CN106066354B - Using polynitrobenzene amine as nitrate ion electrode of sensitive membrane and preparation method thereof - Google Patents
Using polynitrobenzene amine as nitrate ion electrode of sensitive membrane and preparation method thereof Download PDFInfo
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- CN106066354B CN106066354B CN201610347665.9A CN201610347665A CN106066354B CN 106066354 B CN106066354 B CN 106066354B CN 201610347665 A CN201610347665 A CN 201610347665A CN 106066354 B CN106066354 B CN 106066354B
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- G—PHYSICS
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- 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
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Abstract
The invention discloses using polynitrobenzene amine as nitrate ion electrode of sensitive membrane and preparation method thereof.Base material can use the wire of carbon fiber or carbon film coated when preparation, and doped polyaniline is formed by electrochemical action in nitroaniline soiution.The present invention, which has, prepares simplicity, high mechanical strength, toughness is big, high sensitivity, small, probe response is fast, Monitoring lower-cut is low, the advantages that service life is long matches with all-solid-state reference electrode, suitable for carrying out on-line water flushing and long-term in-situ monitoring to the acid group content seawater, breeding water and chemistry, chemical industry aqueous medium.
Description
Technical field
The present invention relates to electrochemical detection technologies, more particularly to using polynitrobenzene amine as the nitrate ion electrode of sensitive membrane
And preparation method thereof.
Background technology
Nitrate anion is universally present in environment, as all contained various shapes in fertilizer and pesticide, food, industrial products, water body
The nitrate of state.In water environment, excessive nitrate anion can influence the quality of water, cause body eutrophication, to the ecosystem
There is serious harm.The concentration of nitrate ion as reflection Water quality an important indicator, water quality assessment and
Important in inhibiting in water environment treatment.The purpose of the present invention is be directed to this demand to provide a kind of highly sensitive nitrate ion
Electrode and preparation method thereof.
Invention content
The object of the present invention is to provide using polynitrobenzene amine as nitrate ion electrode of sensitive membrane and preparation method thereof.
The purpose of the present invention is achieved through the following technical solutions：
Using polynitrobenzene amine as the nitrate ion electrode of sensitive membrane, it includes carbon substrate, and cladding is on base material
Polynitrobenzene amine sensitive membrane.
The polynitrobenzene amine be one kind in ortho-nitraniline or meta nitro aniline in hydrochloric acid solution through electrochemistry
The polymer covering layer that method is formed in carbon base material surface in-situ polymerization.Ortho-nitraniline or meta nitro aniline are in aniline monomer
There are one nitrate ions for upper grafting.After polymerization, the nitrate ion on aniline monomer to be located at polymerization after polyaniline
The ion selectivity of amido has an impact on strand.Under the action of nitrate ion, the amido on polyaniline molecule chain is to molten
Nitrate ion in liquid has high selectivity, can receive or discharge nitrate ion by reversible oxidation reduction reaction,
It can this spy's response to have to the nitrate ion concentration in solution.This, which is polynitrobenzene amine, to be used as nitrate ion quick
Feel the immanent cause of film.
The carbon substrate (1) is carbon fiber, graphite fibre, carbon fiber, graphite rod, carbon-point, carbon film coated wire
In one kind.The carbon fiber is natural plant fibre, such as cotton, kapok, sisal hemp, abaca, ramie, flax, hemp, jute
Deng being heated to 350 to 650 DEG C of carbonizing productions under anaerobic.
Carbon fiber, graphite fibre, carbon fiber have good conductivity and chemical stability, therefore are adapted for use as electricity
Pole base material.
The step of wire is one kind in Cu, Ni, Ag, Co, Cd, carbon film coated be：
1) polyacrylonitrile is added in polar organic solvent, solution is heated to 70 to 100 DEG C and stirred until dissolving, obtains
To the solution of a concentration of 10-15% (wt), seal spare；
The polar organic solvent is in dimethylformamide (DMF), dimethyl sulfoxide (DMSO) (DMSO), pyridine, formamide
One or several kinds.
2) polyacrylonitrile solution is dipped with wire；Wire is inverted, is warming up in Muffle furnace under nitrogen protection
600 to 700 DEG C and constant temperature 0.5 to 2 hour, obtain carbon film coated wire.
