CN114733537B - Magnetically-driven graphene aerogel composite material and preparation method and application thereof - Google Patents
Magnetically-driven graphene aerogel composite material and preparation method and application thereof Download PDFInfo
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 120
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 119
- 239000004964 aerogel Substances 0.000 title claims abstract description 62
- 239000002131 composite material Substances 0.000 title claims abstract description 55
- 238000002360 preparation method Methods 0.000 title claims abstract description 29
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims abstract description 72
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 29
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims abstract description 28
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- 238000000034 method Methods 0.000 claims description 30
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- 238000011084 recovery Methods 0.000 abstract description 2
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- MCPLVIGCWWTHFH-UHFFFAOYSA-L methyl blue Chemical compound [Na+].[Na+].C1=CC(S(=O)(=O)[O-])=CC=C1NC1=CC=C(C(=C2C=CC(C=C2)=[NH+]C=2C=CC(=CC=2)S([O-])(=O)=O)C=2C=CC(NC=3C=CC(=CC=3)S([O-])(=O)=O)=CC=2)C=C1 MCPLVIGCWWTHFH-UHFFFAOYSA-L 0.000 description 1
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/06—Halogens; Compounds thereof
- B01J27/128—Halogens; Compounds thereof with iron group metals or platinum group metals
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- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
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Abstract
The invention provides a magnetically-driven graphene aerogel composite material and a preparation method and application thereof, and belongs to the technical field of catalytic materials. The invention takes cetyl trimethyl ammonium bromide as a cationic surfactant, and can provide Br ions to interact with bismuth nitrate and citric acid to generate BiOBr; the invention makes Fe through hydrothermal reaction 3 O 4 The BiOBr is uniformly embedded between graphene sheets, so that the photocatalytic activity of the composite material is ensured; the invention introduces Fe 3 O 4 The recovery of the composite material can be realized; the reagent adopted by the invention is environment-friendly, and can solve the technical problem of environmental protection when preparing the photocatalyst. The data of the embodiment show that the composite material prepared by the preparation method can degrade potassium dichromate to 99.8% within 30min, and the material can be directly recycled through a magnet after catalytic degradation.
Description
Technical Field
The invention relates to the technical field of catalytic materials, in particular to a magnetically-driven graphene aerogel composite material, and a preparation method and application thereof.
Background
In many semiconductor photocatalysts, a single-component semiconductor is subjected to photoexcitation, and then rapid recombination of hole/electron pairs is usually generated, so that the problem of low quantum efficiency is caused, and therefore, practical photocatalytic degradation application is greatly limited. For example, bismuth-based semiconductor bismuth oxyhalide, biOX (X=Cl, br or I), as an emerging photocatalytic material, has a narrow and tunable band gap (about 2.3 eV), is non-toxic and has high oxidation potential, and shows good photocatalytic potential. Nevertheless, like many semiconductors, single component bisox charge separation differences limit their photocatalytic activity.
In recent years, the regulation of semiconductor microstructures or carrier-supported carrier transport carriers has been considered as an effective strategy for accelerating interfacial charge transfer and improving photocatalytic activity thereof. For example, compounding other semiconductor materials, adding carbon-based materials with excellent optics and excellent electron transfer properties, including carbon nanotubes, carbon quantum dots, graphene quantum dots, and the like, accelerates and delays recombination of electron-hole species in the semiconductor while improving the microstructure, can improve the activity of the photocatalyst, but has limited improvement in the activity of the photocatalyst.
In recent years, the assembly of low-dimensional nanostructures into three-dimensional hierarchical micro/nanostructures is considered as a promising approach to solve the above-mentioned problems. In general, aerogels are three-dimensional networks composed of numerous micropores and mesopores interpenetrated, which are ideal support frames with larger specific surface area, rapidly transportable pores and surface sites for anchoring catalysts; particularly, graphene with a two-dimensional structure and excellent conductivity and extremely large load specific surface area is used as a photo-generated electron migration carrier of the heterogeneous semiconductor, so that a continuous channel can be provided for electrons and ions, and electron and ion transfer between mutual interfaces is accelerated, and further the separation efficiency of photo-generated electrons and holes is effectively improved. However, the development of inorganic nano-powder is mostly carried out under high temperature and high pressure or by using toxic or corrosive solvents, and the development of subsequent aerogel is mostly carried out by using toxic or corrosive crosslinking agents, which causes the technical problem of environmental protection when preparing photocatalyst.
On the other hand, the inorganic powder material as a semiconductor photocatalyst has serious self-aggregation problems due to its large specific surface area and more exposed active sites, and the inorganic powder material has a problem of difficult recovery, which inevitably limits its further applications.
Therefore, it is needed 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-driven 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-driven graphene aerogel composite material, which comprises the following steps:
(1) Fe is added to 3 O 4 Mixing the nano particles, bismuth salt, citric acid and deionized water to obtain mixed slurry;
(2) Dripping 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 Fe 3 O 4 /BiOBr；
(4) Fe obtained in the step (3) 3 O 4 And mixing the BiOBr with lysine, graphene oxide and deionized water, and performing hydrothermal reaction to obtain the graphene aerogel composite material capable of being driven magnetically.
Preferably, fe in the step (1) 3 O 4 The nano particles are spherical particles, and the particle size of the spherical particles is 20-30 nm.
Preferably, fe in the step (1) 3 O 4 The mass ratio of the nano particles to the bismuth salt to the citric acid to the cetyl trimethyl ammonium bromide in the step (2) is (10-15): 24-25): 3-4): 18-18.5.
Preferably, the temperature of stirring 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 the step (4) 3 O 4 The 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 the magnetically drivable graphene aerogel composite material prepared by the preparation method, which comprises Fe 3 O 4 Nanoparticles, biOBr and graphene, the Fe 3 O 4 Nano particles are inlaid between BiOBr sheets to form Fe 3 O 4 BiOBr heterojunction, fe 3 O 4 the/BiOBr heterojunction is anchored between graphene networks.
The invention also provides application of the magnetically-driven graphene aerogel composite material in photocatalytic degradation of inorganic and/or organic pollutant wastewater solutions.
