CN115069286B - Phosphorus-doped porous hierarchical structure carbon nitride photocatalyst and preparation method and application thereof - Google Patents
Phosphorus-doped porous hierarchical structure carbon nitride photocatalyst and preparation method and application thereof Download PDFInfo
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- JMANVNJQNLATNU-UHFFFAOYSA-N oxalonitrile Chemical compound N#CC#N JMANVNJQNLATNU-UHFFFAOYSA-N 0.000 title claims abstract description 39
- 239000011941 photocatalyst Substances 0.000 title claims abstract description 33
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
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- 239000003054 catalyst Substances 0.000 claims abstract description 21
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 21
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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 claims description 10
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- PYWVYCXTNDRMGF-UHFFFAOYSA-N rhodamine B Chemical compound [Cl-].C=12C=CC(=[N+](CC)CC)C=C2OC2=CC(N(CC)CC)=CC=C2C=1C1=CC=CC=C1C(O)=O PYWVYCXTNDRMGF-UHFFFAOYSA-N 0.000 claims description 10
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- IMQLKJBTEOYOSI-UHFFFAOYSA-N Phytic acid Natural products OP(O)(=O)OC1C(OP(O)(O)=O)C(OP(O)(O)=O)C(OP(O)(O)=O)C(OP(O)(O)=O)C1OP(O)(O)=O IMQLKJBTEOYOSI-UHFFFAOYSA-N 0.000 claims description 5
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- 230000000052 comparative effect Effects 0.000 description 27
- 230000001699 photocatalysis Effects 0.000 description 15
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- 229910052724 xenon Inorganic materials 0.000 description 6
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 6
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- QGBSISYHAICWAH-UHFFFAOYSA-N dicyandiamide Chemical compound NC(N)=NC#N QGBSISYHAICWAH-UHFFFAOYSA-N 0.000 description 4
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- FQENQNTWSFEDLI-UHFFFAOYSA-J sodium diphosphate Chemical compound [Na+].[Na+].[Na+].[Na+].[O-]P([O-])(=O)OP([O-])([O-])=O FQENQNTWSFEDLI-UHFFFAOYSA-J 0.000 description 3
- 229940048086 sodium pyrophosphate Drugs 0.000 description 3
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- 229960004838 phosphoric acid Drugs 0.000 description 2
- 235000011007 phosphoric acid Nutrition 0.000 description 2
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- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Chemical compound OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 0.000 description 1
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- 125000004437 phosphorous atom Chemical group 0.000 description 1
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- 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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- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
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- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
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Abstract
The invention provides a phosphorus-doped porous hierarchical structure carbon nitride photocatalyst, and a preparation method and application thereof, and the phosphorus-doped porous hierarchical structure carbon nitride photocatalyst comprises the following steps: s1, preparing a phosphorus doped carbon nitride precursor with a porous hierarchical structure; s2, preparing the phosphorus doped carbon nitride with the porous hierarchical structure. The preparation process adopts a template-free method, and has the advantages of simple process, mild condition, low cost and good safety. No reagent harmful to the environment is used in the process, so that the preparation method is environment-friendly and efficient, and is very suitable for large-scale production. The phosphorus-doped porous hierarchical structure g-C3N4 catalyst prepared by the process realizes high-efficiency and rapid photodegradation of organic pollutants under the condition of visible light, shortens the degradation time to be within 90min, has the degradation rate up to 99.2 percent, and has good application prospects in the fields of sewage treatment, waste gas treatment and the like.
Description
Technical Field
The invention relates to a photocatalyst, in particular to a phosphorus-doped carbon nitride photocatalyst with a porous hierarchical structure, and a preparation method and application thereof; belonging to the technical field of new materials and preparation thereof.
Background
With the rapid development of society and economy, global environmental pollution and energy crisis problems become increasingly severe, seriously threatening human life safety and global economic development. In recent years, scientists have focused on solving these problems, wherein photocatalytic technology has attracted extensive attention in the scientific community due to its safety and environmental advantages. In the field of catalyst technology, researchers have mainly focused on developing high-performance photocatalytic materials.
