CN105044175B - A kind of preparation method for the electrochemical sensor that nickel oxide microballoon is mixed based on carbon nitrogen - Google Patents
A kind of preparation method for the electrochemical sensor that nickel oxide microballoon is mixed based on carbon nitrogen Download PDFInfo
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- CN105044175B CN105044175B CN201510412377.2A CN201510412377A CN105044175B CN 105044175 B CN105044175 B CN 105044175B CN 201510412377 A CN201510412377 A CN 201510412377A CN 105044175 B CN105044175 B CN 105044175B
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Abstract
The invention discloses a kind of electrochemical sensor that nickel oxide microballoon electrode is mixed based on carbon nitrogen, and for the detection of hydrogen peroxide.The present invention is prepared carbon nitrogen and is mixed nickel oxide microballoon composite using the carbon containing and diblock polymer of nitrogen-atoms and nickel hydroxide, and for being modified glass-carbon electrode, prepare a kind of electrode to hydrogen peroxide with very high electro catalytic activity, carbon nitrogen and nickel oxide Interaction enhanced carbon nitrogen mix electrocatalysis characteristic of the nickel oxide microballoon composite to hydrogen peroxide.Detection of the electrochemical sensor of the present invention to hydrogen peroxide has high sensitivity, fast response time, wide detection range and low test limit, also with extraordinary stability and antijamming capability.
Description
Technical field
The present invention relates to electrochemical sensor field, more particularly to one kind to mix nickel oxide microballoon electrochemistry based on carbon nitrogen and pass
The preparation method of sensor.
Background technology
Hydrogen peroxide plays very important role in daily life, for example is generally adopted in food production processing industry
With hydrogen peroxide to food sterilization, sterilization etc..But the hydrogen peroxide of high residue content gives people to have serious consequences, such as make one
The harm such as vomiting, paralysis.There is clearly regulation in the content country of material residual hydrogen peroxide and required.Other hydrogen peroxide
And the product of cell metabolism, if hydrogen peroxide can excessively cause a variety of organ dysfunctions abnormal in human body, influence human body
Health.Therefore, valuable examine is made to many diseases by measuring the content of human body hydrogen peroxide on clinical medicine
It is disconnected.As can be seen here, the analysis detection to hydrogen peroxide is particularly important.The detection method of conventional hydrogen peroxide, such as chromatography, titration
These detection methods such as analytic approach and spectroscopic methodology have the shortcomings that manipulation is cumbersome, test is complicated and expensive.Electrochemical method has
Have it is quick, stably, high sensitivity the advantages of have been used to the detection of hydrogen peroxide.And hydrogen peroxide electrochemical sensor is big now
Majority fixes biological enzyme modified electrode with biomembrane, Conductive inorganic thing and carries out analysis detection to hydrogen peroxide, as horseradish aoxidizes
Enzyme, glucose oxidase, hemoglobinase etc..But biology enzyme easy in inactivation, structure non-directional, acid-base value and temperature by environment
Influence the shortcomings of very big and costly so that concerned without enzyme electrochemical sensor.
Transition series metal oxide due to there is excellent stability and high electrocatalytic active and electrochemical sensing
Device receives significant attention in field.Especially there are nickel oxide raw material sources extensively often to be answered with high electrocatalysis and its stability
For fields such as catalyst, battery electrode, sensors.Theoretical research shows carbon, nitrogen-doping nickel oxide composite material ratio not
The nickel oxide of doping has higher electro catalytic activity.Although synthesis diblock copolymer is very convenient at present, di-block copolymer
Thing is applied not to be reported also in carbon, N doping nickel oxide composite material.So carbon, N doping oxygen are prepared using diblock copolymer
Changing nickel microballoon composite and being applied to hydrogen peroxide electrochemical sensor has highly important application value.
The content of the invention
It is an object of the invention to provide a kind of electricity that nickel oxide microballoon is mixed based on carbon nitrogen for hydrogen peroxide detection
The preparation method of chemical sensor.
