CN109781822A - A kind of zinc-oxide nano chip arrays/three-dimensional foam graphene biosensor working electrode and its preparation method and application - Google Patents
A kind of zinc-oxide nano chip arrays/three-dimensional foam graphene biosensor working electrode and its preparation method and application Download PDFInfo
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Abstract
The invention discloses a kind of zinc-oxide nano chip arrays/three-dimensional foam graphene biosensor working electrodes and its preparation method and application.The present invention synthesizes high conductance, flawless three-dimensional foam graphene by chemical vapour deposition technique, in combination with hydro-thermal method in the zinc-oxide nano chip arrays of foamy graphite alkene surface growth high-specific surface area, novel oxidized zinc nano-chip arrays/three-dimensional foam graphene biosensor working electrode has been synthesized；The synergistic effect of high conductance graphene and high-specific surface area zinc-oxide nano chip arrays can be played using biosensor prepared by the working electrode, improve the combination of zinc-oxide nano chip arrays and graphene, the zinc-oxide nano chip arrays of growth on the surface of graphene can provide countless active sites, on the electron transmission to graphene that directly reaction is generated, realize the fast transfer of electronics, so that the sensitivity of Electrochemical Detection dopamine is reached 0.95 μ A/ μm ol/L, solves the problems, such as that sensitivity is low and detects limit for height when existing biosensor detection dopamine.
Description
Technical field
The present invention relates to a kind of biosensor working electrode and its preparation method and application, in particular to a kind of zinc oxide
Nano-chip arrays/three-dimensional foam graphene biosensor working electrode and preparation method thereof and answering in detection dopamine
With.The invention belongs to technical field of electrochemical detection.
Background technique
The chemical name of dopamine (Dopamine, DA) is 3,4- dihydroxy-β-phenyl ethylamine, is that one kind is distributed in hypothalamus
With the key neurotransmitter for transmitting biological pulsation in pituitary gland.The content of dopamine in human body is lower, dopamine concentration one
There is exception in denier, may result in neurological disease, such as Alzheimer's disease, parkinsonism etc..Therefore, Accurate Determining human body
The concentration of middle dopamine has very important significance.Currently, still having many problems, such as spirit for the detection of dopamine
Sensitivity is relatively low, and detection limit is excessively high.
Zinc oxide is important semiconductor material, and band gap 3.37eV, exciton bind energy is 60meV at room temperature, has super
Strong electron transfer capabilities are widely used in each field such as sensor, catalysis, solar battery and photoelectron.Due to zinc oxide
With good biocompatibility and excellent chemical property, valence is applied with great in electrochemica biological sensor field
Value.Nano zine oxide it is many kinds of, wherein zinc-oxide nano chip arrays are because having less defect and biggish activity to compare table
Area and be concerned.Currently, the preparation method of zinc-oxide nano chip arrays mainly has hydro-thermal method, electrochemical deposition, vapor phase method
And circumfluence method.Hydro-thermal method has the advantages such as easy to operate, low in cost and reaction condition is mild, can be used for large scale preparation oxygen
Change zinc nano-chip arrays.
Graphene is single layer of carbon atom with sp2The hexagon cellular shape two-dimensional material that hydridization is formed, it has good machinery
Performance, conduction and heating conduction and stronger chemical stability, application prospect are boundless.The main of graphene is prepared at present
Method has mechanical stripping method, chemical oxidization method, crystal epitaxy method, chemical vapour deposition technique, organic synthesis method and carbon nanometer
Pipe stripping method etc..Wherein, there is less defect and higher electric conductivity using graphene made from chemical vapour deposition technique.With
Nickel foam is the templated chemistry vapor deposition foamy graphite alkene with tridimensional network obtained, have biggish porosity and
Specific surface area active provides good platform, and graphite for the combination of grapheme material and metal oxide nano-material
Good synergistic effect between alkene and metal oxide is so that its composite material shows more excellent chemical property.
Summary of the invention
Higher technical problem, passing through of the present invention are limited for lower for the detection sensitivity of dopamine at present and detection
It learns vapour deposition process and prepares foamy graphite alkene, then by hydro-thermal reaction in three-dimensional foam graphene surface vertical-growth zinc oxide
Nano-chip arrays, to be prepared for a kind of novel zinc-oxide nano chip arrays/three-dimensional foam graphene biosensor work
Electrode.
