CN110562962A - super-elastic magnetic graphene aerogel and preparation method thereof - Google Patents
super-elastic magnetic graphene aerogel and preparation method thereof Download PDFInfo
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Abstract
The invention belongs to the field of environmental protection, and provides a super-elastic magnetic graphene aerogel and a preparation method thereof, wherein the preparation method comprises the following steps: preparing a graphene oxide mixed solution by using a Hummers oxidation method; preparing polyacrylic acid modified ferroferric oxide nano particles by a surface initiated polymerization method and carrying out amination treatment to obtain modified magnetic nano particles; adding the modified magnetic nanoparticle mixed solution into the graphene oxide mixed solution to obtain a blended solution; carrying out ultrasonic dispersion on the blended solution and then heating to obtain a reaction solution; cooling the reaction liquid to room temperature, adding ascorbic acid, and placing the mixture in an oven for reaction to obtain magnetic graphene hydrogel; dialyzing the magnetic graphene hydrogel, freeze-drying, and then thermally annealing in an inert atmosphere to obtain the super-elastic magnetic graphene aerogel. Graphene sheets in the super-elastic magnetic graphene aerogel prepared by the invention are bonded with each other to form a macroporous structure, so that oil pollutants in a water body can be separated quickly and efficiently.
Description
Technical Field
the invention belongs to the technical field of environmental protection, and particularly relates to a super-elastic magnetic graphene aerogel and a preparation method thereof.
Background
Crude oil, as an important natural resource, has brought about a great change to human lives. However, the frequent occurrence of oil spill events during oil exploration and transportation, such as foreign "eksen vardet" tanker leakage and U.S. gulf of mexico crude oil leakage events, domestic large and new port tank area crude oil leakage and delley field oil spill events, pollutes the ecological environment of the ocean. The oil spill in water caused by the waste oil products can seriously destroy the ecological environment and is difficult to ignore. How to rapidly treat the spilled oil on the ocean has important significance for various fields such as petrochemical industry, ocean environment protection and the like. In addition to oil spill events, large volumes of industrial oily sewage and poorly water soluble organic waste streams also pose further threats to public health and land ecosystems. Therefore, the development of advanced materials for rapidly separating oil from water is urgently required.
In practical scale application, the existing commercial oil-water separation material (two-dimensional fabric, imitation cloth and the like) has the defects of high material density, weak adsorption capacity, slow adsorption rate, poor recycling performance, difficult recovery of the material and the like. In order to improve the defects, the development of an oil-water separation material by utilizing the characteristics of high porosity and low density of the three-dimensional aerogel material becomes a current research hotspot. However, none of the aerogel materials reported at present can perfectly solve the problems, so that the development of a material which can rapidly and efficiently separate oil from water, is light in weight, is easy to transport and is convenient to recover is a problem which needs to be solved urgently at present.
Disclosure of Invention
The present invention is made to solve the above problems, and an object of the present invention is to provide a superelastic magnetic graphene aerogel and a method for preparing the same, which are used for rapidly separating oil from water.
The invention provides a preparation method of a super elastic magnetic graphene aerogel, which is characterized by comprising the following steps: step 1, preparing a graphene oxide mixed solution with a preset concentration by using a Hummers oxidation method; step 2, preparing polyacrylic acid modified ferroferric oxide nanoparticles by using a surface initiated polymerization method and carrying out amination treatment to obtain modified magnetic nanoparticles; step 3, preparing modified magnetic nanoparticles into a modified magnetic nanoparticle mixed solution, adding the modified magnetic nanoparticle mixed solution into the graphene oxide mixed solution to obtain a blended solution, and adjusting the concentration of graphene oxide in the blended solution to 1 mg/mL-10 mg/mL, wherein the mass ratio of graphene oxide to modified magnetic nanoparticles is 1: 1-8: 1; step 4, heating the blending liquid to 50-90 ℃ after ultrasonic dispersion for reaction for 0.5-30 h to obtain reaction liquid; step 5, cooling the reaction liquid to room temperature, adding ascorbic acid into the reaction liquid according to the mass ratio of 1: 1-10: 1 of ascorbic acid to graphene oxide, performing ultrasonic stirring and dispersion, and then placing the mixture in an oven for reaction to obtain magnetic graphene hydrogel; and 6, putting the magnetic graphene hydrogel into a water-alcohol mixed solution with the volume fraction of alcohol of 5-50%, dialyzing, freeze-drying, and then thermally annealing the freeze-dried magnetic graphene hydrogel for 0.5-2 h at the temperature of 200-800 ℃ in an inert atmosphere to obtain the super-elastic magnetic graphene aerogel.
In the preparation method of the superelastic magnetic graphene aerogel provided by the invention, the preparation method can also have the following characteristics: wherein, step 1 comprises the following substeps: step 1-1, weighing 4.0g of potassium persulfate, 4.0g of phosphorus pentoxide and 3.0g of graphite powder, uniformly mixing, pouring into a reaction container, slowly adding 20mL of concentrated sulfuric acid, heating to 80 ℃, reacting for 6 hours, cooling at room temperature, adding deionized water for dilution, filtering to be neutral, and drying the obtained filter cake at room temperature for 12 hours to obtain a pre-oxidized dry product; step 1-2, adding a pre-oxidized dry product into 120mL of concentrated sulfuric acid, stirring and dissolving under an ice bath condition to obtain a pre-oxidized dry product solution, weighing 9.0g of potassium permanganate, slowly adding the potassium permanganate into the pre-oxidized dry product solution under the ice bath condition, continuously stirring for 30min, heating to 30 ℃, stirring for 2h to obtain a reaction solution, adding 125mL of deionized water into the reaction solution, stirring for 15min, dropwise adding 30% of hydrogen peroxide until the reaction solution becomes bright yellow, then pouring the bright yellow reaction solution into a 3L big beaker, adding 2.5L of deionized water, adding 100 mL-150 mL of concentrated hydrochloric acid, standing and standing for 24h to obtain a precipitate, pouring a supernatant after standing, placing the lower precipitate into a dialysis bag, placing the dialysis bag into water for dialysis for 3-4 days until the pH value of the water outside the dialysis bag is neutral, the mixed liquid in the dialysis bag is graphene oxide mixed liquid.
the preparation method of the superelastic magnetic graphene aerogel provided by the invention can also have the following characteristics that: and (3) concentration determination: and (3) after taking a certain volume of graphene oxide mixed liquor for freeze drying, weighing the obtained solid mass, and then calculating the concentration of the graphene oxide mixed liquor.