The invention provides a preparation method of a magnetically-driven graphene aerogel composite material, which comprises the following steps: fe is added to 3 O 4 Mixing the nano particles, bismuth salt, citric acid and deionized water to obtain mixed slurry; dripping hexadecyl trimethyl ammonium bromide solution into the mixed slurry, and stirring to obtain a precursor; drying the precursor to obtain Fe 3 O 4 BiOBr; the Fe is 3 O 4 And mixing the BiOBr with lysine, graphene oxide and deionized water, and performing hydrothermal reaction to obtain the graphene aerogel composite material capable of being driven magnetically. The invention introduces Fe in the preparation of composite material 3 O 4 The nano particles have excellent magnetism, and can solve the problem that the graphene aerogel composite material is difficult to recycle. The invention takes cetyl trimethyl ammonium bromide as cationic surfactant, can form micelle for regulating and controlling the morphology of a semiconductor in a solution interface, plays a good role in dispersion, can provide Br ions, and can interact with bismuth nitrate and citric acid to generate BiOBr; the invention can control the reaction process by dripping the hexadecyl trimethyl ammonium bromide solution into the mixed slurry and reacting under stirring, so that the precursor distribution is more uniform, the thickness and the size of the BiOBr sheet layer formed in the drying process are more uniform, and the method is more favorable for Fe 3 O 4 The nano particles are uniformly embedded between the BiOBr sheets, so that the photocatalytic activity of the composite material is improved. The invention uses Fe 3 O 4 Carrying out hydrothermal reaction on/BiOBr, lysine and graphene oxide, wherein the lysine and the graphene oxide can be mutually crosslinked to generate amidation reaction, and the graphene oxide is converted into reduced graphene oxide so as to further enable Fe to be obtained 3 O 4 and/BiOBr is uniformly embedded between graphene sheets, so that the photocatalytic activity of the composite material is ensured. The data of the embodiment show that the composite material prepared by the preparation method can degrade potassium dichromate to 99.8% within 30min, and the material can be directly recycled through a magnet after catalytic degradation.
The preparation method provided by the invention adopts the environment-friendly reagent, and can solve the technical problem of environmental protection existing in the preparation of the photocatalyst.
Drawings
FIG. 1 shows Fe prepared in example 1 of the present invention 3 O 4 SEM image of nanoparticles; (a) And (b) are each Fe 3 O 4 SEM images of nanoparticles at different magnifications;
FIG. 2 shows Fe prepared in example 1 of the present invention 3 O 4 SEM image of BiOBr; (c) And (d) are each Fe 3 O 4 SEM images of bitbr at different magnifications;
FIG. 3 shows Fe prepared in example 1 of the present invention 3 O 4 SEM image of/BiOBr/GE-1; (e) And (f) are each Fe 3 O 4 SEM images of/BiOBr/GE-1 at various magnifications;
FIG. 4 shows Fe prepared in example 1 of the present invention 3 O 4 Nanoparticles, fe 3 O 4 BiOBr and Fe 3 O 4 XRD of/BiOBr/GE-1;
FIG. 5 shows Fe prepared in example 1 of the present invention 3 O 4 Nanoparticles, fe 3 O 4 BiOBr and Fe 3 O 4 XPS diagram of/BiOBr/GE-1;
FIG. 6 shows Fe prepared in example 1 of the present invention 3 O 4 Nanoparticles, fe 3 O 4 BiOBr and Fe 3 O 4 Fe2p high resolution XPS diagram of/BiOBr/GE-1;
FIG. 7 shows Fe prepared in example 1 of the present invention 3 O 4 BiOBr and Fe 3 O 4 Bi4f high resolution XPS diagram of/BiOBr/GE-1;
FIG. 8 shows Fe prepared in example 1 of the present invention 3 O 4 Nanoparticles, fe 3 O 4 BiOBr and Fe 3 O 4 An ultraviolet visible absorption spectrum diagram of/BiOBr/GE-1;
FIG. 9 is a graph showing the effect of photocatalytic degradation on potassium dichromate solutions according to application examples 1 to 3 of the present invention.
Detailed Description
The invention provides a preparation method of a magnetically-driven graphene aerogel composite material, which comprises the following steps:
(1) Fe is added to 3 O 4 Mixing the nano particles, bismuth salt, citric acid and deionized water to obtain mixed slurry;
(2) Dripping 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 Fe 3 O 4 /BiOBr；
(4) Fe obtained in the step (3) 3 O 4 And mixing the BiOBr with lysine, graphene oxide and deionized water, and performing hydrothermal reaction to obtain the graphene aerogel composite material capable of being driven magnetically.
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.
The invention uses Fe 3 O 4 The nano particles, bismuth salt, citric acid and deionized water are mixed to obtain mixed slurry.
At the bookIn the invention, the Fe 3 O 4 The nanoparticles are preferably spherical particles. In the present invention, the Fe 3 O 4 The nano particles are narrow band gap semiconductors, and the nano size enables the nano particles to have good conductive metal characteristics and plays an important role in electron transfer; when the Fe is 3 O 4 When the nano particles are spherical particles, the nano particles can form heterojunction with a sphere-plate mosaic structure with the BiOBr, and the combination capability of the nano particles and the BiOBr is strong, so that the light absorption range and the light absorption efficiency of the nano particles are widened, the strength of a built-in electric field is enhanced, the separation efficiency of photo-generated carriers is further improved, and the photocatalytic activity is improved; and due to Fe 3 O 4 The nano particles have excellent ferromagnetism and can enable Fe to be formed 3 O 4 The 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 Fe 3 O 4 The particle diameter of the nanoparticle is preferably 20 to 30nm, more preferably 25 to 28nm. In the present invention, the Fe 3 O 4 When the particle diameter of the nanoparticle is in the above range, fe is more advantageous 3 O 4 The nano particles are well embedded in the BiOBr sheet, so that heterojunction interaction weakening of the ball-sheet mosaic structure caused by oversized can be prevented.
The invention relates to the Fe 3 O 4 The source of the nanoparticle is not particularly limited, and can be prepared by commercially available products known to those skilled in the art or by a known preparation method, and can be used to make Fe 3 O 4 The nanoparticles are spherical particles, and the particle size is within the above range.
In the present invention, the Fe 3 O 4 The method for preparing the nano-particles preferably comprises the following steps: mixing ferrous salt, ferric salt and ammonia water, and performing double decomposition reaction to obtain a precursor; aging the precursor to obtain Fe 3 O 4 And (3) nanoparticles.