Using polynitrobenzene amine as the preparation method of the nitrate ion electrode of sensitive membrane, it is characterised in that its steps is such as
Under：
1) a kind of in ortho-nitraniline or meta nitro aniline is dissolved in 0.5 to 1.0N hydrochloric acid solution, is configured to
A concentration of 0.5 to 1.0 mole of solution stirs to being completely dissolved, obtains nitroaniline soiution；
2) CHI760D electrochemical workstations are adjusted, parameter is：Cyclic voltammetry, scanning voltage 0-1.2V, sensitivity 10- 3A；Using carbon substrate to be plated as working electrode, platinum electrode is auxiliary electrode, and Ag/AgCl electrodes are reference electrode, in nitroaniline
Scanning 5 is recycled to 20 cycles in solution, and surface forms proton and adulterates polynitrobenzene amine.
Nitrate ion electrode provided by the invention is suitable for observing natural water body and chemistry, chemical process aqueous medium
Nitrate ion concentration, the production method provided is simple and easy to do, of low cost.
Specific implementation mode
Include carbon substrate and cladding poly- nitre on base material by the nitrate ion electrode of sensitive membrane of polynitrobenzene amine
Base aniline sensitivities film.
The polynitrobenzene amine be one kind in ortho-nitraniline or meta nitro aniline in hydrochloric acid solution through electrochemistry
The polymer covering layer that method is formed in carbon base material surface in-situ polymerization.Ortho-nitraniline or meta nitro aniline are in aniline monomer
There are one nitrate ions for upper grafting.After polymerization, the nitrate ion on aniline monomer to be located at polymerization after polyaniline
The ion selectivity of amido has an impact on strand.Under the action of nitrate ion, the amido on polyaniline molecule chain is to molten
Nitrate ion in liquid has high selectivity, can receive or discharge nitrate ion by reversible oxidation reduction reaction,
It can this spy's response to have to the nitrate ion concentration in solution.This, which is polynitrobenzene amine, to be used as nitrate ion quick
Feel the immanent cause of film.
The carbon substrate is in carbon fiber, graphite fibre, carbon fiber, graphite rod, carbon-point, carbon film coated wire
It is a kind of.The carbon fiber is natural plant fibre, such as cotton, kapok, sisal hemp, abaca, ramie, flax, hemp, jute exist
350 to 650 DEG C of carbonizing productions are heated under oxygen free condition.
Carbon fiber, graphite fibre, carbon fiber have good conductivity and chemical stability, therefore are adapted for use as electricity
Pole base material.Carbon fiber and carbon fibre lack rigidity, in the occasion for needing electrode to have certain rigidity, it is proposed that use carbon film coated
Wire is as electrode base material.
The step of wire is one kind in Cu, Ni, Ag, Co, Cd, carbon film coated be：
1) polyacrylonitrile is added in polar organic solvent, solution is heated to 70 to 100 DEG C and stirred until dissolving, obtains
To the solution of a concentration of 10-15% (wt), seal spare；
The polar organic solvent is in dimethylformamide (DMF), dimethyl sulfoxide (DMSO) (DMSO), pyridine, formamide
One or several kinds.Recommend DMF.
2) polyacrylonitrile solution is dipped with wire；Wire is inverted, is warming up in Muffle furnace under nitrogen protection
600 to 700 DEG C and constant temperature 0.5 to 2 hour, obtain carbon film coated wire.
The charing of polyacrylonitrile starts from 200 DEG C or so, is continued until 900 DEG C or more.In 600 to 700 DEG C of polyacrylonitrile
Cubical contraction is maximum, and weight tends towards stability, and can be considered best carbonization temperature.
Using polynitrobenzene amine as the preparation method of the nitrate ion electrode of sensitive membrane, it is characterised in that its steps is such as
Under：
1) a kind of in ortho-nitraniline or meta nitro aniline is dissolved in 0.5 to 1.0N hydrochloric acid solution, is configured to
A concentration of 0.5 to 1.0 mole of solution stirs to being completely dissolved, obtains nitroaniline soiution.
Using the amino benzenes compounds of nitrate ion are grafted with as the presoma of ion sensitive membrane, nitrate ion is answered
Positioned at the ortho position of amino or meta position.In the solution of preparation, the molar concentration of amino benzenes compounds and the molar concentration of hydrochloric acid are most
It is good equal.
2) CHI760D electrochemical workstations are adjusted, parameter is：Cyclic voltammetry, scanning voltage 0-1.6V, sensitivity 10- 3A；Using carbon substrate to be plated as working electrode, platinum electrode is auxiliary electrode, and Ag/AgCl electrodes are reference electrode, in nitroaniline
Scanning 5 is recycled to 20 cycles in solution, and surface forms proton and adulterates polynitrobenzene amine.
Electrochemical Scanning makes nitroaniline form fine and close clad in substrate surface in-situ polymerization, and is mixed by proton
It is miscellaneous.Clad has good conductibility, and to the highly selective of nitrate ion.
