CN111569878A - Preparation method and application of loofah sponge genetic porous carbon supported Fenton-like catalyst - Google Patents
Preparation method and application of loofah sponge genetic porous carbon supported Fenton-like catalyst Download PDFInfo
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- 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
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/74—Iron group metals
- B01J23/745—Iron
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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
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/18—Carbon
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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
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/722—Oxidation by peroxides
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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
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/725—Treatment of water, waste water, or sewage by oxidation by catalytic oxidation
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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
- C02F2101/38—Organic compounds containing nitrogen
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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
- 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
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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
- 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 porous carbon supported Fenton-like catalyst relate to a preparation method and application of a Fenton-like catalyst. The invention aims to solve the problems that an active component of a Fenton-like catalytic system is easy to agglomerate and Fe is generated under a neutral condition3+/Fe2+Slow conversion, poor circulation stability and complex process flow of the existing magnetic loofah sponge biochar preparation process, little load capacity of ferroferric oxide, non-uniform and agglomerated particle size, easy damage to the structure of loofah sponge and formation of alkaline environment when being used for water treatment, and no harm to Fenton-like process.The method comprises the following steps: firstly, cleaning, drying and crushing; secondly, treating with NaOH solution; thirdly, thermal dipping deposition; fourthly, high-temperature carbonization; and fifthly, grinding, cleaning and drying. A loofah sponge genetic porous carbon supported Fenton-like catalyst is used for degrading tetracycline hydrochloride in sewage.
Description
Technical Field
The invention relates to a preparation method and application of a Fenton-like catalyst.
Background
Water problems caused by antibiotic abuse can have detrimental effects on human health and the natural ecosystem. In recent years, Fenton-like oxidation has received increasing attention as a viable antibiotic removal technique. At present, heterogeneous Fenton-type catalysts are mainly researched by iron-based catalysts, and particularly, ferromagnetic materials are favored by researchers due to the advantage of easy recovery, but the defects of limited active sites, poor catalytic activity under neutral conditions, poor cycle stability and the like still exist.
The loofah serving as a biomass carbon material has a unique porous structure, a plurality of micron-sized hollow network channels are contained in the loofah, the loofah is densely arranged in a cross-linking mode, and a plurality of small holes are formed among the loofah and the loofah serving as a carrier material to provide a high specific surface area. In addition, the surface of the loofah sponge has a plurality of functional groups, such as (-COOH, -OH), and the loofah sponge can perform electrostatic adsorption and chelation with transition metal cations, so that active components are highly dispersed on the surface of the loofah sponge to prepare the loofah sponge biomass magnetic material, the adsorption and degradation performance on pollutants is enhanced, and the loofah sponge biomass magnetic material has a wide application prospect in the aspect of wastewater treatment.
At present, magnetic materials prepared based on loofah sponge biomass are applied to multiple fields of water treatment, wave absorption and the like, wherein the prepared ecological environment materials are mainly concentrated in the field of adsorption, and the Fenton-like degradation direction is still rarely researched. Although the stage research results have important reference significance, the preparation methods of the materials have many defects, such as small loading of ferroferric oxide in the prepared sample, non-uniform particle size and agglomeration, low calcination temperature and low graphitization degree of carbon; the preparation process is complicated, the cost of the required reagent is high, and the actual industrial production is not facilitated; the structure of the loofah sponge is easy to damage by using strong alkali KOH, and in addition, simple substance potassium generated in the reaction is embedded into a carbon skeleton lattice and is difficult to wash to be neutral, and an alkaline environment is generated during water treatment, so that the Fenton-like process is not facilitated.
Disclosure of Invention
The invention aims to solve the problems that an active component of a Fenton-like catalytic system is easy to agglomerate and Fe is generated under a neutral condition3+/Fe2+The preparation method and the application of the loofah sponge genetic porous carbon supported Fenton-like catalyst are provided.
A preparation method of a loofah sponge morph-genetic porous carbon supported Fenton-like catalyst comprises the following steps:
firstly, removing seeds of mature loofah sponge, cleaning, drying, and shearing to obtain dry loofah sponge;
secondly, firstly adding the dried loofah sponge into a NaOH solution, then stirring, washing with deionized water until the loofah sponge is neutral, and finally drying in an oven to obtain the loofah sponge treated by NaOH;
thirdly, soaking the loofah sponge treated by NaOH into Fe (NO)3)3·9H2Adding O solution, heating and stirring, heating the liquid to volatilize while adding Fe (NO)3)3·9H2The volume of O solution evaporates at least the original volume 1/3 of Fe (NO)3)3·9H2Marking the volume of the O solution as V1, then dropwise adding an ammonia water solution, heating and stirring, and completely evaporating the liquid to obtain the loofah sponge treated by the ammonia water;
fourthly, putting the loofah sponge treated by the ammonia water into a porcelain boat, then putting the porcelain boat into a tube furnace, heating the tube furnace to 600-800 ℃ under the argon atmosphere, and then preserving the heat for 1.5-2.5 h at 600-800 ℃ to obtain the loofah sponge/Fe3O4；
Fifthly, mixing the loofah sponge/Fe3O4Grinding, and repeatedly centrifuging and cleaning with deionized water as cleaning agent until pH value of the supernatant is neutralAnd then putting the loofah sponge into an oven to be dried to obtain the loofah sponge genetic porous carbon supported Fenton-like catalyst.
