CN110773146A - Graphene aerogel supported catalyst composite material and preparation method and application thereof - Google Patents
Graphene aerogel supported catalyst composite material and preparation method and application thereof Download PDFInfo
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/18—Arsenic, antimony or bismuth
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/39—Photocatalytic properties
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- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
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- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/283—Treatment of water, waste water, or sewage by sorption using coal, charred products, or inorganic mixtures containing them
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- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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- C02F1/30—Treatment of water, waste water, or sewage by irradiation
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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Abstract
The invention discloses a graphene aerogel supported catalyst composite material and a preparation method and application thereof.
Description
Technical Field
The invention relates to a graphene aerogel supported catalyst composite material and a preparation method and application thereof, belonging to the technical field of wastewater pollutant photocatalytic degradation materials.
Background
Organic dyes are widely used in various fields such as textile, paper printing, color photography, food, cosmetic, pharmaceutical and leather industries. Very low concentrations of dye will severely affect the clarity and gas solubility of the water body. In addition, dyes may have acute or chronic effects on organisms in the water. On the other hand, they can enter the food chain through the body of water, ultimately affecting human and animal health. The removal of dyes from contaminated water has become an important global problem.
Various adsorbents developed at present for dye wastewater have various disadvantages, such as poor reusability, high preparation cost, high post-treatment cost, great difficulty in industrial application, and the like. Therefore, there is an urgent need to develop an adsorbent which can adsorb dyes efficiently, can be recycled, has low cost and is convenient for industrial large-scale utilization. In addition to adsorption, how to effectively solve the pollutants is also a problem to be solved.
Disclosure of Invention
The purpose of the invention is as follows: in order to solve the technical problems, the invention provides a graphene aerogel supported catalyst composite material and a preparation method and application thereof.
The technical scheme is as follows: in order to achieve the purpose, the invention adopts the following technical scheme:
a preparation method of a graphene aerogel supported catalyst composite material comprises the following steps:
(1) preparing a graphene oxide dispersion liquid;
(2) synthesis of nano metal oxide catalyst: mixing a metal material and antimony trioxide powder, adding nitric acid, heating and stirring, placing in an ice water bath after the heating, slowly dropwise adding hydrogen peroxide, adding ultrapure water for hydrothermal reaction, separating solids after the hydrothermal reaction, and drying to obtain a nano metal oxide catalyst;
(3) synthesizing a graphene aerogel supported catalyst: dissolving the obtained nano metal oxide catalyst in ultrapure water by using amine as a cosolvent, adding the obtained mixed solution into the graphene oxide dispersion liquid prepared in the step (1), uniformly mixing, performing hydrothermal reaction, and freezing and drying after the hydrothermal reaction is finished to obtain the graphene aerogel loaded with the nano metal oxide catalyst;
preferably, the method comprises the following steps:
the method for preparing the graphene oxide dispersion liquid in the step (1) comprises the following steps:
and soaking the graphite oxide paste for 0.6-1 h, stirring at a low speed for 0.5-1 h, and then stirring at a high speed for 1-3 h to obtain the graphene oxide dispersion liquid.
The concentration of the graphene oxide dispersion liquid is 0.1-5 g/L.
In the step (2), the metal material is selected from tin, wherein the molar ratio of tin atoms to antimony atoms in antimony trioxide is 100: (30-40).
And (3) adding nitric acid in the step (2), heating and stirring at the temperature of 80-100 ℃, slowly dropwise adding hydrogen peroxide, and reacting for 1-30 min, wherein the hydrothermal reaction time is 1-20 h and the temperature is 50-200 ℃.
The amine described in step (3) is ethylenediamine, which also acts as a reducing agent and a crosslinking agent.
The mass ratio of the nano metal oxide catalyst in the step (3) to the graphene oxide in the dispersion liquid is 1: (0.1-10), wherein the hydrothermal reaction time is 12-24 h, and the reaction temperature is 80-100 ℃.
A graphene aerogel supported catalyst composite material is prepared by the preparation method.
The graphene aerogel supported catalyst composite material can be simultaneously used as a photocatalyst and an adsorbent.
