CN112121843B - Preparation method and application of loofah sponge genetic-supported nitrogen-doped carbon nanotube coated iron nanoparticle Fenton-like catalyst - Google Patents
Preparation method and application of loofah sponge genetic-supported nitrogen-doped carbon nanotube coated iron nanoparticle Fenton-like catalyst Download PDFInfo
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- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 title claims abstract description 333
- 235000009814 Luffa aegyptiaca Nutrition 0.000 title claims abstract description 108
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 86
- 229910052742 iron Inorganic materials 0.000 title claims abstract description 78
- 239000003054 catalyst Substances 0.000 title claims abstract description 66
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- 238000002360 preparation method Methods 0.000 title claims abstract description 13
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- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonium chloride Substances [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims description 2
- XMEVHPAGJVLHIG-FMZCEJRJSA-N chembl454950 Chemical compound [Cl-].C1=CC=C2[C@](O)(C)[C@H]3C[C@H]4[C@H]([NH+](C)C)C(O)=C(C(N)=O)C(=O)[C@@]4(O)C(O)=C3C(=O)C2=C1O XMEVHPAGJVLHIG-FMZCEJRJSA-N 0.000 abstract description 42
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- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
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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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/24—Nitrogen compounds
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- B01J35/396—
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- B01J35/61—
-
- 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
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/722—Oxidation by peroxides
-
- 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
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/725—Treatment of water, waste water, or sewage by oxidation by catalytic oxidation
-
- 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
-
- 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
- C02F2101/38—Organic compounds containing nitrogen
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
- C02F2103/34—Nature of the water, waste water, sewage or sludge to be treated from industrial activities not provided for in groups C02F2103/12 - C02F2103/32
- C02F2103/343—Nature of the water, waste water, sewage or sludge to be treated from industrial activities not provided for in groups C02F2103/12 - C02F2103/32 from the pharmaceutical industry, e.g. containing antibiotics
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2305/00—Use of specific compounds during water treatment
- C02F2305/02—Specific form of oxidant
- C02F2305/026—Fenton's reagent
Abstract
A preparation method and application of a loofah sponge genetic-supported nitrogen-doped carbon nanotube coated iron nanoparticle Fenton-like catalyst relate to a preparation method and application of a Fenton-like catalyst. The invention aims to solve the problems that the active components of the existing Fenton-like catalyst are easy to agglomerate, the ions are leached out, and Fe is generated under the neutral condition3+/Fe2+Slow conversion and poor cycle stability. The method comprises the following steps: firstly, preparing dried loofah with the grain diameter of 8-10 mm; secondly, alkalization treatment; thirdly, mixing Fe3+Precipitating on the surface of retinervus Luffae fructus; fourthly, doping a nitrogen source; fifthly, pyrolysis; sixthly, cleaning and drying. A nitrogen-doped carbon nanotube-coated iron nanoparticle Fenton-like catalyst supported by loofah sponge in a genetic state is used for degrading tetracycline hydrochloride in sewage. The invention is suitable for degrading antibiotics.
Description
Technical Field
The invention relates to a preparation method and application of a Fenton-like catalyst.
Background
With the wide application of antibiotics, the residual drugs in water not only cause serious environmental problems, but also have potential influence on human health. In recent years, the Fenton-like oxidation method can deeply degrade and mineralize antibiotics by generating strong oxidizing OH, and the technology mainly focuses on the design and development of heterogeneous Fenton-like catalysts, particularly iron-based catalysts. However, the solid-phase catalyst containing iron species has the problems of leaching of Fe ions and poor stability. In which, other materials are used as carriers, such as carbon materials like carbon nanotubes, graphene, activated carbon, biochar and the like, which have high compatibility due to various structures and good conductivity.
The carbon nanotube has sp2The characteristics of hybrid carbon configuration, regular tubular microstructure, rich porosity and the like are favored by researchers. While the doping of the hetero atoms can adjust the original sp2The electronic nature of the hybrid carbon redistributes the charge density of adjacent carbon atoms, modifying the intrinsic electronic structure of the pure carbon matrix, creating a large number of active sites. The atomic radius of N is similar to that of C, and lone-pair electrons in the N atom can generate resonance with a large pi bond in a C atom lattice to form a high-efficiency active site of metal-nitrogen-carbon (M-N-C), so that the N-type metal-nitrogen-carbon composite material shows excellent catalytic performance and is a commonly used doping element at present. A common method for synthesizing N-doped carbon nanotubes (NCNTs) is to carbonize a nitrogen-containing organic precursor using Fe, Co, Ni as a catalyst. Wherein, the iron has low cost and no toxicity, is a common material similar to a Fenton catalyst, and can catalyze the formation of the carbon nano tube. However, the single carbon nanotube prepared by the method is easy to agglomerate and collapse, and the catalytic activity is influenced.
Disclosure of Invention
The invention aims to solve the problems that the active components of the existing Fenton-like catalyst are easy to agglomerate, the ions are leached out, and Fe is generated under the neutral condition3+/Fe2+Slow conversion and poor circulation stability, and provides a method for preparing the nitrogen-doped carbon nanotube-coated iron nanoparticle Fenton-like catalyst supported by loofah sponge in an genetic stateAnd applications.
A preparation method of a loofah sponge genetic-supported nitrogen-doped carbon nanotube coated iron nanoparticle Fenton-like catalyst comprises the following steps:
firstly, removing seeds of mature loofah sponge, cleaning, drying, and then cutting into pieces to obtain dried loofah sponge with the particle size of 8-10 mm;
secondly, alkalization treatment:
firstly, mixing dried loofah sponge with the particle size of 8-10 mm with a KOH solution, and then stirring to obtain a reaction solution I;
secondly, transferring the reaction liquid I into a reaction kettle with a polytetrafluoroethylene lining, performing alkalization treatment, and cooling to room temperature along with a furnace to obtain a reaction product I;
thirdly, washing the reaction product I to be neutral by using deionized water, and then putting the reaction product I into an oven for drying to obtain the KOH-treated loofah sponge;
thirdly, soaking the KOH-treated loofah sponge into FeCl3·6H2Adding O solution, stirring under oil bath heating, adding ammonia water solution, stirring under oil bath heating, and adding Fe3+Precipitating the solution on the surface of the loofah sponge to obtain a reaction solution II;
fourthly, adding melamine into the reaction liquid II, heating and stirring until the liquid is evaporated to dryness, and then putting the liquid into a drying oven for drying to obtain a reaction product II;
fifthly, placing the reaction product II into a porcelain boat, covering another porcelain boat on the porcelain boat, placing the porcelain boat into a tubular furnace, introducing nitrogen into the tubular furnace, heating the tubular furnace to 700-900 ℃, and pyrolyzing the ceramic boat for 1.5-2.5 hours at 700-900 ℃ in nitrogen atmosphere to obtain a reaction product III;
sixthly, taking deionized water as a cleaning agent, centrifugally cleaning the reaction product III to be neutral, and then putting the reaction product III into a vacuum drying oven for drying to obtain Fe/FexC @ NCNTs-CL, namely the nitrogen-doped carbon nanotube coated iron nanoparticle Fenton catalyst supported by the vegetable sponge in a genetic state.
