CN109603882B - Method for treating organic pollutants and carrying out photocatalytic sterilization by using modified carbon quantum dot loaded hollow tubular carbon nitride photocatalyst - Google Patents
Method for treating organic pollutants and carrying out photocatalytic sterilization by using modified carbon quantum dot loaded hollow tubular carbon nitride photocatalyst Download PDFInfo
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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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
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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
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- 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
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- 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
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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
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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 discloses a method for treating organic pollutants and carrying out photocatalytic sterilization by using a modified carbon quantum dot loaded hollow tubular carbon nitride photocatalyst, which comprises the following steps: mixing the modified carbon quantum dot-loaded hollow tubular carbon nitride photocatalyst with organic pollutant wastewater or a bacteria solution for photocatalytic treatment to complete the treatment of organic pollutants or bacteria, wherein the modified carbon quantum dot-loaded hollow tubular carbon nitride photocatalyst takes hollow tubular carbon nitride as a carrier, and is loaded with modified carbon quantum dots, and the hollow tubular carbon nitride is prepared by taking urea and melamine as raw materials in a molar ratio of 1-5: 1 through hydrothermal and calcination. The method for treating organic pollutants and performing photocatalytic sterilization has the advantages of simple process, convenience in operation, simple equipment, low cost, high treatment efficiency/photocatalytic efficiency, good removal effect/sterilization effect, cleanness, no pollution and the like, and has high application value and commercial value.
Description
Technical Field
The invention belongs to the field of visible light catalysis, and relates to a method for treating organic pollutants and carrying out photocatalytic sterilization by using a modified carbon quantum dot loaded hollow tubular carbon nitride photocatalyst.
Background
The rapid growth of population and the rapid development of economy make the demand for water resources increasingly higher, and the problem of water pollution caused by the water environment polluted by organic pollutants is a worldwide problem, and the problem that the water environment is polluted by the organic pollutants is widely concerned, for example, antibiotic wastewater is always a hot point of research. Antibiotics have antibacterial, antifungal, antiviral, antiparasitic properties, and are widely used in medicine and aquaculture. Tetracycline (TC) is one of the antibiotics, considered as a basic drug by the World Health Organization (WHO). However, TC metabolism in animals is poor, resulting in large amounts of prodrugs or metabolites of TC entering the aqueous environment. According to previous reports, the concentration of antibiotics in domestic sewage ranges from 100ng/L to 6mg/L, and the polluted water body seriously harms human health. In addition, biohazardous substances such as bacteria, viruses, fungi and the like widely exist in drinking water (surface water, underground water), and they pose a serious threat to human health and also have adverse effects on aquatic ecosystems. For example, Escherichia coli, as a pathogenic microorganism, can cause various intestinal diseases.
In order to solve the problems of organic pollutant wastewater, bacteria and the like, researchers apply methods such as a chemical flocculation method, a biomembrane filtration method, a physical adsorption method, ultraviolet illumination and the like, but the methods are difficult to achieve ideal treatment effects, so that the finding of a simple and easy method for effectively degrading organic pollutants and killing bacteria has important significance. In recent years, a photocatalytic technology has attracted much attention as an environmentally friendly, efficient, and low-cost technology. However, conventional photocatalysts such as TiO2And ZnO, which can absorb only ultraviolet light but cannot make good use of sunlight because of its wide forbidden band.
Graphite type carbon nitride (g-C)3N4) As a conjugated polymer semiconductor, considerable attention has recently been drawn because it has good physicochemical stability, an attractive electronic structure and an appropriate band gap, i.e., 2.7eV, and has good application prospects in catalysis and energy. But the photocatalyst has inherent problems of small specific surface area, high exciton binding energy, serious photogenerated electron hole recombination and the like, so that the photocatalytic efficiency is low, and the practical application and popularization of the photocatalyst in the fields of energy and environment photocatalysis are seriously restricted. The nano structure of the photocatalyst is closely related to the physical and chemical properties and the photocatalytic performance of the photocatalyst, when the size of the semiconductor material is reduced to a nano range, unique surface effect, small size effect and quantum size effect are presented, and the synergistic effect of the surface effect, the small size effect and the quantum size effect can obviously improve the photocatalytic performance of the nano material. The one-dimensional nano materials such as nanowires, nanorods and the like show potential application prospects in various fields such as nano devices, photocatalysis and the like due to novel optical, electrical, magnetic, mechanical and other properties. However, the existing carbon nitride photocatalysts with different morphologies still have the defects of small specific surface area, few active sites, serious photo-generated carrier recombination, poor light absorption capacity, low photocatalytic activity and the like. In addition, most of the existing preparation processes of the carbon nitride photocatalyst are template methods, and the template needs to be removed in the synthesis process, which is not favorable for improving the preparation efficiency, and causes the complex preparation process, higher preparation cost, time and labor consumption, and the same as the prior preparation processesIn addition, the synthesis process requires extensive use of various organic material additives or high pressure conditions, wherein the organic additives are usually difficult to completely remove, the residual quantity of the organic additives not only affects the photocatalytic performance of the carbon nitride photocatalyst, but also can cause adverse effects on the environment, and the wide application of the carbon nitride photocatalyst is severely limited due to the problems. Therefore, the modified carbon quantum dot supported hollow tubular carbon nitride photocatalyst which has the advantages of large specific surface area, large number of holes, large number of active sites, high separation and migration rate of photogenerated carriers, strong light absorption capacity and high photocatalytic activity, and the preparation method of the modified carbon quantum dot supported hollow tubular carbon nitride photocatalyst which is matched with the modified carbon quantum dot supported hollow tubular carbon nitride photocatalyst and has the advantages of convenient synthesis, simple operation and no secondary pollution to the environment are obtained, and the preparation method has very important significance for effectively removing organic pollutants and harmful microorganisms in the environment.
