CN110903506B - Preparation method of dendritic macromolecule reinforced porous graphene oxide paper - Google Patents
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Abstract
A preparation method of dendritic macromolecule reinforced porous graphene oxide paper belongs to the technical field of graphene oxide production. The invention aims to solve the problems of low tensile strength, stress relaxation, low quality of a finally prepared material due to impermeability of a sheet layer and the like of a graphene oxide film/paper material, erodes an epoxy functional group and adjacent carbon atoms thereof in the graphene oxide sheet layer through the strong oxidizing property of hydrogen peroxide to form a nano-scale hole, then forms covalent crosslinking between graphene oxide sheet layers by introducing polyamide-amine dendrimer (PAMAM), improves the bonding strength between graphene oxide layers, and finally obtains the graphene oxide film/paper material with high strength and good quality in a directional filtration mode. The method is simple to operate, low in cost, high in efficiency and expected to realize large-scale preparation.
Description
Technical Field
The invention belongs to the technical field of graphene oxide production, and particularly relates to a preparation method of dendritic macromolecule reinforced porous graphene oxide paper.
Background
Since the formal discovery of graphene in 2004, graphene and two-dimensional and three-dimensional functionalized components derived from the graphene have attracted much attention because of their excellent properties such as good mechanical properties, thermal conductivity, and electrical conductivity. At the present stage, the simple and large-scale extended preparation of the graphene/graphene oxide film with high density, large size and high quality and the functional derivative material product thereof has great attraction to the application fields of electronics and machinery. However, due to the impermeable property of graphene sheets to most gases and solvents, it is difficult to remove air and solvents trapped between the layers during the preparation process, which poses a challenge in manufacturing dense thin films and high quality modules with high conductivity. In addition, for the graphene oxide paper/film, when the independent carbon-based film/paper-like material formed by self-assembling and stacking single-layer graphene oxide micro/nano-sheets by means of directional filtration, high-temperature compression and the like is subjected to external load, the inter-sheet slippage can cause low material strength and obvious stress relaxation phenomenon, so that the application potential of the material is greatly limited.
Graphene oxide paper materials were first prepared in 2007 by dmitiriy a. dikin et al, northwest university in usa, and it is believed that this particular material structure will play a great role in the fields of protective layers, chemical filters, battery or supercapacitor components, adhesive layers, electronic or optoelectronic components, and the like. However, in the research on the mechanical tensile property of the material, the breaking strength of the material is only 19-31MPa, and although the re-tensile test of the rest part of the sample after tensile breaking shows that the breaking strength of the material is improved, the prepared initial material has great limitation when being used for a functional component of a bearing structure. In addition, the mechanical properties of graphene oxide paper are studied by the university of Zhejiang in 2018, and the laminated assembly structure shows severe relaxation behavior under continuous load, for example, the stress of the graphene paper material is only 14.7% of that of the original state after being subjected to the continuous load for five hours.
In order to solve the problem of air or solvent remaining between graphene oxide sheets and thus improve the quality (such as uniformity, strength, etc.) of graphene oxide paper/film materials, a method of performing high-temperature/high-pressure treatment on a prepared sample is generally adopted at present. However, this method has been proved to seriously damage the chemical structure of the graphene oxide sheet layer locally or wholly, and to cause permanent damage to the material. Moreover, the preparation method has high cost and is difficult to realize large-scale production.
In the aspect of researching the enhancement of the tensile strength of the graphene oxide film/paper material, the method which is commonly adopted at present is to introduce divalent ions to enable the divalent ions to be subjected to a crosslinking reaction with carboxyl functional groups at the end parts of graphene oxide sheets to form covalent bonds, so that the interlayer slippage of the graphene oxide sheets is prevented, and the overall tensile strength of the material is further increased. The method improves the strength of the graphene oxide paper/film material to a great extent and weakens the stress relaxation phenomenon caused by interlayer slippage. However, as described above, due to the characteristic of the graphene oxide lamellar layer that the graphene oxide lamellar layer is not easy to permeate, interlayer gas and solvent cannot be effectively discharged, so that the prepared material layer has large spacing and small volume density. In practical application, the sample needs to be compressed finally, so that the preparation process is complicated, and the experiment cost is increased; in addition, the graphene oxide film/paper material prepared by the method has limited tensile strength enhancement degree (10% -100%), high material modulus and elongation at break of only 0.3%, so that the application potential of the graphene oxide film/paper material is limited.
