CN114733537A - Magnetically-drivable graphene aerogel composite material and preparation method and application thereof - Google Patents
Magnetically-drivable graphene aerogel composite material and preparation method and application thereof Download PDFInfo
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- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 115
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- 238000002360 preparation method Methods 0.000 title claims abstract description 28
- SZVJSHCCFOBDDC-UHFFFAOYSA-N iron(II,III) oxide Inorganic materials O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 claims abstract description 159
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- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 30
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims abstract description 29
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Abstract
The invention provides a magnetically-drivable graphene aerogel composite material, and a preparation method and application thereof, and belongs to the technical field of catalytic materials. According to the invention, cetyl trimethyl ammonium bromide is used as a cationic surfactant, and Br ions can be provided to interact with bismuth nitrate and citric acid to generate BiOBr; the invention leads Fe to react by hydrothermal reaction3O4the/BiOBr is uniformly embedded between the graphene sheet layers, so that the photocatalytic activity of the composite material is ensured; the invention introduces Fe3O4The recovery of the composite material can be realized; the inventionThe adopted reagent is green and environment-friendly, and the technical problem of environmental pollution in the preparation of the photocatalyst can be solved. The data of the embodiment shows that the composite material prepared by the preparation method can degrade the potassium dichromate to 99.8% within 30min, and the material can be directly recycled by a magnet after catalytic degradation.
Description
Technical Field
The invention relates to the technical field of catalytic materials, in particular to a magnetically-drivable graphene aerogel composite material and a preparation method and application thereof.
Background
In many semiconductor photocatalysts, a single-component semiconductor is usually subjected to light excitation and then rapidly recombined to generate a hole/electron pair, so that the problem of low quantum efficiency is caused, and therefore, the practical photocatalytic degradation application is greatly limited. For example, bismuth-based semiconductor bismuth oxyhalide (X ═ Cl, Br, or I) exhibits good photocatalytic potential as an emerging photocatalytic material with narrow and tunable band gap (around 2.3 eV), non-toxicity, and high oxidation capability. Nevertheless, like many semiconductors, the single component BiOX charge separation limits its photocatalytic activity.
In recent years, by regulating the microstructure of a semiconductor or a carrier transporting carrier carried by the semiconductor, it is considered as an effective strategy for accelerating the transfer of interfacial charges and improving the photocatalytic activity thereof. For example, compounding other semiconductor materials, adding carbon-based materials having excellent optical and electron transfer properties, including carbon nanotubes, carbon quantum dots, graphene quantum dots, and the like, accelerates and retards recombination of electron hole species in the semiconductor while improving the microstructure, and can improve the activity of the photocatalyst, but the improvement degree of the activity of the photocatalyst is limited.
In recent years, the assembly of low-dimensional nanostructures into three-dimensional hierarchical micro/nanostructures is considered to be a promising approach to solve the above problems. Generally, aerogels are three-dimensional networks composed of numerous interpenetration of micropores and mesopores, and are ideal support frames with large specific surface area, rapidly transportable pores, and surface sites for anchoring catalysts; particularly, the two-dimensional graphene with excellent conductivity and extremely large specific load surface area is used as a photo-generated electron transfer carrier of the heterogeneous semiconductor, so that a continuous channel can be provided for electrons and ions, the transfer of the electrons and the ions between mutual interfaces is accelerated, and the separation efficiency of photo-generated electrons and holes is effectively improved. However, most of the research and development of inorganic nanopowders use toxic or corrosive solvents at high temperature and high pressure, and most of the research and development work of the following aerogels use toxic or corrosive cross-linking agents, which causes the technical problem of environmental pollution when preparing the photocatalyst.
On the other hand, inorganic powder materials as semiconductor photocatalysts have a serious self-aggregation problem due to their large specific surface area and more exposed active sites, and inorganic powder materials have a problem of difficulty in recovery, which inevitably limits their further applications.
Therefore, it is highly desirable to provide a green synthesis method for preparing a photocatalytic material with excellent catalytic activity and high recycling efficiency.
Disclosure of Invention
The invention aims to provide a magnetically-drivable graphene aerogel composite material, and a preparation method and application thereof.
In order to achieve the above object, the present invention provides the following technical solutions:
the invention provides a preparation method of a magnetically-drivable graphene aerogel composite material, which comprises the following steps:
(1) mixing Fe3O4Mixing the nano particles, bismuth salt, citric acid and deionized water to obtain mixed slurry;
(2) dropwise adding a hexadecyl trimethyl ammonium bromide solution into the mixed slurry obtained in the step (1), and stirring to obtain a precursor;
(3) drying the precursor obtained in the step (2) to obtain Fe3O4/BiOBr；
(4) Fe obtained in the step (3)3O4Mixing the BiOBr with lysine, graphene oxide and deionized water, and carrying out hydrothermal reaction to obtain the magnetically-driven graphene aerogel composite material.
Preferably, Fe in said step (1)3O4The nano particles are spherical particles, and the particle size of the spherical particles is 20-30 nm.
Preferably, Fe in said step (1)3O4The mass ratio of the nano particles, the bismuth salt, the citric acid and the hexadecyl trimethyl ammonium bromide in the step (2) is (10-15): (24-25): (3-4): (18-18.5).
Preferably, the stirring temperature in the step (2) is 25-35 ℃, and the stirring time is 0.5-1 h.
Preferably, the dropping rate in the step (2) is 0.025-0.075 mL/s.
Preferably, the drying temperature in the step (3) is 50-70 ℃, and the drying time is 10-15 h.
Preferably, Fe in said step (4)3O4The mass ratio of the/BiOBr, the lysine and the graphene oxide is (50-66.7): 30-35): 3.5-5.
Preferably, the temperature of the hydrothermal reaction in the step (4) is 160-180 ℃, and the time of the hydrothermal reaction is 8-15 h.
The invention also provides a magnetically-drivable graphene aerogel composite material prepared by the preparation method in the technical scheme, which comprises Fe3O4Nanoparticles, BiOBr and graphene, Fe3O4The nano particles are embedded between the BiOBr sheets to form Fe3O4A BiOBr heterojunction, said Fe3O4the/BiOBr heterojunction is anchored between the graphene networks.
The invention also provides application of the magnetically-drivable graphene aerogel composite material in photocatalytic degradation of inorganic and/or organic pollutant wastewater.
