CN107402247A - A kind of preparation method of electrochemical sensor nano-graphene/chitosan complex film modified electrode - Google Patents
A kind of preparation method of electrochemical sensor nano-graphene/chitosan complex film modified electrode Download PDFInfo
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- CN107402247A CN107402247A CN201710599848.4A CN201710599848A CN107402247A CN 107402247 A CN107402247 A CN 107402247A CN 201710599848 A CN201710599848 A CN 201710599848A CN 107402247 A CN107402247 A CN 107402247A
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- graphene
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
- G01N27/26—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating electrochemical variables; by using electrolysis or electrophoresis
- G01N27/28—Electrolytic cell components
- G01N27/30—Electrodes, e.g. test electrodes; Half-cells
- G01N27/308—Electrodes, e.g. test electrodes; Half-cells at least partially made of carbon
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
- G01N27/26—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating electrochemical variables; by using electrolysis or electrophoresis
- G01N27/28—Electrolytic cell components
- G01N27/30—Electrodes, e.g. test electrodes; Half-cells
- G01N27/307—Disposable laminated or multilayered electrodes
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
- G01N27/26—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating electrochemical variables; by using electrolysis or electrophoresis
- G01N27/28—Electrolytic cell components
- G01N27/30—Electrodes, e.g. test electrodes; Half-cells
- G01N27/333—Ion-selective electrodes or membranes
- G01N27/3335—Ion-selective electrodes or membranes the membrane containing at least one organic component
Abstract
A kind of preparation method the invention discloses electrochemical sensor with nano-graphene/chitosan complex film modified electrode, potassium permanganate and concentrated sulfuric acid oxidation intercalation natural flake graphite are used in the present invention, the oxy radicals such as hydroxyl, epoxide group and carboxyl are introduced in graphite layers, increase graphite layers away from, afterwards under microwave field action, oxy radical thermal decomposition inside graphite, produces CO, CO2And H2The gases such as O, caused impulsive force causes graphite flake layer rapid expansion, graphite linings lamella is softened, further increase graphite layers away from, weaken interlayer Van der Waals force, effectively slow down stacking, the agglomeration traits of graphene oxide, make it have the hole series structure of prosperity, the absorption property of the materials such as specific surface area and the heavy metal of graphene is improved, so that carrier mobility speed improves, shortens the reaction time of detection.
Description
Technical field
The present invention relates to a kind of electrochemical sensor field, and in particular to a kind of electrochemical sensor with nano-graphene/
The preparation method of chitosan complex film modified electrode.
Background technology
At present, with the fast development of industry, while the living standard of the people improves constantly, the degree of environmental pollution
Also increasingly sharpen, the existence of serious threat to the mankind and animals and plants, while also seriously govern economic and society sustainable development
Exhibition, therefore pollutant is sensitively detected extremely important.Electrochemical analysis method has easy to operate, cheap, clever
It is quick, quick, green and be easy to miniaturization the advantages that, have been widely used for water quality monitoring, Pharmaceutical Analysis and ring at present
Border monitoring etc..
2004, graphene was found first.It is widely used because it has many excellent and unique performances
In fields such as micro-nano electronic device, advanced composite material (ACM), sensor materials.Using graphene modified determination of electrode heavy metal ion
Existing more reports, graphene modified electrode, which is used for electrochemical analysis, following characteristics：Adsorption capacity is strong, mass transfer rate is high, anti-
Oxide etch etc..But the graphene specific surface area prepared by reality is general all in 600m2/ g or so, main cause are graphenes
Easily mutually reunite between lamella and lamella, cause the specific surface area of graphene to decline to a great extent.Therefore, prepared using conventional method
The actual performance of obtained graphene modified electrode is than low more in theory.
The content of the invention
In view of the shortcomings of the prior art, it is compound with nano-graphene/chitosan to provide a kind of electrochemical sensor by the present invention
The preparation method of film modified electrode, improve the adsorption capacity of electrode material.
The present invention is achieved by the following technical solutions：
A kind of electrochemical sensor preparation method of nano-graphene/chitosan complex film modified electrode, its preparation technology is such as
Under：
（1）Weigh 30-60 parts by weight crystalline flake graphites to be slowly added into 140-230 part concentrated sulfuric acids, slowly add under agitation
Enter 50-80 part potassium permanganate, under 30-40 DEG C of bath temperature, intermittent stirring 1-2 hours, be washed with deionized to neutrality, mistake
Filter, drying, produce expansible graphite, dried expansible graphite are placed in micro-wave oven expanded afterwards, Bulking Time
For 15-25s, expanded graphite is obtained；
（2）8-19 part chitosans are dissolved in the solution that 0.5wt% is made into 2% acetic acid, ultrasonic 25-35 minutes, are well mixed
After be transferred in constant pressure funnel, funnel remains turned-off and connects the filter flask equipped with expanded graphite below, by filter flask
20-40 minutes are vacuumized in advance, then open dropping funel switch, under pressure inducement, the solution in dropping funel is injected into
The interlayer of expanded graphite, after chitosan solution is added dropwise, ultrasonic disperse 1-2 hours, obtains expanded graphite/chitosan and disperse
Liquid；
（3）The pretreatment of gold electrode：
Gold electrode is soaked into 25-35 minutes in the mixed solution of the concentrated sulfuric acid and hydrogen peroxide, with activated electrode, then with three oxygen
Change the polishing of two aluminum pastes, polishing, then be cleaned by ultrasonic each 3-8 with 5mol/L salpeter solutions, absolute ethyl alcohol, redistilled water respectively and divided
Clock, finally rinsed well with redistilled water, nitrogen drying is standby；
（4）The preparation of film modified electrode：
Above-mentioned gold electrode after pretreatment is placed in above-mentioned expanded graphite/chitosan dispersion, after standing 1-2 days, taken out
Electrode dries, then clean with distilled water flushing, super in 35-45 DEG C in DMF/water mixed solution after drying
Sound 4-6 hours, electrode distilled water flushing is taken out, nitrogen drying, produces nano-graphene/chitosan complex film modified electrode.
