CN106990149A - A kind of preparation of molybdenum disulfide graphene composite nano plate biological sensor electrode - Google Patents
A kind of preparation of molybdenum disulfide graphene composite nano plate biological sensor electrode Download PDFInfo
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- 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
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- G01N27/3275—Sensing specific biomolecules, e.g. nucleic acid strands, based on an electrode surface reaction
- G01N27/3278—Sensing specific biomolecules, e.g. nucleic acid strands, based on an electrode surface reaction involving nanosized elements, e.g. nanogaps or nanoparticles
Abstract
A kind of preparation of molybdenum disulfide graphene composite nano plate biological sensor electrode, is related to a kind of preparation of molybdenum disulfide graphene composite nano plate biological sensor electrode.The problem of levodopa sensitivity is low is detected in biology sensor the present invention is to solve current material.Preparation method of the present invention is as follows：First, chemical vapour deposition technique；2nd, liquid phase ultrasonic wave added stripping method；3rd, liquid phase ultrasonic dispersion；4th, automatic spraying process.A kind of molybdenum disulfide graphene composite nano plate biological sensor electrode conductivity prepared by the present invention is excellent, available for efficient, Sensitive Detection levodopa.
Description
Technical field
The present invention relates to a kind of preparation method and applications of novel nanocomposite materials electrochemica biological sensor electrode.
Background technology
Graphene is that one kind is combined by carbon atom with sp2 hybridized orbits, only the two-dimensional material of monoatomic layer thickness, is structure
Into the elementary cell of carbonaceous material, the chemical stability having had by it, electric conductivity, mechanical strength, as the heat studied at present
Point.At present, the preparation method of graphene mainly has mechanical stripping method, chemical vapour deposition technique and redox graphene method, its
In, the graphene that chemical vapour deposition technique is prepared has higher quality, few defect and good electric conductivity, thus
It is widely used.Chemical vapour deposition technique can use the nickel foam template of three-dimensional structure, prepare identical with formwork structure pattern
Three-dimensional foam graphene (GF), three-dimensional foam graphene has the mesh space structure of three-dimensional communication, with big ratio surface
Product.
Molybdenum disulfide is a kind of transient metal sulfide, and its two-dimensional layered structure is similar to graphene, is considered as in electricity
With having huge potentiality in terms of catalytic applications, substantial amounts of exposed edge makes molybdenum disulfide nano sheet have outstanding catalytic activity
With excellent bio-sensing characteristic, so as to be widely used in field of biosensors.In the preparation method of molybdenum disulfide, liquid
Mutually ultrasonic stripping method operation is simpler, with the features such as cost is low, yield is big.In addition, liquid phase ultrasound peels off obtained curing
Molybdenum nanometer sheet can be preserved with solution also can drying process, be easy to follow-up shift, be combined.
Parkinson's are a kind of common the nervous system diseases, and its clinical manifestation mainly includes static tremor, motion late
Slow, myotonia and posture gait disorder, while patient can be with non-motor symptoms such as depressed, constipation and sleep-disorder.Dopamine
Impaired is to cause the main cause of Parkinson's.Levodopa (L-dopa), also known as levodopa (L-dopa), are antiparkinsonian drug, can
It is changed into dopamine in human body in the presence of aromatic amino acid decarboxylase to do, by blood-brain barrier, plays a role.At present,
Levodopa drug therapy is the topmost treatment means of Parkinson's.After human body supplement levodopa, brain can be made up many
The deficiency of bar amine, still, excessive dopamine can produce toxic side effect to human body.So, accurately detect containing for levodopa
Amount has very important significance.
The content of the invention
The present invention is to solve molybdenum disulfide nano sheet specific surface area itself is limited, relatively low conductivity etc. is limited
It is the problem of field of biosensors is applied.The graphene nanometer sheet of high conductance is equably added to molybdenum disulfide nano sheet
In, a kind of new molybdenum disulfide-graphene composite nano-grade sheet material is developed, so that it is multiple to provide a kind of molybdenum disulfide-graphene
Close the preparation of nanometer sheet biological sensor electrode.
