CN112871145B - Graphene material and preparation method and application thereof - Google Patents
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Abstract
The invention provides a graphene material and a preparation method and application thereof. The graphene material is amidated graphene aerogel with a rough surface, wherein the graphene surface contains amide groups with adsorbability. On one hand, the graphene material provided by the invention is based on amide groups on the surface of graphene, so that heavy metal ions in a water environment can be effectively adsorbed; on the other hand, based on the rough surface structure, the material has larger specific surface area, namely, the material has more adsorption sites per unit volume, thereby being beneficial to improving the adsorption capacity of the material. Therefore, the graphene material provided by the invention has a better adsorption effect on heavy metal ions, and has a wide application scene in the field of sewage treatment.
Description
Technical Field
The invention relates to the field of water treatment, and mainly relates to a graphene material as well as a preparation method and application thereof.
Background
With the continuous development of social economy, the problem of environmental pollution is increasingly prominent. Among them, heavy metal pollution is receiving wide attention from society due to its non-degradability, bioaccumulation and bio-amplification properties and strong biotoxicity. The current treatment method for heavy metal pollution in water bodies comprises the following steps: adsorption, electrochemical, biological extraction, etc. Among them, the adsorption method is the preferred method for treating heavy metal polluted water body because of its simple operation, high efficiency and high speed.
Graphene aerogels of light weight (density can be as low as 1 mg/cm)3) The advantages of compressibility and fire resistance, etc. have become a research hotspot of new adsorption materials.At present, graphene aerogel is mainly obtained by a reduction method, for example, a graphene oxide solution is reduced by a reducing agent such as ascorbic acid and ethylenediamine at a certain temperature (90-120 ℃) to obtain hydrogel, and finally, the graphene aerogel is obtained by freeze drying or supercritical carbon dioxide drying. The reduced graphene layers form a three-dimensional framework structure in a stacked mode through Van der Waals force and pi bonds. The graphene aerogel obtained by the reduction method has a pore structure of about 10-100 microns and also has good elasticity. In addition, pi bonds widely existing on a graphene plane enable the graphene aerogel to be suitable for adsorbing non-polar pollutants such as alkanes and oils, but have poor adsorption performance on ionic pollutants such as heavy metal ions. This is due to the reduction process that occurs during preparation, the oxygen-rich groups that are originally on the graphene oxide layer are removed, and these oxygen-containing groups are good specific adsorption sites. Therefore, the graphene aerogel loses the adsorption capacity for heavy metal and other ionic pollutants by the preparation method based on the reduction process.
Therefore, how to improve the adsorption performance of the graphene material to the heavy metal ions is a technical problem to be solved urgently by those skilled in the art.
Disclosure of Invention
In order to solve the problems, the invention provides a novel graphene material, and a preparation method and application thereof. The specific content is as follows:
in a first aspect, the present invention provides a graphene material, which is an amidated graphene aerogel having a rough surface; the rough surface is used for adsorbing heavy metals.
Optionally, the pore diameter of the graphene material is 1-10 μm;
the surface of a graphene layer of the graphene material contains a group for adsorbing heavy metals; the group includes an amide group.
In a second aspect, the present invention provides a method for preparing a graphene material, the method being used for preparing the graphene material according to the first aspect; the method comprises the following steps:
step 1, adding sodium hydroxide and monochloroacetic acid into a graphene oxide solution, carrying out ultrasonic reaction, and centrifuging a reacted system to obtain a carboxylated graphene primary product;
step 2, washing the primary carboxylated graphene product by using pure water as a cleaning agent to obtain carboxylated graphene with a rough surface;
step 3, ultrasonically dispersing the carboxylated graphene with the rough surface in pure water to obtain a carboxylated graphene solution, adding ethylenediamine into the carboxylated graphene solution, mixing and uniformly mixing, then placing the mixture under a first reaction condition for reaction, and obtaining a first reaction system after the reaction is finished;
and 4, centrifuging the first reaction system, washing the centrifuged solid with pure water, and freeze-drying to obtain the graphene material with a rough surface.
Optionally, in the step 1, a solvent of the graphene oxide solution is pure water, and the concentration of the graphene oxide solution is 1-5 g/L;
the mass ratio of the graphene oxide to the sodium hydroxide is 1: 1-4;
the mass ratio of the graphene oxide to the monochloroacetic acid is 1: 1.5 to 3;
the ultrasonic reaction time is 10-15 h; the temperature of the ultrasonic reaction is room temperature.
