CN109603810B - Molybdenum disulfide nanosheet/porous graphitized biochar composite material and preparation method and application thereof - Google Patents
Molybdenum disulfide nanosheet/porous graphitized biochar composite material and preparation method and application thereof Download PDFInfo
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- CN109603810B CN109603810B CN201811619833.0A CN201811619833A CN109603810B CN 109603810 B CN109603810 B CN 109603810B CN 201811619833 A CN201811619833 A CN 201811619833A CN 109603810 B CN109603810 B CN 109603810B
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- CWQXQMHSOZUFJS-UHFFFAOYSA-N molybdenum disulfide Chemical compound S=[Mo]=S CWQXQMHSOZUFJS-UHFFFAOYSA-N 0.000 title claims abstract description 89
- 229910052982 molybdenum disulfide Inorganic materials 0.000 title claims abstract description 89
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- 238000002360 preparation method Methods 0.000 title claims abstract description 21
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- JJWDELPVPRCLQN-UHFFFAOYSA-N 1-ethyl-6-fluoro-4-oxo-7-piperazin-1-ylquinoline-3-carboxylic acid;hydrochloride Chemical compound Cl.C1=C2N(CC)C=C(C(O)=O)C(=O)C2=CC(F)=C1N1CCNCC1 JJWDELPVPRCLQN-UHFFFAOYSA-N 0.000 description 1
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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
- B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/24—Chromium, molybdenum or tungsten
- B01J23/28—Molybdenum
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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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/39—Photocatalytic properties
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/30—Treatment of water, waste water, or sewage by irradiation
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- 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
- C02F2101/34—Organic compounds containing oxygen
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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
- C02F2101/36—Organic compounds containing halogen
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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
- C02F2305/00—Use of specific compounds during water treatment
- C02F2305/10—Photocatalysts
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Abstract
The invention discloses a molybdenum disulfide nanosheet/porous graphitized biochar composite material, and a preparation method and application thereof. The preparation method comprises the following steps: preparing porous graphitized charcoal powder; ultrasonically dispersing porous graphitized charcoal powder in water, adding sodium molybdate dihydrate and thioacetamide for hydrothermal reaction, centrifuging, washing and drying to obtain the composite material. The composite material has the advantages of large specific surface area, good conductivity, low recombination rate of photo-generated electron-hole pairs, high photocatalytic activity, high universality and the like, and the preparation method has the advantages of simple process, simple and convenient operation, low cost, environmental friendliness, no generation of toxic and harmful byproducts, suitability for large-scale preparation and accordance with the requirements of actual production. The composite material can quickly and efficiently treat antibiotics in the environment, and has good application value and application prospect.
Description
Technical Field
The invention belongs to the field of material science, and relates to a molybdenum disulfide nanosheet/porous graphitized biochar composite material, and a preparation method and application thereof.
Background
In recent years, the abuse of antibiotics has become a common phenomenon, and environmental and ecological problems caused by the abuse of antibiotics are increasing. With the use of antibiotics in large quantities, part of the antibiotics which are not metabolized can be directly excreted by animals and enter the external environment, so that the organisms in the environment are exposed to the antibiotics for a long time, and therefore, the antibiotics can cause harm to the microorganisms in the environment, such as generation of resistant bacteria. Drug-resistant bacteria in the host can accelerate the degradation of the drug, weaken the bacteriostatic action of the drug and reduce the drug effect. Antibiotics, as "new environmental pollutants", have the property of remaining and accumulating in the body and environment, which not only affect the healthy life of humans, but also cause irreparable damage to the environment. Therefore, the knowledge of the current situation of antibiotic pollution in water is deepened, and a scientific and safe method for treating antibiotic pollution is a hotspot researched by scholars at home and abroad in recent years.