The technical scheme is that：
A kind of preparation method for the electrochemical sensor that nickel oxide microballoon is mixed based on carbon nitrogen, is comprised the following steps：
(1) preparation of nickel hydroxide solution：Ethylene glycol and polyethylene glycol are mixed into 60~120min, in stirring condition
Under sequentially add nickel nitrate solution, benzoic acid, sodium hydroxide solution and stir into mixed solution；The ethylene glycol and polyethylene glycol
Volume ratio is 100:0.5~1.5, the nickel nitrate (Ni (NO3)2·6H2O), the mass ratio of benzoic acid and sodium hydroxide be 10~
24:4~6:3~5；
(2) preparation of nickel hydroxide microballoon：Mixed solution obtained by step (1) is gone into the hydro-thermal with polytetrafluoroethyllining lining
In reactor, react 8-12h at a temperature of 170~200 DEG C, reaction is cooled to room temperature after terminating, then by reaction solution carry out from
The heart is separated, and isolated solid sediment is dried in vacuo into 8-12h at 100~150 DEG C, obtains nickel hydroxide microballoon；
(3) carbon nitrogen mixes the preparation of nickel oxide microballoon：Nickel hydroxide microballoon obtained by step (2) is gathered with appropriate diblock
Then solution is put into Muffle furnace by compound AB ultrasonic disperses in DMF solution, in 450~500 DEG C of temperature
2~4h of the lower calcining of degree obtains carbon nitrogen and mixes nickel oxide microballoon；
(4) carbon nitrogen mixes the preparation of nickel oxide microballoon electrode：By glass-carbon electrode respectively with 0.05 μm and 0.03 μm of α-oxygen
Change aluminium powder and polishing grinding is carried out on chamois leather, then carry out ultrasound with salpeter solution, absolute ethyl alcohol and deionized water successively
Cleaning, carbon nitrogen obtained by step (3) is mixed into nickel oxide microballoon ultrasonic disperse in the aqueous solution, takes 3~7 μ L carbon nitrogen to mix nickel oxide
Microballoon hangs dispersant liquid drop and is added on the glass-carbon electrode handled well, and carbon nitrogen is obtained after natural drying and mixes nickel oxide microballoon electrode；Institute
It is 5~8g/L to state carbon nitrogen to mix nickel oxide microballoon dispersion liquid concentration；
(5) preparation of electrochemical sensor：Using modified electrode obtained by step (4) as working electrode, electrochemical sensing is built
Device.
Further, the diblock polymer AB of the step (3), its formula are：
R represents amido, preferably N (CH in formula3)2Or N (CH2CH3)2。
The electrochemical sensor prepared using above-mentioned preparation method.
Using the application of electrochemical sensor prepared by above-mentioned preparation method in hydrogen peroxide detection.
The beneficial effects of the present invention are：
The electrochemical sensor of the present invention, the carbon containing and block copolymer of nitrogen is applied to carbon, N doping nickel oxide
The preparation of microballoon composite.Carbon, N doping nickel oxide microballoon composite than undoped with nickel oxide have higher electro-catalysis
Activity, show that it has stronger electrochemical response signal to hydrogen peroxide.The electrochemical sensor of the present invention is to hydrogen peroxide
Detection range and low test limit of the detection with non-constant width, response is fast, and with good stability, repeatability and anti-
Interference performance.
Brief description of the drawings
Fig. 1 is the scanning electron microscope (SEM) photograph of nickel hydroxide microballoon made from embodiment 1.
Fig. 2 is the scanning electron microscope (SEM) photograph that carbon nitrogen made from embodiment 1 mixes nickel oxide microballoon composite.
Fig. 3 is the energy spectrum diagram that carbon nitrogen made from embodiment 1 mixes nickel oxide microballoon composite.
Fig. 4 is electrochemical sensor made from embodiment 1 to H2O2The obtained different H of detection2O2Concentration and response current
The linear relationship chart of value.
Embodiment
In order to be better understood from the present invention, with reference to the embodiment content that the present invention is furture elucidated, but the present invention
Content is not limited solely to the following examples.
Embodiment 1
(1) preparation of nickel hydroxide solution：60.0mL ethylene glycol and 0.6mL polyethylene glycol 400s are mixed into 60min,
4.0mL nickel nitrate solutions (concentration 1.0mol/L), 0.4g benzoic acid, 4.0mL sodium hydroxides are sequentially added under agitation
Solution (concentration 2.0mol/L) is stirred into homogeneous solution.
(2) preparation of nickel hydroxide microballoon：Mixed solution described in step (1) is gone into 80mL band polytetrafluoroethyllining linings
Hydrothermal reaction kettle in, react 8h at a temperature of 180 DEG C.Reaction is cooled to room temperature after terminating, then reaction solution is centrifuged
Separation, is dried in vacuo 10h at 100 DEG C by isolated solid sediment, obtains nickel hydroxide microballoon.
