CN114011455B - Copper monatomic catalyst, preparation method and application thereof, and method for catalytically degrading tetracycline in wastewater by using copper monatomic catalyst - Google Patents
Copper monatomic catalyst, preparation method and application thereof, and method for catalytically degrading tetracycline in wastewater by using copper monatomic catalyst Download PDFInfo
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Images
Classifications
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- B01J35/39—
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/24—Nitrogen compounds
-
- 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
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/03—Catalysts comprising molecular sieves not having base-exchange properties
- B01J29/0308—Mesoporous materials not having base exchange properties, e.g. Si-MCM-41
- B01J29/0316—Mesoporous materials not having base exchange properties, e.g. Si-MCM-41 containing iron group metals, noble metals or copper
- B01J29/0333—Iron group metals or copper
-
- 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
- C02F1/32—Treatment of water, waste water, or sewage by irradiation with ultraviolet light
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/722—Oxidation by peroxides
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/725—Treatment of water, waste water, or sewage by oxidation by catalytic oxidation
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- 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
Abstract
The invention provides a copper monatomic catalyst, a preparation method and application thereof, and a method for catalytic degradation of tetracycline in wastewater by using the copper monatomic catalyst, and belongs to the technical field of sewage treatment. In the copper monatomic catalyst prepared by the invention, the copper monatomic is loaded on the carrier containing the C-N structure, so that the catalyst has high specific surface area and high catalytic performance, under the condition of ultraviolet light, the removal effect on the low-concentration tetracycline wastewater is good, the purification efficiency is high, the degradation efficiency of the low-concentration tetracycline reaches 90%, the water quality is effectively improved, and the harm of the low-concentration tetracycline in the current water to the environment is effectively solved. The method of the invention has the advantages of simplicity, easy operation, low cost, energy consumption saving, treatment cost reduction and obvious environmental, social and economic benefits.
Description
Technical Field
The invention relates to the technical field of sewage treatment, in particular to a copper monatomic catalyst, a preparation method and application thereof, and a method for catalytically degrading tetracycline in wastewater by using the copper monatomic catalyst.
Background
Since the discovery of penicillin in 1928, antibiotics have been widely used by humans and are also widely used in poultry farming, animal husbandry, aquaculture, and food processing. Most of antibiotic medicines taken by people and livestock can not be fully absorbed and enter sewage along with excrement or are directly discharged into a water environment. The residual antibiotics in the environmental water body mainly come from antibiotic industrial wastewater, human antibiotics and veterinary antibiotics. The concentration of antibiotics in the environmental water body is generally trace (ng/L). The effect of antibiotic residues in water on aquatic organisms is manifested by toxicity to some algae, fish and the like. The presence of low concentrations of antibiotics for a long period of time may have an impact on the microbial communities in the water body and affect higher organisms through the transfer of the food chain, destroying the ecosystem. In addition, the use of antibiotics can lead to the development of resistance by pathogenic microorganisms, resulting in an increasing effective dose of antibiotics to kill bacteria. The drug resistance gene can be transmitted from generation to generation and also can be transmitted among different bacteria. Therefore, some drug-resistant bacteria have no pathogenicity, but can transmit drug-resistant genes to pathogenic bacteria, and the increase and diffusion of drug-resistant pathogenic bacteria cause potential risks to human health. Meanwhile, a plurality of antibiotics coexist in the environment, and favorable conditions are created for inducing strains with drug resistance, particularly cross drug resistance. Finally, antibiotics and their derivatives remain in water and food, and cause potential health effects by long-term enrichment of food chains. For example, long-term accumulation of tetracyclines can inhibit the development and bone growth of infants; sulfonamides are susceptible to allergy in sensitive individuals.
The existing treatment methods of the wastewater containing antibiotics mainly comprise a physical method, a chemical method, a biological method and the like. The physical methods mainly include air floatation method, adsorption method and film technique; the chemical method mainly comprises an ozone oxidation method, a Fenton oxidation method and an electrochemical technology; the biological methods mainly include an SBR method (sequencing batch reactor) method, an MBR method (membrane bioreactor) method, and an upflow anaerobic sludge bed method. However, due to the low concentration of antibiotics (15-30 mg/L) in the wastewater, the existing treatment method is difficult to further purify the low-concentration antibiotic water body.