The photocatalytic oxidation technology is gradually becoming the key point of research of people in various fields due to the advantages of low price, energy conservation, no toxicity, high efficiency and easy operation. Molybdenum disulfide, a typical transition metal sulfide, has a graphene-like layered structure, good optical properties, and electron transport characteristics, and is a light-absorbing semiconductor material of interest. The material has an energy band gap of 1.8eV, can absorb photons of visible light frequency to excite and generate electron-hole pairs, and the edge potentials of a valence band and a conduction band are high, so that carriers can participate in the generation of strong oxidizing substances (oxidizing free radicals). However, the molybdenum disulfide homogeneous catalyst has the problems of high recombination rate of photo-generated electron-hole pairs, poor conductivity and the like, and the molybdenum disulfide nanosheets are easy to agglomerate due to the action of van der waals force. Therefore, the defects of the molybdenum disulfide nanosheet are overcome, and the molybdenum disulfide nanosheet/porous graphitized biochar composite material which is large in specific surface area, good in conductivity, low in recombination rate of photo-generated electron-hole pairs, high in photocatalytic activity and high in universality is obtained, and has very important significance for effectively treating pollutants (such as antibiotics) in the environment.
Disclosure of Invention
The invention aims to overcome the defects of the prior art, provides a molybdenum disulfide nanosheet/porous graphitized biochar composite material which has the advantages of large specific surface area, good conductivity, low recombination rate of photo-generated electron-hole pairs, high photocatalytic activity and high universality, and also provides a method which has the advantages of simple process, simple and convenient operation, low cost and the like and can be used for preparing the molybdenum disulfide nanosheet/porous graphitized biochar composite material on a large scale and the application of the molybdenum disulfide nanosheet/porous graphitized biochar composite material in the treatment of antibiotics.
In order to solve the technical problems, the invention adopts the technical scheme that:
the molybdenum disulfide nanosheet/porous graphitized biochar composite material takes porous graphitized biochar as a carrier, and the surface of the porous graphitized biochar is inlaid with the molybdenum disulfide nanosheet.
As a general inventive concept, the invention also provides a preparation method of the molybdenum disulfide nanosheet/porous graphitized biochar composite material, which comprises the following steps:
s1, soaking the agricultural waste straws in a potassium permanganate solution, and drying to obtain the agricultural waste straws soaked with potassium permanganate;
s2, pyrolyzing and carbonizing the agricultural waste straw soaked with potassium permanganate and obtained in the step S1, washing, drying, grinding and sieving to obtain porous graphitized charcoal powder;
s3, ultrasonically dispersing the porous graphitized charcoal powder obtained in the step S2 in water, adding sodium molybdate dihydrate and thioacetamide to perform hydrothermal reaction, centrifuging, washing and drying to obtain the molybdenum disulfide nanosheet/porous graphitized charcoal composite material.
In the preparation method, the mass ratio of the porous graphitized charcoal powder to the sodium molybdate dihydrate is further improved to be 0.05-0.15: 1; the molar ratio of the sodium molybdate dihydrate to the thioacetamide is 1: 5.
In the step S1, the concentration of the potassium permanganate solution is 0.5 mol/L-1 mol/L, the soaking time is 12-24 h, and the drying is carried out under the vacuum condition.
The preparation method is further improved, in the step S2, the pyrolysis carbonization is carried out in a nitrogen atmosphere, the heating rate in the pyrolysis carbonization process is 5 ℃/min, the pyrolysis carbonization temperature is 700-1000 ℃, the pyrolysis carbonization time is 1-3 h, the washing is carried out by sequentially adopting dilute acid and deionized water to wash the products after the pyrolysis carbonization, the concentration of the dilute acid is 0.1 mol/L-1 mol/L, the dilute acid is a dilute hydrochloric acid solution, the drying is carried out at the temperature of 60 ℃, and the sieving is carried out by sieving with a 200-mesh sieve.
In the above preparation method, further improvement is provided, in the step S3, the time of ultrasonic dispersion is 30min to 60 min; the temperature of the hydrothermal reaction is 160-200 ℃; the time of the hydrothermal reaction is 18-24 h; the washing is to wash the centrifugal product by sequentially adopting absolute ethyl alcohol and deionized water; the drying is carried out at a temperature of 60 ℃.
As a general technical concept, the invention also provides an application of the molybdenum disulfide nanosheet/porous graphitized biochar composite material or the molybdenum disulfide nanosheet/porous graphitized biochar composite material prepared by the preparation method in antibiotic treatment.