In the invention, ferrous salt, ferric salt and ammonia water are preferably mixed to obtain the precursor.
In the method for mixing the ferrous salt, the ferric salt and the ammonia water, the ferrous salt and the ferric salt are preferably dissolved in deionized water to obtain an iron salt solution, and the ammonia water is dropwise added into the iron salt solution after the iron salt solution is heated to 80-100 ℃, preferably 90 ℃. In the invention, the double decomposition reaction occurs when the ferrous salt, the ferric salt and the ammonia water are mixed, the ammonia water is slowly dripped into the ferric salt solution after the ferric salt solution is heated to 80-100 ℃, the excessive temperature can be prevented, the concentration of the solution is easy to change, and the precipitation can be rapidly generated in the process of dripping the ammonia water, so that the full formation of the precipitation of the ferric salt is more facilitated.
In the present invention, the dropping rate is preferably 1mL of ammonia water added every 1 min. In the present invention, when the dropping rate is within the above range, the reaction rate can be controlled so that the iron salt and the aqueous ammonia are sufficiently reacted.
In the present invention, the dropwise addition of the aqueous ammonia to the iron salt solution is preferably performed under stirring. In the invention, the stirring can promote the precipitation generated by the reaction of the ferric salt and the ammonia water to be uniformly distributed in the reaction system, which is 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 substances 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 present invention, the ferrous and ferric salts are used for preparing Fe 3 O 4 The nanoparticles provide iron ions; when the ratio of the amounts of the substances of the ferrous salt and the ferric salt is in the above range, the reaction of the ferrous salt, the ferric salt and the ammonia water to form a precipitate is more favorable for preparing the magnetic Fe 3 O 4 And (3) nanoparticles. In the present invention, the ferrous salt is preferably FeCl 2 ·4H 2 O, the trivalent iron salt is preferably and FeCl 3 ·6H 2 O。
In the present invention, the ammonia water preferably has an ammonia mass fraction concentration of 28 to 30%. In the invention, when the ammonia mass fraction concentration of the ammonia water is in the above range, the reaction of ferrous salt, ferric salt and ammonia water to form a precipitate is more favorable. In the present invention, the amount of the substance of the divalent iron salt is 1.5 to 2.5mol, the amount of the substance of the trivalent iron salt is 4.5 to 5.5mol, and the amount of the ammonia water added is preferably 5 to 8mL, more preferably 6mL.
After the precursor is obtained, the precursor is preferably aged to obtain Fe 3 O 4 And (3) nanoparticles.
In the present invention, the temperature of the aging is preferably 80 to 100 ℃, 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 within the above ranges, the precipitate formed by the formed iron salt and ammonia water is hydrolyzed, the particle length is large, the crystal form is perfect and the crystal form is transformed, and finally spherical Fe is formed 3 O 4 And (3) nanoparticles. In the present invention, the aging is preferably performed under stirring.
After the aging is finished, the method preferably carries out centrifugation, magnetic adsorption, washing and drying on the system obtained by the aging in sequence to obtain Fe 3 O 4 And (3) nanoparticles. In the present invention, the centrifugation, magnetic adsorption, washing and drying can remove Fe 3 O 4 Impurities on the nanoparticle surface and obtain dry Fe 3 O 4 And (3) nanoparticles. The operation modes of centrifugation, magnetic adsorption, washing and drying are not particularly limited, and the operation modes of centrifugation, magnetic adsorption, washing and drying which are well known to those skilled in the art can be adopted. In the present invention, the washing reagent is preferably deionized water, and the number of times of washing is preferably 3 to 5 times; the drying temperature is preferably 60 ℃, and the drying time is preferably 12 hours; the drying mode is preferably vacuum drying.
In the present invention, the Fe 3 O 4 The preparation method of the nano-particles is Fe prepared by the method 3 O 4 The nano particles are regular spherical nano particles, and the Fe is 3 O 4 The particle diameter of the nanoparticles is preferably in the range of 20 to 30nm, more preferably 25 to 30nm.
In the present invention, the bismuth salt is preferably bismuth nitrate pentahydrate. In the present invention, the bismuth salt is capable of providing a bismuth source for BiOBr, and is capable of reacting with citric acid and cetyltrimethylammonium bromide to form BiOBr.
In the present invention, the citric acid is capable of reacting with bismuth salt and cetyltrimethylammonium bromide to form BiOBr.
In the present invention, the Fe 3 O 4 The mass ratio of the nano particles, bismuth salt, citric acid and cetyl trimethyl ammonium bromide is preferably (10-15): 24-25): 3-4): 18-18.5, more preferably (12-14): 24-24.5): 3.5-4): 18-18.5. In the present invention, the Fe 3 O 4 When the mass ratio of the nano particles, bismuth salt, citric acid and cetyltrimethylammonium bromide is in the above range, the bismuth salt, citric acid and cetyltrimethylammonium bromide can be sufficiently reacted to form the tablet-shaped BiOBr, and Fe can be caused 3 O 4 Nanoparticle modification to form Fe on BiOBr nanoplatelets 3 O 4 The BiOBr heterogeneous semiconductor is more beneficial to expanding the light absorption range and efficiency, enhancing the strength of a built-in electric field, and further promoting the separation efficiency of photo-generated carriers, thereby improving the photocatalytic activity.
The invention is not particularly limited in the amount of deionized water, and is based on Fe 3 O 4 The quality of the nano particles, bismuth salt, citric acid and hexadecyl trimethyl ammonium bromide is adjusted.
The invention relates to the Fe 3 O 4 The operation method of mixing the nanoparticles, bismuth salt, citric acid and deionized water is not particularly limited, and the components can be uniformly mixed by a mixing method well known to those skilled in the art. In the present invention, the Fe 3 O 4 The method of operation for mixing the nanoparticles, bismuth salt, citric acid and deionized water is preferably ultrasonic. The invention has no special limitation on the power and time of the ultrasonic wave, 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 the mixed slurry is stirred to obtain a 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 BiOBr is generated by interaction of bismuth salt and citric acid.
