CN114588917A - Preparation method and application of sulfur-doped carbon skeleton-coated octasulfide heptairon nanoparticle double-reaction-center Fenton-like catalyst - Google Patents
Preparation method and application of sulfur-doped carbon skeleton-coated octasulfide heptairon nanoparticle double-reaction-center Fenton-like catalyst Download PDFInfo
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- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/02—Sulfur, selenium or tellurium; Compounds thereof
- B01J27/04—Sulfides
- B01J27/043—Sulfides with iron group metals or platinum group metals
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Abstract
A preparation method and application of a sulfur-doped carbon skeleton-coated hepta-iron sulfide nanoparticle double-reaction-center Fenton-like catalyst relate to a preparation method and application of a Fenton-like catalyst. The invention aims to solve the problems of metal ion leaching, poor stability, easy agglomeration and narrow reaction pH range of the existing Fenton-like catalyst. The method comprises the following steps: firstly preparing an MIL-101(Fe) precursor, and then calcining and vulcanizing to obtain the sulfur-doped carbon skeleton-coated octasulfide heptairon nanoparticle double-reaction-center Fenton-like catalyst. A sulfur-doped carbon skeleton-wrapped heptaferric sulfide nanoparticle double-reaction-center Fenton-like catalyst is used for degrading antibiotics. The degradation rates of tetracycline hydrochloride, norfloxacin and amoxicillin in 40min under a neutral condition can respectively reach 100%, 97.8% and 98.9%, and after 5 times of circulation, the amoxicillin removal rate can still be maintained at 91.1%.
Description
Technical Field
The invention relates to a preparation method and application of a Fenton-like catalyst.
Background
The ecological risks caused by antibiotic discharge are not optimistic. The heterogeneous Fenton-like oxidation method has attracted much attention as a technology for treating stubborn pollutants, and the research focus is mainly on the research and development of Fenton-like catalysts for efficiently removing antibiotic pollutants. The common metal catalyst has the problems of metal ion leaching, poor stability, easy agglomeration, narrow reaction pH range and the like. In order to improve the problems, the poor/rich electron dual reaction center Fenton-like catalyst material constructed based on metal and carbon materials can coat metal nanoparticles to improve the dispersibility and stability and reduce ion dissolution, and can also utilize an electron transmission channel between a catalytic site and an adsorption site which are separated in space to realize the supplement and activation of rich electron center electrons, thereby accelerating the removal of organic pollutants which are difficult to degrade in a wide pH range. The electron transport channels with double reaction centers reported in the literature at present are mostly C-O-Fe, C-S-Mo, C-O-Cu and the like, and the channels satisfy the electron transport in thermodynamics, but the electron transport distance is longer, and the resistance of the kinetic process is increased under the action of vibrational rotation of bonds and the like, so that the efficient transport of electrons in the poor/rich electron double centers is not facilitated.
For this reason, it is proposed that the construction of a short C — M (M ═ Fe, Co, Mo) bond bridge connecting double reaction centers enhances charge transport efficiency. However, the single transmission channel still restricts the transmission efficiency of electrons, and the poor/rich electron dual reaction center type Fenton catalysis still needs to be further improved in the aspect of catalytic degradation performance.
The invention aims to solve the problems of leaching of metal ions, poor stability, easy agglomeration, narrow reaction pH range and the like faced by a Fenton-like catalyst.
Disclosure of Invention
The invention aims to solve the problems of leaching of metal ions, poor stability, easy agglomeration and narrow reaction pH range of the conventional Fenton-like catalyst, and provides a preparation method and application of a sulfur-doped carbon skeleton-coated heptairon octasulfide nanoparticle double-reaction-center Fenton-like catalyst.
