CN106066354A - Nitrate ion electrode with polynitrobenzene amine as sensitive membrane and preparation method thereof - Google Patents
Nitrate ion electrode with polynitrobenzene amine as sensitive membrane and preparation method thereof Download PDFInfo
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- CN106066354A CN106066354A CN201610347665.9A CN201610347665A CN106066354A CN 106066354 A CN106066354 A CN 106066354A CN 201610347665 A CN201610347665 A CN 201610347665A CN 106066354 A CN106066354 A CN 106066354A
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Abstract
The invention discloses nitrate ion electrode with polynitrobenzene amine as sensitive membrane and preparation method thereof.During preparation, base material can use carbon fiber, or the tinsel of carbon film coated, forms doped polyaniline by electrochemical action in nitroaniline soiution.The present invention has preparation simplicity, mechanical strength is high, toughness is big, highly sensitive, volume is little, and probe response is fast, Monitoring lower-cut is low, service life, the advantage such as length, supported the use with all-solid-state reference electrode, it is adaptable to the acid group content in sea water, breeding water and chemistry, chemical industry aqueous medium carries out on-line water flushing and long-term in-situ monitoring.
Description
Technical field
The present invention relates to electrochemical detection technology, particularly relate to the nitrate ion electrode with polynitrobenzene amine as sensitive membrane
And preparation method thereof.
Background technology
Nitrate anion, universally present in environment, all contains various shape as in fertilizer and pesticide, food, industrial products, water body
The nitrate of state.In water environment, the nitrate anion of excess can affect the quality of water, causes body eutrophication, to 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.It is an object of the invention to provide a class high sensitivity nitrate ion for this demand
Electrode and preparation method thereof.
Summary of the invention
It is an object of the invention to provide nitrate ion electrode with polynitrobenzene amine as sensitive membrane and preparation method thereof.
It is an object of the invention to be achieved through the following technical solutions:
Nitrate ion electrode with polynitrobenzene amine as sensitive membrane, it includes carbon substrate, and is coated on base material
Polynitrobenzene amine sensitive membrane.
Described polynitrobenzene amine be the one in ortho-nitraniline or meta nitro aniline in hydrochloric acid solution through electrochemistry
The polymer covering layer that method is formed at carbon base material surface in-situ polymerization.Ortho-nitraniline or meta nitro aniline are at aniline monomer
On be grafted with a nitrate ion.After polymerization, polyaniline after the nitrate ion on aniline monomer is pointed to polymerization
On strand, the ion selectivity of amido has an impact.Under the effect of nitrate ion, the amido on polyaniline molecule chain is to molten
Nitrate ion in liquid has high selectivity, can be accepted by reversible oxidation reduction reaction or discharge nitrate ion,
Thus the nitrate ion concentration in solution is had and can this spy respond.This is that polynitrobenzene amine can be quick as nitrate ion
The immanent cause of sense film.
Described carbon substrate (1) is carbon fiber, graphite fibre, carbon fiber, graphite rod, carbon-point, carbon film coated tinsel
In one.Described carbon fiber is natural plant fibre, such as cotton, kapok, Folium Agaves Sisalanae, abaca, Boehmeria, Caulis et Folium Lini, Fructus Cannabis, Corchorus olitorius L.
Deng being heated to 350 to 650 DEG C of carbonizing productions under anaerobic.
Carbon fiber, graphite fibre, carbon fiber have good electrical conductivity and chemical stability, are thus suitable for being used as electricity
Pole base material.
Described tinsel is the one in Cu, Ni, Ag, Co, Cd silk, and the step of carbon film coated is:
1) polyacrylonitrile is added in polar organic solvent, solution is heated to 70 to 100 DEG C and stirs until dissolving,
To the solution that concentration is 10-15% (wt), seal standby；
Described polar organic solvent is in dimethylformamide (DMF), dimethyl sulfoxide (DMSO), pyridine, Methanamide
One or several.
2) polyacrylonitrile solution is dipped with tinsel；Tinsel 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 tinsel.
The preparation method of the nitrate ion electrode with polynitrobenzene amine as sensitive membrane, it is characterised in that its step is such as
Under:
1) by a kind of hydrochloric acid solution being dissolved in 0.5 to 1.0N in ortho-nitraniline or meta nitro aniline, it is configured to
Concentration is the solution of 0.5 to 1.0 mole, and stirring, to being completely dissolved, obtains nitroaniline soiution；
2) regulation CHI760D electrochemical workstation, 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 electrode is reference electrode, at nitroaniline
Scanning 5 in solution and be recycled to 20 circulations, surface forms proton doping polynitrobenzene amine.
