CN115555042A - Preparation method of carbon nanotube catalyst, carbon nanotube catalyst and application thereof - Google Patents
Preparation method of carbon nanotube catalyst, carbon nanotube catalyst and application thereof Download PDFInfo
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- CN115555042A CN115555042A CN202211550154.9A CN202211550154A CN115555042A CN 115555042 A CN115555042 A CN 115555042A CN 202211550154 A CN202211550154 A CN 202211550154A CN 115555042 A CN115555042 A CN 115555042A
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- 229910021393 carbon nanotube Inorganic materials 0.000 title claims abstract description 94
- 239000003054 catalyst Substances 0.000 title claims abstract description 43
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 39
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 38
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 23
- 238000001354 calcination Methods 0.000 claims abstract description 22
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 19
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- RBTBFTRPCNLSDE-UHFFFAOYSA-N 3,7-bis(dimethylamino)phenothiazin-5-ium Chemical compound C1=CC(N(C)C)=CC2=[S+]C3=CC(N(C)C)=CC=C3N=C21 RBTBFTRPCNLSDE-UHFFFAOYSA-N 0.000 description 3
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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
- B01J27/24—Nitrogen compounds
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/20—Catalysts, in general, characterised by their form or physical properties characterised by their non-solid state
- B01J35/23—Catalysts, in general, characterised by their form or physical properties characterised by their non-solid state in a colloidal state
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- 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
- B01J35/33—Electric or magnetic properties
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- B—PERFORMING OPERATIONS; TRANSPORTING
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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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- C—CHEMISTRY; METALLURGY
- 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
- C02F1/30—Treatment of water, waste water, or sewage by irradiation
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- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/722—Oxidation by peroxides
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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
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- C02F1/725—Treatment of water, waste water, or sewage by oxidation by catalytic oxidation
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- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
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- C02F2305/02—Specific form of oxidant
- C02F2305/026—Fenton's reagent
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- C02F2305/10—Photocatalysts
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Abstract
The invention provides a preparation method of a carbon nano tube catalyst, the carbon nano tube catalyst and application thereof, wherein the preparation method comprises the following steps: mixing a nitrogen source, the carbon nano tube, organic alcohol and pure water, ultrasonically stirring until the mixture is dissolved, heating to evaporate water, freeze-drying, and calcining to obtain a nitrogen-doped carbon nano tube; uniformly mixing nitrogen-doped carbon nanotubes, ferric trichloride hexahydrate, sodium carbonate, sodium fluoride and pure water, heating, cooling, adding pure water and organic alcohol, carrying out solid-liquid centrifugal separation, washing and drying solid components, and calcining the solid components to obtain the carbon nanotube catalyst. The carbon nano tube catalyst prepared by the method can realize high-efficiency separation of photoproduction electrons and holes by utilizing visible light-Fenton synergistic oxidation, effectively improves the visible light utilization rate and catalytic activity of the photocatalyst, and is convenient to recycle.
Description
Technical Field
The invention relates to the field of catalyst materials, in particular to a preparation method of a carbon nano tube catalyst, and also relates to the carbon nano tube catalyst prepared by the method and application thereof.
Background
The problem of water pollution caused by industrial wastewater is always a difficult problem which puzzles social development and environmental protection, so that the development of a green, environment-friendly and efficient environmental management technology is very important. In the existing advanced oxidation method, the Fenton technology is considered by researchers at home and abroad to be one of effective ways for degrading organic pollutants in water. The Fenton reagent mainly takes Fe or other transition metals (Cu, me and the like) as a catalyst, and reacts with H2O2 in a system to generate OH, and the purpose of degrading pollutants in water is achieved through the oxidation of the OH. However, the conventional Fenton oxidation method has many disadvantages, such as: the reaction system is influenced by pH value, and the pH value needs to be controlled so as to achieve higher degradation effect; free iron ions are not easy to recover after entering water, and can generate a large amount of sludge and the like after reacting with pollutants in the water, thereby causing the waste of the catalyst and being not beneficial to the reaction. The photo-Fenton oxidation method of the semiconductor is taken as an advanced oxidation technology, has the advantages of no secondary pollution, high speed and efficiency, strong oxidation capacity and the like, and shows good application value in the aspects of wastewater purification and the like. However, most of semiconductor photocatalysts have wider band gaps, so that the photocatalysts have the problems of fast photon-generated carrier recombination, narrow visible light absorption range and the like in a reaction system, and the catalytic efficiency is low. Fe2O3 has attracted attention in recent years as a narrow bandgap semiconductor photocatalyst, but has a defect of high recombination rate of photo-generated electron-hole pairs.
