CN115779972A - Graphene oxide-based composite aerogel catalyst and preparation method and application thereof - Google Patents
Graphene oxide-based composite aerogel catalyst and preparation method and application thereof Download PDFInfo
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- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 119
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 118
- 239000004964 aerogel Substances 0.000 title claims abstract description 70
- 239000002131 composite material Substances 0.000 title claims abstract description 68
- 239000003054 catalyst Substances 0.000 title claims abstract description 62
- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- 229940005550 sodium alginate Drugs 0.000 claims abstract description 80
- IXPNQXFRVYWDDI-UHFFFAOYSA-N 1-methyl-2,4-dioxo-1,3-diazinane-5-carboximidamide Chemical compound CN1CC(C(N)=N)C(=O)NC1=O IXPNQXFRVYWDDI-UHFFFAOYSA-N 0.000 claims abstract description 78
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- 239000000243 solution Substances 0.000 claims description 33
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- 230000000052 comparative effect Effects 0.000 description 12
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- ISXSCDLOGDJUNJ-UHFFFAOYSA-N tert-butyl prop-2-enoate Chemical compound CC(C)(C)OC(=O)C=C ISXSCDLOGDJUNJ-UHFFFAOYSA-N 0.000 description 8
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- DLYUQMMRRRQYAE-UHFFFAOYSA-N phosphorus pentoxide Inorganic materials O1P(O2)(=O)OP3(=O)OP1(=O)OP2(=O)O3 DLYUQMMRRRQYAE-UHFFFAOYSA-N 0.000 description 2
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
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Images
Classifications
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W10/00—Technologies for wastewater treatment
- Y02W10/30—Wastewater or sewage treatment systems using renewable energies
- Y02W10/37—Wastewater or sewage treatment systems using renewable energies using solar energy
Abstract
The invention discloses a graphene oxide-based composite aerogel catalyst and a preparation method and application thereof. The preparation process of the catalyst comprises the steps of firstly preparing the sodium alginate-graphene oxide composite gel and then loading silver/silver chloride nanoparticles on the surface of the composite gel. The catalyst utilizes the crosslinking of sodium alginate to form a three-dimensional reticular aerogel structure, graphene oxide is stably loaded in the three-dimensional reticular structure of the aerogel as a substrate, the binding force between sodium alginate gel and active component silver/silver chloride nanoparticles and the graphene oxide substrate is strong, the active component can be effectively prevented from falling off from the substrate in the catalytic degradation process, meanwhile, the porous structure and the wrinkle morphology which are rich in the surface of the composite aerogel can be realized, the transmission of electrons in the catalyst and the generation of active free radicals can be accelerated, the catalytic degradation performance of the composite aerogel is improved, the catalyst is convenient to recycle, and the catalyst can be used for the efficient degradation of organic pollutants in sewage.
Description
Technical Field
The invention relates to a composite aerogel catalyst, in particular to a graphene oxide-based composite aerogel catalyst and a preparation method and application thereof, and belongs to the technical field of catalytic materials.
Background
The Graphene Oxide (GO) surface contains a large number of oxygen-containing functional groups such as hydroxyl, carboxyl and epoxy groups, and has the advantages of good hydrophilicity, large specific surface area and the likeHas received wide attention in the field of catalysts. And pure GO is limited in catalytic capability, and in order to enhance the catalytic performance of GO, GO needs to be modified, or metal oxide nanoparticles and the like are selectively introduced into GO to prepare the GO-based composite material. The literature ("Synthesis and characterization of nanostructured composites of graphene oxides/Fe) 3 O 4 NiO for water treatment ", T.Saleem, et al, dig.J.Nanomater.Bios.2022,17 (4): 1203-1210.) reports the introduction of ferroferric oxide and nickel oxide nanoparticles into GO to produce Fe 3 O 4 the/NiO/GO nano catalyst improves the catalytic degradation capability of GO to rhodamine B to a certain extent, but the agglomeration condition of nano particles on the surface of the catalyst is serious, so that the catalyst is not beneficial to completely playing the catalytic performance of the material, and the catalyst needs to be separated and recovered from a dye solution by a centrifugal separation method after the catalytic degradation is finished.
Disclosure of Invention
Aiming at the problems in the prior art, the first object of the invention is to provide a graphene oxide-based composite aerogel catalyst, wherein the composite aerogel catalyst forms a three-dimensional network aerogel structure by utilizing the crosslinking of sodium alginate, graphene oxide is stably loaded in the three-dimensional network structure of the aerogel as a substrate, the sodium alginate gel and the active component silver/silver chloride nanoparticles have strong binding force with the graphene oxide substrate, so that the active component can be effectively prevented from falling off from the substrate in the catalytic degradation process, meanwhile, the composite aerogel has rich pore structure and wrinkle morphology on the surface, the transmission of electrons in the catalyst can be accelerated, the generation of active free radicals can be promoted, the catalytic degradation performance of the composite aerogel is improved, the composite aerogel is convenient to recycle, and the graphene oxide-based composite aerogel catalyst can be used for efficiently degrading organic pollutants in sewage.