The nitrate ion electrode that the present invention provides is applicable to observe natural water body and chemistry, chemical process aqueous medium
Nitrate ion concentration, the manufacture method provided is simple and easy to do, with low cost.
Detailed description of the invention
Nitrate ion electrode with polynitrobenzene amine as sensitive membrane includes carbon substrate 1 and the poly-nitre being coated on base material
Base aniline sensitivities film.
Described polynitrobenzene amine be the one in ortho-nitraniline or meta nitro aniline in hydrochloric acid solution through electrochemistry
The polymer covering layer that method is formed at carbon base material surface in-situ polymerization.Ortho-nitraniline or meta nitro aniline are at aniline monomer
On be grafted with a nitrate ion.After polymerization, polyaniline after the nitrate ion on aniline monomer is pointed to polymerization
On strand, the ion selectivity of amido has an impact.Under the effect of nitrate ion, the amido on polyaniline molecule chain is to molten
Nitrate ion in liquid has high selectivity, can be accepted by reversible oxidation reduction reaction or discharge nitrate ion,
Thus the nitrate ion concentration in solution is had and can this spy respond.This is that polynitrobenzene amine can be quick as nitrate ion
The immanent cause of sense film.
Described carbon substrate (1) is carbon fiber, graphite fibre, carbon fiber, graphite rod, carbon-point, carbon film coated tinsel
In one.Described carbon fiber is natural plant fibre, such as cotton, kapok, Folium Agaves Sisalanae, abaca, Boehmeria, Caulis et Folium Lini, Fructus Cannabis, Corchorus olitorius L.
Deng being heated to 350 to 650 DEG C of carbonizing productions under anaerobic.
Carbon fiber, graphite fibre, carbon fiber have good electrical conductivity and chemical stability, are thus suitable for being used as electricity
Pole base material.Carbon fiber and carbon fibre lack rigidity, in the occasion needing electrode to have certain rigidity, it is proposed that use carbon film coated
Tinsel is as electrode base material.
Described tinsel is the one in Cu, Ni, Ag, Co, Cd silk, and the step of carbon film coated is:
1) polyacrylonitrile is added in polar organic solvent, solution is heated to 70 to 100 DEG C and stirs until dissolving,
To the solution that concentration is 10-15% (wt), seal standby；
Described polar organic solvent is in dimethylformamide (DMF), dimethyl sulfoxide (DMSO), pyridine, Methanamide
One or several.Recommend DMF.
2) polyacrylonitrile solution is dipped with tinsel；Tinsel 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 tinsel.
The carbonization of polyacrylonitrile starts from about 200 DEG C, is continued until more than 900 DEG C.At 600 to 700 DEG C of polyacrylonitrile
Cubical contraction is maximum, and weight tends towards stability, and can be considered optimal carbonization temperature.
The preparation method of the nitrate ion electrode with polynitrobenzene amine as sensitive membrane, it is characterised in that its step is such as
Under:
1) by a kind of hydrochloric acid solution being dissolved in 0.5 to 1.0N in ortho-nitraniline or meta nitro aniline, it is configured to
Concentration is the solution of 0.5 to 1.0 mole, and stirring, to being completely dissolved, obtains nitroaniline soiution.
Using the amino benzenes compounds being grafted with nitrate ion as the presoma of ion sensitive membrane, nitrate ion should
It is positioned at ortho position or the meta of amino.In the solution of preparation, the molar concentration of amino benzenes compounds and the molar concentration of hydrochloric acid are
Good equal.
2) regulation CHI760D electrochemical workstation, 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 electrode is reference electrode, at nitroaniline
Scanning 5 in solution and be recycled to 20 circulations, surface forms proton doping polynitrobenzene amine.
Electrochemical Scanning makes nitroaniline form the clad of densification at substrate surface in-situ polymerization, and is mixed by proton
Miscellaneous.Clad has good conductivity, and the high selectivity to nitrate ion.
It is described further below in conjunction with embodiment.
Embodiment 1
1) by the copper wire 1 of a length of 3 centimetres, first ultrasonic cleaning in acetone soln, remove surface and oil contaminant, then at the dilute salt of 1M
Ultrasonic cleaning in acid, removes oxide, then is dried with after deionized water ultrasonic cleaning；
2) weigh 0.75g polyacrylonitrile in 5g dimethylformamide (DMF), solution is heated to 100 DEG C and stirs straight
To dissolving, obtain the solution that concentration is 15% (wt)；
3) copper wire is inverted, dips polyacrylonitrile solution, in Muffle furnace, be warming up to 700 DEG C and constant temperature under nitrogen protection
2 hours, obtain the copper wire of carbon film coated；
4) weighing 1.281g ortho-nitraniline, be dissolved in the hydrochloric acid of 20mL 1M, the ortho-nitraniline preparing 0.5M is molten
Liquid；The copper wire electroplating surface one strata aniline 2 of carbon film it is being coated with by CHI760D electrochemical workstation cyclic voltammetry,
In three-electrode system, copper wire 1 is working electrode, and auxiliary electrode is Pt electrode, and reference electrode is business Ag/AgCl electrode, circulation volt
Peace method scanning voltage is 0-1.2V, and scanning speed is 50mV/s, and scan cycle number is 20cls.