In the preparation method of the superelastic magnetic graphene aerogel provided by the invention, the preparation method can also have the following characteristics: wherein, step 2 comprises the following substeps: step 2-1, preparing polyacrylic acid modified ferroferric oxide nanoparticles by using a surface initiated polymerization method: weighing 2.0g of nano ferroferric oxide and 1.0g of ammonium persulfate, adding the nano ferroferric oxide and the ammonium persulfate into 100mL of deionized water, ultrasonically stirring and dispersing for 30min, transferring the mixture into a reaction container, dripping 10mL of acrylic acid into the solution, heating the solution to 70 ℃, and keeping the mechanical stirring for 300r/min for reaction for 4h to obtain polyacrylic acid modified ferroferric oxide nanoparticle mixed solution; step 2-2, preparing modified magnetic nanoparticles by amination: adding 20mL of triethylene tetramine dropwise into the polyacrylic acid modified ferroferric oxide nanoparticle mixed solution, heating to 70 ℃, stirring and reacting for 3-4 h to obtain modified magnetic nanoparticle mixed solution, separating solid from the modified magnetic nanoparticle mixed solution by using a magnet, washing the solid with water for 3-4 times, washing the solid with absolute ethyl alcohol for 2 times, and drying in a 50 ℃ drying oven for 12h to obtain the modified magnetic nanoparticles.
In the preparation method of the superelastic magnetic graphene aerogel provided by the invention, the preparation method can also have the following characteristics: wherein, in the step 4, the mechanical stirring of 300r/min is continuously kept in the reaction process.
in the preparation method of the superelastic magnetic graphene aerogel provided by the invention, the preparation method can also have the following characteristics: and 5, ultrasonically stirring and dispersing, and then placing in an oven at 40-180 ℃ for reaction for 2-48 h to obtain the magnetic graphene hydrogel.
In the preparation method of the superelastic magnetic graphene aerogel provided by the invention, the preparation method can also have the following characteristics: and 6, putting the magnetic graphene hydrogel into a hydroalcoholic solution with the volume fraction of 5% -50% of alcohol for dialysis for 6-48 h.
In the preparation method of the superelastic magnetic graphene aerogel provided by the invention, the preparation method can also have the following characteristics: and 6, thermally annealing the magnetic graphene hydrogel in an infrared tube furnace for 2 hours at the temperature of 200-800 ℃ in a nitrogen atmosphere to obtain the super-elastic magnetic graphene aerogel.
The invention also provides a super elastic magnetic graphene aerogel, which has the following characteristics: the super-elastic magnetic graphene aerogel is prepared by a preparation method of the super-elastic magnetic graphene aerogel.
The superelastic magnetic graphene aerogel provided by the invention can also have the following characteristics: the super-elastic magnetic graphene aerogel is composed of modified magnetic nanoparticles and graphene oxide, the modified magnetic nanoparticles are uniformly distributed on the surfaces of graphene oxide sheet layers, the graphene oxide sheet layers are promoted to be bonded with each other to form large sheet layers, and graphene oxide sheets of the large sheet layers are built in a three-dimensional mode to form a large-hole structure.
Action and Effect of the invention
According to the invention, the modified magnetic nanoparticles are uniformly loaded on the graphene oxide sheet layers in a covalent bonding manner, and the graphene oxide sheet layers are promoted to be bonded with each other by the modified magnetic nanoparticles to form large sheet layers, and the large sheet layers are built in a three-dimensional manner to form a large-pore structure. The prepared super-elastic magnetic graphene aerogel is a performance improvement material of the graphene aerogel, and can quickly and efficiently separate oil pollutants and organic solvents in a water body, so that the purposes of purifying sewage, protecting the environment and saving water resources are achieved.
The modified magnetic nanoparticles are uniformly loaded on the graphene oxide sheet layers in a covalent bonding mode, and the amino groups on the modified magnetic particles promote the graphene oxide sheet layers to be bonded with each other through hydrogen bonding, covalent bonding, electrostatic attraction and the like to form larger sheet layers. Under the action of a chemical reducing agent L-ascorbic acid, oxygen-containing groups on the surface of the graphene oxide large lamella are gradually reduced and removed, so that the hydrophobicity of the graphene oxide large lamella is increased, and the graphene oxide large lamella are three-dimensionally built up to form the super-elastic magnetic graphene aerogel with a macroporous structure under the van der Waals force between the lamellae and the attraction force of pi-pi bonds. Therefore, the concentration of the graphene oxide and the mass ratio of the modified magnetic nanoparticles to the graphene oxide affect the formation of the graphene oxide large-sheet layer and the large-pore structure, so that the properties of the magnetic graphene aerogel are affected. If the graphene oxide concentration and the magnetic particle loading capacity are large, the adhesion between graphene oxide sheets is serious, so that a larger sheet structure is formed, the built hole structure is larger, and the structural strength of the aerogel can be weakened to a certain extent by the aid of the large hole structure. If the graphene oxide concentration and the magnetic particle loading are small, the strength of the formed magnetic graphene aerogel structure is low due to the low density of the sheets and the weak attraction between the sheets. Therefore, a better graphene oxide concentration range and a better modified magnetic nanoparticle mass ratio range exist, namely the concentration of the selected graphene oxide is 1 mg/mL-10 mg/mL, and the mass ratio of the graphene oxide to the modified magnetic nanoparticles is 1: 1-8: 1, so that the magnetism can be kept, and the graphene aerogel can have better structural strength and a certain pore diameter structure.
