CN108486544A - A kind of preparation method and applications of the graphene zinc oxide micro-nano grading function material with automatically cleaning super lyophoby characteristic - Google Patents
A kind of preparation method and applications of the graphene zinc oxide micro-nano grading function material with automatically cleaning super lyophoby characteristic Download PDFInfo
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- CN108486544A CN108486544A CN201810125540.0A CN201810125540A CN108486544A CN 108486544 A CN108486544 A CN 108486544A CN 201810125540 A CN201810125540 A CN 201810125540A CN 108486544 A CN108486544 A CN 108486544A
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- graphene
- zinc oxide
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- oxide micro
- grading function
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 141
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 134
- 239000000463 material Substances 0.000 title claims abstract description 108
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- 238000000034 method Methods 0.000 claims abstract description 31
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Classifications
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- C—CHEMISTRY; METALLURGY
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- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/22—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of inorganic material, other than metallic material
- C23C16/26—Deposition of carbon only
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/22—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of inorganic material, other than metallic material
- C23C16/30—Deposition of compounds, mixtures or solid solutions, e.g. borides, carbides, nitrides
- C23C16/40—Oxides
- C23C16/407—Oxides of zinc, germanium, cadmium, indium, tin, thallium or bismuth
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/44—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating
- C23C16/455—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating characterised by the method used for introducing gases into reaction chamber or for modifying gas flows in reaction chamber
- C23C16/45523—Pulsed gas flow or change of composition over time
- C23C16/45525—Atomic layer deposition [ALD]
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/02—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition
- C23C18/12—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition characterised by the deposition of inorganic material other than metallic material
- C23C18/1204—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition characterised by the deposition of inorganic material other than metallic material inorganic material, e.g. non-oxide and non-metallic such as sulfides, nitrides based compounds
- C23C18/1208—Oxides, e.g. ceramics
- C23C18/1216—Metal oxides
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/02—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition
- C23C18/12—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition characterised by the deposition of inorganic material other than metallic material
- C23C18/125—Process of deposition of the inorganic material
- C23C18/1295—Process of deposition of the inorganic material with after-treatment of the deposited inorganic material
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Abstract
The preparation method and applications of the invention discloses a kind of graphene zinc oxide micro-nano grading function material with automatically cleaning super lyophoby characteristic.The preparation method of this graphene zinc oxide micro-nano grading function material includes the following steps：S1：Vertical graphene is generated on substrate；S2：By atomic layer deposition method, dip-coating adsorption and oxidation zinc nanoparticles crystal seed on the surface of graphene；S3：By hydro-thermal method, the growth of zinc oxide nano line on graphene forms graphene zinc oxide micro-nano structure material；S4：Graphene zinc oxide micro-nano structure material is modified processing, you can.The application of this graphene zinc oxide micro-nano grading function material is also disclosed that simultaneously.Graphene zinc oxide micro-nano grading function material produced by the present invention has the superperformance of super-hydrophobic, superoleophobic, super thin blood, is a kind of functional self-cleaning material.This material can be used as electrode or modified electrode, as a sensor to detection substance, has broad application prospects.
Description
Technical field
The system of the present invention relates to a kind of graphene zinc oxide micro-nano grading function material with automatically cleaning super lyophoby characteristic
Preparation Method and its application.
Background technology
Super lyophoby (having both super-hydrophobic, superoleophobic, super thin blood characteristic) material is because its unique reprimand liquid characteristic is in automatically cleaning, anti-
National defence, the daily life fields such as dirty anti-corrosion, liquid transporting, draft reduction material, miniflow management and control design, which are gathered around, to have broad application prospects.With
Deepening continuously for material surface fundamental research, the fast development of new glass forming theory, the research of super lyophoby material increasingly by
To concern.There are many example of super hydrophobic surface in nature, can such as tumble the lotus flower leaf of water droplet like a dream.It need not set
It doubts, the super-hydrophobic biomimetic material based on " lotus leaf effect " confirms that it is extensive in industrial applications such as coating, films
Application value.By fluorine-containing multi-level nanometer titanium dioxide silicon ball with it is carbon nano tube modified on the carbon cloth of micro-meter scale, can be right
Common oil has stable superoleophobic characteristic.There is good antiplatelet to stick on fluorinated titania nanotube surface
Property.