5) with anhydrous alcohol drip washing electrode after having electroplated, remove the nitroaniline oligomer of electrode surface, treat that ethanol is waved
Send out rear stand-by.
Embodiment 2
1) by the nickel wire 1 of a length of 3 centimetres, first ultrasonic cleaning in acetone soln, remove surface and oil contaminant, then at the dilute salt of 1M
Ultrasonic cleaning in acid, removes oxide, then is dried with after deionized water ultrasonic cleaning；
2) weigh 0.75g polyacrylonitrile in 5g dimethyl sulfoxide (DMSO), solution is heated to 70 DEG C and stir until
Dissolve, obtain the solution that concentration is 15% (wt)；
3) nickel wire is inverted, dips polyacrylonitrile solution, in Muffle furnace, be warming up to 700 DEG C and constant temperature under nitrogen protection
2 hours, obtain the nickel wire of carbon film coated；
4) weighing 1.281g ortho-nitraniline, be dissolved in the hydrochloric acid of 20mL 1M, the ortho-nitraniline preparing 0.5M is molten
Liquid；The nickel wire electroplating surface one strata aniline 2 of carbon film it is being coated with by CHI760D electrochemical workstation cyclic voltammetry,
In three-electrode system, copper wire 1 is working electrode, and auxiliary electrode is Pt electrode, and reference electrode is business Ag/AgCl electrode, circulation volt
Peace method scanning voltage is 0-1.2V, and scanning speed is 50mV/s, and scan cycle number is 10cls.
5) with anhydrous alcohol drip washing electrode after having electroplated, remove the nitroaniline oligomer of electrode surface, treat that ethanol is waved
Send out rear stand-by.
Embodiment 3
1) by the filamentary silver 1 of a length of 3 centimetres, first ultrasonic cleaning in acetone soln, remove surface and oil contaminant, then at the dilute salt of 1M
Ultrasonic cleaning in acid, removes oxide, then is dried with after deionized water ultrasonic cleaning；
2) weigh 0.75g polyacrylonitrile in 5g pyridine, solution be heated to 70 DEG C and stir until dissolving, obtaining concentration
It is the solution of 15% (wt)；
3) filamentary silver is inverted, dips polyacrylonitrile solution, in Muffle furnace, be warming up to 700 DEG C and constant temperature under nitrogen protection
2 hours, obtain the filamentary silver of carbon film coated；
4) weighing 1.281g ortho-nitraniline, be dissolved in the hydrochloric acid of 20mL 1M, the ortho-nitraniline preparing 0.5M is molten
Liquid；The filamentary silver electroplating surface one strata aniline 2 of carbon film it is being coated with by CHI760D electrochemical workstation cyclic voltammetry,
In three-electrode system, copper wire 1 is working electrode, and auxiliary electrode is Pt electrode, and reference electrode is business Ag/AgCl electrode, circulation volt
Peace method scanning voltage is 0-1.2V, and scanning speed is 50mV/s, and scan cycle number is 5cls.
5) with anhydrous alcohol drip washing electrode after having electroplated, remove the nitroaniline oligomer of electrode surface, treat that ethanol is waved
Send out rear stand-by.
Embodiment 4
1) by the cobalt silk 1 of a length of 3 centimetres, first ultrasonic cleaning in acetone soln, remove surface and oil contaminant, then at the dilute salt of 1M
Ultrasonic cleaning in acid, removes oxide, then is dried with after deionized water ultrasonic cleaning；
2) weigh 0.75g polyacrylonitrile in 5g Methanamide, solution be heated to 70 DEG C and stir until dissolving, obtaining dense
Degree is the solution of 15% (wt)；
3) cobalt silk is inverted, dips polyacrylonitrile solution, in Muffle furnace, be warming up to 700 DEG C and constant temperature under nitrogen protection
2 hours, obtain the cobalt silk of carbon film coated；
4) weighing 1.281g ortho-nitraniline, be dissolved in the hydrochloric acid of 20mL 1M, the ortho-nitraniline preparing 0.5M is molten
Liquid；The cobalt silk electroplating surface one strata aniline 2 of carbon film it is being coated with by CHI760D electrochemical workstation cyclic voltammetry,
In three-electrode system, copper wire 1 is working electrode, and auxiliary electrode is Pt electrode, and reference electrode is business Ag/AgCl electrode, circulation volt
Peace method scanning voltage is 0-1.2V, and scanning speed is 50mV/s, and scan cycle number is 5cls.