A kind of preparation of molybdenum disulfide that the present invention is provided-graphene composite nano plate biological sensor electrode is by following
Step is carried out：
First, chemical vapour deposition technique
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/
Min heating rate is heated to temperature for 1000 DEG C ~ 1100 DEG C, and is incubated under conditions of temperature is 1000 DEG C ~ 1100 DEG C
30min ~ 60min, first is passed through under conditions of temperature is 1000 DEG C ~ 1100 DEG C into tube furnace with 5sccm ~ 10sccm speed
Alkane gas 5min ~ 20min, then by quartz tube furnace using 80 DEG C/min ~ 100 DEG C/min cooldown rate from temperature as 1000 DEG C
~ 1100 DEG C are cooled to room temperature, obtain by the nickel foam of graphene coated, step one (1) described in nickel foam density be 420g/
m2~440g/m2, thickness is 1.6mm ~ 2.0mm；Step one (1) described in argon gas flow velocity be 480sccm ~ 500sccm, hydrogen
Flow velocity be 180sccm ~ 200sccm；
By polymethyl methacrylate add ethyl lactate in, temperature be 80 DEG C ~ 120 DEG C under conditions of heating stirring 1h ~
2h obtains mixed solution, and mixed solution is added drop-wise into step using sample loading gun by the usage amount every square centimeter for having a μ L of 100 μ L ~ 200
On the rapid one foam nickel surface wrapped up by graphene (1) obtained, spontaneously dry at room temperature, be then 150 DEG C ~ 200 in temperature
0.5h ~ 1h is incubated under conditions of DEG C and obtains the foamy graphite alkene of Surface coating polymethyl methacrylate, step one (2) described in
Mixed solution in methyl methacrylate mass fraction be 4% ~ 5%；
(3) the foamy graphite alkene of the Surface coating polymethyl methacrylate (2) step one obtained cuts into surface area and 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
Middle 4h ~ 6h obtains removing the three-dimensional foam graphene of nickel；The three-dimensional foam graphene of obtained removal nickel is soaked in into temperature is
0.5h ~ 1.5h in 60 DEG C ~ 70 DEG C of acetone, obtains removing the foamy graphite alkene of polymethyl methacrylate, then uses distilled water
The foamy graphite alkene for removing polymethyl methacrylate is cleaned up, then by the removal poly-methyl methacrylate cleaned up
The foamy graphite alkene of ester is transferred to freeze-drying on clean ito glass and obtains graphene；
2nd, liquid phase ultrasonic wave added stripping method
(1) molybdenum disulphide powder is added to the mixed solution of acetone and water（89:11v/v）In, wherein molybdenum disulfide concentration is 30mg
mL-1, stirring makes after molybdenum disulfide is uniformly dispersed, to carry out ultrasound stripping, ultrasonic mistake under 540W power using processor for ultrasonic wave
Journey prevents probe from overheating under low-temperature circulating using the 20s pulse modes for opening 10s passes, and ultrasonic splitting time is 1-4h；
(2) the molybdenum disulfide nano sheet suspension obtained after being peeled off to ultrasound is centrifuged by 3000rpm of centrifugation rate, is centrifuged
30 minutes time, the supernatant that centrifugation is obtained, which is placed in air dry oven, to be dried, by dried molybdenum disulfide nano
Piece is placed in bottle to be disperseed with deionized water, obtains concentration for 20mgmL-1Molybdenum disulfide nano sheet suspension；
3rd, liquid phase ultrasonic dispersion
(1) the foamy graphite alkene by step one (4) middle preparation is added in deionized water, and concentration is 0.07mgmL-1, using super
Sound wave processor carries out ultrasonic stripping under 540W power to dispersion liquid, and ultrasonic procedure opens 10s passes under low-temperature circulating using 20s
Pulse mode prevent probe overheat, ultrasonic splitting time is 1-4h, obtains graphene nanometer sheet suspension；
(2) 0.5mL molybdenum disulfide nano sheet and 19.5mL graphene nanometer sheet suspension are mixed to get concentration ratio 9：1
Molybdenum disulfide-graphene composite nano plate mixed solution, ultrasonic disperse obtains uniform suspension；
4th, automatic spraying process
(1) ITO electro-conductive glass is cleaned by ultrasonic after 20min in acetone soln, ethanol solution and deionized water respectively, at room temperature
Natural cooling is dried, and six pieces of ITO electro-conductive glass are fixed in spraying equipment heating plate, with adhesive tape by ITO electro-conductive glass
Press from both sides the covering of electrode wires side, it is ensured that electrode wires are directly contacted with ITO electro-conductive glass；
(2) finely dispersed molybdenum disulfide-graphene composite nano plate suspension by step 3 (2) middle preparation is placed in spray gun and adopted
Molybdenum disulfide-graphene composite nano plate/ITO electrode is built with automatic spraying process, whole spraying process is at 10 pounds/square inch
Carried out under air inlet pressure；The distance of nozzle to ITO electro-conductive glass is 15cm, and heating dish temperature is 110 DEG C, will be coated with curing
The ITO electrode of molybdenum-graphene composite nano plate is placed in quartz tube furnace, under 400sccm argon gas protection, with 10 DEG C
min-1Speed be warming up to 700 DEG C insulation 2h, last furnace cooling to room temperature, obtain molybdenum disulfide-graphene composite nano plate/
ITO electrode.