A nitrogen-doped carbon nanotube-coated iron nanoparticle Fenton-like catalyst supported by loofah sponge in a genetic state is used for degrading antibiotics in sewage.
The principle and the advantages of the invention are as follows:
the loofah sponge serving as a biomass carbon material has a unique porous vascular bundle structure, and a large number of holes are formed in the surface after activation treatment, so that the loofah sponge serving as a carrier material can provide a high specific surface area; in addition, the loofah sponge has a plurality of functional groups on the surface, such as (-COOH, -OH), and can generate electrostatic adsorption and chelation with Fe metal cations, so that active substances are highly dispersed on the surface, and then Fe catalyzes the growth of nitrogen-doped carbon nanotubes (NCNTs) in situ and coats the nitrogen-doped carbon nanotubes (NCNTs), so that the loofah sponge is an ideal carrier for improving the dispersing capacity and stability of the NCNTs, and the synergistic effect of the loofah sponge and the NCNTs improves the catalytic performance. Therefore, nitrogen-doped carbon nanotube coated iron nanoparticle Fenton-like catalyst (Fe) with loofah sponge morph-genetic support is constructed through pyrolysis in-situ growthxC/Fe @ NCNTs-CL), useful for degrading antibiotic materials;
secondly, the biomass loofah sponge is used as a carrier, is cheap and easily available, is green and renewable, and a large number of functional groups on the surface of the loofah sponge can be complexed with iron ions; with FeCl3·6H2Using O as iron source and ammonia water as precipitant, hot dipping and stirring the volatile solution to make Fe3+Uniformly and fully precipitating on the surface of the loofah sponge, taking melamine as a nitrogen source, having high nitrogen content and low cost, and passing through the loofah sponge and FeCl3·6H2And performing pyrolysis treatment on O and melamine to generate the uniformly dispersed nitrogen-doped carbon nano-tubes wrapping the nano-iron particles on the surface of the loofah sponge biochar in situ. The innovation points are as follows:
(1) the loofah sponge is used as a carrier and can provide stable driving force for degradation circulation, the unique pipeline structure of the loofah sponge provides a channel for the degradation circulation, the concentration difference exists between the degraded solution in the hole and the external undegraded solution, the concentration gradient forms a 'reaction pump', and the degradation product is pushed out in time to supplement new solution; in addition, the inherent three-dimensional porous structure of the loofah sponge has high specific surface area, the loading capacity of the active component is improved, a large number of functional groups on the surface of the loofah sponge can fully and uniformly complex iron ions, and NCNTs with good dispersibility are further synthesized in situ under the catalytic action of iron in the high-temperature pyrolysis process, so that the catalytic efficiency of the active substance is improved;
(2) preparing NCNTs on the surface of the carrier, and fixing the iron nanoparticles in the NCNTs to effectively reduce the outflow of active substances; in addition, in the preparation process, due to the catalytic action of Fe, a layer of carbon shell is formed outside the iron particles and can be used as a protective layer to prevent the nano Fe particles from agglomerating in the pyrolysis process and dissolving out in the catalytic process, and the double protection action of the nano Fe particles and the catalytic process on active substances realizes high-efficiency stable catalysis;
(3) the solution in the NCNTs forms a reaction micro-control area, so that the flow rate and mass transfer of the solution are effectively controlled, the reaction time of active components and antibiotics is prolonged, and the efficient recycling of the catalyst is realized;
(4) the nitrogen-doped carbon nano tube breaks the inertia of a matrix carbon skeleton, improves the conductivity of the matrix, forms high-efficiency active sites of Fe-N-C, and provides a synergistic effect for excellent catalytic performance by the action of a carbon shell, promotes the internal active species Fe3+To Fe2+The rapid transformation of (2).
Thirdly, degrading tetracycline hydrochloride by using the nitrogen-doped carbon nanotube-coated iron nanoparticle Fenton catalyst for the first time, wherein the degradation rate can reach 97%, and the nitrogen-doped carbon nanotube-coated iron nanoparticle-like Fenton catalyst for the first time is prepared by the method disclosed by the invention and is degraded for 40 min;
fourthly, the nitrogen-doped carbon nanotube coated iron nanoparticle Fenton-like catalyst supported by the loofah sponge in the genetic state can be repeatedly used, and the excellent cycle stability is shown.
The invention is suitable for degrading tetracycline hydrochloride.
Drawings
FIG. 1 shows Fe/Fe prepared in examples one, two and threexXRD pattern of C @ NCNTs-CL;
FIG. 2 shows Fe/Fe prepared in examples one, two and threexSEM picture of C @ NCNTs-CL, in which (a) is Fe/Fe prepared in example onexSEM picture of C @ NCNTs-CL-700, (b) Fe/Fe prepared in example twoxSEM picture of C @ NCNTs-CL-800, (C) Fe/Fe prepared in example IIIxSEM picture of C @ NCNTs-CL-900;
FIG. 3 shows preparation of example twoFe/Fe ofxSEM images of C @ NCNTs-CL-800 at different magnifications, wherein (a) is a high magnification image and (b) is a low magnification image;
FIG. 4 shows Fe/Fe prepared in comparative example3SEM picture of C @ NCNTs;
FIG. 5 is Fe/Fe prepared in example twoxC @ NCNTs-CL-800, in which (a) is a first TEM image, (b) is a second TEM image, and (C) is a third TEM image;
FIG. 6 is Fe/Fe prepared in example twoxHR-TEM image of C @ NCNTs-CL-800;
FIG. 7 is Fe/Fe prepared in example twoxC @ NCNTs-CL-800 EDS element map;
FIG. 8 is Fe/Fe prepared in example twoxXPS spectra of C @ NCNTs-CL-800, wherein (a) is a full spectrum, (b) is a C1s spectrum, (C) is an N1s spectrum, and (d) is an Fe2p spectrum;
FIG. 9 is Fe/FexRaman spectrum of C @ NCNTs-CL, in which 1 is Fe/Fe prepared in example onexC @ NCNTs-CL-700, 2 is Fe/Fe prepared in example twoxC @ NCNTs-CL-800, 3 is Fe/Fe prepared in example IIIxC@NCNTs-CL-900；
FIG. 10 is a graph showing the degradation profile of tetracycline hydrochloride in which Fe/FexC @ NCNTs-CL-700 is Fe/Fe prepared in example onexDegradation curve of C @ NCNTs-CL for degrading tetracycline hydrochloride, Fe/FexC @ NCNTs-CL-800 is Fe/Fe prepared in example twoxDegradation curve of C @ NCNTs-CL for degrading tetracycline hydrochloride, Fe/FexC @ NCNTs-CL-900 is Fe/Fe prepared in example threexDegradation curve of C @ NCNTs-CL for degrading tetracycline hydrochloride, Fe/Fe3C @ NCNTs is Fe/Fe prepared in comparative example3C @ NCNTs degradation curve for tetracycline hydrochloride degradation;
FIG. 11 is Fe/Fe prepared in example twoxC @ NCNTs-CL-800, where 1st is the first use of Fe/Fe prepared in example twoxDegradation profile of C @ NCNTs-CL-800 for degradation of tetracycline hydrochloride, 2ed being the second use of Fe/Fe prepared in example twoxDegradation profile of C @ NCNTs-CL-800 for degradation of tetracycline hydrochloride, 3rd being the third use of Fe/Fe prepared in example twoxC @ NCNTs-CL-800 degradation Profile of tetracycline hydrochloride, 4th being the fourth use of Fe/Fe prepared in example twoxDegradation curve diagram of C @ NCNTs-CL-800 for degrading tetracycline hydrochloride.