Disclosure of Invention
The invention aims to overcome the defects of the prior art, provides a method for treating organic pollutants by using a modified carbon quantum dot loaded hollow tubular carbon nitride photocatalyst, which has the advantages of simple process, convenient operation, simple equipment, low cost, high treatment efficiency, good removal effect and cleanness and no pollution, and also provides a method for photocatalytic sterilization by using the modified carbon quantum dot loaded hollow tubular carbon nitride photocatalyst, which has the advantages of simple process, convenient operation, simple equipment, low cost, high photocatalytic efficiency, good sterilization effect, cleanness and no pollution.
In order to solve the technical problems, the invention adopts the technical scheme that:
a method for treating organic pollutants by using a modified carbon quantum dot loaded hollow tubular carbon nitride photocatalyst comprises the following steps: mixing the modified carbon quantum dot supported hollow tubular carbon nitride photocatalyst with organic pollutant wastewater, and carrying out photocatalytic degradation reaction after adsorption balance is achieved to finish treatment on the organic pollutants; the modified carbon quantum dot supported hollow tubular carbon nitride photocatalyst takes hollow tubular carbon nitride as a carrier, and modified carbon quantum dots are supported on the hollow tubular carbon nitride; the hollow tubular carbon nitride is prepared by taking urea and melamine as raw materials and performing hydrothermal treatment and calcination; the molar ratio of the urea to the melamine is 1-5: 1.
In the method, the proportion of the modified carbon quantum dot loaded hollow tubular carbon nitride photocatalyst to the organic pollutant wastewater is 20-30 mg: 30 mL; the organic pollutant wastewater is antibiotic wastewater; the antibiotics in the antibiotic wastewater are tetracycline and/or sulfadimidine and the like; the concentration of the antibiotics in the antibiotic wastewater is less than or equal to 20 mg/L; the mixing is carried out under the dark condition; the rotating speed of the stirring is 400 r/min; the stirring time is 60 min; the photocatalytic degradation reaction is carried out under the condition of illumination; the light source under the illumination condition is a 300W xenon lamp; the time of the photocatalytic degradation reaction is 1-2 h.
In the method, the preparation method of the modified carbon quantum dot supported hollow tubular carbon nitride photocatalyst is further improved, and comprises the following steps: suspending the hollow tubular carbon nitride in water, adding the modified carbon quantum dot solution, and drying to obtain the modified carbon quantum dot supported hollow tubular carbon nitride photocatalyst.
In the above method, further improvement, the preparation method of the hollow tubular carbon nitride comprises the following steps:
s1, dissolving urea and melamine in a solvent, performing ultrasonic treatment, and stirring to obtain a mixed solution;
s2, carrying out hydrothermal reaction on the mixed solution obtained in the step S1, cleaning, filtering and drying to obtain a precursor;
and S3, calcining and grinding the precursor obtained in the step S2 to obtain the hollow tubular carbon nitride.
In the above method, further improvement is provided, in the step S1, the molar ratio of urea to melamine is 1-5: 1; the solvent is water; the ultrasonic time is 0.5 h-3 h, and the stirring time is 8 h-18 h;
in the step S2, the temperature of the hydrothermal reaction is more than or equal to 180 ℃; the time of the hydrothermal reaction is 24-36 h; the drying temperature is 60-85 ℃; the drying time is 8-12 h;
in the step S3, the heating rate in the calcining process is 2.3 ℃/min to 5 ℃/min; the calcining temperature is 550-650 ℃; the calcining time is 4-6 h.
In the method, the preparation method of the modified carbon quantum dot solution is further improved, and comprises the following steps:
(1) dissolving sodium citrate and cysteine in a solvent, and stirring to obtain a precursor solution;
(2) and (2) carrying out hydrothermal reaction on the precursor solution obtained in the step (1), and dialyzing to obtain a modified carbon quantum dot solution.