A preparation method of a sulfur-doped carbon skeleton-coated octasulfide hepta-iron nanoparticle double-reaction-center Fenton-like catalyst comprises the following steps:
firstly, mixing terephthalic acid and FeCl3·6H2Adding O into N, N-dimethylformamide, and stirring to obtain a solution I;
secondly, transferring the solution I into a hydrothermal reaction kettle, and then carrying out hydrothermal reaction at 110-160 ℃ to obtain an orange yellow solution after the reaction is finished;
thirdly, repeatedly cleaning the orange solution by using N, N-dimethylformamide and absolute ethyl alcohol until the supernatant of the solution is colorless, and drying to obtain an MIL-101(Fe) precursor;
putting an MIL-101(Fe) precursor into one side of a porcelain boat, adding sublimed sulfur powder into the other side of the porcelain boat, covering the porcelain boat, reserving gaps on two sides of the two porcelain boats, ensuring that inert gas can enter the porcelain boats to remove air, ensuring that the porcelain boat is fully vulcanized in a relatively closed environment, transferring the porcelain boat into the center of a tubular furnace, placing the side containing the sublimed sulfur powder into an upstream area of the inert gas, introducing the inert gas to remove air, continuously introducing the inert gas, heating the tubular furnace from room temperature to 600-800 ℃ under the protection of the inert gas, preserving heat at 600-800 ℃, and obtaining a reaction product after the heat preservation is finished;
and fifthly, centrifugally cleaning the reaction product, and drying the reaction product in a vacuum drying oven to obtain the sulfur-doped carbon skeleton-coated heptaferric sulfide nanoparticle double-reaction-center Fenton-like catalyst.
A sulfur-doped carbon skeleton-wrapped heptaferric sulfide nanoparticle double-reaction-center Fenton-like catalyst is used for degrading antibiotics.
The principle of the invention is as follows:
firstly, the invention constructs a sulfur-doped carbon skeleton coated Fe through a Fe-MOF in-situ steam vulcanization method7S8Nanoparticles (Fe)7S8@ SC) interface electron transmission multi-channel double-reaction-center Fenton-like catalyst, carbon-coated metal nanoparticles improve the dispersibility and stability and reduce ion dissolution, and electron transmission multi-channel between a spatially-separated electron-rich reaction center (catalytic site) and an electron-poor reaction center (adsorption site) efficiently realizes the supplement and activation of electrons to the electron-rich center, so that the preparation method of the antibiotic degraded by the double-reaction-center Fenton-like catalyst with high activity and electron transmission multi-channel is obtained;
the prepared double-reaction-center Fenton catalytic material with high activity and electron transmission multiple channels not only ensures the activity of the double reaction centers, but also greatly improves the electron transmission capacity of a plurality of transmission channels; in addition, based on electronegativity difference, the surface structures of the metal nano material and the carbon material can be regulated and controlled by doping modification of the non-metal element S, so that the electron density of the metal nano particles and the carbon sites is rearranged, and the activation and adsorption characteristics of the metal nano particles and the carbon sites are enhanced. Therefore, in addition to normally constructing the C-M bond between the metal and the carbon material, the C-S-M bond is generated by utilizing the characteristic that S has activity on both the metal nano-particles and the skeleton carbon, so that a new electron transmission channel is added, and the electron transmission is enhanced.