The invention provides a preparation method of a magnetically-drivable graphene aerogel composite material, which comprises the following steps: mixing Fe3O4Mixing the nano particles, bismuth salt, citric acid and deionized water to obtain mixed slurry; dropwise adding a hexadecyl trimethyl ammonium bromide solution into the mixed slurry, and stirring to obtain a precursor; drying the precursor to obtain the productFe3O4/BiOBr; subjecting said Fe to3O4Mixing the BiOBr with lysine, graphene oxide and deionized water, and carrying out hydrothermal reaction to obtain the magnetically-driven graphene aerogel composite material. The invention introduces Fe when preparing the composite material3O4The nano-particles have excellent magnetism, and can solve the problem that the graphene aerogel composite material is difficult to recover. According to the invention, cetyl trimethyl ammonium bromide is used as a cationic surfactant, micelles for regulating and controlling the morphology of a semiconductor can be formed in a solution interface, a good dispersing effect is achieved, Br ions can be provided, and the Br ions interact with bismuth nitrate and citric acid to generate BiOBr; according to the invention, the hexadecyl trimethyl ammonium bromide solution is dripped into the mixed slurry and reacts under stirring, so that the reaction process can be controlled, the precursor is more uniformly distributed, the thickness and the size of the BiOBr sheet layer formed in the drying process are more uniform, and Fe is more favorably realized3O4The nano particles are uniformly embedded between the BiOBr sheet layers, so that the photocatalytic activity of the composite material is improved. In the invention, Fe3O4Performing hydrothermal reaction on/BiOBr, lysine and graphene oxide, wherein the lysine and the graphene oxide can be mutually crosslinked to perform amidation reaction, and converting the graphene oxide into reduced graphene oxide so as to enable Fe3O4the/BiOBr is uniformly embedded between the graphene sheet layers, so that the photocatalytic activity of the composite material is ensured. The data of the embodiment shows that the composite material prepared by the preparation method can degrade the potassium dichromate to 99.8% within 30min, and the material can be directly recycled by a magnet after catalytic degradation.
The preparation method provided by the invention adopts green and environment-friendly reagents, and can solve the technical problem of environmental pollution in the preparation of the photocatalyst.
Drawings
FIG. 1 shows Fe prepared in example 1 of the present invention3O4SEM images of nanoparticles; (a) and (b) are each Fe3O4SEM images of nanoparticles at different magnifications;
FIG. 2 shows Fe prepared in example 1 of the present invention3O4SEM image of/BiOBr; (c) and (d) are each Fe3O4SEM images of/BiOBr at different magnifications;
FIG. 3 shows Fe prepared in example 1 of the present invention3O4SEM picture of/BiOBr/GE-1; (e) and (f) are each Fe3O4SEM images of/BiOBr/GE-1 at different magnifications;
FIG. 4 shows Fe prepared in example 1 of the present invention3O4Nanoparticles, Fe3O4BiOBr and Fe3O4XRD of/BiOBr/GE-1;
FIG. 5 shows Fe prepared in example 1 of the present invention3O4Nanoparticles, Fe3O4BiOBr and Fe3O4XPS plot of/BiOBr/GE-1;
FIG. 6 shows Fe prepared in example 1 of the present invention3O4Nanoparticles, Fe3O4BiOBr and Fe3O4Fe2p high resolution XPS map of/BiOBr/GE-1;
FIG. 7 shows Fe prepared in example 1 of the present invention3O4BiOBr and Fe3O4Bi4f high resolution XPS diagram of/BiOBr/GE-1;
FIG. 8 shows Fe prepared in example 1 of the present invention3O4Nanoparticles, Fe3O4BiOBr and Fe3O4The ultraviolet-visible absorption spectrum of/BiOBr/GE-1;
FIG. 9 is a graph showing the photocatalytic degradation effect of potassium dichromate solutions in application examples 1 to 3.
Detailed Description
The invention provides a preparation method of a magnetically-drivable graphene aerogel composite material, which comprises the following steps:
(1) mixing Fe3O4Mixing the nano particles, bismuth salt, citric acid and deionized water to obtain mixed slurry;
(2) dropwise adding a hexadecyl trimethyl ammonium bromide solution into the mixed slurry obtained in the step (1), and stirring to obtain a precursor;
(3) drying the precursor obtained in the step (2) to obtain Fe3O4/BiOBr；
(4) Fe obtained in the step (3)3O4Mixing the BiOBr with lysine, graphene oxide and deionized water, and carrying out hydrothermal reaction to obtain the magnetically-driven graphene aerogel composite material.
In the present invention, unless otherwise specified, the reagents used in the present invention may be commercially available products well known to those skilled in the art.
In the invention, Fe3O4Mixing the nano particles, bismuth salt, citric acid and deionized water to obtain mixed slurry.
In the present invention, the Fe3O4The nanoparticles are preferably spherical particles. In the present invention, the Fe3O4The nano particles are a narrow band gap semiconductor, have good conductive metal characteristics due to the nano size and play an important role in electron transfer; when said Fe is present3O4When the nano particles are spherical particles, the nano particles and the BiOBr can form a heterojunction with a ball-sheet mosaic structure, and the combination capability of the nano particles and the BiOBr is strong, so that the light absorption range and efficiency of the nano particles are favorably expanded, the built-in electric field intensity is favorably enhanced, the photo-generated carrier separation efficiency is further promoted, and the photocatalytic activity is improved; and, due to Fe3O4The nanoparticles have excellent ferromagnetism and can enable Fe3O4the/BiOBr heterojunction has magnetism, is convenient to recycle, and can solve the problem that the graphene aerogel composite material is difficult to recycle.
In the present invention, the Fe3O4The particle size of the nanoparticles is preferably 20-30 nm, and more preferably 25-28 nm. In the present invention, the Fe3O4The particle size of the nanoparticles is more favorable for Fe3O4The nano particles are well embedded in the BiOBr sheet, and the heterojunction interaction of the ball-sheet embedded structure caused by overlarge size can be prevented from being weakened.
In the present invention for said Fe3O4The source of the nanoparticles is not particularly limited, and the nanoparticles can be prepared by a commercially available product or a well-known preparation method known to those skilled in the artPrepared by adding Fe3O4The nanoparticles are spherical particles, and the particle diameter is within the above range.
In the present invention, the Fe3O4The method for preparing nanoparticles preferably comprises the following steps: mixing ferrous salt, ferric salt and ammonia water, and carrying out double decomposition reaction to obtain a precursor; aging the precursor to obtain Fe3O4And (3) nanoparticles.
According to the invention, the ferrous salt, the ferric salt and the ammonia water are preferably mixed to obtain the precursor.
