CN108486544B - Preparation method and application of graphene zinc oxide micro-nano grading functional material with self-cleaning and super-lyophobic characteristics - Google Patents
Preparation method and application of graphene zinc oxide micro-nano grading functional material with self-cleaning and super-lyophobic characteristics Download PDFInfo
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Abstract
The invention discloses a preparation method and application of a graphene zinc oxide micro-nano grading functional material with a self-cleaning and super-lyophobic property. The preparation method of the graphene zinc oxide micro-nano grading functional material comprises the following steps: s1: generating vertical graphene on a substrate; s2: dip-coating and adsorbing zinc oxide nano-particle seed crystals on the surface of the graphene by an atomic layer deposition method; s3: growing a zinc oxide nanowire on graphene by a hydrothermal method to form a graphene-zinc oxide micro-nano structure material; s4: and (3) carrying out modification treatment on the graphene-zinc oxide micro-nano structure material. Simultaneously, the application of the graphene zinc oxide micro-nano grading functional material is also disclosed. The graphene zinc oxide micro-nano grading functional material prepared by the invention has good performances of super-hydrophobicity, super-oleophobicity and super-blood-phobicity, and is a functional self-cleaning material. The material can be used as an electrode or a modified electrode, can be used as a sensor to detect substances, and has wide application prospect.
Description
Technical Field
The invention relates to a preparation method and application of a graphene zinc oxide micro-nano grading functional material with a self-cleaning and super-lyophobic property.
Background
The super-lyophobic material (having super-hydrophobic, super-oleophobic and super-blood-phobic properties) has wide application prospect in the fields of national defense and daily life such as self-cleaning, pollution prevention and corrosion prevention, liquid transportation, resistance reduction materials, microflow control design and the like due to the unique liquid repellent property. With the continuous and deep research of the basic theory of the surface of the material and the rapid development of the new preparation technology, the research of the ultra-lyophobic material is increasingly concerned. There are many examples of superhydrophobic surfaces in nature, such as lotus leaves that can roll down water droplets without difficulty. Needless to say, the super-hydrophobic bionic material based on the lotus effect proves wide application value in the industrial application fields of coatings, films and the like. The fluorine-containing multi-layer nano-silica spheres and the carbon nano-tubes are modified on the micron-scale carbon cloth, so that the nano-silica cloth has stable super-oleophobic property to common oil. The fluorinated titanium dioxide nanotube surface has good anti-platelet adhesion property.
For rough surfaces, wetting behavior can be described theoretically by two wetting models, the Wenzel and Cassie models. In the Wenzel state, because the liquid can completely penetrate into the microstructure of the rough surface, such as holes and recesses, the contact area between the liquid and the solid substrate can be increased, so that the wetting or non-wetting property of the solid material is amplified, and the adhesion between the liquid and the solid is stronger. In the Cassie state, air is trapped on the rough surface below the liquid, forming a composite solid-liquid-gas interface that supports the liquid drop, which results in a liquid drop with a large contact angle and a low angle of roll. So in order to allow the material surface to have ultralyophobic properties, the liquid should be in a stable Cassie state at the material surface. The wetting property of the lotus leaf can be explained by using a Cassie model, and the current research reveals that the micro-nano hierarchical structure on the lotus leaf surface plays a key role in the wetting property. The super-hydrophobic surface with a micro-nano hierarchical structure can be prepared by the bionic design of the lotus leaf surface. In general, lyophobic surfaces with a hierarchical structure can achieve the repulsion of liquids through the synergistic effect of the design of surface roughness structure and the low surface energy modification of solid surfaces.
The graphene material has wide application fields due to good electrical, optical, thermal and mechanical properties, and the graphene-based composite material is a very important research direction in a plurality of application fields of graphene. The supercapacitor prepared by compounding the graphene and the conductive polymer or the metal oxide has the advantages of high energy density, short charging and discharging time, long cycle service life, economy, environmental friendliness and the like.