In the method, which is a further improvement, in the step (1), the molar ratio of the sodium citrate to the cysteine is 1: 1; the solvent is water; the stirring speed is 300 r/min-500 r/min; the stirring time is 1-2 h;
in the step (2), the temperature of the hydrothermal reaction is 180-220 ℃; the time of the hydrothermal reaction is 6-8 h; the dialysis time is 12-24 h.
In the method, the ratio of the hollow tubular carbon nitride to the water is further improved to be 0.2 g: 30-50 mL; the ratio of the hollow tubular carbon nitride to the modified carbon quantum dot solution is 0.2 g: 0.5 mL-3 mL; the concentration of the modified carbon quantum dot solution is 1 mg/mL; the drying temperature is 70-80 ℃; the drying time is 18-24 h.
As a general technical concept, the invention also provides a method for photocatalytic sterilization by using the modified carbon quantum dot loaded hollow tubular carbon nitride photocatalyst, which comprises the following steps: mixing the modified carbon quantum dot-loaded hollow tubular carbon nitride photocatalyst with a bacterial solution to perform photocatalytic sterilization reaction, and completing inactivation of bacteria; the modified carbon quantum dot supported hollow tubular carbon nitride photocatalyst takes hollow tubular carbon nitride as a carrier, and modified carbon quantum dots are supported on the hollow tubular carbon nitride; the hollow tubular carbon nitride is prepared by taking urea and melamine as raw materials and performing hydrothermal treatment and calcination; the molar ratio of the urea to the melamine is 1-5: 1.
In the method, the ratio of the modified carbon quantum dot loaded hollow tubular carbon nitride photocatalyst to the bacterial solution is further improved to be 20-30 mg: 0.5 mL; the bacteria in the bacteria solution are escherichia coli and/or staphylococcus aureus; the concentration of bacteria in the bacteria solution is less than or equal to 3 multiplied by 109CFU/mL; the photocatalytic sterilization reaction is carried out under the condition of illumination; the light source under the illumination condition is a 300W xenon lamp; the time of the photocatalytic sterilization reaction is 1-2 h.
In the method, the preparation method of the modified carbon quantum dot supported hollow tubular carbon nitride photocatalyst is further improved, and comprises the following steps: suspending the hollow tubular carbon nitride in water, adding the modified carbon quantum dot solution, and drying to obtain the modified carbon quantum dot supported hollow tubular carbon nitride photocatalyst.
In the above method, further improvement, the preparation method of the hollow tubular carbon nitride comprises the following steps:
s1, dissolving urea and melamine in a solvent, performing ultrasonic treatment, and stirring to obtain a mixed solution;
s2, carrying out hydrothermal reaction on the mixed solution obtained in the step S1, cleaning, filtering and drying to obtain a precursor;
and S3, calcining and grinding the precursor obtained in the step S2 to obtain the hollow tubular carbon nitride.
In the above method, further improvement is provided, in the step S1, the molar ratio of urea to melamine is 1-5: 1; the solvent is water; the ultrasonic time is 0.5 h-3 h, and the stirring time is 8 h-18 h;
in the step S2, the temperature of the hydrothermal reaction is more than or equal to 180 ℃; the time of the hydrothermal reaction is 24-36 h; the drying temperature is 60-85 ℃; the drying time is 8-12 h;
in the step S3, the heating rate in the calcining process is 2.3 ℃/min to 5 ℃/min; the calcining temperature is 550-650 ℃; the calcining time is 4-6 h.
In the method, the preparation method of the modified carbon quantum dot solution is further improved, and comprises the following steps:
(1) dissolving sodium citrate and cysteine in a solvent, and stirring to obtain a precursor solution;
(2) and (2) carrying out hydrothermal reaction on the precursor solution obtained in the step (1), and dialyzing to obtain a modified carbon quantum dot solution.
In the method, which is a further improvement, in the step (1), the molar ratio of the sodium citrate to the cysteine is 1: 1; the solvent is water; the stirring speed is 300 r/min-500 r/min; the stirring time is 1-2 h;
in the step (2), the temperature of the hydrothermal reaction is 180-220 ℃; the time of the hydrothermal reaction is 6-8 h; the dialysis time is 12-24 h.
In the method, the ratio of the hollow tubular carbon nitride to the water is further improved to be 0.2 g: 30-50 mL; the ratio of the hollow tubular carbon nitride to the modified carbon quantum dot solution is 0.2 g: 0.5 mL-3 mL; the concentration of the modified carbon quantum dot solution is 1 mg/mL; the drying temperature is 70-80 ℃; the drying time is 18-24 h.