For coarse surface, wetting behavior can theoretically by two wetting models of Wenzel and Cassie models
Description.Under Wenzel states, in micro-structure such as hole, recessed gap that rough surface can be completely penetrated due to liquid, therefore it can increase
Contact area between liquid feeding body and solid substrate, to amplify wetting or the non wettability of solid material, at this time liquid with it is solid
Adhesive attraction between body is stronger.And under Cassie states, air is trapped on the rough surface below liquid, forms energy
Composite solid-liquid-gas interface that drop is supported, this makes drop have larger contact angle and lower roll angle.So being
Allow material surface can be with the property of super lyophoby, it should liquid be allowed to be in stable Cassie states in material surface.Profit
The wettability of lotus leaf can be explained with Cassie models, current research discloses the micro-nano hierarchical structure of lotus leaf surface to it
Wettability has played key effect.By the Bionic Design of lotus leaf surface, can be prepared super with micro-nano hierarchical structure
Hydrophobic surface.In general, the lyophobic surface with hierarchical structure can pass through the design table low with the surface of solids of surface roughness
It is acted synergistically of both the modification of face energy to realize the repulsion to liquid.
Grapheme material is because of its good electricity, and optics, calorifics, mechanical characteristic has a wide range of applications field, and is based on
The composite material of graphene is even more a highly important research direction, graphene and nanogold in the numerous application fields of graphene
Belong to the compound of oxide and prepare lithium battery material, enhances its electric conductivity and increase specific surface area.Graphene and conductive polymer
Son or the compound of metal oxide prepare ultracapacitor, and ultracapacitor has energy density high, and the charge and discharge time is short, cycle
Service life is long, it is economic and environment-friendly the advantages that.
Application of the graphene in biosensor direction is more and more in recent years, and biosensor is one kind to biological object
Matter is sensitive, and the instrument being detected to it using this sensitivity.Biosensor according to biomaterial sensitive material not
Together, it is divided into immunosensor, enzyme sensor, electrochemical DNA biosensor, animal vegetable tissue sensor and microbiological sensor.
And graphene is cheap, environmental-friendly, bio-compatibility and active group are evenly distributed, also a large amount of carboxyl, hydroxyl etc.
Functional group and good dissolubility can allow graphene to become a kind of ideal biological sensing material.Due to graphene composite wood
The introducing for expecting the electrode of modification, greatly reduces oxidizing potential, improves sensitivity, expand detection range.Small to biology
In terms of Molecular Detection, the electrode of graphene composite material modification can to cigarette phthalein amine arteries and veins he two core former times of cry of certain animals it is sour (NADH), dopamine
(DA) category pyrocatechol substance, paracetamol (APAP), the biological micromolecules such as ascorbic acid, uric acid, tyrosine and tryptophan
Carry out more accurate detection.In terms of biomacromolecule detection, immunity biosensor can be used as to detect protein, disease
Original, bacterium, virus type and cell etc..Meanwhile graphene also has wide application in terms of enzyme biologic sensor.
The unique two-dimensional structure of grapheme material, excellent mechanical property, good photoelectric property, larger specific surface area etc.
All cause the concern of whole world scientist.Its energy storage, liquid crystal device, electronic device, biomaterial, sensing material and
The fields such as catalyst carrier have shown excellent performance, have broad application prospects.But how to improve graphene-based compound
The problems such as control of dispersibility, compatibility, nanostructure and size between material component and the selection of solvent, be worth after
Continuous research and discussion.
Since biosensor is the instrument using biological substance sensitivity to be detected to it, life that can be to being detected
Object molecule carries out fast track, so biosensor needs to have highly selective, high sensitivity, analysis fast, of low cost
The features such as Miniaturized with instrument, grapheme material all extremely meet these conditions in all fields, but due to bio-sensing
Device needs to touch various organic liquid when being detected substance, can inevitably stick some and be detected in liquid
Water, dust, oil or dirt immune, once biosensor is polluted by these liquid, detection performance will decline, cannot
Continue to use as biosensor, to limit the service life of biosensor, stability and durability, sensibility.