A loofah sponge genetic porous carbon supported Fenton-like catalyst is used for degrading tetracycline hydrochloride in sewage.
The invention provides a preparation method of a green, functional and efficient loofah sponge genetic porous carbon supported Fenton-like catalyst; the method uses ferric iron as a unique iron source, ammonia water as a precipitator, and adopts a dynamic stirring hot dipping method to volatilize solution so as to enable Fe3+Uniformly and fully precipitating the mixture on the surface of the loofah sponge, and then sintering the mixture at a high temperature to prepare the loofah sponge morph porous carbon-loaded Fe3O4A fenton-like catalyst. The loofah sponge biomass carbon material is used as a load matrix to form a C-O-Fe electron transmission channel between the carrier and the active component, so that the interface electron transmission rate is accelerated, and Fe is completed3+To Fe2+The Fenton-like degradation performance is improved. Its advantages are as follows:
(1) the loofah sponge biomass is selected as the carrier, on one hand, the biomass loofah sponge is cheap and easy to obtain, green and renewable, and compared with graphene and carbon nano tubes which are complex in preparation process and high in price, the carbon nano tubes can reduce environmental pollution and relieve energy crisis; on the other hand, the loofah sponge has a large number of functional groups on the surface, and the active components and the carrier have strong binding force and are highly dispersed on the surface of the carrier; moreover, the loofah sponge has a unique porous structure with a high specific surface area, so that the loading capacity of active components is improved, and antibiotics and H are enhanced2O2Adsorption of molecules promotes the Fenton-like degradation process of antibiotics;
(2) the Fe loaded by the loofah sponge genetic porous carbon is realized by utilizing a dynamic hot dipping and high-temperature carbothermic method3O4Preparing a Fenton-like catalyst; under the condition of dynamic stirring, the liquid is heated and volatilized by hot dipping, so that Fe is ensured3+Fully reacting with functional groups on the loofah sponge and uniformly precipitating on the surface of the loofah sponge; in order to increase the loading capacity of iron ions, ammonia water which does not contain alkali metal ions and has weak alkalinity is selected as a precipitator to reduce the damage to the surface morphology of the loofah sponge and avoid the alkali metal generated in the reaction from being retained in carbon latticesThe difficulty of water washing to neutrality is high, and the alkaline environment is not beneficial to the Fenton water treatment process; in addition, the graphitization degree of carbon is enhanced through high-temperature calcination, the conductivity of the carrier is improved, and due to the reducibility of C, magnetic iron oxide is formed after sintering, so that the addition of an additional reducing agent is avoided, the catalyst is economical and green, the recovery and separation are convenient, and the efficient recycling of the catalyst is realized;
(3) loofah sponge morph-genetic porous carbon loaded Fe3O4Form a C-O-Fe electron transmission channel to facilitate the electron transfer of the carbon material of the carrier to Fe3O4Accelerate the electron transmission rate of the interface and realize Fe3+To Fe2+To form Fe3+And Fe2+The closed cycle of the method realizes high-efficiency stable catalysis;
(4) the loofah sponge genetic porous carbon supported Fenton-like catalyst prepared by the invention is a stable and efficient Fenton-like catalyst, is degraded almost completely in 40min at the first time under a neutral condition, and can still keep the degradation rate of 50min to be 98% after circulating for 4 times.