The invention has the advantages that:
the invention provides novel, simple and efficient sulfur-doped carbon skeleton coated Fe7S8The preparation method of the nano-particle Fenton-like catalyst has a unique structure under specific conditions due to Metal Organic Framework (MOFs) materials, wherein the derived porous carbon material prepared based on the MOFsThe metal nanoparticle-coated composite has excellent stability and catalytic performance due to the good conductivity of the carbon material and the catalytic activity of the metal center, and is widely applied; fe is rich in natural content, is non-toxic and can be distinguished from various MOF materials; the method comprises the steps of synthesizing an MIL-101(Fe) precursor through liquid phase chemistry, treating the precursor by using sublimed sulfur as a sulfur source and adopting an in-situ steam vulcanization method under a nitrogen reducing atmosphere to obtain octahedral sulfur-doped Fe wrapped by a carbon framework7S8Nanoparticles. Its advantages are as follows:
(1)、Fe7S8the electron transmission multi-channel formed by the nano particles and the sulfur-doped carbon interface not only realizes the spatial separation of rich electron centers and poor electron centers, namely catalytic sites and adsorption sites, but also strengthens the electron transmission efficiency by a plurality of channels, creates more active sites and promotes the Fenton-like degradation process of antibiotics;
(2)、Fe7S8the nano particles are coated in the sulfur-doped octahedral carbon skeleton in a limited mode, so that the dispersity and the stability of the active nano particles are improved; in addition, the carbon layer can be used as a protective layer, so that the problem of dissolution of iron ions in a solution can be effectively solved, the activity of active species is improved, and the carbon layer can protect the active species to realize high-efficiency stable catalysis of the catalyst;
(3) the porous carbon derived from the MOFs material usually retains the regular mesh pore structure and the unique polyhedron form of the MOFs, has large specific surface area and high porosity, and can improve the resistance to antibiotics and H2O2The adsorption capacity of (c); the MOFs derived carbon material subjected to high-temperature pyrolysis has good conductivity, and guarantees are provided for excellent catalytic performance;
(4) the invention realizes the purpose of wrapping Fe by the sulfur-doped carbon skeleton by utilizing a liquid-phase chemical synthesis method and an in-situ steam vulcanization method7S8The controllable preparation of the nano-particle interface electron transmission multi-channel double-reaction-center Fenton-like catalyst has the advantages of simple and safe synthesis method, low production cost, rich raw materials and capability of realizing quantitative production;
(5) the invention constructs sulfur-doped carbon skeleton coated Fe through simple liquid phase chemical synthesis and in-situ steam vulcanization method7S8The electron transmission multi-channel double-reaction-center Fenton-like catalyst for the nanoparticle interface realizes multi-channel enhanced electron transmission efficiency, creates more active sites, promotes the Fenton-like degradation process of antibiotics, and has degradation rates of tetracycline hydrochloride, norfloxacin and amoxicillin within 40min of 100%, 97.8% and 98.9% respectively under a neutral condition, after 5 times of circulation, the amoxicillin removal rate can still be kept at 91.1%, and the iron dissolution is lower than 1ppm, so that the cycle stability is excellent. The method has good inspiration and reference significance for the design of other Fenton catalysts and has good application prospect.
The invention can obtain a sulfur-doped carbon skeleton-coated heptaferric sulfide nanoparticle double-reaction-center Fenton-like catalyst.
Drawings
FIG. 1 preparation of Fe in example 17S8The XRD pattern of @ SC;
FIG. 2 is an SEM image of the MIL-101(Fe) precursor prepared in example 1 together with Fe7S8SEM and TEM images of @ SC, in which (a) is an SEM image of MIL-101(Fe) precursor and (b) is Fe7S8SEM picture of @ SC (c) is Fe7S8TEM image of @ SC, (d) is Fe7S8HR-TEM images of @ SC;
FIG. 3 is Fe prepared in example 17S8XPS spectra of @ SC, in which (a) is C spectrum, (b) is S spectrum, (C) is Fe spectrum, and (d) is Fe spectrum7S8And Fe7S8Comparative Fe spectra of @ SC, upper panel is Fe7S8In the lower diagram, Fe7S8@SC；
FIG. 4 shows Fe prepared in example 17S8The performance diagram of @ SC for degrading antibiotics is shown, wherein TCH is tetracycline hydrochloride, AMX is amoxicillin, and NOR is norfloxacin;
FIG. 5 shows Fe prepared in example 17S8A circulation stability chart of @ SC for degrading amoxicillin, wherein 1st is used for the first time, 2ed is used for the second time, 3rd is used for the third time, 4th is used for the fourth time, and 5th is used for the fifth time;
FIG. 6 is a graph showing the degradation rate of amoxicillin in 40min for catalysts prepared in different examples.
