CN111229279A - Carbon nitride quantum dot-loaded hierarchical-pore inverse opal structure CuO-SiO2Preparation and use thereof - Google Patents
Carbon nitride quantum dot-loaded hierarchical-pore inverse opal structure CuO-SiO2Preparation and use thereof Download PDFInfo
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- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
- B01J37/0018—Addition of a binding agent or of material, later completely removed among others as result of heat treatment, leaching or washing,(e.g. forming of pores; protective layer, desintegrating by heat)
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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
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- B01J35/39—
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- B01J35/50—
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- B01J35/60—
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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
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/722—Oxidation by peroxides
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/725—Treatment of water, waste water, or sewage by oxidation by catalytic oxidation
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
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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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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2305/00—Use of specific compounds during water treatment
- C02F2305/02—Specific form of oxidant
- C02F2305/026—Fenton's reagent
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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
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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Abstract
The invention provides a carbon nitride quantum dot loaded hierarchical-pore inverse opal structure CuO-SiO2The preparation method of (1). The method adopts a double-template method and takes the ordered polystyrene spheres as hard templatesSynthesizing a macroporous structure, and taking a long-chain surfactant as a mesoporous pore-forming agent. The mesoporous template agents F127 and g-C are added3N4The Cu-Si precursor solution of the quantum dots is subjected to a dipping method and a calcination method to remove the template to obtain g-C3N4Quantum dot supported macroporous-mesoporous materials which are three-dimensionally communicated with each other. The method can control the sizes of macropores and mesopores simply by changing the particle sizes of the soft and hard templates, and the prepared hierarchical porous material has the characteristics of high mass transfer rate and strong visible light absorption, g-C3N4The loading of the quantum dots can improve the separation efficiency of photogenerated carriers and further enhance light absorption. By applying the material to a photo-Fenton system, the norfloxacin antibiotic pollutant can be degraded efficiently and rapidly, and the material has a good application prospect in the field of environmental management.
Description
Technical Field
The invention relates to a heterogeneous photo-Fenton catalyst for efficiently degrading antibiotics, belonging to the technical field of advanced oxidation.
Background
In recent years, with the mass growth of population and the acceleration of industrialization process, a large amount of industrial wastewater and domestic sewage are not treated and discharged up to the standard, so that various organic pollutants enter the environment, and great threats are brought to drinking water safety and agricultural product safety. Wherein, various organic pollutants such as endocrine disruptors, antibiotics, pesticides and the like are detected in large quantities in the environment. For example, norfloxacin is one of the widely used human antibiotics, and the wide use thereof leads to the increase of the drug resistance of bacteria, and the higher and higher residual concentration level in the environment seriously threatens the health safety of human beings. Meanwhile, due to the bactericidal property of the antibiotics, the antibiotics cannot be completely removed in the biological treatment process of the urban sewage treatment plant, so that the method for exploring the water treatment method suitable for the water polluted by the antibiotics has outstanding research significance and application value in developing novel green, efficient and strong-adaptability environment function materials and applying the materials to the treatment of the polluted water body. The combination of a multivalent metal ion based on iron, copper, etc. and hydrogen peroxide is called fenton or fenton-like reagent, which is widely used in the treatment of industrial organic wastewater. In practice for many years, the traditional homogeneous Fenton oxidation technology also has the defects of low utilization rate of hydrogen peroxide, time consumption and labor consumption in subsequent iron ion treatment and the like. Therefore, the study of a heterogeneous fenton system which can be recycled and can avoid the generation of a large amount of sludge is attracting much attention.
