Graphene sponge composite material as well as preparation method and application thereof
By preparing graphene-sponge composite materials and utilizing the chemical bonding grafting of alkylamines and graphene oxide and microstructure modification, the problem of poor separation effect of traditional adsorption materials for oily wastewater was solved, and a highly efficient oil-water separation effect was achieved.
Patent Information
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- BEIJING GRAPHENE TECH RES INST CO LTD
- Filing Date
- 2025-12-26
- Publication Date
- 2026-05-08
AI Technical Summary
Traditional adsorption materials are not very effective at separating oily wastewater and are difficult to effectively separate oily substances and organic solvents.
Graphene-sponge composite material was prepared by mixing an aqueous solution of graphene oxide and an organic solution of alkylamine, impregnating the sponge, and then carrying out a hydrothermal reduction reaction. The hydrophobicity and oil absorption of the material were improved by using the chemical bonding between alkylamine and graphene oxide and the microstructure modification.
It significantly improves the separation effect and efficiency of oil-water mixtures. The graphene sponge composite material has a high affinity for oily substances and can be recycled.
Smart Images
Figure CN121990564A_ABST
Abstract
Description
Technical Field
[0001] This application relates to the field of materials technology, and in particular to graphene sponge composite materials, their preparation methods, and applications. Background Technology
[0002] With the rapid development of industries such as petrochemicals, oil and gas extraction, shipping, and food processing, leaks and discharges of oil and organic solvents occur frequently, making oily wastewater one of the major water pollutants that urgently need to be addressed. Currently, adsorption is commonly used to separate oil and organic pollutants from water, but traditional adsorption materials are not very effective at separating oily wastewater.
[0003] Therefore, it is necessary to improve traditional technologies. Summary of the Invention
[0004] Based on this, this application provides a graphene sponge composite material with good separation effect on oily wastewater, its preparation method and application.
[0005] The technical solution to the above-mentioned technical problems in this application is as follows.
[0006] The first aspect of this application provides a method for preparing graphene sponge composite material, comprising the following steps:
[0007] A mixture was prepared by mixing an aqueous solution of graphene oxide and an organic solution of alkylamine.
[0008] After immersing the sponge in the mixture, a reducing agent is added to carry out a hydrothermal reduction reaction to obtain the graphene sponge composite material.
[0009] In some embodiments, in the method for preparing the graphene sponge composite material, the alkylamine organic solution satisfies at least one of the following characteristics:
[0010] (1) The alkylamine organic solution includes alkylamines, and the alkylamines include primary amines having 6 to 18 carbon atoms;
[0011] (2) The alkylamine organic solution includes an organic solvent, and the organic solution includes an alcohol.
[0012] In some embodiments, in the method for preparing the graphene sponge composite material, the alkylamine organic solution satisfies at least one of the following characteristics:
[0013] (1) The alkylamine includes at least one of n-hexylamine, dodecylamine, and hexadecylamine;
[0014] (2) The organic solvent includes ethanol.
[0015] In some embodiments, in the method for preparing the graphene sponge composite material, the aqueous solution of graphene oxide includes graphene oxide, and the preparation method satisfies at least one of the following characteristics:
[0016] (1) The mass ratio of the alkylamine to the graphene oxide in the mixture is 1~8:1;
[0017] (2) The graphene oxide includes at least one of epoxy groups and carboxylic acid groups.
[0018] In some embodiments, the preparation method of the graphene sponge composite material satisfies at least one of the following characteristics:
[0019] (1) The concentration of the graphene oxide aqueous solution is 1 g / L to 10 g / L;
[0020] (2) The concentration of the alkylamine organic solution is 1 g / L to 10 g / L.
[0021] In some embodiments, the preparation method of the graphene sponge composite material satisfies at least one of the following characteristics:
[0022] (1) The reducing agent includes ascorbic acid;
[0023] (2) The temperature of the hydrothermal reduction reaction is 75℃~95℃ and the time is 3 h~8 h.
[0024] In some embodiments, the method for preparing graphene sponge composite material includes at least one of melamine sponge and polyurethane sponge.
[0025] In some embodiments, the preparation method of graphene sponge composite material further includes, after the hydrothermal reduction reaction is completed, washing and drying the resulting product.
[0026] The second aspect of this application provides a graphene sponge composite material, which is prepared using the method for preparing the graphene sponge composite material provided in the first aspect.