5) with anhydrous alcohol drip washing electrode after having electroplated, remove the nitroaniline oligomer of electrode surface, treat that ethanol is waved
Send out rear stand-by.
Embodiment 5
1) by the cadmium wire 1 of a length of 3 centimetres, first ultrasonic cleaning in acetone soln, remove surface and oil contaminant, then at the dilute salt of 1M
Ultrasonic cleaning in acid, removes oxide, then is dried with after deionized water ultrasonic cleaning；
2) weigh 0.75g polyacrylonitrile in 5g Methanamide, solution be heated to 70 DEG C and stir until dissolving, obtaining dense
Degree is the solution of 15% (wt)；
3) cadmium wire is inverted, dips polyacrylonitrile solution, in Muffle furnace, be warming up to 700 DEG C and constant temperature under nitrogen protection
2 hours, obtain the cadmium wire of carbon film coated；
4) weighing 1.281g ortho-nitraniline, be dissolved in the hydrochloric acid of 20mL 1M, the ortho-nitraniline preparing 0.5M is molten
Liquid；The cadmium wire electroplating surface one strata aniline 2 of carbon film it is being coated with by CHI760D electrochemical workstation cyclic voltammetry,
In three-electrode system, copper wire 1 is working electrode, and auxiliary electrode is Pt electrode, and reference electrode is business Ag/AgCl electrode, circulation volt
Peace method scanning voltage is 0-1.2V, and scanning speed is 50mV/s, and scan cycle number is 20cls.
5) with anhydrous alcohol drip washing electrode after having electroplated, remove the nitroaniline oligomer of electrode surface, treat that ethanol is waved
Send out rear stand-by.
Embodiment 6
1) by the copper wire 1 of a length of 3 centimetres, first ultrasonic cleaning in acetone soln, remove surface and oil contaminant, then at the dilute salt of 1M
Ultrasonic cleaning in acid, removes oxide, then is dried with after deionized water ultrasonic cleaning；
2) weigh 0.75g polyacrylonitrile in 5g dimethylformamide (DMF), solution is heated to 100 DEG C and stirs straight
To dissolving, obtain the solution that concentration is 15% (wt)；
3) copper wire is inverted, dips polyacrylonitrile solution, in Muffle furnace, be warming up to 700 DEG C and constant temperature under nitrogen protection
2 hours, obtain the copper wire of carbon film coated；
4) weighing 1.281g meta nitro aniline, be dissolved in the hydrochloric acid of 20mL 1M, the meta nitro aniline preparing 0.5M is molten
Liquid；The copper wire electroplating surface one strata aniline 2 of carbon film it is being coated with by CHI760D electrochemical workstation cyclic voltammetry,
In three-electrode system, copper wire 1 is working electrode, and auxiliary electrode is Pt electrode, and reference electrode is business Ag/AgCl electrode, circulation volt
Peace method scanning voltage is 0-1.2V, and scanning speed is 50mV/s, and scan cycle number is 20cls.
5) with anhydrous alcohol drip washing electrode after having electroplated, remove the nitroaniline oligomer of electrode surface, treat that ethanol is waved
Send out rear stand-by.
Embodiment 7
1) by the nickel wire 1 of a length of 3 centimetres, first ultrasonic cleaning in acetone soln, remove surface and oil contaminant, then at the dilute salt of 1M
Ultrasonic cleaning in acid, removes oxide, then is dried with after deionized water ultrasonic cleaning；
2) weigh 0.75g polyacrylonitrile in 5g dimethyl sulfoxide (DMSO), solution is heated to 70 DEG C and stir until
Dissolve, obtain the solution that concentration is 15% (wt)；
3) nickel wire is inverted, dips polyacrylonitrile solution, in Muffle furnace, be warming up to 700 DEG C and constant temperature under nitrogen protection
2 hours, obtain the nickel wire of carbon film coated；
4) weighing 1.281g meta nitro aniline, be dissolved in the hydrochloric acid of 20mL 1M, the meta nitro aniline preparing 0.5M is molten
Liquid；The nickel wire electroplating surface one strata aniline 2 of carbon film it is being coated with by CHI760D electrochemical workstation cyclic voltammetry,
In three-electrode system, copper wire 1 is working electrode, and auxiliary electrode is Pt electrode, and reference electrode is business Ag/AgCl electrode, circulation volt
Peace method scanning voltage is 0-1.2V, and scanning speed is 50mV/s, and scan cycle number is 10cls.
