CN109164151A - A kind of CoNiO of trace detection copper ion2The method of nanometer-material-modified glass-carbon electrode - Google Patents
A kind of CoNiO of trace detection copper ion2The method of nanometer-material-modified glass-carbon electrode Download PDFInfo
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Abstract
The present invention relates to a kind of CoNiO of trace detection copper ion2The salting liquid of Co, Ni ion and sodium hydroxide hybrid reaction are first generated precipitating by the method for nanometer-material-modified glass-carbon electrode, this method, then by its hydro-thermal at a certain temperature, complete Co, Ni bimetallic material of hydro-thermal are carried out microwave treatment again, obtains CoNiO2Nano material.Finally, dispersed modification is used for heavy metal copper ion detection on glass-carbon electrode.This method is not only able to achieve the highly selective detection to copper ion, but also has many advantages, such as that detection sensitivity is high, stability is good, anti-interference is high, the detection range of linearity is wide.This method substitutes traditional calcination method with microwave method, to solve the problems such as conventional calcination method granularity topographic profile is uneven, manufacturing cycle is too long and energy consumption is serious, provides a kind of excellent effect, new way easy to promote and utilize.
Description
Technical field
The present invention relates to Electrochemical Detection technical field of nano material, and in particular to a kind of trace detection copper ion
CoNiO2The method of nanometer-material-modified glass-carbon electrode.
Background technique
Copper is more toxic unicellular lower eukaryote and crops, and mass concentration can make fish dead up to 0.1-0.2mg/L, with
Toxicity can increase when zinc coexists, bigger to testacean aquatics toxicity, and general fisheries water requires the mass concentration of copper to exist
0.01mg/L or less.For crops, copper is heavy metal poisoning soprano, after plant absorption copper ion, is fixed on root skin
Layer, influences Nutrient Absorption.It when cupric is higher in irrigation water, i.e., is accumulated in soil and crop, crops can be made withered.
Currently, the conventional method for detecting heavy metal copper ion mainly has Atomic fluorophotometry, atomic absorption spectrum
Method, inductively coupled plasma atomic emission, inductively coupled plasma mass spectrometry, high performance liquid chromatography, ultraviolet-visible
The methods of spectrometry.Problem of the prior art and defect: although the above-mentioned method referred to has preferable selectivity and higher spirit
Sensitivity, but equipment required for these methods is expensive, equipment volume is big, is unfavorable for carrying, and prepares the sample consumption time
Long, equipment operation is complicated, professional is needed to detect and may not apply to real-time online detection heavy metal copper ion.Electrochemistry
Stripping voltammetry, since with high sensitivity, shirtsleeve operation, low cost, low detection limit, quickly response etc. is excellent
Point can overcome traditional technology problem encountered, be a kind of promising method for being applied to detection micro heavy copper ion.
And in various Electrochemical Stripping voltammetric methods, DPASV differential pulse anodic stripping voltammetry sensitivity is higher, is more suitably applied to weight
Metal copper ion detection.
Electrochemistry DPASV differential pulse anodic stripping voltammetry detection heavy metal copper ion, including copper ion are rich on the working electrode (s
Two processes of collection and dissolution, therefore modified electrode material is in terms of the detection heavy metal copper ionic nature for improving electrochemical sensor
Play important role.Currently used modified electrode material has graphene, multi-walled carbon nanotube, metal nano ion, gold
Category oxide etc., however the sensor based on the preparation of these above-mentioned materials do not obtain the performance of detection heavy metal copper ion
It is improved to apparent, and materials synthesis is complicated and at high cost thus limit their practical application.In order to improve sensor
Performance and actual application ability, simple, low cost that therefore, it is necessary to researching and designing synthetic methods has high-specific surface area, is good
Catalytic performance and the material of electric conductivity be applied to detection heavy metal copper ion as modified electrode material.