[0027] The third aspect of this application provides the application of the graphene sponge composite material provided in the second aspect in the preparation of adsorbent materials.
[0028] The method for preparing the graphene sponge composite material disclosed in this application involves mixing an aqueous solution of graphene oxide and an organic solution of alkylamine. This allows graphene oxide and alkylamine to freely contact each other in the mixture, improving the dispersion uniformity of graphene oxide and alkylamine in the mixture. Furthermore, the amino groups in the alkylamine undergo a preliminary covalent reaction with the highly active oxygen-containing functional groups on the surface of graphene oxide, forming chemical bonds on the graphene oxide, thus grafting the alkylamine onto the graphene oxide. Simultaneously, the grafting of alkylamine can increase the roughness of the microstructure of graphene oxide, improving the hydrophobicity and oil absorption of the material. The process involves immersing the sponge in the mixture. Due to the good dispersion uniformity of graphene oxide and alkylamine in the mixture, the loading uniformity of graphene oxide and alkylamine on the sponge can be improved. Furthermore, during the hydrothermal reduction reaction with the addition of a reducing agent, the stability of alkylamine grafted onto graphene oxide is promoted. At the same time, the oxygen-containing functional groups on the surface of graphene oxide are gradually reduced to generate reduced graphene oxide. The interaction of these characteristics can effectively improve the hydrophobicity and oil absorption of the graphene sponge composite material, thereby effectively improving the separation effect and efficiency of oil-water mixtures. Attached Figure Description
[0029] To more clearly illustrate the technical solutions in the embodiments of this application and to more completely understand this application and its beneficial effects, the drawings used in the description of the embodiments will be briefly introduced below. Obviously, the drawings described below are only some embodiments of this application. For those skilled in the art, other drawings can be obtained based on these drawings without creative effort.
[0030] Figure 1 This is a photograph of the graphene sponge composite material prepared in Example 1.
[0031] Figure 2 This is a scanning electron microscope image of the graphene sponge composite material prepared in Example 1;
[0032] Figure 3 The images show the water contact angle measurements of the graphene sponge composite materials prepared in Examples 1-3. Detailed Implementation
[0033] The present application will be further described in detail below with reference to the embodiments and examples. It should be understood that these embodiments and examples are only used to illustrate the present application and are not intended to limit the scope of the present application. The purpose of providing these embodiments and examples is to make the disclosure of the present application more thorough and comprehensive.
[0034] It should also be understood that this application can be implemented in many different forms and is not limited to the embodiments and examples described herein. Those skilled in the art can make various alterations or modifications without departing from the spirit of this application, and the resulting equivalent forms also fall within the protection scope of this application. For example, features described or illustrated as part of one embodiment can be combined in a suitable manner in another embodiment to produce new embodiments. Furthermore, numerous specific details are set forth in the following description to provide a fuller understanding of this application; it should be understood that this application can be implemented without one or more of these details.
[0035] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this application belongs. The terminology used herein in the specification of this application is for descriptive purposes only and is not intended to be limiting of the application.
[0036] Unless otherwise stated or in case of contradiction, the terms or phrases used herein shall have the following meanings:
[0037] In this application, the terms "multiple", "various", "multiple times", etc., unless otherwise specified, refer to a quantity greater than or equal to 2. For example, "one or more" means one or more than or equal to two.
[0038] The terms “combinations of,” “any combination of,” and “any combination of” used in this article include all suitable combinations of any two or more of the listed items.
[0039] In this document, the term "suitable" as used in "suitable combination", "suitable method", "any suitable method", etc., refers to the ability to implement the technical solution of this application, solve the technical problem of this application, and achieve the expected technical effect of this application.
[0040] In this document, terms such as "preferred," "better," "more suitable," and "ideal" are merely descriptions of more effective implementation methods or embodiments, and should be understood not to limit the scope of protection of this application. If multiple "preferred" terms appear in a technical solution, unless otherwise specified and there are no contradictions or mutual constraints, each "preferred" term shall be independent.
[0041] In this application, terms such as "further," "even further," and "particularly" are used to describe purposes and indicate differences in content, but should not be construed as limiting the scope of protection of this application.
[0042] In this application, "optionally," "optionally," and "optional" mean that something is optional, that is, it means that it is selected from either "with" or "without." If there are multiple "optional" entries in a technical solution, unless otherwise specified, and there are no contradictions or mutual constraints, each "optional" entry shall be independent.