The principle of the method of the invention is as follows: according to the method, the nanometer metal oxide catalyst is directly mixed into the amine solution, and then the nanometer metal oxide catalyst is naturally loaded on the graphene sheet in the process of crosslinking and reducing the graphene oxide dispersion solution, and the ethylenediamine is used as a cosolvent of the metal oxide, a crosslinking agent of the graphene aerogel and a reducing agent to prepare the novel graphene aerogel composite material.
The graphene aerogel has a mutually staggered porous network structure, large surface area and continuous pores, so that the graphene aerogel becomes an ideal agent for removing pollutants from polluted water and air, and can be used for adsorbing heavy metals, organic dyes, oil, organic solvents and air pollutants, such as toxic gases like NOX and SOX, and toxic organic pollutants like acetone and formaldehyde. Meanwhile, the graphene aerogel with large specific surface area is often used for compounding with a photocatalytic material, so that the photocatalytic performance of the graphene aerogel is improved.
The nano metal oxide catalyst, preferably tin antimony oxide, is used as heat insulating powder and conductive powder due to its good heat insulating property and conductive property, and besides these common properties, tin antimony oxide also has photocatalysis. According to the invention, the tin antimony oxide and the graphene are doped together to form a new composite material (tin antimony oxide/graphene aerogel), and a stronger adsorption effect and a photocatalysis effect are generated under the synergistic effect of the tin antimony oxide and the graphene.
Has the advantages that: compared with the prior art, the carbon-based framework of the graphene aerogel in the composite material has good electron transfer performance and mechanical strength, and is a very excellent carrier of the photocatalyst. The mode of loading the catalyst on the graphene aerogel is not only applied to the field of single photocatalytic degradation of organic pollutants, but also has obvious advantages due to the synergistic effect combination of the adsorbent and the photocatalyst. The composite synthesized by adopting the loading modes of physical dispersion, in-situ growth and the like has excellent adsorption effect of the graphene aerogel on pollutants and excellent degradation capability of the photocatalyst on the pollutants, and realizes efficient and continuous adsorption degradation.
Drawings
Fig. 1 is a diagram of a graphene aerogel preparation object of the present invention;
fig. 2 is a scanning electron microscope image and a transmission electron microscope image of the inventive graphene aerogel (a, B), tin antimony oxide/graphene aerogel (C, D);
FIG. 3 is an X-ray photoelectron spectroscopy analysis spectrum of a tin antimony oxide, graphene aerogel and a tin antimony oxide/graphene aerogel of the present invention;
FIG. 4 is an X-ray diffraction pattern of graphene oxide, antimony tin oxide, graphene aerogel and antimony tin oxide/graphene aerogel in accordance with the present invention;
fig. 5 is an infrared chromatogram of a graphene aerogel and a tin antimony oxide/graphene aerogel of the present invention.
Fig. 6 is a schematic view of photocatalytic degradation of the graphene aerogel according to the present invention.
Detailed Description
The method of the present invention is further described below with reference to the accompanying drawings and specific examples.
Example 1
(1) Synthetic graphene aerogels
Firstly, 10g of a commercially available graphite oxide paste (the mass ratio of the graphene oxide is 50%) is weighed and soaked in 1L of ultrapure water for 1 h. Then stirring is carried out for 30min at a low speed (< 500rpm), and then stirring is carried out for 3h at a high speed (> 2000 rpm). And 5g/L graphene oxide dispersion liquid with the number of graphene oxide layers smaller than 4 and the sheet diameter of about 18 mu m is obtained after stirring, and is collected for later use.
20mL of a 5g/L graphene oxide solution was taken, 30mL of ultrapure water was added thereto, and then, the mixture was stirred uniformly. Then, 500mg of ethylenediamine was added thereto, and stirred for 30 min. Then the mixed solution is transferred to a hydrothermal reaction kettle and reacts in a drying box at the temperature of 95 ℃ for 12 hours. And after the reaction is finished, taking out the hydrothermal reaction kettle for cooling, and then putting the cooled liner and the materials of the hydrothermal reaction kettle into a refrigerator at the temperature of-18 ℃ for freezing. And after completely freezing, putting the sample into a vacuum freeze dryer for freeze-drying operation, and finally obtaining the graphene aerogel reduced and crosslinked by ethylenediamine, namely the graphene aerogel for short.