In a heterogeneous Fenton system, a photo-assisted Fenton oxidation method is concerned by researchers, and is an advanced oxidation treatment wastewater technology based on active free radical reaction, and the photo-assisted Fenton oxidation method utilizes the combined action of light and an oxidant to generate a large amount of strong active free radicals for degrading organic pollutants. The method has the characteristics of simplicity, convenience, quickness and no secondary pollution, and belongs to the green and environment-friendly treatment technology. The selection of a suitable heterogeneous fenton catalyst is the focus of the technology. At present, most photo-Fenton technologies introduce an ultraviolet light source, and visible light photo-Fenton catalysts are rarely reported. Meanwhile, there are few reports that quantum dots are supported on a copper-based catalyst for a photo-Fenton system. In addition, the morphology and structure of the material determine the performance of the material, and many characteristics such as adsorption, separation and catalysis of the material are closely related to the form and structure of the material. The introduction of some specific morphological structures into Fenton catalysts is of great research significance. From the prior studies, g-C has not yet been investigated3N4Quantum dot supported hierarchical porous silicon-copper composite materials have been reported.
Disclosure of Invention
The invention provides a carbon nitride quantum dot loaded hierarchical-pore inverse opal structure CuO-SiO2The preparation method of (1). The method synthesizes macroporous structure by using ordered polystyrene spheres as hard templates and long-chain surfactant as a hard template through a double-template methodA mesoporous pore-forming agent. The mesoporous template agents F127 and g-C are added3N4The Cu-Si precursor solution of the quantum dots is poured into photonic crystals obtained by regularly arranging polystyrene microspheres by a dipping method, and the template is removed by a calcining method to obtain g-C3N4Quantum dot supported macroporous-mesoporous materials which are three-dimensionally communicated with each other. The method can control the sizes of macropores and mesopores simply by changing the particle sizes of the soft and hard templates, and the prepared hierarchical porous material has the characteristics of high mass transfer rate and strong visible light absorption, g-C3N4The loading of the quantum dots can improve the separation efficiency of photogenerated carriers and further enhance light absorption. By applying the material to a photo-Fenton system, the norfloxacin antibiotic pollutant can be degraded efficiently and rapidly, and the material has a good application prospect in the field of environmental management.
The method is characterized in that a double-template method is adopted, the capillary action of an ordered polystyrene photonic crystal (PS) template is utilized to suck the perfusion liquid containing quantum dots into the gaps of the template, and F127 is introduced into the perfusion liquid to be used as a mesoporous pore-forming agent. Finally, a silicon source is slowly hydrolyzed to form a stable structure, and the PS template and the F127 pore-forming agent are removed through calcination. The quantum dot loaded hierarchical porous material with uniform pore size distribution and ordered height is obtained.
The perfusion method used in the present invention is as follows: mixing and stirring ethyl orthosilicate and acetylacetone to obtain a solution A; simultaneously, F127 and g-C were mixed3N4Dissolving quantum dot powder in 16mL of ethanol at 60 ℃, adding HCl, fully mixing, and adding CuCl2·2H2Continuously stirring until the solution is clear to obtain a solution B; adding the solution A into the solution B under magnetic stirring, and stirring for a period of time to be uniform. After the precursor solution is prepared, the PS photonic crystal is soaked into the precursor solution, the precursor solution fully enters the gaps of the photonic crystal, the precursor solution is slowly hydrolyzed to form a framework after completely entering the gaps under the action of acetylacetone, and the organic template agent is removed by a calcination method to obtain the quantum dot loaded hierarchical porous silicon-copper composite material. By using the method, the photonic crystal template without F127 or PS or bothSome samples have a macroporous or mesoporous structure or a block shape. For the hierarchical porous silicon-copper composite material, quantum dot loaded samples and quantum dot unloaded samples can also be prepared. Macroporous or mesoporous structures or Bulk samples were prepared without F127 or PS photonic crystal templating agent or neither, named IOSC, Meso IO and Bulk SC, respectively. For the hierarchical porous silicon-copper composite material, samples loaded with quantum dots and samples without the quantum dots are prepared and named as MM SC and MM SC-QDs respectively.