In the invention, the method for mixing the ferrous salt, the ferric salt and the ammonia water is preferably that the ferrous salt and the ferric salt are dissolved in deionized water to obtain an iron salt solution, the iron salt solution is heated to 80-100 ℃, preferably 90 ℃, and then the ammonia water is dripped into the iron salt solution. According to the invention, double decomposition reaction occurs when the ferrous salt, the ferric salt and ammonia water are mixed, the ferric salt solution is heated to 80-100 ℃, and then the ammonia water is slowly dripped into the ferric salt solution, so that the phenomenon that the temperature is too high and the solution concentration is easy to change can be prevented, and the precipitate can be rapidly generated in the process of dripping the ammonia water, and the full formation of the precipitate by the ferric salt is facilitated.
In the present invention, the dropping rate is preferably 1mL of aqueous ammonia every 1 min. In the present invention, when the dropping rate is in the above range, the reaction rate can be controlled to allow the iron salt and the ammonia water to react sufficiently.
In the present invention, the addition of the aqueous ammonia dropwise to the iron salt solution is preferably performed under stirring. In the invention, the stirring can promote the precipitate generated by the reaction of the ferric salt and the ammonia water to be uniformly distributed in the reaction system, thereby being more beneficial to the full reaction of the ferric salt and the ammonia water.
In the present invention, the ratio of the amounts of the divalent iron salt and the trivalent iron salt is preferably (1.5 to 2.5): (4.5 to 5.5), more preferably (1.8 to 2.2): (4.8 to 5.2). In the invention, the ferrous salt and the ferric salt are used for preparing Fe3O4The nanoparticles provide iron ions; when the ratio of the amounts of the materials of the ferrous salt and the ferric salt is within the above rangeDuring the process, the ferrous salt, the ferric salt and the ammonia water are more favorably reacted to form precipitate so as to prepare the magnetic Fe3O4And (3) nanoparticles. In the present invention, the ferrous salt is preferably FeCl2·4H2O, the trivalent iron salt is preferably FeCl3·6H2O。
In the invention, the ammonia-containing mass fraction concentration of the ammonia water is preferably 28-30%. In the invention, when the ammonia-containing mass fraction concentration of the ammonia water is in the above range, the reaction of ferrous salt, ferric salt and ammonia water is more facilitated to form a precipitate. In the present invention, the amount of the divalent iron salt is 1.5 to 2.5mol, the amount of the trivalent iron salt is 4.5 to 5.5mol, and the amount of the ammonia water added is preferably 5 to 8mL, and more preferably 6 mL.
After obtaining the precursor, the invention preferably ages the precursor to obtain Fe3O4And (3) nanoparticles.
In the invention, the aging temperature is preferably 80-100 ℃, and more preferably 90 ℃; the time of the heat treatment is preferably 0.5 to 2 hours, more preferably 1 hour. In the present invention, when the aging temperature and time are in the above ranges, the precipitate formed by the iron salt and the ammonia water can be hydrolyzed, the particles grow, the crystal form is perfect and the crystal form is transformed, and finally, spherical Fe is formed3O4And (3) nanoparticles. In the present invention, the aging is preferably carried out under stirring.
After the aging is finished, the invention preferably carries out centrifugation, magnetic adsorption, washing and drying on the aged system in sequence to obtain Fe3O4And (3) nanoparticles. In the present invention, the centrifugation, magnetic adsorption, washing and drying can remove Fe3O4Impurities on the surface of the nanoparticles and obtaining dry Fe3O4And (3) nanoparticles. The operation modes of the centrifugation, the magnetic adsorption, the washing and the drying are not particularly limited in the invention, and the operation modes of the centrifugation, the magnetic adsorption, the washing and the drying which are well known to those skilled in the art can be adopted. In the invention, the washing reagent is preferably deionized water, and the washing times are preferably 3-5 times; said driedThe temperature is preferably 60 ℃, and the drying time is preferably 12 h; the drying mode is preferably vacuum drying.
In the present invention, the Fe3O4The preparation method of the nano-particles is Fe prepared in the method3O4The nano-particles are regular spherical nano-particles, and the Fe3O4The particle size range of the nanoparticles is preferably 20-30 nm, and more preferably 25-30 nm.
In the present invention, the bismuth salt is preferably bismuth nitrate pentahydrate. In the invention, the bismuth salt can provide a bismuth source for BiOBr, and can react with citric acid and hexadecyl trimethyl ammonium bromide to generate BiOBr.
In the present invention, the citric acid is capable of reacting with bismuth salt and cetyltrimethylammonium bromide to produce BiOBr.
In the present invention, the Fe3O4The mass ratio of the nanoparticles, the bismuth salt, the citric acid and the hexadecyl trimethyl ammonium bromide is preferably (10-15): 24-25): 3-4): 18-18.5, and more preferably (12-14): 24-24.5): 3.5-4): 18-18.5. In the present invention, the Fe3O4When the mass ratio of the nano particles to the bismuth salt to the citric acid to the cetyltrimethylammonium bromide is within the above range, the bismuth salt, the citric acid and the cetyltrimethylammonium bromide can fully react to generate sheet BiOBr, and Fe can be enabled to be generated3O4Nanoparticle modification on BiOBr nanosheet to form Fe3O4the/BiOBr heterogeneous semiconductor is more beneficial to expanding the light absorption range and efficiency, and is also beneficial to enhancing the built-in electric field intensity, thereby promoting the separation efficiency of photon-generated carriers and further improving the photocatalytic activity.
The amount of the deionized water is not particularly limited in the invention, and is determined according to Fe3O4And (3) adjusting the mass of the nano particles, the bismuth salt, the citric acid and the hexadecyl trimethyl ammonium bromide.
In the present invention for said Fe3O4The operation method of mixing the nanoparticles, the bismuth salt, the citric acid and the deionized water is not particularly limited, and the mixing method well known to those skilled in the art can be used to mix the nanoparticles, the bismuth salt, the citric acid and the deionized waterThe components are mixed evenly. In the present invention, the Fe3O4The operation method of mixing the nano particles, the bismuth salt, the citric acid and the deionized water is preferably ultrasonic. The power and time of the ultrasound are not specially limited, and the components can be uniformly mixed.
After the mixed slurry is obtained, the hexadecyl trimethyl ammonium bromide solution is dripped into the mixed slurry and stirred to obtain the precursor.
In the invention, cetyl trimethyl ammonium bromide is used as a cationic surfactant, micelles for regulating and controlling the morphology of a semiconductor can be formed in a solution interface, a good dispersing effect is achieved, Br ions can be provided, and the Br ions interact with bismuth salt and citric acid to generate BiOBr.
In the invention, the concentration of the cetyl trimethyl ammonium bromide solution is preferably 0.18-0.28 mg/mL. In the present invention, the concentration of the cetyltrimethylammonium bromide solution is in the above range, which is more favorable for the interaction of cetyltrimethylammonium bromide, bismuth salt and citric acid to generate BiOBr.
