CN116351471B - Prussian blue/g-C3N4Composite photocatalyst, preparation method and application thereof - Google Patents

Prussian blue/g-C3N4Composite photocatalyst, preparation method and application thereof Download PDF

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CN116351471B
CN116351471B CN202310242005.4A CN202310242005A CN116351471B CN 116351471 B CN116351471 B CN 116351471B CN 202310242005 A CN202310242005 A CN 202310242005A CN 116351471 B CN116351471 B CN 116351471B
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prussian blue
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CN116351471A (en
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陈训财
施郑正
李佳
潘玉蓬
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Southern Medical University
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Abstract

The invention provides a Prussian blue/g-C 3N4 composite photocatalyst, and a preparation method and application thereof, wherein the preparation method comprises the following steps: dissolving urea in deionized water, heating to 30 ℃, transferring the solution into a ceramic crucible with a cover, and calcining at high temperature to obtain a product g-C 3N4; dripping polyvinylpyrrolidone, potassium ferricyanide and a product g-C 3N4 into an HCl solution to obtain a suspension, and performing hydrothermal reaction in a stainless steel autoclave; and after the reaction is finished, cooling, centrifuging the precipitate, washing the precipitate with deionized water and absolute ethyl alcohol for three times respectively, and vacuum drying to obtain the Prussian blue/g-C 3N4 composite photocatalyst. The Prussian blue/g-C 3N4 composite photocatalyst has the advantages of enlarged visible light absorption area, enhanced absorption capacity and high visible light utilization rate, and has obvious effect on photodegradation of environmental pollutants such as degradation antibiotic medicines and dyes.

Description

Prussian blue/g-C 3N4 composite photocatalyst and preparation method and application thereof
Technical Field
The invention relates to the technical field of photocatalysts, in particular to a Prussian blue/g-C 3N4 composite photocatalyst, and a preparation method and application thereof.
Background
Over the last decades, with the continued development of urbanization, a large number of antibiotics have been widely used to treat human and animal infections. Tetracyclines, a typical antibiotic, have been widely used in human therapy, animal therapy and agricultural production. It has been reported that about 21 ten thousand tons of tetracycline are discharged into the aquatic ecosystem together with wastewater each year due to incomplete treatment by conventional methods. In addition, it has been found that even at nanogram levels, tetracycline in the aquatic ecosystem poses a serious threat to the environment and human health. The heterogeneous light Fenton technology is regarded as an effective method for degrading persistent organic pollutants as an advanced oxidation process due to high efficiency, good circularity, simple operation and no generation of a large amount of iron mud. However, most of the reported photo-Fenton catalysts absorb only ultraviolet rays, accounting for only about 5% of the solar spectrum, which makes it difficult to use natural solar ultraviolet rays as an energy source. In addition, some photo-Fenton catalysts exhibit high activity only at low pH values, or require expensive chemicals and time consuming synthetic processes. Therefore, developing a visible light response pH analyzer with a simple synthesis procedure and a wide operating pH is critical to facilitate the application of the photo Fenton technique.
Graphite carbonitride (g-C 3N4) is widely applied to environmental remediation and water treatment due to the characteristics of rich resources, simple preparation, unique belt structure and the like. However, its degradation performance is severely limited due to its low surface area, limited visible light utilization, and poor charge separation and transfer efficiency.
According to previous reports, it has been demonstrated that the degradation performance of g-C 3N4 can be greatly improved by expanding the light absorption range, increasing the charge separation and transfer ability, and activating the photo Fenton (-like) reaction when g-C 3N4 is coupled with a transition metal-based material. Prussian blue is a class of metal-organic frameworks with face-centered cubic cells in which ferrous (Fe II) and ferric (Fe III) ions are alternately bridged by cyano ligands (C≡N), where high spin FeHS (Fe III) is coupled to N and low spin Fe LS (Fe II) is coordinated to C. Prussian blue and its analogues are considered ideal materials for coupling with g-C 3N4 due to their low cost, low toxicity, relative stability and unique chemical composition. Although Prussian blue degradation contaminants have been reported in Fenton systems, the combination of Prussian blue with g-C 3N4 used in optical Fenton systems has been rarely studied.