Disclosure of Invention
The invention aims to provide a copper monatomic catalyst, a preparation method and application thereof, and a method for catalyzing and degrading tetracycline in wastewater by using the copper monatomic catalyst.
In order to achieve the above object, the present invention provides the following technical solutions:
the invention provides a preparation method of a copper monatomic catalyst, which comprises the following steps:
and evaporating the mixed solution of formaldehyde, dicyandiamide, copper salt and water to dryness, and roasting to obtain the copper monatomic catalyst.
Preferably, the molar ratio of the formaldehyde to the dicyandiamide to the copper salt is 7:7 (0.5-2).
Preferably, the drying time is 4-8 h; the roasting process comprises a first roasting and a second roasting which are sequentially carried out; the first roasting is carried out in Ar atmosphere, the temperature of the first roasting is 550-700 ℃, and the time is 1.5-3 h; and the second roasting is carried out in a mixed atmosphere of H2 and Ar, the temperature of the second roasting is 380-500 ℃, and the time is 1.5-3H.
Preferably, the mixed solution further includes a precursor, and the method for preparing the precursor includes: mixing polyethylene oxide-polypropylene oxide-polyethylene oxide, tetraethoxysilane, acid and water, and crystallizing to obtain a precursor.
Preferably, the molar ratio of the tetraethoxysilane, the polyethylene oxide-polypropylene oxide-polyethylene oxide, the acid and the water is 1: (0.01-0.02): (5.7-6.0): (100-150).
Preferably, the molar ratio of the precursor to the formaldehyde is (10-30): 7.
The invention provides a copper monatomic catalyst prepared by the preparation method in the technical scheme, which comprises a carrier and copper monatomic loaded on the carrier; the carrier is a carbon material containing a C-N structure.
Preferably, the carrier is a carbon material with a C-N structure connected with a mesoporous molecular sieve.
The invention provides application of the copper monatomic catalyst in the technical scheme in catalytic degradation of tetracycline.
The invention provides a method for degrading tetracycline in wastewater by using a copper monatomic catalyst, which comprises the following steps:
mixing a copper monatomic catalyst with tetracycline-containing wastewater and sodium persulfate, and performing catalytic degradation under the ultraviolet condition; the copper monatomic catalyst is the copper monatomic catalyst in the technical scheme.
The invention provides a preparation method of a copper monatomic catalyst, which comprises the following steps: and evaporating the mixed solution of formaldehyde, dicyandiamide, copper salt and water to dryness, and roasting to obtain the copper monatomic catalyst. In the copper monatomic catalyst prepared by the invention, the copper monatomic is loaded on a carrier containing a C-N structure, so that the catalyst has high catalytic performance, and the Cu atom can improve the electron transfer on the surface of C-N in the photocatalysis process, thereby avoiding the quenching of holes and electrons; cu provides electrons for a wastewater system to form an oxidation-reduction system, tetracycline is oxidized, and an energy band formed by a copper monatomic catalyst under photocatalysis meets the requirement of decomposition energy of the tetracycline, so that the copper monatomic catalyst has a good effect of removing low-concentration tetracycline wastewater (15-30 mg/L) under an ultraviolet light condition, is high in purification efficiency, has the degradation efficiency of the low-concentration tetracycline as high as 90%, effectively improves the quality of a water body, and effectively solves the problem of the harm of low-concentration tetracycline in the current water body to the environment.
The method of the invention has the advantages of simplicity, easy operation, low cost, energy consumption saving, treatment cost reduction and obvious environmental, social and economic benefits.
Furthermore, the mesoporous molecular sieve precursor is prepared from polyethylene oxide-polypropylene oxide-polyethylene oxide and tetraethoxysilane, the mesoporous molecular sieve can be subjected to secondary modification and grafted with other groups, so that the catalyst has more functionality, the catalysis efficiency is improved by adjusting the acidity and alkalinity of a reaction system, the adjustability of the copper atom catalyst is enhanced, and the catalysis efficiency is improved.