In the present invention, the solvent of the cetyltrimethylammonium bromide solution is preferably n-hexane or n-octane. In the invention, the solvent can form a water/solvent solution interface with water when the solvent is of the type mentioned above, so that cetyl trimethyl ammonium bromide forms micelles for regulating and controlling the morphology of the semiconductor in the water/solvent solution interface.
In the present invention, the rate of the dropping is preferably 0.025 to 0.075mL/s, more preferably 0.05 mL/s. In the invention, the cetyl trimethyl ammonium bromide solution is dripped into the bismuth salt and Fe3O4During the mixed thick liquids of nano-particle and citric acid, can form the layering interface at the interface, the dropwise add too fast, can cause local surfactant micelle concentration inconsistent, and then influence the thickness of BiOBr lamellar structure and size of a dimension, work as when the speed of dropwise add is above-mentioned scope, more be favorable to making the thickness of BiOBr lamellar structure and size even.
In the invention, the stirring temperature is preferably 25-35 ℃, and more preferably 30-35 ℃; stirring deviceThe stirring time is preferably 25 to 60min, and more preferably 30 to 40 min. In the invention, the stirring can promote the cetyl trimethyl ammonium bromide, the bismuth salt and the citric acid to fully react to form BiOBr, and enable Fe3O4The nanoparticles are uniformly distributed between the BiOBr sheets.
After the stirring is finished, the stirred system is preferably sequentially filtered and washed to obtain the precursor. In the present invention, the filtering and washing can remove impurities on the surface of the precursor. The operation method of the filtration and washing in the present invention is not particularly limited, and the operation method of the filtration and washing known to those skilled in the art may be employed. In the present invention, the filtration membrane for filtration is preferably a 0.45 μm polytetrafluoroethylene filtration membrane.
After obtaining the precursor, the invention dries the precursor to obtain Fe3O4/BiOBr。
In the present invention, the drying can promote Fe3O4The nano particles are embedded between the BiOBr sheets to form Fe3O4a/BiOBr heterojunction. In the invention, the drying temperature is preferably 50-70 ℃, and more preferably 60 ℃; the drying time is preferably 10-15 h, and more preferably 12 h.
To obtain Fe3O4After BiOBr, the invention uses said Fe3O4Mixing the BiOBr with lysine, graphene oxide and deionized water, and carrying out hydrothermal reaction to obtain the magnetically-driven graphene aerogel composite material.
In the invention, the lysine can be crosslinked with graphene oxide, and the graphene oxide is converted into reduced graphene oxide, so that Fe3O4/BiOBr is anchored between graphene networks to cooperatively construct Fe3O4the/BiOBr/graphene hybrid aerogel catalytic material can convert Fe3O4the/BiOBr nano-structure material is fixed on a three-dimensional reticular graphene aerogel carrier framework which has excellent conductivity and can be recycled, not only can be used as a photo-generated electron transfer carrier of a semiconductor heterojunction, but also a three-dimensional porous channel can provide a continuous channel for medium ions,the electron and ion transfer between the mutual interfaces is accelerated, so that the photocatalytic activity and the cyclic catalytic activity are effectively improved, and the three-dimensional reticular graphene aerogel carrier frame can further transfer Fe3O4The BiOBr is dispersed and fixed, the dispersion stability of the BiOBr is improved, agglomeration is avoided, and meanwhile, the three-dimensional network frame with magnetism can effectively and synergistically solve the agglomeration and recycling problems of the nano materials.
In the present invention, the Fe3O4The mass ratio of the/BiOBr, the lysine and the graphene oxide is preferably (50-66.7): 30-35): 3.5-5, and more preferably (60-66): 32-35): 4-5. In the present invention, the Fe3O4When the mass ratio of/BiOBr, lysine and graphene oxide is in the above range, Fe can be added3O4the/BiOBr heterojunction is uniformly anchored between the graphene networks, and the catalytic performance of the composite material is improved.
The amount of the water ions is not particularly limited in the present invention, and is in accordance with Fe3O4And adjusting the mass of the/BiOBr, the lysine and the graphene oxide.
In the present invention for said Fe3O4The operation method for mixing the/BiOBr with the lysine, the graphene oxide and the deionized water is not particularly limited, and the components can be uniformly mixed by adopting a mixing mode well known by the technical personnel in the field. In the present invention, the Fe3O4The mixing mode of the/BiOBr, the lysine, the graphene oxide and the deionized water is preferably ultrasonic. The power and time of the ultrasound are not specially limited, and the components can be uniformly mixed by adjusting according to actual needs.
In the invention, the temperature of the hydrothermal reaction is preferably 160-180 ℃, and more preferably 170-180 ℃; the time of the hydrothermal reaction is preferably 8-15 h, and more preferably 10 h. In the invention, the surface of graphene oxide contains hydrophilic oxygen-containing groups such as carboxyl and hydroxyl, lysine is water-soluble alkalescent amino acid containing carboxyl and amino, and the carboxyl and the amino can undergo amidation reaction at high temperature and high pressure so as to be crosslinked into macromolecules; when the hydrothermal reaction is carried outWhen the temperature is within the above range, the sufficient crosslinking reaction of lysine and graphene oxide can be promoted, and Fe can be caused3O4the/BiOBr is anchored between the graphene networks.
The apparatus for the hydrothermal reaction in the present invention is not particularly limited, and a hydrothermal reaction apparatus known to those skilled in the art may be used. In the present invention, the hydrothermal reaction apparatus is preferably a hydrothermal reaction kettle. In the invention, the hydrothermal reaction kettle can provide a high-pressure closed reaction environment for the hydrothermal reaction, so that the hydrothermal reaction is fully performed, the full crosslinking reaction of lysine and graphene oxide is promoted, and Fe is enabled3O4the/BiOBr is anchored between the graphene networks.
After the hydrothermal reaction is finished, the system after the hydrothermal reaction is preferably washed, precooled and freeze-dried in sequence to obtain the magnetically-driven graphene aerogel composite material.
In the present invention, the washing is preferably performed by washing the gel obtained after the hydrothermal reaction with deionized water, and then soaking the gel in absolute ethyl alcohol. In the present invention, when the washing method is the above-mentioned type, impurities on the surface of the gel product of the hydrothermal reaction can be sufficiently removed.
In the invention, the pre-cooling temperature is preferably-30 to-40 ℃, and more preferably-40 ℃; the pre-cooling time is preferably 1-1.5 h, and more preferably 1.5 h. According to the invention, the precooling can enable the gel obtained after the hydrothermal reaction to be in a low-temperature environment, so that pores in the formed hydrogel can be maintained, and the pore change caused by unstable temperature before and after direct vacuum freezing and instant water vapor pumping can be prevented, thereby being more beneficial to enabling the prepared magnetically-driven graphene aerogel composite material to have a richer network structure and improving the catalytic performance of the composite material.
