CN111252760B - Preparation method of graphene oxide nano roll and composite material thereof - Google Patents
Preparation method of graphene oxide nano roll and composite material thereof Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/15—Nano-sized carbon materials
- C01B32/182—Graphene
- C01B32/198—Graphene oxide
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/15—Nano-sized carbon materials
- C01B32/158—Carbon nanotubes
- C01B32/168—After-treatment
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01D—COMPOUNDS OF ALKALI METALS, i.e. LITHIUM, SODIUM, POTASSIUM, RUBIDIUM, CAESIUM, OR FRANCIUM
- C01D15/00—Lithium compounds
- C01D15/06—Sulfates; Sulfites
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01D—COMPOUNDS OF ALKALI METALS, i.e. LITHIUM, SODIUM, POTASSIUM, RUBIDIUM, CAESIUM, OR FRANCIUM
- C01D15/00—Lithium compounds
- C01D15/10—Nitrates
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01D—COMPOUNDS OF ALKALI METALS, i.e. LITHIUM, SODIUM, POTASSIUM, RUBIDIUM, CAESIUM, OR FRANCIUM
- C01D5/00—Sulfates or sulfites of sodium, potassium or alkali metals in general
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
- C01F11/00—Compounds of calcium, strontium, or barium
- C01F11/20—Halides
- C01F11/24—Chlorides
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G9/00—Compounds of zinc
- C01G9/04—Halides
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/10—Process efficiency
Abstract
A preparation method of a graphene oxide nano roll and a composite material thereof belongs to the field of carbon nano material preparation. The invention solves the defects of complicated process, low efficiency, high energy consumption, complex process, single product and the like of the existing preparation method of the carbon nano roll and the composite material. The method comprises the following steps: ultrasonically dispersing the prepared graphene oxide sponge in deionized water by adopting a liquid phase stripping method and freeze-drying; then dripping the solution on a clean substrate, horizontally placing the substrate in equipment connected with a vacuum pump, and vacuumizing the equipment at normal temperature to quickly evaporate water to obtain the graphene oxide nano coil; by controlling the concentration of the graphene oxide, a one-dimensional or three-dimensional network structure can be obtained; the GO-carbon tube nano coil or the GO-carbon tube-metal salt nano coil composite material is prepared by selectively adding acidified carbon nano tubes and various metal salts. The method has the advantages of low cost, simple operation and high safety, and is convenient for large-scale preparation, popularization and application of various products.
Description
Technical Field
The invention belongs to the field of carbon nano-material preparation; in particular to a preparation method of a graphene oxide nano roll and a preparation method of a graphene oxide nano roll composite material.
Background
Graphene is a compound represented by sp2The two-dimensional nano material composed of hybridized carbon atoms has a hexagonal honeycomb structure, and has excellent performance and wide application prospect. Materials such as graphene sheets, graphene fibers, graphene hydrogel or aerogel, graphene nanocoils and the like can be prepared by various methods at present. The graphene oxide nano roll composite material is formed by wrapping other nano substances with two-dimensional graphene oxide nano sheets and curling, is a carbon nano material with an open structure, and has wide application prospects in the aspects of energy conversion and storage, electronic devices, quantum transportation, flexible materials, optical devices, catalysis, aerospace and the like. At present, methods for preparing graphene oxide nano rolls and graphene oxide nano roll composite materials mainly comprise a liquid nitrogen rapid freezing-freeze drying method, an organic solvent ultrasonic method, a hydrothermal method, a mechanical stripping method and the like. The method has the advantages of complex operation steps, complex process, high energy consumption, fewer obtained curled structures and single type. Therefore, there is an urgent need to develop a method for synthesizing carbon nanocolloid composite materials which is versatile, simple, efficient, and diversified in product.
Disclosure of Invention
The invention aims to solve the defects of complex process, low efficiency, high energy consumption, complex process, single product and the like of the existing preparation method of the carbon nano roll and the composite material. The invention provides a high-efficiency, simple and convenient preparation method of a graphene oxide nano roll and a preparation method of a graphene oxide nano roll composite material. The invention has simple synthesis and various functions of the obtained material.