[0043] In this application, the terms "first aspect," "second aspect," "third aspect," "fourth aspect," etc., are used for descriptive purposes only and should not be construed as indicating or implying relative importance or quantity, nor should they be construed as implicitly indicating the importance or quantity of the indicated technical features. Moreover, "first," "second," "third," "fourth," etc., serve only as a non-exhaustive enumeration and should be understood not to constitute a closed limitation on quantity.
[0044] In this application, the technical features described in an open-ended manner include both closed technical solutions consisting of the listed features and open technical solutions that include the listed features.
[0045] In this application, when numerical intervals (i.e., numerical ranges) are mentioned, unless otherwise specified, the distribution of selectable numerical values within the numerical interval is considered continuous, and includes the two endpoints of the numerical interval (i.e., the minimum and maximum values), as well as every numerical value between these two endpoints. Unless otherwise specified, when a numerical interval refers only to integers within that numerical interval, it includes the two endpoint integers of the numerical range, as well as every integer between the two endpoints, which is equivalent to directly listing every integer. When multiple numerical ranges are provided to describe features or characteristics, these numerical ranges can be merged. In other words, unless otherwise specified, the numerical ranges disclosed herein should be understood to include any and all subranges included therein. The "numerical value" in the numerical interval can be any quantitative value, such as a number, percentage, ratio, etc. The term "numerical interval" can be broadly included to include numerical interval types such as percentage intervals, ratio intervals, and proportion intervals.
[0046] Unless otherwise specified, the temperature parameters in this application are permitted to be either constant-temperature treatment or variations within a certain temperature range. It should be understood that the constant-temperature treatment allows temperature fluctuations within the precision range of the instrument control, such as ±5℃, ±4℃, ±3℃, ±2℃, or ±1℃.
[0047] In this application, the terms "room temperature" or "normal temperature" generally refer to 4℃~35℃, for example, 20℃±5℃. In some embodiments of this application, "room temperature" or "normal temperature" refers to 10℃~30℃. In some embodiments of this application, "room temperature" or "normal temperature" refers to 20℃~30℃.
[0048] In this application, if the unit of a data range is only followed by the right endpoint, it indicates that the units of the left and right endpoints are the same. For example, 3~5 h means that the units of the left endpoint "3" and the right endpoint "5" are both h (hours).
[0049] All references to documents mentioned in this application are incorporated herein by reference as if each document were individually incorporated by reference. Unless they conflict with the inventive purpose and / or technical solution of this application, all cited documents are incorporated herein by reference in their entirety and for all purposes. When citing documents in this application, the definitions of relevant technical features, terms, nouns, phrases, etc., are also incorporated herein by reference. When citing documents in this application, examples and preferred embodiments of the cited technical features may also be incorporated herein by reference, but only to the extent that they enable the implementation of this application. It should be understood that when the cited content conflicts with the description in this application, this application shall prevail or modifications shall be made adaptably to the description in this application.
[0050] The mass or weight of the relevant components mentioned in the embodiments of this application can refer not only to the specific content of each component, but also to the proportional relationship of mass or weight between the components. Therefore, any scaling up or down of the content of the relevant components according to the embodiments of this application is within the scope disclosed in the embodiments of this application. Specifically, the mass or weight mentioned in the embodiments of this application can be units known in the chemical industry, such as μg, mg, g, and kg.
[0051] One embodiment of this application provides a method for preparing a graphene sponge composite material, comprising the following steps:
[0052] Step S100: Mix the aqueous solution of graphene oxide and the organic solution of alkylamine to obtain a mixture.
[0053] Mixing an aqueous solution of graphene oxide with an organic solution of alkylamine allows the graphene oxide and alkylamine to come into free contact in the mixture, improving the uniformity of dispersion of both. Furthermore, the amino groups in the alkylamine undergo a preliminary covalent reaction with the highly reactive oxygen-containing functional groups on the graphene oxide surface, forming chemical bonds and grafting the alkylamine onto the graphene oxide. Simultaneously, the grafting of alkylamine increases the roughness of the graphene oxide microstructure, improving the material's hydrophobicity and oil absorption. It is understandable that the original graphene oxide sheet has a relatively smooth microstructure.