Advantages of the present invention：
(1) the ultrasound stripping of molybdenum disulphide powder liquid phase is obtained molybdenum disulfide nano sheet and uses chemical vapour deposition technique by the inventive method
The three-dimensional foam graphene liquid phase ultrasonic disperse prepared obtains graphene nanometer sheet, is prepared for a kind of molybdenum disulfide-graphene
Composite nano plate biological sensor electrode；
(2) the present invention introduces height prepared by chemical vapor deposition by being peeled off to liquid phase ultrasound in obtained molybdenum disulfide nano sheet
Quality, high conductance, the graphene of bigger serface and few layer, compensate for molybdenum disulfide nano sheet in itself relatively low electrical conductance and
Electrocatalysis characteristic, improves the chemical property of material, may be such that the sensitivity of Electrochemical Detection levodopa reaches 0.36 μ
A·μM-1。
Brief description of the drawings
Fig. 1 is the stereoscan photograph that molybdenum disulfide-graphene composite nano plate prepared by experiment amplifies 5000 times；
Fig. 2 is the stereoscan photograph of 20000 times of the amplification of molybdenum disulfide-graphene composite nano plate prepared by experiment；
Fig. 3 is the X ray diffracting spectrum of molybdenum disulfide and molybdenum disulfide-graphene composite nano plate, and figure intermediate cam morpheme is set to
The diffraction maximum of graphene；
Fig. 4 is the Raman collection of illustrative plates of molybdenum disulfide and molybdenum disulfide-graphene composite nano plate；
Fig. 5 is the Linear Fit Chart of the levodopa concentration that experiment is obtained and oxidation peak current.
Embodiment
Embodiment one：A kind of molybdenum disulfide-graphene composite nano plate biology sensor electricity in present embodiment
The preparation method of pole, is specifically what is carried out according to the following steps：
First, chemical vapour deposition technique
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/
Min heating rate is heated to temperature for 1000 DEG C ~ 1100 DEG C, and is incubated under conditions of temperature is 1000 DEG C ~ 1100 DEG C
30min ~ 60min, first is passed through under conditions of temperature is 1000 DEG C ~ 1100 DEG C into tube furnace with 5sccm ~ 10sccm speed
Alkane gas 5min ~ 20min, then by quartz tube furnace using 80 DEG C/min ~ 100 DEG C/min cooldown rate from temperature as 1000 DEG C
~ 1100 DEG C are cooled to room temperature, obtain by the nickel foam of graphene coated, step one (1) described in nickel foam density be 420g/
m2~440g/m2, thickness be 1.6mm ~ 2.0mm, step one (1) described in argon gas flow velocity be 480sccm ~ 500sccm, hydrogen
Flow velocity be 180sccm ~ 200sccm；
By polymethyl methacrylate add ethyl lactate in, temperature be 80 DEG C ~ 120 DEG C under conditions of heating stirring 1h ~
2h obtains mixed solution, and by the usage amount every square centimeter for having a μ L of 100 μ L ~ 200, mixed solution is added drop-wise into step using sample loading gun
On the rapid one foam nickel surface wrapped up by graphene (1) obtained, spontaneously dry at room temperature, be then 150 DEG C ~ 200 in temperature
0.5h ~ 1h is incubated under conditions of DEG C and obtains the foamy graphite alkene of Surface coating polymethyl methacrylate, step one (2) described in
Mixed solution in methyl methacrylate mass fraction be 4% ~ 5%；
(3) the foamy graphite alkene of the Surface coating polymethyl methacrylate (2) step one obtained cuts into surface area and 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
Middle 4h ~ 6h obtains removing the three-dimensional foam graphene of nickel, and the three-dimensional foam graphene of obtained removal nickel is soaked in into temperature is
0.5h ~ 1.5h in 60 DEG C ~ 70 DEG C of acetone, obtains removing the foamy graphite alkene of polymethyl methacrylate, then uses distilled water
The foamy graphite alkene for removing polymethyl methacrylate is cleaned up, then by the removal poly-methyl methacrylate cleaned up
The foamy graphite alkene of ester is transferred to freeze-drying on clean ito glass and obtains graphene；
2nd, liquid phase ultrasonic wave added stripping method
(1) molybdenum disulphide powder is added to the mixed solution of acetone and water（89:11v/v）In, wherein molybdenum disulfide concentration is 30mg
mL-1, stirring makes after molybdenum disulfide is uniformly dispersed, to carry out ultrasound stripping, ultrasonic mistake under 540W power using processor for ultrasonic wave
Journey prevents probe from overheating under low-temperature circulating using the 20s pulse modes for opening 10s passes, and ultrasonic splitting time is 1-4h；
