CN108751170B - Porous layered graphene framework material and preparation method and application thereof - Google Patents
Porous layered graphene framework material and preparation method and application thereof Download PDFInfo
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Abstract
The invention relates to a porous layered graphene framework material and a preparation method and application thereof. The method comprises the following steps: and (3) reacting the graphene oxide three-dimensional structure with the diamino polyether amine at a certain temperature for a certain time, filtering and washing to remove unreacted polyether amine, and drying to obtain the porous layered graphene frame material. Compared with the prior art, the invention has the advantages of low price of raw materials, mild reaction conditions and simple process. The porous layered graphene framework material obtained by the invention has uniform and controllable micropore/mesoporous pore channels, and can be used in the fields of biological detection, chemical catalysis, electrochemical energy storage, gas storage and gas separation, wastewater treatment, environmental protection and the like.
Description
Technical Field
The invention belongs to the technical field of materials, and relates to a porous layered graphene framework material and a preparation method thereof. Specifically, diamino polyether amine is added into a graphene oxide three-dimensional structure, reaction is carried out for a certain time at a certain temperature, unreacted polyether amine is removed through filtering-washing to obtain a wet-state porous layered graphene framework material, and the wet-state porous layered graphene framework material is dried to obtain a dry-state porous layered graphene framework material.
Background
Porous materials are a class of materials that have a network structure of interconnected or closed pores. Due to the special porous structure, the porous material generally has the characteristics of high specific surface area, high porosity, high permeability, high adsorptivity, assemblability, pore size controllability, structural diversity and the like. The porous material has wide application in various fields such as catalyst and carrier thereof, adsorption and separation, gas storage, environmental management and the like, and has attracted great attention in the industrial and academic fields.
Since the graphene is discovered for the first time in 2004, the graphene has a wide application prospect in the fields of electronic devices, conductive ink, transparent conductive films, polymer composites and the like by virtue of excellent electrical, optical, thermodynamic and other properties. The single-layer graphene sheets are assembled into a porous network structure, so that the aggregation of the graphene sheets can be effectively inhibited, and the graphene porous material with high specific surface area is obtained. The most studied graphene porous material at present is graphene aerogel, and a large number of reports about graphene aerogel exist, and graphene aerogel has the characteristics of high conductivity, high specific strength, low density, high porosity and the like, and is widely used in the fields of electrochemistry, gas/small molecule adsorption, lithium ion batteries, fuel cells and the like. However, the graphene aerogel has the following problems: the pore structure is not uniform, the pore size distribution is very wide, most of the pores are ultra-large pores (1 micron) with very large size, and the proportion of micropores and mesopores (5 nanometers) is very small. Meanwhile, the hole wall of the graphene aerogel is generally formed by graphite-like micro-sheets formed by stacking multiple layers of graphene, and the advantage of high specific surface area of single-layer graphene is not exerted, so that the specific surface area of the whole graphene aerogel is very high. In addition, in graphene aerogels, graphene sheets are stacked in a near random arrangement, resulting in a random distribution of pores in the resulting material with poor regularity. These problems have greatly limited the application of graphene aerogels in a variety of fields. Therefore, how to improve the ordering of graphene lamellar arrangement and the uniformity and regularity of the nanopores to prepare the graphene microporous/mesoporous material becomes a big problem to be solved urgently.
Disclosure of Invention
The invention aims to provide a preparation method of a porous layered graphene framework material, aiming at the problems of large pore diameter, wide pore diameter distribution and poor pore passage arrangement regularity of the existing graphene porous material. The porous layered graphene framework material prepared by the invention has uniform and controllable micropore/mesoporous pore channels, and can be used in the fields of biological detection, chemical catalysis, electrochemical energy storage, gas storage and gas separation, wastewater treatment, environmental protection and the like. The method has the characteristics of low raw material price, mild reaction condition and simple process.
The invention provides a porous layered graphene framework material, which is composed of graphene sheets arranged periodically in parallel, a diamine-based polyether amine molecular chain with two adjacent sheets linked between the sheets, and a micropore/mesopore pore channel, wherein: the mass ratio of the graphene sheet layer to the diamine-based polyether amine is 100: 10-500, and the size of the micropore/mesoporous pore channel is 0.5-50 nanometers.
In the invention, the size of the micropore/mesoporous pore channel can be accurately and controllably adjusted by adjusting the molecular weight, content and conformation of the polyether amine.
The preparation method of the porous layered graphene framework material provided by the invention comprises the following specific steps:
(1): adding diamino polyether amine into water suspension of a graphene oxide three-dimensional structure, uniformly mixing, and reacting for 2-72 hours under the heating condition of 25-100 ℃ to obtain mixed suspension; the mass ratio of the diamino polyether amine to the graphene oxide three-dimensional structure is 0.1-50: 1;
(2): filtering and washing the mixed suspension obtained in the step (1) to remove unreacted diamino polyether amine to obtain a wet porous layered graphene framework material;
(3): and (3) performing any one of spray drying, freeze drying, ultra-zero drying or vacuum drying on the wet porous layered graphene framework material obtained in the step (2) to obtain a dry porous layered graphene framework material.