[0054] Step S200: After immersing the sponge in the mixture, a reducing agent is added to carry out a hydrothermal reduction reaction to obtain the graphene sponge composite material.
[0055] The sponge is immersed in the mixture obtained in step S100. Due to the good dispersion uniformity of graphene oxide and alkylamine in the mixture, the loading uniformity of graphene oxide and alkylamine on the sponge can be improved. In addition, during the hydrothermal reduction reaction with the addition of reducing agent, the stability of alkylamine grafted onto graphene oxide is promoted. At the same time, the oxygen-containing functional groups on the surface of graphene oxide are gradually reduced to generate reduced graphene oxide. The interaction of these features can effectively improve the hydrophobicity and oil absorption of the graphene sponge composite material, thereby effectively improving the separation effect and separation efficiency of oil-water mixture.
[0056] In some examples, in step S100, the alkylamine organic solution includes an alkylamine, which is a primary amine with 6 to 18 carbon atoms. It is understood that a primary amine is an amine compound (general formula: R-NH2, where R is alkyl) in which an amino group (-NH2) is directly attached to a saturated carbon atom; the number of carbon atoms in the alkylamine includes, but is not limited to, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, and 18. In some examples, it can be any two of these point values forming a range, the same applies below. Optionally, the alkylamine includes at least one of n-hexylamine, dodecylamine, and hexadecylamine. By controlling the type of alkylamine, the hydrophobicity and oil absorption of the graphene sponge composite material can be improved.
[0057] In some of these examples, in step S100, the alkylamine organic solution comprises an organic solvent, which includes an alcohol. Optionally, the organic solvent includes ethanol.
[0058] In some examples, in step S100, the mass ratio of alkylamine to graphene oxide in the mixture is 1 to 8:1. It is understood that the mass ratio of alkylamine to graphene oxide in the mixture includes, but is not limited to, 1:1, 2:1, 3:1, 4:1, 5:1, 6:1, 7:1, and 8:1. Optionally, the mass ratio of alkylamine to graphene oxide in the mixture is 2 to 5:1. By controlling the mass ratio of alkylamine to graphene oxide, excessive reduction of graphene oxide by alkylamine and waste of raw materials can be avoided while ensuring sufficient chemical modification of graphene oxide. This allows for precise control of the surface chemical properties and microstructure of graphene oxide, thereby further improving the separation effect and efficiency of oil-water mixtures.
[0059] In some examples, in step S100, the concentration of the graphene oxide aqueous solution is 1 g / L to 10 g / L. It is understood that the concentration of the graphene oxide aqueous solution includes, but is not limited to, 1 g / L, 2 g / L, 3 g / L, 4 g / L, 5 g / L, 6 g / L, 7 g / L, 8 g / L, 9 g / L, and 10 g / L.
[0060] In some examples, in step S100, the concentration of the alkylamine organic solution is 1 g / L to 10 g / L. It is understood that the concentration of the alkylamine organic solution includes, but is not limited to, 1 g / L, 2 g / L, 3 g / L, 4 g / L, 5 g / L, 6 g / L, 7 g / L, 8 g / L, 9 g / L, and 10 g / L.
[0061] It is understood that the graphene oxide aqueous solution includes graphene oxide and water, and graphene oxide has good dispersibility in water. In some examples, step S100, the preparation of the graphene oxide aqueous solution includes: dispersing graphene oxide in water to obtain a graphene oxide dispersion (graphene oxide aqueous solution).
[0062] In some of these examples, step S100, the preparation of the alkylamine organic solution, includes dissolving an alkylamine in an organic solvent to obtain the alkylamine organic solution.
[0063] In some examples, in step S100, the graphene oxide includes at least one of an epoxy group and a carboxylic acid group. It is understood that epoxy and carboxylic acid groups are highly reactive. During the hydrothermal reduction reaction, the amino group in the alkylamine undergoes a covalent reaction with the epoxy group on the surface of the graphene oxide, forming a CN bond through epoxy ring opening; the amino group in the alkylamine reacts with the carboxylic acid group on the surface of the graphene oxide, dehydrating to form an amide bond. The formation of these covalent bonds can effectively improve the stability of the graphene sponge composite material and effectively reduce the risk of graphene shedding during subsequent reduction, cleaning, and extrusion processes.
[0064] In some of these examples, the reducing agent in step S200 includes ascorbic acid.