Traditional photocatalytic materials such as TiO 2, znO, cdS and the like have large forbidden band width and can only absorb light in an ultraviolet region, so that sunlight cannot be fully utilized, and the space for improving the catalytic effect is extremely limited. The research shows that the graphite phase carbon nitride (g-C 3N4) has the advantages of proper forbidden bandwidth, good visible light response, low cost, high stability, easy shape adjustment and the like, and is one of the most ideal photocatalysts in a plurality of catalysts. However, the bulk g-C 3N4 obtained by direct thermal condensation has a low specific surface area and photoresponsive activity, resulting in a limited photocatalytic effect, which severely limits its use. In the research vortex of g-C 3N4, scientists found that macroscopic morphology, size, specific surface area and microscopic atomic arrangement disorder all have an effect on the photocatalytic performance of g-C 3N4. Therefore, the methods of morphology regulation, element doping, heterojunction construction and the like form a research direction for improving the photocatalytic activity by changing the defects of the g-C 3N4.
In the aspect of the g-C 3N4 structural modification, the concept of a hierarchical structure is provided, the hierarchical structure not only provides more photocatalytic reaction contact points, but also creates a new heterogeneous catalytic interface, and more paths are provided for electron transmission. However, due to the agglomeration characteristic of the nano-sheets, the hierarchical structure formed by stacking the nano-sheets also has the disadvantage of structural agglomeration, and the popularization and application of the g-C 3N4 as a photocatalytic material are restricted. In addition, the micro-nano structure g-C 3N4 in the prior art is prepared by a hard template method, and the template is removed by a harmful reagent after the preparation is finished to realize further functionalization. The preparation method has the defects of complex preparation process, harsh conditions, long time consumption, unfriendly environment and the like.
Therefore, a set of preparation method which is safe in operation, mild in condition, convenient and environment-friendly is necessary to study the designed g-C 3N4 micro-nano structure, and the product performance is optimized.
Disclosure of Invention
In order to solve the defects of the prior art, the invention aims to provide a phosphorus-doped carbon nitride photocatalyst with a porous hierarchical structure, and a preparation method and application thereof, so as to solve the problem of deadly nanosheet agglomeration in the structure, display more photocatalytic performance reaction sites and realize the aim of efficiently degrading organic matters under visible light.
In order to achieve the above object, the present invention adopts the following technical scheme:
the invention firstly discloses a preparation method of a phosphorus-doped carbon nitride photocatalyst with a porous hierarchical structure, which comprises the following steps:
S1, preparing a phosphorus doped porous hierarchical structure carbon nitride precursor:
(1) Mixing one or more of urea, dicyandiamide and thiourea with a phosphorus source, dissolving in deionized water, and slowly adding melamine into the deionized water to fully dissolve the melamine to obtain a mixed solution;
(2) Transferring the mixed solution into an autoclave, performing hydrothermal treatment, cooling, taking out the needle-shaped precursor, washing and drying to obtain the phosphorus-doped carbon nitride precursor with the porous hierarchical structure;
s2, preparing phosphorus doped carbon nitride with a porous hierarchical structure:
Calcining the precursor obtained in the step S1, and naturally cooling to room temperature to obtain a target product.
Preferably, the phosphorus source is a substance which generates PH 3 gas during calcination, and is selected from one or more of phytic acid, phosphoric acid or sodium pyrophosphate solution, so that the hierarchical structure of the tube can be exposed, a larger specific surface area is provided, and the catalytic performance is optimized.
More preferably, in the aforementioned step S1, the dissolution is assisted by ultrasonic agitation.
Preferably, in the step S1, the mixed solution is subjected to hydrothermal treatment at 150-200 ℃ for 16-30 hours.
Further preferably, in the step S2, the precursor is heated to 500-550 ℃ at a heating rate of 2-5 ℃/min, and calcined for 2-5 hours.