The thermal annealing step is to further reduce the residual oxygen-containing groups on the graphene oxide sheet layers, so that the covalent interaction between the graphene oxide sheet layers is weakened, and the elasticity of the magnetic graphene aerogel is increased. Under the condition of over-high annealing temperature, the reduction process of the magnetic graphene aerogel is unstable, so that the structure of the aerogel is easily damaged, and the magnetic property is easily lost, especially after the temperature is higher than the Curie temperature of ferroferric oxide; the too low temperature can cause the insufficient reduction process of the graphene aerogel and the poor elasticity of the magnetic graphene aerogel, so that the thermal annealing process has an optimal thermal annealing temperature and thermal annealing retention time, namely the thermal annealing is carried out for 0.5 to 2 hours at the temperature of 200 to 800 ℃ in an inert atmosphere.
Drawings
FIG. 1a is an infrared spectrum of Graphene Oxide (GO) and graphite (G) in accordance with the present invention;
FIG. 1b is a modified magnetic nanoparticle (Fe) in example 1 of the present invention3O4-NH2) And ferroferric oxide nanoparticles (Fe)3O4) An infrared spectrum of (1);
Fig. 2a is an SEM image of a superelastic magnetic graphene aerogel in example 1 of the present invention;
Fig. 2b is a TEM image of a superelastic magnetic graphene aerogel in example 1 of the present invention;
fig. 3 is an SEM image of a graphene aerogel in a comparative example of the present invention;
Fig. 4 shows the adsorption amounts of the superelastic magnetic graphene aerogel in example 1 of the present invention to different oils and fats;
Fig. 5 is a photograph of a magnetic experiment of the superelastic magnetic graphene aerogel in example 1 of the present invention;
Fig. 6 is a photograph of a compression experiment of the superelastic magnetic graphene aerogel in example 1 of the present invention.
Detailed Description
in order to make the technical means, the creation characteristics, the achievement purposes and the effects of the present invention easy to understand, the following embodiments and the accompanying drawings are used to specifically describe a super-elastic magnetic graphene aerogel and a preparation method thereof.
In the examples of the present invention, the materials used were purchased from general commercial sources unless otherwise specified.
In the embodiment of the invention, a preparation method of a super elastic magnetic graphene aerogel specifically comprises the following steps:
Step 1, preparing a graphene oxide mixed solution with a preset concentration by using a Hummers oxidation method.
The method specifically comprises the following substeps:
Step 1-1, weighing 4.0g of potassium persulfate, 4.0g of phosphorus pentoxide and 3.0g of graphite powder, uniformly mixing, pouring into a reaction container, slowly adding 20mL of concentrated sulfuric acid, heating to 80 ℃, reacting for 6h, cooling at room temperature, adding deionized water for dilution, filtering to neutrality, and drying the obtained filter cake at room temperature for 12h to obtain a pre-oxidized dry product.
Step 1-2, adding a pre-oxidized dry product into 120mL of concentrated sulfuric acid, stirring and dissolving under an ice bath condition to obtain a pre-oxidized dry product solution, weighing 9.0g of potassium permanganate, slowly adding the potassium permanganate into the pre-oxidized dry product solution under the ice bath condition, continuously stirring for 30min, heating to 30 ℃, stirring for 2h to obtain a reaction solution, adding 125mL of deionized water into the reaction solution, stirring for 15min, dropwise adding 30% of hydrogen peroxide until the reaction solution becomes bright yellow, then pouring the bright yellow reaction solution into a 3L big beaker, adding 2.5L of deionized water, adding 100 mL-150 mL of concentrated hydrochloric acid, standing and standing for 24h to obtain a precipitate, pouring a supernatant after standing, placing the lower precipitate into a dialysis bag, placing the dialysis bag into water for dialysis for 3-4 days until the pH value of the water outside the dialysis bag is neutral, the mixed liquid in the dialysis bag is graphene oxide mixed liquid.
The method for measuring the concentration of the graphene oxide mixed solution comprises the following steps: and (3) after taking a certain volume of graphene oxide mixed liquor for freeze drying, weighing the obtained solid mass, and then calculating the concentration of the graphene oxide mixed liquor.
And 2, preparing polyacrylic acid modified ferroferric oxide nanoparticles by using a surface initiated polymerization method and carrying out amination treatment to obtain the modified magnetic nanoparticles.
The method specifically comprises the following substeps:
Step 2-1, preparing polyacrylic acid modified ferroferric oxide nanoparticles by using a surface initiated polymerization method: weighing 2.0g of nano ferroferric oxide and 1.0g of ammonium persulfate, adding the mixture into 100mL of deionized water, ultrasonically stirring and dispersing for 30min, transferring the mixture into a reaction container, dripping 10mL of acrylic acid into the solution, heating the solution to 70 ℃, and keeping the mechanical stirring for 300r/min for reaction for 4h to obtain polyacrylic acid modified ferroferric oxide nanoparticle mixed solution.