[0065] In some examples, step S200, the addition of the reducing agent, includes mixing ascorbic acid and water, and then adding the prepared ascorbic acid solution to the impregnation mixture. Optionally, the concentration of the ascorbic acid solution is 10 g / L to 20 g / L.
[0066] In some examples, in step S200, the temperature of the hydrothermal reduction reaction is 75℃~95℃, and the time is 3 h~8 h. It can be understood that the temperature of the hydrothermal reduction reaction includes, but is not limited to, 75℃, 80℃, 85℃, 90℃, and 95℃; and the time includes, but is not limited to, 3 h, 4 h, 5 h, 6 h, 7 h, and 8 h.
[0067] In some examples, in step S200, the sponge includes at least one of melamine sponge and polyurethane sponge. It is understood that the polar groups in melamine and polyurethane sponges can undergo covalent reactions with alkylamines; for example, the "C=O" groups in polyurethane sponge can undergo amidation reactions with alkylamines. The formation of these covalent bonds can effectively improve the stability of the graphene sponge composite material and effectively reduce the risk of graphene shedding during subsequent reduction, cleaning, and extrusion processes. The study also found that compared to polyvinyl alcohol formaldehyde sponge, melamine and polyurethane sponges have better mechanical properties in the wet state; compared to rubber sponges, melamine and polyurethane sponges have better anti-swelling properties; and compared to polyethylene, polypropylene, and other plastic sponges, melamine and polyurethane sponges have better stability.
[0068] It is understood that in step S200, during the process of immersing the sponge in the mixture, the volume of the mixture used must completely submerge and fully wet the sponge; optionally, the volume ratio of the mixture to the sponge is 1 to 5:1. It is understood that the volume ratio of the mixture to the sponge includes, but is not limited to, 1:1, 2:1, 3:1, 4:1, and 5:1.
[0069] In some examples, after the hydrothermal reduction reaction in step S200 is completed, step S300 is also included: washing and drying the product obtained in step S200.
[0070] In some examples, in step S300, the washing agent used includes alcohol and water; optionally, the volume ratio of water to alcohol is 1 to 5:1; optionally, the alcohol includes ethanol. The product is washed by filtration with an ethanol-water mixture to remove unreacted reducing agent (ascorbic acid) and excess alkylamines adsorbed on the surface of the functionalized reduced graphene oxide.
[0071] In some of these examples, in step S300, the drying method includes vacuum drying; optionally, the vacuum drying time is 60°C to 70°C for 24 h to 48 h.
[0072] One embodiment of this application provides a graphene sponge composite material, which is prepared using the above-described method for preparing graphene sponge composite materials.
[0073] In some of these examples, the graphene sponge composite material comprises a sponge and reduced graphene oxide loaded on the sponge, the reduced graphene oxide being grafted with alkylamines.
[0074] It is understood that another embodiment of this application provides a graphene sponge composite material, including a sponge, reduced graphene oxide and an alkylamine, wherein the reduced graphene oxide is loaded on the sponge and the alkylamine is grafted onto the reduced graphene oxide.
[0075] The graphene sponge composite material provided in this application has a high affinity for oil and organic pollutants in water and can be recycled.
[0076] One embodiment of this application provides the application of the above-described graphene sponge composite material in the preparation of adsorbent materials.
[0077] One embodiment of this application provides an adsorption material, including the above-described graphene sponge composite material.
[0078] One embodiment of this application provides an adsorption device, comprising the above-described graphene sponge composite material or the above-described adsorption material.
[0079] The present application will be described in further detail below with reference to specific embodiments, but the embodiments of the present application are not limited thereto.
[0080] Example 1
[0081] (1) Preparation of graphene oxide dispersion: 5g of graphene oxide was dispersed in 1L of water and ultrasonically dispersed for 1h to obtain graphene oxide dispersion with a concentration of 5 g / L.
[0082] (2) Preparation of alkylamine-ethanol solution: Dissolve 1g of alkylamine (n-hexylamine) in 200mL of ethanol to obtain an alkylamine-ethanol solution with a concentration of 5 g / L;
[0083] (3) Preparation of alkylamine-ethanol-graphene oxide mixture: 100 mL of graphene oxide dispersion and 200 mL of alkylamine-ethanol solution were mixed and stirred continuously at room temperature for 1 day to obtain alkylamine-ethanol-graphene oxide mixture. The mass ratio of alkylamine to graphene oxide was 2:1.