In order to achieve the above object, present invention employs following technological means:
A kind of preparation side of zinc-oxide nano chip arrays/three-dimensional foam graphene biosensor working electrode of the present invention
Method follows the steps below:
(1) by nickel foam be placed in quartz tube furnace center, under the protection of argon gas and hydrogen from room temperature with 20 DEG C/min~
It is 1000 DEG C~1100 DEG C that the heating rate of 40 DEG C/min, which is heated to temperature, and under conditions of temperature is 1000 DEG C~1100 DEG C
30min~60min is kept the temperature, into tube furnace with the speed of 5sccm~10sccm under conditions of temperature is 1000 DEG C~1100 DEG C
Rate is passed through methane gas 5min~20min, then by quartz tube furnace with 80 DEG C/min~100 DEG C/min cooling rate from temperature
Degree is cooled to room temperature for 1000 DEG C~1100 DEG C, obtains by the nickel foam of graphene coated；Nickel foam described in step (1) is close
Degree is 420g/m2~440g/m2, with a thickness of 1.6mm~2.0mm；The flow velocity of argon gas described in step (1) be 480sccm~
500sccm, the flow velocity of hydrogen are 180sccm~200sccm；
(2) polymethyl methacrylate is added in ethyl lactate, heating is stirred under conditions of temperature is 80 DEG C~120 DEG C
It mixes 1h~2h and obtains mixed solution, by the usage amount of the 100 μ μ of L~200 L every square centimeter, dripped mixed solution using sample loading gun
It is added on the foam nickel surface wrapped up by graphene that step (1) obtains, spontaneously dries at room temperature, be then 150 in temperature
DEG C~200 DEG C under conditions of heat preservation 0.5h~1h obtain surface cladding polymethyl methacrylate foamy graphite alkene；Step (2)
Described in mixed solution in methyl methacrylate mass fraction be 4%~5%；
(3) the foamy graphite alkene for the surface cladding polymethyl methacrylate that step (2) obtains is cut into surface area is
0.5cm2~2cm2Cube, and be completely soaked molten in the hydrochloric acid that temperature is 80 DEG C~90 DEG C, concentration is 3mol/L~4mol/L
4h~6h obtains the three-dimensional foam graphene of removal nickel in liquid；
(4) the three-dimensional foam graphene for the removal nickel that step (3) obtains is soaked in the acetone that temperature is 60 DEG C~70 DEG C
Middle 0.5h~1.5h obtains the foamy graphite alkene of removal polymethyl methacrylate, will remove polymethylacrylic acid with distilled water
The foamy graphite alkene of methyl esters cleans up, and then shifts the foamy graphite alkene of the removal polymethyl methacrylate cleaned up
Freeze-drying obtains foamy graphite alkene on to clean ito glass；
(5) the clean foamy graphite alkene being placed on ito glass for obtaining step (4) is according to 50 μ L every square centimeter
Zinc oxide seed layer solution is added dropwise using sample loading gun in the usage amount of~100 μ L, keeps the temperature 15min at a temperature of being placed in 150 DEG C~200 DEG C
~30min obtains the foamy graphite alkene/ito glass for being prefabricated with zinc oxide seed layer；Zinc oxide seed layer in step (5) is molten
Liquid is prepared: zinc acetate being dissolved in methanol, then with the revolving speed magnetic agitation 3min of 450r/min~550r/min
~5min obtains zinc oxide seed layer solution；Wherein the concentration of zinc acetate solution is 0.01mol/L~0.5mol/L；
(6) zinc nitrate, hexa, ammonium hydroxide and polyethyleneimine are dissolved in deionized water, with 450r/min~
Revolving speed magnetic agitation 3min~5min of 550r/min, obtains hydrothermal solution；Nitric acid zinc concentration described in step (6) is
0.05mol/L~0.1mol/L；The concentration of hexa is 0.05mol/L~0.1mol/L；The concentration of ammonium hydroxide is
0.05mol/L~0.1mol/L；The concentration of polyethyleneimine is 0.001mol/L~0.002mol/L；
(7) hydrothermal solution obtained in step (6) is poured into reaction kettle, then will be prefabricated with obtained in step (5)
Foamy graphite alkene/ito glass of zinc oxide seed layer is edge-on to be placed in the hydrothermal solution of reaction kettle, while being put into a piece of aluminium
Piece covers reaction kettle lid, is 90 DEG C~120 DEG C heat preservation 6h~13h in temperature, then takes out and be cooled to room temperature, opens reaction
Kettle is cleaned up composite material with distilled water, and in 400 DEG C~450 DEG C heat preservation 1h~1.5h, cool to the furnace room temperature to get
To zinc-oxide nano chip arrays/three-dimensional foam graphene biosensor working electrode.
Wherein, it is preferred that in step (1) temperature be 1000 DEG C~1100 DEG C under conditions of into tube furnace with 7sccm
The rate of~9sccm is passed through methane gas 10min~15min, then by quartz tube furnace with 85 DEG C/min~95 DEG C/min
Cooling rate is 1000 DEG C~1100 DEG C from temperature and is cooled to room temperature, and obtains by the nickel foam of graphene coated.
Wherein, it is preferred that in step (2) by polymethyl methacrylate be added ethyl lactate in, temperature be 90 DEG C~
Heating stirring 1h~1.5h obtains mixed solution under conditions of 110 DEG C, by the usage amount of the 130 μ μ of L~170 L every square centimeter, benefit
Mixed solution is added drop-wise on the foam nickel surface wrapped up by graphene that step (1) obtains with sample loading gun.
Wherein, it is preferred that the clean foamy graphite alkene being placed on ito glass for obtaining step (4) in step (5)
Zinc oxide seed layer solution is added dropwise using sample loading gun according to the usage amount of the 70 μ μ of L~90 L every square centimeter, is placed in 170 DEG C~190
20min~25min is kept the temperature at a temperature of DEG C, obtains the foamy graphite alkene/ito glass for being prefabricated with zinc oxide seed layer.
Wherein, it is preferred that nitric acid zinc concentration described in step (6) is 0.06mol/L~0.08mol/L；Six methylenes
The concentration of urotropine is 0.06mol/L~0.08mol/L；The concentration of ammonium hydroxide is 0.06mol/L~0.08mol/L.
Wherein, it is preferred that pour into the hydrothermal solution that step (6) obtains in reaction kettle in step (7), then by step
(5) the edge-on hydrothermal solution for being placed in reaction kettle of foamy graphite alkene/ito glass of zinc oxide seed layer is prefabricated with obtained in
In, while it being put into a piece of aluminium flake, reaction kettle lid is covered, is 100 DEG C~110 DEG C heat preservation 7h~12h in temperature, then takes out cold
But to room temperature.