Step 2-2, preparing modified magnetic nanoparticles by amination: adding 20mL of triethylene tetramine dropwise into the polyacrylic acid modified ferroferric oxide nanoparticle mixed solution, heating to 70 ℃, stirring and reacting for 3-4 h to obtain modified magnetic nanoparticle mixed solution, separating solid from the modified magnetic nanoparticle mixed solution by using a magnet, washing the solid with water for 3-4 times, washing the solid with absolute ethyl alcohol for 2 times, and drying in a 50 ℃ drying oven for 12h to obtain the modified magnetic nanoparticles.
And 3, preparing the modified magnetic nanoparticles into a modified magnetic nanoparticle mixed solution, adding the modified magnetic nanoparticle mixed solution into the graphene oxide mixed solution to obtain a blended solution, and adjusting the concentration of graphene oxide in the blended solution to 1 mg/mL-10 mg/mL, wherein the mass ratio of graphene oxide to modified magnetic nanoparticles is 1: 1-8: 1.
The specific operation is as follows: measuring a certain volume of the graphene oxide mixed solution, calculating the mass of the graphene oxide according to the concentration, weighing a certain mass of modified magnetic nanoparticles according to the mass ratio of the graphene oxide to the modified magnetic nanoparticles of 1: 1-8: 1, adding the modified magnetic nanoparticles into deionized water, and performing ultrasonic dispersion to obtain the modified magnetic nanoparticle mixed solution. And adding the modified magnetic nanoparticle mixed solution subjected to ultrasonic dispersion into the graphene oxide mixed solution taken out to obtain a blended solution, and adding deionized water to adjust the concentration of the graphene oxide to 1 g/mL-10 g/mL.
And 4, ultrasonically dispersing the blended solution, heating to 50-90 ℃ and reacting for 0.5-30 h to obtain a reaction solution.
The specific operation is as follows: and adding the blended solution into a three-neck flask after ultrasonic dispersion, and heating to 50-90 ℃ for reaction for 0.5-30 h under the condition of keeping mechanical stirring for 300r/min to obtain a reaction solution.
And 5, cooling the reaction liquid to room temperature, adding ascorbic acid into the reaction liquid according to the mass ratio of 1: 1-10: 1 of ascorbic acid to graphene oxide, ultrasonically stirring and dispersing, and then placing the mixture in an oven for reaction to obtain the magnetic graphene hydrogel.
The specific operation is as follows: and cooling the reaction liquid to room temperature, adding ascorbic acid into the reaction liquid according to the mass ratio of 1: 1-10: 1 of the ascorbic acid to the graphene oxide, ultrasonically stirring and dispersing, and then placing the mixture in an oven at 40-180 ℃ for reacting for 2-48 h to obtain the magnetic graphene hydrogel.
And 6, putting the magnetic graphene hydrogel into a water-alcohol mixed solution with the alcohol volume fraction of 5-50%, dialyzing, freeze-drying, and then thermally annealing the freeze-dried magnetic graphene hydrogel in an inert atmosphere to obtain the magnetic graphene aerogel.
The specific operation is as follows: and (2) putting the magnetic graphene hydrogel into a 5-50% ethanol aqueous alcohol solution for dialysis for 6-48 h, freeze-drying, and then thermally annealing the freeze-dried magnetic graphene hydrogel in an infrared tube furnace for 0.5-2 h under an inert atmosphere at 200-800 ℃ in a nitrogen atmosphere to obtain the magnetic graphene aerogel.
In the embodiment of the invention, a graphene oxide mixed solution with a concentration of 14mg/mL is prepared for later use, and the specific preparation process is as follows:
Step 1-1, pre-oxidation process: weighing 4.0g of potassium persulfate, 4.0g of phosphorus pentoxide and 3.0g of graphite powder, uniformly mixing, pouring into a reaction container, slowly adding 20mL of concentrated sulfuric acid, heating to 80 ℃, reacting for 6h, cooling at room temperature, adding deionized water for dilution, filtering to neutrality, and drying the obtained filter cake at room temperature for 12h to obtain a pre-oxidized dry product.
Step 1-2, oxidation process: adding the pre-oxidized dry product into 120mL concentrated sulfuric acid, stirring and dissolving under an ice bath condition to obtain a pre-oxidized dry product solution, weighing 9.0g of potassium permanganate, slowly adding potassium permanganate into the pre-oxidized dry product solution under the ice bath condition, continuously stirring for 30min, heating to 30 ℃, stirring for 2h to obtain a reaction solution, adding 125mL of deionized water into the reaction solution, stirring for 15min, dropwise adding 30% hydrogen peroxide until the reaction solution turns bright yellow, then pouring the bright yellow reaction solution into a 3L big beaker, adding 2.5L deionized water, adding 100-150 mL concentrated hydrochloric acid, standing for 24h to obtain a precipitate, pouring out the supernatant after standing, taking the lower-layer precipitate, putting the lower-layer precipitate into a dialysis bag, and (3) placing the dialysis bag in water for dialysis for 3-4 days until the pH value of water outside the dialysis bag is neutral, wherein the mixed liquid in the dialysis bag is graphene oxide mixed liquid. And pouring the dialyzed graphene oxide mixed solution into a beaker, and ultrasonically stirring for 15min for later use.
The method for measuring the concentration of the graphene oxide mixed solution comprises the following steps: and (3) taking 3mL of graphene oxide solution, freeze-drying for 2 days, weighing the mass of the solid matter, and quantitatively calculating the concentration of the graphene oxide to be 14 mg/mL.
And (3) carrying out infrared detection on the graphite and the obtained graphene oxide, wherein the detection result is shown in figure 1 a.
Fig. 1a is an infrared spectrum of Graphene Oxide (GO) and graphite (G) in the present invention.