Structural defect engineering has received much attention as another popular strategy for improving the photocatalytic performance of g-C 3N4, which can not only modulate the electronic structure but also increase the active sites. In particular, when defects (N, C, O, etc.) are introduced into the framework of g-C 3N4 having a larger surface area, a synergistic improvement effect of photocatalytic performance is exhibited. In addition, various forms of g-C 3N4 (including macropores, nanoplatelets, microtubes) have been widely studied, which exhibit better photocatalytic performance in the photo Fenton reaction than the conventional g-C 3N4 bulk photocatalyst. The two-dimensional ultrathin nanosheets with the porous structures not only provide more pollutant exposure, but also shorten the charge transfer distance and prolong the charge recombination time. Therefore, it is very feasible to construct porous two-dimensional ultrathin g-C 3N4 nanoplatelets with contaminant degradation defects.
According to the background, a carbon vacancy is introduced into a porous two-dimensional ultrathin g-C 3N4 nano sheet, and a high-efficiency photo Fenton catalyst with enhanced degradation performance can be constructed by combining crystalline Prussian blue nano particles. A series of Prussian blue supported and carbon vacancy g-C 3N4 (Prussian blue/porous defective g-C 3N4 nanoplatelets) hybrid catalysts were successfully synthesized by simple hydrothermal methods.
Disclosure of Invention
The technical problems to be solved are as follows: aiming at the defects existing in the prior art, the invention provides the Prussian blue/g-C 3N4 composite photocatalyst, the preparation method and the application thereof, the visible light absorption area of the Prussian blue/g-C 3N4 composite photocatalyst is enlarged, the absorption capacity is enhanced, the visible light utilization rate is high, and the Prussian blue/g-C 3N4 composite photocatalyst has obvious effect on photodegradation of environmental pollutants such as antibiotic medicines and dyes.
The technical scheme is as follows: a preparation method of Prussian blue/g-C 3N4 composite photocatalyst comprises the following steps:
Step one: dissolving urea in deionized water, heating to 30 ℃, transferring the solution into a ceramic crucible with a cover, and calcining at high temperature to obtain a product g-C 3N4, wherein the mass ratio of the urea to the deionized water is 1:1;
Step two: dripping polyvinylpyrrolidone, potassium ferricyanide and the product g-C 3N4 prepared in the first step into HCl solution to obtain suspension, and placing the suspension into a stainless steel autoclave for hydrothermal reaction, wherein the mass ratio of the product g-C 3N4 to the product g-C 3N4 is (50-350) to (2500-3500) to (25-28), and the mass ratio of the product g-C 3N4 to the product g-C mLHCl is (0.08-0.35).
Step three: and (3) after the reaction of the second step is finished, cooling to room temperature, centrifuging the precipitate, washing the precipitate with deionized water and absolute ethyl alcohol for three times respectively, and then drying the precipitate in vacuum to obtain the Prussian blue/g-C 3N4 composite photocatalyst.
The calcination temperature in the first step is 550 ℃ and the time is 4 hours.
The concentration of the HCl solution in the second step is 0.01mol/L.
The specific procedure for the hydrothermal reaction in step two described above was to place the suspension in a stainless steel autoclave with a 50mL capacity teflon liner and to react in an oven at 80 ℃ for 20h.
And in the third step, the vacuum drying temperature is 60 ℃ and the time is 12 hours.
The Prussian blue/g-C 3N4 composite photocatalyst prepared by the preparation method of the Prussian blue/g-C 3N4 composite photocatalyst is provided.
The Prussian blue/g-C 3N4 composite photocatalyst prepared by the preparation method is applied to degradation of antibiotic medicines and dye pollutants.