Graphene has been increasingly used in recent years in the direction of biosensors, which are instruments that are sensitive to biological substances and detect them using such sensitivity. Biosensors are classified into immunosensors, enzyme sensors, electrochemical DNA sensors, animal and plant tissue sensors, and microbial sensors according to the difference of sensitive materials of biomaterials. The graphene is cheap, environment-friendly, biocompatible, uniform in active group distribution, and has a large number of functional groups such as carboxyl and hydroxyl, and good solubility, so that the graphene becomes an ideal biosensing material. Due to the introduction of the electrode modified by the graphene composite material, the oxidation potential is greatly reduced, the sensitivity is improved, and the detection range is enlarged. In the aspect of detecting small biological molecules, the electrode modified by the graphene composite material can be used for more accurately detecting small biological molecules such as nicotinamide, muihine, dinuclear oxylic acid (NADH), Dopamine (DA) belonging to catechol substances, paracetamol (APAP), ascorbic acid, uric acid, tyrosine, tryptophan and the like. In the aspect of biological macromolecule detection, the biosensor can be used as an immune biosensor for detecting proteins, pathogens, bacteria, viruses, cells and the like. Meanwhile, graphene also has wide application in enzyme biosensors.
The unique two-dimensional structure, excellent mechanical property, good photoelectric property, large specific surface area and the like of the graphene material all attract the attention of scientists all over the world. The material shows excellent performance in the fields of energy storage, liquid crystal devices, electronic devices, biological materials, sensing materials, catalyst carriers and the like, and has wide application prospect. However, how to improve the dispersibility, compatibility, control of the nanostructure and size, and selection of the solvent among the graphene-based composite components is worthy of continuous research and discussion.
The biosensor is an instrument for detecting biological substances by utilizing the sensitivity of the biological substances and can quickly track detected biological molecules, so the biosensor needs to have the characteristics of high selectivity, high sensitivity, quick analysis, low cost, miniaturization of the instrument and the like, and the graphene material can meet the conditions in all aspects, but the biosensor needs to be contacted with various organic and inorganic liquids when detecting the substances, so that the contamination caused by adhesion of water, dust, oil or dirt in the detected liquids is avoided, and once the biosensor is contaminated by the liquids, the detection performance of the biosensor is reduced, and the biosensor cannot be continuously used as the biosensor, so that the service life, stability, durability and sensitivity of the biosensor are limited. What has led to this result is that the vertical graphene itself is super-hydrophobic, but its adhesion to water is very large, and even if the vertical graphene is inverted, water droplets adhere to the vertical graphene surface. Generally, solid surface viscosity is related to the three-phase (solid-liquid-gas) line on the solid surface, which is high when the three-phase line is continuous and low when the three-phase line is discontinuous. And the three-phase line of the vertical graphene is continuous, so that the adhesion is high. This is because the adhesion is too high, which may cause some liquid to contaminate the biosensor when used as a biosensor.
Disclosure of Invention
In order to overcome the defect and defect that a graphene material is easy to be polluted when being used as a biological material, a sensor and a catalyst carrier, the invention aims to provide a preparation method and application of a graphene zinc oxide micro-nano grading functional material with self-cleaning and super-lyophobic characteristics.
The technical scheme adopted by the invention is as follows:
a preparation method of a graphene zinc oxide micro-nano grading functional material with a self-cleaning super-lyophobic characteristic comprises the following steps:
s1: generating vertical graphene on a substrate;
s2: dip-coating and adsorbing zinc oxide nano-particle seed crystals on the surface of the graphene by an atomic layer deposition method;
s3: growing a zinc oxide nanowire on graphene by a hydrothermal method to form a graphene-zinc oxide micro-nano structure material;
s4: and carrying out modification treatment on the graphene-zinc oxide micro-nano structure material to obtain the graphene zinc oxide micro-nano grading functional material with the self-cleaning and super-lyophobic characteristics.
In step S1, the method for generating the vertical graphene is a plasma enhanced chemical vapor deposition method.