The application is further improved, the molybdenum disulfide nanosheet/porous graphitized biochar composite material is adopted to treat the antibiotics in the water body, and the method comprises the following steps: mixing the molybdenum disulfide nanosheet/porous graphitized biochar composite material in an antibiotic water body for dark reaction, and after adsorption balance is achieved, carrying out photocatalytic degradation reaction under the illumination condition to complete the treatment of the antibiotic in the water body.
In the application, the mass-volume ratio of the molybdenum disulfide nanosheet/porous graphitized biochar composite material to the antibiotic water body is further improved to be 0.1-0.5 g: 1L.
The application is further improved, the antibiotic in the antibiotic water body is at least one of tetracycline hydrochloride, oxytetracycline, ofloxacin, norfloxacin and sulfamethoxazole, the concentration of the antibiotic in the antibiotic water body is 10 mg/L-50 mg/L, the dark reaction time is 30-60 min, and the photocatalytic degradation reaction time is 60-120 min.
Compared with the prior art, the invention has the advantages that:
(1) the invention provides a molybdenum disulfide nanosheet/porous graphitized biochar composite material, which takes porous graphitized biochar as a carrier, and molybdenum disulfide nanosheets are embedded in the surface of the porous graphitized biochar. In the invention, the porous graphitized biochar has very large specific surface area and good pore distribution, and has very strong adsorption capacity on pollutants. On the basis, the molybdenum disulfide nanosheets are embedded on the surface of the porous graphitized biochar, so that on one hand, the porous graphitized biochar is used as a carrier, the molybdenum disulfide nanosheets can be uniformly distributed, and the phenomenon of stacking and agglomeration of the molybdenum disulfide nanosheets is avoided to the greatest extent; on the other hand, the porous graphitized biochar has higher conductivity due to higher graphitization degree, can quickly transfer electrons, quickens the separation of electron-hole pairs and improves the utilization rate of carriers, so that molybdenum disulfide nanosheets are uniformly embedded on the surface of the porous graphitized biochar, and electrons can be conducted and moved on the semiconductor material molybdenum disulfide and the porous graphitized biochar through contact surfaces, thereby reducing the recombination of photo-generated electron pairs and improving the photocatalysis efficiency. The molybdenum disulfide nanosheet/porous graphitized biochar composite material has the advantages of large specific surface area, good conductivity, low recombination rate of photo-generated electron-hole pairs, high photocatalytic activity, high universality and the like, can quickly and efficiently treat pollutants (such as antibiotics) in the environment, and has good application value and application prospect. The molybdenum disulfide nanosheet/porous graphitized biochar composite material is a photocatalytic material with complete morphology and good photoelectrochemical performance, and has excellent treatment efficiency and stable cycle performance in the aspect of water pollution treatment.
(2) The invention also provides a preparation method of the molybdenum disulfide nanosheet/porous graphitized biochar composite material, wherein the porous graphitized biochar is prepared by taking agricultural waste straws as a carbon precursor, and the molybdenum disulfide nanosheet is uniformly embedded on the surface of the porous graphitized biochar by taking the porous graphitized biochar as a carrier through a hydrothermal synthesis method, so that the molybdenum disulfide/porous graphitized biochar composite material with complete appearance and good photoelectrochemical performance is prepared. According to the invention, the selected materials and reagents are cheap and have wide sources, wherein the straw is used as agricultural waste and contains a large amount of lignin and cellulose, and the straw is used as a biomass precursor for preparing the porous graphite carbon, so that the cost can be effectively reduced, and the reutilization of agricultural organic matters is improved; the novel, efficient and multifunctional green treating agent potassium ferrate can simultaneously realize the porosification and graphitization of the carbon material, not only can simplify the preparation steps and operation of the material, but also can avoid using high-toxicity compounds in the catalytic graphitization process. The preparation method has the advantages of simple process, simple and convenient operation and low cost, is environment-friendly, does not generate toxic and harmful byproducts, is suitable for large-scale preparation, and meets the requirement of actual production.
