CN112371162A - Preparation and application of graphite-phase carbon nitride/titanium tin solid solution heterojunction photocatalytic degradation material - Google Patents
Preparation and application of graphite-phase carbon nitride/titanium tin solid solution heterojunction photocatalytic degradation material Download PDFInfo
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- XMEVHPAGJVLHIG-FMZCEJRJSA-N chembl454950 Chemical compound [Cl-].C1=CC=C2[C@](O)(C)[C@H]3C[C@H]4[C@H]([NH+](C)C)C(O)=C(C(N)=O)C(=O)[C@@]4(O)C(O)=C3C(=O)C2=C1O XMEVHPAGJVLHIG-FMZCEJRJSA-N 0.000 abstract description 10
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- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/39—Photocatalytic properties
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- 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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- 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
-
- 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
- C02F2101/308—Dyes; Colorants; Fluorescent agents
-
- 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
- C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
- C02F2103/34—Nature of the water, waste water, sewage or sludge to be treated from industrial activities not provided for in groups C02F2103/12 - C02F2103/32
- C02F2103/343—Nature of the water, waste water, sewage or sludge to be treated from industrial activities not provided for in groups C02F2103/12 - C02F2103/32 from the pharmaceutical industry, e.g. containing antibiotics
-
- 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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Abstract
The invention discloses a preparation method and application of a graphite-phase carbon nitride/titanium tin solid solution heterojunction photocatalytic degradation material3N4A powdered photocatalytic material; with SnCl4·5H2Ti with core-shell structure synthesized by taking O and butyl titanate as raw materials through hydrothermal method0.7Sn0.3O2A solid solution powder photocatalytic material; g-C3N4Dispersing the powder in deionized water, adding Ti0.7Sn0.3O2Solid solution powderFinally, magnetic stirring is continued, centrifugal washing and vacuum drying are carried out to obtain g-C3N4/Ti0.7Sn0.3O2A heterojunction photocatalytic degradation material. The preparation method is simple in process and low in cost, and the prepared photocatalytic material has excellent separation efficiency of photo-generated electrons and holes and has an efficient effect of degrading rhodamine B and tetracycline hydrochloride under the irradiation of visible light.
Description
Technical Field
The invention belongs to the technical field of photocatalytic degradation of pollutants, and relates to graphite-phase carbon nitride/titanium tin (g-C)3N4/Ti0.7Sn0.3O2) Preparing a solid solution heterojunction photocatalytic degradation material; the invention also relates to the application of the degradation material in degrading dye and antibiotic pollutants.
Background
Over the past few decades, with the rapid development of industry, agriculture, and medicine, the concentration of dyes and antibiotics in water resources has far exceeded standards. Tetracyclines are widely used as broad spectrum antibiotics for the treatment of bacterial infections in humans and animals. However, since tetracyclines are not completely metabolized by humans and animals, they are present in large amounts in water, which is highly likely to induce bacterial evolution, compromising biological systems; on the other hand, dyes in water bodies also have serious effects on ecosystems and public health. To address this problem, various techniques have been developed to remove and degrade dyes and antibiotics in water. The photocatalytic technology is regarded as a promising water pollution treatment strategy as an organic wastewater treatment technology due to the high efficiency and environmental sustainability.