In the present invention, the concentration of the cetyltrimethylammonium bromide solution is preferably 0.18 to 0.28mg/mL. In the present invention, the concentration of the cetyltrimethylammonium bromide solution in the above range is more favorable for the interaction of cetyltrimethylammonium bromide, bismuth salt and citric acid to form 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, so that hexadecyltrimethylammonium bromide forms a micelle for regulating and controlling the morphology of a 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 0.05mL/s. In the invention, the cetyl trimethyl ammonium bromide solution is added dropwise to the bismuth salt and Fe 3 O 4 When the mixed slurry of the nano particles and the citric acid is used, a layered interface is formed at the interface, the dripping speed is too high, the local concentration of surfactant micelles is inconsistent, the thickness and the size of the BiOBr lamellar structure are affected, and when the dripping speed is in the range, the BiOBr lamellar structure is more favorable to be uniform.
In the present invention, the temperature of the stirring is preferably 25 to 35 ℃, more preferably 30 to 35 ℃; the stirring time is preferably 25 to 60 minutes, more preferably 30 to 40 minutes. In the present invention, the stirring promotes the sufficient reaction of cetyltrimethylammonium bromide, bismuth salt and citric acid to form BiOBr, and causes Fe to 3 O 4 The nanoparticles are uniformly distributed between the BiOBr sheets.
After the stirring is completed, the invention preferably filters and washes the stirred system in turn to obtain the precursor. In the present invention, the filtering and washing can remove impurities from the surface of the precursor. The method of operation of the filtration and washing is not particularly limited, and the method of operation of the filtration and washing known to those skilled in the art may be employed. In the present invention, the filtration membrane is preferably a 0.45 μm polytetrafluoroethylene membrane.
After the precursor is obtained, the precursor is dried to obtain Fe 3 O 4 /BiOBr。
In the present invention, the drying can promote Fe 3 O 4 Nano particles are inlaid between BiOBr sheets to form Fe 3 O 4 BiOBr heterojunction. In the present invention, the drying temperature is preferably 50 to 70 ℃, more preferably 60 ℃; the drying time is preferably 10 to 15 hours, more preferably 12 hours.
Obtaining Fe 3 O 4 after/BiOBr, the invention will make the Fe 3 O 4 And mixing the BiOBr with lysine, graphene oxide and deionized water, and performing hydrothermal reaction to obtain the graphene aerogel composite material capable of being driven magnetically.
In the invention, the lysine can be cross-linked with graphene oxide and convert the graphene oxide into reduced graphene oxide to enable Fe to be formed 3 O 4 BiOBr is anchored between graphene networks to cooperatively construct Fe 3 O 4 BiOBr/graphene hybrid aerogel catalytic material capable of catalyzing Fe 3 O 4 The BiOBr nano-structure material is fixed on a three-dimensional reticular graphene aerogel carrier frame which has excellent conductivity and can be recycled, the three-dimensional reticular graphene aerogel carrier frame 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, accelerates electron and ion transfer between mutual interfaces, further effectively improves the photocatalytic activity and the recycling catalytic activity, and the three-dimensional reticular graphene aerogel carrier frame can further carry out Fe 3 O 4 The BiOBr is dispersed and fixed, the dispersion stability of the BiOBr is improved, aggregation is avoided, and meanwhile, the three-dimensional network framework with magnetism is used for more efficiently and cooperatively solving the aggregation and recycling problems of the nano material.
In the present invention, the Fe 3 O 4 The mass ratio of the BiOBr, the lysine and the graphene oxide is preferably (50-66.7): (30-35): (3.5-5), more preferably (60-66): (32-35): (4-5). In the present invention, the Fe 3 O 4 When the mass ratio of/BiOBr, lysine and graphene oxide is in the above range, fe can be contained 3 O 4 The BiOBr heterojunction is uniformly anchored between graphene networks, which is more beneficial to improving the catalytic performance of the composite material.
The amount of the water ions is not particularly limited in the present invention, and is based on Fe 3 O 4 And (3) adjusting the quality of the BiOBr, lysine and graphene oxide.
The invention relates to the Fe 3 O 4 The method of mixing/BiOBr with lysine, graphene oxide and deionized water is not particularly limited, and the above components may be uniformly mixed by a mixing method well known to those skilled in the art. In the present invention, the Fe 3 O 4 The manner in which/BiOBr is mixed with lysine, graphene oxide and deionized water is preferably ultrasonic. The invention has no special limitation on the power and time of the ultrasonic wave, and the ultrasonic wave can be regulated according to actual needs, so that the components can be uniformly mixed.
In the present invention, the temperature of the hydrothermal reaction is preferably 160 to 180 ℃, more preferably 170 to 180 ℃; the time of the hydrothermal reaction is preferably 8 to 15 hours, more preferably 10 hours. In the invention, the graphene oxide surface contains hydrophilic oxygen-containing groups such as carboxyl, hydroxyl and the like, and lysine is a water-soluble weak alkaline amino acid containing carboxyl and amino, and under high temperature and high pressure, amidation reaction can be carried out on the carboxyl and the amino, so that cross-linking polymerization is carried out to obtain macromolecules; when the temperature of the hydrothermal reaction is within the above range, the reaction of sufficiently crosslinking lysine and graphene oxide can be promoted, and Fe can be caused 3 O 4 BiOBr is anchored between graphene networks.
The apparatus for the hydrothermal reaction is not particularly limited, and a hydrothermal reaction apparatus known to those skilled in the art may be used. In the present invention, the apparatus for the hydrothermal reaction is preferably a hydrothermal reaction vessel. In the invention, the hydrothermal reaction kettle can provide a high-pressure airtight reaction environment for the hydrothermal reaction, so that the hydrothermal reaction is fully carried out, the full crosslinking reaction of lysine and graphene oxide is promoted, and Fe is caused 3 O 4 BiOBr anchor toAnd 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 graphene aerogel composite material capable of being magnetically driven.
In the present invention, the washing is preferably to wash the gel obtained after the hydrothermal reaction with deionized water and then soak in absolute ethanol. In the present invention, when the washing means is of the above 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 ℃, more preferably-40 ℃; the pre-cooling time is preferably 1 to 1.5 hours, more preferably 1.5 hours. In the invention, the gel obtained after the hydrothermal reaction can be in a low-temperature environment by the precooling, pores in the formed hydrogel can be kept, pore changes caused by unstable front and rear temperatures and instant water vapor pumping caused by direct vacuum freezing can be prevented, and further the prepared graphene aerogel composite material capable of being driven by magnetism is more favorable to have a richer network structure, and the catalytic performance of the composite material is improved.