(2) Synthesis of tin antimony oxide
First, 1g of tin particles and a corresponding amount of antimony trioxide powder (molar ratio of tin atom to antimony atom: 100: 35) were weighed in a 100mL three-necked flask, and then 5mL of nitric acid was added thereto and then heated and stirred at 95 ℃ for 2 hours. After heating and stirring, the three-neck flask is placed in an ice-water bath, and 20mL of hydrogen peroxide is slowly dropped into the three-neck flask. After 20min, 15mL of ultrapure water was added with stirring. And finally transferring the mixed solution into a hydrothermal reaction kettle, and reacting for 10 hours at 160 ℃. And after the reaction is finished, centrifugally separating the mixed liquid, drying the obtained solid, grinding the dried solid into powder and storing the powder for later use.
(3) Synthesis of tin antimony oxide/graphene aerogel
Take tin antimony oxide/graphene aerogel (graphene oxide: tin antimony oxide ═ 1: 3) as an example. 300mg of tin antimony oxide powder is put into 30mL of ultrapure water, then 500mg of ethylenediamine is added into the ultrapure water, and after violent shaking, the tin antimony oxide can be completely dissolved in the ultrapure water. Then, the mixed solution was added to 20mL of a 5g/L graphene oxide solution, and stirred for 30 min. Then the mixed solution is transferred to a hydrothermal reaction kettle and reacts in a drying box at the temperature of 95 ℃ for 12 hours. And after the reaction is finished, taking out the hydrothermal reaction kettle for cooling, and then putting the cooled liner and the materials of the hydrothermal reaction kettle into a refrigerator at the temperature of-18 ℃ for freezing. And after the sample is completely frozen, putting the sample into a vacuum freeze dryer for freeze-drying operation, and finally obtaining the graphene aerogel loaded with the tin antimony oxide, namely the tin antimony oxide/graphene aerogel for short.
Example 2
The method is basically the same as that of the embodiment 1, except that: the mass ratio of the graphene oxide to the tin antimony oxide is 1: and 2, synthesizing the tin antimony oxide/graphene aerogel. Through detection, the preparation method can successfully load the tin antimony oxide on the graphene aerogel.
Example 3
The method is basically the same as that of the embodiment 1, except that: the mass ratio of the graphene oxide to the tin antimony oxide is 1: and 1, synthesizing the tin antimony oxide/graphene aerogel. Through detection, the preparation method can successfully load the tin antimony oxide on the graphene aerogel.
The graphene aerogel and the tin antimony oxide/graphene aerogel are characterized by a scanning electron microscope and a transmission electron microscope, as shown in fig. 2, it can be seen that the surface of the sheet is smooth whether the graphene aerogel is a three-dimensional sheet or a flat sheet. And the deposition of tin antimony oxide particles can be obviously seen in the graphene sheets in the tin antimony oxide/graphene aerogel, which is a proof that tin antimony oxide is successfully loaded on the graphene aerogel.
Fig. 3 is an X-ray photoelectron spectroscopy analysis spectrum of tin antimony oxide, graphene aerogel and tin antimony oxide/graphene aerogel. From C1s (285.0eV), N1s (398.4eV), Sn3d (497.2eV), O1s (531.8eV), Sb3d3(537.6eV), it can be seen that the tin antimony oxide/graphene aerogel composite material has not only the characteristic peak of graphene aerogel but also the characteristic peak of tin antimony oxide, which proves that the tin antimony oxide and the graphene aerogel are successfully compounded to prepare the tin antimony oxide-loaded graphene aerogel.
Fig. 4 is an X-ray diffraction spectrum of graphene oxide, graphene aerogel, tin antimony oxide, and tin antimony oxide/graphene aerogel. From the figure, it can be seen that the graphene oxide is reduced by ethylenediamine in the process of preparing the graphene aerogel, the original characteristic peak 1 is lost, and the characteristic peak becomes the characteristic peak 2 of the graphene aerogel, and the characteristic peak of the graphene aerogel can be observed from the tin antimony oxide/graphene aerogel. The characteristic peak 3 is a characteristic peak combination of tin antimony oxide, the obvious characteristic peak 3 can be identified from a graph of tin antimony oxide/graphene aerogel, and the synthesis of the tin antimony oxide/graphene aerogel does not change the structures of the tin antimony oxide and the graphene aerogel.