(3) carbon nitrogen mixes the preparation of nickel oxide microballoon：Nickel hydroxide microballoon obtained by step (2) is embedding with containing 0.05g bis-
Then dispersion soln is put into Muffle furnace by section polymer AB solution ultrasonic disperse in DMF solution,
450 DEG C of temperature lower calcination 2h obtain carbon nitrogen and mix nickel oxide microballoon.
(4) carbon nitrogen mixes the preparation of nickel oxide electrode：By diameter 3mm glass-carbon electrodes respectively with 0.05 μm and 0.03 μm of α-
Alumina powder carries out polishing grinding on chamois leather, is then surpassed successively with salpeter solution, absolute ethyl alcohol and deionized water
Sound cleans.Carbon nitrogen prepared by step (3) is mixed into nickel oxide microballoon ultrasonic disperse (concentration 5.0g/L) in the aqueous solution, taken
5 μ L carbon nitrogen mix the outstanding dispersant liquid drop of nickel oxide microballoon and are added on the glass-carbon electrode handled well, and carbon nitrogen is obtained after natural drying and is mixed
Nickel oxide electrode.
(5) preparation of electrochemical sensor：Nickel oxide glass-carbon electrode is mixed as work electricity using the carbon nitrogen prepared by step (4)
Pole, platinum filament are auxiliary electrode, and saturated calomel electrode is that reference electrode builds electrochemical sensor.
Embodiment 2
(1) preparation of nickel hydroxide solution：60.0mL ethylene glycol and 0.8mL polyethylene glycol 400s are mixed into 100min,
6.0mL nickel nitrate solutions (concentration 1.0mol/L), 0.45g benzoic acid, 4.0mL sodium hydroxides are sequentially added under agitation
Solution (concentration 2.0mol/L) is stirred into homogeneous solution.
(2) preparation of nickel hydroxide microballoon：Mixed solution described in step (1) is gone into 80mL band polytetrafluoroethyllining linings
Hydrothermal reaction kettle in, react 10h at a temperature of 190 DEG C.Reaction is cooled to room temperature after terminating, then reaction solution is centrifuged
Separation, is dried in vacuo 10h at 120 DEG C by isolated solid sediment, obtains nickel hydroxide microballoon.
(3) carbon nitrogen mixes the preparation of nickel oxide microballoon：By the nickel hydroxide microballoon described in step (2) and contain 0.05g bis-
Then dispersion soln is put into Muffle furnace by block polymer AB solution ultrasonic disperse in DMF solution,
Carbon nitrogen, which is obtained, in 480 DEG C of temperature lower calcination 3h mixes nickel oxide microballoon.
(4) carbon nitrogen mixes the preparation of nickel oxide electrode：By 3mm glass-carbon electrodes respectively with 0.05 μm and 0.03 μm of alpha-oxidation
Aluminium powder carries out polishing grinding on chamois leather, then carries out ultrasound clearly with salpeter solution, absolute ethyl alcohol and deionized water successively
Wash.Carbon nitrogen prepared by step (3) is mixed into nickel oxide microballoon ultrasonic disperse (concentration 5.5g/L) in the aqueous solution, takes 7 μ L
Carbon nitrogen mixes the outstanding dispersant liquid drop of nickel oxide microballoon and is added on the glass-carbon electrode handled well, and carbon nitrogen is obtained after natural drying and mixes oxidation
Nickel electrode.
(5) preparation of electrochemical sensor：Nickel oxide glass-carbon electrode is mixed as work electricity using the carbon nitrogen prepared by step (4)
Pole, platinum filament are auxiliary electrode, and saturated calomel electrode is that reference electrode builds electrochemical sensor.
Embodiment 3
(1) preparation of nickel hydroxide solution：60.0mL ethylene glycol and 0.9mL polyethylene glycol 400s are mixed into 100min,
8.0mL nickel nitrate solutions (concentration 1.0mol/L), 0.4g benzoic acid, 5.0mL sodium hydroxides are sequentially added under agitation
Solution (concentration 2.0mol/L) is stirred into homogeneous solution.
(2) preparation of nickel hydroxide microballoon：Mixed solution described in step (1) is gone into 80mL band polytetrafluoroethyllining linings
Hydrothermal reaction kettle in, react 10h at a temperature of 170 DEG C.Reaction is cooled to room temperature after terminating, then reaction solution is centrifuged
Separation, is dried in vacuo 12h at 120 DEG C by isolated solid sediment, obtains nickel hydroxide microballoon.
(3) carbon nitrogen mixes the preparation of nickel oxide microballoon：By the nickel hydroxide microballoon described in step (2) and contain 0.05g bis-
Then dispersion soln is put into Muffle furnace by block polymer AB solution ultrasonic disperse in DMF solution,
Carbon nitrogen, which is obtained, in 500 DEG C of temperature lower calcination 3h mixes nickel oxide microballoon.