In the present invention, the temperature of the freeze-drying is preferably-60 to-70 ℃, more preferably-65 to-70 ℃; the time for the freeze-drying is preferably 20 to 24 hours, more preferably 24 hours. According to the invention, the freeze-drying can remove the solvent in the solid, and the magnetically-driven graphene aerogel composite material can be kept to have a rich network structure, so that the catalytic activity of the composite material is improved.
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 BiOBr is generated by interaction with bismuth nitrate and citric acid; the invention can control the reaction process by dripping the hexadecyl trimethyl ammonium bromide solution into the mixed slurry and reacting under stirring, so that the precursor distribution is more uniform, the thickness and the size of the BiOBr sheet layer formed in the drying process are more uniform, and the method is more favorable for Fe 3 O 4 The nano particles are uniformly embedded between the BiOBr sheets, so that the photocatalytic activity of the composite material is improved. The invention uses Fe 3 O 4 Carrying out hydrothermal reaction on/BiOBr, lysine and graphene oxide, wherein the lysine and the graphene oxide can be mutually crosslinked to generate amidation reaction, and the graphene oxide is converted into reduced graphene oxide so as to further enable Fe to be obtained 3 O 4 and/BiOBr is uniformly embedded between graphene sheets, so that the photocatalytic activity of the composite material is ensured. In addition, the reagent adopted by the preparation method provided by the invention is environment-friendly, and the technical problem of environmental protection existing in the preparation of the photocatalyst can be solved.
The invention also provides the magnetically drivable graphene aerogel composite material prepared by the preparation method, which comprises Fe 3 O 4 Nanoparticles, biOBr and graphene, the Fe 3 O 4 Nano particles are inlaid between BiOBr sheets to form Fe 3 O 4 BiOBr heterojunction, fe 3 O 4 the/BiOBr heterojunction is anchored between graphene networks.
In the present invention, the Fe 3 O 4 The mass ratio of the nano particles to the BiOBr to the graphene is preferably (140-180): (160-220): (2.5-3.5), more preferably (160-180): (190-220): (2.5-3). In the present invention, the Fe 3 O 4 When the mass ratio of the nano particles to the BiOBr to the graphene is in the above range, the magnetically drivable graphene aerogel composite material has more excellent photocatalytic activity.
The magnetically-driven graphene aerogel composite material provided by the invention introduces graphene into Fe 3 O 4 BiOBr hetero semiconductor, co-construction of Fe 3 O 4 BiOBr/graphene hybrid aerogel catalytic material capable of catalyzing Fe 3 O 4 The BiOBr nano-structure powder material is fixed on a three-dimensional reticular graphene aerogel carrier frame which has excellent conductivity and can be recycled, and the three-dimensional reticular graphene aerogel carrier frame 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, and accelerates electrons and ions between mutual interfacesThe transfer is carried out, so that the photocatalytic activity and the circulating catalytic activity are effectively improved, the three-dimensional reticular graphene aerogel carrier frame can further disperse and fix nano powder materials, the dispersion stability of the nano powder materials is improved, the agglomeration is avoided, and meanwhile, the three-dimensional network frame with magnetism is expected to be more efficiently cooperated to solve the problems of the agglomeration and the recycling of the nano materials.
The invention also provides application of the magnetically-driven graphene aerogel composite material in photocatalytic degradation of inorganic and/or organic pollutant wastewater solutions.
The application method of the magnetically-driven graphene aerogel composite material in the photocatalytic degradation of the inorganic and/or organic pollutant wastewater solution is not particularly limited, and a method for treating wastewater by adopting a photocatalyst well known to a person skilled in the art can be adopted. In the invention, the application method of the magnetically drivable graphene aerogel composite material in the photocatalytic degradation of inorganic and/or organic pollutant wastewater solution is that the magnetically drivable graphene aerogel composite material is preferably suspended in the inorganic and/or organic pollutant wastewater solution, the pH value of the system is regulated to be neutral, preferably the pH value is 7, and the mixture is stirred for a period of time after uniform mixing to achieve adsorption balance; 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 contaminant wastewater solution preferably includes 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 preferably comprises one or more of methyl orange, rhodamine B and methyl blue. The concentration of the wastewater solution of the inorganic and/or organic pollutants is not particularly limited in the present invention, and the concentration of the wastewater solution which can be obtained by a person skilled in the art may be adopted. In the present invention, the concentration of the inorganic and/or organic contaminant wastewater solution is preferably 5 to 50mg/L, more preferably 10mg/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 solutions of the present invention will be clearly and completely described in the following in connection with the embodiments of the present invention. It will be apparent that the described embodiments are only some, but not all, embodiments of the invention. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Example 1
A preparation method of a magnetically driven graphene aerogel composite material comprises the following steps:
(1)Fe 3 O 4 the preparation method of the nano-particles comprises the following steps: 0.81g FeCl 2 ·4H 2 O、2.0g FeCl 3 ·6H 2 O is mixed with 110mL of deionized water to obtain a transparent orange solution, wherein the mass ratio of ferrous salt and ferric salt is 0.86:1; heating the transparent orange solution to 90 ℃, adding 1mL of ammonia water with the ammonia mass fraction concentration of 28-30% into the transparent orange solution every 1min, 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, the product is subjected to centrifugation, magnetic adsorption and washing with deionized water for 3 to 5 times, and vacuum drying is carried out for 12 hours at 60 ℃ to obtain Fe 3 O 4 And (3) nanoparticles.
(2) Fe prepared in the step (1) 3 O 4 The nanoparticle 0.25g was mixed with bismuth nitrate pentahydrate 0.485g, citric acid 0.072g and deionized water 7.5mL under ultrasonic conditions to obtain a mixed slurry.