Detailed Description
The following examples further illustrate the present invention but are not to be construed as limiting the invention. Modifications and substitutions to methods, procedures, or conditions of the invention may be made without departing from the spirit of the invention.
The first embodiment is as follows: the embodiment is a preparation method of a nitrogen-doped carbon nanotube coated iron nanoparticle Fenton-like catalyst supported by loofah sponge in a genetic state, which is completed according to the following steps:
firstly, removing seeds of mature loofah sponge, cleaning, drying, and then cutting into pieces to obtain dried loofah sponge with the particle size of 8-10 mm;
secondly, alkalization treatment:
firstly, mixing dried loofah sponge with the particle size of 8-10 mm with a KOH solution, and then stirring to obtain a reaction solution I;
secondly, transferring the reaction liquid I into a reaction kettle with a polytetrafluoroethylene lining, performing alkalization treatment, and cooling to room temperature along with a furnace to obtain a reaction product I;
thirdly, washing the reaction product I to be neutral by using deionized water, and then putting the reaction product I into an oven for drying to obtain the KOH-treated loofah sponge;
thirdly, soaking the KOH-treated loofah sponge into FeCl3·6H2Adding O solution, stirring under oil bath heating, adding ammonia water solution, stirring under oil bath heating, and adding Fe3+Precipitating the solution on the surface of the loofah sponge to obtain a reaction solution II;
fourthly, adding melamine into the reaction liquid II, heating and stirring until the liquid is evaporated to dryness, and then putting the liquid into a drying oven for drying to obtain a reaction product II;
fifthly, placing the reaction product II into a porcelain boat, covering another porcelain boat on the porcelain boat, placing the porcelain boat into a tubular furnace, introducing nitrogen into the tubular furnace, heating the tubular furnace to 700-900 ℃, and pyrolyzing the ceramic boat for 1.5-2.5 hours at 700-900 ℃ in nitrogen atmosphere to obtain a reaction product III;
sixthly, taking deionized water as a cleaning agent, centrifugally cleaning the reaction product III to be neutral, and then putting the reaction product III into a vacuum drying oven for drying to obtain Fe/FexC @ NCNTs-CL, namely the nitrogen-doped carbon nanotube coated iron nanoparticle Fenton catalyst supported by the vegetable sponge in a genetic state.
The principle and advantages of the embodiment are as follows:
the loofah sponge serving as a biomass carbon material has a unique porous vascular bundle structure, and a large number of holes are formed in the surface after activation treatment, so that the loofah sponge serving as a carrier material can provide a high specific surface area; in addition, the loofah sponge has a plurality of functional groups on the surface, such as (-COOH, -OH), and can generate electrostatic adsorption and chelation with Fe metal cations, so that active substances are highly dispersed on the surface, and then Fe catalyzes the growth of nitrogen-doped carbon nanotubes (NCNTs) in situ and coats the nitrogen-doped carbon nanotubes (NCNTs), so that the loofah sponge is an ideal carrier for improving the dispersing capacity and stability of the NCNTs, and the synergistic effect of the loofah sponge and the NCNTs improves the catalytic performance. Therefore, nitrogen-doped carbon nanotube coated iron nanoparticle Fenton-like catalyst (Fe) with loofah sponge morph-genetic support is constructed through pyrolysis in-situ growthxC/Fe @ NCNTs-CL), useful for degrading antibiotic materials;
secondly, the biomass loofah sponge is used as a carrier, is cheap and easily available, is green and renewable, and a large number of functional groups on the surface of the loofah sponge can be complexed with iron ions; with FeCl3·6H2Using O as iron source and ammonia water as precipitant, hot dipping and stirring the volatile solution to make Fe3+Uniformly and fully precipitating on the surface of the loofah sponge, taking melamine as a nitrogen source, having high nitrogen content and low cost, and passing through the loofah sponge and FeCl3·6H2And performing pyrolysis treatment on O and melamine to generate the uniformly dispersed nitrogen-doped carbon nano-tubes wrapping the nano-iron particles on the surface of the loofah sponge biochar in situ. The innovation points are as follows:
(1) the loofah sponge is used as a carrier and can provide stable driving force for degradation circulation, the unique pipeline structure of the loofah sponge provides a channel for the degradation circulation, the concentration difference exists between the degraded solution in the hole and the external undegraded solution, the concentration gradient forms a 'reaction pump', and the degradation product is pushed out in time to supplement new solution; in addition, the inherent three-dimensional porous structure of the loofah sponge has high specific surface area, the loading capacity of the active component is improved, a large number of functional groups on the surface of the loofah sponge can fully and uniformly complex iron ions, and NCNTs with good dispersibility are further synthesized in situ under the catalytic action of iron in the high-temperature pyrolysis process, so that the catalytic efficiency of the active substance is improved;
(2) preparing NCNTs on the surface of the carrier, and fixing the iron nanoparticles in the NCNTs to effectively reduce the outflow of active substances; in addition, in the preparation process, due to the catalytic action of Fe, a layer of carbon shell is formed outside the iron particles and can be used as a protective layer to prevent the nano Fe particles from agglomerating in the pyrolysis process and dissolving out in the catalytic process, and the double protection action of the nano Fe particles and the catalytic process on active substances realizes high-efficiency stable catalysis;
(3) the solution in the NCNTs forms a reaction micro-control area, so that the flow rate and mass transfer of the solution are effectively controlled, the reaction time of active components and antibiotics is prolonged, and the efficient recycling of the catalyst is realized;
(4) the nitrogen-doped carbon nano tube breaks the inertia of a matrix carbon skeleton, improves the conductivity of the matrix, forms high-efficiency active sites of Fe-N-C, and provides a synergistic effect for excellent catalytic performance by the action of a carbon shell, promotes the internal active species Fe3+To Fe2+The rapid transformation of (2).