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 preparation method of the sulfur-doped carbon skeleton-coated hepta-iron sulfide nanoparticle double-reaction-center fenton-like catalyst comprises the following steps:
firstly, mixing terephthalic acid and FeCl3·6H2Adding O into N, N-dimethylformamide, and stirring to obtain a solution I;
secondly, transferring the solution I into a hydrothermal reaction kettle, and then carrying out hydrothermal reaction at 110-160 ℃ to obtain an orange yellow solution after the reaction is finished;
thirdly, repeatedly cleaning the orange solution by using N, N-dimethylformamide and absolute ethyl alcohol until the supernatant of the solution is colorless, and drying to obtain an MIL-101(Fe) precursor;
putting an MIL-101(Fe) precursor into one side of a porcelain boat, adding sublimed sulfur powder into the other side of the porcelain boat, covering the porcelain boat, and leaving gaps on two sides of the two porcelain boats to ensure that inert gas can enter the porcelain boat to remove air and fully vulcanize the porcelain boat in a relatively closed environment, transferring the porcelain boat into the center of a tubular furnace, putting the side containing the sublimed sulfur powder into an upstream area of the inert gas, introducing the inert gas to remove air, continuously introducing the inert gas, heating the tubular furnace from room temperature to 600-800 ℃ under the protection of the inert gas, preserving the heat at 600-800 ℃, and obtaining a reaction product after the heat preservation is finished;
and fifthly, centrifugally cleaning the reaction product, and drying the reaction product in a vacuum drying oven to obtain the sulfur-doped carbon skeleton-coated heptaferric sulfide nanoparticle double-reaction-center Fenton-like catalyst.
The second embodiment is as follows: the present embodiment differs from the present embodiment in that: the quality and N, N-The volume ratio of the dimethyl formamide is (0.4 g-0.5 g) to (40 mL-60 mL); FeCl as described in step one3·6H2The ratio of the mass of O to the volume of N, N-dimethylformamide is (1.3-1.6 g): 40-60 mL. 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 time in the step one is 1-2 h, and the stirring speed is 800-1000 r/min. 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 time of the hydrothermal reaction in the second step is 20-24 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: the drying temperature in the third step is 60-80 ℃, and the drying time is 10-15 h. 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 mass ratio of the MIL-101(Fe) precursor to the sublimed sulfur powder in the fourth step is 1 (1-3); in the fourth step, the temperature is kept for 2 to 4 hours at the temperature of 600 to 800 ℃; the heating rate in the fourth step is 2-5 ℃/min; and the inert gas in the fourth step is nitrogen, and the inert gas is introduced for 20-30 min to remove air. 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: and step five, centrifugally cleaning the reaction product for 3-5 times by using deionized water, and then drying the reaction product for 10-12 hours in a vacuum drying oven at the temperature of 60-80 ℃ to obtain the sulfur-doped carbon skeleton-coated heptaferric sulfide nanoparticle double-reaction-center Fenton-like catalyst. The other steps are the same as those in the first to sixth embodiments.
The specific implementation mode is eight: the embodiment is that a sulfur-doped carbon skeleton wrapped heptairon sulfide nanoparticle double-reaction-center Fenton-like catalyst is used for degrading antibiotics.
The specific implementation method nine: the difference between this embodiment and the first to eighth embodiments is: the antibiotic is tetracycline hydrochloride, norfloxacin or amoxicillin. The other steps are the same as those in the first to eighth embodiments.
The detailed implementation mode is ten: the difference between this embodiment and one of the first to ninth embodiments is as follows: the method for degrading antibiotics by using the sulfur-doped carbon skeleton wrapped hepta-iron sulfide nanoparticle double-reaction-center Fenton-like catalyst is completed according to the following steps:
adding a sulfur-doped carbon skeleton-wrapped heptasulfide iron nanoparticle double-reaction-center Fenton-like catalyst into water containing antibiotics, uniformly stirring, and adding 30% by mass of H2O2Solution of H in the system2O2The concentration of the catalyst is 2 mmol/L-15 mmol/L, the reaction is carried out for 10 min-40 min to obtain water with antibiotic removed, the catalyst is attracted by a magnet, and the catalyst is taken out and washed by deionized water and dried to obtain a recovered catalyst;
the volume ratio of the mass of the sulfur-doped carbon skeleton-coated heptaferric sulfide nanoparticle double-reaction-center Fenton-like catalyst to the water containing the antibiotic is (5 mg-20 mg):50 mL;
the concentration of the water containing the antibiotics is 10 mg/L-50 mg/L;
the drying temperature is 60-80 ℃, and the drying time is 10-15 h. The other steps are the same as those in the first to ninth embodiments.