(3) Preparing 0.364g of cetyltrimethylammonium bromide and 12.5mL of n-octane solution of cetyltrimethylammonium bromide, dripping the solution into the mixed slurry obtained in the step (2) at the rate of 0.05mL/s, stirring the mixed slurry for 25min at 25 ℃, filtering the product by a polytetrafluoroethylene filter membrane with the concentration of 0.45 mu m, and washing the product by deionized water to obtain a precursor; wherein Fe is 3 O 4 The mass ratio of the nano particles, the bismuth nitrate pentahydrate, the citric acid and the cetyl trimethyl ammonium bromide n-octyl is as follows12.5:24.25:3.6:18.2。
(4) Drying the precursor obtained in the step (3) for 12 hours at 60 ℃ to obtain Fe 3 O 4 /BiOBr；
(5) 0.4g of Fe obtained in the step (4) 3 O 4 Mixing BiOBr with 200mg of lysine, 25.2mg of graphene oxide and 6mL of deionized water under ultrasonic, reacting for 10 hours at 160 ℃, performing hydrothermal reaction, flushing and soaking deionized water and absolute ethyl alcohol, precooling for 1.5 hours at-40 ℃, and freeze-drying for 24 hours at-70 ℃ to obtain a magnetically drivable graphene aerogel composite material; wherein Fe is 3 O 4 The mass ratio of the BiOBr, the lysine and the graphene oxide is 60:30:3.78.
The magnetically drivable graphene aerogel composite material prepared in the embodiment is simply referred to as Fe 3 O 4 BiOBr/GE-1 wherein Fe 3 O 4 BiOBr stands for Fe 3 O 4 BiOBr heterojunction, GE stands for graphene, fe 3 O 4 The mass ratio of the nanoparticles, the BiOBr and the graphene is preferably 180:220:2.5.
Example 2
A preparation method of a magnetically driven graphene aerogel composite material comprises the following steps:
preparation of Fe by the method of example 1 Steps (1) to (4) 3 O 4 /BiOBr。
0.35g of Fe obtained in the step (3) 3 O 4 Mixing BiOBr with 200mg of lysine, 30mg of graphene oxide and 6mL of deionized water under ultrasonic, reacting for 10 hours at 160 ℃, performing hydrothermal reaction, flushing and soaking deionized water and absolute ethyl alcohol, pre-cooling for 1.5 hours at-40 ℃, and freeze-drying for 24 hours at-70 ℃ to obtain a magnetically drivable graphene aerogel composite material; wherein Fe is 3 O 4 The 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 in the embodiment is simply referred to as Fe 3 O 4 /BiOBr/GE-2，Fe 3 O 4 The mass ratio of the nanoparticles, the BiOBr and the graphene is preferably 160:190:3.
Example 3
A preparation method of a magnetically driven graphene aerogel composite material comprises the following steps:
preparation of Fe by the method of example 1 Steps (1) to (4) 3 O 4 /BiOBr。
0.4g of Fe obtained in the step (3) 3 O 4 Mixing BiOBr with 200mg of lysine, 30mg of graphene oxide and 6mL of deionized water under ultrasonic, reacting for 10 hours at 160 ℃, performing hydrothermal reaction, flushing and soaking deionized water and absolute ethyl alcohol, pre-cooling for 1.5 hours at-40 ℃, and freeze-drying for 24 hours at-70 ℃ to obtain a magnetically drivable graphene aerogel composite material; wherein Fe is 3 O 4 The mass ratio of the BiOBr, the lysine and the graphene oxide is 60:30:4.5.
The magnetically drivable graphene aerogel composite material prepared in the embodiment is simply referred to as Fe 3 O 4 /BiOBr/GE-3，Fe 3 O 4 The mass ratio of the nanoparticles, the BiOBr and the graphene is preferably 180:220:3.
Test example 1
(1) Fe prepared in example 1 was subjected to scanning electron microscopy 3 O 4 Nanoparticles were tested to give Fe prepared in example 1 3 O 4 An SEM image of the nanoparticle is shown in fig. 1. Wherein (a) and (b) are each Fe 3 O 4 SEM images of nanoparticles at different magnifications.
Fe prepared in example 1 was subjected to scanning electron microscopy 3 O 4 BiOBr was tested to give Fe prepared in example 1 3 O 4 An SEM of the/BiOBr is shown in FIG. 2. Wherein (c) and (d) are each Fe 3 O 4 SEM images of bitbr at different magnifications.
Fe prepared in example 1 was subjected to scanning electron microscopy 3 O 4 BiOBr/GE-1 to give Fe prepared in example 2 3 O 4 SEM of BiOBr/GE-1 is shown in FIG. 3. Wherein (e) and (f) are each Fe 3 O 4 SEM pictures of BiOBr/GE-1 at different magnifications.
From FIG. 1 (a, b)To see, fe 3 O 4 The nanoparticles exhibit a regular-sized spherical structure, with spherical dimensions of about 20-25 nm. From FIG. 2 (c, d), fe can be seen 3 O 4 After the nano particles are compounded with BiOBr, the spherical Fe 3 O 4 The nanoparticles are embedded in the BiOBr lamellar structure. From FIG. 3 (e, f) Fe 3 O 4 after/BiOBr is compounded with graphene oxide, spherical Fe 3 O 4 The BiOBr lamellar structures inlaid by the nano particles are mutually fused into a larger lamellar structure, and the lamellar structure has a multi-cavity structure in the middle, fe 3 O 4 the/BiOBr heterojunction is anchored between graphene networks.
(2) Fe prepared in example 1 by XRD diffractometer 3 O 4 Nanoparticles, fe 3 O 4 BiOBr and Fe 3 O 4 BiOBr/GE-1 to give Fe prepared in example 1 3 O 4 Nanoparticles, fe 3 O 4 BiOBr and Fe 3 O 4 The XRD pattern of/BiOBr/GE-1 is shown in FIG. 4.
As can be seen from FIG. 4, fe 3 O 4 The diffraction peak of the nano-particles is matched and corresponds to the standard card (JCPDS 19-0629); the BiOBr diffraction peak corresponds to the standard card ((JCPDS No. 73-2061) and Fe 3 O 4 Not only with Fe in XRD pattern of BiOBr 3 O 4 Diffraction peaks corresponding to the nanoparticles, and also to BiOBr, indicate that the reaction was successful in converting Fe 3 O 4 The nanoparticle and the BiOBr are composited together. In the XRD pattern, the inset is pure reduced graphene oxide aerogel generated by directly crosslinking commercial graphene oxide according to the synthesis process, and the pure reduced graphene oxide aerogel has a (002) crystal face which is positioned near 21.8 degrees and corresponds to a superimposed graphene layer; and for Fe 3 O 4 BiOBr/GE-1, which shows the corresponding pure BiOBr and Fe in XRD pattern 3 O 4 But a diffraction peak having a significantly different shift from that of BiOBr appears near 24.5 deg., which may be a (002) crystal plane corresponding to the superimposed graphene layer belonging to the graphene aerogel or a (101) crystal plane corresponding to the diffraction peak belonging to BiOBr, which may be derived from the formed graphiteOlefine aerogel and Fe 3 O 4 The BiOBr material has strong diffraction peak migration caused by interaction, which indicates that the reaction successfully leads to Fe 3 O 4 The nanoparticle, the BiOBr and the graphene are composited together.