(4) carbon nitrogen mixes the preparation of nickel oxide electrode：By 3mm glass-carbon electrodes respectively with 0.05 μm and 0.03 μm of alpha-oxidation
Aluminium powder carries out polishing grinding on chamois leather, then carries out ultrasound clearly with salpeter solution, absolute ethyl alcohol and deionized water successively
Wash.Carbon nitrogen prepared by step (3) is mixed into nickel oxide microballoon ultrasonic disperse (concentration 8.0g/L) in the aqueous solution, takes 6 μ L
Carbon nitrogen mixes the outstanding dispersant liquid drop of nickel oxide microballoon and is added on the glass-carbon electrode handled well, and carbon nitrogen is obtained after natural drying and mixes oxidation
Nickel electrode.
(5) preparation of electrochemical sensor：Nickel oxide glass-carbon electrode is mixed as work electricity using the carbon nitrogen prepared by step (4)
Pole, platinum filament are auxiliary electrode, and saturated calomel electrode is that reference electrode builds electrochemical sensor.
Claims (5)
1. a kind of preparation method for the electrochemical sensor that nickel oxide microballoon is mixed based on carbon nitrogen, it is characterised in that including following step
Suddenly：
(1) preparation of nickel hydroxide solution：Ethylene glycol and polyethylene glycol are mixed into 60~120min, under agitation according to
Secondary addition nickel nitrate solution, benzoic acid, sodium hydroxide solution stir into mixed solution, the volume of the ethylene glycol and polyethylene glycol
Than for 100:0.5~1.5, the nickel nitrate is 10~24 with the mass ratio of benzoic acid and sodium hydroxide:4~6:3~5；
(2) preparation of nickel hydroxide microballoon：Mixed solution obtained by step (1) is gone in hydrothermal reaction kettle, at 170~200 DEG C
At a temperature of react 8-12h, reaction is cooled to room temperature after terminating, then reaction solution is centrifuged, by isolated solid
Sediment is dried in vacuo 8-12h at 100~150 DEG C, obtains nickel hydroxide microballoon；
(3) carbon nitrogen mixes the preparation of nickel oxide microballoon：By nickel hydroxide microballoon obtained by step (2) and appropriate diblock polymer
Then solution is put into Muffle furnace by AB ultrasonic disperses in DMF solution, at a temperature of 450~500 DEG C
2~4h of calcining obtains carbon nitrogen and mixes nickel oxide microballoon；
(4) carbon nitrogen mixes the preparation of nickel oxide microballoon electrode：By glass-carbon electrode respectively with 0.05 μm and 0.03 μm of Alpha-alumina
Powder carries out polishing grinding on chamois leather, is then cleaned by ultrasonic successively with salpeter solution, absolute ethyl alcohol and deionized water,
Carbon nitrogen obtained by step (3) is mixed into nickel oxide microballoon ultrasonic disperse in the aqueous solution, takes 3~7 μ L carbon nitrogen to mix nickel oxide microballoon
Outstanding dispersant liquid drop is added on the glass-carbon electrode handled well, and carbon nitrogen is obtained after natural drying and mixes nickel oxide microballoon electrode；
(5) preparation of electrochemical sensor：Using step (4) the electrode obtained as working electrode, structure mixes nickel oxide based on carbon nitrogen
The electrochemical sensor of microballoon.
2. the preparation method of electrochemical sensor according to claim 1, it is characterised in that：The two of the step (3) are embedding
Section polymer AB, its formula are：
R represents amido in formula.
3. the preparation method of electrochemical sensor according to claim 1 or 2, it is characterised in that：The carbon nitrogen mixes oxygen
The concentration for changing nickel microballoon dispersion liquid is 5~8g/L.
4. electrochemical sensor prepared by the preparation method described in any one of claims 1 to 3.
5. electrochemical sensor prepared by the preparation method described in any one of claims 1 to 3 answering in hydrogen peroxide detection
With.
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| CN102126762A (en) * | 2011-04-28 | 2011-07-20 | 北京化工大学 | Method for preparing NiO nano flowerlike microspheres with surface topography controllable |
| CN104030371A (en) * | 2014-06-08 | 2014-09-10 | 吕仁江 | Method for synthesizing NiO microsphere consisting of mesoporous sheet structures by soft template process |
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| CN102126762A (en) * | 2011-04-28 | 2011-07-20 | 北京化工大学 | Method for preparing NiO nano flowerlike microspheres with surface topography controllable |
| CN104030371A (en) * | 2014-06-08 | 2014-09-10 | 吕仁江 | Method for synthesizing NiO microsphere consisting of mesoporous sheet structures by soft template process |
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| 基于二嵌段聚合物复合材料的电化学传感器研究;汤帅;《中国知网》;20150501;第36-46页 * |
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