(2) the molybdenum disulfide nano sheet suspension obtained after being peeled off to ultrasound is centrifuged by 3000rpm of centrifugation rate, is centrifuged
30 minutes time, the supernatant that centrifugation is obtained, which is placed in air dry oven, to be dried, by dried molybdenum disulfide nano
Piece is placed in bottle to be disperseed with deionized water, obtains concentration for 20mgmL-1Molybdenum disulfide nano sheet suspension；
3rd, liquid phase ultrasonic dispersion
(1) the foamy graphite alkene by step one (4) middle preparation is added in deionized water, and concentration is 0.07mgmL-1, using super
Sound wave processor carries out ultrasonic stripping under 540W power to dispersion liquid, and ultrasonic procedure opens 10s passes under low-temperature circulating using 20s
Pulse mode prevent probe overheat, ultrasonic splitting time is 1-4h, obtains graphene nanometer sheet suspension；
(2) 0.5mL molybdenum disulfide nano sheet and 19.5mL graphene nanometer sheet suspension are mixed to get concentration ratio 9：1
Molybdenum disulfide-graphene composite nano plate mixed solution, ultrasonic disperse obtains uniform suspension；
4th, automatic spraying process
(1) ITO electro-conductive glass is cleaned by ultrasonic after 20min in acetone soln, ethanol solution and deionized water respectively, at room temperature
Natural cooling is dried, and six pieces of ITO electro-conductive glass are fixed in spraying equipment heating plate, with adhesive tape by ITO electro-conductive glass
Press from both sides the covering of electrode wires side, it is ensured that electrode wires are directly contacted with ITO electro-conductive glass；
(2) finely dispersed molybdenum disulfide-graphene composite nano plate suspension by step 3 (2) middle preparation is placed in spray gun and adopted
Molybdenum disulfide-graphene composite nano plate/ITO electrode is prepared with automatic spraying process, whole spraying process is at 10 pounds/square inch
Carried out under air inlet pressure, the distance of nozzle to ITO electro-conductive glass is 15cm, and heating dish temperature is 110 DEG C, will be coated with curing
The ITO electrode of molybdenum-graphene composite nano plate is placed in quartz tube furnace, under 400sccm argon gas protection, with 10 DEG C
min-1Speed be warming up to 700 DEG C insulation 2h, last furnace cooling to room temperature, obtain molybdenum disulfide-graphene composite nano plate/
ITO electrode；
Embodiment two：Present embodiment from unlike embodiment one：Step one (1) in nickel foam is placed in
Quartz tube furnace center, is heated under the protection of argon gas and hydrogen from room temperature with 25 DEG C/min ~ 35 DEG C/min heating rate
Temperature is 1000 DEG C ~ 1100 DEG C, and is incubated 35min ~ 55min under conditions of temperature is 1000 DEG C ~ 1100 DEG C, is in temperature
Methane gas 10min ~ 15min is passed through with 7sccm ~ 9sccm speed into tube furnace under conditions of 1000 DEG C ~ 1100 DEG C, so
Quartz tube furnace is cooled to room temperature from temperature as 1000 DEG C ~ 1100 DEG C using 85 DEG C/min ~ 95 DEG C/min cooldown rate afterwards, obtained
To by the nickel foam of graphene coated；Step one (1) described in nickel foam density be 425g/m2~435g/m2, thickness is 1.6mm
~ 2.0mm, step one (1) described in the flow velocity of argon gas be 480sccm, the flow velocity of hydrogen is 180sccm, other with specific implementation
Mode one is identical；
Embodiment three：Present embodiment from unlike embodiment one or two：Step one (2) in by poly- methyl
Methyl acrylate is dissolved in ethyl lactate, and heating stirring 1h ~ 2h is mixed under conditions of temperature is 90 DEG C ~ 110 DEG C
Solution, is added drop-wise to step one by mixed solution using sample loading gun by the usage amount every square centimeter for having the μ L of 120 μ L ~ 180 and (1) obtains
The foam nickel surface wrapped up by graphene on, spontaneously dry at room temperature, then temperature be 150 DEG C ~ 200 DEG C under conditions of
Insulation 0.5h ~ 1h obtains the foamy graphite alkene of Surface coating polymethyl methacrylate, step one (2) described in mixed solution
The mass fraction of middle methyl methacrylate is 4% ~ 5 %, other identical with embodiment one or two；
Embodiment four：Unlike one of present embodiment and embodiment one to three：Step one is (3) middle will step
The foamy graphite alkene of the rapid one Surface coating polymethyl methacrylate (2) obtained cuts into surface area for 1.0cm2~1.5cm2's
Cube, and be completely soaked 4.5h ~ 5.5h in the hydrochloric acid solution that temperature is 80 DEG C ~ 90 DEG C, concentration is 3mol/L ~ 4mol/L and obtain
It is other identical with embodiment one to three to the three-dimensional foam graphene for removing nickel.