In order to solve the technical problem, the preparation method of the graphene oxide nano-coil is carried out according to the following steps:
preparing graphene oxide sponge (namely spongy graphene oxide) by adopting a liquid phase stripping method and a freeze-drying method, and ultrasonically dispersing the graphene oxide sponge in deionized water to obtain a graphene oxide dispersion liquid;
and secondly, dripping the graphene oxide nano roll on a clean substrate, horizontally placing the graphene oxide nano roll in equipment connected with a vacuum pump, and vacuumizing the equipment at normal temperature to quickly evaporate water to obtain the pure graphene oxide nano roll.
Under the condition that the addition of the graphene oxide dispersion liquid in the step is 1mL, the concentration of the graphene oxide is less than 0.01mg/mL, and a one-dimensional pure graphene oxide nano roll is obtained; and when the concentration of the graphene oxide is more than or equal to 0.01mg/mL, obtaining the pure graphene oxide nano-roll with the three-dimensional network structure.
Further limiting, in the first step, the concentration of the graphene oxide in the graphene oxide dispersion liquid is 0.01-2 mg/mL, and the ultrasonic dispersion time is 30-60 min.
Further limiting the step two to be vacuumized until the vacuum degree is 1 Pa-20 Pa, and treating for 5 min-20 min under the vacuum degree of 1 Pa-20 Pa.
Further limiting the substrate in the second step to be glass or silicon wafer; the silicon wafer cleaning method comprises the steps of soaking the silicon wafer in acetone and water in a volume ratio of 1:1, and performing ultrasonic treatment for at least 30 min; the glass cleaning method comprises soaking glass in anhydrous ethanol, and performing ultrasonic treatment for at least 30 min.
The preparation method of the graphene oxide nano-coil composite material is carried out according to the following steps:
step 2, acidifying the carbon nano tube, washing the carbon nano tube with deionized water until the pH value is neutral, freezing and drying the carbon nano tube, and ultrasonically dispersing the carbon nano tube in the deionized water to obtain a carbon nano tube dispersion liquid;
step 3, mixing the graphene oxide dispersion liquid obtained in the step 1 with the carbon nanotube dispersion liquid obtained in the step 2, and then carrying out ultrasonic treatment;
and 4, dripping the graphene oxide nano coil on a clean substrate, horizontally placing the substrate in equipment connected with a vacuum pump, and vacuumizing the equipment at normal temperature to quickly evaporate water to obtain the graphene oxide nano coil composite material.
The preparation method of the graphene oxide nano-coil composite material can also comprise the step 3 of adding water-soluble metal salt after ultrasonic treatment until the metal salt is completely dissolved, and then carrying out the operation of the step 4.
Further limited, the metal salt accounts for 30% -60% of the total mass of the graphene oxide sponge and the carbon nanotube.
Further, the metal salt is one of lithium sulfate, lithium nitrate, zinc chloride, calcium chloride and sodium sulfate.
Further, the step 2 of acidifying the carbon nanotubes is realized by the following operations: 150mL of concentrated sulfuric acid and 50mL of concentrated nitric acid are added into 2g of carbon nano tube, and the mixture is magnetically stirred and condensed and refluxed for 3 to 24 hours at the temperature of between 35 and 70 ℃.
Further limiting, the concentration of the graphene oxide in the graphene oxide dispersion liquid in the step 1 is 0.01-2 mg/mL, and the ultrasonic dispersion time in the graphene oxide dispersion liquid preparation process is 30-60 min.
Further limiting, the concentration of the carbon nano tubes in the carbon nano tube dispersion liquid in the step 2 is 0.5-1 mg/mL, and the ultrasonic dispersion time in the process of preparing the carbon nano tube dispersion liquid is 30-60 min.
Further, in step 3, the graphene oxide dispersion liquid and the carbon nanotube dispersion liquid are mixed according to the mass ratio of the graphene oxide sponge to the carbon nanotube of (3:2) - (9: 1).
Further limiting, the ultrasonic treatment time in the step 3 is 100 min-200 min.
Further limiting, the substrate in the step 4 is glass or silicon wafer; the silicon wafer cleaning method comprises the steps of soaking the silicon wafer in acetone and water in a volume ratio of 1:1, and performing ultrasonic treatment for at least 30 min; the glass cleaning method comprises soaking glass in anhydrous ethanol, and performing ultrasonic treatment for at least 30 min.
Further limiting, in the step 4, vacuumizing is carried out until the vacuum degree is 1 Pa-20 Pa, and the treatment is carried out for 5 min-20 min under the vacuum degree of 1 Pa-20 Pa.