The following examples were used to demonstrate the beneficial effects of the present invention:
example 1: a preparation method of a sulfur-doped carbon skeleton-coated octasulfide hepta-iron nanoparticle double-reaction-center Fenton-like catalyst comprises the following steps:
firstly, mixing terephthalic acid and FeCl3·6H2Adding O into N, N-dimethylformamide, and stirring to obtain a solution I;
the stirring time in the step one is 1h, and the stirring speed is 800r/min
The volume ratio of the mass of the terephthalic acid to the N, N-dimethylformamide in the step one is 0.4g:40 mL;
FeCl as described in step one3·6H2The volume ratio of the mass of O to the volume of N, N-dimethylformamide is 1.3g:40 mL;
secondly, transferring the solution I into a hydrothermal reaction kettle, and then carrying out hydrothermal reaction at 110 ℃ to obtain an orange yellow solution after the reaction is finished;
the hydrothermal reaction time in the step two is 20 hours;
thirdly, repeatedly cleaning the orange solution by using N, N-dimethylformamide and absolute ethyl alcohol until the supernatant of the solution is colorless, and drying to obtain an MIL-101(Fe) precursor;
the drying temperature in the third step is 60 ℃, and the drying time is 10 hours;
putting an MIL-101(Fe) precursor into one side of a porcelain boat, adding sublimed sulfur powder into the other side of the porcelain boat, covering the porcelain boat, reserving gaps on two sides of the two porcelain boats, ensuring that inert gas can enter the porcelain boats to remove air, ensuring that the porcelain boat is fully vulcanized in a relatively closed environment, transferring the porcelain boat to the center of a tube furnace, placing the side containing the sublimed sulfur powder into an upstream area of the inert gas, introducing the inert gas to remove air, continuously introducing the inert gas, heating the tube furnace from room temperature to 700 ℃ under the protection of the inert gas, preserving the heat at 700 ℃ for 2 hours, and obtaining a reaction product after the heat preservation is finished;
fe described in step four7S8The mass ratio of the powder to the sublimed sulfur powder is 1: 3;
the heating rate in the fourth step is 5 ℃/min;
the inert gas in the fourth step is nitrogen, and the inert gas is introduced for 30min to remove air;
fifthly, centrifugally cleaning the reaction product for 5 times by using deionized water, and then drying the reaction product in a vacuum drying oven at the temperature of 60 ℃ for 10 hours to obtain the sulfur-doped carbon skeleton-coated heptaferric sulfide nanoparticle double-reaction-center Fenton-like catalyst (Fe)7S8@SC-700)。
FIG. 1 preparation of Fe in example 17S8The XRD pattern of @ SC;
as can be seen from fig. 1, the sample showed diffraction peaks at 2 θ of 30.0 °, 34.0 °, 44.0 ° and 53.3 °, which are respectively attributed to Fe7S8(JCPDS No.24-0220) (200), (203), (206) and (220) crystal plane characteristic peaks, which indicate that the active species in the synthesized sample is pure phase Fe7S8。
FIG. 2 is an SEM image of the MIL-101(Fe) precursor prepared in example 1 together with Fe7S8SEM and TEM images of @ SC, in which (a) is an SEM image of MIL-101(Fe) precursor and (b) is Fe7S8SEM picture of @ SC (c) is Fe7S8TEM image of @ SC, (d) is Fe7S8HR-TEM images of @ SC;
from (a) in FIG. 2, MIL-101(Fe) is seen to be a regular octahedral structure with smooth surface and uniform size; fe in FIG. 2 (b)7S8The @ SC can well maintain the shape of the MIL-101(Fe) precursor, but the particle size is obviously shrunk, and the surface is in a rough porous structure; in FIG. 2, (c) is Fe7S8TEM image of @ SC, Fe can be seen7S8The nanoparticles are tightly wrapped by an octahedral cage-shaped carbon skeleton, and due to the confinement of the carbon skeleton, Fe7S8The particles are uniformly embedded in the carbon shell, and the particle size is about 20 nm; in FIG. 2, (d) is Fe7S8HR-TEM image of @ SC, lattice fringe spacing of nanoparticles 0.206nm, corresponding to Fe7S8And (206) crystal plane of (a) and shows grain edge carbon and Fe7S8Coexistence is carried out. The synthesized sample is carbon-coated Fe7S8And (3) nanoparticles.