Compared with the prior art, the invention has the advantages that:
(1) the invention provides a method for treating organic pollutants by using a modified carbon quantum dot loaded hollow tubular carbon nitride photocatalyst, which can realize the high-efficiency degradation of organic pollutants by mixing the modified carbon quantum dot loaded hollow tubular carbon nitride photocatalyst with organic pollutant wastewater to carry out photocatalytic degradation reaction. Taking tetracycline as an example, the modified carbon quantum dot loaded hollow tubular carbon nitride photocatalyst is adopted for photocatalytic degradation reaction for 60min, the degradation rate of the tetracycline is up to 82.67%, the high-efficiency removal of the tetracycline is realized, meanwhile, the degradation removal rate after four times of circulation is still up to 79.87%, only 2.8% of the degradation rate is lost, and the practical application requirements can be met.
(2) The invention also provides a method for photocatalytic sterilization by using the modified carbon quantum dot loaded hollow tubular carbon nitride photocatalyst, the modified carbon quantum dot loaded hollow tubular carbon nitride photocatalyst is mixed with a bacterial solution for photocatalytic sterilization reaction, so that bacteria can be rapidly and thoroughly catalytically inactivated in a short time, and the high-efficiency inactivation of the bacteria is realized.
(3) In the method, the hollow tubular carbon nitride photocatalyst is loaded by the modified carbon quantum dots, the hollow tubular carbon nitride is used as a carrier, and the modified carbon quantum dots are loaded on the hollow tubular carbon nitride. In the invention, the hollow tubular carbon nitride has the advantages of large specific surface area, large number of holes, high separation and migration rate of photon-generated carriers, strong light absorption capacity, high photocatalytic activity and the like, and is a novel carrier with novel morphology and structure and excellent photocatalytic performance. On the basis, as the modified carbon quantum dots have the characteristics of strong up-conversion capability, low toxicity, good biocompatibility and the like, when the modified carbon quantum dots are loaded on the hollow tubular carbon nitride, the modified carbon quantum dots are used as an electron conduction field, so that photo-generated electrons and holes generated by the carbon nitride under illumination can be separated more quickly, the absorption spectrum of the carbon nitride can be improved, a wider absorption spectrum can be obtained, visible light can be utilized more effectively, and better photocatalytic activity can be obtained. Therefore, the modified carbon quantum dot supported hollow tubular carbon nitride photocatalyst has the advantages of large specific surface area, large number of holes, many active sites, high separation and migration rate of photo-generated carriers, strong light absorption capacity, high photocatalytic activity and the like, has high stability and strong photocatalytic efficiency, can be widely used for treating organic pollutants in the environment, can also be used for killing harmful bacteria in the environment, and has good application value and application prospect.
(4) According to the preparation method of the modified carbon quantum dot supported hollow tubular carbon nitride photocatalyst, hollow tubular carbon nitride and a modified carbon quantum dot solution are used as raw materials, and the modified carbon quantum dots are supported on the hollow tubular carbon nitride through mixing and drying, so that the modified carbon quantum dot supported hollow tubular carbon nitride photocatalyst with large specific surface area, a large number of holes and a large number of active sites can be prepared. The preparation method of the modified carbon quantum dot supported hollow tubular carbon nitride photocatalyst has the advantages of convenient synthesis, simple operation, no secondary pollution to the environment, accordance with the actual production requirement, suitability for large-scale preparation and convenience for industrial utilization.
(5) In the method, the hollow tubular carbon nitride is prepared by taking urea and melamine as raw materials through hydrothermal and high-temperature calcination, wherein a carbon nitride nanotube precursor (cyanuric acid) is formed through hydrothermal reaction, then calcination is carried out at high temperature, the melamine and the cyanuric acid self-assemble to form the hollow tubular carbon nitride photocatalyst, and in the preparation process, the urea can generate ammonia and carbon dioxide at high temperature, so that the hollow tubular carbon nitride tube forms a hole. According to the invention, the template-free method is adopted for preparing the hollow tubular carbon nitride for the first time, and the prepared hollow tubular carbon nitride can reduce the band gap width of a photocatalyst semiconductor while enhancing the surface area and the size of holes of the photocatalyst, so that the photocatalytic efficiency is improved, and the hollow tubular carbon nitride is a novel carrier with a novel morphology structure and excellent photocatalytic performance. In addition, the template-free method adopted by the invention has no raw materials harmful to the environment, the preparation process is simple and convenient, and the preparation can be carried out rapidly in large quantity. The preparation method of the hollow tubular carbon nitride photocatalyst has the advantages of simple process, wide raw material source, low cost, high preparation efficiency, high yield, no secondary pollution to the environment and the like.
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 modified carbon quantum dot supported hollow tubular carbon nitride photocatalyst (HTCN-C2) prepared in example 1 of the present invention.
Fig. 2 is a transmission electron microscope image of a modified carbon quantum dot supported hollow tubular carbon nitride photocatalyst (HTCN-C2) prepared in example 1 of the present invention.
FIG. 3 is an X-ray diffraction contrast diagram of the modified carbon quantum dot supported hollow tubular carbon nitride photocatalyst (HTCN-C0.5, HTCN-C1, HTCN-C2 and HTCN-C3) prepared in example 1 of the present invention.