Disclosure of Invention
The invention provides a preparation method of a carbon nano tube catalyst, which has higher catalytic activity.
A method for preparing a carbon nanotube catalyst, the method comprising the steps of: mixing a nitrogen source, the carbon nano tube, organic alcohol and pure water, ultrasonically stirring until the mixture is dissolved, heating to evaporate water, freeze-drying, and calcining at 650-750 ℃ to prepare the nitrogen-doped carbon nano tube; uniformly mixing the nitrogen-doped carbon nanotube, ferric trichloride hexahydrate, sodium carbonate, sodium fluoride and pure water, heating to 180-220 ℃, cooling, adding pure water and organic alcohol, carrying out solid-liquid centrifugal separation, washing solid components, drying, and calcining the solid components at 280-320 ℃ to obtain the carbon nanotube catalyst.
Further, the nitrogen source includes at least one of melamine and urea.
Further, the organic alcohol includes at least one of methanol, ethanol, isopropanol, n-butanol, and n-pentanol.
Further, when the obtained nitrogen-doped carbon nanotube is calcined, the nitrogen-doped carbon nanotube is calcined in the atmosphere of nitrogen or inert gas, the temperature rising speed of the calcination is 5-10 ℃/min, and the calcination time is 0.9-1.1h.
Further, when the solid component is dried, drying is carried out for 11-13h at 60-70 ℃ by using a vacuum drying oven.
Further, the solid component calcination time is 2.9-3.1h.
According to the invention, the electric conductivity of the carbon nano tube is utilized to realize the rapid transfer of charges, the defect structure formed by doping nitrogen on the surface of the carbon nano tube is improved by the method, the atomic activity is improved, and further, the iron oxide is loaded on the surface of the carbon nano tube to prepare the carbon nano tube catalyst, the visible light-Fenton synergistic oxidation can be utilized to realize the efficient separation of photoproduction electrons and holes, the visible light utilization rate and the catalytic activity of the photocatalyst are effectively improved, and the photocatalyst is convenient to recycle.
The invention also provides a carbon nano tube catalyst, and the carbon nano tube catalyst is prepared by adopting the preparation method of the carbon nano tube catalyst.
The carbon nano tube catalyst can realize the high-efficiency separation of photoproduction electrons and holes by utilizing visible light-Fenton synergistic oxidation, effectively improves the visible light utilization rate and catalytic activity of the photocatalyst, and is convenient to recycle.
The invention further provides an application of the carbon nano tube catalyst, and the carbon nano tube catalyst is used for catalyzing and degrading organic pollutants.
Drawings
The accompanying drawings, which are incorporated in and constitute a part of this specification, illustrate an embodiment of the invention and, together with the description, serve to explain the invention and not to limit the invention. In the drawings:
FIG. 1 is a schematic diagram of the mechanism of degrading pollutants by N-CNTs @ Fe2O3 in the photo-Fenton system;
FIG. 2 is a crystal structure XRD spectrum of N-CNTs @ Fe2O3 and Fe2O3 and CNTs-Fe2O3 in accordance with the present invention;
FIG. 3 is an XPS full scan spectrum of N-CNTs-Fe2O3 and CNTs-Fe2O3 according to the present invention;
FIG. 4 is a graph showing the organic matter degradation cycle test of N-CNTs @ Fe2O3 in accordance with the present invention;
FIG. 5 is a graph of the degradation rate of N-CNTs @ Fe2O3 in the light-Fenton system for different pollutants;
FIG. 6 is the effect of different quenchers on the degradation of RhB by N-CNTs @ Fe2O3;
FIG. 7 is a graph showing the efficiency of degrading RhB in a photo-Fenton system for samples of each example.
Detailed Description
It should be noted that the embodiments and features of the embodiments of the present invention may be combined with each other without conflict.
The experimental procedures in the following examples are all conventional ones unless otherwise specified. The test materials used in the following examples were purchased from a conventional biochemical reagent store unless otherwise specified. In addition, unless otherwise specified, all terms and processes related to the present embodiment should be understood according to the conventional knowledge and conventional methods in the art.