And traditional modified electrode material, such as mercury film, bismuth film, antimony film because its environment it is unfriendly and expensive
The problems such as, thus many researchers be dedicated to it is nonmetallic be applied to detection of heavy metal ion.This patent first passage microwave method
Synthesize CoNiO2Nano material substitutes traditional calcination method using microwave method, can high degree save energy consumption, simultaneously
The CoNiO that microwave method is prepared2Nanometer has the characteristics that material morphology is uniform, even particle size distribution.
Therefore, microwave method is a kind of novel chemical method for preparing nm-class, shows that beyond tradition is calcined
The many advantages of method, including synthesis cycle is short, low energy consumption, material internal crystalline texture is more uniform, consistency is higher, improves
The performance of material；It realizes selective sintering, generates the material with new microstructure and excellent performance.
Summary of the invention
Present invention aims at provide a kind of CoNiO of trace detection copper ion2The side of nanometer-material-modified glass-carbon electrode
The salting liquid of Co, Ni ion and sodium hydroxide hybrid reaction are first generated precipitating by method, this method, then by its water at a certain temperature
Complete Co, Ni bimetallic material of hydro-thermal is carried out microwave treatment again, obtains CoNiO by heat2Nano material, then dispersed modification
Heavy metal copper ion detection is used on glass-carbon electrode.The method of the invention is not only able to achieve the highly selective inspection to copper ion
It surveys, and has many advantages, such as that detection sensitivity is high, stability is good, anti-interference is high, the detection range of linearity is wide.Side of the present invention
Method substitutes traditional calcination method with microwave method, and to solve, conventional calcination method granularity topographic profile is uneven, manufacturing cycle
The problems such as too long and energy consumption is serious, provides a kind of excellent effect, new way easy to promote and utilize.
A kind of CoNiO of trace detection copper ion of the present invention2The method of nanometer-material-modified glass-carbon electrode, is pressed
Column step carries out:
Hydro-thermal method prepares hydroxide:
A, 1:1 weighs nickel nitrate and cobalt nitrate mixing in molar ratio, is dissolved in deionized water, uniform stirring, is configured to dense
Range is spent in the mixed solution of 0.1-5mol/L；
B, sodium hydroxide is weighed by the molar ratio 1.2:1 of sodium hydroxide and nickel nitrate and cobalt nitrate mixture again, and be made into
Concentration range then the solution of preparation is added dropwise in the mixed solution that step a is obtained in the solution of 0.1-5mol/L, at room temperature
Magnetic agitation 1-3h, then 12-48h is staticly settled, filtering and washing to neutrality dries 6-12h at 50-100 DEG C of temperature, is sunk
It forms sediment；
C, the precipitating for obtaining step b is dispersed in the polyvinylpyrrolidone deionized water containing 0.5-8wt%, magnetic force
1-3h is stirred, is put into 100mL high pressure water heating kettle, in 50-80%, hydrothermal temperature is 100-200 DEG C for packing ratio control, when reaction
Between to carry out hydrothermal synthesis under 6-24h, resulting powder will be reacted and be washed with deionized 2-3 time, dry, grinding is to get hydrogen
Oxide；
Microwave method prepares CoNiO2Nano material:
D, the hydroxide for obtaining step c carries out microwave heating treatment 10-30 minutes under 480-800W power, then grinds
Honed sieve, obtains CoNiO2Modified electrode material；
Dispersion method prepares CoNiO2/ Nafion modified glassy carbon electrode:
E, the CoNiO for obtaining step d2Being dispersed in concentration is 1-10mg/mL, and the mass fraction of Nafion is 0.1-
In dehydrated alcohol-Nafion solution of 1wt%, ultrasonic disperse 1h is configured to CoNiO2The modification of/Nafion nano material electrode is molten
Liquid；
F, the aluminium oxide powder for successively using glass-carbon electrode partial size to be 50nm for 1-0.3 μm and partial size carries out at polishing
Reason, is then successively ultrasonically treated in second alcohol and water, is finally dried in a nitrogen atmosphere, and pretreated glass carbon electricity is obtained
Pole；
G, the obtained CoNiO of step e will be instilled on the obtained glass-carbon electrode of step f2/ Nafion nano material electrode is repaired
Solution is adornd, dripping quantity is 5-20 μ L, and naturally dry obtains CoNiO2/ Nafion modified glassy carbon electrode；
Ultra trace copper ion Electrochemical Detection:
H, electrochemistry detecting apparatus by electrochemical workstation, electrolytic cell, magnetic stirring apparatus, working electrode, to electrode and ginseng
It is formed than electrode；It is used as using platinum filament to electrode, for silver/silver chlorate as reference electrode, it is base that working electrode, which is by glass-carbon electrode,
Bottom, CoNiO2The glass-carbon electrode of/Nafion modification is working electrode；Using differential pulse anodic stripping voltammetry, detection parameters
Are as follows: accumulating potential is set as -0.8--1.5V, and enrichment time is set as 80-200s, scans current potential 1-50mV/s, scanning range X
For -1.5-0.4V, for detecting copper ion.