FIG. 4 is a UV-visible diffuse reflection diagram of the modified carbon quantum dot supported hollow tubular carbon nitride photocatalyst (HTCN-C0.5, HTCN-C1, HTCN-C2 and HTCN-C3) prepared in example 1 of the present invention.
Fig. 5 is a diagram illustrating the photocatalytic degradation of tetracycline by different modified carbon quantum dot-supported hollow tubular carbon nitride photocatalysts in example 1 of the present invention.
FIG. 6 is a cycle chart of the modified carbon quantum dot supported hollow tubular carbon nitride photocatalyst (HTCN-C2) for degrading tetracycline by recycling in example 1 of the present invention.
Fig. 7 is an X-ray diffraction pattern of the modified carbon quantum dot supported hollow tubular carbon nitride photocatalyst (HTCN-C2) before and after the reaction in example 1 of the present invention.
FIG. 8 is a diagram of the photocatalytic degradation of the modified carbon quantum dot supported hollow tubular carbon nitride photocatalyst (HTCN-C2) on Escherichia coli in example 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 method for treating organic pollutants by using a modified carbon quantum dot loaded hollow tubular carbon nitride photocatalyst, in particular to a method for treating tetracycline wastewater by using a modified carbon quantum dot loaded hollow tubular carbon nitride photocatalyst, which comprises the following steps:
weighing modified carbon quantum dot-loaded hollow tubular carbon nitride photocatalysts (HTCN-C0.5, HTCN-C1, HTCN-C2 and HTCN-C3), adding 30mg of the modified carbon quantum dot-loaded hollow tubular carbon nitride photocatalysts into 30mL of tetracycline wastewater with the concentration of 20mg/L respectively, magnetically stirring for 1h in a dark place at the rotating speed of 400r/min, turning on a light source (300W xenon lamp) after adsorption balance is achieved, and carrying out photocatalytic reaction for 1h under irradiation of simulated sunlight to finish degradation of tetracycline.
In this example, the modified carbon quantum dots supported hollow tubular carbon nitride photocatalyst (HTCN-C0.5) used in the present invention uses hollow tubular carbon nitride as a carrier, and the hollow tubular carbon nitride supports the modified carbon quantum dots. The hollow tubular carbon nitride is prepared by taking urea and melamine as raw materials through hydrothermal and calcination, wherein the molar ratio of the urea to the melamine is 3: 1.
In this embodiment, the preparation method of the modified carbon quantum dot supported hollow tubular carbon nitride photocatalyst (HTCN-C0.5) includes the following steps:
suspending 0.2g of hollow tubular carbon nitride in 30mL of ultrapure water, adding 0.5mL of modified carbon quantum dot solution, uniformly mixing, and drying at 80 ℃ to obtain the modified carbon quantum dot supported hollow tubular carbon nitride photocatalyst, which is numbered as HTCN-C0.5.
In this embodiment, the hollow tubular carbon nitride is prepared by using urea and melamine as raw materials and performing hydrothermal and calcination processes, wherein the molar ratio of urea to melamine is 3: 1, and the preparation method specifically includes the following steps:
s1, grinding the urea and the melamine respectively, dissolving 9.56g of the urea and 6g of the melamine in 70mL of deionized water, performing ultrasonic treatment for 1h, stirring for 8h, and uniformly mixing to obtain a mixed solution.
S2, transferring the mixed solution obtained in the step S1 into a 100mL autoclave, carrying out hydrothermal reaction for 24 hours at 180 ℃, after natural cooling, washing the obtained reaction product with water and ethanol for 3 times respectively, filtering (specifically, carrying out suction filtration), and drying at 70 ℃ for 12 hours to obtain a precursor.
S3, placing the precursor obtained in the step S2 into a crucible, placing the crucible into a muffle furnace, heating to 550 ℃ at the heating rate of 2.3 ℃/min, calcining, preserving heat at 550 ℃ for 240min, taking out after natural cooling, and grinding to obtain hollow tubular carbon nitride, wherein the number of the hollow tubular carbon nitride is HTCN.
In this embodiment, the preparation method of the modified quantum dot solution includes the following steps:
(1) and (3) mixing 5mmol of sodium citrate and 5mmol of cysteine in ultrapure water, stirring for 1h at the rotation speed of 400r/min, and uniformly mixing to obtain a precursor solution.
(2) And (2) transferring the precursor solution obtained in the step (1) to a 100mL hydrothermal reaction kettle, preserving the temperature at 200 ℃ for 6 hours, naturally cooling, and dialyzing the hydrothermal reaction product by using a dialysis bag for 12 hours to obtain a modified quantum dot solution (CQD).
In this example, the preparation method of the modified carbon quantum dot supported hollow tubular carbon nitride photocatalyst (HTCN-C1) and the preparation method of the modified carbon quantum dot supported hollow tubular carbon nitride photocatalyst (HTCN-C0.5) used in this example are basically the same, except that: the volume of the modified carbon quantum dot solution is 1 mL.