(3) The molybdenum disulfide nanosheet/porous graphitized biochar composite material can be used for treating antibiotics, and the molybdenum disulfide nanosheet/porous graphitized biochar composite material is mixed with an antibiotic water body, so that the antibiotics in the water body can be efficiently removed through a dark reaction and a photocatalytic degradation reaction. By taking tetracycline hydrochloride as an example, the removal rate of the molybdenum disulfide nanosheet/porous graphitized biochar composite material on the tetracycline hydrochloride in the water body is up to 91.82%, so that the antibiotics can be effectively removed, and the ecological risk of pollutants in the water body on an ecological system can be effectively reduced.
Drawings
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention.
Fig. 1 is a scanning electron microscope image of a molybdenum disulfide nanosheet/porous graphitized biochar composite material prepared in embodiment 1 of the present invention.
Fig. 2 is a transmission electron microscope image of the molybdenum disulfide nanosheet/porous graphitized biochar composite prepared in embodiment 1 of the present invention.
Fig. 3 is a graph of the efficiency of photocatalytic degradation of tetracycline hydrochloride by a molybdenum disulfide nanosheet/porous graphitized biochar composite in embodiment 2 of the present invention.
Detailed Description
The invention is further described below with reference to the drawings and specific preferred embodiments of the description, without thereby limiting the scope of protection of the invention.
In the following examples of the present invention, unless otherwise specified, materials and instruments used are commercially available, processes used are conventional, apparatuses used are conventional, and the obtained data are average values of three or more repeated experiments.
Example 1
A molybdenum disulfide nanosheet/porous graphitized biochar composite material takes porous graphitized biochar as a carrier, and molybdenum disulfide nanosheets are inlaid in the surface of the porous graphitized biochar.
The preparation method of the molybdenum disulfide nanosheet/porous graphitized biochar composite material comprises the following steps:
(1) preparation of Porous Graphitized Biochar (PGBC):
(1.1) taking naturally air-dried, ground and sieved agricultural waste straws as a carbon precursor, putting the carbon precursor into a potassium ferrate solution with the concentration of 1 mol/L, soaking for 24 hours under the condition of stirring, and then putting the carbon precursor into a vacuum drying oven for drying to obtain the agricultural waste straws soaked with potassium permanganate.
(1.2) transferring the powder obtained after drying in the step (1.1) (namely the agricultural waste straw soaked with potassium permanganate) to a tubular furnace, heating to 900 ℃ at the heating rate of 5 ℃/min under the condition of nitrogen for pyrolysis carbonization for 1h, naturally cooling after the reaction is finished, washing the product after the pyrolysis carbonization by sequentially adopting a dilute hydrochloric acid solution with the concentration of 1 mol/L and deionized water, drying at the temperature of 60 ℃, grinding, and sieving by a 200-mesh sieve to obtain the Porous Graphitized Biochar (PGBC) powder.
(2) Loading molybdenum disulfide nanosheets:
respectively placing 16mg, 24mg and 32mg of the porous graphitized charcoal powder prepared in the step (1) into deionized water, carrying out ultrasonic dispersion for 30 minutes, respectively and sequentially adding 240mg of sodium molybdate dihydrate and 375mg of thioacetamide (the molar ratio is 1: 5) into the obtained porous graphitized charcoal powder dispersion liquid, and uniformly mixing under magnetic stirring to obtain a precursor mixed liquid; respectively transferring the obtained precursor mixed solution into a stainless steel reaction kettle with a polytetrafluoroethylene inner container, and reacting for 24 hours at 180 ℃; naturally cooling after the reaction is finished, centrifuging, sequentially washing the black precipitate obtained by centrifuging by adopting absolute ethyl alcohol and deionized water, and drying at 60 ℃ to obtain the molybdenum disulfide nanosheet/porous graphitized biochar composite material, wherein when the mass of the porous graphitized biochar powder is 16mg, 24mg and 32mg, the corresponding molybdenum disulfide nanosheet/porous graphitized biochar composite material is respectively numbered as MoS2/PGBC16、MoS2/PGBC24、MoS2/PGBC32。
In this embodiment, when the mass ratio of the porous graphitized charcoal powder to the sodium molybdate dihydrate is 0.1: 1, the mass ratio of the porous graphitized charcoal to the molybdenum disulfide nanosheet in the corresponding molybdenum disulfide nanosheet/porous graphitized charcoal composite material is 0.15: 1.
