circulation Carbon nano-tube/poly naphthylenediamine/nano Pd particle modified glassy carbon electrode of voltammetric scan method preparation.
2. a kind of modified electrode as described in claim 1, which is characterized in that the carbon nano-tube/poly naphthylenediamine/nanometer Carbon nanotube is multi-walled carbon nanotube or single-walled carbon nanotube in Pd modified electrode.
3. a kind of modified electrode as described in claim 1, which is characterized in that the carbon nano-tube/poly naphthylenediamine/nanometer Pd nano particle is that the spherical nanostructure of uniform particle sizes forms in Pd modified electrode, 30~100nm of average-size.
4. a kind of modified electrode as described in claim 1, which is characterized in that the scanning electricity of the cyclic voltammetry scan method Position is in -0.2~1.2V.
5. a kind of modified electrode as described in claim 1, which is characterized in that the scanning speed of the cyclic voltammetry scan method Rate is in 50~200mV/s.
6. a kind of application of modified electrode as described in claim 1, which is characterized in that for detecting the sample to be tested Central Asia The content of nitrate.
7. a kind of preparation method of modified electrode as described in claim 1, which comprises the following steps:
(a) by uniform carbon nano tube suspension drop coating to the surface of basal electrode, carbon nano tube modified electrode CNTs/ is formed GCE；
(b) it is working electrode by carbon nano tube modified electrode CNTs/GCE, prepares and contain HNO3, polydiaminonaphthalene and PbCl2Solution, benefit Electrode described in claim 1 is made with cyclic voltammetry scan method.
8. a kind of nitrite detects electrolysis system, which is characterized in that containing as described in claim 1 in the electrolysis system Electrode.
9. electrolysis system as claimed in claim 10, which is characterized in that also contain in the electrolysis system:
One reference electrode；With
A pair of electrodes.
10. a kind of method of content of nitrite in test sample, which comprises the following steps:
(a) sample to be tested is added in electrolysis system described in any one of claim 10, contains certain density nitrite, circulation Voltammetry scans potential range -0.2~1.2V, sweeps 50~200mV/s of speed；
(b) Amperometric i-t curve is used, 0.8~1.0V of oxidation voltage is set, solution is in stirring, the electricity to blank PBS After stream baseline walks steady 20s, successively nitrite solution injection is entered with microsyringe, carries out ampere detection；
(c) it is acted on by the concerted catalysis of carbon nanotube, polydiaminonaphthalene and nano Pd particle, reduces the mistake of nitrite electrocatalytic oxidation Voltage provides catalytic current, establishes the quantitative relationship between catalytic current and nitrite concentration.
CN201910287799.XA 2019-04-11 2019-04-11 The method of content of nitrite in electrode, electrolysis system and test sample Pending CN110006983A (en)

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Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101982764A (en) * 2010-11-01 2011-03-02 湖南大学 Composite membrane modified biosensor and preparation method and application thereof
CN105738441A (en) * 2016-02-26 2016-07-06 运城学院 Modified glassy carbon electrode and preparation method and application thereof

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101982764A (en) * 2010-11-01 2011-03-02 湖南大学 Composite membrane modified biosensor and preparation method and application thereof
CN105738441A (en) * 2016-02-26 2016-07-06 运城学院 Modified glassy carbon electrode and preparation method and application thereof

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Title
BADEA, MICAELA ET AL.: "New electrochemical sensors for detection of nitrites and nitrates", 《JOURNAL OF ELECTROANALYTICAL CHEMISTRY》 *
GANAS, K. ET AL.: "Total nitrite/nitrate in expired breath condensate of patients with asthma", 《RESPIRATORY MEDICINE》 *
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Application publication date: 20190712