CN109231186B - Preparation method for inducing graphene three-dimensional network by using metal ions - Google Patents
Preparation method for inducing graphene three-dimensional network by using metal ions Download PDFInfo
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Abstract
A preparation method for inducing a graphene three-dimensional network by utilizing metal ions relates to a preparation method for the graphene three-dimensional network, the graphene three-dimensional network takes graphene oxide or derivatives thereof as initial raw materials, metal nanoclusters, nanogold and metal salts are used as assistance, a mutual solution system with a stable structure is formed in a water phase, an ethanol phase or an organic phase, the graphene three-dimensional network structure with communicated pores, controllable size and local order is prepared by means of chemical reduction, thermal reduction and solvent thermal reduction, and then the graphene three-dimensional network with regular pores and stable structure is obtained by repeated dissolution and washing. The graphene three-dimensional network structure can be used for substrates or reinforced materials of photoelectric functional materials, advanced composite materials and ultra-light materials, and has wide application prospects in the fields of high-power supplies, sewage treatment, high-efficiency catalysts, photoelectric detectors and the like.
Description
Technical Field
The invention relates to a preparation method of a graphene three-dimensional network, in particular to a preparation method of a graphene three-dimensional network induced by metal ions.
Background
The graphene three-dimensional network is an ultra-light graphene framework material with a continuous through hole structure, and has very important application value in the field of reinforced materials and functional materials. The main structure is composed of a graphene continuous structure and intercommunicated pores, and has the characteristics of light weight, high strength, good conductivity, optical controllability and the like. At present, similar graphene three-dimensional network materials (graphene foam and graphene aerogel) are generally prepared by a template method and a freeze-drying method, the former method can be used for preparing a graphene three-dimensional network with a controllable structure, but a template cannot be completely removed, a large amount of microsphere template is consumed for preparing a graphene framework, and the cost is increased; the graphene three-dimensional network can be prepared by the latter method at low cost, but the method has low efficiency, the prepared product has a large number of structures and strong randomness, the prepared graphene aerogel has an obvious closed pore structure and is not beneficial to being used as an advanced reinforcing material, and the development of the graphene three-dimensional network material is restricted by the problems. Therefore, the metal center is used as an artificial construction point to regulate the three-dimensional structure of the graphene, so that a continuously communicated ultra-light graphene three-dimensional network structure is formed, and the method has important practical significance for realizing controllability of preparation of the graphene three-dimensional material and further implementing application of the graphene three-dimensional material.
Disclosure of Invention
The invention aims to provide a preparation method for inducing a graphene three-dimensional network by utilizing metal ions, which is used for preparing the graphene three-dimensional network with different pore sizes by adjusting the types of the metal ions and the types of functional groups and has good pore controllability; different functional particles are embedded for compounding, a graphene three-dimensional network composite structure can be obtained, and a multifunctional platform is provided, so that the application is facilitated. And a reinforced framework support is provided for performance optimization of the graphene material and preparation of the light composite material.
The purpose of the invention is realized by the following technical scheme:
the preparation method comprises the steps of inducing a graphene three-dimensional network by using metal ions, wherein graphene oxide or a graphene oxide derivative is used as a raw material, the metal ions, metal clusters and surface metal ions of metal nanocrystals are used as metal centers, so that the graphene oxide or the graphene oxide derivative is induced by the metal centers to form a metal-graphene oxide three-dimensional interconnected grid structure with a topological structure, and the metal is reduced and removed to prepare the graphene three-dimensional network; the preparation method comprises the following preparation processes:
(1) carrying out ultrasonic oscillation on graphene oxide (or a graphene oxide derivative) in a dispersion medium to form a stable solution, wherein the concentration of the stable solution is 0.1-10 mg/mL, and the dispersion medium is water, an organic solvent and various aprotic solvents;
(2) adding a surface ionized metal nano-cluster and metal nano-crystal solution into a graphene oxide (or graphene oxide derivative) stable solution to form a semi-stable metal center-graphene oxide three-dimensional space network structure;
(3) synchronously reducing a solution system of a metal center-graphene oxide (or graphene oxide derivative) three-dimensional space network to prepare a graphene three-dimensional network structure containing metal nano-clusters or nano-crystals or metal ions;
(4) or removing metal ions from the prepared metal-containing graphene three-dimensional network structure, and drying or removing a solvent to finally prepare the high-purity graphene three-dimensional network.