In the present invention, the temperature of the freeze-drying is preferably-60 to-70 ℃, more preferably-65 to-70 ℃; the freeze drying time is preferably 20-24 hours, and more preferably 24 hours. In the invention, the freeze drying can remove the solvent in the solid, and can keep the magnetically-drivable graphene aerogel composite material to have rich network structure, thereby improving the catalytic activity of the composite material.
According to the preparation method provided by the invention, cetyl trimethyl ammonium bromide is used as a cationic surfactant, micelles for regulating and controlling the morphology of a semiconductor can be formed in a solution interface, a good dispersing effect is achieved, Br ions can be provided, and the Br ions interact with bismuth nitrate and citric acid to generate BiOBr; according to the invention, the hexadecyl trimethyl ammonium bromide solution is dripped into the mixed slurry and reacts under stirring, so that the reaction process can be controlled, the precursor is more uniformly distributed, the thickness and the size of the BiOBr sheet layer formed in the drying process are more uniform, and Fe is more favorably realized3O4The nano particles are uniformly embedded between the BiOBr sheet layers, so that the photocatalytic activity of the composite material is improved. In the invention, Fe3O4Performing hydrothermal reaction on/BiOBr, lysine and graphene oxide, wherein the lysine and the graphene oxide can be mutually crosslinked to perform amidation reaction, and converting the graphene oxide into reduced graphene oxide so as to enable Fe3O4the/BiOBr is uniformly embedded between the graphene sheet layers, so that the photocatalytic activity of the composite material is ensured. In addition, the preparation method provided by the invention adopts green and environment-friendly reagents, and can solve the technical problem of environmental pollution during the preparation of the photocatalyst.
The invention also provides a magnetically-drivable graphene aerogel composite material prepared by the preparation method in the technical scheme, which comprises Fe3O4Nanoparticles, BiOBr and graphene, Fe3O4The nano particles are embedded between the BiOBr sheets to form Fe3O4A BiOBr heterojunction, said Fe3O4the/BiOBr heterojunction is anchored between the graphene networks.
In the present invention, the Fe3O4The mass ratio of the nanoparticles to the BiOBr to the graphene is preferably (140-180): 160-220): 2.5-3.5, and more preferably (160-180): 190-220): 2.5-3. In the present invention, the Fe3O4When the mass ratio of the nanoparticles to the BiOBr to the graphene is within the above range, the magnetically drivable graphene aerogel composite material has a higher degree of strengthExcellent photocatalytic activity.
The magnetically-drivable graphene aerogel composite material provided by the invention introduces graphene into Fe3O4BiOBr hetero-semiconductor with Fe3O4the/BiOBr/graphene hybrid aerogel catalytic material can convert Fe3O4the/BiOBr nano-structure powder material is fixed on a three-dimensional reticular graphene aerogel carrier framework which has excellent conductivity and can be recycled, the powder material not only can be used as a photo-generated electron migration carrier of a semiconductor heterojunction, but also can provide a continuous channel for medium ions through a three-dimensional porous channel, so that the electron and ion transfer between mutual interfaces is accelerated, the photocatalytic activity and the cyclic catalytic activity are effectively improved, the three-dimensional reticular graphene aerogel carrier framework can further disperse and fix the nano-powder material, the dispersion stability of the nano-powder material is improved, the agglomeration is avoided, and meanwhile, the three-dimensional network framework which has magnetism is hopeful to more efficiently and synergistically solve the agglomeration and cyclic utilization problems of the nano-material.
The invention also provides application of the magnetically-drivable graphene aerogel composite material in photocatalytic degradation of inorganic and/or organic pollutant wastewater.
The application method of the magnetically drivable graphene aerogel composite material in photocatalytic degradation of inorganic and/or organic pollutant wastewater solution is not particularly limited, and the method for treating wastewater by using the photocatalyst known to those skilled in the art can be adopted. In the invention, the application method of the magnetically drivable graphene aerogel composite material in photocatalytic degradation of inorganic and/or organic pollutant wastewater is preferably to suspend the magnetically drivable graphene aerogel composite material in the inorganic and/or organic pollutant wastewater, adjust the pH value of the system to be neutral, preferably 7, mix uniformly and stir for a period of time to make it reach adsorption equilibrium; and then carrying out photocatalytic degradation reaction on the mixed slurry under the irradiation of sunlight or simulated sunlight.
In the present invention, the inorganic pollutant wastewater solution preferably comprises a solution of a heavy metal salt, more preferably a solution of one or more of potassium dichromate, lead acetate and mercury chloride; the organic pollutant wastewater solution is preferably a solution containing one or more of methyl orange, rhodamine B and methyl blue. The concentration of the inorganic and/or organic pollutant wastewater solution is not particularly limited in the present invention, and the wastewater solution concentration that can be obtained by those skilled in the art can be adopted. In the invention, the concentration of the inorganic and/or organic pollutant wastewater solution is preferably 5-50 mg/L, and more preferably 10 mg/L.
The magnetically-drivable graphene aerogel composite material provided by the invention has excellent photocatalytic activity and cyclic catalytic activity, and can be used for efficiently catalyzing and degrading inorganic and/or organic pollutant wastewater solutions.
The technical solution of the present invention will be clearly and completely described below with reference to the embodiments of the present invention. It is to be understood that the described embodiments are merely exemplary of the invention, and not restrictive of the full scope of the invention. All other embodiments, which can be obtained by a person skilled in the art without making any creative effort based on the embodiments in the present invention, belong to the protection scope of the present invention.
Example 1
A preparation method of a magnetically drivable graphene aerogel composite material comprises the following steps:
(1)Fe3O4the preparation method of the nano-particles comprises the following steps: 0.81g FeCl2·4H2O、2.0g FeCl3·6H2Mixing O with 110mL of deionized water to obtain a transparent orange solution, wherein the mass ratio of ferrous salt to ferric salt is 0.86: 1; heating the transparent orange solution to 90 ℃, adding 1mL of ammonia water containing 28-30% of ammonia by mass percent every 1min into the transparent orange solution, dropwise adding for 6 times, and carrying out double decomposition reaction to obtain a precursor; standing the obtained precursor at 90 ℃ for 1h for aging; after aging is finished, centrifuging and magnetically adsorbing the product, washing the product for 3-5 times by using deionized water, and drying the product in vacuum at 60 ℃ for 12 hours to obtain Fe3O4And (3) nanoparticles.