The preparation method provided by the invention is based on rapid evaporation of water, and induces self-assembly of graphene oxide on a gas-liquid interface. The invention adopts liquid drop evaporation to construct a large-scale micro-nano structure. In the preparation process of the method, the monodisperse nano-substances are self-assembled at the gas-liquid interface to form an ordered array. The material is vacuumized at normal temperature, the gasified water vapor is rapidly pumped out to enable the periphery of the material to form a negative pressure state, a large humidity difference is formed between the inner layer and the outer layer of the material and between the surface of the material and the surrounding medium, the gasification speed is accelerated, rapid evaporation is realized, the material is self-assembled under the induction of the microscopic acting force of a gas-liquid interface, and a large-scale ordered array is formed. The invention induces the graphene oxide nano sheets to carry out self-assembly on the interface of liquid drop water evaporation, and forms the uniform one-dimensional graphene oxide nano roll composite material with a unique topological structure. In addition, in the present invention, a graphene oxide carbon nanocolloid composite having a three-dimensional structure can also be obtained by adjusting the concentration of graphene oxide and the kind of nanoparticles. The unique one-dimensional nano-roll structure has better electronic, phonon and photon conduction capabilities, and is expected to become an ideal quantum transmission material. The three-dimensional network topology graphene oxide nano-roll composite material is connected with each other point-line, thereby being beneficial to the rapid conduction of electrons in the whole structure and having great application space in the fields of batteries, catalysis and the like.
The preparation method has the advantages of simple synthesis, avoidance of liquid nitrogen quick freezing and long-time freeze drying, use of organic solvents, long-time hydrothermal method and the like, and quick and efficient preparation of the nano-coil with controllable microscopic morphology and the nano-coil composite material.
According to the invention, a surfactant and an organic solvent are not required to be added, water evaporation is accelerated in vacuum in a normal-temperature environment, the method is simple and easy to control, and the safety is high; the product is diversified, the nano-roll graphene oxide nano-roll can be formed, the number of substances for coating can be selected, and various graphene oxide nano-roll composite materials can be formed, so that the preparation, popularization and application on a large scale can be facilitated under the conditions of low cost, simple operation and high safety.
Drawings
FIG. 1 is a one-dimensional SEM image of graphene oxide nanocolloid prepared in example 1;
FIG. 2 is a TEM image of graphene oxide nanocolumns prepared in example 1;
FIG. 3 is a SEM image of the three-dimensional morphology of the graphene oxide nanocolloid prepared in example 2;
fig. 4 is a topographical SEM image of the graphene oxide nanoscroll composite of example 4.
Detailed Description
The method of cleaning a silicon wafer substrate in the following examples: soaking the silicon wafer substrate in a solution of acetone and water (volume ratio of 1:1), and performing ultrasonic treatment for 30 min. Method for cleaning glass substrate: soaking the glass substrate in absolute ethyl alcohol, and carrying out ultrasonic treatment for 30 min.
Example 1: the preparation method of the one-dimensional pure graphene oxide nano-roll in the embodiment is carried out according to the following steps:
preparing graphene oxide by adopting a liquid phase stripping method (Hummers), centrifugally washing until the pH value of the solution is neutral, freeze-drying at-10 ℃ to obtain graphene oxide sponge, adding the graphene oxide sponge into deionized water, and ultrasonically dispersing for 60min to obtain 0.01mg/mL graphene oxide dispersion liquid;
and secondly, dripping 1ml of the solution onto a clean 3cm multiplied by 3cm silicon chip, horizontally placing the silicon chip in equipment connected with a vacuum pump, vacuumizing the equipment to 10Pa of vacuum degree under the condition of normal temperature, and treating the silicon chip for 10min under the vacuum degree of 10Pa to obtain the graphene oxide nano coil which is uniformly curled.
In the embodiment, the graphene oxide is prepared by adopting the existing liquid phase stripping method (Hummers), specifically, 98% concentrated sulfuric acid is cooled to 0 ℃ by using ice bath, stirred, and 10g of natural crystalline flake graphite and 5g of NaNO are added3And 30g of KMnO4 powder, controlling the temperature of the reaction solution at 10 ℃, stirring and reacting for 12h, removing the ice bath, placing the ice bath into a warm water bath which is preheated to 35 ℃, and continuing stirring and reacting for 30min when the temperature of the reaction solution is raised to 35 ℃, thus finishing the medium-temperature reaction. Finally, theAnd (3) carrying out high-temperature reaction, namely adding 460mL of deionized water while stirring, and continuing stirring for reaction for 30min when the reaction temperature rises to 100 ℃. The stirrer and warm water bath were removed, the reaction was diluted with 1000mL of deionized water and 100mL of 5% by mass H was added2O2Filtering while hot, fully washing the filter cake by using prepared 5 percent HCl and deionized water until no sulfate radical exists in the filtrate, drying for 48 hours, and grinding.