Using following verification experimental verifications effect of the present invention：
Experiment one：A kind of preparation method of molybdenum disulfide of this experiment-graphene composite nano plate biological sensor electrode be by
Following methods are realized：
First, chemical vapour deposition technique
(1) nickel foam is placed in quartz tube furnace center, from room temperature with 40 DEG C/min heating speed under the protection of argon gas and hydrogen
Rate is heated to 1010 DEG C, is incubated 30min, and first is passed through into tube furnace with 20sccm speed under conditions of temperature is 1010 DEG C
Alkane gas 10min, is then cooled to room temperature from 1010 DEG C with 100 DEG C/min cooldown rate by quartz tube furnace, obtains by stone
The nickel foam of black alkene cladding, step one (1) described in nickel foam density be 430g/m2, thickness is 1.6mm, step one (1) middle institute
The flow velocity for the argon gas stated is 500sccm, and the flow velocity of hydrogen is 200sccm；
(2) polymethyl methacrylate is dissolved in ethyl lactate, and heating stirring 2h is obtained under conditions of temperature is 100 DEG C
To mixed solution, mixed solution is added drop-wise to step one using sample loading gun by the usage amount every square centimeter for there are 120 μ L and (1) obtained
The foam nickel surface wrapped up by graphene on, spontaneously dry at room temperature, then temperature be 200 DEG C under conditions of be incubated
0.5h obtains the foamy graphite alkene of Surface coating polymethyl methacrylate, step one (2) described in mixed solution in methyl-prop
The mass fraction of e pioic acid methyl ester is 4%；
(3) the foamy graphite alkene of the Surface coating polymethyl methacrylate (2) step one obtained cuts into surface area for 1cm2
Cube, and be completely soaked the three-dimensional bubble that the 6h in the hydrochloric acid solution that temperature is 90 DEG C, concentration is 3mol/L obtains removing nickel
Foam graphene, is soaked in 1.5h in the acetone that temperature is 60 DEG C by the three-dimensional foam graphene of obtained removal nickel, is removed
The foamy graphite alkene of polymethyl methacrylate is then clear by the foamy graphite alkene for removing polymethyl methacrylate with distilled water
The foamy graphite alkene of the removal polymethyl methacrylate cleaned up, is then transferred on clean ito glass by wash clean
Freeze-drying obtains foamy graphite alkene；
2nd, liquid phase ultrasonic wave added stripping method
(1) molybdenum disulphide powder is added to the mixed solution of acetone and water（89:11v/v）In, wherein molybdenum disulfide concentration is 30mg
ML-1, stirring makes after molybdenum disulfide is uniformly dispersed, to carry out ultrasound stripping, ultrasonic mistake under 540W power using processor for ultrasonic wave
Journey prevents probe from overheating under low-temperature circulating using the 20s pulse modes for opening 10s passes, and ultrasonic splitting time is 1-4h；
(2) the molybdenum disulfide nano sheet suspension obtained after being peeled off to ultrasound is centrifuged by 3000rpm of centrifugation rate, is centrifuged
30 minutes time, the supernatant that centrifugation is obtained, which is placed in air dry oven, to be dried, by dried molybdenum disulfide nano
Piece is placed in bottle to be disperseed with deionized water, obtains the molybdenum disulfide nano sheet suspension that concentration is 20mgmL-1；
3rd, liquid phase ultrasonic dispersion
(1) the foamy graphite alkene by step one (4) middle preparation is added in deionized water, and concentration is 0.07mgmL-1.Using super
Sound wave processor carries out ultrasonic stripping under 540W power to dispersion liquid, and ultrasonic procedure opens 10s passes under low-temperature circulating using 20s
Pulse mode prevent probe overheat, ultrasonic splitting time is 1-4h, obtains graphene nanometer sheet suspension；
(2) 0.5mL molybdenum disulfide nano sheet and 19.5mL graphene nanometer sheet suspension are mixed to get concentration ratio 9：1
Molybdenum disulfide-graphene composite nano plate mixed solution, ultrasonic disperse obtains uniform suspension；
4th, automatic spraying process
(1) ITO electro-conductive glass is cleaned by ultrasonic after 20min in acetone soln, ethanol solution and deionized water respectively, at room temperature
Natural cooling is dried, and six pieces of ITO electro-conductive glass are fixed in spraying equipment heating plate, with adhesive tape by ITO electro-conductive glass
Press from both sides the covering of electrode wires side, it is ensured that electrode wires are directly contacted with ITO electro-conductive glass；
(2) finely dispersed molybdenum disulfide-graphene composite nano plate suspension by step 3 (2) middle preparation is placed in spray gun and adopted
Molybdenum disulfide-graphene composite nano plate/ITO electrode is prepared with automatic spraying process, whole spraying process is at 10 pounds/square inch
Carried out under air inlet pressure, the distance of nozzle to ITO electro-conductive glass is 15cm, and heating dish temperature is 110 DEG C, will be coated with curing
The ITO electrode of molybdenum-graphene composite nano plate is placed in quartz tube furnace, under 400sccm argon gas protection, with 10 DEG C
min-1Speed be warming up to 700 DEG C insulation 2h, last furnace cooling to room temperature, obtain molybdenum disulfide-graphene composite nano plate/
ITO electrode.