Wherein, step（1）Described in microwave expansion actual conditions be：Microwave power is 10kW, temperature 900-980
℃。
Wherein, step（3）Described in the concentrated sulfuric acid and hydrogen peroxide mixed solution in the body of the concentrated sulfuric acid and hydrogen peroxide
Product is than being 3：1.
Wherein, step（4）Described in N,N-dimethylformamide/water mixed solution in both volume ratio be 10:1.
Compared with prior art, the present invention has advantages below：
（1）In the present invention using potassium permanganate and the concentrated sulfuric acid oxidation intercalation natural flake graphite, graphite layers introduce hydroxyl,
The oxy radical such as epoxide group and carboxyl, increase graphite layers away from, afterwards under microwave field action, oxy radical inside graphite
Thermal decomposition, produce CO, CO2And H2The gases such as O, caused impulsive force cause graphite flake layer rapid expansion, and graphite linings lamella is supportted
Open, further increase graphite layers away from, weaken interlayer Van der Waals force, effectively slow down graphene oxide stacking, reunite ask
Topic, the hole series structure of prosperity is made it have, improve the absorption property of the materials such as specific surface area and the heavy metal of graphene, from
And carrier mobility speed is improved, shorten the reaction time of detection.
（2）Chitosan solution is injected into graphite layers under pressure inducement in the present invention, and dispersion liquid is placed in into dimethyl methyl
Simple ultrasound is peeled off in acid amides/water mixed solution, and under ul-trasonic irradiation, the faint Van der Waals force of graphite layers is combined and broken
Bad, graphite synusia is substantially thinned, and has obtained graphene nanometer sheet, by covalently forming complexing between chitosan and graphite flake layer
Thing, stability between the two is improved, can effectively prevent stacking, the agglomeration traits of graphene, improve the inspection of electrode material
Survey sensitivity.
Embodiment
A kind of preparation method that graphene sheet layer load nanometer nickle composite powder is prepared using microwave expansion method, it prepares work
Skill is as follows：
（1）18 parts sulfuric acid nickel are configured to the solution that concentration is 0.5mol/L first, add 0.3 part of cetomacrogol 1000,
4 parts of oxalic acid solutions are added after continuous uniform stirring, precipitation reaction is carried out, generates single precursor solution, dripped afterwards using constant pressure
15 parts of 0.5mol/L liquor zinci chloridi and 3 parts of oxalic acid solutions are slowly added into single precursor solution by liquid funnel,
Generation cladding salt precursor liquid solution；
（2）Weigh 45 parts of crystalline flake graphites to be slowly added into 180 parts of concentrated sulfuric acids, be slowly added to 70 parts of permanganic acid under agitation
Potassium, under 35 DEG C of bath temperatures, intermittent stirring 2 hours, it is washed with deionized to neutrality, filtering, drying, produces inflatable stone
Ink, dried expansible graphite is placed in micro-wave oven expanded afterwards, Bulking Time 20s, obtain expanded graphite；
（3）By step（1）Precursor solution is placed in constant pressure funnel, and funnel is remained turned-off and connected below equipped with expansion
The filter flask of graphite, filter flask is vacuumized in advance 40 minutes, then open dropping funel switch, under pressure inducement, dropping liquid
Solution in funnel is injected into the interlayer of expanded graphite；
（4）By step（3）The expanded graphite of injection precursor solution is transferred in reactor, is heated in reducing atmosphere stove
900 DEG C sinter 20 minutes, obtain zinc oxide/graphene coated nickel powder complex after being cooled to room temperature, are then soaked with hydrochloric acid solution
Bubble 20 minutes, cleaning removes zinc oxide, after being washed repeatedly with absolute ethyl alcohol, deionized water, vacuum drying, produces.
Wherein, the concentration of described oxalic acid solution is 3mol/L.
Wherein, step（2）Described in microwave expansion actual conditions be：Microwave power is 10kW, and temperature is 950 DEG C.
Wherein, step（4）Described in hydrochloric acid solution concentration be 20%.
Wherein, the step（4）Middle vacuum drying temperature is 70 DEG C.