Lead to this result be vertical graphene itself is super-hydrophobic, but it is very big to the adhesive force of water, even if by vertical
Graphene inverts, and water droplet still adheres to vertical graphene surface.In general, the three of surface of solids viscosity and the surface of solids
Phase line (solid-liquid-gas) is related, and continuously then tackness is high for triple line, and discontinuously then tackness is low for triple line.And vertical graphene
Triple line is continuous, so its tackness is high.It is exactly to cause to allow when as biosensor because tackness is too high
Liquid polluted biosensor.
Invention content
In order to overcome grapheme material when as biomaterial, sensor and catalyst carrier easily contaminated defect and
Deficiency, the purpose of the present invention is to provide a kind of graphene zinc oxide micro-nano grading function material with automatically cleaning super lyophoby characteristic
The preparation method and applications of material.
The technical solution used in the present invention is：
A kind of preparation method of the graphene zinc oxide micro-nano grading function material with automatically cleaning super lyophoby characteristic, including
Following steps：
S1：Vertical graphene is generated on substrate；
S2：By atomic layer deposition method, dip-coating adsorption and oxidation zinc nanoparticles crystal seed on the surface of graphene；
S3：By hydro-thermal method, the growth of zinc oxide nano line on graphene forms graphene-zinc oxide micro-nano structure material
Material；
S4：Graphene-zinc oxide micro-nano structure material is modified processing, obtains that there is automatically cleaning super lyophoby characteristic
Graphene zinc oxide micro-nano grading function material.
In step S1, the method for generating vertical graphene is plasma enhanced chemical vapor deposition method.
In step S1, the control condition that plasma enhanced chemical vapor deposition method generates vertical graphene is：Substrate is
Stainless steel lining bottom；It is CH to grow the sources C4And H2；Growth power 800W~1200W；800 DEG C~1000 DEG C of growth temperature；Growth time
For 15min~20min；Cooling time is 20min~40min.
In step S2, the presoma of atomic layer deposition method is organic zinc compound and water；The temperature of deposition is 95 DEG C~105
℃；The time deposited every time is 45s~55s；The number of cycle is 280 times~320 times.
In step S3, hydro-thermal method is specially：By the graphene of adsorption and oxidation zinc nanoparticles crystal seed, water, zinc nitrate and six
Methenamine sealing carries out hydrothermal synthesis reaction.
In step S3, the temperature of hydro-thermal reaction is 80 DEG C~100 DEG C, and the time of reaction is 80min~100min.
In step S4, modification is specially：Graphene-zinc oxide micro-nano structure material is mixed with modifying agent, true
Reciprocal of duty cycle is that 10h~14h is reacted under 0.05MPa~0.1MPa.
In step S4, the modifying agent used in modification is fluorochemical, carbon nanotube, organosilicon-modified acrylic tree
At least one of fat.
This graphene zinc oxide micro-nano grading function material with automatically cleaning super lyophoby characteristic is in preparing sensor
Application.
The beneficial effects of the invention are as follows：
A kind of graphene zinc oxide micro-nano grading function material has been prepared in the present invention, this material has super-hydrophobic, super
The superperformance of oleophobic, super thin blood is a kind of functional self-cleaning material.High contact angle due to super hydrophobic material and low rolling
Angle can allow drop freely to be rolled on surface, reach automatically cleaning effect itself by the effect of water and taken away by the rolling of water droplet
Dirt.The graphene zinc oxide micro-nano hierarchical structure of the present invention can be used as electrode or modified electrode, as a sensor to detection
Some substances, such as the various biomolecule of hydrogen peroxide, glucose, urea, pH, amino acid, protein, DNA, have
Wide application prospect.
Description of the drawings
Fig. 1 is the process schematic that the present invention prepares graphene zinc oxide micro-nano grading function material；
Fig. 2 is the scanning electron microscope (SEM) photograph of graphene zinc oxide micro-nano grading function material made from embodiment 1；
Fig. 3 is design sketch of the graphene zinc oxide micro-nano grading function material of the present invention when there is drop to drop in surface.
Specific implementation mode
A kind of preparation method of the graphene zinc oxide micro-nano grading function material with automatically cleaning super lyophoby characteristic, including
Following steps：
S1：Vertical graphene is generated on substrate；
S2：By atomic layer deposition method, dip-coating adsorption and oxidation zinc nanoparticles crystal seed on the surface of graphene；
S3：By hydro-thermal method, the growth of zinc oxide nano line on graphene forms graphene-zinc oxide micro-nano structure material
Material；
S4：Graphene-zinc oxide micro-nano structure material is modified processing, obtains that there is automatically cleaning super lyophoby characteristic
Graphene zinc oxide micro-nano grading function material.