From FIG. 1a, we can see that the infrared spectrum of graphene oxide shows a distinct difference compared to graphite powder, at 1735cm-1stretching vibration of carbonyl carbon-oxygen double bond C ═ O, 1617cm-1Stretching vibration of C-C double bond at 1220cm-1stretching vibration of 1047cm under the action of C-O single bond-1The position is the stretching vibration absorption peak of the epoxy bond C-O-C. The appearance of these peaks indicates that the graphene oxide surface contains abundant oxygen-containing functional groups and graphite is successfully oxidized.
in the embodiment of the invention, the modified magnetic nanoparticles are prepared for standby, and the specific preparation process is as follows:
Step 2-1, preparing polyacrylic acid modified ferroferric oxide nanoparticles by using a surface initiated polymerization method: weighing 2.0g of nano ferroferric oxide and 1.0g of ammonium persulfate, adding the mixture into 100mL of deionized water, ultrasonically stirring and dispersing for 30min, transferring the mixture into a reaction container, dripping 10mL of acrylic acid into the solution, heating the solution to 70 ℃, and keeping the mechanical stirring for 300r/min for reaction for 4h to obtain polyacrylic acid modified ferroferric oxide nanoparticle mixed solution.
Step 2-2, preparing modified magnetic nanoparticles by amination: and (2) dripping 20mL of triethylene tetramine into the polyacrylic acid modified ferroferric oxide nanoparticle mixed solution, heating to 70 ℃, stirring at 300r/min for reaction for 3-4 h to obtain modified magnetic nanoparticle mixed solution, separating a solid from the modified magnetic nanoparticle mixed solution by using a magnet, washing the solid with water for 3-4 times, washing with absolute ethyl alcohol for 2 times, and drying in a 50 ℃ oven for 12h to obtain the modified magnetic nanoparticles. And grinding the dried product for later use.
For ferroferric oxide nano particle (Fe)3O4) And the resulting modified magnetic nanoparticles (Fe)3O4-NH2) Infrared detection was performed and the results are shown in fig. 1 b.
FIG. 1b is a modified magnetic nanoparticle (Fe) in example 1 of the present invention3O4-NH2) And ferroferric oxide nanoparticles (Fe)3O4) An infrared spectrum of (1).
From the comparison result of FIG. 1b, it can be seen that the pure ferroferric oxide nanoparticles are only 545cm-1The stretching vibration peak of the ferrite bond Fe-O appears on the left and the right, and the infrared spectrogram of the modified magnetic ferroferric oxide nano particle is 1557cm-1，1400cm-1The absorption peak of the stretching vibration of the N-H bond and the absorption peak of the stretching vibration of the C-N bond appear, which indicates that the surface amination modification of the nano ferroferric oxide is successful.
< example 1>
weighing 20mL of prepared graphene oxide mixed liquor, weighing modified magnetic particles according to the mass ratio of 2:1 of graphene oxide to modified magnetic nanoparticles, adding the weighed modified magnetic nanoparticles into 50mL of deionized water, ultrasonically stirring for 5min, and ultrasonically dispersing to obtain the modified magnetic nanoparticle mixed liquor. And adding the modified magnetic nanoparticle mixed solution subjected to ultrasonic dispersion into the graphene oxide mixed solution taken out to obtain a mixed solution, adding deionized water to adjust the concentration of the graphene oxide to 3g/mL, and performing ultrasonic stirring and dispersion for 10 min. Adding the blend after ultrasonic dispersion into a three-neck flask, heating to 50 ℃ and reacting for 4h to obtain reaction liquid. And cooling the reaction liquid to room temperature, adding ascorbic acid into the reaction liquid according to the mass ratio of 5:1 of ascorbic acid to graphene oxide, ultrasonically stirring and dispersing for 10min, and then placing the mixture in a 40 ℃ drying oven for reaction for 8h to obtain the magnetic graphene hydrogel. And (3) putting the magnetic graphene hydrogel into a 5% ethanol water-alcohol solution by volume fraction, dialyzing for 4h, and freeze-drying. And then, thermally annealing the freeze-dried magnetic graphene hydrogel at 300 ℃ for 12h in a nitrogen atmosphere to prepare the super-elastic magnetic graphene aerogel.
scanning Electron Microscope (SEM) and projection electron microscope (TEM) are performed on the prepared superelastic magnetic graphene aerogel, and the detection results are shown in fig. 2a and 2 b.
fig. 2a is an SEM image of the superelastic magnetic graphene aerogel in example 1 of the present invention, and fig. 2b is a TEM image of the superelastic magnetic graphene aerogel in example 1 of the present invention.
As shown in fig. 2a and 2b, graphene oxide is of a lamellar structure, modified magnetic nanoparticles are uniformly distributed on the surface of a graphene oxide lamellar layer (small particles in fig. 2b are modified magnetic nanoparticles), a large number of folds exist on the lamellar layer due to the action between amino groups of the modified magnetic nanoparticles and groups on the graphene oxide lamellar layer, and meanwhile, the amino groups on the surface of the modified magnetic nanoparticles enable the graphene oxide lamellar layers to be bonded to form a larger and thicker graphene oxide lamellar layer, and a macroporous structure is formed by three-dimensional building of the lamellar layers.