The second purpose of the invention is to provide a preparation method of the graphene oxide-based composite aerogel catalyst, which is simple to operate, mild in conditions, low in cost and beneficial to large-scale production.
The third purpose of the invention is to provide an application of the graphene oxide composite aerogel catalyst in catalytic degradation of organic pollutants in sewage, wherein the catalyst can be used for rapidly and efficiently catalytically degrading the organic pollutants in the sewage, and has good stability and easy recovery.
In order to achieve the technical purpose, the invention provides a preparation method of a graphene oxide-based composite aerogel catalyst, which comprises the steps of uniformly mixing a sodium alginate solution and a graphene oxide suspension, and carrying out ultrasonic treatment to obtain a graphene oxide/sodium alginate mixed solution; slowly injecting the graphene oxide/sodium alginate mixed solution into a calcium chloride solution for gelling and aging, and washing with water to obtain sodium alginate-graphene oxide hydrogel; the sodium alginate-graphene oxide hydrogel is firstly placed in an alcohol aqueous solution containing tetrabutylammonium chloride for pretreatment, then placed in a silver nitrate aqueous solution for immersion treatment, and then washed with water and freeze-dried, so that the sodium alginate-graphene oxide hydrogel is obtained.
According to the technical scheme, the sodium alginate-graphene oxide composite gel is prepared, and then silver/silver chloride nanoparticles are loaded on the surface of the composite gel. The three-dimensional structure that graphene oxide passes through modes such as hydrogen bond effect and physics parcel, embedding and sodium alginate formation closely combines, improves composite gel material's stability greatly, can prevent effectively that catalytic degradation in-process active component from droing from the base member, and composite aerogel presents lamella overlap and porous structure, produces abundant fold and hole, can accelerate the electron in the inside transmission of catalyst and promote the production of active free radical, has improved the catalytic degradation performance of aerogel. Meanwhile, silver/silver halide is loaded on the composite gel, and the catalytic performance of the composite material is greatly improved through the synergistic effect between the graphene oxide and the silver/silver halide.
As a preferable scheme, the concentration of the graphene oxide suspension is 1-20 mg/mL. More preferably, the concentration of the graphene oxide suspension is 1 to 10mg/mL. The concentration of the graphene oxide suspension is preferably controlled in an optimal range, and if the concentration of the graphene oxide suspension is too low, the proportion of the catalytic active ingredients is too low, so that the transfer of electrons in the gel in the subsequent degradation process is influenced, and the degradation effect is reduced; the graphene oxide suspension with too high concentration is easy to cause the agglomeration of the graphene oxide, and is not beneficial to dispersion.
As a preferable scheme, the mass percent concentration of the sodium alginate solution is 1-10%. The concentration of the sodium alginate solution is controlled in an optimal range, so that the uniform mixing of the graphene and the sodium alginate and the generation of composite gel are facilitated.
As a preferable scheme, the mass ratio of the graphene oxide to the sodium alginate in the graphene oxide/sodium alginate mixed solution is 1. Further preferably, the mass ratio of the graphene oxide to the sodium alginate in the graphene oxide/sodium alginate mixed solution is 1. If the proportion of the sodium alginate is too low, the gel forming and the maintenance of the complete shape of the catalyst in the degradation process are not facilitated; and the sodium alginate with too high proportion is not beneficial to the uniform mixing and dispersion of the sodium alginate and the graphene oxide.
As a preferable scheme, the sodium alginate solution and the graphene oxide suspension are heated to 50-70 ℃ in the process of uniformly mixing, so that the sodium alginate is fully dissolved, and the sodium alginate and the graphene oxide are highly dispersed.
Preferably, the aging time is 1 to 12 hours. More preferably, the aging time is 4 to 8 hours. The aging time is too short, so that the gel is not beneficial to fully absorbing water and swelling, the situations of obvious volume reduction and internal structure collapse of the gel after freeze drying are caused, and the degradation effect is influenced; and the gel surface is provided with more calcium ions due to the overlong aging time, so that the subsequent deionized water washing time is prolonged, and the degradation effect is influenced by the carried calcium ions.
As a preferable scheme, the concentration of the tetrabutylammonium chloride in the tetrabutylammonium chloride-containing alcohol aqueous solution is 0.5-2.5 mg/mL. The alcohol-water solution is preferably a mixed solution of ethanol and water, and more preferably, the volume ratio of ethanol to water is 1.