Graphite phase carbon nitride (g-C)3N4) The photocatalyst is a typical nonmetal polymer semiconductor photocatalyst and has the characteristics of enough pollutant degradation oxidation reduction capability, high thermal stability, no toxicity, low cost and the like. However, pure phase g-C3N4Due to the problems of narrow visible light absorption range, high rate recombination of photo-generated charge carriers and the like, the efficiency of degrading dye and antibiotic pollutants is still low. Therefore, efforts are made to develop and construct G-C-based materials3N4The photocatalytic material of the heterojunction structure not only helps to enhance visible light absorption, but also can remarkably promote separation and migration of photon-generated carriers. For example, patent application3N4Heterojunction photocatalytic degradation material and preparation method thereof (application No. 202010395628.1) disclose a heteroatom-doped modified g-C3N4HeterojunctionA photocatalytic degradation material. The catalytic material is prepared by a thermal polymerization method to obtain phosphorus-oxygen co-doped g-C3N4While reducing the band gap width and simultaneously doping SnS by Cr2Co-doping with phosphorus and oxygen g-C3N4The Z-type composite heterojunction is formed between the two, so that the recombination rate of photo-generated electrons and holes is reduced, and the excellent performance of photocatalytic degradation of rhodamine B is realized. Patent application A Cu-doped Nitrogen-deficient g-C3N4/ZnCo2O4A heterojunction photocatalytic degradation material (application No. 202010651397.6) discloses a Cu doped nitrogen deficient g-C3N4/ZnCo2O4A photocatalytic degradation material of a heterojunction. The photocatalytic degradation material has nitrogen defect g-C doped by Cu3N4And honeycomb ZnCo2O4A heterojunction structure is formed between the two layers, and the recombination of photogenerated electrons and holes is inhibited, so that the nitrogen defect g-C doped with Cu3N4/ZnCo2O4The heterojunction photocatalytic material has excellent performance in the aspect of tetracycline degradation.
The preparation method disclosed above shows that the construction of the heterojunction structure is to improve g-C3N4An efficient method for separating photogenerated charge carriers to give them efficient photocatalytic degradation of dyes and tetracyclines.
Disclosure of Invention
The invention aims to provide a method for preparing the significantly promoted g-C3N4Graphite phase carbon nitride/titanium tin (g-C) with photogenerated carrier separation and migration3N4/Ti0.7Sn0.3O2) A preparation method of a heterojunction photocatalytic degradation material.
The invention also aims to provide application of the heterojunction photocatalytic degradation material prepared by the preparation method in degradation of dye and antibiotic pollutants.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows: a preparation method of a graphite-phase carbon nitride/titanium tin heterojunction photocatalytic degradation material comprises the following steps:
1) system for makingPreparation of lamellar g-C3N4Powder: weighing 5-15 g of urea, filling the urea into a crucible with the volume of 50-100 mL, putting the crucible into a muffle furnace under a semi-sealed condition, heating to 510-550 ℃ at the heating rate of 2.2-10 ℃/min, preserving heat for 3-5 h, naturally cooling to 20-25 ℃, putting the crucible into a mortar, and grinding for 5-10 min to obtain g-C3N4Powder;
2) preparation of core-shell structured Ti0.7Sn0.3O2Solid solution powder: weighing 0.3-3 mmol SnCl4·5H2Dispersing O into a beaker filled with 50-70 mL of absolute ethyl alcohol, adding 0.7-7 mmol of butyl titanate under the condition of magnetic stirring, and continuing to stir vigorously for 15-30 min to obtain a mixed solution; transferring the mixed solution into a 100-200 mL hydrothermal kettle, carrying out hydrothermal reaction for 16-20 h at the temperature of 170-200 ℃, naturally cooling to 20-25 ℃, carrying out centrifugal washing with deionized water and absolute ethyl alcohol for several times, placing in a vacuum drying oven, and drying at the temperature of 50-80 ℃ for 8-12 h to obtain the Ti with the core-shell structure0.7Sn0.3O2A solid solution powder;
3) weighing g-C3N40.2-2 g of powder, dispersing the powder into a beaker filled with 50-100 mL of deionized water under the condition of magnetic stirring, continuing stirring for 5-10 min, and then adding 0.01-0.6 g of Ti with a core-shell structure under the condition of magnetic stirring0.7Sn0.3O2And (3) adjusting the pH value of the mixed liquid to 3-11, continuously and violently stirring for 2-8 h, centrifugally washing with deionized water and absolute ethyl alcohol for several times, and drying in vacuum for 8-12 h at the temperature of 50-80 ℃ to obtain the graphite-phase carbon nitride/titanium tin heterojunction photocatalytic degradation material.