Wherein, it is preferred that zinc-oxide nano chip arrays/three-dimensional foam graphene biosensor preparation method, according to
Following steps carry out:
(1) nickel foam is placed in quartz tube furnace center, from room temperature with 30 DEG C/min's under the protection of argon gas and hydrogen
It is 1000 DEG C that heating rate, which is heated to temperature, and keeps the temperature 30min under conditions of temperature is 1000 DEG C, is 1000 DEG C in temperature
Under the conditions of rate into tube furnace with 10sccm be passed through methane gas 10min, then by quartz tube furnace with 100 DEG C/min's
Cooling rate is 1000 DEG C from temperature and is cooled to room temperature, and obtains by the nickel foam of graphene coated；Foam described in step (1)
Nickel density is 420g/m2, with a thickness of 1.6mm；The flow velocity of argon gas described in step (1) is 500sccm, and the flow velocity of hydrogen is
200sccm；
(2) polymethyl methacrylate is added in ethyl lactate, heating stirring 2h is obtained under conditions of temperature is 100 DEG C
To mixed solution, by the usage amount of 180 μ L every square centimeter, mixed solution is added drop-wise to what step (1) obtained using sample loading gun
It on the foam nickel surface wrapped up by graphene, spontaneously dries at room temperature, then heat preservation 1h is obtained under conditions of temperature is 200 DEG C
The foamy graphite alkene of polymethyl methacrylate is coated to surface；Methyl methacrylate in mixed solution described in step (2)
The mass fraction of ester is 4%；
(3) the foamy graphite alkene for the surface cladding polymethyl methacrylate that step (2) obtains is cut into surface area is
1cm2Cube, and be completely soaked the 6h in the hydrochloric acid solution that temperature is 80 DEG C, concentration is 3mol/L obtain removal nickel three
Tie up foamy graphite alkene；
(4) the three-dimensional foam graphene for the removal nickel that step (3) obtains is soaked in 1.5h in the acetone that temperature is 60 DEG C,
The foamy graphite alkene of removal polymethyl methacrylate is obtained, the foamy graphite of polymethyl methacrylate will be removed with distilled water
Alkene cleans up, and the foamy graphite alkene of the removal polymethyl methacrylate cleaned up is then transferred to clean ITO glass
Freeze-drying obtains foamy graphite alkene on glass；
(5) the clean foamy graphite alkene being placed on ito glass for obtaining step (4) is according to 80 μ L every square centimeter
Usage amount using sample loading gun be added dropwise zinc oxide seed layer solution, keep the temperature 30min at a temperature of being placed in 200 DEG C, obtain prefabricated aerobic
Change foamy graphite alkene/ito glass of zinc seed layer；Zinc oxide seed layer solution in step (5) is prepared: by acetic acid
Zinc is dissolved in methanol, then with the revolving speed magnetic agitation 5min of 500r/min, obtains zinc oxide seed layer solution；Wherein zinc acetate
The concentration of solution is 0.01mol/L；
(6) zinc nitrate, hexa, ammonium hydroxide and polyethyleneimine are dissolved in deionized water, with 500r/min's
Revolving speed magnetic agitation 5min, obtains hydrothermal solution；Nitric acid zinc concentration described in step (6) is 0.05mol/L；Hexa-methylene
The concentration of tetramine is 0.05mol/L；The concentration of ammonium hydroxide is 0.05mol/L；The concentration of polyethyleneimine is 0.001mol/L；
(7) hydrothermal solution obtained in step (6) is poured into reaction kettle, then will be prefabricated with obtained in step (5)
Foamy graphite alkene/ito glass of zinc oxide seed layer is edge-on to be placed in the hydrothermal solution of reaction kettle, while being put into a piece of aluminium
Piece covers reaction kettle lid, is 100 DEG C of heat preservation 12h in temperature, then takes out and be cooled to room temperature, opens reaction kettle distilled water
Composite material is cleaned up, and in 450 DEG C of heat preservation 1h, cools to room temperature with the furnace to get zinc-oxide nano chip arrays/three-dimensional is arrived
Foamy graphite alkene biosensor working electrode.
Further, the invention also provides the Zinc oxide nano sheets being prepared according to method described in any of the above item
Array/three-dimensional foam graphene biosensor working electrode.
Further, the invention also provides zinc-oxide nano chip arrays/three-dimensional foam graphene biologies to pass
Application of the sense device working electrode in the biosensor of preparation detection dopamine.
Compared to the prior art, the beneficial effects of the present invention are:
(1) the method for the present invention synthesizes high conductance, flawless three-dimensional foam graphene by chemical vapour deposition technique, together
When in conjunction with hydro-thermal method foamy graphite alkene surface growth high-specific surface area zinc-oxide nano chip arrays, synthesized novel oxidation
Zinc nano-chip arrays/three-dimensional foam graphene biosensor working electrode；
(2) zinc-oxide nano chip arrays/three-dimensional foam graphene biosensor working electrode that the present invention is prepared
The synergistic effect that high conductance graphene and high-specific surface area zinc-oxide nano chip arrays can be played, can be mentioned using seed layer process
The combination of high oxidation zinc nano-chip arrays and graphene, and the zinc-oxide nano chip arrays grown on the surface of graphene can provide nothing
Several active sites can realize the fast transfer of electronics, therefore can be significant directly by the electron transmission to graphene of reaction generation
Electrocatalysis characteristic is improved, the sensitivity of Electrochemical Detection dopamine can be made to reach 0.95 μ A/ μm ol/L.