Preferably, in step S1, the method for generating vertical graphene is plasma enhanced chemical vapor deposition method.
Preferably, in step S1, the control condition that plasma enhanced chemical vapor deposition method generates vertical graphene is：
Substrate is stainless steel lining bottom；It is CH to grow the sources C4And H2；Growth power 800W~1200W；800 DEG C~1000 DEG C of growth temperature；It is raw
It is 15min~20min for a long time；Cooling time is 20min~40min.
Preferably, in step S2, the presoma of atomic layer deposition method is organic zinc compound and water；The temperature of deposition is 95
DEG C~105 DEG C；The time deposited every time is 45s~55s；The number of cycle is 280 times~320 times；It is further preferred that step
In S2, organic zinc compound is diethyl zinc；The temperature of deposition is 100 DEG C；The time deposited every time is 50s；The number of cycle
It is 300 times.
Preferably, in step S3, hydro-thermal method is specially：By the graphene, water, nitric acid of adsorption and oxidation zinc nanoparticles crystal seed
Zinc and hexa (HTMA) sealing carry out hydrothermal synthesis reaction.
Preferably, in step S3, a concentration of 0.2mol/L~0.3mol/L of zinc nitrate；Hexa it is a concentration of
0.2mol/L~0.3mol/L.
Preferably, in step S3, the temperature of hydro-thermal reaction is 80 DEG C~100 DEG C, time of reaction be 80min~
100min。
Preferably, in step S4, modification is specially：Graphene-zinc oxide micro-nano structure material is mixed with modifying agent
It closes, reacts 10h~14h in the case where vacuum degree is 0.05MPa~0.1MPa.
Preferably, in step S4, modifying agent used in modification is fluorochemical, carbon nanotube, organic-silicon-modified
At least one of acrylic resin；It is further preferred that in step S4, the modifying agent used in modification is fluorine-containing chemical combination
Object；Still further preferably, in step S4, the modifying agent used in modification is 1H, 1H, 2H, 2H- perfluoro capryl triethoxies
Silane.
Further, in step S4, when the modifying agent used is fluorochemical, modification is fluorination treatment；Tool
Body, the fluorination treatment is fluorinated for vacuum gas-phase.
The visible attached drawing of the preparation process schematic diagram of graphene zinc oxide micro-nano grading function material of the present invention 1.Fig. 1 is only indicated
To the example of preparation method, method of the invention is not limited only to the related substances indicated in figure.
This graphene zinc oxide micro-nano grading function material with automatically cleaning super lyophoby characteristic is in preparing sensor
Application.
Preferably, in, sensor is electrochemical sensor and/or biosensor；The biosensor can
To be field-effect transistor biosensor or optical biosensor.
Further, the graphene zinc oxide micro-nano grading function material with automatically cleaning super lyophoby characteristic can be used for repairing
Decorations electrode directly prepares electrode, is used as to glucose, urea, pH, amino acid, protein, DNA, hydrogen peroxide etc.
The biosensor that various biomolecule are detected.
The graphene zinc oxide micro-nano grading function material that the present invention is prepared is that have self-cleaning functionalization material,
Protection biosensor is can be very good, prevents it by the various complicated molecules in biological tissue's liquid or biological sample, such as egg
In vain, the adherency of polypeptide, small molecule etc. can not be polluted by biological tissue's liquid or biological sample, can be extended it and be used the longevity
Life, durability and its sensitivity of maintenance and stability.In addition, graphene zinc oxide micro-nano grading function material prepared by the present invention
Material, moreover it is possible to can detect H when electrode as electrochemical sensor2O2, H2S, NO, ascorbic acid etc.；As field-effect transistor
Biosensor detects pH；Utilize the characteristic of graphene fluorescent quenching in DNA bio-sensings, moreover it is possible to optical bio sensing be made
Device detects DNA.
The invention thinking that the present invention is further illustrated below is as follows：
By the present invention in that manufacturing the piece with vertical orientation with the vapour deposition process (PECVD) of plasma enhanced chemical
Shape graphene, by changing temperature, power, the time controls the density of graphene growth, controllable preparation vertical orientation
Graphene.By atom deposition method, the series of steps such as hydro-thermal method prepare graphene zinc oxide micro-nano hierarchical structure, hydro-thermal method
By controlling growth agents concentration, growth temperature, the time grows number to control the growth length of zinc oxide nanowire, diameter.