Fig. 1 is that molybdenum disulfide-graphene composite nano plate of synthesis amplifies 5000 times of stereoscan photograph；Fig. 2 is to close
Into molybdenum disulfide-graphene composite nano plate amplify 20000 times of stereoscan photograph, as can be seen from the figure composite Nano
Piece surface is smooth, and graphene sheet layer is thin, transparent shape.Molybdenum disulfide nano sheet lamella is smaller, size uniform；Fig. 3 is curing
The X ray diffracting spectrum of molybdenum and molybdenum disulfide-graphene composite nano plate, mark triangle position is the diffraction maximum of graphene,
Correspondence graphene is occurred in that in molybdenum disulfide-graphene composite nano-grade sheet material homologous thread 26.5 ° of positions（002）Crystal face
Diffraction maximum, and the characteristic peak intensity decreases of molybdenum disulfide, especially（002）The characteristic peak of crystal face even disappears, and illustrates graphene
In the presence of the restructuring for effectively preventing molybdenum disulfide nano sheet；Fig. 4 is molybdenum disulfide and molybdenum disulfide-graphene composite nano plate
Raman collection of illustrative plates, wherein in 1352cm-1, 1585cm-1With 2685 cm-1Occur the characteristic peak of three correspondence graphenes at position, point
Wei not be by SP3D bands, SP caused by the coplanar vibration of orbital hybridization carbon atom2G bands caused by the coplanar vibration of the carbon atom of hydridization
With due to 2D bands caused by double resonance Raman scattering, show that composite construction is made up of molybdenum disulfide with graphene, D bands represent hexagonal
The destructiveness of lattice structure；I D/I GAbout 0.2, show that the graphene prepared has a small amount of defect, this is due to ultrasonication
The process of three-dimensional foam graphene smashes complete graphene, destroys the integrality of graphene, causes graphene nanometer sheet
Marginal texture is destroyed, andI G/I 2DIt is few layer of graphene to show what is obtained more than 1.
Experiment two：Molybdenum disulfide-graphene composite nano plate is tested as the detection of working electrode, and concrete operations are as follows：
Using molybdenum disulfide-graphene composite nano plate together with ito glass as working electrode, effective material area is
0.7cm2, silver/silver chlorate passes through Pulse Voltammetry side as to electrode as reference electrode, platinum filament using traditional three-electrode system
Method is tested, current potential increase 50mV, the mV of pulse height 4, the mV/s of sweep speed 8, so that it is left-handed to various concentrations to obtain the material
The oxidation peak current value of DOPA；Described molybdenum disulfide-graphene composite nano plate is prepared by experiment one；
(2) the line of levodopa concentration and oxidation peak current is obtained by electrochemistry pulse voltammetry using traditional three-electrode system
Property fitted figure, Fig. 5 is the Linear Fit Chart for testing two obtained levodopa concentrations and oxidation peak current, in 0 μM ~ 60 μM of model
In enclosing, levodopa concentration changes, molybdenum disulfide-graphene composite nano plate/ITO electrode linear with oxidation peak current
The sensitivity for detecting levodopa is 0.36 μ A μM-1。
Claims (10)
1. a kind of preparation of molybdenum disulfide-graphene composite nano plate biological sensor electrode, it is characterised in that molybdenum disulfide-stone
The preparation method of black alkene composite nano plate biological sensor electrode is carried out according to the following steps：
First, chemical vapour deposition technique
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/
Min heating rate is heated to temperature for 1000 DEG C ~ 1100 DEG C, and is incubated under conditions of temperature is 1000 DEG C ~ 1100 DEG C
30min ~ 60min, first is passed through under conditions of temperature is 1000 DEG C ~ 1100 DEG C into tube furnace with 5sccm ~ 10sccm speed
Alkane gas 5min ~ 20min, then by quartz tube furnace using 80 DEG C/min ~ 100 DEG C/min cooldown rate from temperature as 1000 DEG C
~ 1100 DEG C are cooled to room temperature, obtain by the nickel foam of graphene coated, step one (1) described in nickel foam density be 420g/
m2~440g/m2, thickness be 1.6mm ~ 2.0mm, step one (1) described in argon gas flow velocity be 480sccm ~ 500sccm, hydrogen
Flow velocity be 180sccm ~ 200sccm；
By polymethyl methacrylate add ethyl lactate in, temperature be 80 DEG C ~ 120 DEG C under conditions of heating stirring 1h ~
2h obtains mixed solution, and by the usage amount every square centimeter for having a μ L of 100 μ L ~ 200, mixed solution is added drop-wise into step using sample loading gun
On the rapid one foam nickel surface wrapped up by graphene (1) obtained, spontaneously dry at room temperature, be then 150 DEG C ~ 200 in temperature
0.5h ~ 1h is incubated under conditions of DEG C and obtains the foamy graphite alkene of Surface coating polymethyl methacrylate, step one (2) described in
Mixed solution in methyl methacrylate mass fraction be 4% ~ 5%；
（3）The foamy graphite alkene for the Surface coating polymethyl methacrylate that (2) step one is obtained cuts into surface area and 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