Detailed description of the invention
Fig. 1 is the zinc-oxide nano chip arrays/three-dimensional foam graphene biosensor working electrode for testing a preparation
Stereoscan photograph (X200)；
Fig. 2 is the zinc-oxide nano chip arrays/three-dimensional foam graphene biosensor working electrode for testing a preparation
Stereoscan photograph (X500)；
Fig. 3 is the zinc-oxide nano chip arrays/three-dimensional foam graphene biosensor working electrode for testing a preparation
Stereoscan photograph (X5000)；
Fig. 4 is the zinc-oxide nano chip arrays/three-dimensional foam graphene biosensor working electrode X for testing a preparation
X ray diffraction map；
Wherein: ◆ it is the diffraction maximum of graphene, is the diffraction maximum of zinc oxide；
Fig. 5 is the zinc-oxide nano chip arrays/three-dimensional foam graphene biosensor working electrode for testing a preparation
Raman map；
Fig. 6 is the differential pulse voltammetry curve graph for testing the various concentration dopamine that two obtain；
Fig. 7 is the Linear Fit Chart for testing dopamine concentration and oxidation peak current that two obtain.
Specific embodiment
It elaborates with reference to the accompanying drawing to specific embodiment provided by the invention.Those skilled in the art
It is contemplated that a variety of modifications and adaptations carried out, without changing the spirit or scope of the present invention.This modifications and adaptations include
Within the scope of the invention.Following embodiments are not limit the invention in any way.
Embodiment 1: zinc-oxide nano chip arrays/three-dimensional foam graphene biosensor working electrode preparation
The preparation of zinc-oxide nano chip arrays/three-dimensional foam graphene biosensor working electrode, according to the following steps into
Row:
(1) by nickel foam be placed in quartz tube furnace center, under the protection of argon gas and hydrogen from room temperature with 20 DEG C/min~
It is 1000 DEG C~1100 DEG C that the heating rate of 40 DEG C/min, which is heated to temperature, and under conditions of temperature is 1000 DEG C~1100 DEG C
30min~60min is kept the temperature, into tube furnace with the speed of 5sccm~10sccm under conditions of temperature is 1000 DEG C~1100 DEG C
Rate is passed through methane gas 5min~20min, then by quartz tube furnace with 80 DEG C/min~100 DEG C/min cooling rate from temperature
Degree is cooled to room temperature for 1000 DEG C~1100 DEG C, obtains by the nickel foam of graphene coated；Nickel foam described in step (1) is close
Degree is 420g/m2~440g/m2, with a thickness of 1.6mm~2.0mm；The flow velocity of argon gas described in step (1) be 480sccm~
500sccm, the flow velocity of hydrogen are 180sccm~200sccm；
(2) polymethyl methacrylate is added in ethyl lactate, heating is stirred under conditions of temperature is 80 DEG C~120 DEG C
It mixes 1h~2h and obtains mixed solution, by the usage amount of the 100 μ μ of L~200 L every square centimeter, dripped mixed solution using sample loading gun
It is added on the foam nickel surface wrapped up by graphene that step (1) obtains, spontaneously dries at room temperature, be then 150 in temperature
DEG C~200 DEG C under conditions of heat preservation 0.5h~1h obtain surface cladding polymethyl methacrylate foamy graphite alkene；Step (2)
Described in mixed solution in methyl methacrylate mass fraction be 4%~5%；
(3) the foamy graphite alkene for the surface cladding polymethyl methacrylate that step (2) obtains is cut into surface area is
0.5cm2~2cm2Cube, and be completely soaked molten in the hydrochloric acid that temperature is 80 DEG C~90 DEG C, concentration is 3mol/L~4mol/L
4h~6h obtains the three-dimensional foam graphene of removal nickel in liquid；
(4) the three-dimensional foam graphene for the removal nickel that step (3) obtains is soaked in the acetone that temperature is 60 DEG C~70 DEG C
Middle 0.5h~1.5h obtains the foamy graphite alkene of removal polymethyl methacrylate, will remove polymethylacrylic acid with distilled water
The foamy graphite alkene of methyl esters cleans up, and then shifts the foamy graphite alkene of the removal polymethyl methacrylate cleaned up
Freeze-drying obtains foamy graphite alkene on to clean ito glass；
(5) the clean foamy graphite alkene being placed on ito glass for obtaining step (4) is according to 50 μ L every square centimeter
Zinc oxide seed layer solution is added dropwise using sample loading gun in the usage amount of~100 μ L, keeps the temperature 15min at a temperature of being placed in 150 DEG C~200 DEG C
~30min obtains the foamy graphite alkene/ito glass for being prefabricated with zinc oxide seed layer；Zinc oxide seed layer in step (5) is molten
Liquid is prepared: zinc acetate being dissolved in methanol, then with the revolving speed magnetic agitation 3min of 450r/min~550r/min
~5min obtains zinc oxide seed layer solution；Wherein the concentration of zinc acetate solution is 0.01mol/L~0.5mol/L；
(6) zinc nitrate, hexa, ammonium hydroxide and polyethyleneimine are dissolved in deionized water, with 450r/min~
Revolving speed magnetic agitation 3min~5min of 550r/min, obtains hydrothermal solution；Nitric acid zinc concentration described in step 2 (2) is
0.05mol/L~0.1mol/L；The concentration of hexa is 0.05mol/L~0.1mol/L；The concentration of ammonium hydroxide is
0.05mol/L~0.1mol/L；The concentration of polyethyleneimine is 0.001mol/L~0.002mol/L；
(7) hydrothermal solution obtained in step (6) is poured into reaction kettle, then will be prefabricated with obtained in step (5)
Foamy graphite alkene/ito glass of zinc oxide seed layer is edge-on to be placed in the hydrothermal solution of reaction kettle, while being put into a piece of aluminium
Piece covers reaction kettle lid, is 90 DEG C~120 DEG C heat preservation 6h~13h in temperature, then takes out and be cooled to room temperature, opens reaction
Kettle is cleaned up composite material with distilled water, and in 400 DEG C~450 DEG C heat preservation 1h~1.5h, cool to the furnace room temperature to get
To zinc-oxide nano chip arrays/three-dimensional foam graphene biosensor working electrode.