Graphene zinc oxide micro-nano hierarchical structure makes its air when contacting drop be trapped within due to the distribution of zinc oxide nanowire
On rough surface below liquid, the composite solid-liquid-gas interface that drop can be supported is formed, liquid is in steady in material surface
Fixed Cassie states, this makes drop have larger contact angle and lower roll angle.And by fluorinated processing, it can
Further decrease the surface energy of material surface so that the lyophoby performance of material is improved.In terms of hydrophobic oleophobic performance, make it
With super-hydrophobicity, superoleophobic property, water droplet or oil droplet can be easy to slide from functional surface.In thin blood aspect of performance,
Sticking experiment by antiplatelet and can obtaining the functional surface of graphene zinc oxide micro-nano hierarchical structure can make blood light
Pine slides, and has achieved the effect that super thin blood.
Graphene zinc oxide micro-nano grading structure material can obtain outstanding waterproof, anti-blood and the performances such as grease proofing, provide
The method for creating the graphene zinc oxide micro-nano hierarchical structure with self-cleaning performance, this answers protection as electrode with other
Graphene is extremely important from polluting.As detection sensor, use graphene zinc oxide micro-nano hierarchical structure as electrode
Or modified electrode, it can be as a sensor to some substances be detected, such as hydrogen peroxide, glucose, urea, pH, amino acid, egg
The various biomolecule such as white matter, DNA.
Present disclosure is described in further detail below by way of specific embodiment, but embodiment is not to this
Invention limits in any form.Unless stated otherwise, the present invention uses reagent, method and apparatus is the art routines
Reagent, method and apparatus.
Embodiment 1：
One, preparation method
The preparation of the graphene zinc oxide micro-nano grading function material with automatically cleaning super lyophoby characteristic of embodiment 1 includes
Following steps：
The growth of S1, vertical graphene
(1) deionized water, ethyl alcohol is used to clean stainless steel lining bottom, then nitrogen removes moisture；
(2) stainless steel lining bottom is emitted in PECVD chamber inner foundation, is vacuumized；Control PECVD power is 1200W, raw
Long temperature is 900 DEG C, and the sources growth C are CH4And H2, growth time is 15 minutes, is cooled to the time 30 minutes, goes out after growth
Vertical graphene is made in stove；
S2, by atomic layer deposition method step 1 graphene surface dip-coating adsorption and oxidation zinc nanoparticles crystal seed
The sample of step S1 is arranged to the inside cavity for being put into ALD instruments, controlled at 100 DEG C, presoma two
Zinc ethyl and oxygen, oxygen source are water, and time 50s repeats 300 cycles, on the surface of graphene dip-coating with argon cleaning sample surfaces
Adsorption and oxidation zinc nanoparticles crystal seed, so as in next step being capable of growth of zinc oxide nano line on the surface of graphene；
S3, hydrothermal synthesis method the growth of zinc oxide nano line on graphene
Reagent needed for configuration growth first：0.25mol/L zinc nitrate hexahydrates and 0.25mol/L HTMA (hexa-methylenes four
Amine)；Then the graphene substrate of step 2 adsorption and oxidation zinc nanoparticles crystal seed is inverted in the beaker of appropriate volume size,
Respectively plus 4mL deionized waters, 0.5mL zinc nitrates and 0.5mL HTMA, it is sealed with preservative film, is positioned in drying box 90 DEG C, water
It thermally grown 90 minutes, is taken out after having grown and extra ZnO is rinsed out with deionized water.It repeats the above steps, makes flake graphite alkene
Channel is filled up by zinc oxide nanowire between piece, forms secondary oxidative zinc nano wire branch, that is, it is micro- that graphene zinc oxide is prepared
Receive grading function material；
The fluorination of S4, graphene zinc oxide micro-nano grading function material
Vacuum gas-phase fluoride process is fluorinated：The graphene zinc oxide micro-nano grading function material that step 3 is prepared is taken to place
In vacuum desiccator, 100 μ L 1H, 1H, 2H, 2H- perfluoro capryl triethoxysilanes are added, vacuumize, vacuum degree reaches
0.08MPa vacuumizes 2min, and the fluorination time is 12 hours or so, after fluorination is completed, rinses sample with acetone or alcohol, goes
Except extra fluorination reagent, the graphene zinc oxide micro-nano grading function material of embodiment 1 is obtained.