Fig. 5 is an infrared spectrum of graphene aerogel and tin antimony oxide/graphene aerogel. Compared with the graphene aerogel, the tin antimony oxide/graphene aerogel has three more peaks, 614cm
-1Indicating characteristic peaks considered as Sn-O and Sb-O. 1115 and 1483cm
-1The peak is derived from the reduction of interlayer C-C bonds and the enhancement of intra-layer C ═ C bonds after the insertion of tin antimony oxide particles between graphene layers. The results show that the preparation method can successfully load the tin antimony oxide on the graphene aerogel.
Fig. 6 is a schematic view of photocatalytic degradation of the tin antimony oxide-loaded graphene aerogel having fenton-like photocatalytic characteristics in example 1. In fig. 6, it can be clearly observed that under the action of adding hydrogen peroxide and ultraviolet light, the tin antimony oxide/graphene aerogel generates obvious degradation to the brilliant yellow solution, and the ultraviolet absorption spectrum corresponding to the degradation of the brilliant yellow solution can be obviously observed to be reduced from 0.910 at 0min to 0.286 at 50min at the position of maximum 402nm, which shows that the tin antimony oxide/graphene aerogel synthesized in example 1 has good fenton-like photocatalytic properties.
Claims (9)
1. The preparation method of the graphene aerogel supported catalyst composite material is characterized by comprising the following steps:
(1) preparing a graphene oxide dispersion liquid;
(2) synthesis of nano metal oxide catalyst: mixing a metal material and antimony trioxide powder, adding nitric acid, heating and stirring, placing in an ice water bath after the heating, slowly dropwise adding hydrogen peroxide, adding ultrapure water for hydrothermal reaction, separating solids after the hydrothermal reaction, and drying to obtain a nano metal oxide catalyst;
(3) synthesizing a graphene aerogel supported catalyst: dissolving the obtained nano metal oxide catalyst in ultrapure water by using amine as a cosolvent, adding the obtained mixed solution into the graphene oxide dispersion liquid prepared in the step (1), uniformly mixing, carrying out hydrothermal reaction to obtain the graphene hydrogel loaded with the nano metal oxide catalyst, and freezing and drying after the hydrothermal reaction to obtain the graphene aerogel loaded with the nano metal oxide catalyst.
2. The preparation method of the graphene aerogel supported catalyst composite material according to claim 1, wherein the method for preparing the graphene oxide dispersion liquid in the step (1) is as follows:
and soaking the graphite oxide paste for 0.6-1 h, stirring at a low speed for 0.5-1 h, and then stirring at a high speed for 1-3 h to obtain the graphene oxide dispersion liquid.
3. The preparation method of the graphene aerogel supported catalyst composite material according to claim 1, wherein the concentration of the graphene oxide dispersion liquid is 0.1-5 g/L.
4. The preparation method of the graphene aerogel supported catalyst composite material according to claim 1, wherein the metal material in the step (2) is selected from tin, wherein the molar ratio of tin atoms to antimony atoms in antimony trioxide is 100: (30-40).
5. The preparation method of the graphene aerogel supported catalyst composite material according to claim 1, wherein the temperature for heating and stirring by adding nitric acid in the step (2) is 80-100 ℃, hydrogen peroxide is slowly dripped and then the reaction is carried out for 1-30 min, the hydrothermal reaction time is 1-20 h, and the temperature is 50-200 ℃.
6. The method for preparing the graphene aerogel supported catalyst composite according to claim 1, wherein the amine in the step (3) is ethylenediamine, which also serves as a reducing agent and a crosslinking agent.
7. The preparation method of the graphene aerogel supported catalyst composite material according to claim 1, wherein the mass ratio of the nano metal oxide catalyst to the graphene oxide in the dispersion liquid in the step (3) is 1: (0.1-10), wherein the hydrothermal reaction time is 12-24 h, and the reaction temperature is 80-100 ℃.
8. A graphene aerogel supported catalyst composite, characterized in that the composite is prepared by the preparation method of any one of claims 1 to 7.
9. The graphene aerogel supported catalyst composite of claim 8 for use as both a photocatalyst and an adsorbent.
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