Thirdly, degrading tetracycline hydrochloride by using the nitrogen-doped carbon nanotube-coated iron nanoparticle Fenton catalyst prepared by the loofah sponge genetic support for the first time for 40min, wherein the degradation rate can reach 97%;
fourthly, the nitrogen-doped carbon nanotube-coated iron nanoparticle Fenton-like catalyst supported by the loofah sponge in the genetic state can be repeatedly used, and excellent cycle stability is shown.
The embodiment is suitable for degrading tetracycline hydrochloride.
The second embodiment is as follows: the present embodiment differs from the present embodiment in that: the cleaning in the step one is to use deionized water to clean for 3 to 5 times, and then use absolute ethyl alcohol to clean for 3 to 5 times; the drying temperature is 60-80 ℃, and the drying time is 10-12 h. Other steps are the same as in the first embodiment.
The third concrete implementation mode: the present embodiment differs from the first or second embodiment in that: the ratio of the mass of the dried loofah with the particle size of 8-10 mm to the volume of the KOH solution in the second step (8 g-10 g) is 100 mL; the concentration of the KOH solution in the second step is 1 mol/L; the stirring speed in the second step is 800 r/min-1000 r/min, and the stirring time is 1 h-3 h. The other steps are the same as in the first or second embodiment.
The fourth concrete implementation mode: the difference between this embodiment and one of the first to third embodiments is as follows: the alkalization temperature in the second step is 155-165 ℃, and the alkalization time is 8-12 h; the drying temperature in the second step is 60-80 ℃, and the drying time is 10-12 h. The other steps are the same as those in the first to third embodiments.
The fifth concrete implementation mode: the difference between this embodiment and one of the first to fourth embodiments is: FeCl described in step three3·6H2The concentration of the O solution is 0.05 mol/L; the quality and FeCl of the loofah sponge treated by KOH in the step three3·6H2The volume ratio of the O solution (0.3 g-0.5 g) was 40 mL. The other steps are the same as those in the first to fourth embodiments.
The sixth specific implementation mode: the difference between this embodiment and one of the first to fifth embodiments is as follows: in the third step, the KOH-treated loofah sponge is immersed into FeCl3·6H2Stirring the mixture for 1 to 3 hours in the O solution under the heating of an oil bath at the temperature of between 65 and 75 ℃, then adding an ammonia solution, and continuously stirring the mixture for 1 to 3 hours under the heating of the oil bath at the temperature of between 65 and 75 ℃, wherein the stirring speed is between 800 and 1000 r/min; the mass fraction of the ammonia water solution in the third step is 1-2%; the ammonia water solution and FeCl in the step three3·6H2The volume ratio of the O solution is (1-3) to 40. The other steps are the same as those in the first to fifth embodiments.
The seventh embodiment: the difference between this embodiment and one of the first to sixth embodiments is: the mass ratio of the melamine in the fourth step to the loofah sponge treated by the KOH in the third step is (3-5) to 0.5; the heating and stirring temperature in the fourth step is 65-75 ℃, and the stirring speed is 800-1000 r/min; the drying temperature is 60-65 ℃, and the drying time is 10-12 h. The other steps are the same as those in the first to sixth embodiments.
The specific implementation mode is eight: the difference between this embodiment and one of the first to seventh embodiments is: the temperature rise rate in the fifth step is 4-6 ℃/min; and the drying temperature in the sixth step is 60-65 ℃, and the drying time is 10-12 h. The other steps are the same as those in the first to seventh embodiments.
The specific implementation method nine: the embodiment is that the nitrogen-doped carbon nanotube-coated iron nanoparticle Fenton-like catalyst supported by the loofah sponge in the genetic state is used for degrading antibiotics in sewage.
The detailed implementation mode is ten: the present embodiment differs from the ninth embodiment in that: the nitrogen-doped carbon nanotube coated iron nanoparticle Fenton-like catalyst supported by loofah sponge in a genetic state is used for degrading antibiotics in sewage and is prepared by the following steps:
firstly, adding a nitrogen-doped carbon nanotube coated iron nanoparticle Fenton catalyst supported by loofah sponge in a genetic state into sewage with the antibiotic concentration of 35-50 mg/L, uniformly stirring, and then adding H with the mass fraction of 30%2O2Timing the solution, and degrading for 40-60 min to obtain treated sewage;
h with the mass fraction of 30% in the step one2O2The volume ratio of the solution to the sewage (30-40 mu L) is 50 mL;
the ratio of the mass of the nitrogen-doped carbon nanotube coated iron nanoparticle Fenton catalyst supported by the loofah sponge in the step one to the volume of sewage (20-25 mg) is 50 mL;
secondly, absorbing the nitrogen-doped carbon nanotube coated iron nanoparticle Fenton catalyst supported by the loofah sponge in the genetic state by using a magnet, washing the catalyst for 5 to 10 times by using deionized water, and drying the catalyst for 10 to 12 hours in an oven at the temperature of between 60 and 65 ℃ to obtain the recovered nitrogen-doped carbon nanotube coated iron nanoparticle Fenton catalyst supported by the loofah sponge in the genetic state; the other steps are the same as those in the first to ninth embodiments.
The antibiotic according to the present embodiment is tetracycline hydrochloride.
The present invention will be described in detail below with reference to the accompanying drawings and examples.