(2) Fe prepared in the step (1)3O40.25g of nanoparticles was mixed with 0.485g of bismuth nitrate pentahydrate, 0.072g of citric acid and 7.5mL of deionized water under ultrasound to obtain a mixed slurry.
(3) 0.364g of hexadecyl trimethyl ammonium bromide and 12.5mL of n-octane solution of hexadecyl trimethyl ammonium bromide are prepared, the n-octane solution of hexadecyl trimethyl ammonium bromide is dropwise added into the mixed slurry obtained in the step (2) at the speed of 0.05mL/s, the mixture is stirred for 25min at the temperature of 25 ℃, a product is filtered by a 0.45-micrometer polytetrafluoroethylene filter membrane, and then deionized water is adopted for washing, so that a precursor is obtained; wherein, Fe3O4The mass ratio of the nano particles, the bismuth nitrate pentahydrate, the citric acid and the n-octyl hexadecyltrimethylammonium bromide is 12.5:24.25:3.6: 18.2.
(4) Drying the precursor obtained in the step (3) at 60 ℃ for 12h to obtain Fe3O4/BiOBr；
(5) 0.4g of Fe obtained in the step (4)3O4Mixing BiOBr with 200mg of lysine, 25.2mg of graphene oxide and 6mL of deionized water under ultrasonic waves, reacting for 10 hours at 160 ℃, carrying out hydrothermal reaction, washing and soaking the product with deionized water and absolute ethyl alcohol, precooling for 1.5 hours at-40 ℃, and carrying out freeze drying for 24 hours at-70 ℃ to obtain the magnetically-driven graphene aerogel composite material; wherein Fe3O4The mass ratio of the/BiOBr to the lysine to the graphene oxide is 60:30: 3.78.
The magnetically-drivable graphene aerogel composite material prepared by the embodiment is referred to as Fe for short3O4/BiOBr/GE-1, wherein Fe3O4/BiOBr stands for Fe3O4a/BiOBr heterojunction, GE stands for graphene, Fe3O4The mass ratio of nanoparticles, BiOBr and graphene is preferably 180:220: 2.5.
Example 2
A preparation method of magnetically-drivable graphene aerogel composite material comprises the following steps:
fe was produced by the method of steps (1) to (4) of example 13O4/BiOBr。
0.35g of Fe obtained in the step (3)3O4BiOBr with 200mg lysine, 30mMixing graphene oxide and 6mL of deionized water under ultrasonic waves, reacting for 10 hours at 160 ℃, carrying out hydrothermal reaction, washing and soaking the product by using the deionized water and absolute ethyl alcohol, precooling for 1.5 hours at-40 ℃, and freeze-drying for 24 hours at-70 ℃ to obtain the magnetically-drivable graphene aerogel composite material; wherein Fe3O4The mass ratio of the/BiOBr, the lysine and the graphene oxide is 52.5:30: 4.5.
The magnetically-drivable graphene aerogel composite material prepared by the embodiment is referred to as Fe for short3O4/BiOBr/GE-2，Fe3O4The mass ratio of nanoparticles, BiOBr and graphene is preferably 160:190: 3.
Example 3
A preparation method of magnetically-drivable graphene aerogel composite material comprises the following steps:
fe was produced by the method of steps (1) to (4) of example 13O4/BiOBr。
0.4g of Fe obtained in the step (3)3O4Mixing BiOBr with 200mg of lysine, 30mg of graphene oxide and 6mL of deionized water under ultrasonic waves, reacting for 10 hours at 160 ℃, carrying out hydrothermal reaction, washing and soaking the product with deionized water and absolute ethyl alcohol, precooling for 1.5 hours at-40 ℃, and freeze-drying for 24 hours at-70 ℃ to obtain the magnetically-drivable graphene aerogel composite material; wherein Fe3O4The mass ratio of the/BiOBr to the lysine to the graphene oxide is 60:30: 4.5.
The magnetically-drivable graphene aerogel composite material prepared by the embodiment is referred to as Fe for short3O4/BiOBr/GE-3，Fe3O4The mass ratio of nanoparticles, BiOBr and graphene is preferably 180:220: 3.
Test example 1
(1) Scanning Electron microscopy on Fe prepared in example 13O4The nanoparticles were tested to obtain Fe as prepared in example 13O4The SEM image of the nanoparticles is shown in figure 1. Wherein (a) and (b) are each Fe3O4SEM images of nanoparticles at different magnifications.
By sweepingScanning Electron microscope for Fe prepared in example 13O4BiOBr test gave Fe as prepared in example 13O4SEM image of/BiOBr is shown in FIG. 2. Wherein (c) and (d) are each Fe3O4SEM images of/BiOBr at different magnifications.
Scanning Electron microscopy on Fe prepared in example 13O4Test with/BiOBr/GE-1 to obtain Fe as prepared in example 23O4The SEM image of/BiOBr/GE-1 is shown in FIG. 3. Wherein (e) and (f) are each Fe3O4SEM images of/BiOBr/GE-1 at different magnifications.
As can be seen from FIGS. 1(a, b), Fe3O4The nanoparticles are shown as spherical structures with regular size, the size of the spheres is about 20-25 nm. From FIG. 2(c, d), Fe can be seen3O4The nano particles are compounded with BiOBr to form spherical Fe3O4The nanoparticles are embedded in the BiOBr lamellar structure. From FIG. 3(e, f) Fe3O4Spherical Fe after being compounded with BiOBr and graphene oxide3O4The BiOBr lamellar structures embedded with the nano particles are mutually fused into a larger lamellar structure, and a multi-cavity structure is arranged in the middle of the lamellar structure, namely Fe3O4the/BiOBr heterojunction is anchored between the graphene networks.
(2) XRD diffractometer for Fe prepared in example 13O4Nanoparticles, Fe3O4BiOBr and Fe3O4the/BiOBr/GE-1 test gave Fe as prepared in example 13O4Nanoparticles, Fe3O4BiOBr and Fe3O4The XRD pattern of/BiOBr/GE-1 is shown in FIG. 4.
As can be seen from FIG. 4, Fe3O4The diffraction peaks of the nanoparticles correspond to those of a standard card (JCPDS 19-0629); BiOBr diffraction peak and standard card ((JCPDS No. 73-2061); Fe3O4The XRD pattern of BiOBr not only shows the appearance of Fe3O4The diffraction peak corresponding to the nano-particles also appears, and the diffraction peak corresponding to the BiOBr shows that the reaction is successful and Fe is reacted3O4Nano-particlesThe granules and BiOBr are compounded together. In an XRD (X-ray diffraction) pattern, an inset is pure reduced graphene oxide aerogel generated by directly crosslinking commercial graphene oxide according to the synthesis process, and a (002) crystal face of a corresponding superposed graphene layer appears near 21.8 ℃; and for Fe3O4BiOBr/GE-1, with the corresponding pure BiOBr and Fe appearing in the XRD pattern3O4But a diffraction peak with a significantly different shift from the BiOBr diffraction peak appears near 24.5 °, which may be the (002) crystal plane corresponding to the superimposed graphene layer belonging to the graphene aerogel, or the (101) crystal plane corresponding to the diffraction peak belonging to the BiOBr, and this may be both the result of the formed graphene aerogel and Fe3O4the/BiOBr material has strong diffraction peak shift caused by interaction, which shows that the reaction succeeds in converting Fe3O4The nanoparticles, the BiOBr and the graphene are compounded together.