Specifically, the invention provides a carbon nitride quantum dot loaded hierarchical-pore inverse opal structure CuO-SiO2The method for preparing the compound (A) is as follows,
1) synthesis of ordered polystyrene photonic crystal (PS)
Adding sodium dodecyl sulfate, potassium persulfate, ethanol and deionized water into a container; then, under the protection of nitrogen, the temperature is increased to a preset temperature, and styrene is injected into the container; then stirring for a predetermined time at that temperature; packaging the polystyrene spheres into colloidal crystals by centrifugation, and drying to obtain an ordered polystyrene photonic crystal template;
2)、g-C3N4synthesis of quantum dots
Grinding and mixing urea and sodium citrate, then transferring the mixture into a high-pressure kettle, and washing an obtained product by using ethanol after heat treatment for preset time; preparing yellow g-C by 3500 molecular weight cut-off dialysis membrane dialysis method3N4An aqueous quantum dot solution; followed by g-C3N4Drying the quantum dot aqueous solution, and then collecting the solid product g-C3N4Quantum dots;
3)、g-C3N4quantum dot loaded multi-level pore channel CuO-SiO2Synthesis of
Mixing ethyl orthosilicate and acetylacetone to prepare a solution A; simultaneously adding F127, HCl, deionized water and solid g-C3N4Dissolving quantum dots in ethanol; stirring, adding CuCl2·6H2Continuously stirring until the solution is clear; then adding a mixture of ethyl orthosilicate and acetylacetone, stirring, and immersing the PS photonic crystal into a precursor solution; air drying the sample overnight; baking (a)And (3) sintering to prepare the material with the macroporous and mesoporous hierarchical pore structure.
Further, the predetermined temperature in step 1 was 71 ℃.
Further, the roasting temperature in the step 3 is 500 ℃, and the temperature is kept for 4 hours at 500 ℃.
Further, in the above-mentioned case,
1) synthesis of ordered polystyrene photonic crystal (PS)
Adding 0.45 g of sodium dodecyl sulfate, 0.6 g of potassium persulfate, 150 ml of ethanol and 270 ml of deionized water into a container; then, the temperature was raised to 71 ℃ under nitrogen protection, and 36 ml of styrene was injected into the vessel; then stirring for 19h at 71 ℃; packaging the polystyrene spheres into colloidal crystals by centrifugation, and drying at 70 ℃ for 12 hours to prepare an ordered polystyrene photonic crystal template;
2)、g-C3N4synthesis of quantum dots
Grinding and mixing 0.101g of urea and 0.081g of sodium citrate, then transferring the mixture into a high-pressure kettle, carrying out heat treatment at 180 ℃ for 2 hours, and washing the obtained product with ethanol for 3 times; preparing yellow g-C by 3500 molecular weight cut-off dialysis membrane dialysis method3N4An aqueous quantum dot solution; followed by g-C3N4Drying the quantum dot aqueous solution at 70 ℃ for 72h, and collecting a solid product g-C3N4Quantum dots;
3)、g-C3N4quantum dot loaded multi-level pore channel CuO-SiO2Synthesis of
2.2mL of ethyl orthosilicate and 2.5mg of acetylacetone were mixed for 30min to prepare a solution A; while simultaneously adding 1.0gF127, 0.1mL of 2M HCl, 0.8mL of deionized water, and 0.1g of solid g-C3N4Dissolving the quantum dots in 16mL of ethanol at the dissolving temperature of 60 ℃; after stirring for 1h, 0.34g of CuCl was added2·6H2Continuously stirring until the solution is clear; then adding a mixture of ethyl orthosilicate and acetylacetone, continuously stirring for 1h at 60 ℃, and then immersing the PS photonic crystal into the precursor solution; air-drying the sample at 25 deg.C overnight; roasting, heating to 500 deg.C from 25 deg.C, and keeping the temperature at 500 deg.C for 4 hr to obtain the final productThe material has a hierarchical porous structure with macropores and mesopores.
Further, carbon nitride quantum dot loaded hierarchical pore inverse opal structure CuO-SiO2The material has a pore channel structure with interconnected macropores and mesopores, copper is uniformly dispersed in a silicon dioxide framework in the form of copper oxide, and quantum dots are g-C3N4The quantum dots are uniformly distributed on the framework and the surface of the quantum dots, and are prepared by the preparation method.