It is described further with reference to embodiment.
Embodiment 1
1) copper wire for being 3 centimetres by length is first cleaned by ultrasonic in acetone soln, removes surface and oil contaminant, then in the dilute salt of 1M
It is cleaned by ultrasonic in acid, removes oxide, then is dried after being cleaned by ultrasonic with deionized water；
2) 0.75g polyacrylonitrile is weighed in 5g dimethylformamides (DMF), and solution is heated to 100 DEG C and is stirred straight
To dissolving, the solution of a concentration of 15% (wt) is obtained；
3) copper wire is inverted, dips polyacrylonitrile solution, be warming up to 700 DEG C and constant temperature in Muffle furnace under nitrogen protection
2 hours, obtain the copper wire of carbon film coated；
4) 1.281g ortho-nitranilines are weighed, are dissolved in the hydrochloric acid of 20mL 1M, the ortho-nitraniline that 0.5M is made is molten
Liquid；By CHI760D electrochemical workstations with cyclic voltammetry in the one strata nitrobenzene of copper wire electroplating surface for having coated carbon film
Amine, copper wire is working electrode in three-electrode system, and auxiliary electrode is Pt electrodes, and reference electrode is business Ag/AgCl electrodes, cycle
Voltammetry scanning voltage is 0-1.2V, and sweep speed 50mV/s, scan cycle number is 20cls.
5) electrode is eluted with absolute alcohol after the completion of being electroplated, removes the nitroaniline oligomer of electrode surface, waits for that alcohol is waved
It is for use after hair.
Embodiment 2
1) nickel wire for being 3 centimetres by length is first cleaned by ultrasonic in acetone soln, removes surface and oil contaminant, then in the dilute salt of 1M
It is cleaned by ultrasonic in acid, removes oxide, then is dried after being cleaned by ultrasonic with deionized water；
2) weigh 0.75g polyacrylonitrile in 5g dimethyl sulfoxide (DMSO)s (DMSO), by solution be heated to 70 DEG C and stir until
Dissolving, obtains the solution of a concentration of 15% (wt)；
3) nickel wire is inverted, dips polyacrylonitrile solution, be warming up to 700 DEG C and constant temperature in Muffle furnace under nitrogen protection
2 hours, obtain the nickel wire of carbon film coated；
4) 1.281g ortho-nitranilines are weighed, are dissolved in the hydrochloric acid of 20mL 1M, the ortho-nitraniline that 0.5M is made is molten
Liquid；By CHI760D electrochemical workstations with cyclic voltammetry in the one strata nitrobenzene of nickel wire electroplating surface for having coated carbon film
Amine, copper wire is working electrode in three-electrode system, and auxiliary electrode is Pt electrodes, and reference electrode is business Ag/AgCl electrodes, cycle
Voltammetry scanning voltage is 0-1.2V, and sweep speed 50mV/s, scan cycle number is 10cls.
5) electrode is eluted with absolute alcohol after the completion of being electroplated, removes the nitroaniline oligomer of electrode surface, waits for that alcohol is waved
It is for use after hair.
Embodiment 3
1) filamentary silver for being 3 centimetres by length is first cleaned by ultrasonic in acetone soln, removes surface and oil contaminant, then in the dilute salt of 1M
It is cleaned by ultrasonic in acid, removes oxide, then is dried after being cleaned by ultrasonic with deionized water；
2) 0.75g polyacrylonitrile is weighed in 5g pyridines, and solution is heated to 70 DEG C and is stirred until dissolving, obtains concentration
For the solution of 15% (wt)；
3) filamentary silver is inverted, dips polyacrylonitrile solution, be warming up to 700 DEG C and constant temperature in Muffle furnace under nitrogen protection
2 hours, obtain the filamentary silver of carbon film coated；
4) 1.281g ortho-nitranilines are weighed, are dissolved in the hydrochloric acid of 20mL 1M, the ortho-nitraniline that 0.5M is made is molten
Liquid；By CHI760D electrochemical workstations with cyclic voltammetry in the one strata nitrobenzene of filamentary silver electroplating surface for having coated carbon film
Amine, copper wire is working electrode in three-electrode system, and auxiliary electrode is Pt electrodes, and reference electrode is business Ag/AgCl electrodes, cycle
Voltammetry scanning voltage is 0-1.2V, and sweep speed 50mV/s, scan cycle number is 5cls.
5) electrode is eluted with absolute alcohol after the completion of being electroplated, removes the nitroaniline oligomer of electrode surface, waits for that alcohol is waved
It is for use after hair.