(3) Use of XPS photoelectron spectrometer for Fe prepared in example 13O4Nanoparticles, Fe3O4BiOBr and Fe3O4the/BiOBr/GE-1 test gave Fe as prepared in example 13O4Nanoparticles, Fe3O4BiOBr and Fe3O4XPS map of/BiOBr/GE-1 is shown in FIG. 5.
Shown in FIG. 5 as pure Fe3O4Nanoparticles, Fe3O4BiOBr and Fe3O4The full spectrogram of/BiOBr/GE-1 contains different elements, and the comparison proves that Fe3O4Five elements of Fe, Br, Bi, C and O exist in the/BiOBr/GE-1.
Combining FIG. 5 with FIG. 4, Fe prepared in example 1 was obtained3O4Nanoparticles, Fe3O4BiOBr and Fe3O4FIG. 6 shows a high resolution XPS map of Fe2p for/BiOBr/GE-1. As can be seen from FIG. 6, it is compared with pure Fe3O4Compared with the nano-particles, Fe after being compounded with BiOBr3O4BiOBr and Fe after continuing to react with reduced graphene oxide3O4in/BiOBr/GE-1, Fe2p7/2And Fe2p5/2Is apparently combined withAnd (4) moving.
Combining FIG. 5 with FIG. 4, Fe prepared in example 1 was obtained3O4BiOBr and Fe3O4The high resolution XPS map of Bi4f for/BiOBr/GE-1 is shown in FIG. 7. As can be seen from FIG. 7, Bi4f7/2And Bi4f5/2The binding energy of (A) also changed significantly, which indicates that Fe3O4With BiOBr and Fe3O4The strong interface interaction exists between the BiOBr and the reduced graphene oxide.
(4) The Fe prepared in example 1 was subjected to UV-visible absorption spectroscopy3O4Nanoparticles, Fe3O4BiOBr and Fe3O4the/BiOBr/GE-1 test gave Fe as prepared in example 13O4Nanoparticles, Fe3O4BiOBr and Fe3O4The ultraviolet-visible absorption spectrum of/BiOBr/GE-1 is shown in FIG. 8.
As can be seen from FIG. 8, pure Fe3O4Nanoparticles, Fe3O4BiOBr and Fe3O4the/BiOBr/GE-1 has good light absorption in a visible light region; and the BiOBr are compounded and modified, particularly the compounded Fe3O4The aerogel generated after the BiOBr and the graphene oxide are subjected to the composite reaction again has extremely high visible light absorption efficiency, and the graphene aerogel material subjected to the composite modification has the advantages that the visible light absorption range and the absorption intensity are obviously improved, and the photocatalytic performance of the graphene aerogel material under sunlight is favorably improved.
Application example 1
Fe prepared in example 13O4The application of BiOBr/GE-1 in the photocatalytic degradation experiment of pollutant potassium dichromate comprises the following steps:
(1) preparing a color developing agent: weighing 0.2g of diphenyl carbonyl dihydrazide, dispersing and dissolving in 50mL of ethanol, slowly adding ultrapure water to a constant volume of 100mL, shaking up, transferring into a brown bottle, and storing at a low temperature of 4 ℃;
diluting the sulfuric acid solution: 50mL of pure sulfuric acid was slowly added to 50mL of ultrapure water;
diluting the phosphoric acid solution: 50mL of pure phosphoric acid was slowly added to 50mL of ultrapure water.
(2) 50mg of Fe prepared in example 13O4the/BiOBr/GE-1 is dispersed in 50mL potassium dichromate solution (the concentration is 10mg/L), and is stirred for a period of time after being uniformly dispersed so as to reach adsorption and desorption balance; then transferring the dispersion liquid into a photoreaction quartz cup with circulating condensed water; 300W under simulated sunlight irradiation, sampling at intervals of 5-20 min after the photocatalytic reaction starts, after 30min of reaction, magnetically separating the extracted dispersion, measuring 6mL of supernatant, transferring the supernatant into a quartz cuvette, dropwise adding 0.16mL of the color developing agent prepared in the step (1), 40 mu L of dilute sulfuric acid solution and 40 mu L of dilute phosphoric acid solution, and measuring the absorbance of the diluted phosphoric acid solution at the maximum absorption wavelength of 540nm at different photocatalytic times by using an ultraviolet-visible spectrophotometer to obtain Fe at different times3O4The photocatalytic degradation effect of/BiOBr/GE-1 on potassium dichromate solution is shown in FIG. 9.
As can be seen from FIG. 9, in the dark reaction, a single magnetic powder material Fe3O4The nano particles can absorb and desorb about 17.9 percent of potassium dichromate in 30min, while Fe3O4The adsorption and desorption capacity of BiOBr/GE-1 to potassium dichromate can reach about 65.1 percent in 30 min; after illumination, the degradation degree of various catalytic systems to the potassium dichromate is increased along with the increase of illumination, but the degradation degree difference is obvious, and Fe3O4The nano particles can only degrade 18.9 percent of potassium dichromate within 50min, while Fe3O4the/BiOBr/GE-130 min can degrade the potassium dichromate to 99.8 percent, and after the catalytic degradation, the material can be directly recycled by a magnet.
Application example 2
Fe prepared in example 23O4The application of/BiOBr/GE-2 in the photocatalytic degradation experiment of pollutant potassium dichromate comprises the following specific processes and steps:
50mg of Fe prepared in example 23O4the/BiOBr/GE-2 is dispersed in 50mL potassium dichromate solution (the concentration is 10mg/L), and is stirred for a period of time after being uniformly dispersed so as to reach adsorption and desorption balance; the dispersion is then transferred to a circulating condensateThe photoreaction quartz cup; 300W under simulated sunlight irradiation, sampling at intervals of 5-20 min after the photocatalytic reaction starts, after 30min of reaction, magnetically separating the extracted dispersion, measuring 6mL of supernatant, transferring the supernatant into a quartz cuvette, dropwise adding 0.16mL of color developing agent prepared in the step (1) of application example 1, 40 mu L of dilute sulfuric acid solution and 40 mu L of dilute phosphoric acid solution, and measuring the absorbance of the diluted phosphoric acid solution at the maximum absorption wavelength of 540nm at different photocatalytic times by using an ultraviolet-visible spectrophotometer to obtain Fe at different times3O4The results of the photocatalytic degradation effect of/BiOBr/GE-2 on the potassium dichromate solution are shown in FIG. 9.