According to the preparation method for inducing the graphene three-dimensional network by using the metal ions, the metal nanocluster with the ionized surface and the metal nanocrystal solution are one or a combination of more than one of the metal nanoclusters of Au, Ag, Cu, Al, Fe, Co, Ni, Zn and Mn transition metals, chlorides, bromides, iodides and hydroxide solutions of the metal nanocrystals and strong acid solutions of sulfuric acid, nitric acid and cyanic acid, and are used as artificial creation points of metal centers.
In the preparation method for inducing the graphene three-dimensional network by using the metal ions, the concentration of the metal nanocluster and metal nanocrystal solution subjected to surface ionization is 0.01-20% of the concentration of the used graphene oxide or graphene oxide derivative) stabilizing solution by mass ratio.
According to the preparation method for inducing the graphene three-dimensional network by using the metal ions, the metal center and the functional group of the graphene oxide form a semi-stable three-dimensional network structure, and the stable graphene three-dimensional network can be formed through synchronous reduction/drying treatment and metal ion removal.
The invention has the advantages and effects that:
1. the method has good pore controllability, and the graphene three-dimensional networks with different pore sizes can be prepared by adjusting the type of the metal ions and the type of the functional groups.
2. The method has the advantages of short period, low cost, simple steps, easy realization of the treatment process and capability of carrying out large-scale production without complex equipment.
3. The graphene three-dimensional network has excellent performance, and the graphene three-dimensional network has stable supporting performance and excellent electric conduction and heat insulation performance.
4. The invention is convenient to apply and put into practical use, different functional particles are embedded for compounding, a graphene three-dimensional network composite structure can be obtained, and a multifunctional platform is provided for convenient application.
The graphene three-dimensional network prepared by the method can be used in various high-technology fields such as special composite materials, aircraft weight reduction, microelectronic equipment, lithium ion batteries and catalysts.
Drawings
Fig. 1 is a morphology diagram of a three-dimensional graphene network manufactured in twenty-one of the embodiments.
Detailed Description
The present invention will be described in detail with reference to examples.
The graphene three-dimensional network structure obtained by metal ion induction is formed by taking graphene oxide or graphene oxide derivatives as raw materials, forming a skeleton structure through ion assistance, and synchronously reducing the graphene oxide through ion exchange, wherein the density of the graphene three-dimensional network is 0.001-0.1 gcm3Conductivity of 103~105S/m, and the strength is 0.1-10 MPa.
The preparation method of the ion-assisted graphene three-dimensional network is realized by the following steps: firstly, graphene oxide (or graphene oxide derivatives) is ultrasonically oscillated in a dispersion medium to form a stable solution, the concentration of the stable solution is 0.1-10 mg/mL, and the dispersion medium is water, an organic solvent and various aprotic solvents. Secondly, adding a surface ionized metal nano-cluster and metal nano-crystal solution into a graphene oxide (or graphene oxide derivative) stable solution to form a semi-stable metal center-graphene oxide three-dimensional space network structure. And thirdly, synchronously reducing the graphene oxide (or graphene oxide derivative) -metal three-dimensional complex solution to prepare the graphene three-dimensional network structure containing the metal ions. And fourthly, removing ions from the prepared graphene three-dimensional network structure containing the metal ions, and drying or removing the ions by using a solvent to finally prepare the graphene three-dimensional network.
In the preparation method of the ion-assisted graphene three-dimensional network, the graphene oxide obtained in the first step is commercially available or synthesized by chemical oxidation and electrochemical oxidation in a laboratory. Step one, the graphene oxide derivative is prepared by modifying functional groups such as amino, carboxyl, hydroxyl, cyano and the like to prepare the graphene oxide derivative with structures such as amination, carboxylation, hydroxylation, cyanation and the like, and the specific process is that organic amine, organic acid, organic alcohol, silane, borane, organic cyanide and the like are added into graphene oxide for modification, the reaction is carried out for 1-5 hours under the reflux condition, and the graphene oxide derivative with the surface grafted with active functional groups such as amino, carboxyl, hydroxyl, cyano and the like is prepared, wherein the concentration range is 0.1-5 mg/mL.