Embodiment 2: zinc-oxide nano chip arrays/three-dimensional foam graphene biosensor working electrode preparation
The present embodiment is unlike the first embodiment: to pipe under conditions of temperature is 1000 DEG C~1100 DEG C in step (1)
Rate in formula furnace with 7sccm~9sccm is passed through methane gas 10min~15min, then by quartz tube furnace with 85 DEG C/min
The cooling rate of~95 DEG C/min is 1000 DEG C~1100 DEG C from temperature and is cooled to room temperature, and obtains by the foam of graphene coated
Nickel.It is other same as Example 1.
Embodiment 3: zinc-oxide nano chip arrays/three-dimensional foam graphene biosensor working electrode preparation
The present embodiment is unlike embodiment 1 or embodiment 2: cream is added in polymethyl methacrylate in step (2)
In acetoacetic ester, heating stirring 1h~1.5h obtains mixed solution under conditions of temperature is 90 DEG C~110 DEG C, by every square centimeter
Mixed solution is added drop-wise to the bubble wrapped up by graphene that step (1) obtains using sample loading gun by the usage amount of 130 μ of μ L~170 L
On foam nickel surface.It is other identical as embodiment 1 or embodiment 2.
Embodiment 4: zinc-oxide nano chip arrays/three-dimensional foam graphene biosensor working electrode preparation
The present embodiment is unlike embodiment 1-3: being placed on ito glass in step (5) by what step (4) obtained
Clean foamy graphite alkene is molten using sample loading gun dropwise addition zinc oxide seed layer according to the usage amount of the 70 μ μ of L~90 L every square centimeter
Liquid keeps the temperature 20min~25min at a temperature of being placed in 170 DEG C~190 DEG C, obtain being prefabricated with the foamy graphite alkene of zinc oxide seed layer/
Ito glass.It is other identical as embodiment 1-3.
Embodiment 5: zinc-oxide nano chip arrays/three-dimensional foam graphene biosensor working electrode preparation
The present embodiment is unlike embodiment 1-4: nitric acid zinc concentration described in step (6) be 0.06mol/L~
0.08mol/L；The concentration of hexa is 0.06mol/L~0.08mol/L；The concentration of ammonium hydroxide be 0.06mol/L~
0.08mol/L.It is other identical as embodiment 1-4.
Embodiment 6: zinc-oxide nano chip arrays/three-dimensional foam graphene biosensor working electrode preparation
The present embodiment is unlike embodiment 1-5: the hydrothermal solution that step (6) obtains being poured into reaction in step (7)
In kettle, then by foamy graphite alkene/ito glass that zinc oxide seed layer is prefabricated with obtained in step (5) it is edge-on be placed in it is anti-
Answer in the hydrothermal solution of kettle, while being put into a piece of aluminium flake, cover reaction kettle lid, temperature be 100 DEG C~110 DEG C heat preservation 7h~
12h then takes out and is cooled to room temperature.It is other identical as embodiment 1-5.