FIG. 3 is Fe prepared in example 17S8XPS spectra of @ SC, in which (a) is C spectrum, (b) is S spectrum, (C) is Fe spectrum, and (d) is Fe spectrum7S8And Fe7S8Comparative Fe spectra of @ SC, upper panel is Fe7S8In the lower diagram, Fe7S8@SC；
The C1S spectrum of FIG. 3 (a) has peaks for C-Fe bonds and C-S, illustrating the carbon layers and the presence of Fe7S8The interface forms a C-Fe electron transport channel, ands is doped into the carbon skeleton; s is excluded from the spectrum of S2p ((b) in FIG. 3)2-And Sn 2-Fe2p1/2And Fe2p3/2In addition to the spin orbit peak, there is a peak of C-S. Fe was present in the Fe2p spectrum ((c) in FIG. 3)2+And Fe3+Fe2p1/2And Fe2p3/2Spin orbit peak. In addition, Fe7S8Fe2p spectrum of @ SC with pure Fe7S8The comparison (FIG. 3 (d)) shows a significant right shift in binding energy, indicating Fe7S8The Fe-S in the carbon layer and the carbon layer have strong interaction of C-S-Fe.
Application test 1: the preparation of the sulfur-doped carbon skeleton-coated heptairon octasulfide nanoparticle double-reaction-center fenton-like catalyst for degrading antibiotics, which is prepared in example 1, is completed according to the following steps:
adding a sulfur-doped carbon skeleton-coated heptaferric sulfide nanoparticle double-reaction-center Fenton-like catalyst into water containing tetracycline hydrochloride, uniformly stirring, adding H with the mass fraction of 30%2O2Solution of H in the system2O2The concentration of (2) is 6mmol/L, timing, taking 1mL of solution at intervals of 5min, adding 1.0mL of methanol solution to quench reaction, filtering off catalyst in the solution with 0.22 μm filter membrane, measuring the concentration of tetracycline hydrochloride solution by high performance liquid chromatography, and calculating the ratio of the concentration to the initial concentration, C/C0Reacting for 40min to obtain water with tetracycline hydrochloride removed, wherein a degradation curve is shown in figure 4, then absorbing the catalyst by using a magnet, taking out the catalyst, washing the catalyst by using deionized water, and drying the catalyst to obtain a recovered catalyst;
the volume ratio of the mass of the sulfur-doped carbon skeleton-coated heptaferric sulfide nanoparticle double-reaction-center Fenton-like catalyst to the water containing tetracycline hydrochloride is 10mg:50 mL;
the concentration of the water containing the tetracycline hydrochloride is 35 mg/L;
the drying temperature is 60 ℃, and the drying time is 10 h.
Application test 2: the differences between this test and application test 1 are: adding a sulfur-doped carbon skeleton-wrapped heptairon sulfide nanoparticle double-reaction-center Fenton-like catalyst into water containing norfloxacin; the concentration of the water containing norfloxacin is 20 mg/L. The other steps and parameters were exactly the same as in application test 1, and the degradation curve is shown in FIG. 4.
Application test 3: the differences between this test and application test 1 are: adding a sulfur-doped carbon skeleton-wrapped heptaferric sulfide nanoparticle double-reaction-center fenton-like catalyst into water containing amoxicillin; the concentration of the water containing amoxicillin is 35 mg/L. The other steps and parameters were exactly the same as in application test 1, and the degradation curve is shown in FIG. 4.