In this example, the preparation method of the modified carbon quantum dot supported hollow tubular carbon nitride photocatalyst (HTCN-C2) and the preparation method of the modified carbon quantum dot supported hollow tubular carbon nitride photocatalyst (HTCN-C0.5) used in this example are basically the same, except that: the volume of the modified carbon quantum dot solution is 2 mL.
In this example, the preparation method of the modified carbon quantum dot supported hollow tubular carbon nitride photocatalyst (HTCN-C3) and the preparation method of the modified carbon quantum dot supported hollow tubular carbon nitride photocatalyst (HTCN-C0.5) used in this example are basically the same, except that: the volume of the modified carbon quantum dot solution is 3 mL.
Fig. 1 is a scanning electron microscope image of a modified carbon quantum dot supported hollow tubular carbon nitride photocatalyst (HTCN-C2) prepared in example 1 of the present invention. Fig. 2 is a transmission electron microscope image of a modified carbon quantum dot supported hollow tubular carbon nitride photocatalyst (HTCN-C2) prepared in example 1 of the present invention. As can be seen from fig. 1 and fig. 2, the modified carbon quantum dot-loaded hollow tubular carbon nitride of the present invention has a distinct hollow tubular structure, and the surface thereof has some nano-pores; meanwhile, as can be seen from fig. 2, the modified carbon quantum dots are supported on the hollow tubular carbon nitride.
FIG. 3 is an X-ray diffraction contrast diagram of the modified carbon quantum dot supported hollow tubular carbon nitride photocatalyst (HTCN-C0.5, HTCN-C1, HTCN-C2 and HTCN-C3) prepared in example 1 of the present invention. As shown in FIG. 3, all the sample peaks were sharp and prominent, indicating that the crystallinity of the sample was good, in which two distinct XRD diffraction peaks ascribed to the (100) and (002) crystal planes of graphite-phase carbon nitride appeared at 13.1 ℃ and 27.2 ℃ and confirming that the product produced was g-C3N4(ii) a Meanwhile, the X-ray diffraction patterns of the modified carbon quantum dot supported hollow tubular carbon nitride photocatalyst prepared by adopting the modified carbon quantum dot solutions with different volumes are similar, and no other miscellaneous peak appears, which indicates that g-C is not caused by the loading of the modified carbon quantum dot3N4Change in topology.
FIG. 4 is a UV-visible diffuse reflection diagram of the modified carbon quantum dot supported hollow tubular carbon nitride photocatalyst (HTCN-C0.5, HTCN-C1, HTCN-C2 and HTCN-C3) prepared in example 1 of the present invention. As shown in fig. 4, the light absorption wavelengths of the modified carbon quantum dot supported hollow tubular carbon nitride photocatalyst prepared by adopting modified carbon quantum dot solutions with different volumes are all about 500nm, and compared with the light absorption wavelength (about 470 nm) of single carbon nitride, the light absorption range is improved to a certain extent, and the light utilization rate is also improved.
In the magnetic stirring process of this example, 2mL of sample was taken every 15min and centrifuged. And (3) measuring absorbance of the supernatant obtained by centrifugation by using an ultraviolet-visible spectrophotometer, and determining the concentration of the tetracycline, so as to obtain the photocatalytic effect of different modified carbon quantum dot-loaded hollow tubular carbon nitride photocatalysts on the tetracycline.
Fig. 5 is a diagram illustrating the photocatalytic degradation of tetracycline by different modified carbon quantum dot-supported hollow tubular carbon nitride photocatalysts in example 1 of the present invention. Fig. 5 shows that the modified carbon quantum dot-loaded hollow tubular carbon nitride photocatalyst of the present invention can effectively remove tetracycline in wastewater, and has a good removal effect, wherein the removal rate of the modified carbon quantum dot-loaded hollow tubular carbon nitride photocatalyst (HTCN-C2) can reach 82.67%, and the total removal rate of the monomeric carbon nitride and the hollow tubular carbon nitride is only 30.16% and 51.85%, which indicates that the photocatalytic performance of the hollow tubular carbon nitride is greatly improved by loading the modified carbon quantum dots, and therefore, selecting an appropriate modified carbon quantum dot loading has a great significance for improving the photocatalytic performance of the modified carbon quantum dot-loaded hollow tubular carbon nitride photocatalyst.
FIG. 6 is a cycle chart of the modified carbon quantum dot supported hollow tubular carbon nitride photocatalyst (HTCN-C2) for degrading tetracycline by recycling in example 1 of the present invention. As can be seen from fig. 6, the modified carbon quantum dot supported hollow tubular carbon nitride photocatalyst (HTCN-C2) is very stable, the degradation removal rate still remains 79.87% after four cycles, and only 2.8% of the degradation removal rate is lost, so that the photocatalytic stability of the modified carbon quantum dot supported hollow tubular carbon nitride photocatalyst (HTCN-C2) can be seen.