[0084] (4) Preparation of ascorbic acid solution: 10g of ascorbic acid was dispersed in 1L of water and ultrasonically dispersed for 1h to obtain ascorbic acid solution;
[0085] (5) The sponge was fully impregnated in the alkylamine-ethanol-graphene oxide mixture prepared in step (3), and 100 mL of the ascorbic acid solution prepared in step (4) was added. The hydrothermal reduction reaction was carried out at 90 °C for 3 h. The modified sponge was washed with an ethanol-water mixture with a volume ratio of 1:1 and dried in a vacuum oven at 60 °C under a vacuum of 1 degree to obtain the graphene sponge composite material. The actual object is shown in the figure. Figure 1 As shown, the scanning electron microscope image is as follows. Figure 2 As shown, from Figure 2It can be seen that the graphene modified with alkylamine uniformly covers the sponge skeleton, forming a three-dimensional composite material with both porous network and layered structure. This structure has a large specific surface area, rough surface and good structural stability, providing a carrier support for its adsorption of oil and oil separation.
[0086] Example 2
[0087] The process is basically the same as in Example 1, except that in step (2), the alkylamine is replaced with an equal mass of dodecylamine; in step (3), 100 mL of graphene oxide dispersion and 400 mL of alkylamine-ethanol solution are mixed to obtain an alkylamine-ethanol-graphene oxide mixture in which the mass ratio of alkylamine to graphene oxide is 4:1.
[0088] Example 3
[0089] The process is basically the same as in Example 1, except that in step (2), the alkylamine is replaced with an equal mass of hexadecylamine; in step (3), 100 mL of graphene oxide dispersion and 500 mL of alkylamine-ethanol solution are mixed to obtain an alkylamine-ethanol-graphene oxide mixture in which the mass ratio of alkylamine to graphene oxide is 5:1.
[0090] Example 4
[0091] The process is basically the same as in Example 1, except that in step (3), 100 mL of graphene oxide dispersion and 100 mL of alkylamine-ethanol solution are mixed to obtain an alkylamine-ethanol-graphene oxide mixture in which the mass ratio of alkylamine to graphene oxide is 1:1.
[0092] Example 5
[0093] The process is basically the same as in Example 1, except that in step (3), 100 mL of graphene oxide dispersion and 800 mL of alkylamine-ethanol solution are mixed to obtain an alkylamine-ethanol-graphene oxide mixture in which the mass ratio of alkylamine to graphene oxide is 8:1.
[0094] Comparative Example 1
[0095] (1) Take 300 mL of the alkylamine-ethanol solution obtained in step (2) of Example 1, immerse the sponge completely in it, and ensure that the sponge is fully wetted by the solution. After soaking at room temperature for 1 hour, take out the sponge with tweezers and drain the excess solution to obtain the alkylamine modified sponge.
[0096] (2) Take 100 mL of the graphene oxide dispersion prepared in step (1) of Example 1, immerse the alkylamine modified sponge completely in it, let it stand at room temperature for 1 day, add 100 mL of the ascorbic acid solution prepared in step (4) of Example 1, and carry out a hydrothermal reduction reaction at 90°C for 3 hours. Wash the modified sponge with a 1:1 volume ratio ethanol-water mixed solution, and dry it in a vacuum oven at 60°C under a vacuum degree to obtain the sponge composite material. The sponge has uneven color, dark spots and lumps on the surface, and some areas are lighter in color, indicating that in Comparative Example 1, alkylamine was first modified on the sponge, and then graphene oxide was added. Graphene oxide will quickly gather and precipitate on the sponge surface, blocking the sponge pores.
[0097] Comparative Example 2
[0098] The process is basically the same as in Example 1, except that the hydrothermal reduction reaction is omitted in step (5). Step (5) is as follows: After the sponge is fully impregnated in the alkylamine-ethanol-graphene oxide mixture obtained in step (3), it is dried in a vacuum oven at 60°C under a vacuum of 1 degree to obtain the sponge composite material.
[0099] The above samples were observed using a scanning electron microscope (SEM), and the hydrophobicity and oleophilicity of the sponge were determined by the water contact angle. The results are shown in Table 1 and... Figure 3 As shown, where, Figure 3 (a), (b), and (c) in the figure correspond to the water contact angles of the graphene sponge composite materials prepared in Examples 1, 2, and 3, respectively.