In summary, how to effectively solve the problems of low tensile strength, stress relaxation, low quality of the finally prepared material due to the impermeability of the sheet layer and the like of the graphene oxide film/paper material, so as to obtain the high-strength and high-quality carbon-based film/paper-like material, which is of great significance for the development of the fields of electronic/photoelectric components, batteries, supercapacitors and the like.
Disclosure of Invention
The invention aims to solve the problems of low tensile strength, stress relaxation, low material quality caused by impermeability of a sheet layer and the like of a graphene oxide film/paper material, and provides a preparation method of a porous graphene oxide paper with enhanced dendritic macromolecules. The preparation method provided by the invention can effectively solve the problem of removing air or solvent retained between layers in the preparation process, improve the tensile strength of the material and improve the quality of the material. In addition, the method is simple to operate, low in cost, high in efficiency and expected to realize large-scale preparation.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows:
a preparation method of dendritic macromolecule reinforced perforated graphene oxide paper comprises the following steps:
s1: preparing graphene oxide dispersion liquid by adopting an improved Hummers method, wherein the concentration of graphene oxide in the dispersion liquid is 2-3 mg/ml;
s2: corroding the graphene oxide dispersion liquid by using 30 wt.% hydrogen peroxide solution to prepare a graphene oxide dispersion liquid with holes;
s3: preparation of porous graphene oxide and polyamide-amine type films: mixing the polyamide-amine dendrimer with the oxidized graphene dispersion liquid with the holes obtained in S2, uniformly stirring to obtain a mixed solution, performing suction filtration to form a film by using a suction filtration device through a directional flow vacuum suction filtration method, drying the dispersion liquid at room temperature for 12-15 hours after the suction filtration is finished, keeping the suction filtration state, then closing the suction filtration device, and standing at room temperature for 12-24 hours to obtain the prepared product shown in figures 1 and 2.
Compared with the prior art, the invention has the beneficial effects that:
(1) hydrogen peroxide (H)2O2) The strong oxidizing property of the graphene oxide can erode epoxy groups in graphene oxide lamella and carbon atoms connected with the graphene oxide lamella, so that nano-scale holes are formed in the graphene oxide lamella, and air and solvent remained between the layers in the preparation process are effectively discharged. And, by regulating H2O2The reaction time with the graphene oxide dispersion liquid can effectively adjust the size of the formed holes, so that the overall strength and quality of the material can be adjusted.
(2) Currently, in the research of enhancing the tensile strength of graphene oxide film/paper materials, a commonly adopted method is to introduce divalent ions to perform a cross-linking reaction with carboxyl groups at the end parts of graphene oxide sheetsForming covalent bonds, thereby preventing the graphene oxide sheets from sliding between layers. However, due to the structure of the graphene oxide sheet layer itself, carboxyl groups are formed only at the end portions thereof, and relatively few, and H is present2O2After the graphene oxide lamella is corroded, carboxyl functional groups can be formed at the end parts of the formed holes, so that the number of the carboxyl groups is greatly increased, a large number of crosslinking sites can be provided for divalent ions or macromolecules containing groups such as amide groups and the like, the crosslinking strength between the graphene oxide lamella layers is increased, the slippage between the lamella layers is effectively prevented, and the strength of the material is further increased.
(3) Amine groups contained in the polyamide-amine dendrimer (PAMAM) can perform a crosslinking reaction with carboxyl groups of the h-GO sheet layer to form an amide covalent bond. In addition, compared with divalent ions, the entanglement of the high molecular chain segment of the PAMAM is more effective in preventing the graphene oxide sheet from sliding, and the prepared carbon-based film/paper-like material has higher strength.