FIG. 4 shows Fe prepared in example 17S8The performance diagram of @ SC for degrading antibiotics is shown, wherein TCH is tetracycline hydrochloride, AMX is amoxicillin, and NOR is norfloxacin;
the invention constructs sulfur-doped carbon skeleton coated Fe through simple liquid phase chemical synthesis and in-situ steam vulcanization method7S8The electron transmission multi-channel double-reaction-center Fenton-like catalyst for the nanoparticle interface realizes multi-channel enhanced electron transmission efficiency, creates more active sites, and promotes the Fenton-like degradation process of antibiotics, and the degradation rates of tetracycline hydrochloride, norfloxacin and amoxicillin in 40min under a neutral condition respectively reach 100%, 97.8% and 98.9%.
Repeated Recycling of Fe prepared in example 17S8@ SC degrades amoxicillin, and the cycle test is shown in FIG. 5;
FIG. 5 shows Fe prepared in example 17S8The circulation stability chart of the @ SC for degrading amoxicillin is shown in the figure, wherein 1st is used for the first time, 2ed is used for the second time, 3rd is used for the third time, 4th is used for the fourth time, and 5th is used for the fifth time.
As is clear from FIG. 5, after 5 cycles, the amoxicillin removal rate was maintained at 91.1%, and the iron elution was less than 1ppm, resulting in excellent cycle stability. Has better inspiration and reference significance for the design of other Fenton catalysts and has good application prospect.
Example 2: the present embodiment is different from embodiment 1 in that: step fourHeating the tube furnace from room temperature to 600 ℃ under the protection of inert gas, and then preserving heat for 2 hours at 600 ℃; the obtained catalyst is Fe7S8@ SC-600. The other steps and parameters were the same as in example 1.
Example 3: the present embodiment is different from embodiment 1 in that: in the fourth step, the temperature of the tube furnace is raised from room temperature to 800 ℃ under the protection of inert gas, and then the temperature is kept for 2 hours at 800 ℃; the obtained catalyst is Fe7S8@ SC-800. The other steps and parameters were the same as in example 1.
FIG. 6 is a graph showing the degradation rate of amoxicillin in 40min for catalysts prepared in different examples.
Fe prepared in example 2 under neutral conditions7S8@ SC-600, Fe prepared in example 17S8@ SC-700, and Fe prepared in example 37S8The degradation rate of @ SC-800 to amoxicillin within 40min is 89.7%, 98.9% and 96.0% respectively.
Claims (10)
1. A preparation method of a sulfur-doped carbon skeleton-coated octasulfide hepta-iron nanoparticle double-reaction-center Fenton-like catalyst is characterized by comprising the following steps:
firstly, mixing terephthalic acid and FeCl3·6H2Adding O into N, N-dimethylformamide, and stirring to obtain a solution I;
secondly, transferring the solution I into a hydrothermal reaction kettle, and then carrying out hydrothermal reaction at 110-160 ℃ to obtain an orange yellow solution after the reaction is finished;
thirdly, repeatedly cleaning the orange solution by using N, N-dimethylformamide and absolute ethyl alcohol until the supernatant of the solution is colorless, and drying to obtain an MIL-101(Fe) precursor;
putting an MIL-101(Fe) precursor into one side of a porcelain boat, adding sublimed sulfur powder into the other side of the porcelain boat, covering the porcelain boat, reserving gaps on two sides of the two porcelain boats, ensuring that inert gas can enter the porcelain boats to remove air, ensuring that the porcelain boat is fully vulcanized in a relatively closed environment, transferring the porcelain boat into the center of a tubular furnace, placing the side containing the sublimed sulfur powder into an upstream area of the inert gas, introducing the inert gas to remove air, continuously introducing the inert gas, heating the tubular furnace from room temperature to 600-800 ℃ under the protection of the inert gas, preserving heat at 600-800 ℃, and obtaining a reaction product after the heat preservation is finished;
and fifthly, centrifugally cleaning the reaction product, and drying the reaction product in a vacuum drying oven to obtain the sulfur-doped carbon skeleton-coated heptaferric sulfide nanoparticle double-reaction-center Fenton-like catalyst.