Optionally, in the step 3, the concentration of the carboxylated graphene solution is 8-12 g/L;
the dosage ratio of the carboxylated graphene to the ethylenediamine is 1 g: 30-50 mL;
the first reaction condition is as follows: the reaction temperature is 85-95 ℃, and the reaction time is 9-15 h.
Optionally, before the step 1, the preparation method further comprises:
step 1-1, adding graphite powder into a sulfuric acid/phosphoric acid mixed solution with a ratio of 10-8: 1, uniformly stirring, placing the mixture into an ice water bath, slowly adding potassium permanganate into the mixed solution, and uniformly stirring to obtain a first mixed system;
step 1-2, reacting the first mixed system at 50-70 ℃ for 9-15 hours to obtain a second reaction system;
step 1-3, mixing the second reaction system with ice, placing the mixture in an ice water bath for cooling, and slowly dropwise adding 0.1-1% of hydrogen peroxide solution until the second reaction system mixed with the ice turns yellow to obtain a yellow mixed system;
and 1-4, performing centrifugal separation on the yellow mixed system to obtain a brown yellow solid, washing the brown yellow solid with pure water, dilute hydrochloric acid and ethanol in sequence, and performing vacuum drying to obtain the graphene oxide.
Optionally, in the step 1-1, the mass ratio of the graphite powder to the potassium permanganate is 1: 4-8;
in the steps 1 to 3, the mass ratio of the second reaction system to ice is 1: 1-3;
in the step 1-4, the dilute hydrochloric acid is 10% hydrochloric acid, and the temperature of vacuum drying is 30-60 ℃.
In a third aspect of the present invention, an application of the graphene material according to the first aspect is provided, where the graphene material is applied to absorb heavy metals.
Optionally, the heavy metal comprises Cd2+、Cu2+And Cr3+Any one or more of them.
The invention provides a graphene material and a preparation method and application thereof. The graphene material is amidated graphene aerogel with a rough surface, wherein the graphene surface contains amide groups with adsorbability. Compared with the prior art, the graphene material provided by the invention at least has the following beneficial effects:
1. according to the graphene material provided by the invention, the amide group on the surface of the graphene has strong adsorbability on heavy metal ions, so that the graphene material can effectively adsorb heavy metal plasma pollutants in a water environment. Meanwhile, the surface of the graphene material provided by the invention is a rough surface, so that the material has a larger specific surface area based on the rough surface, namely the material in unit volume has more adsorption sites, thereby being beneficial to improving the adsorption capacity of the material.
2. Compared with the existing graphene material, the graphene material provided by the invention has the advantages that heavy metal ion adsorption sites (amide groups, carboxyl groups, hydroxyl groups and the like) for adsorbing heavy metal ions all exist on the surface of the graphene layer, so that the graphene material provided by the invention can realize high-efficiency adsorption of the heavy metal ions, and a technical means of additionally adding other materials with high adsorption performance on the basis of the graphene material in the prior art is not required to be adopted, so that the adsorption performance of the graphene aerogel on the heavy metal ions is improved. Therefore, the graphene material provided by the invention has the characteristics of economy and economization because other materials with high adsorption performance are not required to be additionally consumed, and has a wide application prospect in the field of sewage treatment.
Drawings
Fig. 1 shows a method flowchart of a method for preparing a graphene material in an embodiment of the present invention;
fig. 2 shows XPS C1s images of the graphene material prepared in example 1;
fig. 3 shows an SEM image of the graphene material prepared in example 1;
FIG. 4 shows the graphene material prepared in example 2 and the conventional graphene aerogel adsorbing Cd2+Adsorption isotherm at 30 deg.C;
fig. 5 shows that the graphene material prepared in example 3 and the conventional graphene aerogel adsorb Cu2+Adsorption kinetics curve at 30 ℃;
FIG. 6 shows that amidated graphene aerogel and conventional graphene aerogel in example 4 adsorb Cr3+Adsorption kinetics curve at 30 ℃.
Detailed Description
The following examples are provided to further understand the present invention, not to limit the scope of the present invention, but to provide the best mode, not to limit the content and the protection scope of the present invention, and any product similar or similar to the present invention, which is obtained by combining the present invention with other prior art features, falls within the protection scope of the present invention.