Drawings
FIG. 1 is an SEM image of a copper monatomic catalyst prepared in example 2;
FIG. 2 is a graph showing the tetracycline degradation curves of application examples 1-4;
FIG. 3 is a graph showing tetracycline degradation curves of examples 5-8.
Detailed Description
The invention provides a preparation method of a copper monatomic catalyst, which comprises the following steps:
and evaporating the mixed solution of formaldehyde, dicyandiamide, copper salt and water to dryness, and roasting to obtain the copper monatomic catalyst.
In the present invention, unless otherwise specified, all the starting materials required for the preparation are commercially available products well known to those skilled in the art.
The invention evaporates the mixed solution of formaldehyde, dicyandiamide, copper salt and water to dryness. In the present invention, the copper salt is preferably Cu (NO) 3 ) 2 ·3H 2 O; the molar ratio of the formaldehyde to the dicyandiamide to the copper salt is preferably 7:7 (0.5-2), more preferably 7:7 (0.5-1.5), and still more preferably 7:7: 1. The invention uses the waterThe raw material may be sufficiently dissolved, with special restrictions. The process of mixing the formaldehyde, the dicyandiamide, the copper salt and the water is not particularly limited, and the materials are uniformly mixed according to the process well known in the art.
After the mixing is completed, the mixed solution obtained is evaporated to dryness by the invention. Before the evaporation, the obtained mixed solution is preferably violently stirred for 4-6 min, heated to boil and evaporated to dryness; the drying time is preferably 4-8 h, and more preferably 5-6 h. The Cu-dicyandiamide-formaldehyde complex is formed by evaporation.
After the drying to dryness is completed, the invention carries out roasting on the obtained solid substance. In the present invention, the roasting process preferably includes a first roasting and a second roasting performed in sequence; the first roasting is preferably carried out in Ar atmosphere, the temperature of the first roasting is preferably 550-700 ℃, more preferably 600 ℃, and the time is preferably 1.5-3 h, more preferably 2 h.
After the first roasting is finished, the natural cooling is preferably carried out to the room temperature, and the second roasting is carried out; the second calcination is preferably in H 2 And Ar, wherein the temperature of the second roasting is preferably 380-500 ℃, more preferably 400 ℃, and the time is preferably 1.5-3 h, more preferably 2 h. In the present invention, said H 2 And Ar mixed atmosphere, the H 2 Is preferably 5%; the temperature rise rate when the temperature rises to the first roasting temperature and the second roasting temperature is preferably 5-10 ℃/min independently.
In the roasting process, the first roasting is carried out under the anaerobic condition, so that the residual nitrogen oxide in the Cu-dicyandiamide-formaldehyde complex is decomposed; the second roasting is a reduction reaction, and the CuO in the system is reduced into Cu.
In a preferred embodiment of the present invention, the mixed solution preferably further includes a precursor, and the method for preparing the precursor preferably includes: mixing polyethylene oxide-polypropylene oxide-polyethylene oxide, tetraethoxysilane, acid and water, and crystallizing to obtain a precursor. In the present invention, the process of mixing the precursor with other raw materials in the mixed solution is not particularly limited, and the precursor and other raw materials may be mixed according to a process known in the art.
In the present invention, the acid is preferably dilute hydrochloric acid; the concentration of the dilute hydrochloric acid is not particularly limited in the present invention, and commercially available products well known in the art may be used.
In the present invention, the molar ratio of the tetraethoxysilane, the polyethylene oxide-polypropylene oxide-polyethylene oxide, the acid and the water is preferably 1: (0.01-0.02): (5.7-6.0): (100 to 150), more preferably 1:0.015:5.88: 130.
in the present invention, the process of mixing the polyethylene oxide-polypropylene oxide-polyethylene oxide, the tetraethoxysilane, the acid and the water is preferably carried out by dissolving the polyethylene oxide-polypropylene oxide-polyethylene oxide in the water, adding the tetraethoxysilane and the acid to the resulting solution, and continuously and vigorously stirring for 24 hours.