Still further preferably, the preparation method of the phosphorus doped porous hierarchical structure carbon nitride photocatalyst comprises the following steps:
S1, preparing a phosphorus doped porous hierarchical structure carbon nitride precursor:
(1) Dissolving urea and phytic acid in deionized water, continuously and ultrasonically treating for a period of time, slowly adding melamine into the deionized water, continuously stirring, and fully dissolving to obtain a mixed solution;
(2) Transferring the mixed solution into an autoclave, performing hydrothermal treatment at 200 ℃ for 16 hours, cooling, taking out the needle-shaped precursor, washing for multiple times, and drying at 80 ℃ for 3 hours to obtain the phosphorus-doped porous hierarchical carbon nitride precursor;
s2, preparing phosphorus doped carbon nitride with a porous hierarchical structure:
And (3) placing the precursor obtained in the step (S1) in a 200mL airtight porcelain crucible, heating to 530 ℃ at a heating rate of 5 ℃/min, continuously calcining for 4 hours, and naturally cooling to room temperature to obtain a target product.
The invention also discloses a phosphorus-doped porous hierarchical structure carbon nitride photocatalyst prepared by the preparation method.
Preferably, the foregoing catalyst exhibits a hierarchical structure of stacked porous sheets, with porous g-C 3N4 nanoplatelets connected into g-C 3N4 microtubes, with a unique and novel microstructure.
More preferably, the specific surface area of the catalyst is 55 to 80 square meters per gram.
Finally, the invention also discloses application of the phosphorus-doped porous hierarchical structure carbon nitride photocatalyst in degradation of rhodamine and tetracycline hydrochloride.
The beneficial effects are that:
(1) According to the invention, the novel phosphorus doped porous hierarchical structure g-C 3N4 is prepared by a simple hydrothermal method and a pyrolysis method, the porous g-C 3N4 nano-sheet is skillfully connected into a special g-C 3N4 microtube, the agglomeration of the nano-sheet is effectively avoided, and more photocatalytic performance reaction sites are displayed. In addition, the unique hierarchical structure creates a new heterogeneous catalytic interface and inherits the advantage of directional electron transport of the microtubes along the axial direction, which provides more electron transport paths and accelerates the separation of electrons and holes.
(2) By introducing organic phosphoric acid or phosphate, phosphorus element is doped into the chemical framework of g-C 3N4, so that the optical property of g-C 3N4 is changed, the visible light absorption range is enhanced, and more visible light is absorbed and utilized in the photocatalytic reaction; meanwhile, PH 3 gas can be generated in the calcining process of the substances, so that the wall of the g-C 3N4 pipe can be corroded, the layered structure of the pipe is exposed, and a larger specific surface area is provided. Along with the different added contents of the substances, the reaction temperature, the reaction time and the like and the technological parameters are reasonably controlled, so that a product with unique structural appearance is formed, and a new thought is provided for the novel structural design of the material.
(3) The preparation process adopts a template-free method, and has the advantages of simple process, mild condition, low cost and good safety. No reagent harmful to the environment is used in the process, so that the preparation method is environment-friendly and efficient, and is very suitable for large-scale production. The phosphorus-doped porous hierarchical structure g-C 3N4 catalyst prepared by the process realizes high-efficiency and rapid photodegradation of organic pollutants under the condition of visible light, shortens the degradation time to be within 90min, ensures that the degradation rate can reach 99.2%, and provides a new idea for industrial application of the visible light catalyst.
Drawings
FIG. 1 shows XRD patterns of the products of related examples and comparative examples of the present invention;
FIG. 2 is a Scanning Electron Microscope (SEM) image of the product of comparative example 2 of the present invention;
FIG. 3 is a Scanning Electron Microscope (SEM) image of a photocatalyst of example 1 of the present invention;
FIG. 4 is a Scanning Electron Microscope (SEM) image of a photocatalyst according to example 2 of the present invention;
FIG. 5 is a Scanning Electron Microscope (SEM) image of a photocatalyst according to example 3 of the present invention;
FIG. 6 is a graph showing specific surface area (BET) of products of related examples and comparative examples of the present invention;
FIG. 7 shows ultraviolet-visible (UV-vis) absorption spectra of the products of the related examples and comparative examples of the present invention;
FIG. 8 is a graph showing the concentration change of the degradation dye rhodamine for the related examples and comparative examples of the present invention under 300W xenon lamp irradiation;
FIG. 9 is a graph showing the concentration change of the antibiotic tetracycline hydrochloride degradation under 300W xenon lamp irradiation of the related examples and comparative examples of the present invention.