As a preferable scheme, the mass ratio of the tetrabutylammonium chloride to the graphene oxide is 1. More preferably, the mass ratio of the tetrabutylammonium chloride to the graphene oxide is 2. The proportion of tetrabutylammonium chloride is too low, which is not beneficial to the uniform loading of silver/silver chloride nanoparticles on the surface of the gel, thereby affecting the degradation effect of the composite material; and the proportion of tetrabutylammonium chloride is too high, so that the silver/silver chloride nanoparticle layer loaded on the surface of the gel is too thick, the transmission of electrons in the gel is influenced, and the degradation effect of the composite material is also reduced.
As a preferred scheme, the pretreatment conditions are as follows: stirring for 4-8 h at 50-70 ℃. Under the condition, chloride ions in tetrabutylammonium chloride are successfully grafted on the surface of the sodium alginate-reduced graphene oxide gel, so that the subsequent uniform loading of silver/silver chloride nanoparticles on the surface of the gel is facilitated.
As a preferable scheme, the concentration of the silver nitrate solution is 0.5-2.5 mg/mL.
Preferably, the time of the impregnation treatment is 8 to 16 hours. If the concentration of the silver nitrate solution is too low or the dipping treatment time is too short, the ratio of the silver/silver chloride nanoparticles loaded on the composite gel is low, so that the degradation effect of the composite material is influenced; and if the silver nitrate concentration is too high or the soaking time is too long, the silver/silver chloride nanoparticle layer loaded on the surface of the gel is too thick, so that the transmission of electrons in the gel is influenced, and the degradation effect of the composite material is reduced.
Preferably, the freeze-drying time is 12 to 36 hours. More preferably, the freeze-drying time is 18 to 24 hours. The too short freeze-drying time is not beneficial to completely removing the water in the gel, so that the quantity and the structure of the holes in the gel are influenced; and the gel internal structure is easy to collapse and the degradation effect is reduced if the freeze drying time is too long.
The invention also provides a graphene oxide-based composite aerogel catalyst, which is prepared by the preparation method.
According to the graphene oxide-based composite aerogel catalyst, sodium alginate is used for constructing a three-dimensional network structure gel through crosslinking, and graphene oxide is used as a matrix and stably loaded in the three-dimensional network structure of the aerogel. The graphene oxide and the sodium alginate are compounded in the modes of hydrogen bond action, wrapping, embedding and the like, so that the stability is good, and the whole catalytic material is in a three-dimensional porous structure. The gel has a large number of hydroxyl and carboxyl functional groups, has good binding performance with graphene oxide, and simultaneously carries silver/silver chloride nanoparticles on the surface of the composite aerogel, so that the graphene oxide and the silver/silver chloride nanoparticles generate a synergistic catalytic effect, and the catalytic performance of the composite gel is greatly improved. And the three-dimensional structure can not only ensure that the catalyst keeps the stability of the external appearance and the internal structure in the pollutant degradation process, but also prevent the agglomeration of nano particles and furthest keep the stability of the catalytic performance. Abundant fold and holes increase the contact area of the catalyst and organic matters in sewage on one hand, and on the other hand, the catalyst can be combined with silver/silver chloride nano particles to achieve the purpose of accelerating the transfer of electrons in the catalyst, and is favorable for adsorbing oxygen to promote the generation of more active free radicals.
The invention also provides application of the graphene oxide-based composite aerogel catalyst, which is used for catalyzing and degrading organic pollutants in sewage.
As a preferred scheme, the graphene oxide-based composite aerogel catalyst is used in combination with sodium borohydride.
The invention provides a preparation method of a graphene oxide-based composite aerogel catalyst, which comprises the following steps:
1) Mixing a sodium alginate solution with the concentration of 1-10 wt% and a graphene oxide suspension with the concentration of 1-20 mg/mL under the condition of the temperature of 50-70 ℃ for 1-2 h by magnetic stirring, and then carrying out ultrasonic degassing for 2-4 h to obtain a graphene oxide/sodium alginate mixed solution; wherein the mass ratio of the graphene oxide to the sodium alginate is 1;
2) Slowly injecting the graphene oxide/sodium alginate mixed solution into 3-8 wt% calcium chloride solution to form gel through crosslinking, aging for 1-12 h, and washing with deionized water to obtain sodium alginate-reduced graphene oxide hydrogel;
3) Adding sodium alginate-reduced graphene oxide hydrogel into ethanol aqueous solution with the concentration of 0.5-2.5 mg/mL and containing tetrabutylammonium chloride, heating to 50-70 ℃, and stirring for 4-8 h; the mass ratio of tetrabutylammonium chloride to graphene oxide is 1;
4) Transferring the hydrogel treated in the step 3) into a silver nitrate aqueous solution with the concentration of 0.5-2.5 mg/mL, soaking for 8-16 h to load silver/silver chloride, wherein the mass ratio of silver nitrate to graphene oxide is 1-1, and then sequentially washing and freeze-drying for 12-36 h to obtain the silver-loaded/silver-chloride hydrogel.