The beneficial effects are that: the Prussian blue/g-C 3N4 composite photocatalyst and the preparation method and application thereof provided by the invention have the following beneficial effects:
1. According to the invention, due to the interfacial interaction between g-C 3N4 and Prussian blue and the synergistic effect of carbon defects, the utilization rate of the material to visible light is effectively improved, the photogenerated charge transfer efficiency is maximized, the charge transfer and conduction capacity is stronger, and the higher oxidation-reduction capacity of the material is also maintained; the visible light absorption capacity of the prepared catalyst is improved, the absorption area is enlarged, and the utilization rate of visible light is improved;
2. the composite photocatalyst prepared by the invention has obvious effect on photodegradation of environmental pollutants such as antibiotic medicines, dyes and the like;
3. The preparation method has the advantages of simplicity in operation, good repeatability, low cost, easiness in condition control and the like;
4. According to the invention, the urea is selected to prepare the g-C 3N4 at high temperature, and the Prussian blue loaded and carbon vacancy g-C 3N4 (Prussian blue/porous defective g-C 3N4 nano-sheet) hybrid catalyst is synthesized by a simple hydrothermal method, so that the catalyst is applied to degradation of environmental pollutants such as antibiotic medicines and dyes, and has good photocatalytic activity;
5. The invention provides new insight for designing a high-efficiency photoelectric Fenton catalyst for environmental remediation.
Drawings
FIG. 1 is a Scanning Electron Microscope (SEM) image of Prussian blue/g-C 3N4 (I) composite photocatalyst.
FIG. 2 is a Prussian blue/g-C 3N4 (I) composite photocatalyst Transmission Electron Microscope (TEM) diagram and an energy spectrum element distribution diagram.
FIG. 3 is an X-ray photoelectron (XPS) spectrum of Prussian blue/g-C 3N4 (I) composite photocatalyst.
FIG. 4 is an X-ray diffraction (XRD) spectrum of Prussian blue/g-C 3N4 (I) composite photocatalyst, g-C 3N4 and Prussian blue.
FIG. 5 is a graph of photo-Fenton degradation of tetracycline for Prussian blue/g-C 3N4 (I), prussian blue/g-C 3N4 (II), and Prussian blue/g-C 3N4 (III).
FIG. 6 is a graph of photo-Fenton degradation of tetracycline for bulk g-C 3N4、g-C3N4 and Prussian blue/g-C 3N4 (I).
FIG. 7 is a graph showing photo-Fenton degradation of tetracyclines with different amounts of Prussian blue/g-C 3N4 (I) composite photocatalyst.
FIG. 8 is a graph of photo-Fenton degradation of tetracycline at different pH conditions for Prussian blue/g-C 3N4 (I) composite photocatalyst.
FIG. 9 is a graph showing the degradation rate of 20 cycles of Prussian blue/g-C 3N4 (I) composite photocatalyst for degrading tetracycline.
FIG. 10 is a graph of photo-Fenton degradation of ciprofloxacin, ranitidine, methylene blue, and rhodamine B for Prussian blue/g-C 3N4 (I) composite photocatalyst.
FIG. 11 is an ultraviolet-visible diffuse reflectance absorption spectrum of bulk g-C 3N4、g-C3N4 and Prussian blue/g-C 3N4 (I).
FIG. 12 is a graph of photocurrent and electrochemical impedance spectra of bulk g-C 3N4、g-C3N4 and Prussian blue/g-C 3N4 (I).
Detailed Description
Example 1
The embodiment provides a preparation method of Prussian blue/g-C 3N4 (I) composite photocatalyst, which comprises the following steps:
step one: 20g of urea is dissolved in 20mL of deionized water, the temperature is raised to 30 ℃, then the solution is transferred into a ceramic crucible (100 mL) with a cover, and the solution is calcined for 4 hours at 550 ℃ to obtain a product g-C 3N4;
Step two: 3g of polyvinylpyrrolidone, 26.4mg of potassium ferricyanide and 172mg of C 3N4 of the product prepared in the first step are dripped into 30mL of 0.01mol/L HCl solution to obtain a suspension, the suspension is placed into a stainless steel autoclave with a 50mL capacity Teflon lining, and the suspension is placed into an oven at 80 ℃ for hydrothermal reaction for 20 hours;
step three: and (3) after the reaction of the second step is finished, cooling to room temperature, centrifuging the precipitate, washing the precipitate with deionized water and absolute ethyl alcohol for three times respectively, and vacuum drying the precipitate for 12 hours at 60 ℃ to obtain the Prussian blue/g-C 3N4 (I) composite photocatalyst.
The SEM image of the Prussian blue/g-C 3N4 (I) composite photocatalyst prepared in the example is shown in figure 1, and as can be seen from figure 1, the Prussian blue/g-C 3N4 (I) composite photocatalyst has a porous layered structure.