FIG. 1 shows a molybdenum disulfide nanosheet/porous graphitized charcoal composite (MoS) prepared in example 1 of the present invention2/PGBC24) Scanning electron micrograph (c). ByAs can be seen from fig. 1, the surface of the molybdenum disulfide nanosheet/porous graphitized biochar composite becomes rougher, and a large number of wrinkled sheets with bent edges are inlaid on the roughened surface, so that the successful generation of the molybdenum disulfide nanosheets on the porous graphitized biochar is proved, and the edge portions of the sheets can be maximally exposed to improve the catalytic activity.
FIG. 2 shows a molybdenum disulfide nanosheet/porous graphitized charcoal composite (MoS) prepared in example 1 of the present invention2/PGBC24) Transmission electron micrograph (D). The specific lattice spacing of molybdenum disulfide (-0.66 nm) and graphitized carbon (-0.35 nm) can be observed simultaneously in fig. 2, which fully demonstrates the interaction of the two materials, i.e., the successful synthesis of the molybdenum disulfide nanosheet/porous graphitized biochar composite catalyst.
Example 2
An application of a molybdenum disulfide nanosheet/porous graphitized biochar composite material in antibiotic treatment, specifically, the molybdenum disulfide nanosheet/porous graphitized biochar composite material (MoS) prepared in example 1 is adopted2/PGBC16、MoS2/PGBC24、MoS2/PGBC32) The method for treating the tetracycline hydrochloride in the water body comprises the following steps:
the molybdenum disulfide nanosheet/porous graphitized biochar composite (MoS) prepared in example 1 was taken2/PGBC16、MoS2/PGBC24、MoS2/PGBC32) Molybdenum disulfide nanosheet (MoS)2) Respectively placing 20mg of the above into tetracycline hydrochloride solution with concentration of 20 mg/L and 50m L, mixing, dark reacting for 30min in dark condition, and placing in xenon lamp (300W, lambda)>420nm) under the irradiation for 60min, and completing the treatment of tetracycline hydrochloride in the water body.
Samples were taken at different time intervals to determine the tetracycline hydrochloride removal from the assay solution, and the results are shown in FIG. 3 and Table 1.
Table 1 influence of molybdenum disulfide nanosheet/porous graphitized biochar composite and molybdenum disulfide nanosheet in example 2 of the present invention on tetracycline hydrochloride removal effect in solution
| MoS2/PGBC16 | MoS2/PGBC24 | MoS2/PGBC32 | MoS2 | |
| Removal Rate (%) | 82.58 | 91.82 | 73.34 | 43.85 |
Fig. 3 is a graph of the efficiency of photocatalytic degradation of tetracycline hydrochloride by a molybdenum disulfide nanosheet/porous graphitized biochar composite in embodiment 2 of the present invention. As can be seen from table 1 and fig. 3, compared with the blank test and the simple molybdenum disulfide control test, the molybdenum disulfide nanosheet/porous graphitized biochar composite material of the present invention has a very high removal rate of antibiotics (tetracycline hydrochloride) in the water body, wherein when the amount of the porous graphitized biochar used in synthesizing the composite material is 24mg, the highest removal rate of antibiotics can be achieved, so that the ecological risk of the pollutants in the water body to the ecological system can be effectively reduced.
Molybdenum disulfide nanosheet/porous graphitized biochar composite material prepared in embodiment 1 of the invention
(MoS2/PGBC24) For different antibiotics(oxytetracycline, ofloxacin, norfloxacin and sulfamethoxazole) solutions (all at a concentration of 20 mg/L) were degraded in the same manner as in example 2, and the removal results are shown in Table 2.