The modified carbon quantum dot-supported hollow tubular carbon nitride photocatalyst (HTCN-C2) before and after tetracycline treatment in example 1 was subjected to X-ray diffraction analysis, and the results are shown in fig. 7. Fig. 7 is an X-ray diffraction pattern of the modified carbon quantum dot supported hollow tubular carbon nitride photocatalyst (HTCN-C2) before and after the reaction in example 1 of the present invention. As shown in fig. 7, the X-ray diffraction patterns before and after the reaction of the modified carbon quantum dot-loaded hollow tubular carbon nitride photocatalyst of the present invention remain unchanged and the peak shape is sharp, which indicates that the structure before and after the reaction remains unchanged, the crystallinity is good, and the modified carbon quantum dot-loaded hollow tubular carbon nitride photocatalyst has good stability.
Example 3:
a method for photocatalytic sterilization by using a modified carbon quantum dot loaded hollow tubular carbon nitride photocatalyst, in particular to a method for treating escherichia coli by using a modified carbon quantum dot loaded hollow tubular carbon nitride photocatalyst, which comprises the following steps:
30mg of the modified carbon quantum dot-supported hollow tubular carbon nitride photocatalyst (HTCN-C2) prepared in example 1 was weighed, added to 49.5mL of sterile water, and added thereto 0.5mL of 30mL of a 3X 1 carbon quantum dot-supported hollow tubular carbon nitride photocatalyst09CFU/mL of E.coli solution, at which the E.coli concentration in the system was diluted to 3X 107And (3) CFU/mL, turning on a light source (300W xenon lamp), and irradiating under simulated sunlight for photocatalytic sterilization reaction for 1h to complete inactivation of escherichia coli.
Taking 100uL of reaction liquid every 15 minutes, then properly diluting the bacteria liquid, finally calculating the escherichia coli colony by using a plate counting method, and finally obtaining the inactivation performance of the modified carbon quantum dot supported hollow tubular carbon nitride photocatalyst (HTCN-C2).
FIG. 8 is a diagram of the photocatalytic degradation of the modified carbon quantum dot supported hollow tubular carbon nitride photocatalyst (HTCN-C2) on Escherichia coli in example 2 of the present invention. As can be seen from fig. 8, the modified carbon quantum dot-supported hollow tubular carbon nitride photocatalyst (HTCN-C2) exhibited excellent bactericidal performance after 1 hour of light irradiation.
In conclusion, the method for treating organic pollutants and carrying out photocatalytic sterilization by using the modified carbon quantum dot-loaded hollow tubular carbon nitride photocatalyst has a unique morphology structure, a large specific surface area and a pore structure, and the capability of fast separation and migration of photo-generated carriers, can efficiently carry out photocatalytic degradation on organic pollutants (such as antibiotics) in wastewater and remove bacteria in a water body environment, and has a wide prospect in the field of photocatalysis.
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. A method for treating organic pollutants by using a modified carbon quantum dot loaded hollow tubular carbon nitride photocatalyst is characterized by comprising the following steps: mixing the modified carbon quantum dot supported hollow tubular carbon nitride photocatalyst with organic pollutant wastewater, and carrying out photocatalytic degradation reaction after adsorption balance is achieved to finish treatment on the organic pollutants; the modified carbon quantum dot supported hollow tubular carbon nitride photocatalyst takes hollow tubular carbon nitride as a carrier, and modified carbon quantum dots are supported on the hollow tubular carbon nitride; the hollow tubular carbon nitride is prepared by taking urea and melamine as raw materials and performing hydrothermal treatment and calcination; the molar ratio of the urea to the melamine is 1-5: 1; the preparation method of the hollow tubular carbon nitride comprises the following steps:
(a) dissolving urea and melamine in a solvent, performing ultrasonic treatment, and stirring to obtain a mixed solution; the ultrasonic time is 0.5 h-3 h, and the stirring time is 8 h-18 h;
(b) carrying out hydrothermal reaction on the mixed solution obtained in the step (a), cleaning, filtering and drying to obtain a precursor;
(c) calcining and grinding the precursor obtained in the step (b) to obtain hollow tubular carbon nitride; the heating rate in the calcining process is 2.3 ℃/min to 5 ℃/min; the calcining temperature is 550-650 ℃; the calcining time is 4-6 h.
2. The method according to claim 1, wherein the ratio of the modified carbon quantum dot supported hollow tubular carbon nitride photocatalyst to the organic pollutant wastewater is 20 mg-30 mg: 30 mL; the organic pollutant wastewater is antibiotic wastewater; the antibiotics in the antibiotic wastewater are tetracycline and/or sulfadimidine and the like; the concentration of the antibiotics in the antibiotic wastewater is less than or equal to 20 mg/L; the mixing is carried out under the dark condition; the rotating speed of the stirring is 400 r/min; the stirring time is 60 min; the photocatalytic degradation reaction is carried out under the condition of illumination; the light source under the illumination condition is a 300W xenon lamp; the time of the photocatalytic degradation reaction is 1-2 h.