In step S1, the control conditions for generating vertical graphene by the plasma enhanced chemical vapor deposition method are as follows: the substrate is a stainless steel substrate; the source of growth C is CH4And H2(ii) a The growth power is 800W-1200W; the growth temperature is 800-1000 ℃; the growth time is 15 min-20 min; the cooling time is 20min to 40 min.
In step S2, precursors of the atomic layer deposition method are an organozinc compound and water; the deposition temperature is 95-105 ℃; the time of each deposition is 45-55 s; the number of cycles is 280 to 320.
In step S3, the hydrothermal method specifically includes: and sealing the graphene adsorbing the zinc oxide nanoparticle seed crystal, water, zinc nitrate and hexamethylenetetramine for hydrothermal synthesis reaction.
In step S3, the temperature of the hydrothermal reaction is 80-100 ℃, and the reaction time is 80-100 min.
In step S4, the modification treatment specifically includes: mixing the graphene-zinc oxide micro-nano structure material with a modifier, and reacting for 10-14 h under the vacuum degree of 0.05-0.1 MPa.
In step S4, the modifier used in the modification treatment is at least one of a fluorine-containing compound, a carbon nanotube, and an organosilicon-modified acrylic resin.
The graphene zinc oxide micro-nano grading functional material with the self-cleaning and super-lyophobic characteristics is applied to the preparation of sensors.
The invention has the beneficial effects that:
the graphene zinc oxide micro-nano grading functional material prepared by the invention has good performances of super-hydrophobicity, super-oleophobicity and super-hemophobicity, and is a functional self-cleaning material. Due to the high contact angle and the low rolling angle of the super-hydrophobic material, liquid drops can roll freely on the surface, the self-cleaning effect is achieved under the action of water, and dirt is taken away through the rolling of the water drops. The graphene zinc oxide micro-nano hierarchical structure can be used as an electrode or a modified electrode, can be used as a sensor to detect substances such as hydrogen peroxide, glucose, urea, pH, amino acid, protein, DNA and other various biomolecules, and has a wide application prospect.
Drawings
FIG. 1 is a schematic diagram of a process for preparing a graphene zinc oxide micro-nano hierarchical functional material according to the present invention;
FIG. 2 is a scanning electron microscope image of the graphene zinc oxide micro-nano grading functional material prepared in example 1;
FIG. 3 is an effect diagram of the graphene zinc oxide micro-nano hierarchical functional material of the invention when liquid drops are dropped on the surface.
Detailed Description
A preparation method of a graphene zinc oxide micro-nano grading functional material with a self-cleaning super-lyophobic characteristic comprises the following steps:
s1: generating vertical graphene on a substrate;
s2: dip-coating and adsorbing zinc oxide nano-particle seed crystals on the surface of the graphene by an atomic layer deposition method;
s3: growing a zinc oxide nanowire on graphene by a hydrothermal method to form a graphene-zinc oxide micro-nano structure material;
s4: and carrying out modification treatment on the graphene-zinc oxide micro-nano structure material to obtain the graphene zinc oxide micro-nano grading functional material with the self-cleaning and super-lyophobic characteristics.
Preferably, in step S1, the method for generating the vertical graphene is a plasma enhanced chemical vapor deposition method.
Preferably, in step S1, the control conditions for the pecvd process to generate vertical graphene are as follows: the substrate is a stainless steel substrate; the source of growth C is CH4And H2(ii) a The growth power is 800W-1200W; the growth temperature is 800-1000 ℃; the growth time is 15 min-20 min; the cooling time is 20min to 40 min.
Preferably, in step S2, the precursors of the atomic layer deposition method are an organozinc compound and water; the deposition temperature is 95-105 ℃; the time of each deposition is 45-55 s; the number of cycles is 280 to 320; further preferably, in step S2, the organozinc compound is diethyl zinc; the deposition temperature is 100 ℃; the time for each deposition was 50 s; the number of cycles was 300.
Preferably, in step S3, the hydrothermal method specifically includes: and sealing the graphene adsorbing the zinc oxide nanoparticle seed crystal, water, zinc nitrate and Hexamethylenetetramine (HTMA) for hydrothermal synthesis reaction.