A preparation method of a carbon nano tube catalyst specifically comprises the following steps:
weighing the following raw materials in parts by weight: 3-7 parts of nitrogen source, 3-7 parts of carbon nano tube, 25-35 parts of organic alcohol, 20-35 parts of ferric chloride hexahydrate, 1.5-2.5 parts of sodium carbonate and 4-8 parts of sodium fluoride. Mixing nitrogen source, carbon nanotube, partial organic alcohol and pure water, and ultrasonic stirring to dissolve. And then heating in a water bath to evaporate water, wherein the temperature of the water bath can be set to be 80-90 ℃, the time of the water bath is 3-4h, and a small amount of water is evaporated from the solution to be thickened according to practical conditions. And then freeze-drying to obtain the N-CNTs precursor. And calcining the N-CNTs precursor at 650-750 ℃ to prepare the nitrogen-doped carbon nano tube which is recorded as N-CNTs.
Uniformly mixing nitrogen-doped carbon nanotubes, ferric trichloride hexahydrate, sodium carbonate, sodium fluoride and pure water, heating to 180-220 ℃, and reacting for 24 hours. Naturally cooling, adding pure water and organic alcohol, carrying out solid-liquid centrifugal separation, washing solid components, drying the solid components to form a product N-CNTs @ FeOOH of the iron oxyhydroxide loaded on the carbon nano tube, and calcining the solid components at 280-320 ℃ to prepare the carbon nano tube catalyst, which is marked as N-CNTs @ Fe2O3.
According to the invention, the electric conductivity of the carbon nano tube is utilized to realize the rapid transfer of charges, the nitrogen is doped on the surface of the carbon nano tube to form a defect structure through the method, the atomic activity is improved, and further, the iron oxide (Fe 2O 3) is synthesized in situ on the surface of the carbon nano tube, so that the iron oxide-loaded nitrogen-doped carbon nano tube composite photocatalyst is prepared.
The sodium carbonate added in the preparation process can reduce the reaction time for generating the ferric oxide, and the shape of the formed ferric oxide is changed from the naturally crystallized X type into an I type rod-shaped structure, so that the ferric oxide is easier to be firmly loaded on the nitrogen-doped carbon nano tube. The nitrogen-doped carbon nanotube, ferric trichloride hexahydrate, sodium carbonate, sodium fluoride and pure water are uniformly mixed and heated to 180-220 ℃, so that the generated iron oxyhydroxide has a porous structure and good adsorption property, and the photocatalytic activity is improved.
The invention carries out nitrogen (N) doping modification on the carbon nano tube, adopts a Carbon Nano Tube (CNTs) loading mode to improve the separation efficiency of Fe2O3 photon-generated carriers, realizes the high-efficiency separation of photon-generated electrons and holes, effectively improves the visible light utilization rate and the catalytic activity of the photocatalyst, can enhance the adsorption performance of the surface of the composite material, and is convenient to recover and recycle. The amount of the above raw materials can also be adjusted according to the design of the loading of nitrogen atoms and iron oxide to obtain products with different light utilization rates and catalytic activities, and the invention is not specifically limited herein.
The carbon nano tube can adopt a single-walled carbon nano tube and/or a multi-walled carbon nano tube, preferably adopts a multi-walled carbon nano tube, when the multi-walled tube is formed, the layers can easily become trap centers to capture various defects, so that the tube wall of the multi-walled tube is usually full of small-hole-like defects, and hybrid elements and semiconductors can be loaded more easily. Nitrogen sources of the present invention for reasons of cost and ease of access, organic nitrogen sources such as at least one of melamine and urea may preferably be used, and organic alcohols such as at least one of methanol, ethanol, isopropanol, n-butanol and n-pentanol may preferably be used.
When the obtained nitrogen-doped carbon nano tube is calcined, the nitrogen-doped carbon nano tube is calcined in the atmosphere of nitrogen or inert gas, the temperature rise speed of the calcination is 5-10 ℃/min, and the calcination time is 0.9-1.1h. When the solid component is dried, drying for 11-13h at 60-70 deg.C by vacuum drying oven. The solid component calcination time is 2.9-3.1h.
The invention also provides a carbon nano tube catalyst, and the carbon nano tube catalyst is prepared by adopting the preparation method of the carbon nano tube catalyst.