Drawings
FIG. 1 is a schematic view of a porous graphene oxide/polyamidoamine (h-GO/PAMAM) membrane according to the present invention;
FIG. 2 is an XPS characterization image of a porous graphene oxide/polyamide-amine (h-GO/PAMAM) film according to the present invention.
Detailed Description
The technical solution of the present invention is further described below with reference to the accompanying drawings, but the present invention is not limited thereto, and modifications and equivalent substitutions may be made to the technical solution of the present invention without departing from the spirit of the technical solution of the present invention, and the technical solution of the present invention is covered by the protection scope of the present invention.
The invention provides a method for improving the quality of a material by hydrogen peroxide (H) in order to effectively solve the problem of removing air and/or solvent retained between layers in the preparation process and improve the tensile strength of the material2O2) Eroding epoxy functional groups and adjacent carbon atoms in graphene oxide lamella to form nano-scale holes, introducing dendritic Polymers (PAMAM) to form covalent cross-linking between the graphene oxide lamella to improve bonding strength between the graphene oxide layers, and finally obtaining the graphene oxide with higher strength and better quality in a directional filtration modeGraphene oxide film/paper material. The method is simple to operate, low in cost, high in efficiency and expected to realize large-scale preparation.
The first embodiment is as follows: the embodiment describes a method for preparing a dendritic macromolecule reinforced perforated graphene oxide paper, which comprises the following steps:
s1: preparing graphene oxide dispersion liquid by adopting an improved Hummers method, wherein the concentration of graphene oxide in the dispersion liquid is 2-3 mg/ml, and the dispersion liquid is neutral, and the specific method comprises the following steps:
(1) 7.5mL of concentrated H2SO4(98 vol.%) was placed in a 100mL beaker and heated to 80 ℃;
(2) 2.5g K was added sequentially2S2O8And 2.5g P2O5Continuously stirring until the reactants are completely dissolved;
(3) adding 5g of graphite powder into the mixture, stirring to obtain a blue-black mixture, reacting at 80 ℃ for 6h, naturally cooling to room temperature, diluting with distilled water, filtering and washing until the pH value is about 7, removing all soluble substances to obtain pre-oxidized graphite, transferring the pre-oxidized graphite into a drying dish, and drying at 50 ℃ for 12 h-24 h;
(4) another 115ml of H was taken2SO4(98 vol.%) was placed in a 500ml flask, which was then cooled to 0 ℃ in an ice bath;
(5) mixing the dried pre-oxidized graphite (3) with 15g of KMnO4Slowly adding into the flask of (4), stirring until the mixture is completely dissolved, controlling the temperature below 20 ℃, and then stirring the mixture for 2h at 35 ℃; then, 230ml of distilled water was slowly added, and after stirring for 15min, 700ml of distilled water was added, and 30 vol.% of H was added2O212.5 mL, the solution turned bright yellow in color;
(6) the mixture was allowed to stand for at least 12h, then the clear supernatant was decanted and the remaining mixture was diluted with 1.1L of a 1: cleaning with 10HCl aqueous solution (aiming at removing metal ions), centrifuging the obtained mixed solution at 5000rpm for 5min, collecting precipitates, mixing the precipitates with water, centrifuging for 2-3 times by using the same method, removing all residual graphene oxide which is not peeled off, and then washing with distilled water;
(7) finally, dialyzing and purifying the graphite for at least one week to remove all residual salt impurities to obtain graphite oxide;
(8) adding graphite oxide (2 mg/mL-3 mg/mL) into deionized water according to a certain concentration, stripping for 2h by using ultrasonic waves, and then centrifuging for 5min at 5000rpm to remove any residual non-exfoliated graphene oxide.
S2: eroding the graphene oxide dispersion liquid by adopting 30 wt.% hydrogen peroxide solution to prepare a graphene oxide (h-GO) dispersion liquid with holes;
the erosion is specifically: mixing a hydrogen peroxide solution and a graphene oxide dispersion liquid according to a certain proportion, fully and uniformly stirring, carrying out oil bath at 100 ℃ for 3-5H, continuously stirring and cooling to room temperature, carrying out high-speed centrifugation at 12000r/min on the obtained solution for 1H, washing, and removing residual H2O2And adding water again into the obtained graphene oxide, and performing ultrasonic dispersion until the concentration is 2 mg/ml-3 mg/ml.