Middle 4h ~ 6h obtains removing the three-dimensional foam graphene of nickel, and the three-dimensional foam graphene of obtained removal nickel is soaked in into temperature is
0.5h ~ 1.5h in 60 DEG C ~ 70 DEG C of acetone, obtains removing the foamy graphite alkene of polymethyl methacrylate, then uses distilled water
The foamy graphite alkene for removing polymethyl methacrylate is cleaned up, then by the removal poly-methyl methacrylate cleaned up
The foamy graphite alkene of ester is transferred to freeze-drying on clean glass and obtains foamy graphite alkene；
2nd, liquid phase ultrasonic wave added stripping method
(1) molybdenum disulphide powder is added to the mixed solution of acetone and water（89:11v/v）In, wherein molybdenum disulfide concentration is 30mg
mL-1, stirring makes after molybdenum disulfide is uniformly dispersed, to carry out ultrasound stripping, ultrasonic mistake under 540W power using processor for ultrasonic wave
Journey prevents probe from overheating under low-temperature circulating using the 20s pulse modes for opening 10s passes, and ultrasonic splitting time is 1-4h；
(2) the molybdenum disulfide nano sheet suspension obtained after being peeled off to ultrasound is centrifuged by 3000rpm of centrifugation rate, is centrifuged
30 minutes time, the supernatant that centrifugation is obtained, which is placed in air dry oven, to be dried, by dried molybdenum disulfide nano
Piece is placed in bottle to be disperseed with deionized water, obtains concentration for 20mgmL-1Molybdenum disulfide nano sheet suspension；
3rd, liquid phase ultrasonic dispersion
(1) the foamy graphite alkene by step one (4) middle preparation is added in deionized water, and concentration is 0.07mgmL-1, use ultrasound
Ripple processor carries out ultrasonic stripping under 540W power to dispersion liquid, and ultrasonic procedure opens 10s passes under low-temperature circulating using 20s
Pulse mode prevents probe from overheating, and ultrasonic splitting time is 1-4h, obtains graphene suspension；
(2) 0.5mL molybdenum disulfide nano sheet and 19.5mL graphene nanometer sheet suspension are mixed to get concentration ratio 9：1
Molybdenum disulfide-graphene composite nano plate mixed solution, ultrasonic disperse obtains uniform suspension；
4th, automatic spraying process
(1) ITO electro-conductive glass is cleaned by ultrasonic after 20min in acetone soln, ethanol solution and deionized water respectively, at room temperature
Natural cooling is dried, and six pieces of ITO electro-conductive glass are fixed in spraying equipment heating plate, with adhesive tape by ITO electro-conductive glass
Press from both sides the covering of electrode wires side, it is ensured that electrode wires are directly contacted with ITO electro-conductive glass；
(2) finely dispersed molybdenum disulfide-graphene composite nano plate suspension by step 3 (2) middle preparation is placed in spray gun,
Molybdenum disulfide-graphene composite nano plate/ITO electrode is prepared using automatic spraying process, whole spraying process is in 10 pound/square English
Carried out under little progress air pressure, the distance of nozzle to ITO electro-conductive glass is 15cm, and heating dish temperature is 110 DEG C, will be coated with curing
The ITO electrode of molybdenum-graphene composite nano plate is placed in quartz tube furnace, under 400sccm argon gas protection, with 10 DEG C
min-1Speed be warming up to 700 DEG C insulation 2h, last furnace cooling to room temperature, obtain molybdenum disulfide-graphene composite nano plate/
ITO electrode.
2. a kind of preparation of molybdenum disulfide according to claim 1-graphene composite nano plate biological sensor electrode, its
Nickel foam is placed in quartz tube furnace center in being characterised by step one (1), from room temperature with 20 under the protection of argon gas and hydrogen
DEG C/min ~ 40 DEG C/min heating rate is heated to temperature for 1000 DEG C ~ 1100 DEG C, and is 1000 DEG C ~ 1100 DEG C in temperature
Under the conditions of be incubated 30min ~ 60min, temperature be 1000 DEG C ~ 1100 DEG C under conditions of into tube furnace with 5sccm ~ 10sccm's
Speed is passed through methane gas 5min ~ 20min, then by quartz tube furnace using the cooldown rate of 80 DEG C/min ~ 100 DEG C from temperature as
1000 DEG C ~ 1100 DEG C are cooled to room temperature, obtain by the nickel foam of graphene coated, step one (1) described in nickel foam density be
420g/m2~440g/m2, thickness be 1.6mm ~ 2.0mm, step one (1) described in argon gas flow velocity be 480sccm ~ 500sccm,
The flow velocity of hydrogen is 180sccm ~ 200sccm.
3. a kind of preparation of molybdenum disulfide according to claim 1-graphene composite nano plate biological sensor electrode, its
Polymethyl methacrylate is added in ethyl lactate in being characterised by step one (2), under conditions of temperature is 80 DEG C ~ 120 DEG C
Heating stirring 1h ~ 2h obtains mixed solution, by the usage amount every square centimeter for having a μ L of 100 μ L ~ 200, will be mixed using sample loading gun
Solution is added drop-wise on the foam nickel surface wrapped up by graphene that (1) step one obtains, and is spontaneously dried at room temperature, then in temperature
Spend to be incubated the foamy graphite alkene that 0.5h ~ 1h obtains Surface coating polymethyl methacrylate under conditions of 150 DEG C ~ 200 DEG C, step
Rapid one (2) described in mixed solution in methyl methacrylate mass fraction be 4% ~ 5%.