Electrolyte in step h in electrolytic cell is Cu to be measured2+Acetic acid-sodium acetate and ammonium hydroxide-ammonium chloride buffer solution, delay
The pH range for rushing solution is 3.5-8.0, Cu2+Concentration Testing range is 0.1-1000 μ g/L, and detection is limited to 0.1-1.0 μ g/L.
Detailed description of the invention
Fig. 1 is CoNiO prepared by the embodiment of the present invention 12X-ray diffraction characterization；
Fig. 2 is that the differential pulse anodic stripping voltammetry of 2 electrochemical sensor analysis detection copper ion of the embodiment of the present invention is bent
Line.
Specific embodiment
Embodiment 1
Hydro-thermal method prepares hydroxide:
A, nickel nitrate and cobalt nitrate mixing are weighed for 1:1 in molar ratio, be dissolved in deionized water, uniform stirring is configured to
0.1mol/L mixed solution；
It b, is that 1.2:1 weighs sodium hydroxide, and is made into dense according still further to the molar ratio of sodium hydroxide and nickel nitrate and cobalt nitrate
The solution of 0.1mol/L is spent, then the solution of preparation is added dropwise in the mixed solution that step a is obtained, at room temperature magnetic agitation
1h, then 12h is staticly settled, filtering and washing to neutrality is dried 6h under temperature 50 C, is precipitated；
C, the precipitating for obtaining step b is dispersed in the polyvinylpyrrolidone deionized water containing 0.5wt%, and magnetic force stirs
Mix 1h, be put into 100mL high pressure water heating kettle, 50%, hydrothermal temperature is 100 DEG C for packing ratio control, the reaction time be under 6h into
Row hydrothermal synthesis will react resulting powder and be washed with deionized 2 times, dry, grind to get hydroxide；
Microwave method prepares CoNiO2Nano material:
D, the hydroxide for obtaining step c carries out microwave heating treatment 10 minutes under 480W power, then is ground up, sieved,
Obtain CoNiO2Modified electrode material；
Dispersion method prepares CoNiO2/ Nafion modified glassy carbon electrode:
E, the CoNiO for obtaining step d2It is 1mg/mL, the mass fraction of Nafion that modified electrode material, which is dispersed in concentration,
For in dehydrated alcohol-Nafion solution of 0.1wt%, ultrasonic disperse 1h is configured to CoNiO2/ Nafion nano material electrode is repaired
Adorn solution；
F, the aluminium oxide powder for successively using glass-carbon electrode partial size to be 50nm for 1-0.3 μm and partial size carries out at polishing
Reason, is then successively ultrasonically treated in second alcohol and water, is finally dried in a nitrogen atmosphere, and pretreated glass carbon electricity is obtained
Pole；
G, the obtained CoNiO of step e will be instilled on the obtained glass-carbon electrode of step f2/ Nafion nano material electrode is repaired
Solution is adornd, dripping quantity is 5 μ L, and naturally dry obtains CoNiO2/ Nafion modified glassy carbon electrode；
Ultra trace copper ion Electrochemical Detection:
H, electrochemistry detecting apparatus by electrochemical workstation, electrolytic cell, magnetic stirring apparatus, working electrode, to electrode and ginseng
It is formed than electrode；It is used as using platinum filament to electrode, for silver/silver chlorate as reference electrode, it is base that working electrode, which is by glass-carbon electrode,
Bottom, CoNiO2The glass-carbon electrode of/Nafion modification is working electrode；Using differential pulse anodic stripping voltammetry, detection parameters
Are as follows: accumulating potential is set as -0.8V, and enrichment time is set as 80s, scans current potential 1mV/s, and scanning range X is -0.8-0.4V,
Electrolyte in electrolytic cell is Cu to be measured2+Acetic acid-sodium acetate and ammonium hydroxide-ammonium chloride buffer solution, the pH of buffer solution is