(3) Fe prepared in example 1 by XPS photoelectron spectrometer 3 O 4 Nanoparticles, fe 3 O 4 BiOBr and Fe 3 O 4 BiOBr/GE-1 to give Fe prepared in example 1 3 O 4 Nanoparticles, fe 3 O 4 BiOBr and Fe 3 O 4 XPS diagram of/BiOBr/GE-1 is shown in FIG. 5.
In FIG. 5, pure Fe is shown 3 O 4 Nanoparticles, fe 3 O 4 BiOBr and Fe 3 O 4 The full spectrum of/BiOBr/GE-1 contains different elements, and the comparison of the results proves that Fe 3 O 4 Five elements Fe, br, bi, C, O are present in/BiOBr/GE-1.
Combining FIG. 5 with FIG. 4 gives Fe prepared in example 1 3 O 4 Nanoparticles, fe 3 O 4 BiOBr and Fe 3 O 4 A high resolution XPS plot of Fe2p for/BiOBr/GE-1 is shown in FIG. 6. As can be seen from FIG. 6, with pure Fe 3 O 4 Compared with the nano particles, fe after being compounded with BiOBr 3 O 4 BiOBr and Fe after continuing to react with reduced graphene oxide 3 O 4 in/BiOBr/GE-1, fe2p 7/2 And Fe2p 5/2 Can be significantly shifted.
Combining FIG. 5 with FIG. 4 gives Fe prepared in example 1 3 O 4 BiOBr and Fe 3 O 4 A high resolution XPS diagram of Bi4f of/BiOBr/GE-1 is shown in FIG. 7. As can be seen from FIG. 7, bi4f 7/2 And Bi4f 5/2 The binding energy of (C) also changed significantly, indicating Fe 3 O 4 And BiOBr and Fe 3 O 4 There is a strong interfacial interaction between/BiOBr and reduced graphene oxide.
(4) Fe prepared in example 1 by ultraviolet-visible absorption spectrometer 3 O 4 Nanoparticles, fe 3 O 4 BiOBr and Fe 3 O 4 BiOBr/GE-1 to give Fe prepared in example 1 3 O 4 Nanoparticles, fe 3 O 4 BiOBr and Fe 3 O 4 The ultraviolet-visible absorption spectrum of the/BiOBr/GE-1 is shown in FIG. 8.
As can be seen from FIG. 8, pure Fe 3 O 4 Nanoparticles, fe 3 O 4 BiOBr and Fe 3 O 4 The BiOBr/GE-1 has good light absorption in the visible light region; and after being modified by BiOBr and BiOBr, especially after being compounded, fe 3 O 4 The aerogel generated after the re-composite reaction of the BiOBr and the graphene oxide has extremely high visible light absorption efficiency, and the graphene aerogel material subjected to composite modification has obviously improved visible light absorption range and absorption intensity, and is beneficial to improving the photocatalytic performance under sunlight.
Application example 1
Fe prepared in example 1 3 O 4 The BiOBr/GE-1 is applied to a photocatalytic degradation experiment of the pollutant potassium dichromate, and the specific process and steps are as follows:
(1) Preparation of a color-developing agent: weighing 0.2g of diphenyl carbodihydrazide, dispersing and dissolving in 50mL of ethanol, slowly adding ultrapure water to a volume of 100mL, shaking uniformly, transferring into a brown bottle, and standing at a low temperature of 4 ℃ for preservation;
dilute 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 1 3 O 4 BiOBr/GE-1 is dispersed in 50mL of potassium dichromate solution (the concentration is 10 mg/L), and after uniform dispersion, the solution is stirred for a period of time to reach adsorption and desorption equilibrium; transferring the dispersion liquid into a photoreaction quartz cup with circulating condensed water; sampling at intervals of 5-20 min after the start of photocatalytic reaction under the irradiation of simulated sunlight at 300W, magnetically separating the extracted dispersion liquid after the reaction for 30min, measuring 6mL of supernatant, transferring the supernatant into a quartz cuvette, and dropwise adding 0.16mL of the color reagent prepared in the step (1), 40 mu L of dilute sulfuric acid solution and dilute phosphorus40 mu L of acid solution is measured by an ultraviolet-visible spectrophotometer to obtain the absorbance at 540nm of maximum absorption wavelength under different photocatalysis time, thereby obtaining Fe under different time 3 O 4 The 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 Fe 3 O 4 The nanoparticle can adsorb and desorb potassium dichromate about 17.9% in 30min, and Fe 3 O 4 The absorption and desorption amount of the/BiOBr/GE-1 to the potassium dichromate can reach about 65.1% in 30 min; after illumination, the degradation degree of various catalytic systems on potassium dichromate increases with the increase of illumination with time, but the degradation degree difference is obvious, fe 3 O 4 The nano particles can only degrade 18.9% of potassium dichromate within 50min, and Fe 3 O 4 the/BiOBr/GE-130 min can degrade potassium dichromate to 99.8%, and after catalytic degradation, the material can be directly recycled through a magnet.
Application example 2
Fe prepared in example 2 3 O 4 The BiOBr/GE-2 is applied to a photocatalytic degradation experiment of the pollutant potassium dichromate, and the specific process and steps are as follows:
50mg of Fe prepared in example 2 3 O 4 BiOBr/GE-2 is dispersed in 50mL of potassium dichromate solution (the concentration is 10 mg/L), and after uniform dispersion, the mixture is stirred for a period of time to reach adsorption and desorption equilibrium; transferring the dispersion liquid into a photoreaction quartz cup with circulating condensed water; sampling at intervals of 5-20 min after the start of the photocatalytic reaction under the irradiation of simulated sunlight, magnetically separating the extracted dispersion liquid after the reaction for 30min, measuring 6mL of supernatant, transferring to a quartz cuvette, dropwise adding 0.16mL of the color reagent prepared in the step (1) of application example 1, 40 mu L of the dilute sulfuric acid solution and 40 mu L of the dilute phosphoric acid solution, and measuring the absorbance at the maximum absorption wavelength of 540nm under different photocatalytic time by using an ultraviolet-visible spectrophotometer to obtain Fe under different time 3 O 4 The photocatalytic degradation effect of/BiOBr/GE-2 on potassium dichromate solution is shown in FIG. 9.