The first embodiment is as follows: a preparation method of a loofah sponge genetic-supported nitrogen-doped carbon nanotube coated iron nanoparticle Fenton-like catalyst is characterized by comprising the following steps:
firstly, removing seeds of 10g of mature loofah sponge, washing the loofah sponge with deionized water for 5 times, washing the loofah sponge with absolute ethyl alcohol for 5 times, drying the loofah sponge at 60 ℃ for 10 hours, and shearing the loofah sponge to obtain dried loofah sponge with the particle size of 8-10 mm;
secondly, alkalization treatment:
mixing 10g of dried loofah with the particle size of 8-10 mm with 100mL of 1mol/L KOH solution, and stirring at the stirring speed of 800r/min for 2 hours to obtain a reaction solution I;
secondly, transferring the reaction liquid I into a reaction kettle with a polytetrafluoroethylene lining, then carrying out alkalization treatment for 10 hours at 160 ℃, and then cooling to room temperature along with a furnace to obtain a reaction product I;
thirdly, washing the reaction product I to be neutral by using deionized water, and then putting the reaction product I into a baking oven with the temperature of 60 ℃ for baking for 10 hours to obtain the KOH-treated loofah sponge;
thirdly, soaking 0.5g of KOH-treated loofah sponge into 40mL of FeCl with the concentration of 0.05mol/L3·6H2Stirring the mixture for 2 hours in O solution under the heating of 70 ℃ oil bath, wherein the stirring speed is 1000r/min, then adding 2mL of ammonia water solution with the mass fraction of 1.25%, and continuing stirring the mixture for 2 hours under the heating of 70 ℃ oil bath, wherein the stirring speed is 1000r/min, and Fe3+Precipitating the solution on the surface of the loofah sponge to obtain a reaction solution II;
adding 4g of melamine into the reaction liquid II, heating and stirring at 70 ℃, wherein the stirring speed is 1000r/min until the liquid is evaporated to dryness, and then putting the liquid into an oven at 60 ℃ to be dried for 10 hours to obtain a reaction product II;
fifthly, placing the reaction product II into a porcelain boat, covering another porcelain boat on the porcelain boat, placing the porcelain boat into a tubular furnace, introducing nitrogen into the tubular furnace, heating the tubular furnace to 700 ℃ at the heating rate of 5 ℃/min, and pyrolyzing the tubular furnace for 2 hours at 700 ℃ in the nitrogen atmosphere to obtain a reaction product III;
sixthly, taking deionized water as a cleaning agent, centrifugally cleaning the reaction product III to be neutral, and then drying the reaction product III in a vacuum drying oven at the temperature of 60 ℃ for 12 hours to obtain Fe/FexC @ NCNTs-CL-700, namely the nitrogen-doped carbon nanotube coated iron nanoparticle Fenton catalyst supported by the loofah sponge in a genetic state.
Example two: the present embodiment is different from the first embodiment in that: putting the reaction product II into a porcelain boat, covering another porcelain boat on the porcelain boat, putting the porcelain boat into a tubular furnace, introducing nitrogen into the tubular furnace, heating the tubular furnace to 800 ℃ at the heating rate of 5 ℃/min, and pyrolyzing the tubular furnace for 2 hours at 800 ℃ in the nitrogen atmosphere to obtain a reaction product III; taking deionized water as a cleaning agent, centrifugally cleaning the reaction product III to be neutral, and then drying the reaction product III in a vacuum drying oven at the temperature of 60 ℃ for 12 hours to obtain Fe/FexC @ NCNTs-CL-800, namely the nitrogen-doped carbon nanotube coated iron nanoparticle Fenton catalyst supported by the loofah sponge in a genetic state. Other steps and parameters are the same as those in the first embodiment.
Example three: the present embodiment is different from the first embodiment in that: putting the reaction product II into a porcelain boat, covering another porcelain boat on the porcelain boat, putting the porcelain boat into a tubular furnace, introducing nitrogen into the tubular furnace, heating the tubular furnace to 900 ℃ at the heating rate of 5 ℃/min, and pyrolyzing the tubular furnace for 2 hours at 900 ℃ in the nitrogen atmosphere to obtain a reaction product III; taking deionized water as a cleaning agent, centrifugally cleaning the reaction product III to be neutral, and then drying the reaction product III in a vacuum drying oven at the temperature of 60 ℃ for 12 hours to obtain Fe/FexC @ NCNTs-CL-900, namely the nitrogen-doped carbon nanotube coated iron nanoparticle Fenton catalyst supported by the loofah sponge in a genetic state. Other steps and parameters are the same as those in the first embodiment.
Comparative example: Fe/Fe3C @ NCNTs was prepared as follows:
FeCl of 0.05mol/L is prepared3·6H240mL of O solution, to 40mL of 0.05mol/L FeCl3·6H2Adding 4g of melamine into the O solution, carrying out oil bath heating and stirring at 70 ℃, wherein the stirring speed is 1000r/min until the liquid is evaporated to dryness, and then putting the mixture into an oven at 60 ℃ to bake for 10 hours; putting the obtained reaction product into a porcelain boat, covering another porcelain boat on the porcelain boat, putting the porcelain boat into a tubular furnace, introducing nitrogen into the tubular furnace, heating the tubular furnace to 800 ℃ at the heating rate of 5 ℃/min, and pyrolyzing the ceramic boat for 2 hours at 800 ℃ in the nitrogen atmosphere to obtain the reaction product Fe/Fe3C@NCNTs。
FIG. 1 shows Fe/Fe prepared in examples one, two and threexXRD pattern of C @ NCNTs-CL;
as can be seen from fig. 1, all three samples had a diffraction peak of the graphitic carbon (002) crystal plane at θ ═ 26.2 °. Comparing with X-ray diffraction standard card, the iron species at 700 deg.C are Fe and Fe2.5The intergrowth of C is transformed into Fe and Fe when the temperature is increased to 800 DEG C3C, raising the temperature to 900 ℃, and Fe3The proportion of C is changed, and the amount of Fe is increased, which indicates that the chemical composition in the composite material is adjusted by the pyrolysis temperature.
FIG. 2 shows Fe/Fe prepared in examples one, two and threexSEM picture of C @ NCNTs-CL, in which (a) is Fe/Fe prepared in example onexSEM picture of C @ NCNTs-CL-700, (b) Fe/Fe prepared in example twoxSEM picture of C @ NCNTs-CL-800, (C) Fe/Fe prepared in example IIIxSEM picture of C @ NCNTs-CL-900;
it is clear from FIG. 2 that the diameter of the NCNTs increases with increasing pyrolysis temperature. At 700 ℃, NCNTs just start to form under the catalytic action of iron, and the diameter is only about 40-60 nm; the diameter of NCNTs is increased to 80-120nm at 800 deg.C, and the NCNTs are orderly combined on the surface of retinervus Luffae fructus; the temperature was raised to 900 ℃ and the diameter of the NCNTs was further increased to 160-200nm, but the NCNTs began to agglomerate.
FIG. 3 is Fe/Fe prepared in example twoxDifferent magnification of C @ NCNTs-CL-800SEM images of numbers in which (a) is a high magnification and (b) is a low magnification;
FIG. 4 shows Fe/Fe prepared in comparative example3SEM picture of C @ NCNTs;
obviously, the NCNTs with complete morphology are uniformly dispersed on the surface of the loofah sponge, which indicates that the loofah sponge not only can provide a place for the growth of the carbon nanotubes, but also can prevent the aggregation and the rupture of the carbon nanotubes; the NCNTs (as shown in figure 4) which is synthesized by the method and does not contain loofah sponge matrix has obvious agglomeration and rupture phenomena, and iron particles are not well coated on the NCNTs, so that iron particles outside the CNTs are stacked, and the loofah sponge effectively improves the dispersibility and stability of active substances.