As can be seen from fig. 1, the two-dimensional graphene oxide sheets self-assemble into a uniform one-dimensional nanoscroll.
As can be seen from fig. 2, the internal coiled structure of the one-dimensional graphene oxide nano roll is relatively uniform and clear.
Example 2: the preparation method of the three-dimensional pure graphene oxide nano-roll in the embodiment is carried out according to the following steps:
preparing graphene oxide by adopting a liquid phase stripping method (Hummers), centrifugally washing until the pH value of the solution is neutral, freeze-drying at-10 ℃ to obtain graphene oxide sponge, adding the graphene oxide sponge into deionized water, and ultrasonically dispersing for 60min to obtain 2mg/mL graphene oxide dispersion liquid;
and secondly, dripping 1ml of the solution on clean 3cm multiplied by 3cm glass, horizontally placing the glass in equipment connected with a vacuum pump, vacuumizing the glass at normal temperature until the vacuum degree is 10Pa, and treating the glass for 10min under the vacuum degree of 10Pa to obtain the graphene oxide nano roll which is uniform in curling and can form a three-dimensional network structure.
Graphene oxide in this example was prepared as in example 1.
As can be seen from fig. 3, the graphene oxide can be connected to form a three-dimensional network structure by changing the concentration of the graphene oxide.
Example 3: the preparation method of the graphene oxide-carbon nanotube nano-roll composite material in the embodiment is carried out according to the following steps:
step 2, adding 150mL of concentrated sulfuric acid and 50mL of concentrated nitric acid into 2g of carbon nano tube, magnetically stirring, condensing and refluxing for 3h at 55 ℃, washing with deionized water until the pH value is neutral after the reaction is finished, freeze-drying at-10 ℃, adding into deionized water, and performing ultrasonic dispersion for 30min to obtain 0.5mg/mL of carbon nano tube dispersion liquid;
step 3, mixing 5mL of the graphene oxide dispersion liquid obtained in the step 1 with 2mL of the carbon nanotube dispersion liquid obtained in the step 2, and then carrying out ultrasonic treatment for 10 min;
and 4, dripping the mixture onto clean 3cm multiplied by 3cm glass, horizontally placing the glass in equipment connected with a vacuum pump, vacuumizing the equipment at normal temperature until the vacuum degree is 10Pa, and treating the glass for 10min under the vacuum degree of 10Pa to obtain the graphene oxide-carbon nanotube nano-roll composite material.
Example 4: the preparation method of the graphene oxide-carbon nanotube-metal salt nano-roll composite material in the embodiment is performed according to the following steps:
step 2, adding 150mL of concentrated sulfuric acid and 50mL of concentrated nitric acid into 2g of carbon nano tube, magnetically stirring, condensing and refluxing for 3h at 55 ℃, washing with deionized water until the pH value is neutral after the reaction is finished, freeze-drying at-10 ℃, adding into deionized water, and performing ultrasonic dispersion for 30min to obtain 0.5mg/mL of carbon nano tube dispersion liquid;
step 3, mixing 5mL of the graphene oxide dispersion liquid obtained in the step 1 with 2mL of the carbon nanotube dispersion liquid obtained in the step 2, then carrying out ultrasonic treatment for 10min, and adding 0.012g of lithium sulfate until the lithium sulfate is completely dissolved;
and 4, dripping 1mL of the solution onto a clean 3cm × 3cm silicon chip, horizontally placing the silicon chip in equipment connected with a vacuum pump, vacuumizing the equipment at normal temperature until the vacuum degree is 10Pa, and treating the silicon chip for 10min under the vacuum degree of 10Pa to obtain the graphene oxide-carbon nanotube-lithium sulfate nano coil composite material.
As can be seen from fig. 4, a graphene oxide-carbon nanotube-lithium sulfate nanocolloid composite having a coating structure was formed.