The examples do not show the specific experimental steps or conditions, and can be performed according to the conventional experimental steps described in the literature in the field. The reagents and other instruments used are not indicated by manufacturers, and are all conventional reagent products which can be obtained commercially.
At present, in the technical scheme of preparing the graphene aerogel with heavy metal adsorption capacity by adopting a reduction method, the adsorption performance of the aerogel is enhanced by adding other high-adsorption-capacity materials, and heavy metal ion adsorption sites of the aerogel mostly exist on other materials except graphene. Therefore, on one hand, the graphene aerogel in the prior art has the problem of complex operation and the problem of excessive investment in economic cost in the preparation method; on the other hand, most of the heavy metal ion adsorption sites exist on other materials except graphene, so that the graphene has weak adsorption performance on heavy metal ions, and has poor adsorption effect on heavy metal ions in sewage.
In order to overcome the defects of the graphene aerogel prepared by the traditional reduction method in the aspect of heavy metal adsorption, the technical concept provided by the invention is as follows: through carrying out the functionalization to graphite alkene layer for generate the group that has adsorption function on graphite alkene layer surface, promptly, establish heavy metal ion adsorption site on graphite alkene layer surface, in order to obtain the graphene materials that heavy metal ion adsorption site exists on graphite alkene, thereby realize under the prerequisite that does not need additionally to add other high adsorption capacity materials, can realize the high-efficient absorption to heavy metal ion based on this graphite alkene material, simultaneously, owing to need not add other high adsorption capacity materials, therefore simplified preparation technology and saved economic cost.
Based on the technical concept, the invention provides a novel synthesis route of a graphene material, namely, the novel graphene material with a three-dimensional framework structure formed by connecting graphene layers through amide groups is obtained by carboxylating graphene oxide so as to enable carboxyl functional groups and ethylenediamine to have amidation reaction. In the synthetic route, because the amidation reaction time is short and most of ethylenediamine participates in the amidation reaction, only a small amount of carboxyl groups on the graphene layer are reduced, and original groups (such as carboxyl, hydroxyl, epoxy and the like with adsorbability and affinity) on the carboxylated graphene layer are reserved, so that the prepared novel graphene material has excellent adsorbability on heavy metal ions; in addition, the graphene material prepared by the synthetic route has smaller 1-10 micron-sized pore diameter and a rough surface, and is suitable for heavy metal adsorption, so that the adsorption capacity of the graphene material is further improved.
In this embodiment, the graphene material provided by the invention, and the preparation method and the application thereof are specifically as follows:
in a first aspect, the present embodiment provides a graphene material, which is an amidated graphene aerogel with a rough surface, and the pore size of the graphene material is 1 to 10 μm. The graphene layer surface of the graphene material contains groups for adsorbing heavy metal ions, and specifically includes amide groups, carboxyl groups, hydroxyl groups, epoxy groups, and the like. Meanwhile, other high-adsorption-capacity materials are not added into the graphene material to enhance the adsorption performance of the graphene material, and heavy metal ion adsorption sites of the graphene material are on the surface of the graphene and are connected with the graphene layer in a radical form. The specific structure of the graphene material is as follows: the graphene layers are connected with each other through amide groups to form a three-dimensional framework structure.
In a second aspect, this embodiment provides a method for preparing a graphene material, where the method is used to prepare the graphene material provided in the first aspect; as shown in fig. 1, the method includes:
step 1(S11), adding sodium hydroxide and monochloroacetic acid into the graphene oxide solution, performing an ultrasonic reaction, and centrifuging the reacted system to obtain a carboxylated graphene primary product.
In specific implementation, graphene oxide is dissolved in pure water, sodium hydroxide and monochloroacetic acid are added, and after uniform stirring, ultrasonic reaction is carried out for 10-15 hours. And after the reaction is finished, performing high-speed centrifugal separation to obtain a brownish black solid (namely a carboxylated graphene primary product).
In the implementation step, optionally, the concentration of a graphene oxide solution obtained by dissolving graphene oxide in pure water may be 1-5 g/L; the mass ratio of the graphene oxide to the sodium hydroxide can be 1: 1-4; the mass ratio of the graphene oxide to the monochloroacetic acid is 1: 1.5 to 3.