Drawings
Fig. 1 is an XRD pattern of a carbonized luffa, in which 1 is an XRD curve of a carbonized luffa obtained in comparative example one, 2 is an XRD curve of a carbonized luffa obtained in comparative example two, and 3 is an XRD curve of a carbonized luffa obtained in comparative example three;
FIG. 2 is an XRD pattern with 1 being PDF #19-0629Fe3O4The standard XRD curve of (1), 2 is the XRD curve of the carbonized loofah sponge obtained in comparative example b, and 3 is the XRD curve of the loofah sponge morph porous carbon supported fenton-like catalyst prepared in example b;
FIG. 3 is a SME graph of a primary mature retinervus Luffae fructus;
FIG. 4 is SEM image of cut surface of original mature retinervus Luffae fructus;
fig. 5 is an SEM image of the loofah sponge morph-genetic porous carbon supported fenton-like catalyst prepared in example two;
fig. 6 is an SEM image of the loofah sponge morph-genetic porous carbon supported fenton-like catalyst prepared in example three;
fig. 7 is a cross-sectional SEM image of the loofah sponge morph-genetic porous carbon supported fenton-like catalyst prepared in the first example;
fig. 8 is a partial SEM image of the loofah sponge morph-genetic porous carbon supported fenton-like catalyst prepared in the first example;
fig. 9 is a graph showing degradation curves of tetracycline hydrochloride in sewage, in which fig. 1 is a degradation curve of tetracycline hydrochloride in sewage degraded by the loofah sponge genetic porous carbon-supported fenton-like catalyst prepared in example two in example four, fig. 2 is a degradation curve of tetracycline hydrochloride in sewage degraded by the loofah sponge genetic porous carbon-supported fenton-like catalyst prepared in example three in example five, and fig. 3 is a degradation curve of tetracycline hydrochloride in sewage degraded by the loofah sponge genetic porous carbon-supported fenton-like catalyst prepared in example one in example six;
fig. 10 is a circulation stability curve of the loofah sponge genetic porous carbon supported fenton-like catalyst prepared in the first embodiment for degrading tetracycline hydrochloride in sewage, where 1st is a degradation curve of the loofah sponge genetic porous carbon supported fenton-like catalyst prepared in the first embodiment for degrading tetracycline hydrochloride in sewage for the first time, 2ed is a degradation curve of the loofah sponge genetic porous carbon supported fenton-like catalyst prepared in the first embodiment for degrading tetracycline hydrochloride in sewage for the second time, 3rd is a degradation curve of the loofah sponge genetic porous carbon supported fenton-like catalyst prepared in the first embodiment for degrading tetracycline hydrochloride in sewage for the third time, and 4th is a degradation curve of the loofah sponge genetic porous carbon supported fenton-like catalyst prepared in the first embodiment for degrading tetracycline hydrochloride in sewage for the fourth time.
Detailed Description
The first embodiment is as follows: the embodiment is a preparation method of the loofah sponge genetic porous carbon supported Fenton-like catalyst, which is completed according to the following steps:
firstly, removing seeds of mature loofah sponge, cleaning, drying, and shearing to obtain dry loofah sponge;
secondly, firstly adding the dried loofah sponge into a NaOH solution, then stirring, washing with deionized water until the loofah sponge is neutral, and finally drying in an oven to obtain the loofah sponge treated by NaOH;
thirdly, soaking the loofah sponge treated by NaOH into Fe (NO)3)3·9H2Adding O solution, heating and stirring, heating the liquid to volatilize while adding Fe (NO)3)3·9H2The volume of O solution evaporates at least the original volume 1/3 of Fe (NO)3)3·9H2Marking the volume of the O solution as V1, then dropwise adding an ammonia water solution, heating and stirring, and completely evaporating the liquid to obtain the loofah sponge treated by the ammonia water;
fourthly, putting the loofah sponge treated by the ammonia water into a porcelain boat, then putting the porcelain boat into a tube furnace, heating the tube furnace to 600-800 ℃ under the argon atmosphere, and then preserving the heat for 1.5-2.5 h at 600-800 ℃ to obtain the loofah sponge/Fe3O4；
Fifthly, mixing the loofah sponge/Fe3O4Grinding, repeatedly centrifuging and cleaning by using deionized water as a cleaning agent until the pH value of the centrifugal supernatant is neutral, and drying in an oven to obtain the loofah sponge genetic porous carbon supported Fenton-like catalyst.
The embodiment provides a preparation method of a green, functional and efficient loofah sponge genetic porous carbon supported Fenton-like catalyst; the method uses ferric iron as a unique iron source, ammonia water as a precipitator, and adopts a dynamic stirring hot dipping method to volatilize solution so as to enable Fe3+Uniformly and fully precipitating the mixture on the surface of the loofah sponge, and then sintering the mixture at a high temperature to prepare the loofah sponge morph porous carbon-loaded Fe3O4A fenton-like catalyst. The loofah sponge biomass carbon material is used as a load matrix to form a C-O-Fe electron transmission channel between the carrier and the active component, so that the interface electron transmission rate is accelerated, and Fe is completed3+To Fe2+The Fenton-like degradation performance is improved. Its advantages are as follows:
(1) the loofah sponge biomass is selected as the carrier, on one hand, the biomass loofah sponge is cheap and easy to obtain, green and renewable, and compared with graphene and carbon nano tubes which are complex in preparation process and high in price, the carbon nano tubes can reduce environmental pollution and relieve energy crisis; on the other hand, the loofah sponge has a large number of functional groups on the surface, and the active component and the carrier have strong binding force and are arranged on the carrierThe surface is highly dispersed; moreover, the loofah sponge has a unique porous structure with a high specific surface area, so that the loading capacity of active components is improved, and antibiotics and H are enhanced2O2Adsorption of molecules promotes the Fenton-like degradation process of antibiotics;
(2) the Fe loaded by the loofah sponge genetic porous carbon is realized by utilizing a dynamic hot dipping and high-temperature carbothermic method3O4Preparing a Fenton-like catalyst; under the condition of dynamic stirring, the liquid is heated and volatilized by hot dipping, so that Fe is ensured3+Fully reacting with functional groups on the loofah sponge and uniformly precipitating on the surface of the loofah sponge; in order to increase the loading capacity of iron ions, ammonia water which does not contain alkali metal ions and is weak in alkalinity is used as a precipitator, so that damage to the surface morphology of the loofah sponge is reduced, the difficulty that the alkali metal generated in the reaction is retained in carbon lattices to be washed to be neutral is high, and the alkaline environment is not beneficial to the Fenton water treatment process; in addition, the graphitization degree of carbon is enhanced through high-temperature calcination, the conductivity of the carrier is improved, and due to the reducibility of C, magnetic iron oxide is formed after sintering, so that the addition of an additional reducing agent is avoided, the catalyst is economical and green, the recovery and separation are convenient, and the efficient recycling of the catalyst is realized;
(3) loofah sponge morph-genetic porous carbon loaded Fe3O4Form a C-O-Fe electron transmission channel to facilitate the electron transfer of the carbon material of the carrier to Fe3O4Accelerate the electron transmission rate of the interface and realize Fe3+To Fe2+To form Fe3+And Fe2+The closed cycle of the method realizes high-efficiency stable catalysis;
(4) the loofah sponge genetic porous carbon supported Fenton-like catalyst prepared by the embodiment is a stable and efficient Fenton-like catalyst, is degraded almost completely in 40min at the first time under a neutral condition, and can still keep the degradation rate of 50min to be 98% after circulating for 4 times.