Using following verification experimental verifications effect of the present invention:
A kind of test one: zinc-oxide nano chip arrays/three-dimensional foam graphene biosensor working electrode of this test
Preparation be to realize by the following method:
(1) nickel foam is placed in quartz tube furnace center, from room temperature with 30 DEG C/min's under the protection of argon gas and hydrogen
It is 1000 DEG C that heating rate, which is heated to temperature, and keeps the temperature 30min under conditions of temperature is 1000 DEG C, is 1000 DEG C in temperature
Under the conditions of rate into tube furnace with 10sccm be passed through methane gas 10min, then by quartz tube furnace with 100 DEG C/min's
Cooling rate is 1000 DEG C from temperature and is cooled to room temperature, and obtains by the nickel foam of graphene coated；Foam described in step (1)
Nickel density is 420g/m2, with a thickness of 1.6mm；The flow velocity of argon gas described in step (1) is 500sccm, and the flow velocity of hydrogen is
200sccm；
(2) polymethyl methacrylate is added in ethyl lactate, heating stirring 2h is obtained under conditions of temperature is 100 DEG C
To mixed solution, by the usage amount of 180 μ L every square centimeter, mixed solution is added drop-wise to what step (1) obtained using sample loading gun
It on the foam nickel surface wrapped up by graphene, spontaneously dries at room temperature, then heat preservation 1h is obtained under conditions of temperature is 200 DEG C
The foamy graphite alkene of polymethyl methacrylate is coated to surface；Methyl methacrylate in mixed solution described in step (2)
The mass fraction of ester is 4%；
(3) the foamy graphite alkene for the surface cladding polymethyl methacrylate that step (2) obtains is cut into surface area is
1cm2Cube, and be completely soaked the 6h in the hydrochloric acid solution that temperature is 80 DEG C, concentration is 3mol/L obtain removal nickel three
Tie up foamy graphite alkene；
(4) the three-dimensional foam graphene for the removal nickel that step (3) obtains is soaked in 1.5h in the acetone that temperature is 60 DEG C,
The foamy graphite alkene of removal polymethyl methacrylate is obtained, the foamy graphite of polymethyl methacrylate will be removed with distilled water
Alkene cleans up, and the foamy graphite alkene of the removal polymethyl methacrylate cleaned up is then transferred to clean ITO glass
Freeze-drying obtains foamy graphite alkene on glass；
(5) the clean foamy graphite alkene being placed on ito glass for obtaining step (4) is according to 80 μ L every square centimeter
Usage amount using sample loading gun be added dropwise zinc oxide seed layer solution, keep the temperature 30min at a temperature of being placed in 200 DEG C, obtain prefabricated aerobic
Change foamy graphite alkene/ito glass of zinc seed layer；Zinc oxide seed layer solution in step (5) is prepared: by acetic acid
Zinc is dissolved in methanol, then with the revolving speed magnetic agitation 5min of 500r/min, obtains zinc oxide seed layer solution；Wherein zinc acetate
The concentration of solution is 0.01mol/L；
(6) zinc nitrate, hexa, ammonium hydroxide and polyethyleneimine are dissolved in deionized water, with 500r/min's
Revolving speed magnetic agitation 5min, obtains hydrothermal solution；Nitric acid zinc concentration described in step (6) is 0.05mol/L；Hexa-methylene
The concentration of tetramine is 0.05mol/L；The concentration of ammonium hydroxide is 0.05mol/L；The concentration of polyethyleneimine is 0.001mol/L；
(7) hydrothermal solution obtained in step (6) is poured into reaction kettle, then will be prefabricated with obtained in step (5)
Foamy graphite alkene/ito glass of zinc oxide seed layer is edge-on to be placed in the hydrothermal solution of reaction kettle, while being put into a piece of aluminium
Piece covers reaction kettle lid, is 100 DEG C of heat preservation 12h in temperature, then takes out and be cooled to room temperature, opens reaction kettle distilled water
Composite material is cleaned up, and in 450 DEG C of heat preservation 1h, cools to room temperature with the furnace to get zinc-oxide nano chip arrays/three-dimensional is arrived
Foamy graphite alkene biosensor working electrode.
Fig. 1-3 is the zinc-oxide nano chip arrays/three-dimensional foam graphene biosensor working electrode for testing a preparation
The stereoscan photograph gradually amplified.It is clear that Zinc oxide nano sheet array growth in three-dimensional foam stone from figure
Black alkene surface, nanometer chip size are about 10 μm, and thickness is about 200-500nm.
Fig. 4 is the zinc-oxide nano chip arrays/three-dimensional foam graphene biosensor working electrode X for testing a preparation
X ray diffraction map.This it appears that the presence of zinc oxide and graphene diffraction maximum from figure, illustrate the composite material be by
What zinc oxide and graphene formed.
Fig. 5 is the zinc-oxide nano chip arrays/three-dimensional foam graphene biosensor working electrode for testing a preparation
Raman map.It can be seen from the figure that, there are also the peak of zinc oxide, also indicating that this is multiple other than having the G band of graphene and 2D band
Condensation material is made of zinc oxide and graphene.
Test two: zinc-oxide nano chip arrays/three-dimensional foam graphene biosensor working electrode detection test
Concrete operations are as follows:
Using zinc-oxide nano chip arrays/three-dimensional foam graphene as the working electrode of biosensor, effective material
Area is 0.7cm2, for silver/silver chlorate as reference electrode, platinum filament, which is used as, passes through arteries and veins using traditional three-electrode system to electrode
It is more to difference to obtain the material to rush voltammetric method test (current potential increment 50mV, pulse height 4mV, sweep speed 8mV/s)
The current-responsive of bar amine concentration, the concentration of dopamine are followed successively by 0 μm of ol/L, 1 μm of ol/L, 5 μm of ol/L, 20 μm of ol/L, 35 μm of ol/
L,50μmol/L,65μmol/L,80μmol/L；The zinc-oxide nano chip arrays/three-dimensional foam graphene biosensor work
It is one preparation of test as electrode.
Fig. 6 is the differential pulse voltammetry curve graph for testing the various concentration dopamine that two obtain.As can be seen that with DOPA
The increase of amine concentration, oxidation peak current value increase therewith, and actually detected are limited to 1 μm of ol/L.
Fig. 7 is the Linear Fit Chart for testing dopamine concentration and oxidation peak current that two obtain.Available, dopamine is dense
The linear relation of degree variation and oxidation peak current, the straight line that dopamine obtains in 1 μm of ol/L~80 μm ol/L concentration range are oblique
Rate is to detect the sensitivity of dopamine, i.e. 0.95 μ A/ μm ol/L.