In the present invention, the crystallization is preferably carried out in a polytetrafluoroethylene bottle; the crystallization time is preferably 24 hours; in the crystallization process, under the action of a template agent (polyethylene oxide-polypropylene oxide-polyethylene oxide), crystals grow directionally to form a precursor with a mesoporous structure.
After the crystallization is finished, the obtained materials are preferably sequentially filtered, washed and dried, and the obtained solid is subjected to Soxhlet extraction to obtain a precursor. The filtration, washing and drying processes are not particularly limited in the present invention and may be performed according to processes well known in the art.
In the present invention, the reagent for soxhlet extraction preferably comprises ethanol and hydrochloric acid, and the ratio of the solid matter, ethanol and hydrochloric acid is preferably 1 g: (180-230) mL: (2-4) g, more preferably 1 g: (200-200) mL: (3-4) g; the number of times of Soxhlet extraction is preferably 2-3, the temperature of each extraction is 55-70 ℃, more preferably 60-65 ℃, and the time is preferably 5-8 hours, more preferably 6-7 hours. The invention removes the template agent by Soxhlet extraction.
In the invention, the precursor is SBA-15 molecular sieve; the molar ratio of the precursor to the formaldehyde is preferably (10-30): 7, and more preferably (10-20): 7.
The invention provides a copper monatomic catalyst prepared by the preparation method of the technical scheme, which comprises a carrier and copper monatomic loaded on the carrier; the carrier is a carbon material containing a C-N structure. In the invention, a precursor Cu-dicyandiamide-formaldehyde is roasted to form a carrier with a C-N structure, Cu monoatomic atoms are loaded on the carrier, and the copper monoatomic atoms are loaded on the carrier through complexation.
In the invention, when the mixed solution further comprises a precursor, in the prepared copper monatomic catalyst, the carrier is a carbon material with a C-N structure connected with a mesoporous molecular sieve, the copper monatomic is connected with the mesoporous molecular sieve, and the mesoporous molecular sieve is connected with the C-N structure of the carbon material in an embedded manner.
In the present invention, the loading amount of the copper monoatomic atom on the carrier is preferably 20 to 30 wt%, and more preferably 25 wt%.
The invention provides application of the copper monatomic catalyst in the technical scheme in catalytic degradation of tetracycline. The method of the present invention is not particularly limited, and the method may be applied according to a method known in the art.
The invention provides a method for degrading tetracycline in wastewater by using a copper monatomic catalyst, which comprises the following steps:
mixing a copper monatomic catalyst with tetracycline-containing wastewater and sodium persulfate, and performing catalytic degradation under the ultraviolet condition; the copper monatomic catalyst is the copper monatomic catalyst in the technical scheme.
In the invention, the reaction liquid containing tetracycline is preferably adopted to simulate the wastewater containing tetracycline, and the concentration of the reaction liquid containing tetracycline is preferably 10-40 mg/L, and more preferably 20-30 mg/L; the concentration of the copper monatomic catalyst in the tetracycline-containing reaction liquid is preferably 0.05-0.2 mg/L; the concentration of the sodium persulfate in the reaction solution containing tetracycline is preferably 0.1 mmol/L.
In the invention, the illumination wavelength of the ultraviolet light is preferably 360-420 nm, more preferably 365nm, and the time of catalytic degradation is preferably 30 min.
The technical solution of the present invention will be clearly and completely described below with reference to the embodiments of the present invention. It is to be understood that the described embodiments are merely exemplary of the invention, and not restrictive of the full scope of the invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
Formaldehyde, dicyandiamide and Cu (NO) in a molar ratio of 7:7:0.5 3 ) 2 ·3H 2 O is mixed in deionized water, the obtained mixed solution is heated to boiling after being vigorously stirred for 4min, the boiling is maintained for 4h, the obtained solid matter is roasted after the water is evaporated, the temperature is raised to 600 ℃ at the rate of 5 ℃/min under the Ar atmosphere, and the heating lasts for 2 h; after natural cooling to room temperature, at 5% (volume fraction) H 2 Heating the solid to 400 ℃ in the Ar atmosphere at the heating rate for 2 hours to obtain the copper monatomic catalyst taking the carbon material with the C-N structure as the carrier, wherein the loading amount of copper monatomic on the carrier is 20 wt%.