3.5, detect copper ion:
By the CoNiO of preparation2The glass-carbon electrode of/Nafion modification, is immersed in one end of electrode respectively and contains reference electrode
Have in the NaAc_HAc buffer solution (pH=3.5) of copper ion to be measured, the other end of each of three electrodes is connected to electrochemical operation
It stands, differential pulse anodic stripping voltammetry technology is selected on electrochemical workstation, accumulating potential is set as -0.8V, when enrichment
Between be set as 80s, electrolytic cell is placed on electric mixer, in electrolytic cell place a stirrer, be arranged electric stirring
The mixing speed of device is 500rpm/min, by running i-t enrichment on electrochemical workstation, after running enrichment time,
Copper ion to be measured can be enriched on the working electrode for having modified electrolyte, complete CoNiO2The preparation of/Nafion modified electrode
And the enrichment of copper ion to be measured, then by electrochemical workstation record current-voltage situation of change, current -voltage curve is obtained,
The Anodic Stripping peak current under different copper ion concentrations is measured, the differential pulse anodic stripping voltammetry curve of copper ion is recorded, it is right
The relationship dissolved out between peak current and copper ion concentration carries out linear fit, obtains between copper ion concentration and dissolution peak current
Linear equation, for the concentration of quantitative detection copper ion to be measured, the linear detection range for detecting copper ion is 100-1000 μ g/L,
The detection limit (SN=3) of copper ion is 0.5 μ g/L, and the drinking water standard lower than the World Health Organization requires (1 μ g/L)；
The result shows that: the linearly increasing copper ion for showing the sensing electrode and capable of successfully detecting unknown concentration of peak current, it should
Modified electrode has good linear dependence, the wider range of linearity, higher sensitivity and lower detection limit to copper ion.
Embodiment 2
Hydro-thermal method prepares hydroxide:
A, it is that 1:1 weighs nickel nitrate and cobalt nitrate mixes according to molar ratio, is dissolved in deionized water, uniform stirring, prepares
At 3mol/L mixed solution；
It b, is that 1.2:1 weighs sodium hydroxide, and is made into dense according still further to the molar ratio of sodium hydroxide and nickel nitrate and cobalt nitrate
The solution of 3mol/L is spent, then the solution of preparation is added dropwise in the mixed solution that step a is obtained, at room temperature magnetic agitation 2h,
It staticly settles again for 24 hours, filtering and washing to neutrality, dries 10h at 80 DEG C of temperature, precipitated；
C, the precipitating for obtaining step b is dispersed in the polyvinylpyrrolidone deionized water containing 4wt%, magnetic agitation
2h is put into 100mL high pressure water heating kettle, and 70%, hydrothermal temperature is 140 DEG C for packing ratio control, and the reaction time is to carry out under 12h
Hydrothermal synthesis will react resulting powder and be washed with deionized 3 times, dry, grind to get hydroxide；
Microwave method prepares CoNiO2Nano material:
D, the hydroxide for obtaining step c carries out microwave heating treatment 20 minutes under 640W power, then is ground up, sieved,
Obtain CoNiO2Modified electrode material；
C, dispersion method prepares CoNiO2/ Nafion modified glassy carbon electrode material: by CoNiO2Being dispersed in concentration is 4mg/mL,
The mass fraction of Nafion is in the ethyl alcohol-Nafion of 0.5wt%, and ultrasonic disperse 1h is configured to CoNiO2The electricity of nano material
Solution is modified in pole；
Dispersion method prepares CoNiO2/ Nafion modified glassy carbon electrode:
E, the CoNiO for obtaining step d2It is 4mg/mL, the mass fraction of Nafion that modified electrode material, which is dispersed in concentration,
For in the dehydrated alcohol-Nafion of 0.5wt%, ultrasonic disperse 1h is configured to CoNiO2The electrode modification solution of nano material；
F, the aluminium oxide powder for successively using glass-carbon electrode partial size to be 50nm for 1-0.3 μm and partial size carries out at polishing
Reason, is then successively ultrasonically treated in second alcohol and water, is finally dried in a nitrogen atmosphere, and pretreated glass carbon electricity is obtained
Pole；
G, the obtained CoNiO of step e will be instilled on the obtained glass-carbon electrode of step f2/ Nafion nano material electrode is repaired
Solution is adornd, dripping quantity is 10 μ L, and naturally dry obtains CoNiO2/ Nafion modified glassy carbon electrode；
Ultra trace copper ion Electrochemical Detection:
H, electrochemistry detecting apparatus by electrochemical workstation, electrolytic cell, magnetic stirring apparatus, working electrode, to electrode and ginseng
It is formed than electrode；It is used as using platinum filament to electrode, for silver/silver chlorate as reference electrode, it is base that working electrode, which is by glass-carbon electrode,
Bottom, CoNiO2The glass-carbon electrode of/Nafion modification is working electrode；Using differential pulse anodic stripping voltammetry, detection parameters
Are as follows: accumulating potential is set as -1.2V, and enrichment time is set as 150s, scans current potential 10mV/s, and scanning range X is -0.25-
0.25V, the electrolyte in electrolytic cell are Cu to be measured2+Acetic acid-sodium acetate and ammonium hydroxide-ammonium chloride buffer solution, buffer solution
PH is 5, detects copper ion:
By the CoNiO of preparation2The glass-carbon electrode of/Nafion modification, is immersed in one end of electrode respectively and contains reference electrode
Have in the NaAc_HAc buffer solution (pH=5) of copper ion to be measured, the other end of each of three electrodes is connected to electrochemical operation
It stands, differential pulse anodic stripping voltammetry technology is selected on electrochemical workstation, accumulating potential is set as -1.2V, when enrichment
Between be set as 150s, electrolytic cell is placed on electric mixer, in electrolytic cell place a stirrer, be arranged electric stirring
The mixing speed of device is 500rpm/min, by running i-t enrichment on electrochemical workstation, after running enrichment time,
Copper ion to be measured can be enriched on the working electrode for having modified electrolyte, complete CoNiO2The preparation of/Nafion modified electrode
And the enrichment of copper ion to be measured, then by electrochemical workstation record current-voltage situation of change, current -voltage curve is obtained,
The Anodic Stripping peak current under different copper ion concentrations is measured, the differential pulse anodic stripping voltammetry curve of copper ion is recorded, it is right
The relationship dissolved out between peak current and copper ion concentration carries out linear fit, obtains between copper ion concentration and dissolution peak current
Linear equation, for the concentration of quantitative detection copper ion to be measured, the linear detection range for detecting copper ion is 0.1-100 μ g/L,
The detection limit (SN=3) of copper ion is 0.1 μ g/L, and the drinking water standard lower than the World Health Organization requires (1 μ g/L)；
The result shows that: the linearly increasing copper ion for showing the sensing electrode and capable of successfully detecting unknown concentration of peak current, it should
Modified electrode has good linear dependence, the wider range of linearity, higher sensitivity and lower detection limit to copper ion.