Embodiment 4
1) the cobalt silk for being 3 centimetres by length is first cleaned by ultrasonic in acetone soln, removes surface and oil contaminant, then in the dilute salt of 1M
It is cleaned by ultrasonic in acid, removes oxide, then is dried after being cleaned by ultrasonic with deionized water；
2) 0.75g polyacrylonitrile is weighed in 5g formamides, and solution is heated to 70 DEG C and is stirred until dissolving, obtains dense
Degree is the solution of 15% (wt)；
3) cobalt silk is inverted, dips polyacrylonitrile solution, be warming up to 700 DEG C and constant temperature in Muffle furnace under nitrogen protection
2 hours, obtain the cobalt silk of carbon film coated；
4) 1.281g ortho-nitranilines are weighed, are dissolved in the hydrochloric acid of 20mL 1M, the ortho-nitraniline that 0.5M is made is molten
Liquid；By CHI760D electrochemical workstations with cyclic voltammetry in the one strata nitrobenzene of cobalt silk electroplating surface for having coated carbon film
Amine, copper wire is working electrode in three-electrode system, and auxiliary electrode is Pt electrodes, and reference electrode is business Ag/AgCl electrodes, cycle
Voltammetry scanning voltage is 0-1.2V, and sweep speed 50mV/s, scan cycle number is 5cls.
5) electrode is eluted with absolute alcohol after the completion of being electroplated, removes the nitroaniline oligomer of electrode surface, waits for that alcohol is waved
It is for use after hair.
Embodiment 5
1) cadmium wire for being 3 centimetres by length is first cleaned by ultrasonic in acetone soln, removes surface and oil contaminant, then in the dilute salt of 1M
It is cleaned by ultrasonic in acid, removes oxide, then is dried after being cleaned by ultrasonic with deionized water；
2) 0.75g polyacrylonitrile is weighed in 5g formamides, and solution is heated to 70 DEG C and is stirred until dissolving, obtains dense
Degree is the solution of 15% (wt)；
3) cadmium wire is inverted, dips polyacrylonitrile solution, be warming up to 700 DEG C and constant temperature in Muffle furnace under nitrogen protection
2 hours, obtain the cadmium wire of carbon film coated；
4) 1.281g ortho-nitranilines are weighed, are dissolved in the hydrochloric acid of 20mL 1M, the ortho-nitraniline that 0.5M is made is molten
Liquid；By CHI760D electrochemical workstations with cyclic voltammetry in the one strata nitrobenzene of cadmium wire electroplating surface for having coated carbon film
Amine, copper wire is working electrode in three-electrode system, and auxiliary electrode is Pt electrodes, and reference electrode is business Ag/AgCl electrodes, cycle
Voltammetry scanning voltage is 0-1.2V, and sweep speed 50mV/s, scan cycle number is 20cls.
5) electrode is eluted with absolute alcohol after the completion of being electroplated, removes the nitroaniline oligomer of electrode surface, waits for that alcohol is waved
It is for use after hair.
Embodiment 6
1) copper wire for being 3 centimetres by length is first cleaned by ultrasonic in acetone soln, removes surface and oil contaminant, then in the dilute salt of 1M
It is cleaned by ultrasonic in acid, removes oxide, then is dried after being cleaned by ultrasonic with deionized water；
2) 0.75g polyacrylonitrile is weighed in 5g dimethylformamides (DMF), and solution is heated to 100 DEG C and is stirred straight
To dissolving, the solution of a concentration of 15% (wt) is obtained；
3) copper wire is inverted, dips polyacrylonitrile solution, be warming up to 700 DEG C and constant temperature in Muffle furnace under nitrogen protection
2 hours, obtain the copper wire of carbon film coated；
4) 1.281g meta nitro anilines are weighed, are dissolved in the hydrochloric acid of 20mL 1M, the meta nitro aniline that 0.5M is made is molten
Liquid；By CHI760D electrochemical workstations with cyclic voltammetry in the one strata nitrobenzene of copper wire electroplating surface for having coated carbon film
Amine, copper wire is working electrode in three-electrode system, and auxiliary electrode is Pt electrodes, and reference electrode is business Ag/AgCl electrodes, cycle
Voltammetry scanning voltage is 0-1.2V, and sweep speed 50mV/s, scan cycle number is 20cls.
5) electrode is eluted with absolute alcohol after the completion of being electroplated, removes the nitroaniline oligomer of electrode surface, waits for that alcohol is waved
It is for use after hair.