Compared with the prior art, the invention has the beneficial technical effects that:
1) The graphene oxide-based composite aerogel catalyst provided by the invention is high in catalytic activity based on the synergistic effect among the components, and graphene oxide is loaded in a three-dimensional structure formed by sodium alginate to form an aerogel matrix, so that the stability of the composite aerogel material is greatly improved, the composite aerogel has a laminated overlapping and porous structure, and abundant folds and holes are generated, so that the contact area of the catalyst and organic matters in sewage is increased, the transfer of electrons in the catalyst can be accelerated, and the catalyst is favorable for adsorbing oxygen to promote the generation of more active free radicals.
2) According to the invention, graphene oxide is used as a catalyst substrate, on one hand, the surface of the graphene oxide is provided with a large number of oxygen-containing functional groups, so that the graphene oxide is convenient to combine with sodium alginate, and is also beneficial to compounding with silver/silver chloride nanoparticles; on the other hand, the sheet structure has small damage degree and high stability. Furthermore, the graphene oxide is compounded with the sodium alginate, so that the stability of the composite gel is improved, a three-dimensional porous structure and abundant folds are formed, and the situation that the catalytic performance is reduced due to agglomeration of the loaded silver/silver chloride nanoparticles in the subsequent degradation process can be prevented.
3) The graphene oxide-based aerogel catalyst can be used for catalyzing and degrading organic pollutants in sewage, can accelerate the transfer of electrons in the material and promote the generation of active free radicals under the condition that sodium borohydride is used as a cocatalyst, and can quickly and efficiently degrade organic matters in the sewage.
4) The preparation method of the graphene oxide-based composite aerogel catalyst is simple to operate, mild in condition, low in cost and beneficial to large-scale production.
Drawings
Fig. 1 is a high-power scanning electron microscope image of the graphene oxide-based composite aerogel catalyst prepared in example 1 of the present invention;
FIG. 2 is a high power scanning electron micrograph of silver/silver chloride nanoparticles prepared according to comparative example 1 of the present invention;
fig. 3 is a high-power scanning electron microscope image of the graphene oxide-based composite aerogel prepared in comparative example 2 of the present invention;
FIG. 4 is a high-power scanning electron microscope image of the sodium alginate composite aerogel prepared in comparative example 3 of the invention.
Detailed Description
The following examples are intended to further illustrate the present disclosure, but not to limit the scope of the claims.
The graphene oxides used in the following examples and comparative examples are prepared by a modified Hummers method, which is a conventional mature method, and the graphene oxides prepared according to the existing modified Hummers method all satisfy the technical scheme of the present invention.
The specific process for preparing the graphene oxide by the improved Hummers method comprises the following steps: adding 1g of potassium persulfate and 1g of phosphorus pentoxide into 20mL of 98 mass percent concentrated sulfuric acid, stirring and heating to 80 ℃, adding 2g of graphite after the potassium persulfate and the phosphorus pentoxide are fully dissolved, and continuing to heat for 4.5 hours under the condition. Cooling, filtering, washing with distilled water to neutrality, and naturally drying in air to obtain pre-oxidized graphite. Adding pre-oxidized graphite into 75mL concentrated sulfuric acid, and slowly adding 10.0031g potassium permanganate under ice bath, wherein the temperature of the process is controlled not to exceed 20 ℃. After the addition is finished, the temperature is raised to 35 ℃, the mixture is transferred to an ice bath after reacting for 2h, 160mL of distilled water is slowly added, the temperature is controlled to be lower than 50 ℃ in the water adding process, 500mL of distilled water is added after reacting for 2h, 8.3mL of hydrogen peroxide aqueous solution with the mass concentration of 30% is dropwise added, the mixture is continuously stirred for 30min, and then the mixture is kept stand for 8h. The supernatant was decanted off, 800mL of 10% HCl solution was added, stirred for 3h and allowed to stand for 8h. The supernatant was again decanted, 400mL of distilled water was added, and the mixture was stirred for 3h. Centrifuging the obtained mixed solution at 5000rpm for 1h, pouring out clear liquid, adding distilled water into the rest part again, centrifuging for 1h, washing for many times until the pH is neutral, adding water to adjust the concentration of the graphene oxide suspension to be 5mg/mL, and storing for later use. The graphene oxides in the following examples were all prepared using this method.