Detailed Description
The invention is described in detail below with reference to the drawings and the specific embodiments.
In the invention, all raw materials are commercially available unless specified.
Example 1
The product was prepared in this example using the following steps:
(1) 8g of thiourea and 2mL of phosphoric acid were added to 40mL of deionized water, and the mixture was completely dissolved by continuous ultrasonic treatment for 20 minutes, and 4g of melamine was slowly added thereto, followed by continuous stirring for 2 hours to obtain a mixed solution.
(2) The mixed solution was transferred to a 100 ml teflon stainless steel autoclave and hydrothermally treated at 180 ℃ 24 h. And cooling, taking out the needle-shaped precursor, washing for 3 times to remove surface impurities, and then drying at 60 ℃ for 6 hours to obtain the phosphorus-doped carbon nitride precursor with the porous hierarchical structure.
(3) The dried needle-like precursor is placed in a 200mL airtight porcelain crucible, heated to 550 ℃ at a heating rate of 3 ℃/min, and continuously calcined for 3 hours at the temperature. And finally, naturally cooling the product to room temperature to obtain the phosphorus doped carbon nitride with the porous hierarchical structure.
Example 2
(1) 6G of urea and 5mL of phytic acid are added into 60mL of deionized water, continuous ultrasonic treatment is carried out for 30 minutes to completely dissolve the mixture, and then 6g of melamine is slowly added, and stirring is continued for 0.5h to obtain a mixed solution.
(2) The mixed solution was transferred to a 100 ml teflon stainless steel autoclave and hydrothermally treated at 200 ℃ 16 h. And cooling, taking out the needle-shaped precursor, washing for 4 times to remove surface impurities, and drying at 80 ℃ for 3 hours to obtain the phosphorus-doped carbon nitride precursor with the porous hierarchical structure.
(3) The dried needle-like precursor is placed in a 200mL closed porcelain crucible, heated to 530 ℃ at a heating rate of 5 ℃/min, and continuously calcined for 4 hours at the temperature. And finally, naturally cooling the product to room temperature to obtain the phosphorus doped carbon nitride with the porous hierarchical structure.
Example 3
(1) 8G of dicyandiamide and 7mL of sodium pyrophosphate solution were added to 70mL of deionized water, the mixture was completely dissolved by continuous sonication for 5 minutes, and 8g of melamine was slowly added thereto, followed by continuous stirring for 0.5h to obtain a mixed solution.
(2) The mixed solution was transferred to a 100 ml teflon stainless steel autoclave and hydrothermally treated at 160 ℃ for 22h. And cooling, taking out the needle-shaped precursor, washing for 5 times to remove surface impurities, and drying at 60 ℃ for 5 hours to obtain the phosphorus-doped carbon nitride precursor with the porous hierarchical structure.
(3) The dried needle-like precursor is placed in a 200mL airtight porcelain crucible, heated to 520 ℃ at a heating rate of 4 ℃/min, and continuously calcined for 2 hours at the temperature. And finally, naturally cooling the product to room temperature to obtain the phosphorus doped carbon nitride with the porous hierarchical structure.
Comparative example 1
6G of melamine are heated to 550℃in a 200ml closed ceramic crucible at a temperature increase rate of 5℃per minute and calcined at this temperature for 4 hours. Naturally cooling to room temperature to obtain g-C 3N4 powder.
Comparative example 2
The product was prepared by the following procedure:
(1) 6g of dicyandiamide is added into 60mL of deionized water, continuous ultrasonic treatment is carried out for 15 minutes to completely dissolve the mixture, and then 6g of melamine is slowly added, and stirring is continued for 1 hour to obtain a mixed solution.
(2) The mixed solution was transferred to a 100 ml teflon stainless steel autoclave and hydrothermally treated at 160 ℃ for 18h. And cooling, taking out the needle-shaped precursor, washing for 4 times to remove surface impurities, and drying at 70 ℃ for 4 hours to obtain the phosphorus-doped carbon nitride precursor with the porous hierarchical structure.
(3) The dried needle-like precursor is placed in a 200 mL airtight porcelain crucible, heated to 520 ℃ at a heating rate of 4 ℃/min, and continuously calcined for 4 hours at the temperature. And finally, naturally cooling the product to room temperature to obtain the porous carbon nitride microtube.