Embodiment 7
1) nickel wire for being 3 centimetres by length is first cleaned by ultrasonic in acetone soln, removes surface and oil contaminant, then in the dilute salt of 1M
It is cleaned by ultrasonic in acid, removes oxide, then is dried after being cleaned by ultrasonic with deionized water；
2) weigh 0.75g polyacrylonitrile in 5g dimethyl sulfoxide (DMSO)s (DMSO), by solution be heated to 70 DEG C and stir until
Dissolving, obtains the solution of a concentration of 15% (wt)；
3) nickel wire is inverted, dips polyacrylonitrile solution, be warming up to 700 DEG C and constant temperature in Muffle furnace under nitrogen protection
2 hours, obtain the nickel wire of carbon film coated；
4) 1.281g meta nitro anilines are weighed, are dissolved in the hydrochloric acid of 20mL 1M, the meta nitro aniline that 0.5M is made is molten
Liquid；By CHI760D electrochemical workstations with cyclic voltammetry in the one strata nitrobenzene of nickel wire electroplating surface for having coated carbon film
Amine, copper wire is working electrode in three-electrode system, and auxiliary electrode is Pt electrodes, and reference electrode is business Ag/AgCl electrodes, cycle
Voltammetry scanning voltage is 0-1.2V, and sweep speed 50mV/s, scan cycle number is 10cls.
5) electrode is eluted with absolute alcohol after the completion of being electroplated, removes the nitroaniline oligomer of electrode surface, waits for that alcohol is waved
It is for use after hair.
Embodiment 8
1) filamentary silver for being 3 centimetres by length is first cleaned by ultrasonic in acetone soln, removes surface and oil contaminant, then in the dilute salt of 1M
It is cleaned by ultrasonic in acid, removes oxide, then is dried after being cleaned by ultrasonic with deionized water；
2) 0.75g polyacrylonitrile is weighed in 5g pyridines, and solution is heated to 70 DEG C and is stirred until dissolving, obtains concentration
For the solution of 15% (wt)；
3) filamentary silver is inverted, dips polyacrylonitrile solution, be warming up to 700 DEG C and constant temperature in Muffle furnace under nitrogen protection
2 hours, obtain the filamentary silver of carbon film coated；
4) 1.281g meta nitro anilines are weighed, are dissolved in the hydrochloric acid of 20mL 1M, the meta nitro aniline that 0.5M is made is molten
Liquid；By CHI760D electrochemical workstations with cyclic voltammetry in the one strata nitrobenzene of filamentary silver electroplating surface for having coated carbon film
Amine, copper wire is working electrode in three-electrode system, and auxiliary electrode is Pt electrodes, and reference electrode is business Ag/AgCl electrodes, cycle
Voltammetry scanning voltage is 0-1.2V, and sweep speed 50mV/s, scan cycle number is 5cls.
5) electrode is eluted with absolute alcohol after the completion of being electroplated, removes the nitroaniline oligomer of electrode surface, waits for that alcohol is waved
It is for use after hair.
Embodiment 9
1) the cobalt silk for being 3 centimetres by length is first cleaned by ultrasonic in acetone soln, removes surface and oil contaminant, then in the dilute salt of 1M
It is cleaned by ultrasonic in acid, removes oxide, then is dried after being cleaned by ultrasonic with deionized water；
2) 0.75g polyacrylonitrile is weighed in 5g formamides, and solution is heated to 70 DEG C and is stirred until dissolving, obtains dense
Degree is the solution of 15% (wt)；
3) cobalt silk is inverted, dips polyacrylonitrile solution, be warming up to 700 DEG C and constant temperature in Muffle furnace under nitrogen protection
2 hours, obtain the cobalt silk of carbon film coated；
4) 1.281g meta nitro anilines are weighed, are dissolved in the hydrochloric acid of 20mL 1M, the meta nitro aniline that 0.5M is made is molten
Liquid；By CHI760D electrochemical workstations with cyclic voltammetry in the one strata nitrobenzene of cobalt silk electroplating surface for having coated carbon film
Amine, copper wire is working electrode in three-electrode system, and auxiliary electrode is Pt electrodes, and reference electrode is business Ag/AgCl electrodes, cycle
Voltammetry scanning voltage is 0-1.2V, and sweep speed 50mV/s, scan cycle number is 5cls.
5) electrode is eluted with absolute alcohol after the completion of being electroplated, removes the nitroaniline oligomer of electrode surface, waits for that alcohol is waved
It is for use after hair.