Two, performance test
Graphene zinc oxide micro-nano grading function material made from embodiment 1 is subjected to phenetic analysis, SEM figures are shown in attached drawing
2。
Graphene zinc oxide micro-nano grading function material made from embodiment 1 is subjected to hydrophobicity, oleophobic property, dredges courageous and upright survey
Examination：
(1) hydrophobicity is tested
A drop water is added dropwise on graphene zinc oxide micro-nano grading material surface by contact angle measurement and drips (4 microlitres), sees
Examine the motion conditions of water droplet.As a result as shown in Fig. 3, drop drops in the function wetting table of graphene zinc oxide micro-nano hierarchical structure
Face, and due to the low-surface-energy after sample fluorination, drop is made to form the contact angle more than 150 ° on function wetting surface, and
Angle of lag very little, drop freely slide on graphene zinc oxide micro-nano grading structure material surface, have hydrophobicity and automatically cleaning
Performance.
(2) oleophobic property is tested
It is identical as step (1), change water droplet into oil droplet.The results show that oil droplet is in graphene zinc oxide micro-nano hierarchical structure
Material liquid surface freely slides, and has oleophobic property.
(3) courageous and upright test is dredged
It is identical as step (1), change water droplet into drop of blood.The results show that drop of blood is in graphene zinc oxide micro-nano hierarchical structure
Material liquid surface freely slides, and has achieved the effect that super thin blood.
Embodiment 2：
One, preparation method
The preparation of the graphene zinc oxide micro-nano grading function material with automatically cleaning super lyophoby characteristic of embodiment 2 includes
Following steps：
The growth of S1, vertical graphene
(1) deionized water, ethyl alcohol is used to clean stainless steel lining bottom, then nitrogen removes moisture；
(2) stainless steel lining bottom is emitted in PECVD chamber inner foundation, is vacuumized；Control PECVD power is 1000W, raw
Long temperature is 800 DEG C, and the sources growth C are CH4And H2, growth time is 20 minutes, is cooled to the time 30 minutes, goes out after growth
Vertical graphene is made in stove；
S2, by atomic layer deposition method step 1 graphene surface dip-coating adsorption and oxidation zinc nanoparticles crystal seed
It is same as Example 1；
S3, hydrothermal synthesis method the growth of zinc oxide nano line on graphene
Reagent needed for configuration growth first：0.25mol/L zinc nitrate hexahydrates and 0.25mol/L HTMA (hexa-methylenes four
Amine)；Then the graphene substrate of step 2 adsorption and oxidation zinc nanoparticles crystal seed is inverted in the beaker of appropriate volume size,
Respectively plus 4mL deionized waters, 0.5mL zinc nitrates and 0.5mL HTMA, it is sealed with preservative film, is positioned in drying box 80 DEG C, water
It thermally grown 100 minutes, is taken out after having grown and extra ZnO is rinsed out with deionized water.It repeats the above steps, makes flake graphite alkene
Channel is filled up by zinc oxide nanowire between piece, forms secondary oxidative zinc nano wire branch, that is, it is micro- that graphene zinc oxide is prepared
Receive grading function material；
The fluorination of S4, graphene zinc oxide micro-nano grading function material
Vacuum gas-phase fluoride process is fluorinated：The graphene zinc oxide micro-nano grading function material that step 3 is prepared is taken to place
In vacuum desiccator, 100 μ L 1H, 1H, 2H, 2H- perfluoro capryl triethoxysilanes are added, vacuumize, vacuum degree reaches
0.08MPa vacuumizes 2min, and the fluorination time is 14 hours or so, after fluorination is completed, rinses sample with acetone or alcohol, goes
Except extra fluorination reagent, the graphene zinc oxide micro-nano grading function material of embodiment 2 is obtained.
Two, performance test
The carry out hydrophobicity for the graphene zinc oxide micro-nano grading function material that embodiment 2 is prepared, is dredged oleophobic property
Courage and uprightness test；The results show that the graphene zinc oxide micro-nano grading function material of embodiment 2 have it is super-hydrophobic, it is superoleophobic, it is super thin
The superperformance of blood has automatically cleaning super lyophoby characteristic.