The second embodiment is as follows: the present embodiment differs from the present embodiment in that: the particle size of the dried loofah sponge in the step one is 8-10 mm; 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 4-6 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 stirring speed in the step two is 800 r/min-1000 r/min; and the drying temperature in the second step is 60-80 ℃, and the drying time is 4-6 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 concentration of the NaOH solution in the step two is 1-3 mol/L; the ratio of the mass of the dried loofah sponge in the step two to the volume of the NaOH solution is (10 g-15 g):100 mL. 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: fe (NO) as described in step three3)3·9H2The concentration of the O solution is 0.08mol/L to 0.12 mol/L; the quality and Fe (NO) of the loofah sponge treated by NaOH in the third step3)3·9H2The volume ratio of the O solution is (6 g-10 g) 100 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: the heating and stirring temperature in the third step is 85-95 ℃, and the stirring speed is 800-1000 r/min. 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 concentration of the ammonia water solution in the third step is 0.3-0.8 mol/L; the volume ratio of the ammonia water solution to the V1 in the third step is (1-3): 30. 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: in the fourth step, the heating rate is 3-8 ℃/min; the drying temperature in the step five is 60-80 ℃, and the drying time is 6-8 h; the particle size of the loofah sponge morph-genetic porous carbon supported Fenton-like catalyst is 1-2 mm. The other steps are the same as those in the first to seventh embodiments.
The specific implementation method nine: the embodiment is that the loofah sponge genetic porous carbon supported Fenton-like catalyst is used for degrading tetracycline hydrochloride in sewage.
The detailed implementation mode is ten: the present embodiment differs from the ninth embodiment in that: the loofah sponge genetic porous carbon supported Fenton-like catalyst for degrading tetracycline hydrochloride in sewage is prepared by the following steps:
adding the loofah sponge genetic porous carbon loaded Fenton-like catalyst into sewage with the tetracycline hydrochloride concentration of 35-50 ppm, uniformly stirring, and adding H with the mass fraction of 30%2O2Timing the solution, and degrading for 40-60 min to obtain treated sewage;
the mass fraction of H is 30 percent2O2The volume ratio of the solution to the sewage (30-40 mu L) is 50 mL;
the mass ratio of the loofah sponge morph-genetic porous carbon loaded Fenton-like catalyst to the volume of sewage is (40-60 mg):50 mL. The other steps are the same as in the ninth embodiment.
The following examples were used to demonstrate the beneficial effects of the present invention:
comparative example one: the preparation method of the carbonized loofah sponge comprises the following steps:
firstly, removing seeds of mature loofah sponge, cleaning, drying at 60 ℃ for 6 hours, and then cutting into pieces to obtain dried loofah sponge with the particle size of 8-10 mm;
secondly, firstly, adding 12g of dried loofah sponge with the particle size of 8-10 mm into 100mL of 2mol/L NaOH solution, then stirring for 12h at the stirring speed of 1000r/min, then washing with deionized water until the loofah sponge is neutral, and finally drying in an oven at the temperature of 60 ℃ for 6h to obtain the loofah sponge treated by NaOH;
thirdly, putting the loofah sponge processed by NaOH into a porcelain boat, putting the porcelain boat into a tube furnace, heating the tube furnace from room temperature to 600 ℃ at the heating rate of 5 ℃/min under the argon atmosphere, and then preserving heat at 600 ℃ for 2 hours to obtain a sintered product;
grinding the sintered product, repeatedly centrifuging and cleaning by using deionized water as a cleaning agent until the pH value of the centrifugal supernatant is neutral, and drying in a 60 ℃ oven for 8h to obtain carbonized loofah with the particle size of 1-2 mm.