The TEM image of the Prussian blue/g-C 3N4 (I) composite photocatalyst prepared in this example is shown in FIG. 2, and it can be seen from FIG. 2 that Prussian blue/g-C 3N4 (I) has a porous layered structure, prussian blue Nanoparticles (NPS) with a diameter of about 250nm are closely adhered to the porous g-C 3N4, wherein a significant and uniform Fe signal confirms successful doping and uniform distribution of Prussian blue.
The XPS spectrum of the Prussian blue/g-C 3N4 (I) composite photocatalyst prepared in the embodiment is shown in figure 3, and as can be seen from figure 3, prussian blue/g-C 3N4 (I) has C, N, O and Fe elements, wherein two peaks 705.1eV and 717.8eV appearing in the Fe2p spectrum correspond to Fe2p3/2 and Fe2p1/2 well, and successful loading of Prussian blue is confirmed.
The XRD spectrum of the Prussian blue/g-C 3N4 (I) composite photocatalyst prepared in the embodiment is shown in figure 4, and as can be seen from figure 4, the Prussian blue/g-C 3N4 (I) has characteristic peaks of both Prussian blue and g-C 3N4, and successful synthesis of the Prussian blue/g-C 3N4 (I) composite photocatalyst is verified.
Example 2
Example 2 differs from example 1 in that: in the second step, the mass of the g-C 3N4, the mass of the polyvinylpyrrolidone and the mass of the potassium ferricyanide are 344mg, 3g and 26.4mg respectively.
The Prussian blue/g-C 3N4 (II) composite photocatalyst is finally obtained in the embodiment.
Example 3
Example 3 differs from example 1 in that: in the second step, the mass of the g-C 3N4, the mass of the polyvinylpyrrolidone and the mass of the potassium ferricyanide are 86mg, 3g and 26.4mg respectively.
The Prussian blue/g-C 3N4 (III) composite photocatalyst is finally obtained in the embodiment.
The three composite photocatalysts of Prussian blue/g-C 3N4 (I), prussian blue/g-C 3N4 (II) and Prussian blue/g-C 3N4 (III) prepared in examples 1, 2 and 3 are subjected to performance test, and the process and the result are as follows:
Respectively taking 50mg of Prussian blue/g-C 3N4 (I), 50mg of Prussian blue/g-C 3N4 (II) and 50mg of Prussian blue/g-C 3N4 (III), respectively adding into 30mL of 50mg/L tetracycline solution, and continuously stirring for 30min to ensure that the suspension reaches adsorption equilibrium. 150 μ L H 2O2 (30%) was then added to the suspension. Two milliliter aliquots were collected at specific time intervals and at desired intervals using a 0.45mm syringe. The concentration was assessed by taking the supernatant after centrifugation of the suspension and recording the maximum absorbance with a UV-vis spectrophotometer. The resulting tetracycline degradation graph is shown in FIG. 5. As can be seen from FIG. 5, after 120min of illumination, prussian blue/g-C 3N4 (I), prussian blue/g-C 3N4 (II) and Prussian blue/g-C 3N4 (III) all reach more than 85%, wherein the photocatalytic efficiency of Prussian blue/g-C 3N4 (I) is highest.
In addition, 50mg of bulk g-C 3N4 (self-made), g-C 3N4 (self-made) and Prussian blue/g-C 3N4 (I) are respectively taken and then respectively added into 30ml of 50mg/L tetracycline solution, and the suspension is continuously stirred for 30min to reach adsorption equilibrium. 150. Mu. LH 2O2 (30%) was then added to the suspension. Two milliliter aliquots were collected at specific time intervals and at desired intervals using a 0.45mm syringe. The concentration was assessed by taking the supernatant after centrifugation of the suspension and recording the maximum absorbance with a UV-vis spectrophotometer. The resulting tetracycline degradation graph is shown in FIG. 6. As can be seen from FIG. 6, after 120min of illumination, prussian blue/g-C 3N4 (I) has the highest degradation effect on tetracycline, and the degradation rate can reach about 93.3%. The single catalyst bulk-C 3N4 and g-C 3N4 have lower degradation to tetracycline, and the photocatalysis efficiency of the composite material is obviously higher than that of the single catalyst.