Structural characterization and performance detection
(1) XRD characterization
Fig. 1 shows an X-ray diffraction pattern (XRD), which is comparative example 1, comparative example 2, and examples 1 to 3 in this order from top to bottom.
As can be seen from the XRD pattern, all samples showed two distinct peaks at 13.0 ° and 27.3 °, which are (100) and (002) diffraction planes belonging to g-C 3N4, consisting of in-plane repeating tris-s-triazine units and oriented stacked conjugated aromatic systems, respectively. Meanwhile, the peak intensities of comparative example 2 and examples 1 to 3 are weakened compared with comparative example 1, because of the unique shell-core type hierarchical structure in comparative example 2 and examples 1 to 3, resulting in a decrease in crystallinity.
(2) SEM morphology characterization
FIG. 2 is a Scanning Electron Microscope (SEM) image of the porous tubular photocatalyst g-C 3N4 produced in comparative example 2 of the present invention. The product is shown to have a porous tubular micro-morphology, and the diameter is 6-10 mu m. This is due to: melamine is easily converted to cyanuric acid during the hydrothermal reaction, and spontaneously assembles together due to the three hydrogen bonds that they all exist, forming a stable hexamer. The hexamers then further align and assemble to form supramolecular precursors via pi-pi interactions. Subsequently, the hydrogen bonds and pi-pi interactions in the supramolecular precursor may break during thermal polycondensation and shrink or stretch in the axial direction to form a hollow tubular structure.
FIG. 3 is a Scanning Electron Microscope (SEM) image of a phosphorus-doped porous hierarchical structure g-C 3N4 produced in example 1 of the present invention. It can be seen that there are many porous nanosheet structures attached inside the complete tubular structure. The applicant analyzed that this might be due to the two-dimensional g-C 3N4 nano-sheets formed during calcination of urea, dicyandiamide, thiourea and the like, which remained in the carbon nitride tube. Interestingly, this tubular structure was larger in size, up to 20-25 μm, than comparative example 2, probably because the acidic environment was more suitable for the self-assembly reaction of melamine.
FIG. 4 is a Scanning Electron Microscope (SEM) image of a phosphorus-doped porous hierarchical structure g-C 3N4 produced in example 2 of the present invention. It can be seen that the porous nanoplatelet structure is exposed from the tube, exhibiting a distinct hierarchical structure of porous platelet stacks. The applicant analyzed that this is because phytic acid or phosphoric acid, sodium pyrophosphate solutions, and the like, generate PH 3 gas during calcination, and can erode the wall of the g-C 3N4 tube, exposing the hierarchical structure of the tube, and providing a larger specific surface area.
FIG. 5 is a Scanning Electron Microscope (SEM) image of a phosphorus-doped porous hierarchical structure g-C 3N4 produced in example 3 of the present invention. It can be seen that no significant hierarchy of porous sheet packing was observed, and applicant's analysis was probably due to significant changes in microstructure due to collapse of the structure after the generation of significant amounts of PH 3 gas.
(3) Specific surface area detection
FIG. 6 is a graph showing specific surface areas (BET) of comparative example 1, comparative example 2 and examples 1 to 3 according to the present invention. As can be seen from the graph, the specific surface area of the product of comparative example 2 of the present invention was 51.57m 2/g, which is 2.93 times that of comparative example 1 (17.60 m 2/g). And the specific surface area of examples 1 to 3 was 57.78m 2/g 、79.29m2/g、55.39m2/g in order.
This indicates that: the construction of the hierarchical structure can remarkably improve the specific surface area of the photocatalyst, the hierarchical structure after the shell is peeled off can expose the largest specific surface area, the reactive sites are greatly increased, more photo-generated electrons are promoted to be generated, and the photocatalytic activity is greatly improved, so that the method can be verified in later application detection.
(4) Ultraviolet-visible (UV-vis) absorption spectrogram
FIG. 7 shows ultraviolet-visible (UV-vis) absorption spectra of comparative example 1, comparative example 2 and examples 1 to 3 of the present invention. Comparative example 2 shows enhanced light absorption characteristics compared to comparative example 1, because of its unique tubular structure with a large surface area and various scattering effects. For examples 1-3, the absorption edge further showed a significant red shift.