The other technical scheme adopted by the invention is as follows: the application of the graphite-phase carbon nitride/titanium tin heterojunction photocatalytic material prepared by the method in degradation of dyes and tetracycline antibiotics.
The preparation method of the invention uses urea as raw material to prepare laminated g-C by a simple thermal sintering method3N4Powder, and then Ti with a core-shell structure is stirred by a simple mechanical stirring method0.7Sn0.3O2g-C with solid solution growing into lamellar shape3N4On the surface, the whole preparation process is simple; ti of core-shell structure0.7Sn0.3O2Solid solution is compounded with g-C3N4Form g-C3N4/Ti0.7Sn0.3O2A photocatalytic Z-type heterojunction in which Ti is present0.7Sn0.3O2Photo-generated electrons generated by illumination on the solid solution conduction band are excited to jump to g-C3N4In the valence band of (2) with g-C3N4The photogenerated holes in the valence band are consumed by recombination of electron-hole pairs, so that g-C3N4The electrons generated in (1) remain in the conduction band thereof, Ti0.7Sn0.3O2The holes generated in the solid solution remain on the valence band thereof, thereby making g-C3N4/Ti0.7Sn0.3O2The photocatalytic Z-type heterojunction generates a large amount of separated photo-generated electrons and holes, and reduces oxygen into O2-And tetracycline hydrochloride and rhodamine B are oxidized into small molecular substances, so that the high-efficiency photocatalytic degradation of dyes and antibiotics is realized.
The preparation method prepares Ti with a core-shell structure by a hydrothermal method0.7Sn0.3O2The solid solution photocatalyst has simple whole preparation process, and the prepared catalyst has stable photocatalytic performance and strong pollutant oxidation capacity. Ti0.7Sn0.3O2The good nanometer appearance of the solid solution can be combined with lamellar g-C3N4Close contact accelerates Ti0.7Sn0.3O2Solid solution photocatalyst and g-C3N4The carrier migration between the powders improves the photocatalytic performance of the heterojunction material to a certain extent.
Drawings
FIG. 1 is a sheet g-C obtained in example 13N4A TEM image of (a).
FIG. 2 shows Ti obtained in example 10.7Sn0.3O2SEM image of solid solution.
FIG. 3 is g-C obtained in example 13N4/Ti0.7Sn0.3O2XRD pattern of the heterojunction photocatalyst;
FIG. 4 shows g-C obtained in example 13N4/Ti0.7Sn0.3O2A TEM image of the heterojunction photocatalyst;
FIG. 5 is g-C obtained in example 13N4/Ti0.7Sn0.3O2EDX spectra of the heterojunction photocatalyst;
FIG. 6 is g-C obtained in example 13N4/Ti0.7Sn0.3O2PL spectrum of the heterojunction photocatalyst;
FIG. 7 is g-C obtained in example 13N4/Ti0.7Sn0.3O2EIS spectrum of the heterojunction photocatalyst;
FIG. 8 is g-C obtained in example 13N4/Ti0.7Sn0.3O2A comparison graph of the performance of the heterojunction photocatalytic material for degrading rhodamine B and the performance of the photocatalytic material prepared in the comparative examples 1 and 2 for degrading rhodamine B is shown.
FIG. 9 is g-C from example 13N4/Ti0.7Sn0.3O2The performance of the heterojunction photocatalytic material for degrading tetracycline by photocatalysis is compared with the performance of the photocatalytic material prepared in comparative examples 1 and 2 for degrading tetracycline.
Detailed Description
The present invention will be described in detail below with reference to the accompanying drawings and specific embodiments.