Embodiment 3
Hydro-thermal method prepares hydroxide:
A, nickel nitrate and cobalt nitrate mixing are weighed for 1:1 in molar ratio, be dissolved in deionized water, uniform stirring is configured to
5mol/L mixed solution；
It b, is again that 1.2:1 weighs sodium hydroxide, and is made into concentration by the molar ratio of sodium hydroxide and nickel nitrate and cobalt nitrate
The solution of 5mol/L, then the solution of preparation is added dropwise in the mixed solution that step a is obtained, magnetic agitation 3h at room temperature, then
48h is staticly settled, filtering and washing to neutrality is dried 12h at 100 DEG C of temperature, precipitated；
C, the precipitating for obtaining step b is dispersed in the polyvinylpyrrolidone deionized water containing 8wt%, magnetic agitation
3h is put into 100mL high pressure water heating kettle, and 80%, hydrothermal temperature is 200 DEG C for packing ratio control, and the reaction time is lower for 24 hours carry out
Hydrothermal synthesis will react resulting powder and be washed with deionized 3 times, dry, grind to get hydroxide；
Microwave method prepares CoNiO2Nano material:
D, the hydroxide for obtaining step c carries out microwave heating treatment 30 minutes under 800W power, then is ground up, sieved,
Obtain CoNiO2Modified electrode material；
B, microwave method prepares CoNiO2Nano material: microwave heating treatment is carried out under 800W power to above-mentioned hydroxide
30min, then be ground up, sieved, obtain CoNiO2Modified electrode material；
C, dispersion method prepares CoNiO2/ Nafion modified glassy carbon electrode material: will.
Dispersion method prepares CoNiO2/ Nafion modified glassy carbon electrode:
E, the CoNiO for obtaining step d2It is 10mg/mL, the mass fraction of Nafion that modified electrode material, which is dispersed in concentration,
For in the ethyl alcohol-Nafion of 1wt%, ultrasonic disperse 1h is configured to CoNiO2The electrode modification solution of nano material；
F, the aluminium oxide powder for successively using glass-carbon electrode partial size to be 50nm for 1-0.3 μm and partial size carries out at polishing
Reason, is then successively ultrasonically treated in second alcohol and water, is finally dried in a nitrogen atmosphere, and pretreated glass carbon electricity is obtained
Pole；
G, the obtained CoNiO of step e will be instilled on the obtained glass-carbon electrode of step f2/ Nafion nano material electrode is repaired
Solution is adornd, dripping quantity is 20 μ L, and naturally dry obtains CoNiO2/ Nafion modified glassy carbon electrode；
Ultra trace copper ion Electrochemical Detection:
H, electrochemistry detecting apparatus by electrochemical workstation, electrolytic cell, magnetic stirring apparatus, working electrode, to electrode and ginseng
It is formed than electrode；It is used as using platinum filament to electrode, for silver/silver chlorate as reference electrode, it is base that working electrode, which is by glass-carbon electrode,
Bottom, CoNiO2The glass-carbon electrode of/Nafion modification is working electrode；Using differential pulse anodic stripping voltammetry, detection parameters
Are as follows: accumulating potential is set as -1.5V, and enrichment time is set as 200s, scans current potential 50mV/s, and scanning range X is -1.5-
0.1V, the electrolyte in electrolytic cell are Cu to be measured2+Acetic acid-sodium acetate and ammonium hydroxide-ammonium chloride buffer solution, the pH of buffer solution
It is 8.0, detects copper ion:
By the CoNiO of preparation2The glass-carbon electrode of/Nafion modification, is immersed in one end of electrode respectively and contains reference electrode
Have in ammonium hydroxide-ammonium chloride buffer solution system (pH=8) of copper ion to be measured, the other end of each of three electrodes is connected to electrochemistry work
It stands.Differential pulse anodic stripping voltammetry technology is selected on electrochemical workstation, accumulating potential is set as -1.5V, is enriched with
Time is set as 200s, and electrolytic cell is placed on electric mixer, and a stirrer is placed in electrolytic cell, and electric mixing is arranged
The mixing speed for mixing device is 500rpm/min, and by running i-t enrichment on electrochemical workstation, operation enrichment time terminates
Afterwards, copper ion to be measured can be enriched on the working electrode for having modified electrolyte, complete CoNiO2The system of/Nafion modified electrode
The enrichment of copper ion standby and to be measured, then by electrochemical workstation record current-voltage situation of change, obtain current-voltage song
Line measures the Anodic Stripping peak current under different copper ion concentrations, records the differential pulse anodic stripping voltammetry curve of copper ion,
Linear fit is carried out to the relationship between dissolution peak current and copper ion concentration, is obtained between copper ion concentration and dissolution peak current
Linear equation, for the concentration of quantitative detection copper ion to be measured, the linear detection range for detecting copper ion is 30-500 μ g/L,
The detection limit (SN=3) of copper ion is 1.0 μ g/L, and the drinking water standard lower than the World Health Organization requires (1 μ g/L)；
The result shows that: the linearly increasing copper ion for showing the sensing electrode and capable of successfully detecting unknown concentration of peak current, it should
Modified electrode has good linear dependence, the wider range of linearity, higher sensitivity and lower detection limit to copper ion.