Example 1
Dissolving 0.5g of Sodium Alginate (SA) in 15mL of deionized water, adding 10mL of 5mg/mL GO suspension after the SA is completely dissolved, stirring and mixing for 2h under the heating condition of 60 ℃ to obtain a graphene oxide/sodium alginate mixed solution, and then carrying out ultrasonic degassing treatment; slowly injecting the graphene oxide/sodium alginate mixed solution into 300mL of calcium chloride solution with the mass fraction of 5% to carry out gelling to obtain sodium alginate-graphene oxide hydrogel (SA-GO), after the graphene oxide/sodium alginate mixed solution is completely added into the calcium chloride solution, aging the whole gel for 6 hours, and repeatedly stirring and washing the gel for 3 times by using deionized water after the aging is finished; taking 150mg tetrabutylammonium chloride (TBAC) into a flask, adding 50mL deionized water and 50mL absolute ethyl alcohol, adding the aged SA-GO into the flask, and heating and stirring at 60 ℃ for 6 hours; the SA-GO thus obtained was added to 100mL of silver nitrate (AgNO) at a concentration of 1.5mg/mL 3 ) Soaking in water solution for 12h to load silver/silver chloride (Ag/AgCl) nanoparticles; and after the loading is finished, the gel is washed twice by deionized water, and is frozen and dried for 20 hours to obtain the graphene oxide-based composite aerogel, wherein the sample is marked as Ag/AgCl @ SA-GO (1).
Example 2
Dissolving 0.25g of SA in 15mL of deionized water, adding 10mL of GO suspension with the concentration of 5mg/mL after the SA is completely dissolved, stirring and mixing for 2 hours under the heating condition of 60 ℃ to obtain a graphene oxide/sodium alginate mixed solution, and then carrying out ultrasonic degassing treatment; slowly injecting the graphene oxide/sodium alginate mixed solution into 300mL of calcium chloride solution with the mass fraction of 5% to gelatinize to obtain SA-GO, after the graphene oxide/sodium alginate mixed solution is completely added into the calcium chloride solution, aging the whole gel for 6 hours, and repeatedly stirring and washing the gel for 3 times by using deionized water after the aging is finished; taking 150mg of TBAC (tunnel boring machine) in a flask, adding 50mL of deionized water and 50mL of absolute ethyl alcohol, adding the aged SA-GO into the flask, and heating and stirring at 60 ℃ for 6 hours; the obtained SAdding A-GO into 100mL AgNO with concentration of 1.5mg/mL 3 Dipping in water solution for 12h to load Ag/AgCl nano particles; and after the loading is finished, the gel is washed twice by deionized water, and is frozen and dried for 20 hours to obtain the graphene oxide-based composite aerogel, wherein the sample is marked as Ag/AgCl @ SA-GO (2).
Example 3
Dissolving 1g of SA in 15mL of deionized water, adding 10mL of GO suspension with the concentration of 5mg/mL after the SA is completely dissolved, stirring and mixing for 2 hours under the heating condition of 60 ℃ to obtain a graphene oxide/sodium alginate mixed solution, and then carrying out ultrasonic degassing treatment; slowly injecting the graphene oxide/sodium alginate mixed solution into 300mL of calcium chloride solution with the mass fraction of 5% to gelatinize to obtain SA-GO, after the graphene oxide/sodium alginate mixed solution is completely added into the calcium chloride solution, aging the whole gel for 6 hours, and repeatedly stirring and washing the gel for 3 times by using deionized water after the aging is finished; taking 150mg of TBAC (tunnel boring machine) in a flask, adding 50mL of deionized water and 50mL of absolute ethyl alcohol, adding the aged SA-GO into the flask, and heating and stirring at 60 ℃ for 6 hours; adding the obtained SA-GO to 100mL of AgNO with a concentration of 1.5mg/mL 3 Soaking in water solution for 12h to load Ag/AgCl nano particles; and after loading is finished, washing the gel with deionized water twice, and then carrying out freeze drying for 20 hours to obtain the graphene oxide-based composite aerogel, wherein the sample is marked as Ag/AgCl @ SA-GO (3).
Comparative example 1
Taking 150mg TBAC in a 250mL round-bottom flask, and adding 50mL deionized water to obtain 50mL of 3mg/mL TBAC solution; another 150mg AgNO 3 In a 100mL beaker, 50mL deionized water was added to give 50mL3mg/mL of AgNO 3 A solution; mixing AgNO 3 Slowly adding the solution into a TBAC solution, and mixing and stirring at room temperature for 12 hours; and after stirring, carrying out suction filtration and washing on the mixed solution for 3 times, and carrying out freeze drying on a filter cake after suction filtration and washing for 12 hours to obtain Ag/AgCl nanoparticles, wherein the sample is marked as Ag/AgCl.