The carbon nano tube catalyst can be compounded with H2O2, realizes high-efficiency separation of photo-generated electrons and holes by utilizing visible light-Fenton synergistic oxidation, effectively improves the visible light utilization rate and catalytic activity of the photocatalyst, and is convenient to recycle.
The crystal structure information of the carbon nanotube catalyst N-CNTs @ Fe2O3 of the present invention, pure Fe2O3 and carbon nanotube supported iron oxide CNTs-Fe2O3 (carbon nanotube supported iron oxide doped with nitrogen atoms without using nitrogen source) was analyzed and compared by XRD spectrogram, as shown in FIG. 2. The main diffraction peaks of pure Fe2O3 are located at 24.14 degrees, 33.15 degrees, 35.61 degrees, 40.85 degrees, 49.48 degrees, 54.09 degrees, 62.45 degrees, 63.99 degrees and the like, and respectively correspond to crystal faces (012), (104), (110), (113), (024), (116), (214) and (300), the main diffraction peaks can be matched with Fe2O3 standard cards (JCPDS NO. 33-0664), the main characteristic peaks have high intensity and sharp peak shapes, and no impurity diffraction peaks exist, which indicates that Fe2O3 is successfully synthesized, and the prepared sample has high purity and crystallinity. The characteristic peaks of the synthesized compound N-CNTs-Fe2O3 and CNTs-Fe2O3 are similar, wherein the diffraction peak of the CNTs-Fe2O3 at 26.54 degrees is a (002) crystal face corresponding to the carbon nano tube, and is matched with a standard card (JCPDS NO. 65-6212). However, it should be noted here that N-CNTs-Fe2O3 doped with nitrogen atoms does not have a new diffraction peak, and the peak shifts, indicating that nitrogen atoms are successfully introduced into the carbon nanotube lattice.
On the other hand, XPS full-scan spectrum analysis is performed on the compounds N-CNTs-Fe2O3 and CNTs-Fe2O3, as shown in FIG. 3. The CNTs-Fe2O3 can detect characteristic peaks of O, fe and C, and in addition, the N-CNTs-Fe2O3 element N can be detected in the N-CNTs-Fe2O3 compound, so that the successful doping of the N element into the carbon nano tube is further verified.
The invention further provides application of the carbon nano tube catalyst, and particularly relates to application of the carbon nano tube catalyst in catalytic degradation of organic pollutants.
Stability and universality of N-CNTs @ Fe2O3
In order to test the stability performance of the N-CNTs @ Fe2O3 composite material under the photo-Fenton system, 3 times of cycle tests were carried out, and the results are shown in FIG. 4. Through three times of cycle experiments on organic matter degradation, the degradation rate of the N-CNTs @ Fe2O3 composite material is slightly reduced (from 96.9% to 95.5%), and therefore the composite material has high catalytic activity and cyclic use performance.
In order to further verify the universality of the N-CNTs @ Fe2O3 composite material, rhodamine B (RhB), methylene Blue (MB), bisphenol A (BPA) and Phenol (Phenol) are respectively used as target pollutants, and the degradation effect of the target pollutants in a light-Fenton system is measured, and the result is shown in FIG. 5. After visible light irradiation for two hours, the degradation rates of RhB, MB, BPA and Phenol are respectively 96.9%, 72.7%, 87.5% and 85.4%, and N-CNTs @ Fe2O3 can be seen to have better degradation activity on various pollutants and certain universal performance.
N-CNTs @ Fe2O3 degradation mechanism
In order to further research the active components which play main roles in the photo-Fenton synergistic degradation process of N-CNTs @ Fe2O3, a quenching experiment is carried out, and a primary study is carried out on the degradation mechanism of the active components. The results of experiments with different quenchers added to the system are shown in fig. 6. Wherein, the tert-butyl alcohol (TBA), the Benzoquinone (BQ) and the ethylene diamine tetraacetic acid (EDTA-2 Na) are quenchers of OH, O2-and h +. As can be seen from the figure, the degradation efficiency of the reaction system was slightly changed after the addition of BQ, which indicates that O2-is not the main active component. After TBA and EDTA-2Na are added, the degradation activity of the N-CNTs @ Fe2O3 composite material is obviously changed, and the catalytic activity is obviously reduced, which indicates that OH and h + play a main role in degrading RhB and are main active components, wherein OH is the most main active substance.