Furthermore, the carbon nitride quantum dots load hierarchical pore inverse opal structure CuO-SiO2Use of a material for the degradation of heterogeneous photo-fenton catalysts for antibiotics.
The invention has the following beneficial effects:
1. compared with a mesoporous structure, the material with the multilevel pore structure can not only accelerate the transmission and diffusion of substances, but also has the property of photonic crystal, so that the material has special performance in the aspects of photonic modulation and the like, and can effectively enhance light absorption; compared with a macroporous structure, the material with the hierarchical porous structure has higher specific surface area and better adsorption performance.
2.g-C3N4The loading of the quantum dots can improve the separation efficiency of photon-generated carriers and further enhance light absorption.
3. The copper-based material shows stronger Fenton catalytic activity in the pH range of 3-10, and the application range of the copper-based material is greatly widened.
4. The raw materials involved in the preparation process of the material are economical and easy to obtain, and the experimental steps are simple and easy to operate.
Drawings
FIG. 1 Wide-Angle XRD spectra (a) and FTIR spectra (b) of Bulk SC, Meso SC, IO SC, MM SC and MM SC-QDs
FIG. 2 MM SEM (a, b) and high resolution TEM (c, d) of SC-QDs
FIG. 3 FESEM pictures of MM SC-QDs and corresponding elemental pictures of O, Cu, N
FIG. 4 (a) UV-VIS diffuse reflectance spectra, (b) EIS Nyquist plots for different samples under dark or visible light conditions, (c) different photoluminescence spectra and (d) time-resolved PL attenuation spectra for different samples of Bulk SC, Meso SC, IO SC, MM SC and MM SC-QDs samples.
FIG. 5(a) degradation of NOR during photo-Fenton with different catalysts, (b) K-value over different catalysts, (c) cyclic stability in NOR degradation over MM SC-QDs, and (d) NOR degradation over MM SC-QDs under different pH conditions.
Detailed Description
The present invention will be described in more detail below with reference to specific examples, but the scope of the present invention is not limited to these examples.
Example 1
g-C3N4Quantum dot loaded multi-level pore channel CuO-SiO2，MM SC
1) Synthesis of ordered polystyrene photonic crystal (PS)
In a three-neck flask were added 0.45 g of sodium lauryl sulfate, 0.6 g of potassium persulfate, 150 ml of ethanol and 270 ml of water. Then, the temperature was raised to 71 ℃ under a nitrogen blanket, and 36 ml of styrene was injected into the flask with a syringe. Then stirred at 71 ℃ for 19 h. The polystyrene spheres were encapsulated into colloidal crystals by centrifugation (4000rpm, 4h) and dried at 70 ℃ for 12h, leaving the PS template with a photonic color.
2)、g-C3N4Synthesis of quantum dots
0.101g of urea and 0.081g of sodium citrate were thoroughly ground and mixed and then transferred to a teflon lined stainless steel autoclave. After heat treatment at 180 ℃ for 2h, the product obtained is washed 3 times with ethanol. Preparing yellow g-C by 3500 molecular weight cut-off dialysis membrane dialysis method3N4Quantum dot aqueous solution (20 ml). Subsequently, the aqueous quantum dot solution was dried at 70 ℃ for 72 hours, and then the solid product was collected.
3)、g-C3N4Quantum dot loaded multi-level pore channel CuO-SiO2Synthesis of
Solution A was prepared by mixing 2.2mL of ethyl orthosilicate and 2.5mg of acetylacetone for 30 min. While simultaneously adding 1.0g F127, 0.1mL HCl (2M), 0.8mL deionized water, and 0.1g solid g-C3N4The quantum dots are respectively dissolved in 16mL of ethanol, and the dissolving temperature is 60 ℃. After stirring for 1h, 0.34g of CuCl was added2·6H2And O, continuously stirring until the solution is clear. Then adding a mixture of tetraethoxysilane and acetylacetone, continuously stirring for 1h at 60 ℃, and then immersing the PS photonic crystal into the precursor solution. The sample was air dried overnight at 25 ℃. In order to remove the template agent, the roasting temperature is increased from 25 ℃ to 500 ℃, and the temperature is kept at 500 ℃ for 4 hours, so that the hierarchical pore structure material with macropores and mesopores is prepared and named as MM SC.