S3: preparation of porous graphene oxide and polyamidoamine (h-GO/PAMAM) films: taking polyamide-amine type dendritic polymer (PAMAM, generation 0) as a cross-linking agent, mixing with the oxidized graphene dispersion liquid with holes obtained in S2, uniformly stirring to obtain a mixed solution, performing suction filtration to form a film by using a suction filtration device and adopting a directional flow vacuum suction filtration method (SHB-III/IIIA circulating water vacuum pump, Zheng Changcheng department of China), after the suction filtration of the dispersion liquid is finished, drying at room temperature for 12-15 h, keeping the suction filtration state, closing the suction filtration device, and standing at room temperature for 12-24 h to obtain the product shown in figures 1 and 2.
The second embodiment is as follows: in a method for preparing a dendritic macromolecule reinforced perforated graphene oxide paper, in S2, a volume ratio of the hydrogen peroxide solution to the graphene oxide dispersion is 5 to 20 ml: 50-70 ml.
The third concrete implementation mode: in a method for preparing a dendritic macromolecule enhanced graphene oxide paper with holes according to a specific embodiment, in S2, the specific conditions of the etching are as follows: stirring and heating for 3-5 h under 100 ℃ oil bath.
The fourth concrete implementation mode: in a method for preparing a dendritic macromolecule-reinforced perforated graphene oxide paper, in S3, a mixing ratio of the polyamide-amine type dendritic macromolecule to the perforated graphene oxide dispersion liquid is 0.13mg to 1.3 mg: 25-50 ml.
The fifth concrete implementation mode: in a method for preparing the dendritic macromolecule-reinforced perforated graphene oxide paper, in S3, a water-based microporous filter membrane with a filter diameter of 0.45 μm to 0.85 μm is used for suction filtration, and the dispersion is successively suction filtered in batches during suction filtration.
Claims (5)
1. A preparation method of dendritic macromolecule reinforced perforated graphene oxide paper is characterized by comprising the following steps: the method comprises the following steps:
s1: preparing graphene oxide dispersion liquid by adopting an improved Hummers method, wherein the concentration of graphene oxide in the dispersion liquid is 2-3 mg/ml;
s2: corroding the graphene oxide dispersion liquid by using 30 wt.% hydrogen peroxide solution to prepare a graphene oxide dispersion liquid with holes;
s3: preparation of porous graphene oxide and polyamide-amine type films: mixing the polyamide-amine type dendritic polymer with the oxidized graphene dispersion liquid with the holes obtained in S2, uniformly stirring to obtain a mixed solution, performing suction filtration to form a film by using a suction filtration device through a directional flow vacuum suction filtration method, drying the dispersion liquid at room temperature for 12-15 hours after the suction filtration is finished, keeping the suction filtration state, closing the suction filtration device, and standing at room temperature for 12-24 hours.
2. The method for preparing the dendrimer-reinforced perforated graphene oxide paper according to claim 1, wherein: in S2, the volume ratio of the hydrogen peroxide solution to the graphene oxide dispersion liquid is 5-20 ml: 50-70 ml.
3. The method for preparing the dendrimer-reinforced perforated graphene oxide paper according to claim 1, wherein: in S2, the specific conditions of the erosion are: stirring and heating for 3-5 h under 100 ℃ oil bath.
4. The method for preparing the dendrimer-reinforced perforated graphene oxide paper according to claim 1, wherein: in S3, the mixing ratio of the polyamide-amine dendrimer to the graphene oxide dispersion liquid with holes is 0.13-1.3 mg: 25-50 ml.
5. The method for preparing the dendrimer-reinforced perforated graphene oxide paper according to claim 1, wherein: in S3, an aqueous microporous filter membrane with a filter diameter of 0.45-0.85 μm is used for the suction filtration, and the dispersion is successively suction filtered in batches during the suction filtration.
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