4. a kind of preparation of molybdenum disulfide according to claim 1-graphene composite nano plate biological sensor electrode, its
The foamy graphite alkene for the Surface coating polymethyl methacrylate for (2) obtaining step one in being characterised by step one (3) is cut into
Surface area is 0.5cm2~2cm2Cube, and be completely soaked in temperature be 80 DEG C ~ 90 DEG C, concentration be 3mol/L ~ 4mol/L's
4h ~ 6h obtains removing the three-dimensional foam graphene of nickel in hydrochloric acid solution, and the three-dimensional foam graphene of obtained removal nickel is soaked
0.5h ~ 1.5h in temperature is 60 DEG C ~ 70 DEG C of acetone, obtains removing the foamy graphite alkene of polymethyl methacrylate, then
The foamy graphite alkene for removing polymethyl methacrylate is cleaned up with distilled water, then by the poly- methyl of the removal cleaned up
The foamy graphite alkene of methyl acrylate is transferred to freeze-drying on clean glass and obtains foamy graphite alkene.
5. a kind of preparation of molybdenum disulfide according to claim 1-graphene composite nano plate biological sensor electrode, its
Molybdenum disulphide powder is added to the mixed solution of acetone and water in being characterised by step 2 (1)（89:11v/v）In, wherein molybdenum disulfide
Concentration is 30mgmL-1；Stirring makes after molybdenum disulfide is uniformly dispersed, to carry out ultrasound under 540W power using processor for ultrasonic wave
Peel off, ultrasonic procedure prevents probe from overheating under low-temperature circulating using the 20s pulse modes for opening 10s passes, and ultrasonic splitting time is
1-4h。
6. a kind of preparation of molybdenum disulfide according to claim 1-graphene composite nano plate biological sensor electrode, its
The molybdenum disulfide nano sheet suspension obtained after being peeled off in being characterised by step 2 (2) to ultrasound enters by 3000rpm of centrifugation rate
Row centrifugation, centrifugation time 30 minutes；The supernatant that centrifugation is obtained, which is placed in air dry oven, to be dried, by dried two
Molybdenum sulfide nanometer sheet is placed in bottle is disperseed with deionized water, obtains concentration for 20mgmL-1Molybdenum disulfide nano sheet
Suspension.
7. a kind of preparation of molybdenum disulfide according to claim 1-graphene composite nano plate biological sensor electrode, its
Foamy graphite alkene in being characterised by step 3 (1) by step one (4) middle preparation is added in deionized water, and concentration is 0.07mg
mL-1, ultrasonic stripping is carried out to dispersion liquid under 540W power using processor for ultrasonic wave, ultrasonic procedure is used under low-temperature circulating
The pulse mode that 20s opens 10s passes prevents probe from overheating, and ultrasonic splitting time is 1-4h, obtains graphene nanometer sheet suspension.
8. a kind of preparation of molybdenum disulfide according to claim 1-graphene composite nano plate biological sensor electrode, its
0.5mL molybdenum disulfide nano sheet and 19.5mL graphene nanometer sheet suspension are mixed to get in being characterised by step 3 (2)
Concentration ratio 9：1 molybdenum disulfide-graphene composite nano plate mixed solution, ultrasonic disperse obtains uniform suspension.
9. a kind of preparation of molybdenum disulfide according to claim 1-graphene composite nano plate biological sensor electrode, its
ITO electro-conductive glass is cleaned by ultrasonic in acetone soln, ethanol solution and deionized water respectively in being characterised by step 4 (1)
After 20min, natural cooling is dried at room temperature, and six pieces of ITO electro-conductive glass are fixed in spraying equipment heating plate, transparent adhesive tape is used
ITO electro-conductive glass is pressed from both sides electrode wires side and covered by band, it is ensured that electrode wires are directly contacted with ITO electro-conductive glass.
10. a kind of preparation of molybdenum disulfide according to claim 1-graphene composite nano plate biological sensor electrode,
It is characterized in that step 4 (2) in the finely dispersed molybdenum disulfide-graphene composite nano plate of step 3 (2) middle preparation is suspended
Liquid is placed in spray gun prepares molybdenum disulfide-graphene composite nano plate/ITO electrode, whole spraying process using automatic spraying process
Carried out under 10 pounds/square inch of air inlet pressures, the distance of nozzle to ITO electro-conductive glass is 15cm, and heating dish temperature is 110 DEG C,
The ITO electrode for being coated with molybdenum disulfide-graphene composite nano plate is placed in quartz tube furnace, protected in 400sccm argon gas
Under shield, with 10 DEG C of min-1Speed be warming up to 700 DEG C of insulation 2h, last furnace cooling obtains molybdenum disulfide-graphite to room temperature
Alkene composite nano plate/ITO electrode.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107902920A (en) * | 2017-06-07 | 2018-04-13 | 哈尔滨理工大学 | A kind of preparation of molybdenum disulfide graphene composite nano plate |
| CN108797097A (en) * | 2018-05-08 | 2018-11-13 | 哈尔滨理工大学 | A kind of preparation of graphene/carbon nano-fiber composite material |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107902920A (en) * | 2017-06-07 | 2018-04-13 | 哈尔滨理工大学 | A kind of preparation of molybdenum disulfide graphene composite nano plate |
| CN108797097A (en) * | 2018-05-08 | 2018-11-13 | 哈尔滨理工大学 | A kind of preparation of graphene/carbon nano-fiber composite material |
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