Comparative example 1
Non-load multi-stage pore canal CuO-SiO2，MM SC-QDs
1) Synthesis of ordered polystyrene photonic crystal (PS)
In a three-neck flask were added 0.45 g of sodium lauryl sulfate, 0.6 g of potassium persulfate, 150 ml of ethanol and 270 ml of water. Then, the temperature was raised to 71 ℃ under a nitrogen blanket, and 36 ml of styrene was injected into the flask with a syringe. Then stirred at 71 ℃ for 19 h. The polystyrene spheres were encapsulated into colloidal crystals by centrifugation (4000rpm, 4h) and dried at 70 ℃ for 12h, leaving the PS template with a photonic color.
2) And multi-stage pore canal CuO-SiO2Synthesis of
Solution A was prepared by mixing 2.2mL of ethyl orthosilicate and 2.5mg of acetylacetone for 30 min. While 1.0gF127, 0.1mL HCl (2M), and 0.8mL deionized water were dissolved in 16mL ethanol, respectively, at a dissolution temperature of 60 ℃. After stirring for 1h, 0.34g of CuCl was added2·6H2And O, continuously stirring until the solution is clear. Then adding a mixture of tetraethoxysilane and acetylacetone, continuously stirring for 1h at 60 ℃, and then immersing the PS photonic crystal into the precursor solution. The sample was air dried overnight at 25 ℃. To remove the template, the calcination temperature was raised from 25 ℃ to 500 ℃ and incubated at 500 ℃ for 4h, and the prepared sample was named MMSC-QDs.
Comparative example 2
Sample without F127, IO SC
1) Synthesis of ordered polystyrene photonic crystal (PS)
In a three-neck flask were added 0.45 g of sodium lauryl sulfate, 0.6 g of potassium persulfate, 150 ml of ethanol and 270 ml of water. Then, the temperature was raised to 71 ℃ under a nitrogen blanket, and 36 ml of styrene was injected into the flask with a syringe. Then stirred at 71 ℃ for 19 h. The polystyrene spheres were encapsulated into colloidal crystals by centrifugation (4000rpm, 4h) and dried at 70 ℃ for 12h, leaving the PS template with a photonic color.
2)、g-C3N4Synthesis of quantum dots
0.101g of urea and 0.081g of sodium citrate were thoroughly ground and mixed and then transferred to a teflon lined stainless steel autoclave. After heat treatment at 180 ℃ for 2h, the product obtained is washed 3 times with ethanol. Preparing yellow g-C by 3500 molecular weight cut-off dialysis membrane dialysis method3N4Quantum dot aqueous solution (20 ml). Subsequently, the aqueous quantum dot solution was dried at 70 ℃ for 72 hours, and then the solid product was collected.
3)、g-C3N4Quantum dot loaded multi-level pore channel CuO-SiO2Synthesis A solution A was prepared by mixing 2.2mL of ethyl orthosilicate and 2.5mg of acetylacetone for 30 min. While 0.1mL HCl (2M), 0.8mL deionized water, and 0.1g solid g-C3N4The quantum dots are respectively dissolved in 16mL of ethanol, and the dissolving temperature is 60 ℃. After stirring for 1h, 0.34g of CuCl was added2·6H2And O, continuously stirring until the solution is clear. Then adding a mixture of tetraethoxysilane and acetylacetone, continuously stirring for 1h at 60 ℃, and then immersing the PS photonic crystal into the precursor solution. The sample was air dried overnight at 25 ℃. To remove the template, the firing temperature was raised from 25 ℃ to 500 ℃ and incubated at 500 ℃ for 4h, and the prepared sample was named IO SC.