In the first step of the invention, the dispersion medium is water, alcohols, ketones, hydrocarbons, and aprotic solvents (DMF, DMAC, DMSO, NMP).
In the first step of the invention, graphene oxide (or graphene oxide derivatives) is dispersed in a medium by ultrasonic waves, and nanoparticles, a dispersing agent and a stabilizing agent can be added respectively or freely in combination for compounding and stabilization, so as to form a stable solution which is a semitransparent solution or a suspension. The action nanoparticles comprise: the nano-gold particle comprises nano-gold, semiconductor quantum dots, polyacid and metal organic compounds, wherein the particle size of the nano-gold particle is 1-50 nm. The dispersant comprises: DMP-30, and the stabilizer comprises: PVP.
The metal nanocluster and the metal nanocrystal solution with ionized surfaces in the step two of the invention mainly comprise metal nanoclusters of transition metals of Fe, Co, Ni, Cu, Zn and Mn, chlorides, bromides, iodides and hydroxide solutions of metal nanocrystals and strong acid solutions of sulfuric acid, nitric acid and cyanic acid.
In the second step of the invention, the metal-graphene oxide three-dimensional complex structure is a three-dimensional self-assembled network structure formed by taking metal ions as centers and taking graphene oxide (or graphene oxide derivative) functional groups as ligands.
The synchronous reduction method in the third step of the invention comprises hydrogen reduction, thermal reduction, chemical reduction of a reducing agent, plasma reduction, solvothermal reduction and hydrothermal reduction.
The three-dimensional network structure of the graphene containing the metal ions in the step three is a composite structure formed by embedding transition metals of Fe, Co, Ni, Cu, Zn and Mn into the three-dimensional network of the graphene.
The ion removal method in the fourth step of the invention adopts acid washing, solvent cleaning and ultrasonic cleaning modes.
The drying or solvent removing method in the fourth step of the invention comprises evaporation, rotary drying, vacuum drying and low-temperature natural drying.
The graphene three-dimensional network prepared by the third step and the fourth step is light in weight, high in specific strength, good in conductivity and controllable in pore. Meanwhile, the composite material has higher mechanical strength and structural stability.
The examples are as follows:
the technical solution of the present invention is not limited to the following specific embodiments, but includes any combination of the specific embodiments.
The specific implementation method comprises the following steps: according to the invention, graphene oxide is used as a raw material, ultrasonic oscillation is carried out to disperse the graphene oxide in an aqueous solution, a metal nano cluster is used as a structure control agent, metal ions are removed through stabilization and synchronous reduction and water washing, and a graphene three-dimensional network can be prepared through chemical reduction. The graphene oxide is commercially available or prepared by a chemical oxidation method or an electrochemical oxidation method.
The specific implementation method II comprises the following steps: the difference between the method and the method I is that the graphene oxide derivative is used as a raw material, and the graphene oxide derivative is an aminated graphene oxide derivative formed by the action of graphene oxide and organic amine. Other parameters are the same as in the first embodiment.
The specific implementation method comprises the following steps: the method is different from the above method in that organic acid is used as modification to prepare and form the carboxylated graphene oxide derivative. Other parameters are the same as in the first embodiment.
The specific implementation method four: the method is different from the above method in that organic alcohol is used as modification to prepare and form the hydroxylated graphene oxide derivative. Other parameters are the same as in the first embodiment.
The concrete implementation method comprises the following steps: the difference between the method and the above method is that silane is used as modification to prepare and form the alkylated graphene oxide derivative. Other parameters are the same as in the first embodiment.
The specific implementation method six: the difference between the method and the above method is that borane is used as modification to prepare and form the alkylated graphene oxide derivative. Other parameters are the same as in the first embodiment.
The specific implementation method is seven: the method is different from the method in that organic cyanide is used as modification to prepare and form the cyanated graphene oxide derivative. Other parameters are the same as in the first embodiment.
The specific implementation method eight: the method is different from the method in that the graphene oxide derivative with the surface grafted with the functional group is prepared by reacting for 1-5 hours under the reflux condition, and other parameters are the same as those of the first embodiment.