As can be seen from FIG. 9, in the dark reaction, a single magnetic powder material Fe3O4The nano particles can absorb and desorb about 17.9 percent of potassium dichromate in 30min, while Fe3O4The absorption and desorption amount of/BiOBr/GE-2 to potassium dichromate can reach about 40 percent in 30 min; after illumination, the degradation degree of various catalytic systems to the potassium dichromate is increased along with the increase of illumination, but the degradation degree difference is obvious, and Fe3O4The nano particles can only degrade 18.9 percent of potassium dichromate within 50min, while Fe3O4the/BiOBr/GE-230 min can degrade the potassium dichromate to 88 percent, and after the catalytic degradation, the material can be directly recycled by a magnet.
Application example 3
Fe prepared in example 33O4The application of/BiOBr/GE-3 in the photocatalytic degradation experiment of pollutant potassium dichromate comprises the following specific processes and steps:
50mg of Fe prepared in example 33O4the/BiOBr/GE-3 is dispersed in 50mL potassium dichromate solution (the concentration is 10mg/L), and is stirred for a period of time after being uniformly dispersed so as to reach adsorption and desorption balance; then transferring the dispersion liquid into a photoreaction quartz cup with circulating condensed water; 300W under simulated sunlight irradiation, sampling at intervals of 5-20 min after the photocatalytic reaction starts, magnetically separating the extracted dispersion liquid after 30min of reaction, measuring 6mL of supernatant, transferring the supernatant into a quartz cuvette, dropwise adding 0.16mL of color developing agent prepared in the step (1) of application example 1, 40 mu L of dilute sulfuric acid solution and 40 mu L of dilute phosphoric acid solution, and using ultraviolet ion-dopingMeasuring the absorbance of the Fe film at the maximum absorption wavelength of 540nm under different photocatalytic times on a visible spectrophotometer to obtain the Fe film at different times3O4The photocatalytic degradation effect of/BiOBr/GE-3 on potassium dichromate solution is shown in FIG. 9.
As can be seen from FIG. 9, in the dark reaction, a single magnetic powder material Fe3O4The nano particles can absorb and desorb about 17.9 percent of potassium dichromate in 30min, while Fe3O4The absorption and desorption amount of/BiOBr/GE-3 to potassium dichromate can reach about 62.5 percent in 30 min; after illumination, the degradation degree of various catalytic systems to the potassium dichromate is increased along with the increase of illumination, but the degradation degree difference is obvious, and Fe3O4The nano particles can only degrade 18.9 percent of potassium dichromate within 50min, while Fe3O4the/BiOBr/GE-330 min can degrade the potassium dichromate to 97.5 percent, and after the catalytic degradation, the material can be directly recycled by a magnet.
From the experimental data of application example 1, it can be seen that the photolysis effect of potassium dichromate is not obvious without a catalyst. Under light irradiation, with pure Fe3O4Compared with nano particles, the photolysis experiment of the nano particles and potassium dichromate under dark conditions proves that Fe3O4The adsorption and photodegradation performance of the/BiOBr/GE aerogel material to potassium dichromate are obviously improved, and the adsorption performance and the photodegradation performance of the material follow the Fe3O4The addition proportion of BiOBr and the concentration of graphene oxide are changed, and Fe3O4the/BiOBr/GE-1 aerogel has higher adsorption performance and photodegradation performance, can degrade potassium dichromate to about 99.8 percent in 30min under simulated sunlight, and Fe under the same condition3O4BiOBr/GE-2 aerogel, Fe3O4BiOBr/GE-3 aerogel and pure Fe3O4The nanoparticles can degrade about 97.5% and 87.5% and 19.4% of potassium dichromate, which shows that the magnetically drivable graphene aerogel composite material prepared by the invention has excellent photocatalytic effect.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and amendments can be made without departing from the principle of the present invention, and these modifications and amendments should also be considered as the protection scope of the present invention.
Claims (10)
1. A preparation method of a magnetically drivable graphene aerogel composite material comprises the following steps:
(1) mixing Fe3O4Mixing the nano particles, bismuth salt, citric acid and deionized water to obtain mixed slurry;
(2) dropwise adding a hexadecyl trimethyl ammonium bromide solution into the mixed slurry obtained in the step (1), and stirring to obtain a precursor;
(3) drying the precursor obtained in the step (2) to obtain Fe3O4/BiOBr；
(4) Fe obtained in the step (3)3O4Mixing the BiOBr with lysine, graphene oxide and deionized water, and carrying out hydrothermal reaction to obtain the magnetically-driven graphene aerogel composite material.
2. The method according to claim 1, wherein the Fe in the step (1)3O4The nano particles are spherical particles, and the particle size of the spherical particles is 20-30 nm.
3. The method according to claim 1, wherein the Fe in the step (1)3O4The mass ratio of the nano particles, the bismuth salt, the citric acid and the hexadecyl trimethyl ammonium bromide in the step (2) is (10-15): (24-25): (3-4): (18-18.5).
4. The method according to claim 1, wherein the stirring temperature in the step (2) is 25 to 35 ℃ and the stirring time is 0.5 to 1 hour.
5. The preparation method according to claim 1, wherein the dropping rate in the step (2) is 0.025 to 0.075 mL/s.
6. The method according to claim 1, wherein the drying temperature in step (3) is 50 to 70 ℃ and the drying time is 10 to 15 hours.
7. The method according to claim 1, wherein the Fe in the step (4)3O4The mass ratio of the/BiOBr, the lysine and the graphene oxide is (50-66.7): 30-35): 3.5-5.
8. The preparation method according to claim 1, wherein the temperature of the hydrothermal reaction in the step (4) is 160 to 180 ℃ and the time of the hydrothermal reaction is 8 to 15 hours.
9. Magnetically drivable graphene aerogel composite material prepared by the preparation method of any one of claims 1 to 8, comprising Fe3O4Nanoparticles, BiOBr and graphene, Fe3O4The nano particles are embedded between the BiOBr sheets to form Fe3O4A BiOBr heterojunction, said Fe3O4the/BiOBr heterojunction is anchored between the graphene networks.
10. Use of the magnetically drivable graphene aerogel composite of claim 9 for photocatalytic degradation of inorganic and/or organic pollutant waste water solutions.
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