5) with anhydrous alcohol drip washing electrode after having electroplated, remove the nitroaniline oligomer of electrode surface, treat that ethanol is waved
Send out rear stand-by.
Embodiment 8
1) by the filamentary silver 1 of a length of 3 centimetres, first ultrasonic cleaning in acetone soln, remove surface and oil contaminant, then at the dilute salt of 1M
Ultrasonic cleaning in acid, removes oxide, then is dried with after deionized water ultrasonic cleaning；
2) weigh 0.75g polyacrylonitrile in 5g pyridine, solution be heated to 70 DEG C and stir until dissolving, obtaining concentration
It is the solution of 15% (wt)；
3) filamentary silver is inverted, dips polyacrylonitrile solution, in Muffle furnace, be warming up to 700 DEG C and constant temperature under nitrogen protection
2 hours, obtain the filamentary silver of carbon film coated；
4) weighing 1.281g meta nitro aniline, be dissolved in the hydrochloric acid of 20mL 1M, the meta nitro aniline preparing 0.5M is molten
Liquid；The filamentary silver electroplating surface one strata aniline 2 of carbon film it is being coated with by CHI760D electrochemical workstation cyclic voltammetry,
In three-electrode system, copper wire 1 is working electrode, and auxiliary electrode is Pt electrode, and reference electrode is business Ag/AgCl electrode, circulation volt
Peace method scanning voltage is 0-1.2V, and scanning speed is 50mV/s, and scan cycle number is 5cls.
5) with anhydrous alcohol drip washing electrode after having electroplated, remove the nitroaniline oligomer of electrode surface, treat that ethanol is waved
Send out rear stand-by.
Embodiment 9
1) by the cobalt silk 1 of a length of 3 centimetres, first ultrasonic cleaning in acetone soln, remove surface and oil contaminant, then at the dilute salt of 1M
Ultrasonic cleaning in acid, removes oxide, then is dried with after deionized water ultrasonic cleaning；
2) weigh 0.75g polyacrylonitrile in 5g Methanamide, solution be heated to 70 DEG C and stir until dissolving, obtaining dense
Degree is the solution of 15% (wt)；
3) cobalt silk is inverted, dips polyacrylonitrile solution, in Muffle furnace, be warming up to 700 DEG C and constant temperature under nitrogen protection
2 hours, obtain the cobalt silk of carbon film coated；
4) weighing 1.281g meta nitro aniline, be dissolved in the hydrochloric acid of 20mL 1M, the meta nitro aniline preparing 0.5M is molten
Liquid；The cobalt silk electroplating surface one strata aniline 2 of carbon film it is being coated with by CHI760D electrochemical workstation cyclic voltammetry,
In three-electrode system, copper wire 1 is working electrode, and auxiliary electrode is Pt electrode, and reference electrode is business Ag/AgCl electrode, circulation volt
Peace method scanning voltage is 0-1.2V, and scanning speed is 50mV/s, and scan cycle number is 5cls.
5) with anhydrous alcohol drip washing electrode after having electroplated, remove the nitroaniline oligomer of electrode surface, treat that ethanol is waved
Send out rear stand-by.
Embodiment 10
1) by the cadmium wire 1 of a length of 3 centimetres, first ultrasonic cleaning in acetone soln, remove surface and oil contaminant, then at the dilute salt of 1M
Ultrasonic cleaning in acid, removes oxide, then is dried with after deionized water ultrasonic cleaning；
2) weigh 0.75g polyacrylonitrile in 5g Methanamide, solution be heated to 70 DEG C and stir until dissolving, obtaining dense
Degree is the solution of 15% (wt)；
3) cadmium wire is inverted, dips polyacrylonitrile solution, in Muffle furnace, be warming up to 700 DEG C and constant temperature under nitrogen protection
2 hours, obtain the cadmium wire of carbon film coated；
4) weighing 1.281g meta nitro aniline, be dissolved in the hydrochloric acid of 20mL 1M, the meta nitro aniline preparing 0.5M is molten
Liquid；The cadmium wire electroplating surface one strata aniline 2 of carbon film it is being coated with by CHI760D electrochemical workstation cyclic voltammetry,
In three-electrode system, copper wire 1 is working electrode, and auxiliary electrode is Pt electrode, and reference electrode is business Ag/AgCl electrode, circulation volt
Peace method scanning voltage is 0-1.2V, and scanning speed is 50mV/s, and scan cycle number is 20cls.