Embodiment 4
Working electrode (the CoNiO of embodiment 1- embodiment 32/ Nafion modified glassy carbon electrode) anti-interference capability testing:
By CoNiO2The glass-carbon electrode of/Nafion modification, is immersed in respectively containing 50 μ one end of electrode reference electrode
In the NaAc_HAc buffer solution (pH=5.0) of g/L copper ion, interfering ion, copper then are added into test solution respectively
Ion release peak current is compared to variation when being not added with interfering ion, and interfering ion has 500 times of copper ion concentration respectively
Ca2+, 200 times of Mg2+, 10 times of Cd3+, 10 times of Pb2+, 2 times of Hg2+, 2 times of Zn2+；
The other end of each of three electrodes is connected to electrochemical workstation, selects differential pulse anode molten on electrochemical workstation
Voltammetric techniques out, accumulating potential are set as -1.2V, and enrichment time is set as 120s, and electrolytic cell is placed into electric mixer
On, a stirrer is placed in electrolytic cell, the mixing speed that electric mixer is arranged is 500rpm/min, by electrochemistry
I-t enrichment is run on work station, after running enrichment time, copper ion to be measured can be enriched to the work electricity for having modified electrolyte
On extremely, the enrichment of copper ion to be measured is completed；Again by electrochemical workstation record current-voltage situation of change, electric current-is obtained
Voltage curve measures the Anodic Stripping peak current under different copper ion concentrations, records the differential pulse Anodic Stripping volt of copper ion
Pacify curve, linear fit is carried out to the relationship between dissolution peak current and copper ion concentration, obtains copper ion concentration and dissolution peak
Linear equation between electric current measures under disturbance ion interference, copper ion Anodic Stripping peak current situation of change, and 6 kinds dry
The influence of differential pulse anodic stripping voltammetry dissolution peak current variation of ion pair copper ion is disturbed all within 5%；
The Performance Evaluation of electrochemical sensor detection copper ion: CoNiO2The glass-carbon electrode of/Nafion modification is to copper ion
With very strong selectivity, and to Ca2+, Mg2+, Zn2+, Cr3+, Pb2+,Hg2+Plasma has strong anti-interference ability；I.e.
Make in various zwitterions, such as Cl-,NO3 -, H2PO4 -,SO4 2-Etc. in simultaneous complex environment, the electrochemistry of copper ion is rung
It should be also without significant change, to exclude the interference of some common anion and cation.
The embodiment of the present invention is illustrated in conjunction with attached drawing above, but the present invention is not limited to the above embodiments, it can be with
The purpose of innovation and creation according to the present invention makes a variety of variations, under the Spirit Essence and principle of all technical solutions according to the present invention
The changes, modifications, substitutions, combinations, simplifications done should be equivalent substitute mode, as long as meeting goal of the invention of the invention, only
Otherwise deviate from CoNiO of the present invention2Nano material constructs the method for modified glassy carbon electrode, ultra trace heavy metal ion electrochemical gaging
Method and the technical principle and inventive concept of application, belong to protection scope of the present invention.