Example 2
Formaldehyde, dicyandiamide and Cu (NO) in a molar ratio of 7:7:2 3 ) 2 ·3H 2 Mixing O in deionized water, violently stirring the obtained mixed solution for 6min, heating to boil, maintaining for 8h, after water is evaporated, roasting the obtained solid matter, heating to 600 ℃ at a heating rate of 7 ℃/min under an Ar atmosphere, and keeping for 2 h; after natural cooling to room temperature, at 5% (volume fraction) H 2 Heating the solid to 400 ℃ in the Ar atmosphere at the heating rate for 2 hours to obtain the copper monatomic catalyst taking the carbon material with the C-N structure as the carrier, wherein the loading amount of copper monatomic on the carrier is 30 wt%.
Example 3
Formaldehyde, dicyandiamide and Cu (NO) in a molar ratio of 7:7:1 3 ) 2 ·3H 2 O is mixed in deionized water, the obtained mixed solution is heated to boiling after being vigorously stirred for 5min, the boiling is maintained for 6h, the obtained solid matter is roasted after the water is evaporated, and the solid matter is heated to 600 ℃ for 2h at the heating rate of 9 ℃/min under the Ar atmosphere; naturally cooling to room temperature, and then cooling to 5% (body)Integral fraction) H 2 Heating the solid to 400 ℃ in the Ar atmosphere at the heating rate for 2 hours to obtain the copper monatomic catalyst taking the carbon material with the C-N structure as the carrier, wherein the loading amount of copper monatomic on the carrier is 25 wt%.
Example 4
Dissolving polyethylene oxide-polypropylene oxide-polyethylene oxide in deionized water, adding tetraethoxysilane and hydrochloric acid into the deionized water, wherein the molar ratio of tetraethoxysilane to polyethylene oxide-polypropylene oxide-polyethylene oxide to hydrochloric acid to deionized water is 1:0.01:5.7:100, continuously and violently stirring the mixture for 24 hours, filling the mixture into a polytetrafluoroethylene bottle for crystallization for 24 hours, and sequentially filtering, washing and drying the product, and performing Soxhlet extraction on the obtained solid under the extraction conditions that: ethanol: hydrochloric acid 1 g: 180 mL: 2g, extracting at 55 ℃ for 5h for 2 times to obtain a precursor;
mixing the precursor with formaldehyde, dicyandiamide and Cu (NO) at a molar ratio of 7:7:0.5 3 ) 2 ·3H 2 O is mixed in deionized water, and the molar ratio of the precursor to formaldehyde is 20: 7; violently stirring the obtained mixed solution for 4min, heating to boil, maintaining for 4h, after water is evaporated, roasting the obtained solid matter, heating to 600 ℃ at the heating rate of 5 ℃/min under the Ar atmosphere, and keeping for 2 h; after natural cooling to room temperature, at 5% (volume fraction) H 2 Heating the solid to 400 ℃ for 2 hours under the Ar atmosphere according to the heating rate to obtain the copper monatomic catalyst taking the carbon material with the C-N structure as the carrier, wherein the loading amount of copper monatomic on the carrier is 20 wt%.
Example 5
Dissolving polyethylene oxide-polypropylene oxide-polyethylene oxide in deionized water, adding tetraethoxysilane and hydrochloric acid into the deionized water, wherein the molar ratio of tetraethoxysilane to polyethylene oxide-polypropylene oxide-polyethylene oxide to hydrochloric acid to deionized water is 1:0.02:6.0:150, continuously and violently stirring the mixture for 24 hours, filling the mixture into a polytetrafluoroethylene bottle for crystallization for 24 hours, and sequentially filtering, washing and drying the product, and then performing Soxhlet extraction on the obtained solid under the extraction conditions of solid: ethanol: hydrochloric acid 1 g: 230 mL: 4g, extracting at 55 ℃ for 5h for 3 times to obtain a precursor;
mixing the precursor with formaldehyde, dicyandiamide and Cu (NO) at a molar ratio of 7:7:2 3 ) 2 ·3H 2 O is mixed in deionized water, and the molar ratio of the precursor to formaldehyde is 10: 7; violently stirring the obtained mixed solution for 6min, heating to boil, maintaining for 8h, roasting the obtained solid matter after water is evaporated, heating to 600 ℃ at a heating rate of 10 ℃/min under an Ar atmosphere, and keeping for 2 h; after natural cooling to room temperature, at 5% (volume fraction) H 2 Heating the solid to 400 ℃ for 2 hours under the Ar atmosphere according to the heating rate to obtain the copper monatomic catalyst taking the carbon material with the C-N structure as the carrier, wherein the loading amount of copper monatomic on the carrier is 30 wt%.