Preferably, in step S3, the concentration of zinc nitrate is 0.2mol/L to 0.3 mol/L; the concentration of the hexamethylene tetramine is 0.2 mol/L-0.3 mol/L.
Preferably, in step S3, the hydrothermal reaction temperature is 80-100 ℃ and the reaction time is 80-100 min.
Preferably, in step S4, the modification treatment specifically includes: mixing the graphene-zinc oxide micro-nano structure material with a modifier, and reacting for 10-14 h under the vacuum degree of 0.05-0.1 MPa.
Preferably, in step S4, the modifying agent used in the modification treatment is at least one of a fluorine-containing compound, a carbon nanotube, and an organosilicon-modified acrylic resin; further preferably, in step S4, the modifying agent used in the modification treatment is a fluorine-containing compound; still more preferably, in step S4, the modifier used in the modification treatment is 1H,1H,2H, 2H-perfluorooctyltriethoxysilane.
Further, in step S4, when the modifying agent used is a fluorine-containing compound, the modifying treatment is a fluorination treatment; specifically, the fluorination treatment is vacuum gas phase fluorination.
The schematic diagram of the preparation process of the graphene zinc oxide micro-nano hierarchical functional material can be seen in an attached figure 1. Fig. 1 shows only an example of the preparation method, and the method of the present invention is not limited to the related substances shown in the figure.
The graphene zinc oxide micro-nano grading functional material with the self-cleaning and super-lyophobic characteristics is applied to the preparation of sensors.
Preferably, in use, the sensor is an electrochemical sensor and/or a biosensor; the biosensor may be a field effect transistor biosensor or an optical biosensor.
Furthermore, the graphene zinc oxide micro-nano hierarchical functional material with the self-cleaning and super-lyophobic characteristics can be used for modifying electrodes or directly preparing electrodes and used as a biosensor for detecting various biomolecules such as glucose, urea, pH, amino acid, protein, DNA, hydrogen peroxide and the like.
The graphene zinc oxide micro-nano grading functional material prepared by the invention is a self-cleaning functional material, can well protect a biosensor, prevents the biosensor from being adhered by various complex molecules in biological tissue fluid or a biological sample, such as protein, polypeptide, small molecules and the like, so that the biosensor can not be polluted by the biological tissue fluid or the biological sample, and can prolong the service life, the durability and maintain the sensitivity and the stability of the biosensor. In addition, the graphene zinc oxide micro-nano grading prepared by the inventionFunctional material capable of detecting H when used as electrode of electrochemical sensor2O2，H2S, NO, ascorbic acid, etc.; as a field effect transistor biosensor to detect pH; the characteristic of fluorescence quenching of graphene in DNA biosensing is utilized, and an optical biosensor can be prepared to detect DNA.
The inventive idea of the invention is further illustrated below:
the invention can controllably prepare the vertically-oriented graphene by manufacturing the vertically-oriented flake graphene by using a Plasma Enhanced Chemical Vapor Deposition (PECVD) method and controlling the growth density of the graphene by changing temperature, power and time. The graphene zinc oxide micro-nano hierarchical structure is prepared by a series of steps such as an atomic deposition method and a hydrothermal method, and the growth length and the diameter of a zinc oxide nanowire are controlled by controlling the concentration of a growth reagent, the growth temperature, the growth time and the growth times of the hydrothermal method. According to the graphene zinc oxide micro-nano hierarchical structure, due to the distribution of zinc oxide nanowires, air is trapped on a rough surface below liquid when the zinc oxide nanowires contact liquid drops, a composite solid-liquid-gas interface capable of supporting the liquid drops is formed, and the liquid is in a stable Cassie state on the surface of a material, so that the liquid drops have large contact angles and low rolling angles. And the surface energy of the material surface can be further reduced through fluorination treatment, so that the lyophobic performance of the material is improved. In the aspect of hydrophobic and oleophobic performance, the water-repellent and super-oleophobic surface has super-hydrophobicity and super-oleophobic performance, and water drops or oil drops can easily slide off from the functional surface. In the aspect of blood dredging performance, the functional surface of the graphene zinc oxide micro-nano hierarchical structure can be obtained through a platelet adhesion resistance experiment, so that blood can easily slide down, and the effect of super blood dredging is achieved.