[0100] The saturated adsorption capacities of the above graphene sponge composite material for hexane, cyclohexane, toluene, and decane were determined, with units of g / g. The results are shown in Table 1.
[0101] Table 1
[0102]
[0103] From Table 1 and Figure 3 It can be seen that, compared with the comparative example, the graphene sponge composite materials obtained in each embodiment have a larger water contact angle, better hydrophobicity, and a larger saturated adsorption capacity for various organic solvents such as hexane, cyclohexane, toluene, and decane, indicating that they have better separation effect and efficiency for oil-water mixtures. In Comparative Example 1, alkylamine was first modified onto the sponge, and then graphene oxide was added. The graphene oxide rapidly aggregated and precipitated on the sponge surface, blocking the sponge pores and affecting the adsorption performance.
[0104] The technical features of the above embodiments can be combined in any way. For the sake of brevity, not all possible combinations of the technical features in the above embodiments are described. However, as long as there is no contradiction in the combination of these technical features, they should be considered to be within the scope of this specification.
[0105] The embodiments described above are merely illustrative of several implementation methods of this application, intended to facilitate a detailed understanding of the technical solutions of this application, but should not be construed as limiting the scope of protection of the invention patent. It should be noted that those skilled in the art can make various modifications and improvements without departing from the concept of this application, and these all fall within the scope of protection of this application. It should be understood that technical solutions obtained by those skilled in the art based on the technical solutions provided in this application through logical analysis, reasoning, or limited experimentation are all within the scope of protection of the appended claims. Therefore, the scope of protection of this patent application should be determined by the content of the appended claims, and the specification can be used to interpret the content of the claims.
Claims
1. A method for preparing a graphene sponge composite material, characterized in that, Includes the following steps: A mixture was prepared by mixing an aqueous solution of graphene oxide and an organic solution of alkylamine. After immersing the sponge in the mixture, a reducing agent is added to carry out a hydrothermal reduction reaction to obtain the graphene sponge composite material.
2. The preparation method of the graphene sponge composite material as described in claim 1, characterized in that, The alkylamine organic solution satisfies at least one of the following characteristics: (1) The alkylamine organic solution includes alkylamines, and the alkylamines include primary amines having 6 to 18 carbon atoms; (2) The alkylamine organic solution includes an organic solvent, and the organic solution includes an alcohol.
3. The preparation method of the graphene sponge composite material as described in claim 2, characterized in that, The alkylamine organic solution satisfies at least one of the following characteristics: (1) The alkylamine includes at least one of n-hexylamine, dodecylamine, and hexadecylamine; (2) The organic solvent includes ethanol.
4. The method for preparing the graphene sponge composite material according to any one of claims 2 to 3, characterized in that, The aqueous solution of graphene oxide includes graphene oxide, and the preparation method satisfies at least one of the following characteristics: (1) The mass ratio of the alkylamine to the graphene oxide in the mixture is 1~8:1; (2) The graphene oxide includes at least one of epoxy groups and carboxylic acid groups.
5. The method for preparing the graphene sponge composite material as described in claim 4, characterized in that, The preparation method satisfies at least one of the following characteristics: (1) The concentration of the graphene oxide aqueous solution is 1 g / L to 10 g / L; (2) The concentration of the alkylamine organic solution is 1 g / L to 10 g / L.
6. The method for preparing the graphene sponge composite material according to any one of claims 1 to 3 and 5, characterized in that, The preparation method satisfies at least one of the following characteristics: (1) The reducing agent includes ascorbic acid; (2) The temperature of the hydrothermal reduction reaction is 75℃~95℃ and the time is 3 h~8 h.
7. The method for preparing the graphene sponge composite material according to any one of claims 1 to 3 and 5, characterized in that, The sponge includes at least one of melamine sponge and polyurethane sponge.
8. The method for preparing the graphene sponge composite material according to claims 1-3 and 5, characterized in that, After the hydrothermal reduction reaction is completed, the process also includes washing and drying the resulting product.
9. A graphene-sponge composite material, characterized in that, The graphene sponge composite material was prepared using the preparation method described in any one of claims 1 to 8.
10. The application of the graphene sponge composite material as described in claim 9 in the preparation of adsorbent materials.