FIG. 5 is Fe/Fe prepared in example twoxC @ NCNTs-CL-800, in which (a) is a first TEM image, (b) is a second TEM image, and (C) is a third TEM image;
it can be seen in fig. 5 that Fe particles are wrapped in carbon nanotubes with a diameter of 80-120nm and a length of several micrometers, and it can be further observed from fig. 5c that these carbon nanotubes are bonded on the surface of the luffa.
FIG. 6 is Fe/Fe prepared in example twoxHR-TEM image of C @ NCNTs-CL-800;
FIG. 6 further confirms that the lattice fringe spacing of the Fe particles is 0.20nm and 0.24nm, respectively, corresponding to Fe0Of (110) plane and Fe3The (210) plane of C illustrates that a part of reduced elemental iron is embedded into the carbon skeleton during pyrolysis to form Fe0And Fe3C, which is also consistent with the results of XRD analysis. In addition, 0.34nm lattice fringes were observed for the outer layer of the iron nanoparticles, which corresponds to the (002) plane of the graphitic carbon, indicating that ordered carbon shells are regularly arranged around the iron particles, and are very effective in preventing iron leaching.
FIG. 7 is Fe/Fe prepared in example twoxC @ NCNTs-CL-800 EDS element map;
fig. 7 clearly reveals C, N, O, Fe distribution, and it can be seen that the N element is uniformly distributed throughout the carbon tube, indicating that the N element was successfully doped into the carbon tube.
FIG. 8 is Fe/Fe prepared in example twoxXPS spectra of C @ NCNTs-CL-800, wherein (a) is a full spectrum, (b) is a C1s spectrum, (C) is an N1s spectrum, and (d) is an Fe2p spectrum;
from the full spectrum of FIG. 8(a), peaks at about 285eV, 399eV, 532eV, and 710eV for C1s, N1s, O1s, and Fe2p can be seen. FIG. 8(b) shows the C1s spectrum with peaks for C-N bonds and C-Fe, indicating Fe in the material3C, and N is doped into the carbon nano tube; the N1s spectrum (fig. 8(c)) was divided into four distinct peaks: pyridine N (398.5eV), pyrrole N (399.9eV), graphite N (401.3eV), and oxidized N (403.7 eV). Fe was present in the Fe2p spectrum (FIG. 8(d))0、Fe2+And Fe3+Fe2p1/2And Fe2p3/2Spin orbit peak, indicating that the composite material contains Fe and Fe3In addition to C, some oxides are present due to the inevitable surface oxidation characteristics.
FIG. 9 is Fe/FexRaman spectrum of C @ NCNTs-CL, in which 1 is Fe/Fe prepared in example onexC @ NCNTs-CL-700, 2 is Fe/Fe prepared in example twoxC @ NCNTs-CL-800, 3 is Fe/Fe prepared in example IIIxC@NCNTs-CL-900；
As can be seen from FIG. 9, when the pyrolysis temperature increased from 700 ℃ to 900 ℃, ID/IGThe value is reduced from 0.96 to 0.82, which indicates that partial defect carbon is converted into graphitized carbon, the graphitization degree of the material is increased, and the catalytic performance is improved.
Example four: Fe/Fe prepared by example onexThe C @ NCNTs-CL-700 degradation of tetracycline hydrochloride in sewage is completed according to the following steps:
one, 20mg of Fe/Fe prepared in example onexC @ NCNTs-CL-700 is added into 50mL of sewage with tetracycline hydrochloride concentration of 35mg/L, stirred evenly and then 34 mu L of H with mass fraction of 30 percent is added2O2Timing the solution, degrading for 0-60 min to obtain treated sewage, timing the reaction, taking 1mL of solution at certain time intervals, adding 1.0mL of methanol solution to quench the reaction, filtering by a 0.22-micron filtration membrane to remove the catalyst, and measuring the residual concentration of the tetracycline hydrochloride by adopting a liquid chromatography;
second, Fe prepared in example one was mixed with a magnet/FexC @ NCNTs-CL-700, washing with deionized water for 5 times, and drying in an oven at 60 deg.C for 10h to obtain recovered Fe/Fe prepared in example onexC @ NCNTs-CL-700, degradation curve is shown in FIG. 10.
Example five: Fe/Fe prepared using example twoxThe C @ NCNTs-CL-800 degradation of tetracycline hydrochloride in sewage is completed according to the following steps:
one, 20mg of Fe/Fe prepared in example twoxC @ NCNTs-CL-800 is added into 50mL of sewage with tetracycline hydrochloride concentration of 35mg/L, stirred evenly and then 34 mu L of H with mass fraction of 30 percent is added2O2Timing the solution, degrading for 0-60 min to obtain treated sewage, timing the reaction, taking 1mL of solution at certain time intervals, adding 1.0mL of methanol solution to quench the reaction, filtering by a 0.22-micron filtration membrane to remove the catalyst, and measuring the residual concentration of the tetracycline hydrochloride by adopting a liquid chromatography;
II, Fe/Fe prepared in example IIxC @ NCNTs-CL-800, washing with deionized water for 5 times, and drying in an oven at 60 ℃ for 10h to obtain the recovered Fe/Fe prepared in example twoxC @ NCNTs-CL-800, degradation curves are shown in FIG. 10 and 1st in FIG. 11.
Example six: Fe/Fe prepared by example IIIxThe C @ NCNTs-CL-900 degradation of tetracycline hydrochloride in sewage is completed according to the following steps:
one, 20mg of Fe/Fe prepared in example IIIxC @ NCNTs-CL-900 is added into 50mL of sewage with tetracycline hydrochloride concentration of 35mg/L, stirred evenly and then 34 mu L of H with mass fraction of 30 percent is added2O2Timing the solution, degrading for 0-60 min to obtain treated sewage, timing the reaction, taking 1mL of solution at certain time intervals, adding 1.0mL of methanol solution to quench the reaction, filtering by a 0.22-micron filtration membrane to remove the catalyst, and measuring the residual concentration of the tetracycline hydrochloride by adopting a liquid chromatography;
II, Fe/Fe prepared in example IIIxC @ NCNTs-CL-900, washing with deionized water for 5 times, and placing at 60 deg.CThen dried in an oven for 10h to obtain the recovered Fe/Fe prepared in the third embodimentxC @ NCNTs-CL-900, the degradation curve is shown in FIG. 10.