The graphene zinc oxide micro-nano hierarchical structure material can obtain excellent performances of water resistance, blood resistance, oil resistance and the like, and provides a method for creating a graphene zinc oxide micro-nano hierarchical structure with self-cleaning performance, which is very important for protecting graphene used as an electrode and other applications from pollution. As a detection sensor, a graphene zinc oxide micro-nano hierarchical structure is used as an electrode or a modified electrode, and a substance such as hydrogen peroxide, glucose, urea, pH, amino acid, protein, DNA, and various biomolecules can be detected as a sensor.
The present invention will be described in further detail with reference to specific examples, which are not intended to limit the present invention in any manner. Reagents, methods and apparatus used in the present invention are conventional in the art unless otherwise indicated.
Example 1:
first, preparation method
The preparation method of the graphene zinc oxide micro-nano grading functional material with the self-cleaning and super-lyophobic characteristics in the embodiment 1 comprises the following steps:
s1 growth of vertical graphene
(1) Cleaning a stainless steel substrate by using deionized water and ethanol, and then removing moisture by using nitrogen;
(2) arranging a stainless steel substrate on an inner substrate of a PECVD chamber, and vacuumizing; controlling the PECVD power to be 1200W, the growth temperature to be 900 ℃, and the growth C source to be CH4And H2The growth time is 15 minutes, the cooling time is 30 minutes, and the vertical graphene is obtained after the growth is finished and the furnace is taken out;
s2, dip-coating and adsorbing zinc oxide nano-particle seed crystals on the surface of the graphene in the step 1 by an atomic layer deposition method
Arranging the samples obtained in the step S1, placing the samples into a cavity of an ALD instrument, controlling the temperature to be 100 ℃, using diethyl zinc and oxygen as precursors, using water as an oxygen source, washing the surfaces of the samples for 50S, repeating 300 cycles, and dip-coating and adsorbing zinc oxide nanoparticle seed crystals on the surfaces of the graphene so as to grow zinc oxide nanowires on the surfaces of the graphene in the next step;
s3 hydrothermal synthesis method for growing zinc oxide nanowire on graphene
Firstly, preparing a reagent required for growth: 0.25mol/L zinc nitrate hexahydrate and 0.25mol/L HTMA (hexamethylenetetramine); and (3) then, pouring the graphene substrate adsorbing the zinc oxide nanoparticle seed crystal in the step (2) into a beaker with a proper volume, respectively adding 4mL of deionized water, 0.5mL of zinc nitrate and 0.5mL of HTMA, sealing the beaker by using a preservative film, placing the beaker in a drying oven at 90 ℃, carrying out hydrothermal growth for 90 minutes, and taking out the beaker after growth and washing away excessive ZnO by using deionized water. Repeating the steps to fill the inter-sheet channels of the sheet graphene with the zinc oxide nanowires to form secondary zinc oxide nanowire branches, so as to prepare the graphene zinc oxide micro-nano grading functional material;
s4 fluorination of graphene zinc oxide micro-nano grading functional material
Fluorination by vacuum gas phase fluorination: and (3) placing the graphene zinc oxide micro-nano grading functional material prepared in the step (3) in a vacuum drier, adding 100 mu L of 1H,1H,2H, 2H-perfluorooctyltriethoxysilane, vacuumizing until the vacuum degree reaches 0.08MPa, vacuumizing for 2min, wherein the fluorination time is about 12 hours, after the fluorination is finished, washing the sample with acetone or ethanol, and removing redundant fluorination reagents to obtain the graphene zinc oxide micro-nano grading functional material in the embodiment 1.
Second, performance test
The graphene zinc oxide micro-nano grading functional material prepared in the example 1 is characterized and analyzed, and an SEM image of the material is shown in an attached figure 2.