Example 6
Dissolving polyethylene oxide-polypropylene oxide-polyethylene oxide in deionized water, adding tetraethoxysilane and hydrochloric acid into the deionized water, wherein the molar ratio of tetraethoxysilane to polyethylene oxide-polypropylene oxide-polyethylene oxide to hydrochloric acid to deionized water is 1:0.015:5.88:130, continuously and violently stirring the mixture for 24 hours, filling the mixture into a polytetrafluoroethylene bottle for crystallization for 24 hours, and sequentially filtering, washing and drying the product, and then performing Soxhlet extraction on the obtained solid under the extraction conditions of solid: ethanol: hydrochloric acid 1 g: 200mL of the solution: 3g, extracting at 60 ℃ for 8h for 3 times to obtain a precursor;
mixing the precursor with formaldehyde, dicyandiamide and Cu (NO) at a molar ratio of 7:7:1 3 ) 2 ·3H 2 O is mixed in deionized water, and the molar ratio of the precursor to formaldehyde is 30: 7; violently stirring the obtained mixed solution for 5min, heating to boil, maintaining for 6h, roasting the obtained solid matter after water is evaporated, heating to 600 ℃ at a heating rate of 10 ℃/min under an Ar atmosphere, and keeping for 2 h; after natural cooling to room temperature, at 5% (volume fraction) H 2 Heating the solid to 400 ℃ in the Ar atmosphere at the heating rate for 2 hours to obtain the copper monatomic catalyst taking the carbon material with the C-N structure as the carrier, wherein the loading amount of copper monatomic on the carrier is 20 wt%.
Application example 1
The copper monatomic catalyst prepared in example 1 was mixed with a reaction solution containing tetracycline in an amount of 40mg/L and sodium persulfate at a concentration of 0.2mg/L in the reaction solution containing tetracycline and 0.1mmol/L in the reaction solution containing tetracycline, and catalytic degradation was carried out for 30min at a wavelength of 365nm of ultraviolet light.
Application example 2
The copper monatomic catalyst prepared in example 2 was mixed with a reaction solution containing tetracycline at 30mg/L and sodium persulfate at a concentration of 0.15mg/L in the reaction solution containing tetracycline and at a concentration of 0.1mmol/L in the reaction solution containing tetracycline, and catalytic degradation was carried out for 30min at a wavelength of 365nm of ultraviolet light.
Application example 3
The copper monatomic catalyst prepared in example 2 was mixed with a reaction solution containing 20mg/L of tetracycline and sodium persulfate, the concentration of the copper monatomic catalyst in the reaction solution containing tetracycline was 0.2mg/L, the concentration of the sodium persulfate in the reaction solution containing tetracycline was 0.1mmol/L, and catalytic degradation was carried out for 30min at a wavelength of 365nm of ultraviolet light.
Application example 4
The copper monatomic catalyst prepared in example 3 was mixed with a reaction solution containing 10mg/L of tetracycline and sodium persulfate, the concentration of the copper monatomic catalyst in the reaction solution containing tetracycline was 0.1mg/L, the concentration of the sodium persulfate in the reaction solution containing tetracycline was 0.1mmol/L, and catalytic degradation was carried out for 30min at a wavelength of 365nm of ultraviolet light.
Application example 5
The copper monatomic catalyst prepared in example 4 was mixed with a reaction solution containing tetracycline in an amount of 40mg/L and sodium persulfate at a concentration of 0.2mg/L in the reaction solution containing tetracycline and 0.1mmol/L in the reaction solution containing tetracycline, and catalytic degradation was carried out for 30min at a wavelength of 365nm of ultraviolet light.