Comparative example two: the present embodiment is different from the first embodiment in that: and step three, putting the loofah sponge treated by NaOH into a porcelain boat, putting the porcelain boat into a tube furnace, heating the tube furnace from room temperature to 700 ℃ at the heating rate of 5 ℃/min under the argon atmosphere, and then preserving heat at 700 ℃ for 2h to obtain a sintered product. Other steps and parameters are the same as those in the first embodiment.
Comparative example three: the present embodiment is different from the first embodiment in that: and step three, putting the loofah sponge treated by NaOH into a porcelain boat, putting the porcelain boat into a tube furnace, heating the tube furnace from room temperature to 800 ℃ at the heating rate of 5 ℃/min under the argon atmosphere, and then preserving heat at 800 ℃ for 2h to obtain a sintered product. Other steps and parameters are the same as those in the first embodiment.
Fig. 1 is an XRD pattern of a carbonized luffa, in which 1 is an XRD curve of a carbonized luffa obtained in comparative example one, 2 is an XRD curve of a carbonized luffa obtained in comparative example two, and 3 is an XRD curve of a carbonized luffa obtained in comparative example three;
from fig. 1, it can be seen that CLS at different calcination temperatures has a broad peak at 23 °, and the temperature rises from 600 ℃ to 800 ℃, and gradually shows a peak around 44.5 °, indicating that the graphitization degree of carbon increases after the biomass loofah is pyrolyzed at high temperature.
FIG. 2 is an XRD pattern with 1 being PDF #19-0629Fe3O4The standard XRD curve of (1), 2 is the XRD curve of the carbonized loofah sponge obtained in comparative example b, and 3 is the XRD curve of the loofah sponge morph porous carbon supported fenton-like catalyst prepared in example b;
comparing the X-ray diffraction standard card, it can be seen that the loofah sponge morph porous carbon-loaded fenton-like carbon prepared in the first embodiment of fig. 2The catalyst contains Fe3O4And no other diffraction peaks appear, which indicates that the method can obtain the pure loofah sponge genetic porous carbon supported Fenton-like catalyst.
The first embodiment is as follows: the preparation method of the loofah sponge morph-genetic porous carbon supported Fenton-like catalyst is specifically completed according to the following steps:
firstly, removing seeds of mature loofah sponge, cleaning, drying at 60 ℃ for 6 hours, and then cutting into pieces to obtain dried loofah sponge with the particle size of 8-10 mm;
secondly, firstly, adding 12g of dried loofah sponge with the particle size of 8-10 mm into 100mL of 2mol/L NaOH solution, then stirring for 12h at the stirring speed of 1000r/min, then washing with deionized water until the loofah sponge is neutral, and finally drying in an oven at the temperature of 60 ℃ for 6h to obtain the loofah sponge treated by NaOH;
thirdly, soaking 8g of NaOH treated loofah sponge into 100mL of 0.1mol/L Fe (NO)3)3·9H2Heating and stirring at 90 deg.C in O solution, and volatilizing the liquid when Fe (NO)3)3·9H2When the volume of the O solution is evaporated to 30mL, dropwise adding 2mL of ammonia water solution with the concentration of 0.5mol/L, heating and stirring at 90 ℃, and completely evaporating the liquid to obtain the loofah sponge treated by the ammonia water;
fourthly, putting the loofah sponge treated by the ammonia water into a porcelain boat, then putting the porcelain boat into a tube furnace, then heating the tube furnace from room temperature to 700 ℃ at the heating rate of 5 ℃/min under the argon atmosphere, and then preserving the heat at 700 ℃ for 2 hours to obtain the loofah sponge/Fe3O4；
Fifthly, mixing the loofah sponge/Fe3O4Grinding, repeatedly centrifuging and cleaning by using deionized water as a cleaning agent until the pH value of the centrifugal supernatant is neutral, and drying in a drying oven at the temperature of 60 ℃ for 8h to obtain the loofah sponge genetic porous carbon supported Fenton-like catalyst with the particle size of 1-2 mm.
Example two: the present embodiment is different from the first embodiment in that: fourthly, the loofah sponge treated by the ammonia water is put into a porcelain boat, then the porcelain boat is put into a tube furnace, and then the tube furnace is put under the argon atmosphereHeating from room temperature to 600 deg.C at a heating rate of 5 deg.C/min, and maintaining at 600 deg.C for 2 hr to obtain retinervus Luffae fructus/Fe3O4. 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: fourthly, putting the loofah sponge treated by the ammonia water into a porcelain boat, then putting the porcelain boat into a tube furnace, then heating the tube furnace from room temperature to 800 ℃ at the heating rate of 5 ℃/min under the argon atmosphere, and then preserving the heat at 800 ℃ for 2 hours to obtain the loofah sponge/Fe3O4. Other steps and parameters are the same as those in the first embodiment.