5) with anhydrous alcohol drip washing electrode after having electroplated, remove the nitroaniline oligomer of electrode surface, treat that ethanol is waved
Send out rear stand-by.
Embodiment 11
1) by the copper wire 1 of a length of 3 centimetres, first ultrasonic cleaning in acetone soln, remove surface and oil contaminant, then at the dilute salt of 1M
Ultrasonic cleaning in acid, removes oxide, then is dried with after deionized water ultrasonic cleaning；
2) weigh 0.75g polyacrylonitrile in 5g dimethyl sulfoxide (DMSO), solution is heated to 100 DEG C and stir until
Dissolve, obtain the solution that concentration is 15% (wt)；
3) copper wire is inverted, dips polyacrylonitrile solution, in Muffle furnace, be warming up to 700 DEG C and constant temperature under nitrogen protection
2 hours, obtain the copper wire of carbon film coated；
4) weighing 1.281g ortho-nitraniline, be dissolved in the hydrochloric acid of 20mL 1M, the ortho-nitraniline preparing 0.5M is molten
Liquid；The copper wire electroplating surface one strata aniline 2 of carbon film it is being coated with by CHI760D electrochemical workstation cyclic voltammetry,
In three-electrode system, copper wire 1 is working electrode, and auxiliary electrode is Pt electrode, and reference electrode is business Ag/AgCl electrode, circulation volt
Peace method scanning voltage is 0-1.2V, and scanning speed is 50mV/s, and scan cycle number is 20cls.
5) with anhydrous alcohol drip washing electrode after having electroplated, remove the nitroaniline oligomer of electrode surface, treat that ethanol is waved
Send out rear stand-by.
Embodiment 12
1) by the nickel wire 1 of a length of 3 centimetres, first ultrasonic cleaning in acetone soln, remove surface and oil contaminant, then at the dilute salt of 1M
Ultrasonic cleaning in acid, removes oxide, then is dried with after deionized water ultrasonic cleaning；
2) weigh 0.75g polyacrylonitrile in 5g pyridine, solution be heated to 70 DEG C and stir until dissolving, obtaining concentration
It is the solution of 15% (wt)；
3) nickel wire is inverted, dips polyacrylonitrile solution, in Muffle furnace, be warming up to 700 DEG C and constant temperature under nitrogen protection
2 hours, obtain the nickel wire of carbon film coated；
4) weighing 1.281g ortho-nitraniline, be dissolved in the hydrochloric acid of 20mL 1M, the ortho-nitraniline preparing 0.5M is molten
Liquid；The nickel wire electroplating surface one strata aniline 2 of carbon film it is being coated with by CHI760D electrochemical workstation cyclic voltammetry,
In three-electrode system, copper wire 1 is working electrode, and auxiliary electrode is Pt electrode, and reference electrode is business Ag/AgCl electrode, circulation volt
Peace method scanning voltage is 0-1.2V, and scanning speed is 50mV/s, and scan cycle number is 10cls.
5) with anhydrous alcohol drip washing electrode after having electroplated, remove the nitroaniline oligomer of electrode surface, treat that ethanol is waved
Send out rear stand-by.
Embodiment 13
1) by the filamentary silver 1 of a length of 3 centimetres, first ultrasonic cleaning in acetone soln, remove surface and oil contaminant, then at the dilute salt of 1M
Ultrasonic cleaning in acid, removes oxide, then is dried with after deionized water ultrasonic cleaning；
2) weigh 0.75g polyacrylonitrile in 5g Methanamide, solution be heated to 70 DEG C and stir until dissolving, obtaining dense
Degree is the solution of 15% (wt)；
3) filamentary silver is inverted, dips polyacrylonitrile solution, in Muffle furnace, be warming up to 700 DEG C and constant temperature under nitrogen protection
2 hours, obtain the filamentary silver of carbon film coated；
4) weighing 1.281g ortho-nitraniline, be dissolved in the hydrochloric acid of 20mL 1M, the ortho-nitraniline preparing 0.5M is molten
Liquid；The filamentary silver electroplating surface one strata aniline 2 of carbon film it is being coated with by CHI760D electrochemical workstation cyclic voltammetry,
In three-electrode system, copper wire 1 is working electrode, and auxiliary electrode is Pt electrode, and reference electrode is business Ag/AgCl electrode, circulation volt
Peace method scanning voltage is 0-1.2V, and scanning speed is 50mV/s, and scan cycle number is 5cls.
5) with anhydrous alcohol drip washing electrode after having electroplated, remove the nitroaniline oligomer of electrode surface, treat that ethanol is waved
Send out rear stand-by.