Application example 6
The copper monatomic catalyst prepared in example 5 was mixed with a reaction solution containing tetracycline at 30mg/L and sodium persulfate at a concentration of 0.15mg/L in the reaction solution containing tetracycline and 0.1mmol/L in the reaction solution containing tetracycline, and catalytic degradation was carried out for 30min at a wavelength of 365nm of ultraviolet light.
Application example 7
The copper monatomic catalyst prepared in example 6 was mixed with a reaction solution containing 20mg/L of tetracycline and sodium persulfate at a concentration of 0.2mg/L in the tetracycline-containing reaction solution, and the catalytic degradation was carried out for 30min at a wavelength of 365nm in ultraviolet light at a concentration of 0.1mmol/L in the tetracycline-containing reaction solution.
Application example 8
The copper monatomic catalyst prepared in example 6 was mixed with a reaction solution containing 10mg/L of tetracycline and sodium persulfate, the concentration of the copper monatomic catalyst in the reaction solution containing tetracycline was 0.1mg/L, the concentration of the sodium persulfate in the reaction solution containing tetracycline was 0.1mmol/L, and catalytic degradation was carried out for 30min at a wavelength of 365nm of ultraviolet light.
Characterization and Performance testing
1) SEM characterization of the copper monatomic catalyst prepared in example 2 was performed, and the results are shown in fig. 1; as can be seen from fig. 1, Cu is distributed in the catalyst support in a monoatomic form.
2) Detecting the concentration of tetracycline in the degraded effluent of the application examples 1-6, and obtaining results shown in the figures 2-3; FIG. 2 is a graph showing the tetracycline degradation curves of application examples 1-4; FIG. 3 is a graph showing tetracycline degradation curves of examples 5-8; in both FIG. 2 and FIG. 3, the ordinate represents the post-degradation tetracycline concentration C/the original tetracycline concentration C 0 (efficiency of degradation); as can be seen from FIGS. 2 to 3, with the extension of the reaction time, the low-concentration tetracycline is significantly degraded, and the high-concentration (40mg/L) tetracycline is also degraded, with the degradation efficiency reaching 90%.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.
Claims (6)
1. The application of the copper monatomic catalyst in catalytic degradation of tetracycline is characterized by comprising the following steps:
mixing a copper monatomic catalyst with tetracycline-containing wastewater and sodium persulfate, and performing catalytic degradation under the ultraviolet condition;
the preparation method of the copper monatomic catalyst comprises the following steps:
evaporating a mixed solution containing formaldehyde, dicyandiamide, copper salt and water to dryness, and roasting to obtain a copper monatomic catalyst;
the mixed solution also comprises a precursor, and the preparation method of the precursor comprises the following steps: mixing polyethylene oxide-polypropylene oxide-polyethylene oxide, tetraethoxysilane, acid and water, and crystallizing to obtain a precursor;
the molar ratio of the precursor to the formaldehyde is (10-30) to 7;
the concentration of tetracycline in the wastewater is 10-30 mg/L.
2. The use of claim 1, wherein the molar ratio of formaldehyde to dicyandiamide to the copper salt is 7:7 (0.5-2).
3. The use according to claim 1, wherein the evaporation time is 4-8 h; the roasting process comprises a first roasting and a second roasting which are sequentially carried out; the first roasting is carried out in Ar atmosphere, the temperature of the first roasting is 550-700 ℃, and the time is 1.5-3 h; the second roasting is carried out in H 2 And Ar is mixed, the temperature of the second roasting is 380-500 ℃, and the time is 1.5-3 h.
4. Use according to claim 1, wherein the molar ratio of tetraethoxysilane, polyethylene oxide-polypropylene oxide-polyethylene oxide, acid and water is 1: (0.01-0.02): (5.7-6.0): (100-150).
5. The use according to any one of claims 1 to 4, wherein the copper monatomic catalyst comprises a carrier and a copper monatomic supported on the carrier; the carrier is a carbon material containing a C-N structure.
6. The use according to claim 5, wherein the support is a carbon material of C-N structure linked to a mesoporous molecular sieve.
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