The preparation method of bulk g-C 3N4 (homemade) comprises the following steps: 3g of melamine is transferred into a covered ceramic crucible and calcined at 550 ℃ to obtain the product bulk-C 3N4.
G-C 3N4 (homemade) is the product obtained in step one of example 1.
In addition, specific tests are carried out on each influencing factor of Prussian blue/g-C 3N4 (I) composite photocatalyst prepared in example 1, and the process and the result are as follows:
(1) Relation between degradation efficiency and Prussian blue/g-C 3N4 (I) addition
Prussian blue/g-C 3N4 (I) is respectively taken as 1mg, 5mg, 10mg, 25mg and 50mg, then respectively added into 30mL of 50mg/L tetracycline solution, and continuously stirred for 30min to ensure that the suspension reaches adsorption equilibrium. 150. Mu. LH 2O2 (30%) was then added to the suspension. Two milliliter aliquots were collected at specific time intervals and at desired intervals using a 0.45mm syringe. The concentration was assessed by taking the supernatant after centrifugation of the suspension and recording the maximum absorbance with a UV-vis spectrophotometer. The resulting tetracycline degradation graph is shown in FIG. 7. As can be seen from FIG. 7, after 120min of illumination, the degradation effect of Prussian blue/g-C 3N4 (I) on tetracycline is positively correlated with the addition amount.
(2) Relation between visible light degradation performance and acid and alkali conditions
50Mg of Prussian blue/g-C 3N4 (I) was added to 30mL of a 50mg/L tetracycline solution, the pH was adjusted to 3 to 9, and stirring was continued for 30min to bring the suspension to adsorption equilibrium. 150. Mu. LH 2O2 (30%) was then added to the suspension. Two milliliter aliquots were collected at specific time intervals and at desired intervals using a 0.45mm syringe. The concentration was assessed by taking the supernatant after centrifugation of the suspension and recording the maximum absorbance with a UV-vis spectrophotometer. The resulting tetracycline degradation graph is shown in FIG. 8. As can be seen from FIG. 8, after 120min of illumination, the pH value of the solution is between 3 and 9, and Prussian blue/g-C 3N4 is more than 89.6%, so that the solution has stronger degradation efficiency. When the pH of the solution is 7, the degradation efficiency can reach 98.4 percent. The Prussian blue/g-C 3N4 has good visible light degradation performance under acidic or weak alkaline conditions.
(3) Cyclic degradation of tetracycline
The result of the photocatalytic experiment for circularly degrading tetracycline by the Prussian blue/g-C 3N4 (I) composite photocatalyst prepared in example 1 is shown in FIG. 9. As can be seen from fig. 9, the photocatalyst was not significantly deactivated after 20 consecutive cycles. The stability is good, and the method has great potential value in the aspect of environmental purification.
(4) Universality of application
50Mg Prussian blue/g-C 3N4 (I) was added to 30mL of 50mg/L ciprofloxacin, ranitidine, methylene blue and rhodamine solutions, respectively, and the suspension was allowed to reach adsorption equilibrium by continuous stirring for 30 min. 150 μ L H 2O2 (30%) was then added to the suspension. Two milliliter aliquots were collected at specific time intervals and at desired intervals using a 0.45mm syringe. The concentration was assessed by taking the supernatant after centrifugation of the suspension and recording the maximum absorbance with a UV-vis spectrophotometer. The resulting degraded ciprofloxacin, ranitidine, methylene blue and rhodamine solutions are shown in the graph of fig. 10. As can be seen from FIG. 10, after 120min of illumination, the degradation efficiencies of ciprofloxacin, ranitidine, methylene blue and rhodamine can reach 59.8%, 98.4%, 99.4% and 100.0%, respectively, and the results show that Prussian blue/g-C 3N4 has good universality.
(5) Visible light absorption capacity, absorption region
The light absorption characteristics of the different samples were measured using uv-vis diffuse reflectance spectroscopy as shown in fig. 11. As can be seen from fig. 11, it is confirmed that the Prussian blue/g-C 3N4 (I) composite material has both the absorption characteristics of Prussian blue and g-C 3N4, and that Prussian blue/g-C 3N4 has a wider and stronger light absorption, which means that after loading Prussian blue, light collection is improved, the visible light absorption capacity of Prussian blue/g-C 3N4 (I) is also improved, and the absorption region is also widened.