Example 1
Weighing 10g of urea, placing the urea in a 100mL crucible, placing the crucible in a muffle furnace under a semi-sealed condition, heating to 550 ℃ at a heating rate of 2.2/min, preserving heat for 4h, naturally cooling to 25 ℃, and grinding in a mortar for 5min to obtain lamellar g-C3N4Powder (abbreviated CN); 1.5mmol of SnCl are weighed4·5H2Dispersing O into a beaker filled with 70mL of absolute ethyl alcohol, adding 3.5mmol of butyl titanate under the condition of magnetic stirring, and continuing to stir vigorously for 30min to ensure that SnCl4·5H2Mixing O and butyl titanate uniformly to obtain mixed solution, and mixing the mixed solutionThe mixed solution was transferred to a 100mL hydrothermal kettle and subjected to hydrothermal reaction at 190 ℃ for 18 hours. Naturally cooling to 25 ℃, centrifuging and washing with deionized water and absolute ethyl alcohol for several times respectively, and drying in a vacuum drying oven at 60 ℃ for 12h to obtain Ti with a core-shell structure0.7Sn0.3O2Solid solution powder (abbreviated as TSO). 0.2g of g-C3N4Dispersing the powder into a beaker filled with 50mL of deionized water, and magnetically stirring for 10 min; under the condition of magnetic stirring, 20mg of Ti is added0.7Sn0.3O2Stirring the solid solution powder for 4h under the condition that the pH value is 7, centrifuging and washing with deionized water and absolute ethyl alcohol for several times, respectively, and drying in a vacuum drying oven at 60 deg.C for 12h to obtain g-C3N4/Ti0.7Sn0.3O2A heterojunction photocatalytic material. The photocatalyst is abbreviated as CNTSO-10, and the CNTSO-10 is Ti0.7Sn0.3O2And g-C3N4The theoretical mass ratio of (2) is 10%, and the rest is analogized in turn.
g-C obtained in example 13N4TEM image of the powder, as in FIG. 1. As can be seen from FIG. 1, g-C was prepared3N4Is in the form of a laminated sheet. FIG. 2 shows Ti obtained in example 10.7Sn0.3O2SEM image of solid solution powder, as can be seen from FIG. 2, Ti0.7Sn0.3O2The solid solution is a core-shell structure. FIG. 3 is g-C obtained in example 13N4、Ti0.7Sn0.3O2And the XRD pattern of CNTSO-10. As can be seen from FIG. 3, g-C3N4Two characteristic diffraction peaks appear at 13.1 degrees and 27.5 degrees and can be respectively assigned to (100) crystal faces and (002) crystal faces, which indicates that g-C is successfully synthesized3N4。Ti0.7Sn0.3O2Three characteristic diffraction peaks appear at 27.2 °, 35.4 ° and 53.5 °, which can be assigned to (110), (101) and (211), respectively, consistent with standard PDF cards. Further, Ti0.7Sn0.3O2The characteristic peak of the compound is also weakly expressed in the CNTSO-10, which indicates that the prepared heterojunction photocatalytic material is g-C3N4/Ti0.7Sn0.3O2And (c) a complex. TEM image of the composite, as shown in FIG. 4, and as can be seen in FIG. 4, Ti0.7Sn0.3O2g-C with solid solution apparently layered like3N4Surrounding, the two apparently grow together. This is also confirmed by the EDX spectrum of FIG. 5, in which the four elements C, N, Ti and Sn are uniformly distributed at the same position of the composite material. CNTSO-10 has a ratio g-C in FIG. 63N4Lower PL Signal response (Ti in FIG. 6)0.7Sn0.3O2The photoluminescence intensity of solid solutions, i.e. the PL signal intensity, is much lower than that of g-C3N4And CNTSO-10 is a normal phenomenon), it was confirmed that g-C3N4/Ti0.7Sn0.3O2The photogenerated electrons and holes in the heterojunction photocatalytic material have higher separation efficiency. FIG. 7 is g-C obtained in example 13N4、Ti0.7Sn0.3O2And an EIS map of the CNTSO-10, the CNTSO-10 photocatalytic material has a smaller curvature radius, which shows that the carriers can be transferred more quickly, so that the carriers can participate in the redox reaction more effectively, and the performance of photocatalytic degradation of dyes and tetracycline antibiotics is improved.