2. The method for preparing a sulfur-doped carbon skeleton-wrapped hepta-iron sulfide nanoparticle double-reaction-center fenton-like catalyst according to claim 1, wherein the volume ratio of the mass of the terephthalic acid to the volume of the N, N-dimethylformamide in the step one is (0.4 g-0.5 g): 40 mL-60 mL); FeCl as described in step one3·6H2The ratio of the mass of O to the volume of N, N-dimethylformamide is (1.3-1.6 g): 40-60 mL.
3. The preparation method of the sulfur-doped carbon skeleton-coated heptairon sulfide nanoparticle double-reaction-center fenton-like catalyst according to claim 1, wherein the stirring time in the first step is 1-2 h, and the stirring speed is 800-1000 r/min.
4. The method for preparing the sulfur-doped carbon skeleton-coated hepta-iron sulfide nanoparticle double-reaction-center fenton-like catalyst according to claim 1, wherein the hydrothermal reaction time in the second step is 20-24 hours.
5. The preparation method of the sulfur-doped carbon skeleton-wrapped heptairon sulfide nanoparticle double-reaction-center fenton-like catalyst according to claim 1, wherein the drying temperature in the third step is 60-80 ℃, and the drying time is 10-15 h.
6. The preparation method of the sulfur-doped carbon skeleton-coated hepta-iron sulfide nanoparticle double-reaction-center Fenton-like catalyst according to claim 1, wherein the mass ratio of the MIL-101(Fe) precursor to the sublimed sulfur powder in the fourth step is 1 (1-3); in the fourth step, the temperature is kept for 2 to 4 hours at the temperature of 600 to 800 ℃; the heating rate in the fourth step is 2-5 ℃/min; and the inert gas in the fourth step is nitrogen, and the inert gas is introduced for 20-30 min to remove air.
7. The preparation method of the sulfur-doped carbon skeleton-wrapped hepta-iron sulfide nanoparticle double-reaction-center fenton-like catalyst according to claim 1, wherein in the fifth step, deionized water is used for centrifugally cleaning the reaction product for 3 to 5 times, and then the reaction product is placed in a vacuum drying oven at a temperature of 60 to 80 ℃ for drying for 10 to 12 hours, so that the sulfur-doped carbon skeleton-wrapped hepta-iron sulfide nanoparticle double-reaction-center fenton-like catalyst is obtained.
8. The application of the sulfur-doped carbon skeleton-coated seven iron sulfide nanoparticle double-reaction-center Fenton-like catalyst prepared by the preparation method of claim 1, wherein the sulfur-doped carbon skeleton-coated seven iron sulfide nanoparticle double-reaction-center Fenton-like catalyst is used for degrading antibiotics.
9. The use of the sulfur-doped carbon skeleton-coated heptairon sulfide nanoparticle double-reaction-center fenton-like catalyst according to claim 8, wherein the antibiotic is tetracycline hydrochloride, norfloxacin or amoxicillin.
10. The application of the sulfur-doped carbon skeleton-wrapped seven iron sulfide nanoparticle double-reaction-center Fenton-like catalyst according to claim 8, wherein the application of the sulfur-doped carbon skeleton-wrapped seven iron sulfide nanoparticle double-reaction-center Fenton-like catalyst in degrading antibiotics is completed according to the following steps:
adding a sulfur-doped carbon skeleton-wrapped heptasulfide nanoparticle double-reaction-center Fenton-like catalyst into water containing antibiotics, uniformly stirring, and adding mass componentsNumber 30% of H2O2Solution of H in the system2O2The concentration of the catalyst is 2 mmol/L-15 mmol/L, the reaction is carried out for 10 min-40 min to obtain water without antibiotics, the catalyst is absorbed by a magnet, and the catalyst is taken out, washed by deionized water and dried to obtain a recovered catalyst;
the volume ratio of the mass of the sulfur-doped carbon skeleton-coated heptaferric sulfide nanoparticle double-reaction-center Fenton-like catalyst to the water containing the antibiotic is (5 mg-20 mg):50 mL;
the concentration of the water containing the antibiotics is 10 mg/L-50 mg/L;
the drying temperature is 60-80 ℃, and the drying time is 10-15 h.
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