Comparative example 2
Dissolving 0.5g of SA in 15mL of deionized water, adding 10mL of 5mg/mL GO suspension after the SA is completely dissolved, stirring and mixing for 2 hours under the heating condition of 60 ℃ to obtain a graphene oxide/sodium alginate mixed solution, and then carrying out ultrasonic degassing treatment; slowly injecting the graphene oxide/sodium alginate mixed solution into 300mL of calcium chloride solution with the mass fraction of 5% to gelatinize to obtain SA-GO, after the graphene oxide/sodium alginate mixed solution is completely added into the calcium chloride solution, aging the whole gel for 6 hours, and repeatedly stirring and washing the gel for 3 times by using deionized water after the aging is finished; and (3) freeze-drying the gel for 12 hours to obtain the graphene oxide-based aerogel, wherein the sample is marked as SA-GO.
Comparative example 3
Dissolving 0.5g of SA in 25mL of deionized water, and carrying out ultrasonic degassing treatment on the SA after the SA is completely dissolved; slowly injecting the SA solution into 300mL of 5% calcium chloride solution to gelatinize to obtain SA gel, aging the whole gel for 6 hours after the SA solution is completely added into the calcium chloride solution, and repeatedly stirring and washing the gel for 3 times by using deionized water after the aging is finished; taking 150mg of TBAC (tert-butyl acrylate) in a flask, adding 50mL of deionized water and 50mL of absolute ethyl alcohol, adding the aged SA gel into the flask, and heating and stirring for 6 hours at the temperature of 60 ℃; the SA gel obtained was added to 100mL of AgNO at a concentration of 1.5mg/mL 3 Dipping in water solution for 12h to load Ag/AgCl nano particles; after loading is finished, the gel is washed twice by deionized water; and freeze-drying for 20h to obtain the sodium alginate composite aerogel, wherein the sample is marked as Ag/AgCl @ SA.
As can be seen from the high-power scanning electron micrographs (fig. 1 to fig. 4), the graphene oxide-based composite aerogel catalyst prepared by the invention (fig. 1) has a lamellar overlapping and porous structure, and because a large number of hydrophilic groups are arranged in the gel, the gel is easy to absorb water and swell, and water molecules contained in the hydrogel can form ice crystals and induce a pore structure in the freeze-drying process. The fold and hole structures increase the contact area of the catalyst and organic matters in sewage on one hand, and on the other hand, the Ag/AgCl nano particles are combined to accelerate the transfer of electrons in the catalyst, so that the Ag/AgCl nano particles are favorable for adsorbing oxygen to promote the generation of more active free radicals. In addition, ag/AgCl nanoparticles can be uniformly dispersed on the surface of the graphene oxide-based composite aerogel catalyst prepared by the invention, so that the condition that the catalytic performance is reduced due to the agglomeration of the nanoparticles in the catalytic degradation process can be effectively avoided. The Ag/AgCl nanoparticles prepared in comparative example 1 (fig. 2) are not agglomerated due to the absence of a three-dimensional structure substance as a carrier, which greatly affects the catalytic degradation effect thereof. The Ag/AgCl nanoparticle-unsupported graphene oxide-based composite aerogel prepared in comparative example 2 (fig. 3) has a lamellar overlapping and porous structure as in example 1, has a sufficient number of wrinkles and pores, but has no Ag/AgCl nanoparticles supported on the surface, so that it cannot accelerate the transfer of electrons inside the catalyst and promote the generation of active radicals under the condition of sodium borohydride as a co-catalyst. The GO-free sodium alginate composite aerogel prepared in comparative example 3 (shown in figure 4) has large holes, but the whole surface is smooth and lacks folds, so that the contact area between the gel and pollutants is greatly reduced, and the catalytic performance of the material is influenced.
The catalytic performance tests were carried out on examples 1, 2 and 3, comparative examples 1, 2 and 3, respectively: taking 20mg of graphene oxide based aerogel (or Ag/AgCl nano-particles or sodium alginate composite aerogel), adding the graphene oxide based aerogel (or Ag/AgCl nano-particles or sodium alginate composite aerogel) into 30mL of Methyl Orange (MO) solution with the concentration of 100mg/L, and adding 1.2mL of sodium borohydride (NaBH) with the concentration of 1mg/mL 4 ) And (3) carrying out catalytic degradation on the solution at the temperature of 40 ℃. At t =0min and t =20min, 300 μ L of the solution supernatant was taken, diluted to 3mL of solution (10-fold dilution), and the absorbance of the MO (wavelength λ max =464 nm) solution was measured using a 722G visible spectrophotometer. The corresponding concentration is obtained according to the standard curve, the degradation rate of the catalyst to MO is calculated, and the test results are shown in Table 1. The degradation rate calculation formula is as follows:
in the formula, C 0 Is the initial concentration of the organic dye, C t The concentration of the organic dye after 20min of degradation.