Claims (9)
1. a kind of zinc-oxide nano chip arrays/three-dimensional foam graphene biosensor working electrode preparation method, feature
It is, follows the steps below:
(1) by nickel foam be placed in quartz tube furnace center, under the protection of argon gas and hydrogen from room temperature with 20 DEG C/min~40 DEG C/
It is 1000 DEG C~1100 DEG C that the heating rate of min, which is heated to temperature, and is kept the temperature under conditions of temperature is 1000 DEG C~1100 DEG C
30min~60min is logical with the rate of 5sccm~10sccm into tube furnace under conditions of temperature is 1000 DEG C~1100 DEG C
Enter methane gas 5min~20min, is then from temperature with 80 DEG C/min~100 DEG C/min cooling rate by quartz tube furnace
1000 DEG C~1100 DEG C are cooled to room temperature, and obtain by the nickel foam of graphene coated；Nickel foam density described in step (1) is
420g/m2~440g/m2, with a thickness of 1.6mm~2.0mm；The flow velocity of argon gas described in step (1) be 480sccm~
500sccm, the flow velocity of hydrogen are 180sccm~200sccm；
(2) polymethyl methacrylate is added in ethyl lactate, heating stirring 1h under conditions of temperature is 80 DEG C~120 DEG C
~2h obtains mixed solution, by the usage amount of the 100 μ μ of L~200 L every square centimeter, is added drop-wise to mixed solution using sample loading gun
Step (1) obtain by graphene wrap up foam nickel surface on, spontaneously dry at room temperature, then temperature be 150 DEG C~
0.5h~1h is kept the temperature under conditions of 200 DEG C obtains the foamy graphite alkene of surface cladding polymethyl methacrylate；Institute in step (2)
The mass fraction of methyl methacrylate is 4%~5% in the mixed solution stated；
(3) the foamy graphite alkene for the surface cladding polymethyl methacrylate that step (2) obtains is cut into surface area is 0.5cm2
~2cm2Cube, and be completely soaked in the hydrochloric acid solution that temperature is 80 DEG C~90 DEG C, concentration is 3mol/L~4mol/L
4h~6h obtains the three-dimensional foam graphene of removal nickel；
(4) the three-dimensional foam graphene for the removal nickel that step (3) obtains is soaked in the acetone that temperature is 60 DEG C~70 DEG C
0.5h~1.5h obtains the foamy graphite alkene of removal polymethyl methacrylate, will remove poly-methyl methacrylate with distilled water
The foamy graphite alkene of ester cleans up, and is then transferred to the foamy graphite alkene of the removal polymethyl methacrylate cleaned up
Freeze-drying obtains foamy graphite alkene on clean ito glass；
(5) the clean foamy graphite alkene being placed on ito glass for obtaining step (4) according to 50 μ L every square centimeter~
The usage amount of 100 μ L using sample loading gun be added dropwise zinc oxide seed layer solution, at a temperature of being placed in 150 DEG C~200 DEG C keep the temperature 15min~
30min obtains the foamy graphite alkene/ito glass for being prefabricated with zinc oxide seed layer；Zinc oxide seed layer solution in step (5)
Be prepared: zinc acetate be dissolved in methanol, then with the revolving speed magnetic agitation 3min of 450r/min~550r/min~
5min obtains zinc oxide seed layer solution；Wherein the concentration of zinc acetate solution is 0.01mol/L~0.5mol/L；
(6) zinc nitrate, hexa, ammonium hydroxide and polyethyleneimine are dissolved in deionized water, with 450r/min~550r/
Revolving speed magnetic agitation 3min~5min of min, obtains hydrothermal solution；Nitric acid zinc concentration described in step (6) is
0.05mol/L~0.1mol/L；The concentration of hexa is 0.05mol/L~0.1mol/L；The concentration of ammonium hydroxide is
0.05mol/L~0.1mol/L；The concentration of polyethyleneimine is 0.001mol/L~0.002mol/L；
(7) hydrothermal solution obtained in step (6) is poured into reaction kettle, then oxidation will be prefabricated with obtained in step (5)
Foamy graphite alkene/ito glass of zinc seed layer is edge-on to be placed in the hydrothermal solution of reaction kettle, while being put into a piece of aluminium flake, lid
Upper reaction kettle lid is 90 DEG C~120 DEG C heat preservation 6h~13h in temperature, then takes out and be cooled to room temperature, and opens reaction kettle and steams
Distilled water cleans up composite material, and in 400 DEG C~450 DEG C heat preservation 1h~1.5h, cools to room temperature with the furnace to get oxidation is arrived
Zinc nano-chip arrays/three-dimensional foam graphene biosensor working electrode.
2. the method as described in claim 1, which is characterized in that the condition for being 1000 DEG C~1100 DEG C in temperature in step (1)
The lower rate into tube furnace with 7sccm~9sccm is passed through methane gas 10min~15min, then by quartz tube furnace with 85
DEG C/min~95 DEG C/min cooling rate from temperature be 1000 DEG C~1100 DEG C be cooled to room temperature, obtain by graphene coated
Nickel foam.
3. the method as described in claim 1, which is characterized in that lactic acid second is added in polymethyl methacrylate in step (2)
In ester, heating stirring 1h~1.5h obtains mixed solution under conditions of temperature is 90 DEG C~110 DEG C, by 130 μ every square centimeter
Mixed solution is added drop-wise to the nickel foam wrapped up by graphene that step (1) obtains using sample loading gun by the usage amount of the μ of L~170 L
On surface.