Carrying out hydrophobic, oleophobic and blood phobic tests on the graphene zinc oxide micro-nano grading functional material prepared in the embodiment 1:
(1) hydrophobicity test
And (3) dropwise adding a drop of water drop (4 microliter) on the surface of the graphene zinc oxide micro-nano graded material by using a contact angle measuring instrument, and observing the motion condition of the water drop. The result is shown in fig. 3, the liquid drop is dropped on the functional wetting surface of the graphene zinc oxide micro-nano hierarchical structure, and due to the low surface energy after the sample is fluorinated, the liquid drop forms a contact angle larger than 150 degrees on the functional wetting surface, the lag angle is small, the liquid drop freely slides on the surface of the graphene zinc oxide micro-nano hierarchical structure material, and the graphene zinc oxide micro-nano hierarchical structure material has hydrophobicity and self-cleaning performance.
(2) Test for oleophobic Properties
The water droplets were changed to oil droplets in the same manner as in step (1). The result shows that oil drops freely slide on the surface of the graphene zinc oxide micro-nano hierarchical structure material liquid and have oleophobic property.
(3) Blood phobicity test
The drop was changed to a blood drop as in step (1). The result shows that blood drops freely slide on the surface of the graphene zinc oxide micro-nano hierarchical structure material liquid, so that the effect of super-dredging blood is achieved.
Example 2:
first, preparation method
The preparation method of the graphene zinc oxide micro-nano grading functional material with the self-cleaning and super-lyophobic characteristics in the embodiment 2 comprises the following steps:
s1 growth of vertical graphene
(1) Cleaning a stainless steel substrate by using deionized water and ethanol, and then removing moisture by using nitrogen;
(2) arranging a stainless steel substrate on an inner substrate of a PECVD chamber, and vacuumizing; controlling the PECVD power to be 1000W, the growth temperature to be 800 ℃, and the growth C source to be CH4And H2Growing for 20 minutes, cooling for 30 minutes, and discharging after growth to prepare vertical graphene;
s2, dip-coating and adsorbing zinc oxide nano-particle seed crystals on the surface of the graphene in the step 1 by an atomic layer deposition method
Same as example 1;
s3 hydrothermal synthesis method for growing zinc oxide nanowire on graphene
Firstly, preparing a reagent required for growth: 0.25mol/L zinc nitrate hexahydrate and 0.25mol/L HTMA (hexamethylenetetramine); and (3) then, pouring the graphene substrate adsorbing the zinc oxide nanoparticle seed crystal in the step (2) into a beaker with a proper volume, respectively adding 4mL of deionized water, 0.5mL of zinc nitrate and 0.5mL of HTMA, sealing the beaker by using a preservative film, placing the beaker in a drying oven at 80 ℃, carrying out hydrothermal growth for 100 minutes, and taking out the beaker after growth and washing away excessive ZnO by using deionized water. Repeating the steps to fill the inter-sheet channels of the sheet graphene with the zinc oxide nanowires to form secondary zinc oxide nanowire branches, so as to prepare the graphene zinc oxide micro-nano grading functional material;
s4 fluorination of graphene zinc oxide micro-nano grading functional material
Fluorination by vacuum gas phase fluorination: and (3) placing the graphene zinc oxide micro-nano grading functional material prepared in the step (3) in a vacuum drier, adding 100 mu L of 1H,1H,2H, 2H-perfluorooctyltriethoxysilane, vacuumizing until the vacuum degree reaches 0.08MPa, vacuumizing for 2min, wherein the fluorination time is about 14 hours, after the fluorination is finished, washing the sample with acetone or ethanol, and removing redundant fluorination reagents to obtain the graphene zinc oxide micro-nano grading functional material of the embodiment 2.
Second, performance test
Testing the hydrophobicity, the oleophobicity and the blood phobicity of the graphene zinc oxide micro-nano grading functional material prepared in the embodiment 2; the result shows that the graphene zinc oxide micro-nano grading functional material of the embodiment 2 has good performances of super hydrophobicity, super oleophobicity and super blood thinning, and has the self-cleaning super lyophobic property.