Characterization of photocatalytic degradation Properties of samples (taking rhodamine B and tetracycline solution as examples)
1) Respectively preparing a rhodamine B solution with the mass volume concentration of 10mg/L and a tetracycline hydrochloride solution with the mass volume concentration of 20 mg/L; taking six quartz tubes, wherein 50mL of rhodamine B solution is respectively added into three quartz tubes, and 50mL of tetracycline hydrochloride solution is respectively added into the other three quartz tubes;
2) CNTSO-10 and g-C prepared in example 1 were weighed separately3N4And Ti0.7Sn0.3O2Two parts of CNTSO-10 and g-C are respectively added into three quartz tubes filled with rhodamine B solution, wherein each part is 25mg3N4Powder and Ti0.7Sn0.3O2Powder, adding one part of CNTSO-10 and g-C into three quartz tubes filled with tetracycline hydrochloride solution respectively3N4Powder and Ti0.7Sn0.3O2Powder;
3) stirring each quartz tube in a dark environment, placing the quartz tube under visible light for irradiating for a period of time after adsorption-desorption balance is achieved, and taking out a certain amount of solution at fixed time intervals;
4) and calculating the absorbance of the rhodamine B and tetracycline hydrochloride solution at a fixed moment according to the Lambert beer law, thereby representing the photocatalytic degradation performance of each optical material through concentration change.
As can be seen from the solution concentration change curves shown in FIGS. 8 and 9, the CNTSO-10 sample has faster photocatalytic degradation performance for rhodamine B and tetracycline hydrochloride solutions, and the degradation rate for the rhodamine B solution reaches 98.55% at 20 min; at 40min, the degradation rate of tetracycline hydrochloride solution reaches 88.3 percent, and the results show that g-C prepared by the preparation method provided by the invention3N4/Ti0.7Sn0.3O2The heterojunction photocatalytic material has excellent photocatalytic degradation performance on rhodamine B and tetracycline hydrochloride.
Example 2
Weighing 5g of urea, placing the urea in a 100mL crucible, placing the urea in a muffle furnace under a semi-sealed condition, heating to 510 ℃ at a heating rate of 10/min, preserving heat for 3h, naturally cooling to 20 ℃, and grinding the obtained sample in a mortar for 10min to obtain lamellar g-C3N4(ii) a 3mmol of SnCl are weighed4·5H2Dispersing O into a beaker filled with 50mL of absolute ethyl alcohol, adding 7mmol of butyl titanate under the condition of magnetic stirring, and continuing to stir vigorously for 15min to ensure that SnCl4·5H2And mixing the O and the butyl titanate uniformly. After completion of the stirring, the solution was transferred to a 100mL hydrothermal reactor and subjected to hydrothermal reaction at 200 ℃ for 20 hours. Naturally cooling to 22 ℃, centrifuging and washing with deionized water and absolute ethyl alcohol for three times respectively to obtain Ti0.7Sn0.3O2Solid solution is placed in a vacuum drying oven to be dried for 8 hours at the temperature of 80 ℃ to obtain Ti with a core-shell structure0.7Sn0.3O2A solid solution powder; 2g of g-C3N4Dispersing the powder into a beaker filled with 100mL of deionized water, and magnetically stirring for 5 min; under magnetic stirring, 0.6g ofTi0.7Sn0.3O2Stirring the solid solution powder for 8h under the condition that the pH value is 11, centrifuging and washing with deionized water and absolute ethyl alcohol for several times, and drying in a vacuum drying oven at 50 ℃ for 10h to obtain g-C3N4/Ti0.7Sn0.3O2A heterojunction photocatalytic material, the catalyst is abbreviated as CNTSO-5.