FIG. 10 is a graph showing the degradation profile of tetracycline hydrochloride in which Fe/FexC @ NCNTs-CL-700 is Fe/Fe prepared in example onexDegradation curve of C @ NCNTs-CL for degrading tetracycline hydrochloride, Fe/FexC @ NCNTs-CL-800 is Fe/Fe prepared in example twoxDegradation curve of C @ NCNTs-CL for degrading tetracycline hydrochloride, Fe/FexC @ NCNTs-CL-900 is Fe/Fe prepared in example threexDegradation curve of C @ NCNTs-CL for degrading tetracycline hydrochloride, Fe/Fe3C @ NCNTs is Fe/Fe prepared in comparative example3C @ NCNTs degradation curve for tetracycline hydrochloride degradation;
as can be seen in FIG. 10, the Fe/Fe prepared in example twoxThe Fenton-like catalytic performance of C @ NCNTs-CL-800 is the best, and the degradation is 97% at the pH of the initial solution within 40min, mainly because of Fe/FexC @ NCNTs-CL-700 has low Fe content, low graphitization degree of a carbon substrate, incomplete formation of NCNTs, weak protection effect on iron species and weak electron supply capability; and Fe/FexC @ NCNTs-CL-900 has too high pyrolysis temperature, the NCNTs begin to agglomerate, and iron particles do not well coat the NCNTs, so that active iron particles outside the NCNTs are accumulated, and the degradation efficiency is reduced; for Fe/Fe3C @ NCNTs, lacks the synergistic conductive ability of the carbon matrix, and after being separated from the loofah sponge, iron species are accumulated and the carbon nanotubes are aggregated. And Fe/FexThe iron ions of C @ NCNTs-CL-800 are well wrapped in the NCNTs, the NCNTs are uniformly and stably combined on the surface of the loofah sponge, and an electron transmission channel is formed between an active species and a matrix to promote Fe in the Fenton process3+/Fe2+The degradation efficiency is improved.
And (3) testing the cycling stability:
example seven: using the recovered Fe/Fe from example two obtained in example fivexThe C @ NCNTs-CL-800 degradation of tetracycline hydrochloride in sewage is completed according to the following steps:
first, 20mg of the recovered Fe/Fe of example five prepared in example twoxC @ NCNTs-CL-800 plusAdding into 50mL sewage with tetracycline hydrochloride concentration of 35mg/L, stirring, adding 34 μ L H with mass fraction of 30%2O2Timing the solution, degrading for 0-150 min to obtain treated sewage, timing the reaction, taking 1mL of solution at certain time intervals, adding 1.0mL of methanol solution to quench the reaction, filtering by a 0.22-micron filtration membrane to remove the catalyst, and measuring the residual concentration of the tetracycline hydrochloride by adopting a liquid chromatography;
second, use the magnet to mix Fe/FexC @ NCNTs-CL-800, washing with deionized water for 5 times, and drying in an oven at 60 ℃ for 10h to obtain the second recovered Fe/Fe prepared in example twoxC @ NCNTs-CL-800, degradation curve see 2ed in FIG. 11.
Example eight: utilizing the Fe/Fe prepared in example two after the second recovery obtained in example sevenxThe C @ NCNTs-CL-800 degradation of tetracycline hydrochloride in sewage is completed according to the following steps:
first, 20mg of the Fe/Fe alloy prepared in example two after the second recovery obtained in example sevenxC @ NCNTs-CL-800 is added into 50mL of sewage with tetracycline hydrochloride concentration of 35mg/L, stirred evenly and then 34 mu L of H with mass fraction of 30 percent is added2O2Timing the solution, degrading for 0-230 min to obtain treated sewage, timing the reaction, taking 1mL of solution at certain time intervals, adding 1.0mL of methanol solution to quench the reaction, filtering by a 0.22-micron filtration membrane to remove the catalyst, and measuring the residual concentration of the tetracycline hydrochloride by adopting a liquid chromatography;
second, use the magnet to mix Fe/FexC @ NCNTs-CL-800, washing with deionized water for 5 times, and drying in an oven at 60 deg.C for 10h to obtain Fe/Fe prepared in example two after the third recoveryxC @ NCNTs-CL-800, degradation curve is shown as 3rd in FIG. 11.
Example nine: utilizing the Fe/Fe recovered in example two after the third recovery obtained in example eightxThe C @ NCNTs-CL-800 degradation of tetracycline hydrochloride in sewage is completed according to the following steps:
first, after the third recovery of 20mg of the product obtained in example eightExample II Fe/FexC @ NCNTs-CL-800 is added into 50mL of sewage with tetracycline hydrochloride concentration of 35mg/L, stirred evenly and then 34 mu L of H with mass fraction of 30 percent is added2O2Timing the solution, degrading for 0-230 min to obtain treated sewage, timing the reaction, taking 1mL of solution at certain time intervals, adding 1.0mL of methanol solution to quench the reaction, filtering by a 0.22-micron filtration membrane to remove the catalyst, and measuring the residual concentration of the tetracycline hydrochloride by adopting a liquid chromatography;
second, use the magnet to mix Fe/FexC @ NCNTs-CL-800, washing with deionized water for 5 times, and drying in an oven at 60 deg.C for 10h to obtain Fe/Fe prepared in example two after fourth recoveryxC @ NCNTs-CL-800, degradation curve is shown in 4th in FIG. 11.
FIG. 11 is Fe/Fe prepared in example twoxC @ NCNTs-CL-800, where 1st is the first use of Fe/Fe prepared in example twoxDegradation profile of C @ NCNTs-CL-800 for degradation of tetracycline hydrochloride, 2ed being the second use of Fe/Fe prepared in example twoxDegradation profile of C @ NCNTs-CL-800 for degradation of tetracycline hydrochloride, 3rd being the third use of Fe/Fe prepared in example twoxC @ NCNTs-CL-800 degradation Profile of tetracycline hydrochloride, 4th being the fourth use of Fe/Fe prepared in example twoxDegradation curve diagram of C @ NCNTs-CL-800 for degrading tetracycline hydrochloride.
As can be seen from FIG. 11, after 4 cycles, the degradation rate of 60min was still more than 90%, indicating that the Fe/Fe prepared in example twoxC @ NCNTs-CL-800 is a stable and efficient Fenton-like catalyst.