Based on the above results and discussion, the mechanism of N-CNTs @ Fe2O3 in the photo-Fenton system for degrading contaminants was analyzed, as shown in FIG. 1. Under the irradiation of visible light, fe2O3 is excited to generate photo-generated electron-hole pairs. The excited electron transits from the Valence Band (VB) to the Conduction Band (CB), and the hole exists in the valence band. A portion of the holes present in the valence band can directly oxidize organic contaminants, resulting in degradation. Electrons which jump to the conduction band, and a part of the electrons are combined with H2O2 to generate OH; one part of the oxygen reacts with dissolved oxygen (O2) in water to generate superoxide radical (. O2-), and the generated free radicals can oxidize and degrade pollutants; the other part of electrons are transferred and transferred under the action of CNTs, and Fe & lt 3+ & gt is reduced into Fe & lt 2+ & gt, so that the separation efficiency of photon-generated carriers is improved. In addition, fe2+ is easier to react with H2O2 in a reaction system to generate OH and OH < - > to degrade pollutants, and meanwhile, fe2+ is oxidized into Fe3+ again, so that good circulation of Fe3+/Fe2+ is formed, and the utilization rate of iron ions is improved. In the whole degradation system, the problem of secondary pollution caused by iron mud deposition is solved, and the efficiency of degrading pollutants is improved. The above reaction formulae are as follows (formula 1) - (formula 5)
The following describes in detail specific embodiments of the present invention.
Example 1
Weighing 0.5g of melamine, 0.5g of carbon nano tube, 40ml of methanol and 80ml of pure water, uniformly mixing, ultrasonically stirring for 30min until the melamine, the carbon nano tube, the methanol and the pure water are completely dissolved, stirring in a water bath at 80 ℃ until a small amount of water is evaporated, thickening, and then freeze-drying to obtain the N-CNTs precursor. And putting the N-CNTs precursor into a tube furnace, introducing nitrogen (or other inert gases), heating to 700 ℃ at the speed of 5 ℃/min in the nitrogen atmosphere, and calcining for 1h to obtain the N-CNTs.
0.27g (about 1 mmol) of ferric chloride hexahydrate (FeCl3.6H2O), 0.0212g of sodium carbonate (Na 2CO 3), 0.063g of sodium fluoride (NaF) and 0.06g of N-CNTs are respectively added into 60ml of pure water in sequence, are uniformly stirred and are transferred to a 100ml reaction kettle to react for 24 hours at 200 ℃. And taking out the sample after 24h, naturally cooling, adding a proper amount of pure water and absolute ethyl alcohol, centrifuging and washing for four times, and drying in a vacuum drying oven at 60 ℃ for 12h to form a product N-CNTs @ FeOOH of which the carbon nano tube is loaded with the iron oxyhydroxide. Putting N-CNTs @ FeOOH into a forced air drying oven, and calcining for 3h at 300 ℃ to prepare N-CNTs @ Fe2O3.
Comparative example 1
0.27g (1 mmol) of FeCl3.6H2O, 0.0212g (0.2 mmol) of Na2CO3 and 0.063g (1.5 mmol) of NaF are weighed out and added to 60ml of pure water in this order and stirred well, after 20min the mixture is transferred to a 100ml reaction vessel and reacted at 200 ℃ for 24H. And taking out the sample after 24h, naturally cooling to room temperature, putting the sample into a centrifuge tube, adding a proper amount of absolute ethyl alcohol and pure water, centrifuging and washing for four times, and putting the sample into a vacuum drying oven to dry for 12h at 60 ℃ to obtain the product FeOOH. And placing the FeOOH into an air-blast drying oven, and calcining for 3h at 300 ℃ to finally form the Fe2O3 monomer.
Comparative example 2
Weighing 0.5g of melamine, 0.5g of carbon nano tube, 40ml of methanol and 80ml of pure water, uniformly mixing, ultrasonically stirring for 30min until the melamine, the carbon nano tube, the methanol and the pure water are completely dissolved, stirring in a water bath at 80 ℃ until a small amount of water is evaporated and the solution becomes thick, and then freeze-drying to obtain the N-CNTs precursor. And putting the N-CNTs precursor into a tube furnace, introducing nitrogen, heating to 700 ℃ at the speed of 5 ℃/min in the nitrogen atmosphere, and calcining for 1h to obtain the N-CNTs material.