Embodiment 10
1) cadmium wire for being 3 centimetres by length is first cleaned by ultrasonic in acetone soln, removes surface and oil contaminant, then in the dilute salt of 1M
It is cleaned by ultrasonic in acid, removes oxide, then is dried after being cleaned by ultrasonic with deionized water；
2) 0.75g polyacrylonitrile is weighed in 5g formamides, and solution is heated to 70 DEG C and is stirred until dissolving, obtains dense
Degree is the solution of 15% (wt)；
3) cadmium wire is inverted, dips polyacrylonitrile solution, be warming up to 700 DEG C and constant temperature in Muffle furnace under nitrogen protection
2 hours, obtain the cadmium wire of carbon film coated；
4) 1.281g meta nitro anilines are weighed, are dissolved in the hydrochloric acid of 20mL 1M, the meta nitro aniline that 0.5M is made is molten
Liquid；By CHI760D electrochemical workstations with cyclic voltammetry in the one strata nitrobenzene of cadmium wire electroplating surface for having coated carbon film
Amine, copper wire is working electrode in three-electrode system, and auxiliary electrode is Pt electrodes, and reference electrode is business Ag/AgCl electrodes, cycle
Voltammetry scanning voltage is 0-1.2V, and sweep speed 50mV/s, scan cycle number is 20cls.
5) electrode is eluted with absolute alcohol after the completion of being electroplated, removes the nitroaniline oligomer of electrode surface, waits for that alcohol is waved
It is for use after hair.
Embodiment 11
1) copper wire for being 3 centimetres by length is first cleaned by ultrasonic in acetone soln, removes surface and oil contaminant, then in the dilute salt of 1M
It is cleaned by ultrasonic in acid, removes oxide, then is dried after being cleaned by ultrasonic with deionized water；
2) weigh 0.75g polyacrylonitrile in 5g dimethyl sulfoxide (DMSO)s (DMSO), by solution be heated to 100 DEG C and stir until
Dissolving, obtains the solution of a concentration of 15% (wt)；
3) copper wire is inverted, dips polyacrylonitrile solution, be warming up to 700 DEG C and constant temperature in Muffle furnace under nitrogen protection
2 hours, obtain the copper wire of carbon film coated；
4) 1.281g ortho-nitranilines are weighed, are dissolved in the hydrochloric acid of 20mL 1M, the ortho-nitraniline that 0.5M is made is molten
Liquid；By CHI760D electrochemical workstations with cyclic voltammetry in the one strata nitrobenzene of copper wire electroplating surface for having coated carbon film
Amine, copper wire is working electrode in three-electrode system, and auxiliary electrode is Pt electrodes, and reference electrode is business Ag/AgCl electrodes, cycle
Voltammetry scanning voltage is 0-1.2V, and sweep speed 50mV/s, scan cycle number is 20cls.
5) electrode is eluted with absolute alcohol after the completion of being electroplated, removes the nitroaniline oligomer of electrode surface, waits for that alcohol is waved
It is for use after hair.
Embodiment 12
1) nickel wire for being 3 centimetres by length is first cleaned by ultrasonic in acetone soln, removes surface and oil contaminant, then in the dilute salt of 1M
It is cleaned by ultrasonic in acid, removes oxide, then is dried after being cleaned by ultrasonic with deionized water；
2) 0.75g polyacrylonitrile is weighed in 5g pyridines, and solution is heated to 70 DEG C and is stirred until dissolving, obtains concentration
For the solution of 15% (wt)；
3) nickel wire is inverted, dips polyacrylonitrile solution, be warming up to 700 DEG C and constant temperature in Muffle furnace under nitrogen protection
2 hours, obtain the nickel wire of carbon film coated；
4) 1.281g ortho-nitranilines are weighed, are dissolved in the hydrochloric acid of 20mL 1M, the ortho-nitraniline that 0.5M is made is molten
Liquid；By CHI760D electrochemical workstations with cyclic voltammetry in the one strata nitrobenzene of nickel wire electroplating surface for having coated carbon film
Amine, copper wire is working electrode in three-electrode system, and auxiliary electrode is Pt electrodes, and reference electrode is business Ag/AgCl electrodes, cycle
Voltammetry scanning voltage is 0-1.2V, and sweep speed 50mV/s, scan cycle number is 10cls.
5) electrode is eluted with absolute alcohol after the completion of being electroplated, removes the nitroaniline oligomer of electrode surface, waits for that alcohol is waved
It is for use after hair.