And 2(S12) washing the primary carboxylated graphene product by using pure water as a cleaning agent to obtain the carboxylated graphene with a rough surface.
In order to prepare a graphene material with a rough surface, in the process of washing the carboxylated graphene, a sharp monoatomic layer edge structure of the carboxylated graphene needs to be reserved, so that the selected cleaning agent needs to damage the monoatomic layer edge structure and ensure that the sharp edge is exposed. In this embodiment, the cleaning agent selected is pure water, so that the sharp edge of the carboxylated graphene is retained and exposed, thereby showing the structural characteristics of a rough surface. Therefore, in the specific implementation of the implementation step, pure water is used as a cleaning agent to wash the carboxylated graphene primary product, and the carboxylated graphene with the rough surface is obtained by vacuum drying at 50 ℃.
And step 3(S13), ultrasonically dispersing the carboxylated graphene with the rough surface in pure water to obtain a carboxylated graphene solution, adding ethylenediamine into the carboxylated graphene solution, mixing and uniformly mixing, then placing the mixture under a first reaction condition for reaction, and obtaining a first reaction system after the reaction is finished.
In specific implementation, the carboxylated graphene with the rough surface obtained in the step 2 is ultrasonically dispersed in pure water to obtain a carboxylated graphene solution, ethylenediamine is added into the carboxylated graphene solution, the mixture is uniformly stirred, the mixed solution is heated and reacted for 9-15 hours at the temperature of 85-95 ℃, and a first reaction system is obtained after the reaction is finished.
In the implementation step, optionally, the concentration of the carboxylated graphene solution can be 8-12 g/L; the dosage ratio of the carboxylated graphene to the ethylenediamine can be 1 g: 30-50 mL.
And 4(S14), centrifuging the first reaction system, washing the centrifuged solid with pure water, and freeze-drying to obtain the graphene material with a rough surface.
In specific implementation, the first reaction system is centrifuged, and the centrifuged solid is soaked in pure water for 5min for washing, and then freeze-dried to obtain the amidated graphene aerogel with a rough surface (i.e. the novel graphene material provided by the invention).
In the present embodiment, in order to ensure that the surface of the finally prepared amidated graphene aerogel is rough, the cleaning agent in each step is pure water.
In this embodiment, optionally, before step 1, the preparation method may further include a graphene oxide preparation process, which is specifically as follows:
step 1-1, adding graphite powder into a sulfuric acid/phosphoric acid mixed solution of 10-8: 1, uniformly stirring, placing in an ice water bath, slowly adding potassium permanganate into the mixed solution, and uniformly stirring to obtain a first mixed system;
step 1-2, reacting the first mixed system at 50-70 ℃ for 9-15 hours to obtain a second reaction system;
step 1-3, mixing the second reaction system with ice, placing the mixture in an ice water bath for cooling, and slowly dropwise adding 0.1-1% of hydrogen peroxide solution until the second reaction system mixed with the ice turns yellow to obtain a yellow mixed system;
and 1-4, carrying out centrifugal separation on the yellow mixed system to obtain a brown yellow solid, washing the brown yellow solid with pure water, dilute hydrochloric acid and ethanol in sequence, and then carrying out vacuum drying to obtain the graphene oxide.
In the implementation of preparing graphene oxide, optionally, in step 1-1, the mass ratio of graphite powder to potassium permanganate is 1: 4-8; in steps 1-3, the mass ratio of the second reaction system to ice is 1: 1-3; in the step 1-4, the dilute hydrochloric acid is 10% hydrochloric acid, and the temperature of vacuum drying is 30-60 ℃.
In a third aspect, the present embodiment provides an application of the graphene material, and the graphene material prepared in the second aspect is applied to adsorb heavy metal ions in a water environment, so as to achieve a purpose of purifying sewage.
Optionally, the heavy metal comprises Cd2+、Cu2+And Cr3+In (1)Meaning one or more.
On the other hand, the surface of the graphene material prepared by the embodiment of the invention also comprises oxygen-containing groups with biological affinity, so that when the graphene material is used for adsorbing heavy metal ions in sewage, a certain amount of microorganisms are adsorbed, and the sewage purification effect is further improved.
In order to make the person skilled in the art better understand the present invention, the following examples are provided to illustrate the preparation method and application of the graphene material provided by the present invention.