(6) Charge transfer and conductivity capabilities
The photocurrent testing process comprises the following steps: 2.0mg of the sample was ultrasonically dispersed in 50. Mu.L of ethanol, 10. Mu.L of Nafion solution (5 wt%) and 50. Mu.L of ultra pure water to form a uniform slurry, and 20. Mu.L of the slurry was dropped to deposit on the FTO electrode. FTP electrode, platinum sheet and saturated Ag/AgCl deposited by slurry are used as working electrode, counter electrode and reference electrode. Photocurrent data was collected using a CHI660C electrochemical workstation in an analysis of photocurrent over time using a 300W Xe lamp (truncated lambda <420 nm) and Na 2SO4 (0.5M) as the light source and electrolyte.
Electrochemical impedance spectroscopy testing process: on the CHI760e workstation, a standard three-electrode system (Pt foil, ag/AgCl and working electrode, electrolyte 0.1M K 4Fe(CN)6·3H2O、0.1M K3[Fe(CN)6, 0.1M KCl mixed solution) was used, 5. Mu.L of slurry was added dropwise to the working electrode, and the electrochemical impedance spectrum was measured at an open circuit potential range of 0.01-1000 kHz.
The results of the photocurrent and electrochemical impedance spectrum tests are shown in fig. 12, and it can be seen from fig. 12 that Prussian blue/g-C 3N4 (I) loaded with Prussian blue shows the highest photocurrent response and the smallest arc radius, indicating that the synergistic effect of Prussian blue and carbon defects maximizes the photogenerated charge transfer efficiency and has the strongest charge transfer and conduction capacity.
While the embodiments of the present invention have been described in detail, those skilled in the art should not understand that the present invention is limited to the specific embodiments and applications.

Claims (7)

1. A preparation method of Prussian blue/g-C 3N4 composite photocatalyst is characterized by comprising the following steps:
Step one: dissolving urea in deionized water, heating to 30 ℃, transferring the solution into a ceramic crucible with a cover, and calcining at high temperature to obtain a product g-C 3N4, wherein the mass ratio of the urea to the deionized water is 1:1;
Step two: dripping polyvinylpyrrolidone, potassium ferricyanide and the product g-C 3N4 prepared in the first step into an HCl solution to obtain a suspension, and placing the suspension into a stainless steel autoclave for hydrothermal reaction, wherein the mass ratio of the product g-C 3N4 to the polyvinylpyrrolidone to the potassium ferricyanide is (1-7) to (50-70) to (0.5-0.56), and 1mg of the product g-C 3N4 corresponds to (0.08-0.35) mL of the HCl solution;
Step three: and (3) after the reaction of the second step is finished, cooling to room temperature, centrifuging the precipitate, washing the precipitate with deionized water and absolute ethyl alcohol for three times respectively, and then drying the precipitate in vacuum to obtain the Prussian blue/g-C 3N4 composite photocatalyst.
2. The method for preparing the Prussian blue/g-C 3N4 composite photocatalyst according to claim 1, which is characterized in that: the calcination temperature in the first step is 550 ℃ and the time is 4 hours.
3. The method for preparing the Prussian blue/g-C 3N4 composite photocatalyst according to claim 1, which is characterized in that: the concentration of the HCl solution in the second step is 0.01mol/L.
4. The method for preparing the Prussian blue/g-C 3N4 composite photocatalyst according to claim 1, which is characterized in that: the specific process of the hydrothermal reaction in the step two is that the suspension is placed in a stainless steel autoclave with a teflon liner with a capacity of 50mL and placed in an oven at 80 ℃ for reaction for 20h.
5. The method for preparing the Prussian blue/g-C 3N4 composite photocatalyst according to claim 1, which is characterized in that: and in the third step, the vacuum drying temperature is 60 ℃ and the time is 12 hours.
6. The Prussian blue/g-C 3N4 composite photocatalyst prepared by the method for preparing the Prussian blue/g-C 3N4 composite photocatalyst according to any one of claims 1-5.
7. The application of the Prussian blue/g-C 3N4 composite photocatalyst prepared by the preparation method of the Prussian blue/g-C 3N4 composite photocatalyst in degrading antibiotic medicines and dye pollutants.
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