Claims (10)
1. A preparation method of a loofah sponge genetic-supported nitrogen-doped carbon nanotube coated iron nanoparticle Fenton-like catalyst is characterized by comprising the following steps:
firstly, removing seeds of mature loofah sponge, cleaning, drying, and then cutting into pieces to obtain dried loofah sponge with the particle size of 8-10 mm;
secondly, alkalization treatment:
firstly, mixing dried loofah sponge with the particle size of 8-10 mm with a KOH solution, and then stirring to obtain a reaction solution I;
secondly, transferring the reaction liquid I into a reaction kettle with a polytetrafluoroethylene lining, performing alkalization treatment, and cooling to room temperature along with a furnace to obtain a reaction product I;
thirdly, washing the reaction product I to be neutral by using deionized water, and then putting the reaction product I into an oven for drying to obtain the KOH-treated loofah sponge;
thirdly, soaking the KOH-treated loofah sponge into FeCl3·6H2Adding O solution, stirring under oil bath heating, adding ammonia water solution, stirring under oil bath heating, and adding Fe3+Precipitating the solution on the surface of the loofah sponge to obtain a reaction solution II;
fourthly, adding melamine into the reaction liquid II, heating and stirring until the liquid is evaporated to dryness, and then putting the liquid into a drying oven for drying to obtain a reaction product II;
fifthly, placing the reaction product II into a porcelain boat, covering another porcelain boat on the porcelain boat, placing the porcelain boat into a tubular furnace, introducing nitrogen into the tubular furnace, heating the tubular furnace to 700-900 ℃, and pyrolyzing the ceramic boat for 1.5-2.5 hours at 700-900 ℃ in nitrogen atmosphere to obtain a reaction product III;
sixthly, taking deionized water as a cleaning agent, centrifugally cleaning the reaction product III to be neutral, and then putting the reaction product III into a vacuum drying oven for drying to obtain Fe/FexC @ NCNTs-CL, namely the nitrogen-doped carbon nanotube coated iron nanoparticle Fenton catalyst supported by the vegetable sponge in a genetic state.
2. The method for preparing the loofah sponge genetic supported nitrogen-doped carbon nanotube coated iron nanoparticle fenton-like catalyst according to claim 1, wherein the cleaning in the step one comprises cleaning with deionized water for 3 to 5 times, and then cleaning with absolute ethyl alcohol for 3 to 5 times; the drying temperature is 60-80 ℃, and the drying time is 10-12 h.
3. The method for preparing the nitrogen-doped carbon nanotube coated iron nanoparticle Fenton-like catalyst supported by loofah sponge in a genetic state according to claim 1, wherein the volume ratio of the mass of the dried loofah sponge with the particle size of 8-10 mm to the KOH solution in the second step (8-10 g) is 100 mL; the concentration of the KOH solution in the second step is 1 mol/L; the stirring speed in the second step is 800 r/min-1000 r/min, and the stirring time is 1 h-3 h.
4. The method for preparing the nitrogen-doped carbon nanotube coated iron nanoparticle Fenton-like catalyst supported by the vegetable sponge in the genetic state according to claim 1, wherein the alkalization temperature in the second step is 155-165 ℃, and the alkalization time is 8-12 h; the drying temperature in the second step is 60-80 ℃, and the drying time is 10-12 h.
5. The method for preparing the retinervus luffae fructus genetic supported N-doped carbon nanotube-coated iron nanoparticle Fenton-like catalyst according to claim 1, wherein the FeCl is obtained in the third step3·6H2The concentration of the O solution is 0.05 mol/L; the quality and FeCl of the loofah sponge treated by KOH in the step three3·6H2The volume ratio of the O solution (0.3 g-0.5 g) was 40 mL.
6. The method for preparing the nitrogen-doped carbon nanotube-coated iron nanoparticle Fenton-like catalyst supported by retinervus Luffae fructus in a genetic manner according to claim 1, wherein the method comprises immersing the retinervus Luffae fructus treated with KOH in FeCl3·6H2Stirring the mixture for 1 to 3 hours in the O solution under the heating of an oil bath at the temperature of between 65 and 75 ℃, then adding an ammonia solution, and continuously stirring the mixture for 1 to 3 hours under the heating of the oil bath at the temperature of between 65 and 75 ℃, wherein the stirring speed is between 800 and 1000 r/min; the mass fraction of the ammonia water solution in the third step is 1-2%; the ammonia water solution and FeCl in the step three3·6H2The volume ratio of the O solution is (1-3) to 40.
7. The method for preparing the nitrogen-doped carbon nanotube-coated iron nanoparticle Fenton-like catalyst supported by retinervus Luffae fructus in a genetic manner according to claim 1, wherein the mass ratio of the melamine in the fourth step to the retinervus Luffae fructus after KOH treatment in the third step is (3-5): 0.5; the heating and stirring temperature in the fourth step is 65-75 ℃, and the stirring speed is 800-1000 r/min; the drying temperature is 60-65 ℃, and the drying time is 10-12 h.
8. The method for preparing the loofah sponge genetic supported nitrogen-doped carbon nanotube coated iron nanoparticle fenton-like catalyst according to claim 1, wherein the temperature rise rate in the fifth step is 4 ℃/min to 6 ℃/min; and the drying temperature in the sixth step is 60-65 ℃, and the drying time is 10-12 h.
9. The use of the nitrogen-doped carbon nanotube-coated iron nanoparticle Fenton-like catalyst supported by loofah sponge in a genetic manner according to the preparation method of claim 1, wherein the nitrogen-doped carbon nanotube-coated iron nanoparticle-like catalyst supported by loofah sponge in a genetic manner is used for degrading antibiotics in sewage.
10. The use of the loofah sponge genetic supported nitrogen-doped carbon nanotube coated iron nanoparticle fenton-like catalyst according to claim 9, wherein the loofah sponge genetic supported nitrogen-doped carbon nanotube coated iron nanoparticle fenton-like catalyst for degrading antibiotics in sewage is prepared by the following steps:
firstly, adding a nitrogen-doped carbon nanotube coated iron nanoparticle Fenton catalyst supported by loofah sponge in a genetic state into sewage with the antibiotic concentration of 35-50 mg/L, uniformly stirring, and then adding H with the mass fraction of 30%2O2Timing the solution, and degrading for 40-60 min to obtain treated sewage;
h with the mass fraction of 30% in the step one2O2The volume ratio of the solution to the sewage (30-40 mu L) is 50 mL;
the ratio of the mass of the nitrogen-doped carbon nanotube coated iron nanoparticle Fenton catalyst supported by the loofah sponge in the step one to the volume of sewage (20-25 mg) is 50 mL;
and secondly, absorbing the nitrogen-doped carbon nanotube coated iron nanoparticle Fenton catalyst supported by the loofah sponge in the genetic state by using a magnet, washing the catalyst for 5 to 10 times by using deionized water, and drying the catalyst for 10 to 12 hours in an oven at the temperature of between 60 and 65 ℃ to obtain the recovered nitrogen-doped carbon nanotube coated iron nanoparticle Fenton catalyst supported by the loofah sponge in the genetic state.
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