FIG. 3 is a SME graph of a primary mature retinervus Luffae fructus;
FIG. 4 is SEM image of cut surface of original mature retinervus Luffae fructus;
as can be seen from fig. 3 and 4, the microscopic luffa still has a long cylindrical shape, and the porous structure of luffa can be seen from the cut surface.
Fig. 5 is an SEM image of the loofah sponge morph-genetic porous carbon supported fenton-like catalyst prepared in example two;
fig. 6 is an SEM image of the loofah sponge morph-genetic porous carbon supported fenton-like catalyst prepared in example three;
fig. 7 is a cross-sectional SEM image of the loofah sponge morph-genetic porous carbon supported fenton-like catalyst prepared in the first example;
fig. 8 is a partial SEM image of the loofah sponge morph-genetic porous carbon supported fenton-like catalyst prepared in the first example;
from fig. 5 to 8, it can be clearly seen that the loofah sponge genetic porous carbon supported fenton-like catalyst obtained by carbonizing at 600 ℃ and 700 ℃ maintains the basic tubular shape of loofah sponge genetic state, and the surface of the loofah sponge genetic porous carbon supported fenton-like catalyst is uniformly coated with Fe particles3O4The particles are covered compactly, and Fe on the surface of the loofah sponge genetic porous carbon supported Fenton-like catalyst is obtained when the carbonization temperature is 600 DEG C3O4The loofah sponge genetic porous carbon supported Fenton-like catalyst is obtained when the particle coverage rate is lower than the carbonization temperature of 700 ℃; when the carbonization temperature is increased to 800 ℃, the tubular shape of the loofah begins to collapse, and surface particles are accumulated.
Example four: the method for degrading tetracycline hydrochloride in the sewage by using the loofah sponge genetic porous carbon supported Fenton-like catalyst prepared in the second embodiment is completed according to the following steps:
adding 50mg of the loofah sponge genetic porous carbon supported Fenton-like catalyst prepared in the second embodiment into 50mL of sewage with tetracycline hydrochloride concentration of 35ppm, uniformly stirring, adding 34 mu L of H with mass fraction of 30%2O2Timing the solution, transferring 0.7-1 mL of degradation solution every 10min in the degradation process, filtering out the loofah sponge genetic porous carbon supported Fenton-like catalyst by using a 0.22-micron filter membrane, and finally determining the concentration of tetracycline hydrochloride by adopting a liquid chromatography, wherein the degradation curve is shown as 1 in figure 9.
Example five: the method for degrading tetracycline hydrochloride in the sewage by using the loofah sponge genetic porous carbon supported Fenton-like catalyst prepared in the third embodiment is completed according to the following steps:
adding 50mg of the loofah sponge genetic porous carbon supported Fenton-like catalyst prepared in the third embodiment into 50mL of sewage with tetracycline hydrochloride concentration of 35ppm, uniformly stirring, adding 34 mu L of H with mass fraction of 30%2O2Timing the solution, transferring 0.7-1 mL of degradation solution every 10min in the degradation process, filtering out the loofah sponge genetic porous carbon supported Fenton-like catalyst by using a 0.22-micron filter membrane, and finally determining the concentration of tetracycline hydrochloride by adopting a liquid chromatography, wherein the degradation curve is shown as 2 in figure 9.
Example six: the method for degrading tetracycline hydrochloride in sewage by using the loofah sponge genetic porous carbon supported Fenton-like catalyst prepared in the first embodiment is completed according to the following steps:
adding 50mg of the loofah sponge genetic porous carbon supported Fenton-like catalyst prepared in the first embodiment into 50mL of sewage with tetracycline hydrochloride concentration of 35ppm, uniformly stirring, adding 34 mu L of H with mass fraction of 30%2O2The solution is started to time, 0.7 mL-1 mL of degradation solution is transferred every 10min in the degradation process, a 0.22 μm filter membrane is used for filtering the loofah vegetable sponge morph porous carbon supported Fenton-like catalyst, finally the concentration of tetracycline hydrochloride is measured by adopting liquid chromatography, and the degradation curve is shown in 3 in fig. 9 and 1st in fig. 10 (namely, the first time, the first preparation of the embodiment is used)The degradation curve of the loofah sponge genetic porous carbon loaded Fenton-like catalyst for degrading tetracycline hydrochloride in the sewage) is prepared.