Comparative example 3
Sample without PS Photonic Crystal template, Meso IO
1)、g-C3N4Synthesis of quantum dots
0.101g of urea and 0.081g of sodium citrate were thoroughly ground and mixed and then transferred to a teflon lined stainless steel autoclave. After heat treatment at 180 ℃ for 2h, the product obtained is washed 3 times with ethanol. Preparing yellow g-C by 3500 molecular weight cut-off dialysis membrane dialysis method3N4Quantum dot aqueous solution (20 ml). Subsequently, the aqueous quantum dot solution was dried at 70 ℃ for 72 hours, and then the solid product was collected.
2)、g-C3N4Quantum dot loaded multi-level pore channel CuO-SiO2Synthesis of
Solution A was prepared by mixing 2.2mL of ethyl orthosilicate and 2.5mg of acetylacetone for 30 min. While simultaneously adding 1.0g F127, 0.1mL HCl (2M), 0.8mL deionized water, and 0.1g solid g-C3N4The quantum dots are respectively dissolved in 16mL of ethanol, and the dissolving temperature is 60 ℃. After stirring for 1h, 0.34g of CuCl was added2·6H2And O, continuously stirring until the solution is clear. Then a mixture of ethyl orthosilicate and acetylacetone was added and stirring was continued at 60 ℃ for 1 h. The sample was air dried overnight at 25 ℃. To remove the template, the firing temperature was raised from 25 ℃ to 500 ℃ and incubated at 500 ℃ for 4h, and the prepared sample was named Meso IO.
Comparative example 4
Sample Bulk SC without F127 and PS photonic crystal templating agent
1)、g-C3N4Synthesis of quantum dots
0.101g of urea and 0.081g of sodium citrate were thoroughly ground and mixed and then transferred to a teflon lined stainless steel autoclave. After heat treatment at 180 ℃ for 2h, the product obtained is washed 3 times with ethanol. Preparing yellow g-C by 3500 molecular weight cut-off dialysis membrane dialysis method3N4Quantum dot aqueous solution (20 ml). Subsequently, the aqueous quantum dot solution was dried at 70 ℃ for 72 hours, and then the solid product was collected.
2)、g-C3N4Quantum dot loaded multi-level pore channel CuO-SiO2Synthesis of
Solution A was prepared by mixing 2.2mL of ethyl orthosilicate and 2.5mg of acetylacetone for 30 min. While 0.1mL HCl (2M), 0.8mL deionized water, and 0.1g solid g-C3N4The quantum dots are respectively dissolved in 16mL of ethanol, and the dissolving temperature is 60 ℃. After stirring for 1h, 0.34g of CuCl was added2·6H2And O, continuously stirring until the solution is clear. Then a mixture of ethyl orthosilicate and acetylacetone was added and stirring was continued at 60 ℃ for 1 h. The sample is ventilated in the environment of 25 DEG CDry overnight. The calcination temperature was raised from 25 ℃ to 500 ℃ and kept at 500 ℃ for 4h, and the prepared sample was named Bulk SC.
Experiment and data
The activity investigation method for degrading norfloxacin by virtue of photo-Fenton provided by the invention comprises the following steps:
photo-Fenton Activity test
In the degradation experiments, all reactions were carried out in 120ml quartz glass tubes of 3.0cm diameter and 20cm height. The light source is a 300w xenon lamp (CEL-HFX300, AULIGHT) equipped with a wavelength cut-off filter (420nm) and a 20A operating current. A10 mg/L norfloxacin solution was used as a contaminant to investigate g-C3N4Quantum dot loaded multi-level pore channel CuO-SiO2The photo-Fenton activity of (1). For a typical photo-fenton process, 25mg of catalyst was added to 50ml of norfloxacin solution with a concentration of 10ppm, and the solution was stirred for 20min with strong magnetic stirring to establish adsorption-desorption equilibrium. On the basis, visible light irradiation is introduced and H is added2O2The photo-Fenton reaction was carried out. During the reaction, 1.5mL samples were collected from the suspension at given time intervals and then centrifuged.