Embodiment 14
1) by the cobalt silk 1 of a length of 3 centimetres, first ultrasonic cleaning in acetone soln, remove surface and oil contaminant, then at the dilute salt of 1M
Ultrasonic cleaning in acid, removes oxide, then is dried with after deionized water ultrasonic cleaning；
2) weigh 0.75g polyacrylonitrile in 5g dimethylformamide (DMF), solution is heated to 70 DEG C and stir until
Dissolve, obtain the solution that concentration is 15% (wt)；
3) cobalt silk is inverted, dips polyacrylonitrile solution, in Muffle furnace, be warming up to 700 DEG C and constant temperature under nitrogen protection
2 hours, obtain the cobalt silk of carbon film coated；
4) weighing 1.281g meta nitro aniline, be dissolved in the hydrochloric acid of 20mL 1M, the meta nitro aniline preparing 0.5M is molten
Liquid；The cobalt silk electroplating surface one strata aniline 2 of carbon film it is being coated with by CHI760D electrochemical workstation cyclic voltammetry,
In three-electrode system, copper wire 1 is working electrode, and auxiliary electrode is Pt electrode, and reference electrode is business Ag/AgCl electrode, circulation volt
Peace method scanning voltage is 0-1.2V, and scanning speed is 50mV/s, and scan cycle number is 5cls.
5) with anhydrous alcohol drip washing electrode after having electroplated, remove the nitroaniline oligomer of electrode surface, treat that ethanol is waved
Send out rear stand-by.
Embodiment 15
1) by the cadmium wire 1 of a length of 3 centimetres, first ultrasonic cleaning in acetone soln, remove surface and oil contaminant, then at the dilute salt of 1M
Ultrasonic cleaning in acid, removes oxide, then is dried with after deionized water ultrasonic cleaning；
2) weigh 0.75g polyacrylonitrile in 5g dimethyl sulfoxide (DMSO), solution is heated to 70 DEG C and stir until
Dissolve, obtain the solution that concentration is 15% (wt)；
3) cadmium wire is inverted, dips polyacrylonitrile solution, in Muffle furnace, be warming up to 700 DEG C and constant temperature under nitrogen protection
2 hours, obtain the cadmium wire of carbon film coated；
4) weighing 1.281g ortho-nitraniline, be dissolved in the hydrochloric acid of 20mL 1M, the ortho-nitraniline preparing 0.5M is molten
Liquid；The cadmium wire electroplating surface one strata aniline 2 of carbon film it is being coated with by CHI760D electrochemical workstation cyclic voltammetry,
In three-electrode system, copper wire 1 is working electrode, and auxiliary electrode is Pt electrode, and reference electrode is business Ag/AgCl electrode, circulation volt
Peace method scanning voltage is 0-1.2V, and scanning speed is 50mV/s, and scan cycle number is 20cls.
5) with anhydrous alcohol drip washing electrode after having electroplated, remove the nitroaniline oligomer of electrode surface, treat that ethanol is waved
Send out rear stand-by.
Embodiment 16
1) kapok of 4 centimetres of 400 DEG C of carbonizations under anaerobic is measured as carbon substrate to be plated；
2) weighing 1.281g ortho-nitraniline, be dissolved in the hydrochloric acid of 20mL 1M, the ortho-nitraniline preparing 0.5M is molten
Liquid；The copper wire electroplating surface one strata aniline 2 of carbon film it is being coated with by CHI760D electrochemical workstation cyclic voltammetry,
In three-electrode system, copper wire 1 is working electrode, and auxiliary electrode is Pt electrode, and reference electrode is business Ag/AgCl electrode, circulation volt
Peace method scanning voltage is 0-1.2V, and scanning speed is 50mV/s, and scan cycle number is 10cls.
3) with anhydrous alcohol drip washing electrode after having electroplated, remove the nitroaniline oligomer of electrode surface, treat that ethanol is waved
Send out rear stand-by.
Embodiment 17
1) carbon fiber of 4 centimetres of 400 DEG C of carbonizations under anaerobic is measured as carbon substrate to be plated；
2) weighing 1.281g meta nitro aniline, be dissolved in the hydrochloric acid of 20mL 1M, the meta nitro aniline preparing 0.5M is molten
Liquid；The copper wire electroplating surface one strata aniline 2 of carbon film it is being coated with by CHI760D electrochemical workstation cyclic voltammetry,
In three-electrode system, copper wire 1 is working electrode, and auxiliary electrode is Pt electrode, and reference electrode is business Ag/AgCl electrode, circulation volt
Peace method scanning voltage is 0-1.2V, and scanning speed is 50mV/s, and scan cycle number is 10cls.