3. A method for photocatalytic sterilization by using a modified carbon quantum dot loaded hollow tubular carbon nitride photocatalyst is characterized by comprising the following steps: mixing the modified carbon quantum dot-loaded hollow tubular carbon nitride photocatalyst with a bacterial solution to perform photocatalytic sterilization reaction, and completing inactivation of bacteria; the modified carbon quantum dot supported hollow tubular carbon nitride photocatalyst takes hollow tubular carbon nitride as a carrier, and modified carbon quantum dots are supported on the hollow tubular carbon nitride; the hollow tubular carbon nitride is prepared by taking urea and melamine as raw materials and performing hydrothermal treatment and calcination; the molar ratio of the urea to the melamine is 1-5: 1; the preparation method of the hollow tubular carbon nitride comprises the following steps:
(a) dissolving urea and melamine in a solvent, performing ultrasonic treatment, and stirring to obtain a mixed solution; the ultrasonic time is 0.5 h-3 h, and the stirring time is 8 h-18 h;
(b) carrying out hydrothermal reaction on the mixed solution obtained in the step (a), cleaning, filtering and drying to obtain a precursor;
(c) calcining and grinding the precursor obtained in the step (b) to obtain hollow tubular carbon nitride; the heating rate in the calcining process is 2.3 ℃/min to 5 ℃/min; the calcining temperature is 550-650 ℃; the calcining time is 4-6 h.
4. The method according to claim 3, wherein the ratio of the modified carbon quantum dot supported hollow tubular carbon nitride photocatalyst to the bacterial solution is 20-30 mg: 0.5 mL; the bacteria in the bacteria solution are escherichia coli and/or staphylococcus aureus; the concentration of bacteria in the bacteria solution is less than or equal to 3 multiplied by 109CFU/mL; the photocatalytic sterilization reaction is carried out under the condition of illumination; the light source under the illumination condition is a 300w xenon lamp; the time of the photocatalytic sterilization reaction is 1-2 h.
5. The method according to any one of claims 1 to 4, wherein the preparation method of the modified carbon quantum dot supported hollow tubular carbon nitride photocatalyst comprises the following steps: suspending the hollow tubular carbon nitride in water, adding the modified carbon quantum dot solution, and drying to obtain the modified carbon quantum dot supported hollow tubular carbon nitride photocatalyst.
6. The method of claim 5, wherein the method of preparing the hollow tubular carbon nitride comprises the steps of:
s1, dissolving urea and melamine in a solvent, performing ultrasonic treatment, and stirring to obtain a mixed solution;
s2, carrying out hydrothermal reaction on the mixed solution obtained in the step S1, cleaning, filtering and drying to obtain a precursor;
and S3, calcining and grinding the precursor obtained in the step S2 to obtain the hollow tubular carbon nitride.
7. The method according to claim 6, wherein in step S1, the molar ratio of urea to melamine is 1-5: 1; the solvent is water; the ultrasonic time is 0.5 h-3 h, and the stirring time is 8 h-18 h;
in the step S2, the temperature of the hydrothermal reaction is more than or equal to 180 ℃; the time of the hydrothermal reaction is 24-36 h; the drying temperature is 60-85 ℃; the drying time is 8-12 h;
in the step S3, the heating rate in the calcining process is 2.3 ℃/min to 5 ℃/min; the calcining temperature is 550-650 ℃; the calcining time is 4-6 h.
8. The method of claim 5, wherein the preparation method of the modified carbon quantum dot solution comprises the following steps:
(1) dissolving sodium citrate and cysteine in a solvent, and stirring to obtain a precursor solution;
(2) and (2) carrying out hydrothermal reaction on the precursor solution obtained in the step (1), and dialyzing to obtain a modified carbon quantum dot solution.
9. The method according to claim 8, wherein in the step (1), the molar ratio of the sodium citrate to the cysteine is 1: 1; the solvent is water; the stirring speed is 300 r/min-500 r/min; the stirring time is 1-2 h;
in the step (2), the temperature of the hydrothermal reaction is 180-220 ℃; the time of the hydrothermal reaction is 6-8 h; the dialysis time is 12-24 h.
10. The method of claim 5, wherein the ratio of hollow tubular carbon nitride to water is 0.2 g: 30-50 mL; the ratio of the hollow tubular carbon nitride to the modified carbon quantum dot solution is 0.2 g: 0.5 mL-3 mL; the concentration of the modified carbon quantum dot solution is 1 mg/mL; the drying temperature is 70-80 ℃; the drying time is 18-24 h.
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