The carbon nanotubes in the above reagent are carboxylated multi-wall carbon nanotubes (average length <10 μm, purity >98wt%, code TNMC 8), and the other reagents are analytically pure (AR).
The samples prepared in the above examples were tested, and fig. 7 is a graph showing the degradation of RhB in the photo-fenton system for the different samples. It can be seen from the figure that the degradation capability of the N-CNTs @ Fe2O3 composite material of example 1 to RhB under the photo-Fenton condition is obviously higher than that of the Fe2O3 monomer of comparative example 1 and the CNTs @ Fe2O3 composite material of comparative example 2. The catalytic performance of CNTs @ Fe2O3 is higher than that of Fe2O3 monomer, which shows that the addition of the carbon nano tube has a promotion effect on the photocatalytic activity of Fe2O3. Because the carbon nano tube belongs to a porous carbon material, functional groups contained on the surface of the carbon nano tube have strong adsorption performance on organic pollutants, and after the carbon nano tube is compounded with Fe2O3, the aggregation of Fe2O3 particles is inhibited, and the adsorption capacity of the carbon nano tube is improved; the carbon nano tube has conductive performance, so that the transfer of electrons is promoted, and the carrier separation efficiency is improved. The N-CNTs @ Fe2O3 has the optimal degradation effect, and due to the introduction of the non-metal dopant N, the synthesized nitrogen-doped carbon nanotube has more active sites compared with a single carbon nanotube, so that the efficiency of degrading pollutants is improved; meanwhile, the nitrogen doping causes the defect structure formed by the carbon nano tube, which is more beneficial to the uniform compounding of Fe2O3 on the surface of the carbon nano tube.
The preferred embodiments of the present invention have been described in detail, however, the present invention is not limited to the specific details of the above embodiments, and various simple modifications may be made to the technical solution of the present invention within the technical idea of the present invention, and these simple modifications are all within the protection scope of the present invention.
It should be noted that the various technical features described in the above embodiments can be combined in any suitable manner without contradiction, and the invention is not described in any way for the possible combinations in order to avoid unnecessary repetition.
Claims (8)
1. A preparation method of a carbon nano tube catalyst is characterized by comprising the following steps: the method comprises the following steps:
mixing a nitrogen source, a carbon nano tube, organic alcohol and pure water, ultrasonically stirring until the nitrogen source, the carbon nano tube, the organic alcohol and the pure water are dissolved, heating to evaporate water, freeze-drying, and calcining at 650-750 ℃ to prepare the nitrogen-doped carbon nano tube;
uniformly mixing the nitrogen-doped carbon nanotube, ferric trichloride hexahydrate, sodium carbonate, sodium fluoride and pure water, heating to 180-220 ℃, cooling, adding pure water and organic alcohol, carrying out solid-liquid centrifugal separation, washing solid components, drying, and calcining the solid components at 280-320 ℃ to obtain the carbon nanotube catalyst.
2. The method for producing a carbon nanotube catalyst according to claim 1, wherein: the nitrogen source comprises at least one of melamine and urea.
3. The method for producing a carbon nanotube catalyst according to claim 1, characterized in that: the organic alcohol includes at least one of methanol, ethanol, isopropanol, n-butanol, and n-pentanol.
4. The method for producing a carbon nanotube catalyst according to claim 1, wherein: and when the obtained nitrogen-doped carbon nanotube is calcined, calcining the nitrogen-doped carbon nanotube in the atmosphere of nitrogen or inert gas, wherein the temperature rise speed in the calcination is 5-10 ℃/min, and the calcination time is 0.9-1.1h.
5. The method for producing a carbon nanotube catalyst according to claim 1, characterized in that: and when the solid component is dried, drying for 11-13h at 60-70 ℃ by adopting a vacuum drying oven.
6. The method for producing a carbon nanotube catalyst according to any one of claims 1 to 5, wherein: the calcining time of the solid component is 2.9-3.1h.
7. A carbon nanotube catalyst, characterized by: the carbon nanotube catalyst prepared by the method of any one of claims 1 to 6.
8. Use of the carbon nanotube catalyst according to claim 7, wherein: the carbon nanotube catalyst is used for catalytically degrading organic pollutants.
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