Fig. 9 is a graph showing degradation curves of tetracycline hydrochloride in sewage, in which fig. 1 is a degradation curve of tetracycline hydrochloride in sewage degraded by the loofah sponge genetic porous carbon-supported fenton-like catalyst prepared in example two in example four, fig. 2 is a degradation curve of tetracycline hydrochloride in sewage degraded by the loofah sponge genetic porous carbon-supported fenton-like catalyst prepared in example three in example five, and fig. 3 is a degradation curve of tetracycline hydrochloride in sewage degraded by the loofah sponge genetic porous carbon-supported fenton-like catalyst prepared in example one in example six;
as can be seen from fig. 9, the loofah sponge genetic porous carbon supported fenton-like catalyst prepared in the first example has the best performance, mainly because the graphitization degree of the carbon substrate in the loofah sponge genetic porous carbon supported fenton-like catalyst obtained at the carbonization temperature of 600 ℃ is low, and the carbon substrate can be used for Fe3O4Weak electron supply capability; when the carbonization temperature is 800 ℃, the sintering temperature is too high, the porous structure of the loofah sponge is damaged, the adsorption capacity to pollutants is reduced, and the degradation efficiency is reduced due to the accumulation of active particles. Loofah sponge genetic porous carbon supported Fenton-like catalyst medium loofah sponge carbon matrix and Fe obtained at carbonization temperature of 700 DEG C3O4The two form an electron transmission channel, and the biomass carbon matrix can provide electrons for iron ions and promote Fe in the Fenton process3+/Fe2+The degradation efficiency is improved.
And (3) testing the cycling stability:
example seven: washing the degraded loofah sponge genetic porous carbon supported Fenton-like catalyst in the sixth embodiment with distilled water for 5 times, drying at 60 ℃, adding 50mg of the dried loofah sponge genetic porous carbon supported Fenton-like catalyst into 50mL of sewage with tetracycline hydrochloride concentration of 35ppm, uniformly stirring, adding 34 μ L of H with mass fraction of 30%2O2Timing, transferring 0.7-1 mL of degradation liquid every 10min in the degradation process of the solution, and filtering out the loofah sponge morph porous carbon load Fenton-like catalyst by using a 0.22-micron filter membraneAnd finally, measuring the concentration of the tetracycline hydrochloride by adopting liquid chromatography, wherein a degradation curve is shown as 2ed in fig. 10 (namely, a degradation curve for degrading the tetracycline hydrochloride in the sewage by using the loofah sponge genetic porous carbon supported Fenton-like catalyst prepared in the first example for the second time).
Example eight: washing the degraded loofah sponge genetic porous carbon supported Fenton-like catalyst in the seventh embodiment with distilled water for 5 times, drying at 60 ℃, adding 50mg of the dried loofah sponge genetic porous carbon supported Fenton-like catalyst into 50mL of sewage with tetracycline hydrochloride concentration of 35ppm, uniformly stirring, adding 34 μ L of H with mass fraction of 30%2O2In the solution degradation process, 0.7-1 mL of degradation solution is transferred every 10min, a 0.22-micrometer filter membrane is used for filtering out the loofah sponge genetic porous carbon supported fenton-like catalyst, and finally the concentration of tetracycline hydrochloride is measured by adopting a liquid chromatography, wherein the degradation curve is shown as 3rd in fig. 10 (namely, the degradation curve of tetracycline hydrochloride in sewage is degraded by using the loofah sponge genetic porous carbon supported fenton-like catalyst prepared in the first embodiment for the third time).
Example nine: washing the degraded loofah sponge genetic porous carbon supported Fenton-like catalyst in the eighth embodiment with distilled water for 5 times, drying at 60 ℃, adding 50mg of the dried loofah sponge genetic porous carbon supported Fenton-like catalyst into 50mL of sewage with tetracycline hydrochloride concentration of 35ppm, uniformly stirring, adding 34 μ L of H with mass fraction of 30%2O2In the solution degradation process, 0.7-1 mL of degradation solution is transferred every 10min, a 0.22-micrometer filter membrane is used for filtering out the loofah sponge genetic porous carbon supported Fenton-like catalyst, and finally the concentration of tetracycline hydrochloride is measured by adopting a liquid chromatography, wherein the degradation curve is shown as 4th in fig. 10 (namely, the degradation curve of tetracycline hydrochloride in sewage is degraded by using the loofah sponge genetic porous carbon supported Fenton-like catalyst prepared in the first embodiment for the third time).
Fig. 10 is a circulation stability curve of the loofah sponge genetic porous carbon supported fenton-like catalyst prepared in the first embodiment for degrading tetracycline hydrochloride in sewage, where 1st is a degradation curve of the loofah sponge genetic porous carbon supported fenton-like catalyst prepared in the first embodiment for degrading tetracycline hydrochloride in sewage for the first time, 2ed is a degradation curve of the loofah sponge genetic porous carbon supported fenton-like catalyst prepared in the first embodiment for degrading tetracycline hydrochloride in sewage for the second time, 3rd is a degradation curve of the loofah sponge genetic porous carbon supported fenton-like catalyst prepared in the first embodiment for degrading tetracycline hydrochloride in sewage for the third time, and 4th is a degradation curve of the loofah sponge genetic porous carbon supported fenton-like catalyst prepared in the first embodiment for degrading tetracycline hydrochloride in sewage for the fourth time.
As can be seen from fig. 10, under a neutral condition, the first degradation is almost complete within 40min, and after the cycle is performed for 4 times, the 50min degradation rate can still reach 98%, which indicates that the loofah sponge genetic porous carbon supported Fenton-like catalyst prepared in the first embodiment is a stable and efficient Fenton-like catalyst.