Table 2 molybdenum disulfide nanosheet/porous graphitized biochar composite (MoS) prepared in inventive example 12/PGBC24)
Effect on the removal of different antibiotics
| Oxytetracycline | Ofloxacin | Norfloxacin hydrochloride | Sulfamethoxazole | |
| Removal Rate (%) | 88.35 | 90.07 | 85.79 | 78.83 |
As can be seen from Table 2, the molybdenum disulfide nanosheet/porous graphitized biochar composite (MoS) of the present invention2/PGBC24) The removal rate of terramycin, ofloxacin, norfloxacin and sulfamethoxazole is 88.35%, 90.07%, 85.79% and 78.83% in sequence. Therefore, the molybdenum disulfide nanosheet/porous graphitized biochar composite material can effectively degrade antibiotics in water and has very important significance for effectively removing the antibiotics in the waterAnd (5) defining.
The above examples are merely preferred embodiments of the present invention, and the scope of the present invention is not limited to the above examples. All technical schemes belonging to the idea of the invention belong to the protection scope of the invention. It should be noted that modifications and embellishments within the scope of the invention may be made by those skilled in the art without departing from the principle of the invention, and such modifications and embellishments should also be considered as within the scope of the invention.
Claims (10)
1. The molybdenum disulfide nanosheet/porous graphitized biochar composite material is characterized in that the molybdenum disulfide nanosheet/porous graphitized biochar composite material takes porous graphitized biochar as a carrier, and molybdenum disulfide nanosheets are embedded in the surface of the porous graphitized biochar; the mass ratio of the porous graphitized biochar to the molybdenum disulfide nanosheet is 0.15: 1.
2. A method for preparing the molybdenum disulfide nanosheet/porous graphitized biochar composite of claim 1, comprising the steps of:
s1, soaking the agricultural waste straws in a potassium permanganate solution, and drying to obtain the agricultural waste straws soaked with potassium permanganate;
s2, pyrolyzing and carbonizing the agricultural waste straw soaked with potassium permanganate and obtained in the step S1, washing, drying, grinding and sieving to obtain porous graphitized charcoal powder;
s3, ultrasonically dispersing the porous graphitized charcoal powder obtained in the step S2 in water, adding sodium molybdate dihydrate and thioacetamide for hydrothermal reaction, centrifuging, washing and drying to obtain a molybdenum disulfide nanosheet/porous graphitized charcoal composite material; the mass ratio of the porous graphitized charcoal powder to the sodium molybdate dihydrate is 0.1: 1.
3. The method of claim 2, wherein the molar ratio of sodium molybdate dihydrate to thioacetamide is 1: 5.
4. The preparation method according to claim 2 or 3, wherein in the step S1, the concentration of the potassium permanganate solution is 0.5 mol/L-1 mol/L, the soaking time is 12-24 h, and the drying is performed under vacuum condition.
5. The preparation method according to claim 2 or 3, wherein in the step S2, the pyrolysis carbonization is performed in a nitrogen atmosphere, the heating rate in the pyrolysis carbonization process is 5 ℃/min, the pyrolysis carbonization temperature is 700-1000 ℃, the pyrolysis carbonization time is 1-3 h, the washing is performed by sequentially washing the pyrolysis carbonized product with dilute acid and deionized water, the concentration of the dilute acid is 0.1 mol/L-1 mol/L, the dilute acid is a dilute hydrochloric acid solution, the drying is performed at the temperature of 60 ℃, and the sieving is performed by sieving with a 200-mesh sieve.
6. The production method according to claim 2 or 3, wherein in the step S3, the ultrasonic dispersion time is 30 to 60 min; the temperature of the hydrothermal reaction is 160-200 ℃; the time of the hydrothermal reaction is 18-24 h; the washing is to wash the centrifugal product by sequentially adopting absolute ethyl alcohol and deionized water; the drying is carried out at a temperature of 60 ℃.
7. The application of the molybdenum disulfide nanosheet/porous graphitized biochar composite material according to claim 1 or the molybdenum disulfide nanosheet/porous graphitized biochar composite material prepared by the preparation method according to any one of claims 2 to 5 in antibiotic treatment.