Example 3
Weighing 15g of urea, placing the urea in a 100mL crucible, placing the urea in a muffle furnace under a semi-sealed condition, heating to 530 ℃ at a heating rate of 6.1/min, preserving heat for 5h, naturally cooling to 22 ℃, and grinding the obtained sample in a mortar for 7.5min to obtain lamellar g-C3N4(ii) a 0.3mmol of SnCl is weighed4·5H2Dispersing O into a beaker containing 60mL of absolute ethyl alcohol, adding 0.7mmol of butyl titanate under the condition of magnetic stirring, and continuing to stir vigorously for 18min to ensure that SnCl4·5H2And mixing the O and the butyl titanate uniformly. After completion of the stirring, the solution was transferred to a 100mL hydrothermal reactor and subjected to hydrothermal reaction at 170 ℃ for 16 hours. Naturally cooling to 20 ℃, centrifuging and washing with deionized water and absolute ethyl alcohol for three times respectively to obtain Ti0.7Sn0.3O2Solid solution is placed in a vacuum drying oven to be dried for 10 hours at the temperature of 50 ℃ to obtain Ti with a core-shell structure0.7Sn0.3O2A solid solution powder; 1.1g of g-C3N4Dispersing the powder into a beaker filled with 75mL of deionized water, and magnetically stirring for 7.5 min; under the condition of magnetic stirring, 10mg of Ti is added0.7Sn0.3O2Continuously stirring the solid solution powder for 2h under the condition that the pH value is 3, centrifuging and washing the powder for a plurality of times by using deionized water and absolute ethyl alcohol respectively after magnetic stirring is finished, and drying the powder for 8h in a vacuum drying oven at the temperature of 80 ℃ to obtain g-C3N4/Ti0.7Sn0.3O2A heterojunction photocatalytic material, the catalyst is abbreviated as CNTSO-30.
For g-C obtained in examples 2 and 33N4/Ti0.7Sn0.3O2The heterojunction photocatalytic material is used for characterizing the photocatalytic degradation performance, and the result isIt is shown that the heterojunction photocatalytic materials prepared in the examples 2 and 3 have excellent photocatalytic degradation performance on rhodamine B and tetracycline hydrochloride as the heterojunction photocatalytic material prepared in the example 1.
Claims (4)
1. A preparation method of a graphite-phase carbon nitride/titanium tin solid solution heterojunction photocatalytic degradation material is characterized by comprising the following steps:
1) placing 5-15 g of urea in an environment with the temperature of 510-550 ℃, preserving heat for 3-5 h, naturally cooling to 20-25 ℃, and grinding to obtain g-C3N4Powder;
2) adding 0.3-3 mmol of SnCl4·5H2Dispersing O into 50-70 mL of absolute ethanol, adding 0.7-7 mmol of butyl titanate under the condition of magnetic stirring, continuously and violently stirring for 15-30 min to obtain a mixed solution, carrying out hydrothermal reaction on the mixed solution at the temperature of 170-200 ℃ for 16-20 h, naturally cooling to 20-25 ℃, centrifuging, washing, and carrying out vacuum drying at the temperature of 50-80 ℃ for 8-12 h to obtain the Ti with the core-shell structure0.7Sn0.3O2A solid solution powder;
3) 0.2 to 2g of g-C3N4Dispersing the powder into 50-70 mL of deionized water, and magnetically stirring for 5-10 min; adding 0.01-0.6 g of Ti under the condition of magnetic stirring0.7Sn0.3O2Continuously stirring the solid solution powder under the condition that the pH value is 3-11, centrifuging, washing and drying in vacuum to obtain g-C3N4/Ti0.7Sn0.3O2A heterojunction photocatalytic material.
2. The method for preparing the graphite-phase carbon nitride/titanium tin solid solution heterojunction photocatalytic degradation material as claimed in claim 1, wherein in the step 1), the temperature is raised to 510-550 ℃ at a temperature raising rate of 2.2-10 ℃/min.
3. g-C obtained by the preparation method of claim 13N4-Ti0.7Sn0.3O2Of materials degraded by heterojunction photocatalysisApplication is carried out.
4. The application of the graphite-phase carbon nitride/TiSn solid solution heterojunction photocatalytic degradation material as claimed in claim 3, wherein the composite photocatalytic material is applied to the treatment of rhodamine B and tetracycline antibiotics in wastewater.
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