(2) Taking 20mg of graphene oxide based aerogel (or Ag/AgCl nano-particles or sodium alginate composite aerogel), adding the graphene oxide based aerogel into 30mL of rhodamine B (RhB) solution with the concentration of 50mg/L, and adding 1.2mL of sodium borohydride (NaBH) with the concentration of 1mg/mL 4 ) And (3) carrying out catalytic degradation on the solution at the temperature of 40 ℃. At t =0min and t =20min, 300 μ L of the solution supernatant was taken, diluted to 3mL of a solution (10-fold dilution), and the absorbance of the RhB (wavelength λ max =554 nm) solution was measured using a 722G visible spectrophotometer. The corresponding concentration is obtained according to the standard curve, the degradation rate of the catalyst to RhB is calculated, and the test results are shown in Table 1.
It can be seen through the degradation rate data table (table 1) to the dyestuff, compare in Ag/AgCl, SA-GO and Ag/AgCl @ SA, ag/AgCl @ SA-GO has better catalytic degradation performance, the leading cause is attributed to Ag/AgCl @ SA-GO has abundanter fold and hole structures, these structures have increased the area of contact of catalyst with organic matter in the sewage on the one hand, on the other hand combine Ag/AgCl nanoparticle can accelerate the transmission of electron in the catalyst is inside, do benefit to the adsorption of oxygen in order to impel to produce more active free radicals, thereby the going on of catalytic degradation process is accelerated. Ag/AgCl @ SA-GO (1), ag/AgCl @ SA-GO (2) and Ag/AgCl @ SA-GO (3) mainly differ in the in-process SA addition of preparing the compound aerogel catalyst of graphene oxide base, thereby influence the abundance of the inside fold of aerogel and hole structure, can know from table 1, the proportion of increase SA is favorable to improving the catalytic performance of aerogel in a certain degree, because SA content crosses lowly makes the aerogel lack hole structure, and the too high hole structure that can make the aerogel of SA content is too big, the contact area of aerogel and pollutant has all been reduced to a certain extent. In addition, the degradation rates of the Ag/AgCl @ SA-GO (1), the Ag/AgCl @ SA-GO (2) and the Ag/AgCl @ SA-GO (3) to the MO and the RhB organic dyes have certain differences, which are caused by different catalytic degradation mechanisms of the Ag/AgCl @ SA-GO to the MO and the RhB.
The mechanism of MO degradation: ag/AgCl nanoparticles coupling BH 4 - Released e - And H + Transferring into MO to convert chromophoric group-N = N-in MO into colorless group-NH-NH-as an unstable intermediate state, which can further receive the coloring material from BH with the aid of Ag/AgCl 4 - Released H + Cleavage to form-NH 2 Or NH 3 A molecule. In addition there are some leads in SA-GOGraphite carbon net with excellent electrical performance and part e of Ag/AgCl - Transferred to the graphite net and directly captured by the dye adsorbed on the graphite net based on the pi-pi acting force, thereby accelerating the catalytic reaction.
Mechanism of RhB degradation: the main active radicals that play a role in RhB degradation process include electron holes (h) + ) Superoxide radical (. O) 2 - ) And a hydroxyl radical (. OH). The Ag/AgCl nano particles can adsorb oxygen and generate h on the surface of the catalyst + ；BH 4 - Released e - Can be quickly transferred in a graphite carbon net with excellent conductivity in SA-GO, is beneficial to capture Ag/AgCl nanoparticles and combines with adsorbed oxygen to form O 2 - ；BH 4 - Liberated fraction H + And a small amount of O 2 - Can combine with water molecules to generate OH. In summary, h + 、·O 2 - OH can be combined with RhB molecules, so that water, carbon dioxide and other inorganic small molecules are generated, and the purpose of degrading the organic dye RhB is achieved.
TABLE 1 data table of degradation rates of examples 1 to 3 and comparative examples 1 to 3 for methyl orange and rhodamine B
Claims (10)
1. A preparation method of a graphene oxide-based composite aerogel catalyst is characterized by comprising the following steps: uniformly mixing a sodium alginate solution and a graphene oxide suspension, and performing ultrasonic treatment to obtain a graphene oxide/sodium alginate mixed solution; slowly injecting the graphene oxide/sodium alginate mixed solution into a calcium chloride solution for gelling and aging, and washing with water to obtain sodium alginate-graphene oxide hydrogel; the sodium alginate-graphene oxide hydrogel is firstly placed in an alcohol aqueous solution containing tetrabutylammonium chloride for pretreatment, then placed in a silver nitrate aqueous solution for immersion treatment, and then washed with water and freeze-dried, thus obtaining the sodium alginate-graphene oxide hydrogel.
2. The preparation method of the graphene oxide-based composite aerogel catalyst according to claim 1, characterized in that:
the concentration of the graphene oxide suspension is 1-20 mg/mL;
the mass percentage concentration of the sodium alginate solution is 1-10%;
the mass ratio of the graphene oxide to the sodium alginate in the graphene oxide/sodium alginate mixed solution is 1.