Claims (10)
1. A preparation method of a loofah sponge genetic porous carbon supported Fenton-like catalyst is characterized in that the preparation method of the loofah sponge genetic porous carbon supported Fenton-like catalyst is completed according to the following steps:
firstly, removing seeds of mature loofah sponge, cleaning, drying, and shearing to obtain dry loofah sponge;
secondly, firstly adding the dried loofah sponge into a NaOH solution, then stirring, washing with deionized water until the loofah sponge is neutral, and finally drying in an oven to obtain the loofah sponge treated by NaOH;
thirdly, soaking the loofah sponge treated by NaOH into Fe (NO)3)3·9H2Adding O solution, heating and stirring, heating the liquid to volatilize while adding Fe (NO)3)3·9H2The volume of O solution evaporates at least the original volume 1/3 of Fe (NO)3)3·9H2Marking the volume of the O solution as V1, then dropwise adding an ammonia water solution, heating and stirring, and completely evaporating the liquid to obtain the loofah sponge treated by the ammonia water;
fourthly, the loofah sponge treated by the ammonia water is put into a porcelain boat, then the porcelain boat is put into a tube furnace, the temperature of the tube furnace is raised to 600 ℃ to 800 ℃ under the argon atmosphere, and then the temperature is raised to 600 ℃ to 800 DEG CPreserving heat for 1.5 h-2.5 h to obtain the loofah sponge/Fe3O4；
Fifthly, mixing the loofah sponge/Fe3O4Grinding, repeatedly centrifuging and cleaning by using deionized water as a cleaning agent until the pH value of the centrifugal supernatant is neutral, and drying in an oven to obtain the loofah sponge genetic porous carbon supported Fenton-like catalyst.
2. The method for preparing the loofah sponge genetic porous carbon supported fenton-like catalyst according to claim 1, wherein the particle size of the dried loofah sponge in the first step is 8mm to 10 mm; 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 4-6 h.
3. The method for preparing the loofah sponge genetic porous carbon supported Fenton-like catalyst according to claim 1, wherein the stirring speed in the second step is 800r/min to 1000 r/min; and the drying temperature in the second step is 60-80 ℃, and the drying time is 4-6 h.
4. The method for preparing the loofah sponge genetic porous carbon supported fenton-like catalyst according to claim 1, wherein the concentration of the NaOH solution in the second step is 1mol/L to 3 mol/L; the ratio of the mass of the dried loofah sponge in the step two to the volume of the NaOH solution is (10 g-15 g):100 mL.
5. The method for preparing the loofah sponge genetic porous carbon supported Fenton-like catalyst according to claim 1, wherein the Fe (NO) in step three is3)3·9H2The concentration of the O solution is 0.08mol/L to 0.12 mol/L; the quality and Fe (NO) of the loofah sponge treated by NaOH in the third step3)3·9H2The volume ratio of the O solution is (6 g-10 g) 100 mL.
6. The method for preparing the loofah sponge genetic porous carbon supported Fenton-like catalyst according to claim 1, wherein the heating and stirring temperature in the third step is 85-95 ℃, and the stirring speed is 800-1000 r/min.
7. The method for preparing the loofah sponge genetic porous carbon supported Fenton-like catalyst according to claim 1, wherein the concentration of the ammonia solution in the third step is 0.3mol/L to 0.8 mol/L; the volume ratio of the ammonia water solution to the V1 in the third step is (1-3): 30.
8. The method for preparing the loofah sponge genetic porous carbon supported Fenton-like catalyst according to claim 1, wherein the temperature rise rate in the fourth step is 3 ℃/min to 8 ℃/min; the drying temperature in the step five is 60-80 ℃, and the drying time is 6-8 h; the particle size of the loofah sponge morph-genetic porous carbon supported Fenton-like catalyst is 1-2 mm.
9. The application of the loofah sponge genetic porous carbon supported Fenton-like catalyst prepared by the preparation method according to claim 1, which is characterized in that the loofah sponge genetic porous carbon supported Fenton-like catalyst is used for degrading tetracycline hydrochloride in sewage.
10. The application of the loofah sponge genetic porous carbon supported Fenton-like catalyst according to claim 9, wherein the loofah sponge genetic porous carbon supported Fenton-like catalyst for degrading tetracycline hydrochloride in sewage is prepared by the following steps:
adding the loofah sponge genetic porous carbon loaded Fenton-like catalyst into sewage with the tetracycline hydrochloride concentration of 35-50 ppm, uniformly stirring, and adding H with the mass fraction of 30%2O2Timing the solution, and degrading for 40-60 min to obtain treated sewage;
the mass fraction of H is 30 percent2O2The volume ratio of the solution to the sewage (30-40 mu L) is 50 mL;
the mass ratio of the loofah sponge morph-genetic porous carbon loaded Fenton-like catalyst to the volume of sewage is (40-60 mg):50 mL.
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