The specific implementation method comprises the following steps: the method is different from the method in that the graphene oxide derivative with the surface grafted with the functional group is prepared, the concentration range is 0.1-5 mg/mL, and other parameters are the same as those of the first embodiment.
The specific implementation method comprises the following steps: the embodiment is a preparation method for inducing a graphene three-dimensional network by using metal ions, as described in the first embodiment, and the preparation method is implemented by the following steps: firstly, graphene oxide (or graphene oxide derivatives) is dispersed in a medium through ultrasound to form a solution with the concentration range of 0.1 mg/mL-5 mg/mL. Secondly, adding metal nanoclusters, nanocrystals and metal ion solution with the content of 0.0001 mg/mL-1 mg/mL into the graphene oxide (or graphene oxide derivative) stable solution to form a metal center-graphene oxide (or graphene oxide derivative) three-dimensional space network structure. And thirdly, performing synchronous chemical reduction on the solution of the metal center-graphene oxide three-dimensional network to prepare a graphene three-dimensional network structure containing 0.01-20% of metal ions. And fourthly, washing the prepared metal-containing graphene three-dimensional network structure with water to remove redundant metal ions, and drying or removing a solvent to finally prepare the metal-containing graphene three-dimensional network.
The specific implementation method eleven: the method is different from the method in that the nano particles, the dispersing agent and the stabilizing agent can be added respectively or freely in combination for compounding and stabilizing to form a stable solution which is a semitransparent solution or a suspension. The action nanoparticles comprise: the nano-particle comprises a metal nano-cluster, a nano-crystal and a metal organic compound, wherein the particle size of the nano-particle ranges from 1 nm to 50 nm. The dispersant comprises: DMP-30, and the stabilizer comprises: PVP. The rest and other parameters are the same as those of the embodiment.
The specific implementation method is twelve: the method is different from the method in that the three-dimensional space of the formed metal center-graphene oxide (or graphene oxide derivative) is in a semi-stable state, and the stable period in the solution is 1-24 h. The rest and other parameters are the same as those of the embodiment.
The specific implementation method thirteen is as follows: the method is different from the method in that the synchronous chemical reducing agent is sodium borohydride, potassium iodide and other reducing agents, and the reducing temperature is as follows: 80-150 ℃. The rest and other parameters are the same as those of the embodiment.
The specific implementation method is fourteen: the method is different from the method in that the solution of the metal center-graphene oxide three-dimensional network is subjected to thermal reduction, and the reduction temperature is as follows: 150-450 ℃. The rest and other parameters are the same as those of the embodiment.
The concrete implementation method is fifteen: the method is different from the method in that the solution of the metal center-graphene oxide three-dimensional network is subjected to thermal reduction, and the reduction needs to be carried out under a vacuum condition. The rest and other parameters are the same as the embodiment fourteen.
The specific implementation method is sixteen: the method is different from the method in that the solution of the metal center-graphene oxide three-dimensional network is subjected to thermal reduction, and the reduction needs to be carried out under the protection of inert gas. The rest and other parameters are the same as the embodiment fourteen.
The specific implementation method comprises the following steps: the method is different from the method in that the reduction method adopted for carrying out thermal reduction on the solution of the metal center-graphene oxide three-dimensional network is solvent thermal reduction, and the used medium solvent is as follows: water, organic solvents such as ethanol, acetone, and toluene, and aprotic solvents. The rest and other parameters are the same as those of the embodiment.
The specific implementation method is eighteen: the method is different from the method in that the temperature of the solvent thermal reduction is as follows: 100 to 250 ℃. The rest and other parameters are the same as those of the embodiment eighteen.
The specific implementation method is nineteen: the method is different from the method in that the metal center-graphene oxide three-dimensional network solution is subjected to synchronous chemical reduction, and the metal ion content in the prepared graphene three-dimensional network structure is as follows: 1% -5%. The rest and other parameters are the same as those of the embodiment eighteen.
The specific implementation method twenty: the method is different from the above methods in that the manner of removing the solvent may be any one of vacuum drying, supercritical drying, and natural drying.