Example 3:
first, preparation method
The preparation method of the graphene zinc oxide micro-nano grading functional material with the self-cleaning and super-lyophobic characteristics in the embodiment 3 comprises the following steps:
s1 growth of vertical graphene
(1) Cleaning a stainless steel substrate by using deionized water and ethanol, and then removing moisture by using nitrogen;
(2) arranging a stainless steel substrate on an inner substrate of a PECVD chamber, and vacuumizing; controlling the PECVD power to be 800W, the growth temperature to be 1000 ℃, and the growth C source to be CH4And H2The growth time is 18 minutes, the cooling time is 30 minutes, and the vertical graphene is obtained after the growth is finished and the furnace is taken out;
s2, dip-coating and adsorbing zinc oxide nano-particle seed crystals on the surface of the graphene in the step 1 by an atomic layer deposition method
Same as example 1;
s3 hydrothermal synthesis method for growing zinc oxide nanowire on graphene
Firstly, preparing a reagent required for growth: 0.25mol/L zinc nitrate hexahydrate and 0.25mol/L HTMA (hexamethylenetetramine); and (3) then, pouring the graphene substrate adsorbing the zinc oxide nanoparticle seed crystal in the step (2) into a beaker with a proper volume, respectively adding 4mL of deionized water, 0.5mL of zinc nitrate and 0.5mL of HTMA, sealing the beaker by using a preservative film, placing the beaker in a drying oven at 100 ℃, carrying out hydrothermal growth for 80 minutes, and taking out the beaker after growth and washing away excessive ZnO by using deionized water. Repeating the steps to fill the inter-sheet channels of the sheet graphene with the zinc oxide nanowires to form secondary zinc oxide nanowire branches, so as to prepare the graphene zinc oxide micro-nano grading functional material;
s4 fluorination of graphene zinc oxide micro-nano grading functional material
Fluorination by vacuum gas phase fluorination: and (3) placing the graphene zinc oxide micro-nano grading functional material prepared in the step (3) in a vacuum drier, adding 100 mu L of 1H,1H,2H, 2H-perfluorooctyltriethoxysilane, vacuumizing until the vacuum degree reaches 0.08MPa, vacuumizing for 2min, wherein the fluorination time is about 10 hours, after the fluorination is finished, washing the sample with acetone or ethanol, and removing redundant fluorination reagents to obtain the graphene zinc oxide micro-nano grading functional material in the embodiment 3.
Second, performance test
Testing the hydrophobicity, the oleophobicity and the blood phobicity of the graphene zinc oxide micro-nano grading functional material prepared in the embodiment 3; the result shows that the graphene zinc oxide micro-nano grading functional material of the embodiment 3 has good performances of super hydrophobicity, super oleophobicity and super blood thinning, and has the self-cleaning super lyophobic property.
Comparative example 1:
first, preparation method
The preparation method of the graphene zinc oxide micro-nano grading functional material in the comparative example 1 comprises the following steps:
s1 growth of vertical graphene
Same as example 1;
s2, dipping and adsorbing zinc oxide nano-particle seed crystal on graphene surface
Slightly dipping the vertical graphene sample obtained in the step 1 in 0.005mol/L zinc acetate methanol solution, evaporating to dryness at 60 ℃ for several times, then reacting at 300 ℃ in a vacuum state, and plating seed crystals on the surface of the graphene;
s3 hydrothermal synthesis method for growing zinc oxide nanowire on graphene
Same as example 1;
s4 fluorination of graphene zinc oxide micro-nano grading functional material
The graphene zinc oxide micro-nano grading functional material of comparative example 1 is prepared in the same way as in example 1.
Second, performance test
The seed crystals prepared in the step 2 are not uniformly distributed, so that the subsequently grown oxidized nanowires are not uniform enough, and the prepared graphene zinc oxide micro-nano grading functional material is poor in hydrophobicity, oleophobicity and hemophobicity (infiltration and non-slip), and cannot be applied to practice.