3) with anhydrous alcohol drip washing electrode after having electroplated, remove the nitroaniline oligomer of electrode surface, treat that ethanol is waved
Send out rear stand-by.
Embodiment 18
1) graphite fibre of 4 centimetres of 400 DEG C of carbonizations under anaerobic is measured as carbon substrate to be plated；
2) weighing 1.281g meta nitro aniline, be dissolved in the hydrochloric acid of 20mL 1M, the meta nitro aniline preparing 0.5M is molten
Liquid；The copper wire electroplating surface one strata aniline 2 of carbon film it is being coated with by CHI760D electrochemical workstation cyclic voltammetry,
In three-electrode system, copper wire 1 is working electrode, and auxiliary electrode is Pt electrode, and reference electrode is business Ag/AgCl electrode, circulation volt
Peace method scanning voltage is 0-1.2V, and scanning speed is 50mV/s, and scan cycle number is 20cls.
3) with anhydrous alcohol drip washing electrode after having electroplated, remove the nitroaniline oligomer of electrode surface, treat that ethanol is waved
Send out rear stand-by.
Claims (7)
1. the nitrate ion electrode with polynitrobenzene amine as sensitive membrane, it is characterised in that it includes carbon substrate (1), polynitrobenzene
Amine (2).
2. the nitrate ion electrode with polynitrobenzene amine as sensitive membrane, it is characterised in that described polynitrobenzene amine is adjacent nitro
A kind of in aniline or meta nitro aniline in hydrochloric acid solution through electrochemical method carbon base material surface in-situ polymerization formed poly-
Compound clad.
Nitrate ion electrode with polynitrobenzene amine as sensitive membrane the most according to claim 1, it is characterised in that described
Carbon substrate (1) be the one in carbon fiber, graphite fibre, carbon fiber, graphite rod, carbon-point, carbon film coated tinsel.
Nitrate ion electrode with polynitrobenzene amine as sensitive membrane the most according to claim 3, it is characterised in that described
Carbon fiber be natural plant fibre, including cotton, kapok, Folium Agaves Sisalanae, abaca, Boehmeria, Caulis et Folium Lini, Fructus Cannabis, Corchorus olitorius L., at oxygen free condition
Under be heated to the carbonizing production of 350 to 650 DEG C.
Nitrate ion electrode with polynitrobenzene amine as sensitive membrane the most according to claim 3, it is characterised in that described
Tinsel be the one in Cu, Ni, Ag, Co, Cd silk, the step of carbon film coated is:
1) polyacrylonitrile is added in polar organic solvent, solution be heated to 70 to 100 DEG C and stir until dissolving, obtaining dense
Degree is the solution of 10-15% (wt), seals standby；
2) polyacrylonitrile solution is dipped with tinsel；By tinsel be 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 tinsel.
Nitrate ion electrode with polynitrobenzene amine as sensitive membrane the most according to claim 5, it is characterised in that described
Polar organic solvent be one or several in dimethylformamide (DMF), dimethyl sulfoxide (DMSO), pyridine, Methanamide.
7. the preparation method of the nitrate ion electrode with polynitrobenzene amine as sensitive membrane, it is characterised in that its step is such as
Under:
1) by a kind of hydrochloric acid solution being dissolved in 0.5 to 1.0N in ortho-nitraniline or meta nitro aniline, it is configured to concentration
Being the solution of 0.5 to 1.0 mole, stirring, to being completely dissolved, obtains nitroaniline soiution；
2) regulation CHI760D electrochemical workstation, parameter is: cyclic voltammetry, scanning voltage 0-1.2V, sensitivity 10-3A；With
Carbon substrate to be plated is as working electrode, and platinum electrode is auxiliary electrode, and Ag/AgCl electrode is reference electrode, at nitroaniline soiution
Middle scanning 5 is recycled to 20 circulations, and surface forms proton doping polynitrobenzene amine.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN111146013A (en) * | 2020-01-10 | 2020-05-12 | 厦门理工学院 | Hollow micro-tube electrode material based on ramie, and synthesis method and application thereof |
| CN111458752A (en) * | 2019-01-21 | 2020-07-28 | 中国海洋大学 | High-sensitivity electric field sensor composed of polyamine molecule modified carbon fiber |
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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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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN111458752A (en) * | 2019-01-21 | 2020-07-28 | 中国海洋大学 | High-sensitivity electric field sensor composed of polyamine molecule modified carbon fiber |
| CN111146013A (en) * | 2020-01-10 | 2020-05-12 | 厦门理工学院 | Hollow micro-tube electrode material based on ramie, and synthesis method and application thereof |
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