Claims (4)
- A kind of 1. electrochemical sensor preparation method of nano-graphene/chitosan complex film modified electrode, it is characterised in that Its preparation technology is as follows：（1）Weigh 30-60 parts by weight crystalline flake graphites to be slowly added into 140-230 part concentrated sulfuric acids, slowly add under agitation Enter 50-80 part potassium permanganate, under 30-40 DEG C of bath temperature, intermittent stirring 1-2 hours, be washed with deionized to neutrality, mistake Filter, drying, produce expansible graphite, dried expansible graphite are placed in micro-wave oven expanded afterwards, Bulking Time For 15-25s, expanded graphite is obtained；（2）8-19 part chitosans are dissolved in the solution that 0.5wt% is made into 2% acetic acid, ultrasonic 25-35 minutes, are well mixed After be transferred in constant pressure funnel, funnel remains turned-off and connects the filter flask equipped with expanded graphite below, by filter flask 20-40 minutes are vacuumized in advance, then open dropping funel switch, under pressure inducement, the solution in dropping funel is injected into The interlayer of expanded graphite, after chitosan solution is added dropwise, ultrasonic disperse 1-2 hours, obtains expanded graphite/chitosan and disperse Liquid；（3）The pretreatment of gold electrode：Gold electrode is soaked into 25-35 minutes in the mixed solution of the concentrated sulfuric acid and hydrogen peroxide, with activated electrode, then with three oxygen Change the polishing of two aluminum pastes, polishing, then be cleaned by ultrasonic each 3-8 with 5mol/L salpeter solutions, absolute ethyl alcohol, redistilled water respectively and divided Clock, finally rinsed well with redistilled water, nitrogen drying is standby；（4）The preparation of film modified electrode：Above-mentioned gold electrode after pretreatment is placed in above-mentioned expanded graphite/chitosan dispersion, after standing 1-2 days, taken out Electrode dries, then clean with distilled water flushing, super in 35-45 DEG C in DMF/water mixed solution after drying Sound 4-6 hours, electrode distilled water flushing is taken out, nitrogen drying, produces nano-graphene/chitosan complex film modified electrode.
- A kind of 2. electrochemical sensor nano-graphene/chitosan complex film modified electrode according to claims 1 Preparation method, it is characterised in that step（1）Described in microwave expansion actual conditions be：Microwave power is 10kW, temperature For 900-980 DEG C.
- A kind of 3. electrochemical sensor nano-graphene/chitosan complex film modified electrode according to claims 1 Preparation method, it is characterised in that step（3）Described in the concentrated sulfuric acid and hydrogen peroxide mixed solution in the concentrated sulfuric acid and peroxide The volume ratio for changing hydrogen is 3：1.
- A kind of 4. electrochemical sensor nano-graphene/chitosan complex film modified electrode according to claims 1 Preparation method, it is characterised in that step（4）Described in N,N-dimethylformamide/water mixed solution in both volume Than for 10:1.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109270140A (en) * | 2018-11-01 | 2019-01-25 | 安阳师范学院 | The preparation method and application of high dispersive graphene/Zn Base Metal organic framework composite material electrochemical sensor |
| CN110082410A (en) * | 2019-05-08 | 2019-08-02 | 甘肃中商食品质量检验检测有限公司 | The preparation and application of gold nanoparticle load beta-cyclodextrin functionalization graphene biosensor |
| CN110161088A (en) * | 2019-05-22 | 2019-08-23 | 电子科技大学 | A kind of cryogenic vulcanization hydrogen body sensor based on chitosan/oxidized graphene composite film |
| CN112174122A (en) * | 2020-09-30 | 2021-01-05 | 李素红 | Antibacterial graphene nano knife and preparation method and application thereof |
| CN116588926A (en) * | 2023-04-22 | 2023-08-15 | 青岛华腾石墨科技有限公司 | Modification process of negative electrode material for battery |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109270140A (en) * | 2018-11-01 | 2019-01-25 | 安阳师范学院 | The preparation method and application of high dispersive graphene/Zn Base Metal organic framework composite material electrochemical sensor |
| CN110082410A (en) * | 2019-05-08 | 2019-08-02 | 甘肃中商食品质量检验检测有限公司 | The preparation and application of gold nanoparticle load beta-cyclodextrin functionalization graphene biosensor |
| CN110082410B (en) * | 2019-05-08 | 2021-02-02 | 甘肃中商食品质量检验检测有限公司 | Preparation and application of gold nanoparticle-loaded beta-cyclodextrin functionalized graphene biosensor |
| CN110161088A (en) * | 2019-05-22 | 2019-08-23 | 电子科技大学 | A kind of cryogenic vulcanization hydrogen body sensor based on chitosan/oxidized graphene composite film |
| CN112174122A (en) * | 2020-09-30 | 2021-01-05 | 李素红 | Antibacterial graphene nano knife and preparation method and application thereof |
| CN116588926A (en) * | 2023-04-22 | 2023-08-15 | 青岛华腾石墨科技有限公司 | Modification process of negative electrode material for battery |
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