Embodiment 3：
One, preparation method
The preparation of the graphene zinc oxide micro-nano grading function material with automatically cleaning super lyophoby characteristic of embodiment 3 includes
Following steps：
The growth of S1, vertical graphene
(1) deionized water, ethyl alcohol is used to clean stainless steel lining bottom, then nitrogen removes moisture；
(2) stainless steel lining bottom is emitted in PECVD chamber inner foundation, is vacuumized；Control PECVD power is 800W, raw
Long temperature is 1000 DEG C, and the sources growth C are CH4And H2, growth time is 18 minutes, is cooled to the time 30 minutes, goes out after growth
Vertical graphene is made in stove；
S2, by atomic layer deposition method step 1 graphene surface dip-coating adsorption and oxidation zinc nanoparticles crystal seed
It is same as Example 1；
S3, hydrothermal synthesis method the growth of zinc oxide nano line on graphene
Reagent needed for configuration growth first：0.25mol/L zinc nitrate hexahydrates and 0.25mol/L HTMA (hexa-methylenes four
Amine)；Then the graphene substrate of step 2 adsorption and oxidation zinc nanoparticles crystal seed is inverted in the beaker of appropriate volume size,
Respectively plus 4mL deionized waters, 0.5mL zinc nitrates and 0.5mL HTMA, it is sealed with preservative film, is positioned in drying box 100 DEG C, water
It thermally grown 80 minutes, is taken out after having grown and extra ZnO is rinsed out with deionized water.It repeats the above steps, makes flake graphite alkene
Channel is filled up by zinc oxide nanowire between piece, forms secondary oxidative zinc nano wire branch, that is, it is micro- that graphene zinc oxide is prepared
Receive grading function material；
The fluorination of S4, graphene zinc oxide micro-nano grading function material
Vacuum gas-phase fluoride process is fluorinated：The graphene zinc oxide micro-nano grading function material that step 3 is prepared is taken to place
In vacuum desiccator, 100 μ L 1H, 1H, 2H, 2H- perfluoro capryl triethoxysilanes are added, vacuumize, vacuum degree reaches
0.08MPa vacuumizes 2min, and the fluorination time is 10 hours or so, after fluorination is completed, rinses sample with acetone or alcohol, goes
Except extra fluorination reagent, the graphene zinc oxide micro-nano grading function material of embodiment 3 is obtained.
Two, performance test
The graphene zinc oxide micro-nano grading function material that embodiment 3 is prepared carries out hydrophobicity, oleophobic property, dredges blood
Property test；The results show that the graphene zinc oxide micro-nano grading function material of embodiment 3 has super-hydrophobic, superoleophobic, super thin blood
Superperformance, have automatically cleaning super lyophoby characteristic.
Comparative example 1：
One, preparation method
The preparation of the graphene zinc oxide micro-nano grading function material of comparative example 1 includes the following steps：
The growth of S1, vertical graphene
It is same as Example 1；
S2, graphene surface dip-coating adsorption and oxidation zinc nanoparticles crystal seed
The vertical graphene sample of step 1 is gently stained with to the methanol solution of 0.005mol/L zinc acetates, weight is evaporated at 60 DEG C
It plural time, then under 300 DEG C of vacuum states, is reacted, plates crystal seed on the surface of graphene；
S3, hydrothermal synthesis method the growth of zinc oxide nano line on graphene
It is same as Example 1；
The fluorination of S4, graphene zinc oxide micro-nano grading function material
It is same as Example 1, the graphene zinc oxide micro-nano grading function material of comparative example 1 is made.
Two, performance test
By above-mentioned steps 2 prepare to crystal seed be unevenly distributed, so as to cause subsequent growth oxidation nanometer line not
It is enough uniform, hydrophobicity, oleophobic property and the thin courageous and upright all poor (leaching of the graphene zinc oxide micro-nano grading function material being prepared
Profit, does not fall off), it can not be applied to practical.