Embodiment 13
1) filamentary silver for being 3 centimetres by length is first cleaned by ultrasonic in acetone soln, removes surface and oil contaminant, then in the dilute salt of 1M
It is cleaned by ultrasonic in acid, removes oxide, then is dried after being cleaned by ultrasonic with deionized water；
2) 0.75g polyacrylonitrile is weighed in 5g formamides, and solution is heated to 70 DEG C and is stirred until dissolving, obtains dense
Degree is the solution of 15% (wt)；
3) filamentary silver is inverted, dips polyacrylonitrile solution, be warming up to 700 DEG C and constant temperature in Muffle furnace under nitrogen protection
2 hours, obtain the filamentary silver of carbon film coated；
4) 1.281g ortho-nitranilines are weighed, are dissolved in the hydrochloric acid of 20mL 1M, the ortho-nitraniline that 0.5M is made is molten
Liquid；By CHI760D electrochemical workstations with cyclic voltammetry in the one strata nitrobenzene of filamentary silver electroplating surface for having coated carbon film
Amine, copper wire is working electrode in three-electrode system, and auxiliary electrode is Pt electrodes, and reference electrode is business Ag/AgCl electrodes, cycle
Voltammetry scanning voltage is 0-1.2V, and sweep speed 50mV/s, scan cycle number is 5cls.
5) electrode is eluted with absolute alcohol after the completion of being electroplated, removes the nitroaniline oligomer of electrode surface, waits for that alcohol is waved
It is for use after hair.
Embodiment 14
1) the cobalt silk for being 3 centimetres by length is first cleaned by ultrasonic in acetone soln, removes surface and oil contaminant, then in the dilute salt of 1M
It is cleaned by ultrasonic in acid, removes oxide, then is dried after being cleaned by ultrasonic with deionized water；
2) weigh 0.75g polyacrylonitrile in 5g dimethylformamides (DMF), by solution be heated to 70 DEG C and stir until
Dissolving, obtains the solution of a concentration of 15% (wt)；
3) cobalt silk is inverted, dips polyacrylonitrile solution, be warming up to 700 DEG C and constant temperature in Muffle furnace under nitrogen protection
2 hours, obtain the cobalt silk of carbon film coated；
4) 1.281g meta nitro anilines are weighed, are dissolved in the hydrochloric acid of 20mL 1M, the meta nitro aniline that 0.5M is made is molten
Liquid；By CHI760D electrochemical workstations with cyclic voltammetry in the one strata nitrobenzene of cobalt silk electroplating surface for having coated carbon film
Amine, copper wire is working electrode in three-electrode system, and auxiliary electrode is Pt electrodes, and reference electrode is business Ag/AgCl electrodes, cycle
Voltammetry scanning voltage is 0-1.2V, and sweep speed 50mV/s, scan cycle number is 5cls.
5) electrode is eluted with absolute alcohol after the completion of being electroplated, removes the nitroaniline oligomer of electrode surface, waits for that alcohol is waved
It is for use after hair.
Embodiment 15
1) cadmium wire for being 3 centimetres by length is first cleaned by ultrasonic in acetone soln, removes surface and oil contaminant, then in the dilute salt of 1M
It is cleaned by ultrasonic in acid, removes oxide, then is dried after being cleaned by ultrasonic with deionized water；
2) weigh 0.75g polyacrylonitrile in 5g dimethyl sulfoxide (DMSO)s (DMSO), by solution be heated to 70 DEG C and stir until
Dissolving, obtains the solution of a concentration of 15% (wt)；
3) cadmium wire is inverted, dips polyacrylonitrile solution, be warming up to 700 DEG C and constant temperature in Muffle furnace under nitrogen protection
2 hours, obtain the cadmium wire of carbon film coated；
4) 1.281g ortho-nitranilines are weighed, are dissolved in the hydrochloric acid of 20mL 1M, the ortho-nitraniline that 0.5M is made is molten
Liquid；By CHI760D electrochemical workstations with cyclic voltammetry in the one strata nitrobenzene of cadmium wire electroplating surface for having coated carbon film
Amine, copper wire is working electrode in three-electrode system, and auxiliary electrode is Pt electrodes, and reference electrode is business Ag/AgCl electrodes, cycle
Voltammetry scanning voltage is 0-1.2V, and sweep speed 50mV/s, scan cycle number is 20cls.
5) electrode is eluted with absolute alcohol after the completion of being electroplated, removes the nitroaniline oligomer of electrode surface, waits for that alcohol is waved
It is for use after hair.
Embodiment 16
1) measure 4 centimetres under anaerobic 400 DEG C charing kapoks as carbon substrate to be plated；
2) 1.281g ortho-nitranilines are weighed, are dissolved in the hydrochloric acid of 20mL 1M, the ortho-nitraniline that 0.5M is made is molten
Liquid；By CHI760D electrochemical workstations with cyclic voltammetry in the one strata nitrobenzene of copper wire electroplating surface for having coated carbon film
Amine, copper wire is working electrode in three-electrode system, and auxiliary electrode is Pt electrodes, and reference electrode is business Ag/AgCl electrodes, cycle
Voltammetry scanning voltage is 0-1.2V, and sweep speed 50mV/s, scan cycle number is 10cls.