4. the method as described in claim 1, which is characterized in that be placed into ito glass for what step (4) obtained in step (5)
On clean foamy graphite alkene according to the 70 μ μ of L~90 L every square centimeter usage amount using sample loading gun be added dropwise zinc oxide seed
Layer solution, keeps the temperature 20min~25min, obtains the foam stone for being prefabricated with zinc oxide seed layer at a temperature of being placed in 170 DEG C~190 DEG C
Black alkene/ito glass.
5. the method as described in claim 1, which is characterized in that nitric acid zinc concentration described in step (6) is 0.06mol/L
~0.08mol/L；The concentration of hexa is 0.06mol/L~0.08mol/L；The concentration of ammonium hydroxide be 0.06mol/L~
0.08mol/L。
6. the method as described in claim 1, which is characterized in that pour into the hydrothermal solution that step (6) obtains instead in step (7)
It answers in kettle, is then placed in the foamy graphite alkene for being prefabricated with zinc oxide seed layer obtained in step (5)/ito glass is edge-on
In the hydrothermal solution of reaction kettle, while it being put into a piece of aluminium flake, cover reaction kettle lid, is 100 DEG C~110 DEG C heat preservation 7h in temperature
~12h, then takes out and is cooled to room temperature.
7. the method as described in claim 1, which is characterized in that follow the steps below:
(1) nickel foam is placed in quartz tube furnace center, from room temperature with the heating of 30 DEG C/min under the protection of argon gas and hydrogen
It is 1000 DEG C that rate, which is heated to temperature, and keeps the temperature 30min under conditions of temperature is 1000 DEG C, the condition for being 1000 DEG C in temperature
The lower rate into tube furnace with 10sccm is passed through methane gas 10min, then by quartz tube furnace with the cooling of 100 DEG C/min
Rate is 1000 DEG C from temperature and is cooled to room temperature, and obtains by the nickel foam of graphene coated；Nickel foam described in step (1) is close
Degree is 420g/m2, with a thickness of 1.6mm；The flow velocity of argon gas described in step (1) is 500sccm, and the flow velocity of hydrogen is
200sccm；
(2) polymethyl methacrylate is added in ethyl lactate, heating stirring 2h is mixed under conditions of temperature is 100 DEG C
Close solution, by the usage amount of 180 μ L every square centimeter, using sample loading gun by mixed solution be added drop-wise to that step (1) obtains by stone
It on the foam nickel surface of black alkene package, spontaneously dries at room temperature, then heat preservation 1h obtains table under conditions of temperature is 200 DEG C
Bread covers the foamy graphite alkene of polymethyl methacrylate；Methyl methacrylate in mixed solution described in step (2)
Mass fraction is 4%；
(3) the foamy graphite alkene for the surface cladding polymethyl methacrylate that step (2) obtains is cut into surface area is 1cm2's
Cube, and be completely soaked the 6h in the hydrochloric acid solution that temperature is 80 DEG C, concentration is 3mol/L and obtain the three-dimensional foam of removal nickel
Graphene；
(4) the three-dimensional foam graphene for the removal nickel that step (3) obtains is soaked in 1.5h in the acetone that temperature is 60 DEG C, obtained
The foamy graphite alkene of polymethyl methacrylate is removed, it is with distilled water that the foamy graphite alkene for removing polymethyl methacrylate is clear
Then the foamy graphite alkene of the removal polymethyl methacrylate cleaned up is transferred on clean ito glass by wash clean
Freeze-drying obtains foamy graphite alkene；
(5) the clean foamy graphite alkene being placed on ito glass for obtaining step (4) makes according to 80 μ L every square centimeter
Zinc oxide seed layer solution is added dropwise using sample loading gun in dosage, keeps the temperature 30min at a temperature of being placed in 200 DEG C, obtains being prefabricated with zinc oxide
Foamy graphite alkene/ito glass of seed layer；Zinc oxide seed layer solution in step (5) is prepared: zinc acetate is molten
In methanol, then with the revolving speed magnetic agitation 5min of 500r/min, zinc oxide seed layer solution is obtained；Wherein zinc acetate solution
Concentration be 0.01mol/L；
(6) zinc nitrate, hexa, ammonium hydroxide and polyethyleneimine are dissolved in deionized water, with the revolving speed of 500r/min
Magnetic agitation 5min, obtains hydrothermal solution；Nitric acid zinc concentration described in step (6) is 0.05mol/L；Hexa
Concentration be 0.05mol/L；The concentration of ammonium hydroxide is 0.05mol/L；The concentration of polyethyleneimine is 0.001mol/L；
(7) hydrothermal solution obtained in step (6) is poured into reaction kettle, then oxidation will be prefabricated with obtained in step (5)
Foamy graphite alkene/ito glass of zinc seed layer is edge-on to be placed in the hydrothermal solution of reaction kettle, while being put into a piece of aluminium flake, lid
Upper reaction kettle lid, temperature be 100 DEG C of heat preservation 12h, then take out and be cooled to room temperature, opening reaction kettle distilled water will be compound
Material clean is clean, and in 450 DEG C of heat preservation 1h, cools to room temperature with the furnace to get zinc-oxide nano chip arrays/three-dimensional foam stone is arrived
Black alkene biosensor working electrode.
8. the zinc-oxide nano chip arrays/three-dimensional foam graphite being prepared according to the described in any item methods of claim 1-7
Alkene biosensor working electrode.
9. prepared by zinc-oxide nano chip arrays/three-dimensional foam graphene biosensor working electrode according to any one of claims 8
Detect the application in the biosensor of dopamine.
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