< example 2>
Weighing 20mL of prepared graphene oxide mixed liquor, weighing modified magnetic nanoparticles according to the mass ratio of graphene oxide to modified magnetic nanoparticles of 8:1, adding the weighed modified magnetic nanoparticles into 35mL of deionized water, ultrasonically stirring for 5min, and ultrasonically dispersing to obtain the modified magnetic nanoparticle mixed liquor. And adding the modified magnetic nanoparticle mixed solution subjected to ultrasonic dispersion into the graphene oxide mixed solution taken out to obtain a blended solution, adding deionized water to adjust the concentration of the graphene oxide to 1g/mL, and performing ultrasonic stirring and dispersion for 10 min. Adding the blend after ultrasonic dispersion into a three-neck flask, heating to 60 ℃ and reacting for 3.5h to obtain reaction liquid. And cooling the reaction liquid to room temperature, adding ascorbic acid into the reaction liquid according to the mass ratio of 1:1 of the ascorbic acid to the graphene oxide, ultrasonically stirring and dispersing for 10min, and then placing the mixture in a 60 ℃ drying oven for reaction for 8h to obtain the magnetic graphene hydrogel. And (3) putting the magnetic graphene hydrogel into a 25% ethanol water-alcohol solution by volume fraction for dialysis for 12h, and freeze-drying. And then, thermally annealing the freeze-dried magnetic graphene hydrogel for 2 hours at 500 ℃ in a nitrogen atmosphere to prepare the super-elastic magnetic graphene aerogel.
< example 3>
Weighing 20mL of prepared graphene oxide mixed liquor, weighing modified magnetic particles according to the mass ratio of the graphene oxide to the modified magnetic nanoparticles of 1:1, adding the weighed modified magnetic nanoparticles into 35mL of deionized water, ultrasonically stirring for 5min, and ultrasonically dispersing to obtain the modified magnetic nanoparticle mixed liquor. And adding the modified magnetic nanoparticle mixed solution subjected to ultrasonic dispersion into the graphene oxide mixed solution taken out to obtain a blended solution, adding deionized water to adjust the concentration of the graphene oxide to 10g/mL, and performing ultrasonic stirring and dispersion for 10 min. Adding the blend after ultrasonic dispersion into a three-neck flask, heating to 70 ℃ and reacting for 7h to obtain reaction liquid. And cooling the reaction liquid to room temperature, adding ascorbic acid into the reaction liquid according to the mass ratio of 10:1 of ascorbic acid to graphene oxide, ultrasonically stirring and dispersing for 10min, and then placing the mixture in a 60 ℃ drying oven for reaction for 8h to obtain the magnetic graphene hydrogel. And (3) putting the magnetic graphene hydrogel into a water-alcohol solution with the volume fraction of 20% of ethanol, dialyzing for 12h, and freeze-drying. And then thermally annealing the freeze-dried magnetic graphene hydrogel for 6 hours at 400 ℃ in a nitrogen atmosphere to prepare the super-elastic magnetic graphene aerogel.
< comparative example >
measuring 20mL of prepared graphene oxide mixed solution, adding deionized water to enable the concentration of the graphene oxide to be 3mg/mL, carrying out ultrasonic and mechanical stirring dispersion for 10 min. Adding the dispersed solution into a three-neck flask, heating to 70 ℃, and keeping mechanical stirring for 300r/min for reaction for 2 h. And cooling the reacted solution to room temperature, adding ascorbic acid into the solution according to the mass ratio of ascorbic acid to graphene oxide of 3:1, ultrasonically stirring and dispersing for 10min, and then placing the solution in an oven at 70 ℃ for reaction for 4h to prepare the magnetic graphene hydrogel. And then putting the prepared magnetic graphene hydrogel into a 15% hydroalcoholic solution for dialysis for 12h, and freeze-drying. And then thermally annealing the freeze-dried graphene hydrogel in an infrared tube furnace at 400 ℃ for 2h in a nitrogen atmosphere to prepare the graphene aerogel.
The prepared graphene aerogel is detected by a Scanning Electron Microscope (SEM), and the detection result is shown in fig. 3.
Fig. 3 is an SEM photograph of the graphene aerogel in the comparative example of the present invention.
From the SEM image of fig. 3, it can be seen that the graphene sheet layer is thinner and smaller, and the wrinkles on the surface of the sheet layer are less, and the pore diameter of the pores in the graphene aerogel is smaller.
< experiments on hydrophobicity and oil-Water separation >
(1) The super elastic magnetic graphene aerogel prepared in example 1 was tested for hydrophobicity using a contact angle measuring instrument, and the contact angle was 135 °.
(2) adsorption test of dyed cyclohexane
the cyclohexane is dyed by Sudan red and then added into water to be mixed to form red oil-water mixed liquid, then the prepared 0.01g of super elastic magnetic graphene aerogel is put into 3 weighing bottles containing 40mL of the oil-water mixed liquid to be subjected to oil-water separation, and the adsorption is finished when the red color disappears. Weigh the quality of the magnetic graphene aerogel after adsorbing the cyclohexane, compare with the magnetic graphene aerogel without adsorbing the cyclohexane, obtain the mass difference before and after adsorption, and obtain the magnetic graphene aerogel adsorption capacity.
the super elastic magnetic graphene aerogel prepared in example 1 completely adsorbed dyed cyclohexane within 25s, so that the red color disappeared.
The superelastic magnetic graphene aerogel prepared in example 2 completely adsorbed dyed cyclohexane within 30s, so that the red color disappeared.
The superelastic magnetic graphene aerogel prepared in example 3 completely adsorbed dyed cyclohexane within 25s, so that the red color disappeared.
(3) Adsorption experiment of sesame oil
Weighing a certain mass of the 0.01g of the superelastic magnetic graphene aerogel prepared in examples 1-3, respectively putting the weighed mass into 3 weighing bottles containing 40mL of sesame oil, and adsorbing for 3 min. Weighing the weight of the weighing bottle adsorbing the sesame oil and the weight of the residual sesame oil, and comparing the weight of the weighing bottle before adsorption with the weight of the sesame oil to obtain the mass difference before and after adsorption, so as to obtain the adsorption quantity of the superelastic magnetic graphene aerogel.