The specific implementation mode is twenty one: the preparation method for inducing the graphene three-dimensional network by using the metal ions is realized by the following steps: firstly, dispersing graphene oxide in ethanol by ultrasonic to form a solution with the concentration range of 1.5 mg/mL. Secondly, adding a copper chloride solution with the content of 0.015mg/mL into the graphene oxide (or graphene oxide derivative) stable solution to form a metal center-graphene oxide (or graphene oxide derivative) three-dimensional space network structure. And thirdly, synchronously chemically reducing the solution of the copper ion center-graphene oxide three-dimensional network by adopting potassium borohydride to prepare the graphene three-dimensional network structure containing 1% of copper ions. And fourthly, washing the prepared copper-containing graphene three-dimensional network structure with water to remove copper ions, and drying to remove the solvent to finally prepare the graphene three-dimensional network.
Table 1 shows performance parameters of the three-dimensional graphene network according to the twenty-first embodiment.
TABLE 1
| Density of | Porosity of the material | Compressive strength | Electrical conductivity of |
| 0.03g/cm3 | 95% | 5MPa | 3.5×103S/m |
The density of the three-dimensional network of the graphene prepared by the method is 0.03g/cm3Conductivity of 3.5X 103S/m, compressive strength 5 MPa.
In the first step of the present embodiment, the graphene oxide is a commercially available product.
In the second step of the embodiment, the copper chloride solution needs to be slowly added into the graphene dispersion liquid, and the mixture is allowed to stand for 8 hours.
In the third step of the present embodiment, the synchronous chemical reduction process needs to be performed in a standing solution, and the reaction time is 4 hours.
In the fourth step of this embodiment, the excess copper ions are removed by washing with an aqueous solution to 6 times.
Specific embodiment twenty-two: the twenty-first difference between the present embodiment and the specific embodiment is that in the first step, graphene oxide is ultrasonically dispersed in ethanol to obtain a graphene oxide solution with a concentration of 4mg/mL, wherein a dispersion medium is water. Other steps and parameters are the same as those of the exemplary embodiment twenty-two.
The density of the graphene three-dimensional network prepared by the embodiment is 0.05g/cm3。
The above embodiments are not all exemplified, and the technical solution for preparing the graphene three-dimensional network by replacing, transforming, improving, etc. steps on the basis of the above embodiments is also within the scope of the claims of the present invention.
Claims (1)
1. The preparation method for inducing the graphene three-dimensional network by using the metal ions is characterized in that graphene oxide or a graphene oxide derivative is used as a raw material, surface metal ions of metal nanoclusters and metal nanocrystals are used as metal centers, the graphene oxide or the graphene oxide derivative is promoted to be induced by the metal centers to form a metal-graphene oxide or metal-graphene oxide derivative three-dimensional interconnected grid structure with a topological structure, and the graphene three-dimensional network is prepared by reducing and removing the metal; the preparation method comprises the following preparation processes:
(1) carrying out ultrasonic oscillation on graphene oxide or a graphene oxide derivative in a dispersion medium to form a stable solution, wherein the concentration of the stable solution is 0.1-10 mg/mL, and the dispersion medium is water, an organic solvent and various aprotic solvents;
(2) adding a metal nanocluster and a metal nanocrystalline solution with ionized surfaces into a graphene oxide or graphene oxide derivative stable solution to form a semi-stable metal center-graphene oxide or metal center-graphene oxide derivative three-dimensional space network structure;
(3) synchronously reducing a solution system of a three-dimensional space network of a metal center-graphene oxide or a metal center-graphene oxide derivative to prepare a graphene three-dimensional network structure containing metal nanoclusters or nanocrystals;
(4) removing metal ions from the prepared metal-containing graphene three-dimensional network structure, and drying to finally prepare a high-purity graphene three-dimensional network;
the metal nanocluster added with the ionized surface and the metal nanocrystal solution are one or a combination of more than one of metal nanoclusters of Cu, Fe, Co, Ni, Zn and Mn, chlorides, bromides, iodides and hydroxide solutions of metal nanocrystals and strong acid solutions of sulfuric acid, nitric acid and cyanic acid, and are used as artificial creation points of metal centers;
the concentration of the metal nanocluster and metal nanocrystal solution subjected to surface ionization is 0.01-20% of the mass ratio of the concentration of the used graphene oxide or graphene oxide derivative stable solution.
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