As can be seen from the view of figure 9,in the dark reaction, single magnetic powder material Fe 3 O 4 The nanoparticle can adsorb and desorb potassium dichromate about 17.9% in 30min, and Fe 3 O 4 The absorption and desorption amount of the/BiOBr/GE-2 to the potassium dichromate can reach about 40% in 30 min; after illumination, the degradation degree of various catalytic systems on potassium dichromate increases with the increase of illumination with time, but the degradation degree difference is obvious, fe 3 O 4 The nano particles can only degrade 18.9% of potassium dichromate within 50min, and Fe 3 O 4 the/BiOBr/GE-230 min can degrade potassium dichromate to 88%, and the material can be directly recycled through a magnet after catalytic degradation.
Application example 3
Fe prepared in example 3 3 O 4 The BiOBr/GE-3 is applied to a photocatalytic degradation experiment of the pollutant potassium dichromate, and the specific process and steps are as follows:
50mg of Fe prepared in example 3 3 O 4 BiOBr/GE-3 is dispersed in 50mL of potassium dichromate solution (the concentration is 10 mg/L), and after uniform dispersion, the mixture is stirred for a period of time to reach adsorption and desorption equilibrium; transferring the dispersion liquid into a photoreaction quartz cup with circulating condensed water; sampling at intervals of 5-20 min after the start of the photocatalytic reaction under the irradiation of simulated sunlight, magnetically separating the extracted dispersion liquid after the reaction for 30min, measuring 6mL of supernatant, transferring to a quartz cuvette, dropwise adding 0.16mL of the color reagent prepared in the step (1) of application example 1, 40 mu L of the dilute sulfuric acid solution and 40 mu L of the dilute phosphoric acid solution, and measuring the absorbance at the maximum absorption wavelength of 540nm under different photocatalytic time by using an ultraviolet-visible spectrophotometer to obtain Fe under different time 3 O 4 The 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 Fe 3 O 4 The nanoparticle can adsorb and desorb potassium dichromate about 17.9% in 30min, and Fe 3 O 4 The absorption and desorption amount of the/BiOBr/GE-3 to the potassium dichromate can reach about 62.5 percent in 30 minutes; after illumination, the degradation degree of various catalytic systems to potassium dichromate increases with the increase of illumination with time, butIs obviously degraded, fe 3 O 4 The nano particles can only degrade 18.9% of potassium dichromate within 50min, and Fe 3 O 4 the/BiOBr/GE-330 min can degrade potassium dichromate to 97.5%, and the material can be directly recycled through a magnet after catalytic degradation.
As can be seen from the experimental data of application example 1, the photolytic effect of potassium dichromate is not obvious without the catalyst. Under the illumination, with pure Fe 3 O 4 Compared with nano particles, the photolysis experiment of potassium dichromate under dark condition proves that Fe 3 O 4 The adsorption and photodegradation performance of the BiOBr/GE aerogel material to potassium dichromate is obviously improved, and the adsorption performance and photodegradation performance follow Fe 3 O 4 BiOBr addition ratio and graphene oxide concentration, fe 3 O 4 The BiOBr/GE-1 aerogel has higher adsorption performance and photodegradation performance, and can degrade potassium dichromate to about 99.8% in 30min under simulated sunlight, and Fe under the same conditions 3 O 4 BiOBr/GE-2 aerogel, fe 3 O 4 BiOBr/GE-3 aerogel and pure Fe 3 O 4 The nano particles can degrade about 97.5% and 87.5% and 19.4% of potassium dichromate, which indicates that the magnetically drivable graphene aerogel composite material prepared by the method has excellent photocatalytic effect.
The foregoing is merely a preferred embodiment of the present invention and it should be noted that modifications and adaptations to those skilled in the art may be made without departing from the principles of the present invention, which are intended to be comprehended within the scope of the present invention.
Claims (9)
1. A preparation method of a magnetically drivable graphene aerogel composite material comprises the following steps:
(1) Fe is added to 3 O 4 Mixing the nano particles, bismuth salt, citric acid and deionized water to obtain mixed slurry;
(2) Dripping 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 Fe 3 O 4 BiOBr; the drying temperature in the step (3) is 50-70 ℃, and the drying time is 10-15 h;
(4) Fe obtained in the step (3) 3 O 4 Mixing BiOBr with lysine, graphene oxide and deionized water, and performing hydrothermal reaction to obtain a magnetically drivable graphene aerogel composite material; the magnetically drivable graphene aerogel composite comprises Fe 3 O 4 Nanoparticles, biOBr and graphene, the Fe 3 O 4 Nano particles are inlaid between BiOBr sheets to form Fe 3 O 4 BiOBr heterojunction, fe 3 O 4 the/BiOBr heterojunction is anchored between graphene networks.
2. The method according to claim 1, wherein Fe in the step (1) 3 O 4 The 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 Fe in the step (1) 3 O 4 The mass ratio of the nano particles to the bismuth salt to the citric acid to the cetyl 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 in the step (2) is carried out at a temperature of 25 to 35 ℃ for a time of 0.5 to 1 hour.
5. The method according to claim 1, wherein the rate of dropping in the step (2) is 0.025 to 0.075mL/s.
6. The method according to claim 1, wherein Fe in the step (4) 3 O 4 Mass of BiOBr, lysine and graphene oxideThe ratio is (50-66.7), (30-35) and (3.5-5).
7. The method according to claim 1, wherein the hydrothermal reaction in the step (4) is carried out at a temperature of 160 to 180 ℃ for a period of 8 to 15 hours.
8. The magnetically drivable graphene aerogel composite prepared by the preparation method of any one of claims 1 to 7, comprising Fe 3 O 4 Nanoparticles, biOBr and graphene, the Fe 3 O 4 Nano particles are inlaid between BiOBr sheets to form Fe 3 O 4 BiOBr heterojunction, fe 3 O 4 the/BiOBr heterojunction is anchored between graphene networks.
9. Use of the magnetically drivable graphene aerogel composite of claim 8 for photocatalytic degradation of inorganic and/or organic contaminant wastewater solutions.
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