The sesame oil adsorbing capacity of the super elastic magnetic graphene aerogel prepared in example 1 is 210 g/g.
The sesame oil adsorbing capacity of the super elastic magnetic graphene aerogel prepared in example 2 was 191 g/g.
The sesame oil adsorbing capacity of the super elastic magnetic graphene aerogel prepared in example 3 is 200 g/g.
(4) adsorption experiment of different kinds of organic substances
The adsorption amounts of the superelastic magnetic graphene aerogel prepared in example 1 to different oils such as ethyl acetate, cyclohexane, dichloromethane, sesame oil, acetone, and the like were respectively determined by using the same experimental method as the sesame oil adsorption experiment.
Fig. 4 is a statistical chart of the amount of adsorbed fat for different amounts of fat. As seen from the figure, the magnetic graphene aerogel shows better adsorption capacity to different oils and fats, and the adsorption amounts to different oils and fats are respectively 215g/g (ethyl acetate), 240g/g (cyclohexane), 150g/g (acetone), 310g/g (dichloromethane) and 210g/g (sesame oil).
From the above experimental results, the magnetic graphene aerogel prepared in embodiments 1 to 3 can well adsorb oily substances in an oil-water mixture, quickly realize oil-water separation, and can adsorb oily substances more than 300 times of the self weight. The magnetic graphene aerogel prepared in example 1 has a super-hydrophobic characteristic, and the contact angle reaches 135 °.
< magnetic test >
And testing the magnetism of the magnetic graphene aerogel before and after the oily substance is adsorbed by using a magnet. The results show that the magnetic graphene aerogel has good magnetic properties before and after adsorption, and the results of example 1 are taken as an example to illustrate.
fig. 5 is a photograph of a magnetic experiment of the magnetic graphene aerogel in example 1 of the present invention.
as shown in fig. 5a, the superelastic magnetic graphene aerogel is placed in the air, and after the magnet is attached to the cup, the superelastic magnetic graphene aerogel is attracted to the wall of the cup placed on one side of the magnet and is suspended.
as shown in fig. 5b, before adsorption, the superelastic magnetic graphene aerogel was dispersed on the surface of the cyclohexane solution to adsorb cyclohexane.
As shown in fig. 5c, after the adsorption, the superelastic magnetic graphene aerogel having cyclohexane adsorbed thereon is gathered on the cup wall placed on the magnet side.
< elasticity test >
The compression performance of the superelastic magnetic graphene aerogel is tested by using a universal tensile testing machine of Shanghai Strength Instrument Equipment Co. The prepared cylindrical super-elastic magnetic graphene aerogel is placed on a test platform, and the compression and resilience performance is measured after the diameter height (the diameter: 15.2mm and the height of 24.6mm) is measured. The elasticity of the superelastic magnetic graphene aerogel was tested under a compression condition of 80% deformation.
Fig. 6 is a photograph of a compression experiment of the superelastic magnetic graphene aerogel in example 1 of the present invention.
FIGS. 6a, 6b, and 6c are photographs of the test before compression and after 80% deformation, respectively, after rebound. It can be seen that the super elastic magnetic graphene aerogel has very excellent elasticity and recovery performance, and can be recovered to an initial state after compression (the diameter is 15.2mm after compression recovery, and the height is 24.6 mm).
effects and effects of the embodiments
the super-elastic magnetic graphene aerogel prepared by the method is an ultra-light material, and the density is only 4.5mg/cm3And has strong adsorption capacity for oils, the adsorption capacity for various oils can reach about 200 times of the self weight, and the oil can still keep good material strength and almost the same adsorption capacity after multiple adsorption-desorption cycles. The material has super-hydrophobic characteristic, the contact angle reaches 135, and rapid oil-water separation can be realized; the oil pollutant in the water body which exceeds 200 times of the self weight can be quickly adsorbed in 30s, and the oil-water separation can be realized for some kinds of oil even reaching 310 times. Meanwhile, the material has good magnetism, and can be attracted by a magnet in the air and hover in the air; after adsorbing 200 times of oil by weight in the oil-water separation process, the oil can still be attracted by a magnet, so that the material can be quickly recovered under the action of an external magnetic field by utilizing the magnetism of the material in practical application. And has good elasticity, and after the compression test of 80% deformation, the materialthe initial state can still be recovered; after 10 compression cycles of 40% deformation, the aerogel can still return to the initial state, shows very good structural strength and has the capacity of multiple compression cycles. In practical application, the elasticity can be utilized to realize regeneration of the material after adsorbing oil through extrusion, thereby achieving the purposes of purifying sewage, protecting environment and saving water resources.
The above embodiments are preferred examples of the present invention, and are not intended to limit the scope of the present invention.
Claims (10)
1. A preparation method of a super elastic magnetic graphene aerogel is characterized by comprising the following steps:
step 1, preparing a graphene oxide mixed solution with a preset concentration by using a Hummers oxidation method;
Step 2, preparing polyacrylic acid modified ferroferric oxide nanoparticles by using a surface initiated polymerization method and carrying out amination treatment to obtain modified magnetic nanoparticles;
Step 3, preparing the modified magnetic nanoparticles into a modified magnetic nanoparticle mixed solution, adding the modified magnetic nanoparticle mixed solution into the graphene oxide mixed solution to obtain a blended solution, and adjusting the concentration of the graphene oxide in the blended solution to 1 mg/mL-10 mg/mL, wherein the mass ratio of the graphene oxide to the modified magnetic nanoparticles is 1: 1-8: 1;
Step 4, heating the blended solution to 50-90 ℃ after ultrasonic dispersion for reaction for 0.5-30 h to obtain a reaction solution;
Step 5, cooling the reaction liquid to room temperature, adding ascorbic acid into the reaction liquid according to the mass ratio of 1: 1-10: 1 of ascorbic acid to graphene oxide, ultrasonically stirring and dispersing, and then placing the mixture in an oven for reaction to obtain magnetic graphene hydrogel;
And 6, putting the magnetic graphene hydrogel into a water-alcohol mixed solution with the volume fraction of alcohol of 5-50%, dialyzing, freeze-drying, and then thermally annealing the freeze-dried magnetic graphene hydrogel at 200-800 ℃ for 0.5-2 h in an inert atmosphere to obtain the magnetic graphene aerogel.