Example 1: preparing the graphene material of the invention
(1) 200mL of 9: 1 sulfuric acid/phosphoric acid mixed solution. 1.5g of graphite powder is weighed and poured into the mixed solution, and the mixture is stirred uniformly. And (3) placing the beaker filled with the mixed solution in an ice water bath for cooling, and slowly adding 9.0g of potassium permanganate, wherein the temperature of the mixed solution system is ensured not to exceed 20 ℃ when the potassium permanganate is added. After the potassium permanganate is added, the beaker filled with the mixed solution is placed on a magnetic heating stirrer, the stirring speed of magnetons is 300rpm, and the temperature of the mixed solution in the beaker is kept at 50 ℃ for reaction for 12 hours. After the reaction was completed, the mixed solution was cooled to room temperature, and then the solution was mixed with 200ml of ice and placed in an ice-water bath. Slowly dripping 0.5% hydrogen peroxide solution into the mixed solution until the color of the mixed solution becomes yellow, and ensuring that the temperature of the mixed solution does not exceed 10 ℃ in the process. And (3) subpackaging the yellow mixed solution into centrifuge tubes, and carrying out centrifugal separation at 8000rpm for 30min to obtain graphene oxide precipitates. The precipitate was washed with 200mL of ultrapure water, 200mL of 10% hydrochloric acid, and 200mL of absolute ethanol in this order, and centrifuged to obtain a precipitate. And drying the precipitate in a vacuum drying oven at 50 ℃ to obtain the graphene oxide.
(2) And (2) ultrasonically dissolving 0.5g of the dried graphene oxide obtained in the step (1) in 250mL of pure water to prepare a 2g/L graphene oxide solution. 1.2g of sodium hydroxide and 1.0g of monochloroacetic acid as a solid are weighed out. And (3) pouring sodium hydroxide and monochloroacetic acid into the graphene oxide solution, and stirring for dissolving. And (3) placing the beaker filled with the mixed solution into a constant-temperature ultrasonic instrument for ultrasonic treatment for 12 hours under the condition that the reaction temperature is not higher than 35 ℃. Then, the pH value of the solution is adjusted to be about 4 by 10 percent hydrochloric acid. The mixed solution was centrifuged at 8000rpm for 20 min. After centrifugation, a carboxylated graphene precipitate is obtained, and the precipitate is repeatedly washed with pure water until the pH value is about 6. And drying the precipitate at 50 ℃ in vacuum to obtain the dried carboxylated graphene.
(3) And (3) weighing 20mg of the dried carboxylated graphene obtained in the step (2), ultrasonically dispersing the weighed dried carboxylated graphene in 2mL of pure water to prepare 10mg/mL of carboxylated graphene dispersion liquid, adding 80 mu L of ethylenediamine, and uniformly mixing. And injecting the mixed solution into a 1.8cm multiplied by 1.8cm silica gel mold, sealing with a plastic film, and heating and reacting in an oven at 95 ℃ for 12 hours to obtain a graphene material crude product. The crude graphene material was immersed in 500mL of pure water for 5min, and then frozen in a-20 ℃ refrigerator until freezing. And finally, freeze-drying the frozen amidated graphene in a freeze dryer at the temperature of-50 ℃ to obtain a dried graphene material.
The prepared graphene material is characterized by X-ray photoelectron spectroscopy (XPS), and the result is shown in figure 2, and the characterization result proves that the surface of the graphene material has rich oxygen-containing groups. The apparent structure of the graphene material is characterized by using a Scanning Electron Microscope (SEM), and the experimental result is shown in FIG. 3, which proves that the graphene material has rich pore structures and the surface of the prepared graphene material is rough.
Example 2:
the preparation process of the amidated graphene aerogel is the same as in the first embodiment.