In the invention, the graphene oxide three-dimensional structure used in the step (1) is graphene oxide aggregate particles obtained by oxidizing raw material graphite without peeling, in the aggregate particles, graphene oxide sheets are arranged in parallel and periodically, and the interlayer spacing is 0.8-50 nm.
In the present invention, the concentration of the aqueous suspension of the graphene oxide three-dimensional structure in the step (1) is 0.1 to 100 mg/ml.
In the invention, the diamino polyether amine used in the step (1) is an oligomer with a polyether main chain and amino groups at two ends of the chain.
In the invention, the molecular weight of the diamino polyether amine used in the step (1) is 50-10000 g/mol.
In the invention, the filtering method in the step (2) adopts any one of centrifugation, vacuum filtration, screen filtration, gauze filtration or natural sedimentation.
In the invention, the washing solvent adopted in the washing in the step (2) is one or a mixture of several of water, ethanol, methanol, ethylene glycol, acetone, chloroform, N-dimethylformamide, N-methylpyrrolidone or toluene and other solvents.
The porous layered graphene framework material provided by the invention is applied to the fields of biological detection, chemical catalysis, electrochemical energy storage, gas storage and gas separation, wastewater treatment or environmental protection and the like.
Compared with the prior art, the invention has the following advantages:
(1) the graphene porous material is prepared from the graphene oxide three-dimensional structure with the layered periodic structure instead of the peeled graphene oxide, the layered periodic structure of the graphene oxide three-dimensional structure is maintained and inherited into the obtained porous material, and the order and uniformity of the pore channels of the obtained graphene porous material are ensured from the source.
(2) The diamino polyether amine oligomer is used as a chemical cross-linking agent instead of small molecules, so that the pore size of the obtained porous material is remarkably increased, and the preparation of the graphene microporous/mesoporous material is realized.
(3) The molecular weight adjustability and molecular weight flexibility of the polyether amine oligomer enable us to easily realize accurate and controllable adjustment of the pore size of the layered graphene framework material by changing the molecular weight, content and conformation of the polyether amine oligomer, and the obtained porous material can realize accurate and controllable adjustment of the pore size in the range of 0.5-5 nanometers.
Drawings
The accompanying drawings, which are included to provide a further understanding of the invention and are incorporated in and constitute a part of this specification, illustrate embodiments of the invention and together with the description serve to explain the principles of the invention without limiting the invention.
FIG. 1 is a structural representation of a wet porous layered graphene framework material; wherein: (a) for the optical photograph, (b) is a small angle X-ray scattering curve, from which it can be seen that the pore size of the resulting porous material is 8.3 nm.
Fig. 2 is a scanning electron microscope photograph of a dry porous layered graphene framework material.
Fig. 3 is a thermal weight loss curve of three materials, namely a graphene oxide three-dimensional structure, a porous layered graphene framework material and polyether amine, in a nitrogen atmosphere.
Detailed Description
The following detailed description of embodiments of the invention refers to the accompanying drawings. It is to be understood that one or more of the steps referred to herein do not exclude the presence of other methods or steps before or after the combined steps, or that other methods or steps may be intervening between the explicitly mentioned steps. It should also be understood that these examples are intended only to illustrate the invention and are not intended to limit the scope of the invention. Unless otherwise indicated, the numbering of the method steps is only for the purpose of identifying the steps, and is not intended to limit the order of arrangement of each method or the scope of the implementation of the invention, and changes or modifications in the relative relationship thereof, without substantial technical changes, should also be considered as the scope of the implementation of the invention.
Example 1
(1) 100 mg of bisamino polyether amine having a molecular weight of 2000 g/mol was added to 50 ml of an aqueous suspension of a graphene oxide three-dimensional structure having a concentration of 1 mg/ml, and after uniformly mixing, the mixture was reacted at 50 ℃ for 10 hours to obtain a mixture.
(2) And (2) centrifuging and washing the mixture obtained in the step (1) for multiple times to remove unreacted polyether amine, so as to obtain the wet porous layered graphene framework material.
(3) And (3) freeze-drying the wet-state porous layered graphene framework material obtained in the step (2) to obtain a dry-state porous layered graphene framework material.
Example 2
(1) 100 mg of bisamino polyether amine with a molecular weight of 600 g/mol was added to 50 ml of an aqueous suspension of a graphene oxide three-dimensional structure with a concentration of 1 mg/ml, and after uniformly mixing, the mixture was reacted at 70 ℃ for 10 hours to obtain a mixture.
(2) And (2) carrying out vacuum filtration-water washing on the mixture obtained in the step (1) for multiple times to remove unreacted polyether amine, so as to obtain the wet porous layered graphene framework material.
(3) And (3) naturally drying the wet-state porous layered graphene framework material obtained in the step (2) to obtain a dry-state porous layered graphene framework material.
Example 3
(1) 100 mg of bisamino polyether amine having a molecular weight of 2000 g/mol was added to 50 ml of an aqueous suspension of a graphene oxide three-dimensional structure having a concentration of 1 mg/ml, and after uniformly mixing, the mixture was reacted under heating at 100 ℃ for 2 hours to obtain a mixture.