In summary：
The preparation of graphene zinc oxide micro-nano compound structure of the present invention, passes through the vapour deposition process of plasma enhanced chemical
Graphene is grown, by controlling temperature, power, the conditions such as time control the stand density length of graphene.In graphene table
Face dip-coating adsorption and oxidation zinc nanoparticles crystal seed, is prepared step by step using hydro-thermal method, ensures that micro-structure controllably adds level by several times,
Prepared dendroid graphene zinc oxide micro-nano hierarchical structure surface further uses the fluorochemical with low-surface-energy
Surface modification is carried out, hydrophobic, oleophobic is made it have, dredges blood or lyophoby performance.The principle of super-hydrophobic automatic cleaning material is to pass through water
Effect reach automatically cleaning effect itself, due to the high contact angle of super hydrophobic material, low roll angle can allow water droplet on surface
It freely rolls, it is possible to which dirt is taken away by the rolling of water droplet.
It, can since the graphene zinc oxide micro-nano grading function material prepared is that have self-cleaning functionalization material
To protect biosensor well, prevent it by the various complicated molecules in biological tissue's liquid or biological sample, such as albumen,
The adherency of polypeptide, small molecule etc. can not be polluted by biological tissue's liquid or biological sample, can extend its service life,
Durability and its sensitivity of maintenance and stability.
Claims (9)
1. a kind of preparation method of the graphene zinc oxide micro-nano grading function material with automatically cleaning super lyophoby characteristic, feature
It is：
Include the following steps：
S1：Vertical graphene is generated on substrate；
S2：By atomic layer deposition method, dip-coating adsorption and oxidation zinc nanoparticles crystal seed on the surface of graphene；
S3：By hydro-thermal method, the growth of zinc oxide nano line on graphene forms graphene-zinc oxide micro-nano structure material；
S4：Graphene-zinc oxide micro-nano structure material is modified processing, obtains the graphite with automatically cleaning super lyophoby characteristic
Alkene zinc oxide micro-nano grading function material.
2. a kind of graphene zinc oxide micro-nano grading function material with automatically cleaning super lyophoby characteristic according to claim 1
The preparation method of material, it is characterised in that：In step S1, it is heavy for plasma enhanced chemical vapor to generate the method for vertical graphene
Area method.
3. a kind of graphene zinc oxide micro-nano grading function material with automatically cleaning super lyophoby characteristic according to claim 2
The preparation method of material, it is characterised in that：In step S1, plasma enhanced chemical vapor deposition method generates the control of vertical graphene
Condition processed is：Substrate is stainless steel lining bottom；It is CH to grow the sources C4And H2；Growth power 800W~1200W；800 DEG C of growth temperature~
1000℃；Growth time is 15min~20min；Cooling time is 20min~40min.
4. a kind of graphene zinc oxide micro-nano grading function material with automatically cleaning super lyophoby characteristic according to claim 1
The preparation method of material, it is characterised in that：In step S2, the presoma of atomic layer deposition method is organic zinc compound and water；Deposition
Temperature be 95 DEG C~105 DEG C；The time deposited every time is 45s~55s；The number of cycle is 280 times~320 times.
5. a kind of graphene zinc oxide micro-nano grading function material with automatically cleaning super lyophoby characteristic according to claim 1
The preparation method of material, it is characterised in that：In step S3, hydro-thermal method is specially：By the graphite of adsorption and oxidation zinc nanoparticles crystal seed
Alkene, water, zinc nitrate and hexa sealing carry out hydrothermal synthesis reaction.
6. a kind of graphene zinc oxide micro-nano grading function material with automatically cleaning super lyophoby characteristic according to claim 5
The preparation method of material, it is characterised in that：In step S3, the temperature of hydro-thermal reaction is 80 DEG C~100 DEG C, and the time of reaction is
80min~100min.
7. a kind of graphene zinc oxide micro-nano grading function material with automatically cleaning super lyophoby characteristic according to claim 1
The preparation method of material, it is characterised in that：In step S4, modification is specially：By graphene-zinc oxide micro-nano structure material with
Modifying agent mixes, and reacts 10h~14h in the case where vacuum degree is 0.05MPa~0.1MPa.
8. a kind of graphene zinc oxide micro-nano grading function material with automatically cleaning super lyophoby characteristic according to claim 7
The preparation method of material, it is characterised in that：In step S4, the modifying agent used in modification is fluorochemical, carbon nanotube, has
At least one of machine fluorine-silicon modified acrylic resin.
9. any one of claim 1~8 prepares the graphene zinc oxide micro-nano grading function material of gained in preparing sensor
Application.
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