Claims (9)
1. A preparation method of a graphene oxide nano coil is characterized by comprising the following steps:
preparing graphene oxide sponge by adopting a liquid phase stripping method and a freeze-drying method, and ultrasonically dispersing in deionized water to obtain a graphene oxide dispersion liquid;
secondly, dripping the graphene oxide nano-roll onto a clean substrate, horizontally placing the substrate in equipment connected with a vacuum pump, and vacuumizing the equipment at normal temperature to quickly evaporate water to obtain the graphene oxide nano-roll;
and in the second step, the vacuum is pumped until the vacuum degree is 1 Pa-20 Pa, and the treatment is carried out for 5 min-20 min under the vacuum degree of 1 Pa-20 Pa.
2. The preparation method of the graphene oxide nano-coil according to claim 1, wherein in the first step, the concentration of graphene oxide in the graphene oxide dispersion liquid is 0.01-2 mg/mL, and the ultrasonic dispersion time is 30-60 min.
3. A preparation method of a graphene oxide nano-coil composite material is characterized by comprising the following steps:
step 1, preparing graphene oxide sponge by adopting a liquid phase stripping method and a freeze-drying method, and ultrasonically dispersing the graphene oxide sponge in deionized water to obtain a graphene oxide dispersion liquid;
step 2, acidifying the carbon nano tube, washing the carbon nano tube with deionized water until the pH value is neutral, freezing and drying the carbon nano tube, and ultrasonically dispersing the carbon nano tube in the deionized water to obtain a carbon nano tube dispersion liquid;
step 3, mixing the graphene oxide dispersion liquid obtained in the step 1 with the carbon nanotube dispersion liquid obtained in the step 2, and then carrying out ultrasonic treatment;
step 4, dripping the graphene oxide nano coil onto a clean substrate, horizontally placing the substrate in equipment connected with a vacuum pump, and vacuumizing the equipment at normal temperature to quickly evaporate water to obtain the graphene oxide nano coil composite material;
wherein, in the step 4, the vacuum is pumped until the vacuum degree is 1 Pa-20 Pa, and the treatment is carried out for 5 min-20 min under the vacuum degree of 1 Pa-20 Pa.
4. The method for preparing the graphene oxide nano-coil composite material according to claim 3, wherein after the ultrasonic treatment in the step 3, a water-soluble metal salt is added until the metal salt is completely dissolved, and then the operation of the step 4 is performed.
5. The method of claim 4, wherein the metal salt is 30-60% of the total mass of the graphene oxide sponge and the carbon nanotubes.
6. The method according to claim 4, wherein the metal salt is one of lithium sulfate, lithium nitrate, zinc chloride, calcium chloride, and sodium sulfate.
7. The method for preparing graphene oxide nano-coil composite material according to claim 3, 4, 5 or 6, wherein the acidification of the carbon nanotubes in the step 2 is achieved by the following operations: 150mL of concentrated sulfuric acid and 50mL of concentrated nitric acid are added into the carbon nano tube, and are magnetically stirred and condensed and refluxed for 3 to 24 hours at the temperature of between 35 and 70 ℃.
8. The preparation method of the graphene oxide nano-coil composite material according to claim 3, 4, 5 or 6, wherein the concentration of graphene oxide in the graphene oxide dispersion liquid in the step 1 is 0.01-2 mg/mL, and the ultrasonic dispersion time in the preparation process of the graphene oxide dispersion liquid is 30-60 min; step 2, the concentration of the carbon nano tubes in the carbon nano tube dispersion liquid is 0.5-1 mg/mL, and the ultrasonic dispersion time in the process of preparing the carbon nano tube dispersion liquid is 30-60 min; and 3, mixing the graphene oxide dispersion liquid and the carbon nano tube dispersion liquid according to the mass ratio of the graphene oxide sponge to the carbon nano tube of (3:2) - (9:1), wherein the ultrasonic treatment time is 100-200 min.
9. The method for preparing the graphene oxide nano-coil composite material according to the claims 3, 4, 5 or 6, wherein the substrate in the step 4 is glass or silicon wafer; the silicon wafer cleaning method comprises the steps of soaking the silicon wafer in acetone and water in a volume ratio of 1:1, and performing ultrasonic treatment for at least 30 min; the glass cleaning method comprises soaking glass in anhydrous ethanol, and performing ultrasonic treatment for at least 30 min.
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