The concentration of pollutants in the degradation process is monitored by using a Shimadzu SPD-M20A high performance liquid chromatograph. An isocratic eluent composed of acetonitrile (20%) and water (0.2% (v/v) formic acid (80%) was used at a flow rate of 1.0mL/min-1. The detection wavelength was 278nm and the sample size was 20. mu.L.
FIG. 1 is a wide angle XRD spectrum and FTIR spectrum of MM SC-QDs sample of example 1. From the XRD spectrogram, the Cu in the material is proved to exist in the form of CuO, which corresponds to JCPDS:44-0706 of CuO. From the FTIR spectrum, the asymmetric vibration of Si-O-Si is seen at 1100cm-1Generates an absorption peak at 700-400cm-1Is the absorption peak of Cu-O bond. Proves that the material is SiO2And a hierarchical porous material with CuO as a framework.
FIG. 2 is an image of MM SC-QDs samples in example 1 under a Field Emission Scanning Electron Microscope (FESEM) and a High Resolution Transmission Electron Microscope (HRTEM). FESEM clearly sees that it shows a 3D ordered and periodic macroporous inverse opal structure, which is a structure of a large poreThese structures inherit the ordered structure of the template PS colloidal crystal. HRTEM image shows that the wall of the large pore is composed of abundant mesopores. Furthermore, g-C can be observed3N4And (3) loading the quantum dots on the hierarchical porous structure material. The small size of the synthesized quantum dots (2-8nm) can be clearly observed. Further confirm g-C3N4Successful binding of quantum dots on MM SC.
FIG. 3 is a FESEM image of MM SC-QDs in example 1 and corresponding elemental images of O, Cu, N. The uniform distribution of the elements Cu, Si and N can be seen from the figure. The distribution of the N element further proves that g-C3N4Successful loading of quantum dots.
FIG. 4 is a UV-VIS diffuse reflectance spectrum, EIS Nyquist plot for different samples under dark or visible conditions, photoluminescence spectrum for different samples, and time-resolved PL decay spectrum for different samples obtained in example 1. Compared with the massive silicon copper material, the quantum dot loaded hierarchical pore silicon copper composite material has higher light absorption intensity, which indicates stronger light absorption capacity; lower impedance, indicating good conductivity; lower fluorescence intensity, meaning good electron-hole separation efficiency; the longer fluorescence lifetime indicates that the catalyst has longer lifetime of photogenerated carriers. Thus illustrating the reason for the high efficiency of contaminant degradation.
FIG. 4 is a graph showing the effect of different catalysts synthesized in example 1 on photo-Fenton degradation of norfloxacin contaminants, the K values of the reaction rates of the different catalysts, the cyclic stability of degradation of norfloxacin solution by MM SC-QDs, and the degradation of norfloxacin solution on MM SC-QDs under different pH conditions. It can be seen that the quantum dot supported hierarchical porous silicon copper composite material has the best photo-fenton degradation activity and very good cycle stability compared with bulk silicon copper material, which has great economic value for industrial application. The activity is hardly weakened under neutral or even alkalescent conditions, and the application prospect is greatly widened.
While the present invention has been described in detail with reference to the preferred embodiments, it should be understood that the above description should not be taken as limiting the invention.