Cd implementation on amidated graphene aerogel2+And (5) heavy metal adsorption experiments. Respectively preparing 10, 20, 30, 40 and 50mg/L of Cd (NO)2Each solution was 50 mL. Weighing certain mass of amidated graphene aerogel and traditional graphene aerogel, adding the amidated graphene aerogel and the traditional graphene aerogel into the solution, and placing the mixed system in a 30 ℃ constant-temperature water bath shaking table for oscillation. 2mL of the solution was taken every 1 hour to determine Cd in the solution2+Concentration up to Cd2+The concentration no longer changes. Finally obtaining amidated graphene aerogel pair Cd according to equilibrium concentration2+Equilibrium adsorption capacity of (1). The experimental results are shown in FIG. 4, and Cd adsorption is performed2+In the case of (1), amidation is carried out at the same equilibrium concentrationThe equilibrium adsorption capacity of the graphene aerogel is more than 6 times that of the graphene aerogel prepared by the traditional reduction method. Fitting with adsorption isotherm to obtain Cd2+The adsorption process on both graphene aerogels followed the Langmuir adsorption isotherm. The amidated graphene aerogel disclosed by the invention can be used for Cd pairing at 30 DEG C2+The maximum adsorption capacity of the graphene aerogel is 56.6mg/g, which is improved by 1 time compared with that of the traditional graphene aerogel (28.0 mg/g).
Example 3:
the preparation process of the amidated graphene aerogel is the same as in the first embodiment.
Cu on amidated graphene aerogel2+And (4) heavy metal adsorption experiments. Respectively preparing 20mg/L of Cu (NO)250mL of the solution. Weighing certain mass of amidated graphene aerogel and traditional graphene aerogel, adding the amidated graphene aerogel and the traditional graphene aerogel into the solution, and placing the mixed system in a 30 ℃ constant-temperature water bath shaking table for oscillation. Taking 2mL of solution at intervals to determine Cu in the solution2+And (4) concentration. Finally drawing unit mass amidated graphene aerogel pair Cu2+Adsorption kinetics curve of (1). As shown in fig. 5, when the adsorption equilibrium is reached, the equilibrium adsorption amount of the amidated graphene aerogel is 18.4mg/g, while the equilibrium adsorption amount of the conventional graphene aerogel is 14.2 mg/g. The amidated graphene aerogel disclosed by the invention can be used for treating Cu at the temperature of 30 DEG C2+The maximum adsorption capacity of the graphene aerogel is improved by about 30 percent compared with that of the traditional graphene aerogel.
Example 4:
the preparation process of the amidated graphene aerogel is the same as in the first embodiment.
Cr is carried out on amidated graphene aerogel3+And (5) heavy metal adsorption experiments. Respectively preparing 20mg/L of Cr (NO)350mL of the solution. Weighing certain mass of amidated graphene aerogel and traditional graphene aerogel, adding the amidated graphene aerogel and the traditional graphene aerogel into the solution, and placing the mixed system in a 30 ℃ constant-temperature water bath shaking table for oscillation. Taking 2mL of solution at intervals to determine Cr in the solution3+And (4) concentration. Finally drawing unit mass amidated graphene aerogel pair Cr3+Adsorption kinetics curve of (1). The experimental result is shown in fig. 6, when the adsorption equilibrium is reached, the equilibrium adsorption amount of the amidated graphene aerogel is 15.7mg/g, while the traditional stone is usedGraphene aerogel vs Cr3+The method has no obvious adsorption effect, proves that functional groups which are not contained in the traditional graphene aerogel exist in the amidated graphene aerogel, and improves the adsorption capacity to heavy metal ions.
It should be noted that the steps and methods in the embodiments of the present application are not limited to the corresponding embodiments, and the details of the operations and the cautions of the embodiments are all corresponding to each other.
For simplicity of explanation, the method embodiments are described as a series of acts or combinations, but those skilled in the art will appreciate that the present invention is not limited by the order of acts, as some steps may occur in other orders or concurrently in accordance with the invention. Further, those skilled in the art will appreciate that the embodiments described in the specification are preferred embodiments and that the acts and elements referred to are not necessarily required to practice the invention.
The graphene material provided by the invention, the preparation method and the application thereof are described in detail, the principle and the embodiment of the invention are explained by applying specific examples, and the description of the examples is only used for helping understanding the method and the core idea of the invention; meanwhile, for a person skilled in the art, according to the idea of the present invention, there may be variations in the specific embodiments and the application scope, and in summary, the content of the present specification should not be construed as a limitation to the present invention.