In summary, the following steps:
according to the preparation method of the graphene zinc oxide micro-nano composite structure, graphene is grown by a plasma enhanced chemical vapor deposition method, and the growth density and length of the graphene are controlled by controlling conditions such as temperature, power and time. The method comprises the steps of dip-coating and adsorbing zinc oxide nanoparticle seed crystals on the surface of graphene, preparing step by adopting a hydrothermal method, ensuring that the microstructure is controllably added with levels in a graded manner, and further performing surface modification on the surface of the prepared dendritic graphene zinc oxide micro-nano hierarchical structure by using a fluorine-containing compound with low surface energy to enable the surface to have hydrophobic, oleophobic, blood-dredging or lyophobic properties. The principle of the super-hydrophobic self-cleaning material is that the self-cleaning effect is achieved under the action of water, and due to the high contact angle and the low rolling angle of the super-hydrophobic material, water drops can roll freely on the surface, so that dirt can be taken away through the rolling of the water drops.
The prepared graphene zinc oxide micro-nano grading functional material is a self-cleaning functional material, so that the biosensor can be well protected, and can be prevented from being adhered by various complex molecules, such as protein, polypeptide, small molecules and the like, in biological tissue fluid or a biological sample, so that the biosensor can not be polluted by the biological tissue fluid or the biological sample, the service life of the biosensor can be prolonged, the durability of the biosensor can be improved, and the sensitivity and the stability of the biosensor can be maintained.
Claims (2)
1. A preparation method of a graphene zinc oxide micro-nano grading functional material with a self-cleaning super-lyophobic characteristic is characterized by comprising the following steps:
the method comprises the following steps:
s1: generating vertical graphene on a substrate;
s2: dip-coating and adsorbing zinc oxide nano-particle seed crystals on the surface of the graphene by an atomic layer deposition method;
s3: growing a zinc oxide nanowire on graphene by a hydrothermal method to form a graphene-zinc oxide micro-nano structure material;
s4: modifying the graphene-zinc oxide micro-nano structure material to obtain a graphene zinc oxide micro-nano grading functional material with self-cleaning and super-lyophobic properties;
in step S1, the method for generating the vertical graphene is a plasma enhanced chemical vapor deposition method;
in step S1, the control conditions for generating vertical graphene by the plasma enhanced chemical vapor deposition method are as follows: the substrate is a stainless steel substrate; the source of growth C is CH4And H2(ii) a The growth power is 800W-1200W; the growth temperature is 800-1000 ℃; the growth time is 15 min-20 min; the cooling time is 20min to 40 min;
in step S2, precursors of the atomic layer deposition method are an organozinc compound and water; the deposition temperature is 95-105 ℃; the time of each deposition is 45-55 s; the number of cycles is 280 to 320;
in step S3, the hydrothermal method specifically includes: sealing graphene adsorbing zinc oxide nanoparticle seed crystals, water, zinc nitrate and hexamethylenetetramine for hydrothermal synthesis reaction;
in step S3, the temperature of the hydrothermal reaction is 80-100 ℃, and the reaction time is 80-100 min;
in step S4, the modification treatment specifically includes: mixing the graphene-zinc oxide micro-nano structure material with a modifier, and reacting for 10-14 h under the vacuum degree of 0.05-0.1 MPa;
in step S4, the modifier used in the modification treatment is at least one of a fluorine-containing compound, a carbon nanotube, and an organosilicon-modified acrylic resin.
2. The application of the graphene zinc oxide micro-nano grading functional material prepared according to the claim 1 in preparing a biosensor.
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| CN110308188B (en) * | 2019-01-11 | 2021-04-13 | 天津理工大学 | Gold-platinum co-modified graphene electrode and preparation method and application thereof |
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| CN111497365B (en) * | 2020-04-03 | 2021-07-06 | 武汉大学 | Hydrophobic material based on two-dimensional material modified micro-nano structure and preparation method and application thereof |
| CN114717533B (en) * | 2022-02-25 | 2023-03-10 | 中国地质大学（北京） | Method for preparing sensor electrode protection film by utilizing bionic structure and application |
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