In addition, the absorbance of examples 1-3 at a wavelength greater than 450nm shows a tendency to become higher as the concentration of the phosphorus-containing species increases, which indicates that the P heteroatom can change the optical properties of g-C 3N4, and the tubular layered structure can effectively utilize more visible light, thereby improving the photocatalytic activity.
(5) Application performance verification of photocatalyst for photocatalytic degradation of dye (rhodamine B) in water
The experimental method comprises the following steps: under the illumination of visible light (lambda > 420 nm), the photocatalytic degradation performance of rhodamine was evaluated by using a 300W xenon lamp (CEL-HXF 300, beijing China education golden light Co., ltd.) with a light cut-off filter, and the light intensity was controlled to be 100mW cm -2 (simulated visible light) by an optical power tester.
The general detection method comprises the following steps:
(a) 30 mg photocatalyst was added to 100 ml rhodamine solution (20 mg/ml) for 30min in the dark to reach adsorption-desorption equilibrium.
(B) During the illumination, 3 ml samples were collected every 15 minutes and the catalyst was separated by centrifugation, and finally the absorbance of the samples was measured by an ultraviolet-visible spectrophotometer.
(C) The degradation rate (%) =1-C t/C0＝1-At/A0 of rhodamine B was calculated from the intensity change of the 550nm absorption peak in the measured solution absorption spectrum. Wherein C 0 and A 0 are the initial concentration of rhodamine B in water before illumination and the absorbance at 550nm, and C t and A t are the concentration of rhodamine B in water after illumination for a certain time and the absorbance at 550 nm.
FIG. 8 is a graph showing the concentration change of the degradation dye rhodamine B under the irradiation of a 300W xenon lamp of the photocatalyst prepared in comparative example 1, comparative example 2 and examples 1 to 3 according to the present invention. From the graph, the composite catalyst prepared in the example 2 has optimal performance, the catalytic degradation time is only 90min, and the degradation rate is as high as 99.2%. It can be seen that example 2 is the best example (which is consistent with the SEM characterization results above), and the hierarchical structure of phosphorus doping and stripping plays a synergistic role, which can significantly improve the photocatalytic reactivity of g-C 3N4.
(6) Application performance verification of photocatalyst for photocatalytic degradation of antibiotics (tetracycline hydrochloride) in water
The experimental method comprises the following steps: the photocatalytic degradation performance of tetracycline hydrochloride was evaluated under illumination with visible light (lambda > 420 nm) using a 300W xenon lamp (CEL-HXF 300, chinese education golden light limited, beijing) with a light cut-off filter, and the light intensity was controlled to 100mW cm -2 by an optical power tester.
The general detection method comprises the following steps:
(a) 30 mg photocatalyst was added to 50ml tetracycline hydrochloride solution (10 mg/ml) and continued in the dark for 30min to reach adsorption-desorption equilibrium.
(B) During the illumination, 3 ml samples were collected every 15 minutes and the catalyst was separated by centrifugation, and finally the absorbance of the samples was measured by an ultraviolet-visible spectrophotometer.
(C) The degradation rate (%) =1-C t/C0＝1-At/A0 of tetracycline hydrochloride was calculated from the intensity change of the 550nm absorption peak in the absorption spectrum of the measured solution. Wherein C 0 and A 0 are the initial concentration of tetracycline hydrochloride in water before illumination and its absorbance at 357nm, and C t and A t are the concentration of tetracycline hydrochloride in water after illumination for a certain period of time and its absorbance at 357 nm.
FIG. 9 is a graph showing the concentration change of the antibiotic tetracycline hydrochloride degradation under 300W xenon lamp irradiation of the photocatalysts prepared in comparative example 1, comparative example 2 and examples 1 to 3 according to the present invention. From the graph, the performance of the composite catalyst prepared in the example 2 still shows the best performance (which is consistent with the SEM characterization result), the catalytic degradation time is only 90min, and the degradation rate is as high as 85.3%. With reference to FIG. 8, it is not difficult to find that the phosphorus doped porous hierarchical structure g-C 3N4 photocatalyst has general excellent photocatalytic performance.