Claims (9)
1. The graphene material is characterized in that the graphene material is amidated graphene aerogel with a rough surface; the rough surface is used for adsorbing heavy metal;
the preparation method of the graphene material comprises the following steps:
step 1, adding sodium hydroxide and monochloroacetic acid into a graphene oxide solution, carrying out ultrasonic reaction, and centrifuging a reacted system to obtain a carboxylated graphene primary product;
step 2, washing the primary carboxylated graphene product by using pure water as a cleaning agent to obtain carboxylated graphene with a rough surface;
step 3, ultrasonically dispersing the carboxylated graphene with the rough surface in pure water to obtain a carboxylated graphene solution, adding ethylenediamine into the carboxylated graphene solution, mixing and uniformly mixing, then placing the mixture under a first reaction condition for reaction, and obtaining a first reaction system after the reaction is finished; wherein the reaction temperature of the carboxylated graphene and the ethylenediamine is 85-95 ℃;
and 4, centrifuging the first reaction system, washing the centrifuged solid with pure water, and freeze-drying to obtain the graphene material with a rough surface.
2. The graphene material according to claim 1, wherein the graphene material has a pore size of 1-10 μm;
the surface of a graphene layer of the graphene material contains a group for adsorbing heavy metals; the group includes an amide group.
3. A method for preparing a graphene material, wherein the method is used for preparing the graphene material according to claim 1 or 2; the method comprises the following steps:
step 1, adding sodium hydroxide and monochloroacetic acid into a graphene oxide solution, carrying out ultrasonic reaction, and centrifuging a reacted system to obtain a carboxylated graphene primary product;
step 2, washing the primary carboxylated graphene product by using pure water as a cleaning agent to obtain the carboxylated graphene with a rough surface;
step 3, ultrasonically dispersing the carboxylated graphene with the rough surface in pure water to obtain a carboxylated graphene solution, adding ethylenediamine into the carboxylated graphene solution, mixing and uniformly mixing, then placing the mixture under a first reaction condition for reaction, and obtaining a first reaction system after the reaction is finished; wherein the reaction temperature of the carboxylated graphene and the ethylenediamine is 85-95 ℃;
and 4, centrifuging the first reaction system, washing the centrifuged solid with pure water, and freeze-drying to obtain the graphene material with a rough surface.
4. The preparation method according to claim 3, wherein in the step 1, the solvent of the graphene oxide solution is pure water, and the concentration of the graphene oxide solution is 1-5 g/L;
the mass ratio of the graphene oxide to the sodium hydroxide is 1: 1-4;
the mass ratio of the graphene oxide to the monochloroacetic acid is 1: 1.5 to 3;
the ultrasonic reaction time is 10-15 h; the temperature of the ultrasonic reaction is room temperature.
5. The preparation method according to claim 3, wherein in the step 3, the concentration of the carboxylated graphene solution is 8-12 g/L;
the dosage ratio of the carboxylated graphene to the ethylenediamine is 1 g: 30-50 mL;
the first reaction condition is as follows: the reaction time is 9-15 h.
6. The method of claim 3, wherein prior to step 1, the method further comprises:
step 1-1, adding graphite powder into a sulfuric acid/phosphoric acid mixed solution of 10-8: 1, uniformly stirring, placing in an ice water bath, slowly adding potassium permanganate into the mixed solution, and uniformly stirring to obtain a first mixed system;
step 1-2, reacting the first mixed system at 50-70 ℃ for 9-15 hours to obtain a second reaction system;
step 1-3, mixing the second reaction system with ice, placing the mixture in an ice water bath for cooling, and slowly dropwise adding 0.1-1% of hydrogen peroxide solution until the second reaction system mixed with the ice turns yellow to obtain a yellow mixed system;
and 1-4, performing centrifugal separation on the yellow mixed system to obtain a brown yellow solid, washing the brown yellow solid with pure water, dilute hydrochloric acid and ethanol in sequence, and performing vacuum drying to obtain the graphene oxide.
7. The preparation method according to claim 6, wherein in the step 1-1, the mass ratio of the graphite powder to the potassium permanganate is 1: 4-8;
in the step 1-3, the mass ratio of the second reaction system to ice is 1: 1-3;
in the step 1-4, the dilute hydrochloric acid is 10% hydrochloric acid, and the temperature of vacuum drying is 30-60 ℃.
8. Use of a graphene material according to claim 1 or 2 for adsorbing heavy metals.
9. Use according to claim 8, wherein the heavy metal comprises Cd2+、Cu2+And Cr3+Any one or more of them.
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