8. The application of claim 7, wherein the treatment of the antibiotics in the water body by using the molybdenum disulfide nanosheet/porous graphitized biochar composite material comprises the following steps: mixing the molybdenum disulfide nanosheet/porous graphitized biochar composite material in an antibiotic water body for dark reaction, and after adsorption balance is achieved, carrying out photocatalytic degradation reaction under the illumination condition to complete the treatment of the antibiotic in the water body.
9. The application of claim 8, wherein the mass-to-volume ratio of the molybdenum disulfide nanosheet/porous graphitized biochar composite to the antibiotic water body is 0.1-0.5 g: 1L.
10. The application of claim 8 or 9, wherein the antibiotic in the antibiotic water body is at least one of tetracycline hydrochloride, oxytetracycline, ofloxacin, norfloxacin and sulfamethoxazole, the concentration of the antibiotic in the antibiotic water body is 10 mg/L-50 mg/L, the dark reaction time is 30 min-60 min, and the photocatalytic degradation reaction time is 60 min-120 min.
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| CN113145067A (en) * | 2021-01-22 | 2021-07-23 | 南京师范大学 | Preparation method and application of vinegar residue biomass charcoal-molybdenum disulfide composite material |
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| CN114797811A (en) * | 2022-04-18 | 2022-07-29 | 武汉理工大学 | MoS applied to tetracycline removal in water 2 Preparation method of hydrothermal activated sludge biochar |
| CN115475606B (en) * | 2022-10-19 | 2024-01-09 | 辽宁大学 | Modified molybdenum sulfide/biochar material, preparation method thereof and application thereof in co-adsorption of antibiotics and heavy metal ions |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103706328A (en) * | 2014-01-17 | 2014-04-09 | 湖南大学 | Nitrogen hybridized magnetic ordered mesoporous carbon adsorbent, and preparation method and application thereof |
| CN106582880A (en) * | 2016-12-22 | 2017-04-26 | 华南协同创新研究院 | Molybdenum disulfide/MIL-101 composite photocatalyst material as well as preparation method and application thereof |
| CN106744915A (en) * | 2016-12-16 | 2017-05-31 | 中国林业科学研究院林产化学工业研究所 | A kind of cellulose base graphitized material and preparation method thereof |
| CN108786855A (en) * | 2017-05-04 | 2018-11-13 | 中国计量大学 | A kind of preparation method of mesoporous molybdenum disulfide visible light catalyst material and its application in degradation antibiotic waste water field |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20130239469A1 (en) * | 2012-03-14 | 2013-09-19 | Board Of Regents, The University Of Texas System | Photochemical Processes and Compositions for Methane Reforming Using Transition Metal Chalcogenide Photocatalysts |
-
2018
- 2018-12-28 CN CN201811619833.0A patent/CN109603810B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103706328A (en) * | 2014-01-17 | 2014-04-09 | 湖南大学 | Nitrogen hybridized magnetic ordered mesoporous carbon adsorbent, and preparation method and application thereof |
| CN106744915A (en) * | 2016-12-16 | 2017-05-31 | 中国林业科学研究院林产化学工业研究所 | A kind of cellulose base graphitized material and preparation method thereof |
| CN106582880A (en) * | 2016-12-22 | 2017-04-26 | 华南协同创新研究院 | Molybdenum disulfide/MIL-101 composite photocatalyst material as well as preparation method and application thereof |
| CN108786855A (en) * | 2017-05-04 | 2018-11-13 | 中国计量大学 | A kind of preparation method of mesoporous molybdenum disulfide visible light catalyst material and its application in degradation antibiotic waste water field |
Non-Patent Citations (2)
| Title |
|---|
| "Highly porous graphitic biomass carbon as advanced electrode materials for supercapacitors";Youning Gong et al.;《Green Chemistry》;20170725;第19卷;第4132-4140页 * |
| "Research on the sustainable efficacy of g-MoS2 decorated biochar nanocomposites for removing tetracycline hydrochloride from antibiotic-polluted aqueous solution";Zhuotong Zeng et al.;《Science of the Total Environment》;20180809;第648卷;第206-217页 * |
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