Claims (6)
1. Carbon nitride quantum dot-loaded hierarchical-pore inverse opal structure CuO-SiO2The preparation method is characterized by comprising the following steps:
1) synthesis of ordered polystyrene photonic crystal (PS)
Adding sodium dodecyl sulfate, potassium persulfate, ethanol and deionized water into a container; then, under the protection of nitrogen, the temperature is increased to a preset temperature, and styrene is injected into the container; then stirring for a predetermined time at that temperature; packaging the polystyrene spheres into colloidal crystals by centrifugation, and drying to obtain an ordered polystyrene photonic crystal template;
2)、g-C3N4synthesis of quantum dots
Grinding and mixing urea and sodium citrate, then transferring the mixture into a high-pressure kettle, and washing an obtained product by using ethanol after heat treatment for preset time; preparing yellow g-C by 3500 molecular weight cut-off dialysis membrane dialysis method3N4An aqueous quantum dot solution; followed by g-C3N4Drying the quantum dot aqueous solution, and then collecting the solid product g-C3N4Quantum dots;
3)、g-C3N4quantum dot loaded multi-level pore channel CuO-SiO2Synthesis of
Mixing ethyl orthosilicate and acetylacetone to prepare a solution A; simultaneously adding F127, HCl, deionized water and solid g-C3N4Dissolving quantum dots in ethanol; stirring, adding CuCl2·6H2Continuously stirring until the solution is clear; then adding a mixture of ethyl orthosilicate and acetylacetone, stirring, and immersing the PS photonic crystal into a precursor solution; air drying the sample overnight; roasting to prepare the material with the macroporous and mesoporous hierarchical pore structure.
2. The method of claim 1, wherein: the predetermined temperature in step 1 was 71 ℃.
3. The method of claim 1, wherein: the roasting temperature in the step 3 is 500 ℃, and the temperature is kept for 4 hours at 500 ℃.
4. The method of claim 1, wherein:
1) synthesis of ordered polystyrene photonic crystal (PS)
Adding 0.45 g of sodium dodecyl sulfate, 0.6 g of potassium persulfate, 150 ml of ethanol and 270 ml of deionized water into a container; then, the temperature was raised to 71 ℃ under nitrogen protection, and 36 ml of styrene was injected into the vessel; then stirring for 19h at 71 ℃; packaging the polystyrene spheres into colloidal crystals by centrifugation, and drying at 70 ℃ for 12 hours to prepare an ordered polystyrene photonic crystal template;
2)、g-C3N4synthesis of quantum dots
Grinding and mixing 0.101g of urea and 0.081g of sodium citrate, then transferring the mixture into a high-pressure kettle, carrying out heat treatment at 180 ℃ for 2 hours, and washing the obtained product with ethanol for 3 times; preparing yellow g-C by 3500 molecular weight cut-off dialysis membrane dialysis method3N4An aqueous quantum dot solution; followed by g-C3N4Drying the quantum dot aqueous solution at 70 ℃ for 72h, and collecting a solid product g-C3N4Quantum dots;
3)、g-C3N4quantum dot loaded multi-level pore channel CuO-SiO2Synthesis of
2.2mL of ethyl orthosilicate and 2.5mg of acetylacetone were mixed for 30min to prepare a solution A; while simultaneously adding 1.0g F127, 0.1mL of 2M HCl, 0.8mL of deionized water, and 0.1g of solid g-C3N4Dissolving the quantum dots in 16mL of ethanol at the dissolving temperature of 60 ℃; after stirring for 1h, 0.34g of CuCl was added2·6H2Continuously stirring until the solution is clear; then adding a mixture of ethyl orthosilicate and acetylacetone, continuously stirring for 1h at 60 ℃, and then immersing the PS photonic crystal into the precursor solution; air-drying the sample at 25 deg.C overnight; roasting, namely heating the temperature from 25 ℃ to 500 ℃, and preserving the heat for 4 hours at 500 ℃ to prepare the hierarchical pore structure material with macropores and mesopores.
5. Carbon nitride quantum dot-loaded hierarchical-pore inverse opal structure CuO-SiO2The material is characterized in that the material has a pore channel structure with interconnected macropores and mesopores, copper is uniformly dispersed in a silicon dioxide framework in the form of copper oxide, and the quantum dots are g-C3N4The quantum dots are uniformly distributed on the framework and the surface of the quantum dots and are prepared by the preparation method of any one of claims 1 to 4.
6. The carbon nitride quantum dot-loaded hierarchical porous inverse opal structure CuO-SiO of claim 52Use of a material for the degradation of heterogeneous photo-fenton catalysts for antibiotics.
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