Claims (2)
1. a kind of CoNiO of trace detection copper ion2The method of nanometer-material-modified glass-carbon electrode, it is characterised in that press following step
It is rapid to carry out:
Hydro-thermal method prepares hydroxide:
A, 1:1 weighs nickel nitrate and cobalt nitrate mixing in molar ratio, is dissolved in deionized water, uniform stirring, is configured to concentration model
It is trapped among the mixed solution of 0.1-5 mol/L；
B, sodium hydroxide is weighed by the molar ratio 1.2:1 of sodium hydroxide and nickel nitrate and cobalt nitrate mixture again, and is made into concentration
Range then the solution of preparation is added dropwise in the mixed solution that step a is obtained in the solution of 0.1-5 mol/L, at room temperature magnetic
Power stirs 1-3 h, then staticly settles 12-48 h, filtering and washing to neutrality, and 6-12 h is dried at 50-100 DEG C of temperature, is obtained
Precipitating；
C, the precipitating for obtaining step b is dispersed in the polyvinylpyrrolidone deionized water containing 0.5-8 wt%, magnetic agitation
1-3 h is put into 100 mL high pressure water heating kettles, and in 50-80%, hydrothermal temperature is 100-200 DEG C for packing ratio control, the reaction time
To carry out hydrothermal synthesis under 6-24 h, resulting powder will be reacted and be washed with deionized 2-3 times, dry, grinding is to get hydrogen-oxygen
Compound；
Microwave method prepares CoNiO2Nano material:
D, the hydroxide for obtaining step c carries out microwave heating treatment 10-30 minutes under 480-800 W power, then grinds
Sieving, obtains CoNiO2Modified electrode material；
Dispersion method prepares CoNiO2/ Nafion modified glassy carbon electrode:
E, the CoNiO for obtaining step d2Being dispersed in concentration is 1-10 mg/mL, and the mass fraction of Nafion is 0.1-1 wt%'s
In dehydrated alcohol-Nafion solution, 1 h of ultrasonic disperse is configured to CoNiO2/ Nafion nano material electrode modifies solution；
F, the aluminium oxide powder for successively using glass-carbon electrode partial size to be 50nm for 1-0.3 μm and partial size is processed by shot blasting,
Then it is successively ultrasonically treated in second alcohol and water, is finally dried in a nitrogen atmosphere, obtain pretreated glass-carbon electrode；
G, the obtained CoNiO of step e will be instilled on the obtained glass-carbon electrode of step f2The modification of/Nafion nano material electrode is molten
Liquid, dripping quantity are 5-20 μ L, and naturally dry obtains CoNiO2/ Nafion modified glassy carbon electrode；
Ultra trace copper ion Electrochemical Detection:
H, electrochemistry detecting apparatus by electrochemical workstation, electrolytic cell, magnetic stirring apparatus, working electrode, to electrode and reference electricity
Pole composition；It being used as using platinum filament to electrode, for silver/silver chlorate as reference electrode, it is substrate that working electrode, which is by glass-carbon electrode,
CoNiO2The glass-carbon electrode of/Nafion modification is working electrode；Using differential pulse anodic stripping voltammetry, detection parameters are as follows:
Accumulating potential is set as-0.8-- 1.5V, and enrichment time is set as 80-200s, scans current potential 1-50 mV/s, scanning range X
For -1.5- 0.4V, for detecting copper ion.
2. a kind of CoNiO of trace detection copper ion according to claim 12The method of nanometer-material-modified glass-carbon electrode,
It is characterized by: the electrolyte in step h in electrolytic cell is Cu to be measured2+Acetic acid-sodium acetate and ammonium hydroxide-chloride buffer it is molten
Liquid, the pH range of buffer solution are 3.5-8.0, Cu2+Concentration Testing range is 0.1-1000 μ g/L, and detection is limited to 0.1-1.0 μ
g/L。
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