In conclusion, the invention obtains the novel phosphorus doped porous hierarchical structure g-C 3N4 photocatalyst capable of efficiently degrading organic pollutants under the condition of visible light, the catalyst successfully connects porous g-C 3N4 nano sheets into special g-C 3N4 microtubes, the agglomeration of the nano sheets is effectively avoided, a novel heterogeneous catalytic interface is created by the unique hierarchical structure formed by stacking the nano sheets, and more photocatalytic performance reaction sites are displayed. Meanwhile, the catalyst also inherits the advantage of directional electron transmission of the microtubes along the axial direction, provides more electron transmission paths for the catalyst, and accelerates the separation of electrons and holes. In addition, the introduction of phosphorus atoms enhances the visible light absorption range, so that the catalyst can utilize more visible light in the photocatalytic reaction.
The synergistic effect of the above factors makes the catalyst have incomparable advantages in photocatalysis, and provides a brand new idea for structural design of catalyst materials. Compared with the traditional material, the novel structure solves the defects of low light utilization rate and reduced charge transmission efficiency of the catalyst, and the g-C 3N4 after element doping and structural modification greatly expands the absorption and utilization rate of visible light. In addition, the preparation process of the catalyst adopts a method of combining environmental protection, safety, hydrothermal and pyrolysis, is simple to operate, is suitable for large-scale production, is favorable for large-scale popularization and application of the catalyst, and has good application prospects in the fields of sewage treatment, waste gas treatment and the like.
The foregoing has shown and described the basic principles, principal features and advantages of the invention. It will be appreciated by persons skilled in the art that the above embodiments are not intended to limit the invention in any way, and that all technical solutions obtained by means of equivalent substitutions or equivalent transformations fall within the scope of the invention.
Claims (7)
1. The preparation method of the phosphorus-doped porous hierarchical structure carbon nitride photocatalyst is characterized by comprising the following steps of:
S1, preparing a phosphorus doped porous hierarchical structure carbon nitride precursor:
(1) Dissolving urea and phytic acid in deionized water, continuously and ultrasonically treating for a period of time, slowly adding melamine into the deionized water, continuously stirring, and fully dissolving to obtain a mixed solution;
(2) Transferring the mixed solution into an autoclave, performing hydrothermal treatment at 150-200 ℃ for 16-30 hours, cooling, taking out the needle-shaped precursor, washing for multiple times, and drying at 80 ℃ for 3 hours to obtain a phosphorus-doped carbon nitride precursor with a porous hierarchical structure;
s2, preparing phosphorus doped carbon nitride with a porous hierarchical structure:
Placing the precursor obtained in the step S1 into a 200mL airtight porcelain crucible, heating the precursor to 500-550 ℃ at a heating rate of 2-5 ℃/min, calcining for 2-5 h, and naturally cooling to room temperature to obtain a target product; the target product presents a hierarchical structure of stacked porous sheets, and the porous g-C 3N4 nano sheets are connected into g-C 3N4 microtubes.
2. The method for preparing a phosphorus-doped porous hierarchical structure carbon nitride photocatalyst according to claim 1, wherein in the step S1, ultrasonic stirring is adopted for assisting dissolution.
3. The method for preparing a phosphorus-doped porous hierarchical-structure carbon nitride photocatalyst according to claim 1, wherein in the step S1, the step is performed for 16 hours at 200 ℃.
4. The method for preparing a phosphorus-doped porous hierarchical-structure carbon nitride photocatalyst according to claim 1, wherein in the step S2, the carbon nitride photocatalyst is heated to 530 ℃ at a heating rate of 5 ℃/min and is continuously calcined for 4 hours.
5. A phosphorus-doped porous hierarchical carbon nitride photocatalyst, characterized by being produced by the production method according to any one of claims 1 to 4.
6. The phosphorus-doped porous hierarchical carbon nitride photocatalyst according to claim 5, wherein the specific surface area of the catalyst is 55-80 square meters per gram.
7. The use of a phosphorus doped porous hierarchical structure carbon nitride photocatalyst in accordance with claim 5 for degrading rhodamine and tetracycline hydrochloride.
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