3) electrode is eluted with absolute alcohol after the completion of being electroplated, removes the nitroaniline oligomer of electrode surface, waits for that alcohol is waved
It is for use after hair.
Embodiment 17
1) measure 4 centimetres under anaerobic 400 DEG C charing carbon fibers as carbon substrate to be plated；
2) 1.281g meta nitro anilines are weighed, are dissolved in the hydrochloric acid of 20mL 1M, the meta nitro aniline that 0.5M is made is molten
Liquid；By CHI760D electrochemical workstations with cyclic voltammetry in the one strata nitrobenzene of copper wire electroplating surface for having coated carbon film
Amine, copper wire is working electrode in three-electrode system, and auxiliary electrode is Pt electrodes, and reference electrode is business Ag/AgCl electrodes, cycle
Voltammetry scanning voltage is 0-1.2V, and sweep speed 50mV/s, scan cycle number is 10cls.
3) electrode is eluted with absolute alcohol after the completion of being electroplated, removes the nitroaniline oligomer of electrode surface, waits for that alcohol is waved
It is for use after hair.
Embodiment 18
1) measure 4 centimetres under anaerobic 400 DEG C charing graphite fibres as carbon substrate to be plated；
2) 1.281g meta nitro anilines are weighed, are dissolved in the hydrochloric acid of 20mL 1M, the meta nitro aniline that 0.5M is made is molten
Liquid；By CHI760D electrochemical workstations with cyclic voltammetry in the one strata nitrobenzene of copper wire electroplating surface for having coated carbon film
Amine, copper wire is working electrode in three-electrode system, and auxiliary electrode is Pt electrodes, and reference electrode is business Ag/AgCl electrodes, cycle
Voltammetry scanning voltage is 0-1.2V, and sweep speed 50mV/s, scan cycle number is 20cls.
3) electrode is eluted with absolute alcohol after the completion of being electroplated, removes the nitroaniline oligomer of electrode surface, waits for that alcohol is waved
It is for use after hair.
Claims (2)
1. using polynitrobenzene amine as the nitrate ion electrode of sensitive membrane, it is characterised in that it includes carbon substrate, polynitrobenzene amine；
The carbon substrate is carbon film coated wire, and the wire is one kind in Cu, Ni, Ag, Co, Cd, carbon film coated
The step of be：
1) polyacrylonitrile is added in polar organic solvent, solution is heated to 70 to 100 DEG C and stirred until dissolving, obtains dense
Degree is the solution of 10-15wt%, and sealing is spare；
2) polyacrylonitrile solution is dipped with wire；Wire is inverted, be warming up in Muffle furnace under nitrogen protection 600 to
700 DEG C and constant temperature 0.5 to 2 hour, obtain carbon film coated wire；
The polynitrobenzene amine be one kind in ortho-nitraniline or meta nitro aniline in hydrochloric acid solution through electrochemical method
In the polymer covering layer that carbon base material surface in-situ polymerization is formed.
2. according to claim 1 using polynitrobenzene amine as the nitrate ion electrode of sensitive membrane, it is characterised in that described
Polar organic solvent be one or several kinds in dimethylformamide, dimethyl sulfoxide (DMSO), pyridine, formamide.
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|---|---|---|---|---|
| CN103063718A (en) * | 2012-12-13 | 2013-04-24 | 浙江大学 | Solid nitrate ion electrode based on conductive polyaniline and preparing method thereof |
| CN103675068A (en) * | 2013-03-28 | 2014-03-26 | 浙江大学 | Bismuth nitrate oxide based solid nitrate electrode and preparation method thereof |
| GB2509127B (en) * | 2012-12-21 | 2015-09-30 | Plant Bioscience Ltd | Soil chemistry sensor |
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| CN103063718A (en) * | 2012-12-13 | 2013-04-24 | 浙江大学 | Solid nitrate ion electrode based on conductive polyaniline and preparing method thereof |
| GB2509127B (en) * | 2012-12-21 | 2015-09-30 | Plant Bioscience Ltd | Soil chemistry sensor |
| CN103675068A (en) * | 2013-03-28 | 2014-03-26 | 浙江大学 | Bismuth nitrate oxide based solid nitrate electrode and preparation method thereof |
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| Determination of Nitrite Ion Using the Reaction with p-Nitroaniline and Azulene;EE Garcia;《Analytical Chemistry》;19671231;第39卷(第13期);1605-1607 * |
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