3. The preparation method of the graphene oxide-based composite aerogel catalyst according to claim 1, characterized in that: the aging time is 1-12 h.
4. The preparation method of the graphene oxide-based composite aerogel catalyst according to claim 1, wherein the preparation method comprises the following steps: the concentration of the tetrabutylammonium chloride in the tetrabutylammonium chloride-containing alcohol aqueous solution is 0.5-2.5 mg/mL.
5. The preparation method of the graphene oxide-based composite aerogel catalyst according to claim 1 or 4, wherein: the mass ratio of the tetrabutylammonium chloride to the graphene oxide is 1.
6. The preparation method of the graphene oxide-based composite aerogel catalyst according to claim 1, characterized in that: the pretreatment conditions are as follows: stirring for 4-8 h at 50-70 ℃.
7. The preparation method of the graphene oxide-based composite aerogel catalyst according to claim 1, wherein the preparation method comprises the following steps: the concentration of the silver nitrate solution is 0.5-2.5 mg/mL.
8. The preparation method of the graphene oxide-based composite aerogel catalyst according to claim 1, wherein the preparation method comprises the following steps: the time of the dipping treatment is 8-16 h.
9. The graphene oxide-based composite aerogel catalyst is characterized in that: the method according to any one of claims 1 to 8.
10. The use of the graphene oxide-based composite aerogel catalyst according to claim 9, wherein:
used for catalyzing and degrading organic pollutants in sewage.
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Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105499600A (en) * | 2015-12-15 | 2016-04-20 | 中国科学院上海高等研究院 | Method for preparing silver nanowire-graphene composite aerogel |
| CN105749970A (en) * | 2016-03-02 | 2016-07-13 | 青岛大学 | Preparation method of calcium alginate-graphene-nano-gold composite hydrogel catalyst |
| CN109107574A (en) * | 2018-08-01 | 2019-01-01 | 兰州大学 | Silver-based oxysalt/graphite oxide aerogel preparation method and its aeroge obtained and application |
| CN110124627A (en) * | 2019-06-27 | 2019-08-16 | 中素新科技有限公司 | Graphene oxide and alginate composite aerogel and its preparation method and application |
| CN110479232A (en) * | 2019-08-20 | 2019-11-22 | 中国航发北京航空材料研究院 | A kind of preparation method of redox graphene base optic catalytic airsetting glue bead |
| CN111001394A (en) * | 2019-12-26 | 2020-04-14 | 武汉工程大学 | Graphene oxide/sodium alginate composite aerogel efficient adsorbent and preparation method and application thereof |
| CN111268669A (en) * | 2020-01-20 | 2020-06-12 | 洛阳理工学院 | Preparation method of graphene/silver nanowire composite aerogel |
| CN113144919A (en) * | 2020-11-23 | 2021-07-23 | 兰州大学 | 3D printing multifunctional filter membrane for sewage treatment and preparation method and application thereof |
-
2022
- 2022-12-27 CN CN202211680161.0A patent/CN115779972A/en active Pending
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105499600A (en) * | 2015-12-15 | 2016-04-20 | 中国科学院上海高等研究院 | Method for preparing silver nanowire-graphene composite aerogel |
| CN105749970A (en) * | 2016-03-02 | 2016-07-13 | 青岛大学 | Preparation method of calcium alginate-graphene-nano-gold composite hydrogel catalyst |
| CN109107574A (en) * | 2018-08-01 | 2019-01-01 | 兰州大学 | Silver-based oxysalt/graphite oxide aerogel preparation method and its aeroge obtained and application |
| CN110124627A (en) * | 2019-06-27 | 2019-08-16 | 中素新科技有限公司 | Graphene oxide and alginate composite aerogel and its preparation method and application |
| CN110479232A (en) * | 2019-08-20 | 2019-11-22 | 中国航发北京航空材料研究院 | A kind of preparation method of redox graphene base optic catalytic airsetting glue bead |
| CN111001394A (en) * | 2019-12-26 | 2020-04-14 | 武汉工程大学 | Graphene oxide/sodium alginate composite aerogel efficient adsorbent and preparation method and application thereof |
| CN111268669A (en) * | 2020-01-20 | 2020-06-12 | 洛阳理工学院 | Preparation method of graphene/silver nanowire composite aerogel |
| CN113144919A (en) * | 2020-11-23 | 2021-07-23 | 兰州大学 | 3D printing multifunctional filter membrane for sewage treatment and preparation method and application thereof |
Non-Patent Citations (1)
| Title |
|---|
| DAXIANG GAO ET AL.: "Preparation of Ag@AgCl/GO Material with Efficient Visible-Light Photocatalytic Performance", MATHEMATICAL PROBLEMS IN ENGINEERING, vol. 2022, pages 1 - 12 * |
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