(2) And (2) performing multiple centrifugation-ethanol washing on the mixture obtained in the step (1) to remove unreacted polyether amine, so as to obtain the wet porous layered graphene framework material.
(3) And (3) freeze-drying the wet-state porous layered graphene framework material obtained in the step (2) to obtain a dry-state porous layered graphene framework material.
Example 4
(1) 100 mg of bisamino polyether amine with molecular weight of 1000 g/mol was added to 50 ml of an aqueous suspension of graphene oxide three-dimensional structures with a concentration of 5 mg/ml, and after mixing uniformly, the mixture was reacted under heating at 60 ℃ for 10 hours to obtain a mixture.
(2) And (2) subjecting the mixture obtained in the step (1) to multiple natural sedimentation-water washing to remove unreacted polyether amine, so as to obtain the wet porous layered graphene framework material.
(3) And (3) carrying out supercritical drying on the wet-state porous layered graphene framework material obtained in the step (2) to obtain a dry-state porous layered graphene framework material.
Example 5
(1) 100 mg of bisamino polyether amine having a molecular weight of 2000 g/mol was added to 50 ml of an aqueous suspension of a graphene oxide three-dimensional structure having a concentration of 1 mg/ml, and after uniformly mixing, the mixture was reacted at 50 ℃ for 10 hours to obtain a mixture.
(2) And (2) filtering and washing the mixture obtained in the step (1) by using a 200-mesh screen for multiple times, and removing unreacted polyether amine to obtain the wet porous layered graphene framework material.
(3) And (3) freeze-drying the wet-state porous layered graphene framework material obtained in the step (2) to obtain a dry-state porous layered graphene framework material.
Comparative example 1
Adding 100 mg of diamino polyether amine with the molecular weight of 2000 g/mol into 50 ml of stripped graphene oxide aqueous solution with the concentration of 1 mg/ml, uniformly mixing, reacting for 10 hours at the temperature of 50 ℃ to obtain a block precipitate, and further washing and drying the precipitate to show that graphene sheets are arranged in a disordered manner and the pore diameter distribution is wide.
Comparative example 2
Adding 100 mg of monoamino polyether amine with the molecular weight of 2000 g/mol into 50 ml of aqueous suspension of graphene oxide three-dimensional structures with the concentration of 1 mg/ml, uniformly mixing, reacting for 10 hours under the heating condition of 50 ℃, and completely dispersing the obtained product in water through simple water bath ultrasound, which indicates that the crosslinked graphene porous material is not obtained.
Claims (6)
1. The porous layered graphene framework material is characterized by being composed of graphene sheets which are periodically arranged in parallel, a diamine-based polyether amine molecular chain and micropore/mesopore channels, wherein two adjacent sheets are connected between the two layers, and the micropore/mesopore channels are formed by: the mass ratio of the graphene sheet layer to the diamino polyether amine is 100: 10-500, the size of a micropore/mesoporous pore channel is 0.5-50 nanometers, and the graphene sheet layer and the diamino polyether amine can be accurately and controllably adjusted by adjusting the molecular weight, the content and the conformation of the polyether amine, and the preparation method comprises the following specific steps:
(1): adding diamino polyether amine into water suspension of a graphene oxide three-dimensional structure, uniformly mixing, and reacting for 2-72 hours under the heating condition of 25-100 ℃ to obtain mixed suspension; the mass ratio of the diamino polyether amine to the graphene oxide three-dimensional structure is 0.1-5: 1; the graphene oxide three-dimensional structure is graphene oxide aggregate particles obtained by oxidizing raw material graphite without stripping, in the aggregate particles, graphene oxide sheets are arranged in parallel and periodically, and the interlayer spacing is 0.8-50 nanometers;
(2): filtering and washing the mixed suspension obtained in the step (1) to remove unreacted diamino polyether amine to obtain a wet porous layered graphene framework material;
(3): and (3) performing any one of spray drying, freeze drying, ultra-zero drying or vacuum drying on the wet porous layered graphene framework material obtained in the step (2) to obtain a dry porous layered graphene framework material.
2. The method for producing a porous layered graphene framework material according to claim 1, wherein the concentration of the aqueous suspension of the graphene oxide three-dimensional structure in the step (1) is 0.1 to 100 mg/ml.
3. The method for preparing a porous layered graphene framework material according to claim 1, wherein the bis-amino polyether amine used in step (1) is an oligomer having a polyether structure as a main chain and amino groups at both ends of the chain.
4. The method for preparing a porous layered graphene framework material according to claim 1, wherein the molecular weight of the bis-amino polyether amine used in step (1) is 50 to 10000 g/mol.
5. The method for preparing the porous layered graphene framework material according to claim 1, wherein the filtering method in the step (2) is any one of centrifugation, vacuum filtration, screen filtration, gauze filtration or natural sedimentation.
6. The method for preparing the porous layered graphene framework material according to claim 1, wherein the washing solvent used in the washing in step (2) is one or a mixture of water, ethanol, methanol, ethylene glycol, acetone, chloroform, N-dimethylformamide, N-methylpyrrolidone, or toluene.
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