2. The preparation method of the superelastic magnetic graphene aerogel according to claim 1, wherein the preparation method comprises the following steps:
Wherein, step 1 comprises the following substeps:
Step 1-1, weighing 4.0g of potassium persulfate, 4.0g of phosphorus pentoxide and 3.0g of graphite powder, uniformly mixing, pouring into a reaction container, slowly adding 20mL of concentrated sulfuric acid, heating to 80 ℃, reacting for 6 hours, cooling at room temperature, adding deionized water for dilution, filtering to be neutral, and drying the obtained filter cake at room temperature for 12 hours to obtain a pre-oxidized dry product;
Step 1-2, adding the pre-oxidized dry product into 120mL of concentrated sulfuric acid, stirring and dissolving under an ice bath condition to obtain a pre-oxidized dry product solution, weighing 9.0g of potassium permanganate, slowly adding the potassium permanganate into the pre-oxidized dry product solution under the ice bath condition, continuously stirring for 30min, heating to 30 ℃, stirring for 2h to obtain a reaction solution, adding 125mL of deionized water into the reaction solution, stirring for 15min, dropwise adding 30% of hydrogen peroxide until the reaction solution becomes bright yellow, then pouring the bright yellow reaction solution into a 3L big beaker, adding 2.5L of deionized water, adding 100 mL-150 mL of concentrated hydrochloric acid, standing and standing for 24h to obtain a precipitate, pouring a supernatant after standing, taking off the precipitate at a lower layer, putting the dialysis bag into water, dialyzing for 3-4 days until the pH value of the water outside the dialysis bag is neutral, the mixed liquid in the dialysis bag is graphene oxide mixed liquid.
3. The method for preparing the superelastic magnetic graphene aerogel according to claim 2, further comprising:
And (3) concentration determination: and (3) after taking a certain volume of the graphene oxide mixed liquid for freeze drying, weighing the obtained solid mass, and then calculating the concentration of the graphene oxide mixed liquid.
4. The preparation method of the superelastic magnetic graphene aerogel according to claim 1, wherein the preparation method comprises the following steps:
Wherein, step 2 comprises the following substeps:
Step 2-1, preparing polyacrylic acid modified ferroferric oxide nanoparticles by using a surface initiated polymerization method: weighing 2.0g of nano ferroferric oxide and 1.0g of ammonium persulfate, adding the nano ferroferric oxide and the ammonium persulfate into 100mL of deionized water, ultrasonically stirring and dispersing for 30min, transferring the mixture into a reaction container, dripping 10mL of acrylic acid into the solution, heating the solution to 70 ℃, and keeping the mechanical stirring for 300r/min for reaction for 4h to obtain polyacrylic acid modified ferroferric oxide nanoparticle mixed solution;
step 2-2, preparing modified magnetic nanoparticles by amination: and (2) dropwise adding 20mL of triethylene tetramine into the polyacrylic acid modified ferroferric oxide nanoparticle mixed solution, heating to 70 ℃, stirring and reacting for 3-4 h to obtain modified magnetic nanoparticle mixed solution, separating a solid from the modified magnetic nanoparticle mixed solution by using a magnet, washing the solid for 3-4 times by using water, washing for 2 times by using absolute ethyl alcohol, and drying in a 50 ℃ drying oven for 12h to obtain the modified magnetic nanoparticles.
5. The preparation method of the superelastic magnetic graphene aerogel according to claim 1, wherein the preparation method comprises the following steps:
Wherein, in the step 4, the mechanical stirring of 300r/min is continuously kept in the reaction process.
6. The preparation method of the superelastic magnetic graphene aerogel according to claim 1, wherein the preparation method comprises the following steps:
And 5, ultrasonically stirring and dispersing, and then placing in an oven at 40-180 ℃ for reaction for 2-48 h to obtain the magnetic graphene hydrogel.
7. the preparation method of the superelastic magnetic graphene aerogel according to claim 1, wherein the preparation method comprises the following steps:
And in the step 6, the magnetic graphene hydrogel is placed in a hydroalcoholic solution with the volume fraction of 5% -50% of alcohol for dialysis for 6-48 h.
8. The preparation method of the superelastic magnetic graphene aerogel according to claim 1, wherein the preparation method comprises the following steps:
And 6, thermally annealing the magnetic graphene hydrogel in an infrared tube furnace for 2 hours at the temperature of 200-800 ℃ in a nitrogen atmosphere to obtain the super-elastic magnetic graphene aerogel.
9. The utility model provides a super elasticity magnetism graphite alkene aerogel which characterized in that: the super elastic magnetic graphene aerogel is prepared by the preparation method of the super elastic magnetic graphene aerogel according to any one of claims 1 to 8.
10. the superelastic magnetic graphene aerogel according to claim 9, wherein:
The super-elastic magnetic graphene aerogel is composed of modified magnetic nanoparticles and graphene oxide, the modified magnetic nanoparticles are uniformly distributed on the surfaces of graphene oxide sheet layers, the graphene oxide sheet layers are enabled to be bonded with each other to form large sheet layers, and the graphene oxide sheets in the large sheet layers are built in a three-dimensional mode to form a large-hole structure.
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